TW201200634A

TW201200634A - Anti-oxidation method for surface of metal film and anti-oxidation liquid

Info

Publication number: TW201200634A
Application number: TW100121043A
Authority: TW
Inventors: Atsushi Mizutani; Tadashi Inaba; Tomonori Takahashi; Kazutaka Takahashi
Original assignee: Fujifilm Corp
Priority date: 2010-06-30
Filing date: 2011-06-16
Publication date: 2012-01-01
Also published as: JP5852303B2; TWI551726B; JP2012031501A

Abstract

This invention provides an anti-oxidation method and an anti-oxidation liquid for suppressing or preventing corrosion (erosion) caused by oxidation of a surface of metal film in a semiconductor substrate. Further, this invention provides an anti-oxidation method and an anti-oxidation liquid for suppressing corrosion of a metal film or an insulating film caused by application of anti-oxidation liquid. The anti-oxidation effects thereof can mitigate the influence of water that is supplied at a large amount especially in the dicing process, and to maintain a good surface of the metal film. In the anti-oxidation method of this invention, when using the anti-oxidation liquid to process the surface of the metal film of the semiconductor device, a solution, which includes water containing at least a phosphorous-containing compound and an alkaline compound and having pH of 6 to 10, is used as the anti-oxidation liquid.

Description

201200634 六、發明說明：【發明所屬之技術領域】本發明是有關於一種在半導體元件的製造過程中應用的金屬膜表面的抗氧化方法以及抗氧化液。【先前技術】半導體元件的製造中的切割（dicing)步驟中，為了將形成於晶圓上的積體電路（半導體基板）區分為各個元件尺寸而貫施切斷加工。該切斷加工時，應用鑽石製圓形旋轉刃等切割刀#，使其高速旋轉*精度良好地切開晶圓上的積體電路。以此時產生的熱的冷卻、及伴隨該切斷而產生的切削屑的沖洗為目的，向半導體晶圓上供給大量水。 ’ 進行切割加工時的半導體基板通常具有金屬膜的表面露出的部^例如，圖2所示的半導體基板中，是構成概塾5,的铭-銅合金膜52,的表面在開口露出的狀態。而且’在該切割步驟之後切開的半導體基板絲於電ς基等上，經由該襯墊而利用金線等來電性連接。因此，期其金屬表面清潔，為確保良好導電性的狀態。但是’由於進行上述切割步驟時供給大量純存在半導縣㈣金屬面祕終該純水巾而 Ϊ的情況。例如’以金屬膜構成的襯墊中，其表面經氧;：备將铭或銅等用作金相㈣時，存在進行稱 (pittinge_sicm)的触（條）e的情況（參昭圖其結果為，產生由導通不良5|起的良率下降。故而欲極力 4 201200634 二=如合上二:卜，最近作為襯塾的構成該銘―金得顯著的傾向。因此，你u + π述的腐蝕的進仃變表面使用曰本專利特開細°9^板2屬膜 _號公報中揭示的抗=== 【發明内容】 *，=在中的特有課題的解 :=::r抗氧化==金= =::r中大量提供二影== 屬、表面的抗氧化方法以及抗氧化液。上述課題是利用下述方法來解決。化方法2述課題的解決方法的本發明金屬膜表面的抗氧膜表面’當利用抗氧化液對半導體基板的金屬仃處理時，使用使水中至少含有含碟化合物及驗液。且pH值调整為6〜10的溶液用作上述抗氧化包含的抗氧化方法較佳為在上述抗氧化液中 201200634 ---- f 劑β 胳t’r月的抗氧化方法較佳為’上述防黴、防菌；^酚(Phen〇1)結構、吡咬(pyridine)結構、三嗪 _咖）結構、嗎琳（贿ph〇line)、结構、異售㈣ isot lazoline)結構"比咬鏽（idin 錢結構巾触-麵化錢。 ^ 另外’較佳為上料磷化合物為無_化合物或者有機罐化合物。此外’本發明的抗氧化方法較佳為上述含墙化合物為構酸化合物。進而，本發明的抗氧化方法較佳為使上述抗氧化液中更包含有機羧酸化合物。另外，本發明的抗氧化方法較佳為，上述鹼性化合物是選自由四級胺化合物或者烷醇胺（alkan〇lamine )化合物所組成的組群中的至少1種化合物。除此之外，本發明的抗氧化方法較佳為，上述有機羧酸化合物是選自由檸檬酸（citric acid)、乳酸（lactic acid)、乙酸（acetic acid)、丙酸（propionic acid)、蘋果酸（malic acid)、酒石酸（tartaric acid)、丙二酸（mai〇nic acid)、乙一酸（oxalic acid)、丁二酸（succinic acid)、葡萄糖酸 (gluconic acid )、甘醇酸（glyC〇iic acid )、二甘醇酸 (diglycolic acid)、順丁稀二酸（maleic acid)、苯甲酸 (benzoic acid)、鄰苯二曱酸（phthalic acid)、水楊酸 (salicylic acid )、水揚基異經聘酸（salicylhydroxamic acid)、以及鄰苯二曱異經蔣酸（phthalhydroxamic acid)所 6 201200634 組成的組群中的至少1種化合物。 =之外，本發明的抗氧化方法别實施利用上述抗氧切的處理。步驟之者施的抗氧化方法較佳為在清洗步驟之後，二〗用上从氧倾的處理，其t ，導體基板上的電_殘渣及/或二= f’上述電隸刻殘渣及/或灰化雜是於對上料導= =電=的_步驟、及/或對上述半導先阻進订灰化的灰化步驟中形成。選磷化合物及驗性化合物，且阳值調整為6〜ι〇的3 =Γ t發^的抗氧化液較佳為更包含防黴、防菌劑。物。❼，林明的抗氧化液較佳為更包含有機魏化合進而，本發明的抗氧化液較佳為pH值為6〜8。 [發明的效果] 利用本發明的抗氧化方法以及抗氧化液， t導體基板的由金屬膜表面的氧化引起的雜（侵^ 另外，由抗氧化㈣應用引起的金屬職絕緣 Θ 到抑制，且可姻其抗氧化效果*發揮緩和尤 = 步驟中大量提供的水的影響，維持良好的金屬面= 201200634 異效果【實施方式】不Γϋΐ導值經調整且含有特有成分的水溶液不會腐料導體基板的金屬膜表面，且表現出高抗性。尤其減少於切割步驟中提供的大量水的影響，有效地抑制或防止金屬膜表面的腐鞋。關於該原因，推測為包含未查明的部分。 “ 首先，認為抗氧化液中所含有的含磷化合物具有在金屬膜表面職賴朗作用。通f可列舉，_或鋼或者其合金表面，藉由上述含磷化合物發揮作用而形成特有的鈍態膜，藉由其後與水的接觸亦使氧化的進行得到抑制。進而本案發明者們發現’藉由上述含罐化合物利用驗性化合物的共存來將該液中的pH值調整為特定範圍，則存在特別高的金屬表面的保護作用與低蝕刻能力兩立的區域。以下，對本發明的較佳實施態樣，包括一部分圖式進行詳細說明。但是，並不解釋為由此來限定本發明。依據本發明的較佳實施形態，可於鋁或銅或者其合金 8 201200634 i面形成數nm以上的鈍態膜層，由此可防止氧化。該鈍態膜的存在刊賴麻學分析電子光譜儀（Electron Spe:tlOsec)Py for Chemical Analysis，ESCA )或穿透式電子顯祕鏡（Transmission Electron Microscope，TEM)等來確認，另外，鈍態膜的抗氧化效果可利用水中的開路電位的上升來確認。 [抗氧化液] (水）本發明的抗氧化液含有水作為溶劑。相對於抗氧化液整體的重量’水的含量較佳為6〇重量百分比（wt%)〜99 9 wt% ’更佳為90wt%〜99·9 wt%。有時將如上所述以水為主成分（50 wt%以上）的抗氧化液特別稱為水系抗氧化液。作為水，可為以不損及本發明效果的範圍包含溶解成分的水性介質，或者亦可包含不可避免的微量混合成分。其中’較佳為蒸鶴水或離子交換水、或者超純水之類的經淨化處理的水，特佳為使用半導體製造時使用的超純水。 (含磷化合物）本發明的抗氧化液含有至少丨種含磷化合物（分子内具有磷原子的化合物）。含磷化合物可為無機磷化合物，亦可為有機磷化合物，其中較佳為磷酸化合物。此處，所謂磷酸化合物，是包括磷酸、聚磷酸、膦酸或者該些酸的鹽的概念。此外，本說明書中稱化合物時，是用於除了該化合物本身以外亦包括其鹽、其離子的含義’通常是指該化合物及/或其鹽。具體而言，除了碟酸、聚碟酸以外，亦可 201200634 JOVUVpAl 使用偏填酸（metaphosphoric acid)、超磷酸（ultraphosphoric acid )、亞磷酸（phosphorous acid )、五氧化二填 (diphosphorus pentoxide )、次璘酸（hypophosphorous acid)。於聚磷酸的情況，重複結構較佳為2〜5，於偏磷酸的情況，較佳為3〜5。有機磷化合物中可列舉：曱基膦酸、乙基膦酸、丙基膦酸、丁基膦酸、膦曱酸（foscarnet)、苄基膦酸、胺基曱基膦酸、亞曱基二膦酸、1-羥基乙烷-1，1-雙（膦酸） (l-hydroxyethane-l，l-bis(phosphonicacid))等。上述含磷化合物可單獨使用1種或者將2種以上混合使用。相對於抗氧化液總量，上述含磷化合物較佳為添加〇·〇01 wt%〜1〇 wt% ’更佳為添加〇·〇ι wt%〜5 wt%，特佳為添加0.1 wt%〜2.5 wt%。就可形成1 nm以上的保護膜的觀點而言，較佳為將含磷化合物的量設為上述下限值以上。另一方面’就可抑制過剩的金屬膜蝕刻的觀點而言，較佳為設為上述上限值以下。〈驗性化合物〉本發明的抗氧化液包含鹼性化合物。鹼性化合物可為驗性有機化合物’亦可級性無機化合物，但較佳為驗性有機化合物。較佳為具有碳及氮作為鹼性有機化合物的構成元素，更佳為具有胺基。具體而言，鹼性有機化合物較 =為選自由有機胺及四級銨氫氧化物所組成的組群中的至少1種化合物。此外，所謂有機胺，是指包含碳作為構成 201200634 元素的胺β 鹼性有機化合物的碳數較佳為4〜30，就沸點或者於水中的溶解度的觀點而言，更佳為6〜16。有機胺包括： •乙醇胺（ethanolamine)、二乙醇胺、三乙醇胺、第三丁基二乙醇胺、異丙醇胺（isopropanolamine)、2-胺基-1-丙醇胺（2-amino-l-propanolamine)、3-胺基-1-丙醇胺、異丁醇胺（isobutanolamine)、2-胺基乙醇胺、2-胺基(2-乙氧基乙醇)胺（2-amino(2-ethoxyethanol)amine)、2-胺基(2-乙氧基丙醇)胺、二乙二醇胺（diethylene glycol amine)、二甘醇胺（diglycol amine )、N-經基乙基旅。秦 (N-hydroxyethylpiperazine)等烧醇胺； •乙胺（ethylamine )、苄胺（benzylamine )、二乙胺、正丁胺、3-曱氧基丙胺、第三丁胺、正己胺、環己胺、正辛胺、2-乙基己胺、鄰苯二曱胺（〇-xylenediamine)、間二甲苯二胺（m-xylylenediamine )、1-曱基丁胺、乙二胺 (ethylene diamine，EDA)、1，3-丙二胺（l，3-peopane diamine)、2-胺基苄胺、N-苄基乙二胺、二伸乙基三胺 (di ethylene triamine )、三伸乙基四胺（triethylene tetramine)等不具有羥基的有機胺。四級銨氫氧化物較佳為四烷基氫氧化銨，更佳為經低級（¼數1〜4)院基取代的四烧基氫氧化録，具體而言可列舉四曱基氫氧化銨（tetramethyl ammonium hydroxide， TMAH )、四乙基氫氧化敍（tetraethyl ammonium 201200634 hydroxide’ TEAH)、四丙基氫氧化敍（tetrapropyl ammonium hydroxide，TPAH)、四丁基氫氧化錄（tetrabutyl ammonium hydroxide，TBAH)等。進而，四級铵氫氧化物亦可列舉：三甲基羥基乙基氫氧化銨（膽鹼（choline))、甲基三(羥基乙基)氫氧化銨、四（羥基乙基)氫氧化銨、苄基三曱基氫氧化敍（benzyl trimethyl ammonium hydroxide，BTMAH )等。除此以外，亦可使用氫氧化銨與1種或者1種以上的四級銨氫氧化物的組合。該些四級銨氫氧化物中，更佳為 TMAH、TEAH、TPAH、TBAH、膽鹼，特佳為 TMAH、 TBAH。無機鹼並無特別限定，可列舉KOH、NaOH、LiOH 等，其中較佳為KOH。上述驗性化合物可單獨使用丨種或者將2種以上混合使用。本發明的抗氧化液中’驗性化合物的含量較佳為0.001 wt%〜20 wt°/〇 ’ 更佳為〇 wt%〜wt%，特佳為〇 1 wt0/0 〜5 wt/ί»。就可調整為適當的值的觀點而言，較佳為將驗性化合物的量設為上述下限值以上、上限值以下。〈pH 值〉本發明的抗氧化液的pH值經調整為6〜1〇，pH值較佳為6〜9，pH值更佳為6〜8。藉由將pH值設為上述範圍，可使抗氧化液實質上為中性或弱鹼性，可確保金屬膜或，，層的耐腐钮性。本發明中’只要無特別說明，則pH 值是指以實例巾那的條制定而得的值。為了將抗氧化 12 201200634 液調整為預定pH值，可藉由調節驗性化合物的添加量的滴定來進行。 (羧酸化合物）本發明的抗氧化液較佳為除了上述各成分以外，更包含魏化合物。有機舰化合物可列舉：摔樣酸、乳酸、乙酸、丙酸、蘋果酸、酒石酸、丙二酸、乙二酸、丁二酸、葡萄糖酸、甘醇酸、二甘醇酸、順丁婦二酸、苯甲酸、鄰苯二曱酸、水楊酸、水楊基異經峨、鄰苯二甲異赌酸、甲酸、或者該些_鹽，其中，難為檸檬酸、乳酸、乙酸、頻果酸、酒石酸、丙二酸、水揚基異羥雜、鄰苯二曱異經㈣。上述有驗酸化合物可翔個丨種或者將 2種以上混合制。本發_抗氧化液中，就防歸的觀點而言，有機紐化合物的含量較佳為_丨痛〜1〇 wt%，更佳為讀Wt%〜5 wt%，特佳為_游。〜3加％。 (防黴、防菌劑）本發明中’較佳為更包含防黴、防菌劑。此與本發明的抗氧化液或者使用該抗氧化液的抗氧化方法實質上規定為中性區域的情況密_關。即，作為於強酸性或驗難以表露存在化的現象，有於中性區域料產生細菌而對其液物性造成影響的情況。另外，相反^，正因為是中性區域，故而可應用有效果的防黴、抗菌劑，可發捏其局效果。尤佳為藉由該防黴、抗_的添加，^ 明中適宜轉抗氧倾果的條_如__#、^ 菌劑。考慮到上述狀況，本發日种，較佳為使用包含^ 13 201200634 構、°比咬結構、三嗪結構、嗎琳結構、異嗔唑琳結構、外匕 β定錯結構、四級鍵結構中的任一者的化合物作為防黴、防菌劑。防黴、防菌劑的具體例可列舉：2-甲基-4-異售嗤淋_3_ 酮（2-methyl-4-isothiazoline-3-one)、1,2-苯幷異。塞唾琳_3_ 酮（l，2-benzoisothiazoline-3-one)、5-氣-2-曱基_4_異嘆嗤琳-3-酮（5-chloro-2-methyl-4-isothiazoline-3-〇ne)、鄰苯基苯紛（o-phenyl phenol )、3-甲基-4-氯苯盼 (3-metliyl-4-chlorophenol )、2-酼基吡啶氧化納 (2-mercaptopyridine_N-oxide sodium)、六氫·ι，3,5_三乙基 -均三0秦（hexahy<iro-l，3,5-triethyl-s-triazine)、對曱苯績酸鹽（p-toluenesulfonate )、4-(2-硝基丁基）嗎淋 (4-(2-nitrobutyl)moi*pholine)、4,4'-(2-乙基-2-硝基三亞甲基）二嗎啉 (4,4'-(2-ethyl-2-nitrotrimethylene)dimorpholine )、氯化四曱基銨（tetramethyl ammonium chloride)、氣化十二烧基π比咬鐵（dodecyl pyridinium chloride )等。本發明中，就上述相互作用的方面而言，防黴、防菌劑的含量較佳為0.001 wt%〜10 wt%，更佳為0.01 Wt%〜5 wt〇/〇，特佳為〇.〇1 wt°/〇〜3 wt〇/〇。此外’防黴、防菌劑包括與符合上述含磷化合物或鹼性化合物的化合物共通的化合物，並不妨礙將該些化合物作為防黴、防菌劑來應用。 (其他成分） 201200634 •含胺基的羧酸化合物除此以外，本發明的抗氧化液亦可含有含胺基的羧酸化合物。含胺基的羧酸化合物就效率良好地防止金屬腐蝕的方面而言較佳。含胺基的羧酸化合物較佳為精胺酸 (arginine)、組胺酸（histidine)、麩胺酸（glutamine)、乙一胺四乙酸（ethylenediamine tetraacetic acid，EDTA )、二伸乙基二胺五乙酸（diethylene triamine pentaacetic acid， DTPA)、羥基亞胺基二乙酸（hydroxy imino diacetic acid， HIDA) ’更佳為精胺酸、組胺酸。該些含胺基的羧酸化合物可單獨使用1種或者將2種以上混合使用。本發明的抗氧化液中’於含有含胺基的羧酸化合物的情況，其添加量可適當選擇，相對於本發明的抗氧化液的總重量，較佳為約 0.01 wt%〜約 5.0 wt%，更佳為〇.〇1 wt%〜3 wt0/〇。 •界面活性劑另外，本發明的抗氧化液可含有界面活性劑。界面活性劑可使用非離子性、陰離子性、陽離子性界面活性劑、以及兩性界面活性劑。相對於抗氧化液的總重量，抗氧化液中的界面活性劑的含量較佳為〇〇〇〇1 wt%〜5 wt%，更佳為0.0001 wt%〜1 wt%。藉由將界面活性劑添加於抗氧化液中，可調整其黏度，改良對於對象物的潤濕性，因此較佳，此外，就對基板或絕緣膜等的損壞性兩者更優異的方面而言錄佳。此種界面活_通常可在商業上獲取。該些界面活性劑可單獨使用或者將多種組合使用。 •抗腐钮劑 201200634 本發明的抗氧化液可含有雜環化合物。雜環化合物更佳為苯幷三唑以及其衍生物。上述衍生物較佳為5,6-二曱基-1，2,3-苯幷三 °坐（5,6-dimethyl-l，2,3-benzotriazole， DBTA ) 、1-(1，2-二羧基乙基）苯幷三唑 (l-(l，2-dicarboxyethyl)benzotriazole，DCEBTA)、1-[N,N- 雙（羥基乙基）胺基甲基]苯幷三唑 (l-[N,N-bis(hydroxyethyl)aminomethyl]benzotriazole ， HEABTA ) 、 1-(羥基甲基）苯幷三唑 (l-(hydroxymethyl)benzotriazole，HMBTA)。本發明中使用的抗腐蝕劑可單獨使用，亦可併用2種以上。另外，本發明中使用的抗腐蝕劑除了可依據常規方法來合成以外，亦可使用市售品。另外，相對於抗氧化液總量，抗腐钮劑的添加量較佳為〇.〇1 wt%以上0.2 wt%以下，更佳為〇 wt%以上〇.2 wt%以下。 [淋洗方法] 接著，對本發明的抗氧化液的較佳應用方法（淋洗方法）進行說明。本實施形態中，較佳為在切割步驟之前實施利用上述抗氧化液的處理。另外，較佳為在清洗步驟之後，貫施利用上述抗氧化液的處理，其中上述清洗步驟是對形成於半導體基板上的電漿蝕刻殘渣及/或灰化殘渣進行β洗，上述電聚飯刻殘潰及/或灰化殘渣是於對半導體某板進行電㈣刻的侧步似/或對半導縣板上的光二進行灰化的灰化步驟+形成。藉由在此賴f施本發明的抗氧化處理，可有效果地紐半導縣板的金屬膜表面避 201200634 =步驟巾的大4水接騎㈣的紐，尤其就獲的方面而言較佳。但’除了該時機以外，並不㈣述抗氧化液。此外，當將由抗·液或清洗液「腐^ β膜的「腐餘」、與由切割步驟中的大量水引起的腐钮」區別而言時，有時將後者稱為「侵I虫」。搜ϊϋ將利用本發明抗氧化液的處理稱為淋洗或淋洗處 …ϊϊ抗氧化液稱為淋洗液。此與上述殘渣的清洗組 Μ# π^液）不同，是指作為與其不同的處理液來應用至用過洗髮精之後的潤絲(rinse)同樣地考慮 B理液之類的方面的稱呼❶此外，此處所謂的將上述賴的清洗之後進—步沖洗該清洗液的 i日本專利特開2007-123787號公報）為了補充 i;=效果而追加清洗的處理（曰本專利特開 2003-5388唬公報）加以區別。 /一曰；利用本發明抗氧化液的處理之前利用其他藥液進打晶圓的前處理。晶_前處理液較水液 =舉四甲基氣氧化錄(TMAH)、四乙二2 (TBAH))、等四丙基4氧化錢（TPAH)、四丁基氮氧化錢本七明的抗氧化液用作殘;查的清洗組成物（清洗液）的月况基本上未經設想。其仙在於，近年來的裝置結構法兼顧殘渣去除、低金屬膜蝕刻、藉由保護 ^ 、几氧化，故而藉由將清洗液及抗氧化液製成2 液’可達成上述3項。較佳為與本發明的抗氧化液加以組 17 201200634 合的清洗液的配方可列舉下述組成物。 •至少使水中含有氟化合物及羧酸的清洗組成物 •至少使水中含有氟化合物及胺的清洗組成物 •至少使水中含有烷醇胺及羥基胺的清洗組成物 •包含有機溶劑的清洗組成物 •包含羥基胺、羧酸及水的清洗組成物藉由將本發明的抗氧化液與上述清洗組成物組合使用，就殘渣去除、金屬膜的低鞋刻能力及抗氧化之類的效果提咼的方面而言較佳。此外，上述清洗組成物的組成 (wt%)可任意設定，例如只要根據其pH值，將酸性化合物與驗性化合物加以調配即可。本發明的抗氧化液並不取決於特定的淋洗方法，可適合於各種實施態樣來使用。例如，使用裝置可為葉片式、分批式中的任一種。淋洗時的溫度較佳為室溫以上。處理時間較佳為30秒至10分鐘。應用量可適當選擇。 [半導體元件的製造] 接著’使用圖1 (圖1_丨〜圖M)，對可適宜應用本發明抗氧化_半導體元㈣結構及其製造難的—例進行 ^月。該®是表示基於本實施形態的半導體元件的製造過程的一部分的概要的步驟剖面圖。本實施形態中，將半導體基板構成為預定結構，於該半導體基板的最上部設置有使所形成的襯墊（襯墊電極）5露出的開口部H (參昭圖 1_4)。其後於電路基板上的安裝時，以該縫的部分為端子來連接金線等。本實施形態中，是級該㈣步驟而於 201200634 该露出的她的金屬縣面μ形成鈍祕來避免氧化腐飿。此外’本說明書t，所謂半導體基板’是作為製造半導，元件財_ (前驅物）的_來使用，是不僅包括石夕晶圓’而且包括於财晶圓上安裝有麟膜或電極等的安裝前的中間製品的含義。化成於半導體基板上的多層配線結構中，於所積層的，間絕緣膜巾形成有配線圖案。另外，連接配線圖案間的通道適讀成於層間絕緣财。圖巾的步驟⑷中，（圖 :U表不-形成至襯塾為止的多層配線結構的最上部的一 ^。如圖示’、於形成於半導體基板（未圖示）上的層間絕哲，1中形成有配線圖案7。配線圖案7包括TiN或Ti膜 P早壁金屬膜7卜及覆蓋於障壁金屬膜71上的紹（A1) μ 72°其旁邊義示有崎蓋於障壁金屬膜81上的A1膜，構成的配線圖案8,但該剖面中未與襯墊連接^此外，曰’絕緣膜1及和絕軸2雖亦表示剖面，但為了避免圖的繁雜化，未標註陰影。绍祕於形成有配線圖案7的層間絕緣膜1丨，形成有層間、:膜2。於層間絕緣膜2 +，形成有連接有配線圖案7 於陪ί 6 °通道6包括氮化鈦膜等障壁金屬膜6卜及覆蓋緣金屬膜61上的鶴膜62。於形成有通道6的層間絕细上，形成該由通道6 *連接於配線®* 7的襯墊 ^塾電^ 5。襯墊5包括依序積層的密著膜51、A1_Cu 社槿者膜52。密著模51、53包括鈦/|U化欽的積層、、.°構或者氮化制單層結構。於如上所述形成有襯塾5的 201200634 l 層間絕緣膜2上，利用例如高密度電漿化學氣相沈積 (chemical vapor deposition ’ CVD)法來形成石夕氧化膜 3 (參照圖1-1的步驟（b))。繼而’於矽氧化膜3上，利用例如電漿CVD法來形成包含矽氮化膜的鈍化膜4 (參照圖1_2的步驟（c))。接著’於鈍化膜4上’利用光微影法，形成使到達襯墊5的開口部的形成區域露出的光阻膜（未圖示）。繼而，以該光阻臈為遮罩，藉由使用電漿的乾式蝕刻，對鈍化膜 4及石夕氧化膜3進行钱刻。此時，襯塾5的密著膜Η以及 Al-Cu膜52的上部亦可經姓刻《如此，於鈍化膜4及石夕氧化膜3上形成使襯墊5露出的開口部H (參照圖1-2的步驟（d))。鈍化膜4及矽氧化膜3的乾式蝕刻分別可利用= 知的方法來進行。繼而’藉由使用電漿的灰化，來去除用作遮罩的光阻膜（參照圖1·3的步驟（e))。光_的灰化可_公知的方法來進行。於用以形賴口部Η的光阻_形成膜4及魏化膜3的乾絲_制时除光阻開口糾周邊的表面的基板表面附著殘澄（電漿触刻殘渣）z。該殘h來自於變質的光阻膜 = 石夕氧化膜3、以及密著制、A1_Cu膜& #。_膜4、據殘渣的種類來區別表示。 T未根因此 %用Μ云除光阻膜的灰化後，來清洗形成至使襯墊52露出關口料為止板（圖1-3的步驟(f))。如此，開口部Η的内壁及底面（ 201200634 膜表面）經清洗，去除附著於其上的殘渣Z。此時的清洗液可使用市售的清洗液等。市售品可列舉：EKC Technology Inc.公司製造的 EKC 265 (¾主冊商標）、Ashland Chemical 公司製造的 ACT935 (在冊商標）、Mitsubishi Gas Chemical 公司製造的ELM C-30 (商品名）等。關於該些製品，亦作為專利文獻來公開（參照美國專利第5279771號說明書、美國專利第5419779號說明書、美國專利第563〇9〇4 號說明書）° 本實施形態中，於上述清洗步驟之後包括應用上述抗氧化液的淋洗步驟C參照圖1-4的步驟（g))。此時的淋洗條件如上所述。依據本實施形態，上述抗氧化液的作用得到發揮’於襯墊表面露出的鋁-銅合金（A1Cu)膜52的表面經處理，於其上形成鈍態膜未圖示的膜（層）為示意化表示者’亦可料作為具有厚麵膜（層）而可辨認者。如此利用抗氧化液’ Al-Cu膜52表面得到保護，經賦予抗氧化性’因此即便在其後繼續的切割步驟中曝露量的水或水性介質中，亦抑制、防止A1心膜㈣# ^ =因此，依據本實施形態，當於該缝上連接金線等時二發揮無孔# (pmmgeorn^ion)等的良現更高的良率。 [實例] 以下，利財例對本發日骑行更詳明不受該些實例的限定。彳一本韻 (實例I) 21 201200634 〈實例、比較例、參考例〉201200634 VI. Description of the Invention: [Technical Field] The present invention relates to an anti-oxidation method and an anti-oxidation liquid for a metal film surface to be applied in a process of manufacturing a semiconductor element. [Prior Art] In the dicing step in the manufacture of a semiconductor element, the cutting process is performed in order to divide the integrated circuit (semiconductor substrate) formed on the wafer into individual element sizes. In the cutting process, a cutting blade # such as a circular rotary blade made of diamond is used to rotate at a high speed*, and the integrated circuit on the wafer is cut accurately. A large amount of water is supplied to the semiconductor wafer for the purpose of cooling the heat generated at this time and flushing the chips generated by the cutting. The semiconductor substrate in the case of performing the dicing process usually has a portion in which the surface of the metal film is exposed. For example, in the semiconductor substrate shown in FIG. 2, the surface of the etch-copper alloy film 52 constituting the outline 5 is exposed. . Further, the semiconductor substrate wire which is cut after the dicing step is electrically connected to the electric raft or the like via a pad, and is electrically connected by a gold wire or the like. Therefore, the metal surface is cleaned to ensure a good electrical conductivity. However, it is a case where a large amount of purely semi-conducting (four) metal surface is supplied to the pure water towel due to the above-mentioned cutting step. For example, in a gasket made of a metal film, the surface thereof is made of oxygen; when a metal or a metal is used as the metallographic phase (4), there is a case where a tap (e) e is called (pittinge_sicm). In order to produce a decrease in yield due to poor conduction 5 | Therefore, I want to do my best 4 201200634 2 = If I close the second: Bu, the composition of the lining has recently become a significant tendency for gold. Therefore, you u + π The surface of the corroded enthalpy is 抗专利专利专利 ^ ^ ^ ^ ^ 2 2 2 2 2 _ 抗抗抗抗【【【【【【【【【【【【【【【【【【【【特特特特Antioxidant == gold = =:: r provides a large number of two shadows == genus, surface anti-oxidation method and anti-oxidation liquid. The above problem is solved by the following method. The present invention of the solution to the problem The surface of the anti-oxidation film on the surface of the metal film is used to treat the metal ruthenium of the semiconductor substrate with an anti-oxidation solution, and the solution containing at least the dish-containing compound and the test liquid in the water is used. The solution having a pH adjusted to 6 to 10 is used as the above-mentioned antioxidant. The antioxidant method included is preferably in the above antioxidant liquid 201200634 ---- f agent β The anti-oxidation method of t'r month is preferably 'the above-mentioned mildewproof, antibacterial; phenol (Phen〇1) structure, pyridine structure, triazine_cafe structure, hualin (bribe ph〇line) Structure, sale (4) isot lazoline) structure " than biting rust (idin money structure towel touch-face money. ^ Also 'preferably the feed phosphorus compound is no compound or organic can compound. In addition' the invention Preferably, the anti-oxidation method of the present invention further comprises the above-mentioned antioxidant compounding method further comprising an organic carboxylic acid compound. Further, the antioxidant method of the present invention is preferably an antioxidant method. The above basic compound is at least one compound selected from the group consisting of a quaternary amine compound or an alkanolamine compound. In addition, the antioxidant method of the present invention is preferably the above The organic carboxylic acid compound is selected from the group consisting of citric acid, lactic acid, acetic acid, propionic acid, malic acid, tartaric acid, malonic acid ( Mai〇nic acid) Oxalic acid, succinic acid, gluconic acid, glycolic acid, diglycolic acid, maleic acid , benzoic acid, phthalic acid, salicylic acid, salicylhydroxamic acid, and phthalhydroxamic acid ) at least one compound of the group consisting of 6 201200634. In addition, the antioxidant method of the present invention does not carry out the treatment using the above-described anti-oxidation. The anti-oxidation method applied by the step is preferably after the washing step, and the treatment is carried out from the oxygen, wherein t, the electric_residue on the conductor substrate and/or the second electric power residue and/or Or ashing is formed in the ash step of the upper material == electric = and/or the ashing step of arranging the above-mentioned semi-conductive first ashing. The anti-oxidation liquid of the phosphorus compound and the test compound, and the positive value is adjusted to 6 to 〇 3 = Γ t hair is preferably further contained in the mold and the antibacterial agent. Things. Preferably, Lin Ming's antioxidant liquid further comprises organic Wei compound. Further, the antioxidant liquid of the present invention preferably has a pH of 6-8. [Effects of the Invention] The anti-oxidation method and the anti-oxidation liquid of the present invention cause the impurities of the t-conductor substrate caused by the oxidation of the surface of the metal film (in addition, the metal-based insulation caused by the application of the anti-oxidation (IV), to the suppression, and It can be used as a tempering effect* to ease the effect of water provided by a large number of steps in the step, maintaining a good metal surface = 201200634 different effects [embodiment] An aqueous solution whose conductivity value is adjusted and contains a specific component will not be a corrosion conductor The surface of the metal film of the substrate exhibits high resistance, in particular, the effect of a large amount of water provided in the cutting step, effectively suppressing or preventing the corrosion of the surface of the metal film. For this reason, it is presumed to contain an unidentified portion. "First of all, it is considered that the phosphorus-containing compound contained in the antioxidant liquid has a role in the surface of the metal film. The surface of the metal film can be exemplified by _ or steel or its alloy surface, which is formed by the action of the above-mentioned phosphorus-containing compound. The passive film, by subsequent contact with water, also inhibits the progress of oxidation. Further, the inventors of the present invention found that 'by the above-mentioned can-containing compound When the pH of the liquid is adjusted to a specific range by the coexistence of the test compound, there is a region in which the protection of the metal surface is particularly high and the low etching ability exists. Hereinafter, preferred embodiments of the present invention include A part of the drawings is described in detail. However, the invention is not limited thereto. According to a preferred embodiment of the present invention, a passive film layer of several nm or more may be formed on the surface of aluminum or copper or its alloy 8 201200634 i. Therefore, oxidation can be prevented. The existence of the passive film is based on the analysis of an electron spectrometer (Electron Spe: tlOsec) Py for Chemical Analysis (ESCA) or a Transmission Electron Microscope (TEM). Further, it was confirmed that the antioxidant effect of the passive film can be confirmed by an increase in the open circuit potential in water. [Antioxidant solution] (Water) The antioxidant liquid of the present invention contains water as a solvent, and the weight of the entire antioxidant liquid is ' The content of water is preferably 6 〇 weight percent (wt%) to 99 9 wt% 'more preferably 90 wt% 〜 99·9 wt%. Sometimes water is used as a main component (50 wt% or more) as described above. anti- The chemical liquid is particularly referred to as a water-based antioxidant liquid. The water may be an aqueous medium containing a dissolved component in a range that does not impair the effects of the present invention, or may contain an unavoidable trace mixed component. The purified water such as ion-exchanged water or ultrapure water is particularly preferably ultrapure water used in the manufacture of a semiconductor. (Phosphorous compound) The antioxidant liquid of the present invention contains at least a phosphorus-containing compound (molecule) a compound having a phosphorus atom therein. The phosphorus-containing compound may be an inorganic phosphorus compound or an organic phosphorus compound, and among them, a phosphoric acid compound is preferred. Here, the phosphoric acid compound includes phosphoric acid, polyphosphoric acid, phosphonic acid or the like. The concept of acid salt. Further, when the compound is referred to in the present specification, it is intended to include a salt thereof and an ion thereof in addition to the compound itself, and generally means the compound and/or a salt thereof. Specifically, in addition to dish acid and poly-disc acid, 201200634 JOVUVpAl can also be used as metaphosphoric acid, ultraphosphoric acid, phosphorous acid, diphosphorus pentoxide, and Hypophosphorous acid. In the case of polyphosphoric acid, the repeating structure is preferably 2 to 5, and in the case of metaphosphoric acid, preferably 3 to 5. Examples of the organophosphorus compound include: mercaptophosphonic acid, ethylphosphonic acid, propylphosphonic acid, butylphosphonic acid, foscarnet, benzylphosphonic acid, aminodecylphosphonic acid, and anthranylene Phosphonic acid, 1-hydroxyethane-1,1-bis(phosphonic acid), and the like. These phosphorus-containing compounds may be used alone or in combination of two or more. The phosphorus-containing compound is preferably added in an amount of wt·〇01 wt% to 1% by weight relative to the total amount of the antioxidant liquid. More preferably, it is added 〇·〇ι wt% to 5 wt%, and particularly preferably 0.1 wt%. ~2.5 wt%. From the viewpoint of forming a protective film of 1 nm or more, the amount of the phosphorus-containing compound is preferably set to the above lower limit value. On the other hand, from the viewpoint of suppressing excessive metal film etching, it is preferably set to be equal to or less than the above upper limit. <Experimental Compound> The antioxidant solution of the present invention contains a basic compound. The basic compound may be an organic compound of the organic compound, but is preferably an organic compound. It is preferably a constituent element having carbon and nitrogen as the basic organic compound, and more preferably an amine group. Specifically, the basic organic compound is at least one compound selected from the group consisting of organic amines and quaternary ammonium hydroxides. In addition, the organic amine means that the carbon number of the amine β basic organic compound containing carbon as the element constituting 201200634 is preferably 4 to 30, and more preferably 6 to 16 from the viewpoint of the boiling point or the solubility in water. Organic amines include: • ethanolamine, diethanolamine, triethanolamine, tert-butyldiethanolamine, isopropanolamine, 2-amino-l-propanolamine , 3-amino-1-propanolamine, isobutanolamine, 2-aminoethanolamine, 2-amino(2-ethoxyethanol)amine 2-Amino (2-ethoxypropanol)amine, diethylene glycol amine, diglycol amine, N-transethylethyl brigade. N-hydroxyethylpiperazine and other alkanolamines; • ethylamine, benzylamine, diethylamine, n-butylamine, 3-methoxypropylamine, tert-butylamine, n-hexylamine, cyclohexylamine , n-octylamine, 2-ethylhexylamine, phthalic acid-xylenediamine, m-xylylenediamine, 1-mercaptobutylamine, ethylene diamine (EDA) , 1, 3-propopane diamine, 2-aminobenzylamine, N-benzylethylenediamine, di ethylene triamine, tri-ethyltetramine An organic amine having no hydroxyl group, such as triethylene tetramine. The quaternary ammonium hydroxide is preferably a tetraalkylammonium hydroxide, more preferably a tetrahydrocarbyl hydroxide substituted by a lower (1⁄4 to 1 to 4) yard group, and specifically, a tetradecyl ammonium hydroxide is exemplified. (tetramethyl ammonium hydroxide, TMAH), tetraethyl ammonium 201200634 hydroxide 'TEAH, tetrapropyl ammonium hydroxide (TPAH), tetrabutyl ammonium hydroxide (TBAH) Wait. Further, the quaternary ammonium hydroxide may also be exemplified by: trimethylhydroxyethylammonium hydroxide (choline), methyltris(hydroxyethyl)ammonium hydroxide, tetrakis(hydroxyethyl)ammonium hydroxide Benzyl trimethyl ammonium hydroxide (BTMAH) and the like. Alternatively, a combination of ammonium hydroxide and one or more kinds of quaternary ammonium hydroxides may be used. Among the quaternary ammonium hydroxides, more preferred are TMAH, TEAH, TPAH, TBAH, choline, and particularly preferably TMAH, TBAH. The inorganic base is not particularly limited, and examples thereof include KOH, NaOH, and LiOH. Among them, KOH is preferable. The above-mentioned test compounds may be used singly or in combination of two or more. The content of the 'intestinal compound in the antioxidant liquid of the present invention is preferably 0.001 wt% to 20 wt%/〇', more preferably 〇wt% to wt%, particularly preferably 〇1 wt0/0 〜5 wt/ί» . From the viewpoint of being able to adjust to an appropriate value, the amount of the test compound is preferably equal to or higher than the lower limit value and equal to or lower than the upper limit value. <pH value> The pH of the antioxidant liquid of the present invention is adjusted to 6 to 1 Torr, the pH is preferably 6 to 9, and the pH is more preferably 6 to 8. By setting the pH to the above range, the antioxidant liquid can be made substantially neutral or weakly alkaline, and the corrosion resistance of the metal film or the layer can be ensured. In the present invention, the pH value is a value determined by the strip of the example towel unless otherwise specified. In order to adjust the antioxidant 12 201200634 to a predetermined pH, it can be carried out by adjusting the titration of the addition amount of the test compound. (Carboxylic Acid Compound) The antioxidant liquid of the present invention preferably contains a Wei compound in addition to the above respective components. Organic ship compounds can be listed as: acid, lactic acid, acetic acid, propionic acid, malic acid, tartaric acid, malonic acid, oxalic acid, succinic acid, gluconic acid, glycolic acid, diglycolic acid, cis-butan Acid, benzoic acid, phthalic acid, salicylic acid, salicyl isomer, phthalic acid, formic acid, or the salt thereof, wherein citric acid, lactic acid, acetic acid, frequency Acid, tartaric acid, malonic acid, water-isolated isophthalic acid, ortho-benzoic acid (4). The above-mentioned acid-testing compound may be produced by a mixture of two or more kinds. In the hair _ antioxidant solution, in terms of anti-return, the content of the organic nucleus compound is preferably _ 丨 pain ~ 1 〇 wt%, more preferably Wt% ~ 5 wt%, especially good _ swim. ~3 plus %. (Moldproof and antibacterial agent) In the present invention, it is preferable to further contain a mold and a fungicide. This is in contrast to the case where the antioxidant solution of the present invention or the antioxidant method using the antioxidant solution is substantially defined as a neutral region. In other words, as a phenomenon in which strong acidity or difficulty is revealed, there is a case where bacteria are generated in the neutral region material to affect the liquid properties. In addition, on the contrary, because it is a neutral region, it is possible to apply an effective mildew-proof and antibacterial agent, and it is possible to pinch its effect. It is especially preferable to add the anti-oxidation fruit to the strip by the addition of the anti-mildew and anti- _, such as __#, ^ bacteria. In view of the above situation, it is preferred to use the composition of the present invention, including the composition of the structure, the ratio of the bite structure, the triazine structure, the morphine structure, the isoxazole structure, the external 匕β-error structure, and the quaternary bond structure. The compound of any of them is used as a mildewproof and antibacterial agent. Specific examples of the mold-proofing and antibacterial agent include 2-methyl-4-isothiazoline-3-one and 1,2-phenylene. 1,2-benzoisothiazoline-3-one, 5-gas-2-mercapto-4_chloro-2-methyl-4-isothiazoline- 3-〇ne), o-phenyl phenol, 3-metliyl-4-chlorophenol, 2-mercaptopyridine-N- Oxide sodium), hexahydro·ι, 3,5_triethyl-all-trimethyl (hexahy<iro-l,3,5-triethyl-s-triazine), p-toluenesulfonate 4-(2-nitrobutyl)moi*pholine, 4,4'-(2-ethyl-2-nitrotrimethylene)dimorpholine (4 , 4'-(2-ethyl-2-nitrotrimethylene) dimorpholine ), tetramethyl ammonium chloride, dodecyl pyridinium chloride, and the like. In the present invention, in terms of the above interaction, the content of the mildewproof and antibacterial agent is preferably 0.001 wt% to 10 wt%, more preferably 0.01 Wt% to 5 wt〇/〇, particularly preferably 〇. 〇1 wt°/〇~3 wt〇/〇. Further, the antifungal and antibacterial agent includes a compound which is common to a compound which satisfies the above-mentioned phosphorus-containing compound or basic compound, and does not prevent the use of these compounds as a mildew-proof or antibacterial agent. (Other components) 201200634 • Amino group-containing carboxylic acid compound Otherwise, the antioxidant liquid of the present invention may contain an amine group-containing carboxylic acid compound. The amine group-containing carboxylic acid compound is preferred in terms of efficiently preventing metal corrosion. The amine group-containing carboxylic acid compound is preferably arginine, histidine, glutamine, ethylenediamine tetraacetic acid (EDTA) or diethylenediamine. Diethylene triamine pentaacetic acid (DTPA) and hydroxy imino diacetic acid (HIDA) are more preferably arginine or histidine. These amine group-containing carboxylic acid compounds may be used alone or in combination of two or more. In the case of containing the amine group-containing carboxylic acid compound in the antioxidant solution of the present invention, the amount thereof may be appropriately selected, and is preferably from about 0.01% by weight to about 5.0% based on the total weight of the antioxidant liquid of the present invention. %, more preferably 〇.〇1 wt%~3 wt0/〇. • Surfactant In addition, the antioxidant liquid of the present invention may contain a surfactant. Nonionic, anionic, cationic surfactants, and amphoteric surfactants can be used as the surfactant. The content of the surfactant in the antioxidant liquid is preferably from wt1 wt% to 5 wt%, more preferably from 0.0001 wt% to 1 wt%, based on the total weight of the antioxidant liquid. By adding a surfactant to the antioxidant liquid, the viscosity can be adjusted, and the wettability to the object can be improved, which is preferable, and the damage to the substrate or the insulating film is more excellent. Good words. Such interface activity is generally commercially available. These surfactants may be used singly or in combination of plural kinds. • Anti-corrosion button 201200634 The antioxidant solution of the present invention may contain a heterocyclic compound. The heterocyclic compound is more preferably benzotriazole or a derivative thereof. The above derivative is preferably 5,6-dimercapto-1,2,3-benzoquinone, (5,6-dimethyl-l,2,3-benzotriazole, DBTA), 1-(1,2- 1-(l,2-dicarboxyethyl)benzotriazole (DCEBTA), 1-[N,N-bis(hydroxyethyl)aminomethyl]benzotriazole (l-[ N,N-bis(hydroxyethyl)aminomethyl]benzotriazole, HEABTA ), 1-(hydroxymethyl)benzotriazole (HMBTA). The anticorrosive agent used in the present invention may be used singly or in combination of two or more. Further, the anticorrosive agent used in the present invention may be synthesized in accordance with a conventional method, and a commercially available product may also be used. Further, the amount of the anti-corrosion button added is preferably 〇. 〇1 wt% or more and 0.2 wt% or less, more preferably 〇 wt% or more 〇. 2 wt% or less, relative to the total amount of the antioxidant liquid. [Draining method] Next, a preferred application method (rinsing method) of the antioxidant liquid of the present invention will be described. In the present embodiment, it is preferred to carry out the treatment using the above antioxidant liquid before the cutting step. Further, it is preferable that after the cleaning step, the treatment using the anti-oxidation liquid is performed, wherein the cleaning step is performing β-washing on the plasma etching residue and/or the ashing residue formed on the semiconductor substrate, and the electric gathering rice The ruin and/or ashing residue is formed by ashing step + of the electric side of the semiconductor plate and/or ashing of the light 2 on the semi-conductive plate. By applying the anti-oxidation treatment of the invention in this way, it is effective to avoid the surface of the metal film of the New Zealand semi-conductor plate avoiding 201200634 = step 4 of the large water connection (four) of the step towel, especially in terms of aspects obtained. good. However, in addition to this timing, the antioxidant liquid is not described. In addition, when the anti-liquid or the cleaning solution "resolves the "corrosion" of the β film and the decay button caused by the large amount of water in the cutting step", the latter is sometimes referred to as "invasion of the insect". . Searching for the treatment with the antioxidant solution of the present invention is referred to as rinsing or rinsing ... ϊϊ The antioxidant solution is referred to as an eluent. This is different from the cleaning group Μ# π^ liquid of the above-mentioned residue, and is referred to as a rinse after the shampoo used as a treatment liquid different from the above, and the name of the B liquid is considered in the same manner. In addition, in the case of the rinsing of the above-mentioned rinsing, the rinsing of the rinsing liquid, the rinsing of the rinsing liquid is described in the Japanese Patent Laid-Open Publication No. 2007-123787. -5388唬 bulletin) to distinguish. / 曰; pre-treatment using other chemical solutions before the treatment of the antioxidant liquid of the present invention. Crystal_pretreatment liquid compared to water liquid = tetramethyl gas oxidation record (TMAH), tetraethylene 2 (TBAH), tetrapropyl 4 oxidized money (TPAH), tetrabutyl oxynitride The antioxidant solution was used as a residue; the monthly condition of the cleaning composition (cleaning solution) was basically unimagined. It is a matter of fact that in recent years, the device structure method has taken care of residue removal, low metal film etching, protection by oxidation, and oxidation, so that the above three items can be achieved by making the cleaning liquid and the antioxidant liquid into two liquids. The formulation of the cleaning liquid which is preferably combined with the antioxidant liquid of the present invention in the group of 17 201200634 is exemplified by the following composition. • A cleaning composition containing at least a fluorine compound and a carboxylic acid in water, a cleaning composition containing at least a fluorine compound and an amine in water, a cleaning composition containing at least an alkanolamine and a hydroxylamine in water, and a cleaning composition containing an organic solvent. • A cleaning composition comprising hydroxylamine, carboxylic acid and water is used in combination with the above-mentioned cleaning composition by using the antioxidant liquid of the present invention, thereby improving the residue removal, the low engraving ability of the metal film, and the antioxidant effect. In terms of aspects, it is better. Further, the composition (wt%) of the above-mentioned cleaning composition can be arbitrarily set, for example, the acidic compound and the test compound can be formulated according to the pH value thereof. The antioxidant liquid of the present invention does not depend on a specific elution method, and can be suitably used in various embodiments. For example, the use device may be any of a blade type and a batch type. The temperature at the time of rinsing is preferably room temperature or higher. The treatment time is preferably from 30 seconds to 10 minutes. The amount of application can be appropriately selected. [Manufacturing of Semiconductor Element] Next, using FIG. 1 (FIG. 1_丨 to FIG. M), an example in which the structure of the oxidation-semiconductor element (IV) of the present invention can be suitably applied and its production is difficult is performed. This is a step sectional view showing an outline of a part of the manufacturing process of the semiconductor element of the present embodiment. In the present embodiment, the semiconductor substrate is formed into a predetermined structure, and an opening portion H for exposing the formed spacer (pad electrode) 5 is provided on the uppermost portion of the semiconductor substrate (see Fig. 1 to 4). Thereafter, when mounting on a circuit board, a gold wire or the like is connected with a portion of the slit as a terminal. In the present embodiment, the step (4) is performed, and at 201200634, the exposed metal surface of the metal is formed to be blunt to avoid oxidative rot. In addition, 'this specification t, the so-called semiconductor substrate' is used as a semi-conductor for manufacturing semi-conductors, and is used not only to include the Shihwa wafer but also to include a film or an electrode on the wafer. The meaning of the intermediate product before installation. In the multilayer wiring structure formed on the semiconductor substrate, a wiring pattern is formed on the interlayer insulating film. In addition, the channel connecting the wiring patterns is suitable for inter-layer insulation. In the step (4) of the figure, (Fig. U: the uppermost part of the multilayer wiring structure formed until the lining is formed. As shown in the figure, the layer formed on the semiconductor substrate (not shown) A wiring pattern 7 is formed in 1. The wiring pattern 7 includes a TiN or Ti film P, an early-wall metal film 7 and a layer covering the barrier metal film 71 (A1) μ 72°, which is covered with a barrier metal. The wiring pattern 8 formed in the A1 film on the film 81 is not connected to the spacer in the cross section. Further, the insulating film 1 and the absolute axis 2 also have a cross section, but are not labeled in order to avoid complication of the drawing. The interlayer insulating film 1 形成 formed with the wiring pattern 7 is formed with interlayers: a film 2. The interlayer insulating film 2 + is formed with a wiring pattern 7 connected thereto, and the titanium nitride layer 6 is formed on the channel 6 a barrier metal film 6 such as a film and a coating film 62 covering the edge metal film 61. The interlayer 6* is connected to the wiring of the wiring layer**5 on the interlayer formed with the channel 6. The gasket 5 includes a film 51 and an A1_Cu film 52 which are sequentially laminated. The adhesion molds 51 and 53 include a laminate of titanium/|U Huaqin. a single-layer structure of a structure of TiO 2 or the like, which is formed on the interlayer dielectric film 2 of the lining 5 as described above, by, for example, a high-density plasma vapor deposition (CVD) method. Forming the iridium oxide film 3 (refer to step (b) of FIG. 1-1). Then, on the ruthenium oxide film 3, a passivation film 4 including a ruthenium nitride film is formed by, for example, a plasma CVD method (refer to FIG. 1_2 Step (c)) Next, a photoresist film (not shown) that exposes the formation region of the opening portion of the spacer 5 is formed by photolithography on the passivation film 4. Then, the photoresist is formed by the photoresist. For the mask, the passivation film 4 and the etched oxide film 3 are etched by dry etching using a plasma. At this time, the adhesion film of the lining 5 and the upper portion of the Al-Cu film 52 may be surnamed. Thus, the opening portion H for exposing the spacer 5 is formed on the passivation film 4 and the etched oxide film 3 (see step (d) of FIG. 1-2). The dry etching of the passivation film 4 and the tantalum oxide film 3 are respectively performed. It can be carried out by using the method of =. Then, by using the ashing of the plasma, the photoresist film used as a mask is removed (refer to Figure 1.3). Step (e)). The ashing of the light _ can be carried out by a known method. The photoresist used to shape the photoresist of the mouth _ 形成形成形成形成形成形成形成形成形成形成形成形成形成形成形成形成形成形成形成形成形成形成The surface of the substrate on the peripheral surface is adhered to the residual plasma (plasma residue) z. The residual h is derived from the deteriorated photoresist film = the stone oxide film 3, and the dense film, A1_Cu film & It is distinguished by the type of the residue. T is not rooted, so the ash is removed by ashing, and then the lining is removed until the liner 52 is exposed to the gate material (step (f) of Fig. 1-3). Thus, the inner wall and the bottom surface (201200634 film surface) of the opening portion are cleaned to remove the residue Z adhering thereto. A commercially available cleaning solution or the like can be used as the cleaning liquid at this time. Commercially available products include EKC 265 (3⁄4 main article trademark) manufactured by EKC Technology Inc., ACT935 (registered trademark) manufactured by Ashland Chemical Co., Ltd., and ELM C-30 (trade name) manufactured by Mitsubishi Gas Chemical Co., Ltd., and the like. These products are also disclosed as patent documents (refer to the specification of U.S. Patent No. 5,297,771, the specification of U.S. Patent No. 5,419,779, and the specification of U.S. Patent No. 563,9,4). In this embodiment, after the above-mentioned cleaning step, The rinsing step C of applying the above antioxidant liquid is referred to step (g) of Figs. 1-4. The rinsing conditions at this time are as described above. According to the present embodiment, the action of the anti-oxidation liquid is such that the surface of the aluminum-copper alloy (A1Cu) film 52 exposed on the surface of the liner is treated, and a film (layer) not shown in the form of a passive film is formed thereon. The schematic representation 'can also be expected to be identifiable as a thick mask (layer). Thus, the surface of the anti-oxidation liquid 'Al-Cu film 52 is protected, and the oxidation resistance is imparted', so that even in the water or aqueous medium exposed in the subsequent cutting step, the A1 pericardium (4) is suppressed and prevented. Therefore, according to the present embodiment, when a gold wire or the like is connected to the slit, the yield of the non-porous # (pmmgeorn) is higher. [Examples] The following is a more detailed explanation of the riding of this day.彳一本韵(Example I) 21 201200634 <Examples, Comparative Examples, Reference Examples>

使以下表1所示的成分以其中所示的組成（wt%)含有於水中來製成抗氧化液（實例、比較例）。水是使用半導體製造步驟中使用的一般超純水。表中表示組成（wt〇/〇) 的成分含有該量，鹼性化合物是含有成為對各試料顯示的 pH值的量。是指該些成分加上水的組成（wt%)而成為 100 wt%。表中的pH值是在室溫（20°C )下利用HORIBA 公司製造的F-51 (商品名）測定而得的值。此外，比較例 1是表示在不含磷酸的藥液中的淋洗實驗。殘渣的去除時使用Mitsubishi Gas Chemical公司製造的ELM C-30 (商品名）的殘渣去除液，於2〇°c下利用葉片式去除裝置（SPS-EuropeB.V.公司製造，POLOS (註冊商標））來進行。於上述殘渣的清洗後，將分別製備的抗氧化液塗佈於具有圖1-4的步驟（e)所示結構的半導體基板上，來進行淋洗處理。半導體基板的金屬膜52是使用應用有鋁·銅合金（含有銅0.5 wt%)的膜，矽氧化膜3是使用應用有Si〇2 的膜。各實例、比較例中應用的金屬膜的材料種類示於表〈藉由切割步驟的腐蝕（侵蝕）〉首先’將上述半導體基板（附有積體電路的晶圓）貼附於預先固定於環狀框上的紫外線（Ultra Violet，UV)帶，接著’將所固定的半導體基板曝露於流水中，然後使用鑽石鑛’沿著切斷線來縱、橫切斷，將半導體基板個片化（切 22 201200634 ^步驟）。此外，經個片化的半導體基板是經由uv帶而固定於框上，因此維持排列的狀態。然後，對uv帶照射uv，藉此使黏著力下降，容易剝離經個片化的半導體基板，從而自uv帶上拾取該些半導體基板❶ 將經由上述步驟而獲得的經個片化的半導體基板供於腐钱性的評價。經個片化的半導體基板是於溫度：坑、濕度：5G%的環境下靜置3G天，然後觀察半導體基板的金屬膜52的表面55，藉此進行評價。該觀察時使用光學顯微鏡’將5G倍的倍率作為主要條件來進行。藉由該觀察，以如下所述的方式加以區別來評價其良否。將其下表1。 ' AA :黑點數為〇個/pm2 A .黑點數為1〜2個/pm2 Β .黑點數為3〜9個/μιη2 c :黑點數為10個/μιη2以上 23 201200634 J-a0908e 【I <】 (.—/Y) 制啭i_f塌 ««oisThe composition shown in the following Table 1 was made into an antioxidant liquid (example, comparative example) in the composition (wt%) shown therein. Water is the general ultrapure water used in the semiconductor manufacturing step. The components in the table (wt〇/〇) are contained in the table, and the basic compound is contained in an amount which is a pH value for each sample. It means that the components are added to the composition (wt%) of water to become 100 wt%. The pH value in the table is a value measured by F-51 (trade name) manufactured by HORIBA Co., Ltd. at room temperature (20 ° C). Further, Comparative Example 1 is a rinsing test showing a chemical solution containing no phosphoric acid. For the removal of the residue, the residue removal liquid of ELM C-30 (trade name) manufactured by Mitsubishi Gas Chemical Co., Ltd. was used, and the blade type removal device (SPS-Europe B.V., POLOS (registered trademark) was used at 2 °C. ) to carry out. After the washing of the above residue, the separately prepared antioxidant liquid is applied onto a semiconductor substrate having the structure shown in the step (e) of Fig. 1-4 to carry out a rinsing treatment. The metal film 52 of the semiconductor substrate is a film using an aluminum-copper alloy (containing 0.5 wt% of copper), and the tantalum oxide film 3 is a film using Si〇2. The material types of the metal films applied in the respective examples and comparative examples are shown in the table <Corrosion (erosion) by the cutting step> First, the above-mentioned semiconductor substrate (wafer with the integrated circuit) is attached to the ring in advance. Ultraviolet (Ultra Violet (UV) tape on the frame, then 'the fixed semiconductor substrate is exposed to the flowing water, and then the diamond ore' is cut longitudinally and horizontally along the cutting line to slice the semiconductor substrate ( Cut 22 201200634 ^Steps). Further, since the individualized semiconductor substrates are fixed to the frame via the uv tape, the aligned state is maintained. Then, the uv tape is irradiated with uv, whereby the adhesive force is lowered, and the diced semiconductor substrate is easily peeled off, thereby picking up the semiconductor substrates from the uv tape. The diced semiconductor substrate obtained through the above steps For the evaluation of rot. The individualized semiconductor substrates were allowed to stand for 3 G days in an environment of temperature: pit, humidity: 5 G%, and then the surface 55 of the metal film 52 of the semiconductor substrate was observed, thereby being evaluated. This observation was carried out using an optical microscope ' with a magnification of 5 G times as a main condition. By this observation, the difference is evaluated in the manner described below to evaluate whether it is good or not. Put it below in Table 1. ' AA : The number of black dots is / / pm2 A . The number of black dots is 1~2 / pm2 Β . The number of black dots is 3~9 / μιη2 c : The number of black dots is 10 / μιη2 or more 23 201200634 J- A0908e [I <] (.—/Y) 啭i_f collapse ««ois

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寸(N 201200634 J-aosooe o 卜 d 00 o 寸 Ο 00 ci (N 21.0 10.0 CN Os T—< CN CN 13.0 25.0 16.0 18.0 u PQ 〇\ vd 寸 CN od o K CN 10.9 m <N CN (N CM d 1 1 1 FRA c U MLA | < C/D 1 1 1 | BTMAH BTMAH MEA KOH | TMAH TMAH TMAH 1 ^T) d 寸 d in 寸 o 1 d Ό O ^Ti d CL, K, 1 PL, 〇 s o Ο c04 實例21 _1 |實例22 實例23 實例24 比較例1 f A較例2 | 比較例3 比較例4Inch (N 201200634 J-aosooe o 卜d 00 o inch Ο 00 ci (N 21.0 10.0 CN Os T-< CN CN 13.0 25.0 16.0 18.0 u PQ 〇\ vd inch CN od o K CN 10.9 m <N CN ( N CM d 1 1 1 FRA c U MLA | < C/D 1 1 1 | BTMAH BTMAH MEA KOH | TMAH TMAH TMAH 1 ^T) d inch d in inch o 1 d Ό O ^Ti d CL, K, 1 PL, 〇so Ο c04 Example 21 _1 | Example 22 Example 23 Example 24 Comparative Example 1 f A Comparative Example 2 | Comparative Example 3 Comparative Example 4

201200634 L 依據本發明的抗氧化方法及抗氧化液（實例）可知’ 與未進行該處理者（比較例丨）相比，可有效果地抑制半導體基板中由金屬膜表面的氧化引起的侵蝕（孔蝕）。另外’由於pH值經調節為較佳範圍，故而不會導致腐蝕金屬膜或絕緣層（對比參照實例、參考例），而且，可緩和於切割步驟中大量提供的水的影響而維持良好的金屬膜表面。此外’上述表1中的略號所表示的化合物如下所述。 (含磷化合物） P1 :填酸（Phosphoric acid ) P2 :聚填酸（Poly phosphoric acid) P3 :膦酸（Phosphonic acid) P4 :五氧化二璘（Phophorouspentoxide) P5 :次填酸（Dihydridohydroxidooxidophosphorus) P6 :膦曱酸（Foscarnet) P7 :乙基膦酸（Ettiyl phosphonic acid ) P8 ： 1-羥基乙烷-1，1-雙（膦酸） (l-Hydroxyethane-l,l-bis(phosphonic acid)) (有機羧酸化合物） AA :乙酸 BA :苯曱酸 CA :檸檬酸 DGA :二甘醇酸（氧二乙酸） FRA :甲酸 26201200634 L According to the antioxidant method and the antioxidant liquid (example) of the present invention, it is possible to effectively suppress the erosion caused by the oxidation of the surface of the metal film in the semiconductor substrate as compared with the case where the treatment is not performed (Comparative Example). Pitting). In addition, since the pH is adjusted to a preferred range, it does not cause corrosion of the metal film or the insulating layer (cf. reference example, reference example), and the metal can be moderated while the effect of the large amount of water supplied in the cutting step can be alleviated. Membrane surface. Further, the compound represented by the abbreviation in Table 1 above is as follows. (phosphorus compound) P1 : Phosphoric acid P2 : Poly phosphoric acid P3 : Phosphonic acid P4 : Phophorous pentoxide P5 : Dihydridohydroxidooxidophosphorus P6 : Phoscarnet P7: Ettiyl phosphonic acid P8 : 1-Hydroxyethane-l, 1-bis(phosphonic acid) ( Organic carboxylic acid compound) AA: acetic acid BA: benzoic acid CA: citric acid DGA: diglycolic acid (oxydiacetic acid) FRA: formic acid 26

201200634 X GA :甘醇酸 GLA :葡萄糖酸 LA :乳酸 MA :蘋果酸 MLA :順丁稀二酸 MNA :丙二酸 OA :乙二酸 PA :丙酸 PHA :鄰苯二曱酸 PHHA :鄰苯二甲異羥肟酸 SA .水楊酸 SHA :水揚基異羥肟酸 SUA : 丁二（琥珀）酸 TA :酒石酸 (驗性化合物） DEA :二乙醇胺 DGAm :二甘醇胺 BTMAH:苄基三甲基氫氧化銨 KOH :氫氧化鉀 MEA : 2-胺基乙醇 TEA :三乙醇胺 TMAH :四甲基氫氧化銨 TBAH ··四丁基氫氧化銨 (實例Π) 27 201200634 另外，使用貫例1的處理液，查明相對於處理時間的黑點數。此時，將基板的經前處理者與未經前處理者進行比較，結果可確認經前處理者與未經前處理者相比，黑點數更快速地減少。作為前處理，是於2 38%TMAH水&液中浸潰30秒後，利用純水進行1分鐘清洗。 (實例III) 使以下表2所示的成分以其中所示的組成（wt%)含有於水中來製成抗氧化液（實例、比較例 > 詳細的製備條件與實例I相同。評價是除了上述的黑點判定以外，使用 Orion Diagnostica Oy公司製造的商品名：Easicult (註冊商標）Μ及Easicult TTC ’於25。(：下培養5天，進行黴、細菌的繁殖試驗。將結果以下述方式分類而示於表2。 3:無法確認繁殖 2 :確認103 CFU/ml以下的繁殖 1 :確認超過103 CFU/ml的繁殖此外，本實例中的黑點的判定試驗中，抗氧化液試料是使用在大氣中以室溫（約28°C )保存7天後的試料，在該7天中容易出現由黴或細菌的產生引起的影響。 28 201200634 J-a0908co 【<N<】201200634 X GA : Glycolic acid GLA: Gluconic acid LA: Lactic acid MA: Malic acid MLA: cis-succinic acid MNA: Malonic acid OA: Oxalic acid PA: Propionic acid PHA: O-phthalic acid PHHA: O-benzene Dimethyl hydroxamic acid SA. Salicylic acid SHA: Salicyl hydroxamic acid SUA: Butane (succinic acid) TA: Tartaric acid (test compound) DEA: Diethanolamine DGAm: Diethylene glycolamine BTMAH: Benzyl Trimethylammonium hydroxide KOH: Potassium hydroxide MEA: 2-Aminoethanol TEA: Triethanolamine TMAH: Tetramethylammonium hydroxide TBAH · Tetrabutylammonium hydroxide (Example Π) 27 201200634 In addition, the use case The treatment liquid of 1 was used to find the number of black spots relative to the treatment time. At this time, comparing the pre-processed person of the substrate with the non-pre-processed person, it was confirmed that the number of black spots was more rapidly reduced than that of the pre-processed person. As a pretreatment, it was immersed in 2 38% TMAH water &amp; for 30 seconds, and then washed with pure water for 1 minute. (Example III) The components shown in the following Table 2 were made into an antioxidant liquid in the composition (wt%) shown therein (Example, Comparative Example) The detailed preparation conditions were the same as in Example 1. The evaluation was except In addition to the above-mentioned black spot determination, the product name: Easicult (registered trademark) Μ and Easicult TTC ' manufactured by Orion Diagnostica Oy Co., Ltd. was used at 25. (The culture was carried out for 5 days, and the propagation test of mold and bacteria was carried out. The results were as follows. The classification is shown in Table 2. 3: Unable to confirm reproduction 2: Confirmation of reproduction below 103 CFU/ml 1: Confirmation of reproduction over 103 CFU/ml In addition, in the determination test of the black spots in this example, the antioxidant liquid sample is A sample which was stored at room temperature (about 28 ° C) for 7 days in the atmosphere was used, and the influence caused by the generation of mold or bacteria was likely to occur in the 7 days. 28 201200634 J-a0908co [<N<]

AlCu 0.5%上的黑點有無 C < < < C < c 防黴、防菌性試驗 Easicult TTC cn ΓΠ m m m cn CN m m m m m cn m 1-H Easicult Μ CO ΓΟ m ro m CO cn ro (N m m m cn m CO m m CN 00 q 〇\ 〇 vd CN 〇6 VO od 寸 od Os vd oo CN OO VO oo m v〇 vd \〇防徽、防菌劑 (wt% ) c> O uo O 产H 1 ID 〇 • 1 <z> 卜 o yn cn d m 〇 Ό) r·^ <N 1 1 1 c ω h-1 ω PQ ω ω s 1 < ω 1 ffi ω EM U ω « Q m o w ω ω Ph W 1 1 1 羧酸化合物（D) (wt%) 1 1 1 1 1 v-H 1 1 1 00 o 1 寸 d 1 1 <Ti »—H 1 r-H 1 1 1 1 1 1 c o 1 1 1 DGA | 1 1 < 1 MLA 1 < CO 1 鹼性化合物 (C) MEA DGAm KOH DEA TEA TMAH TMAH | BTMAH | DGAm | MEA | DGAm DGAm TEA DEA MEA TEA TBAH TEA KOH 含罐化合物 (B) (wt%) 1-H ”磚 Oh CN Oh <N Ph 〇4 K, 5： K, Oh <N Ph Oh CN Ph 5： K, a： < 201 202 203 204 CN 206 | 207 | 208 209 | l2i〇J 211 212 | 213 | 214 215 216 | 217 (N CN CO 實例1 實例2 實例3 實例4 實例5 實例6 實例7 實例8 實例9 實例10 實例11 實例12 實例13 實例14 實例15 實例16 實例17 妹參考實例2 201200634 •含鱗化合物、驗性有機化合物、敌酸化合物的略稱參照上述表1的註釋。（防黴、防菌劑） EA : 2-甲基-4-異噻唑啉-3-酮 EB: 1,2-苯幷異噻唑啉-3-酮 EC . 5-氣2_曱基-4-異β塞坐琳-3-酉同 ED :鄰苯基苯酚 ΕΕ :對氣間曱酚 EF : 3-曱基-4-氯苯酚 EG : 2_吡啶硫醇-1-氧化物鈉 EH.六氫-1，3,5-三乙基-均三唤 EI :對曱苯續酸2,4,6-三甲基0比咬鑌 EJ : 4-(2-硝基丁基)嗎琳 ΕΚ · 4,4’-(2-乙基-2-确基三亞曱基)二嗎淋 EL :氣化四曱基銨 EM :氣化十二烷基吡啶鑌根據上述結果可知，依據本發明的較佳實施形態，黴或細菌的產生得到適當抑制，於大氣中保存預定期間之後亦獲得高抗氧化效果。 —雖然本發明已以較佳實施例揭露如上，然其並非用以 P艮，本發明，任何熟習此技藝者，在*脫離本發明之精神内’當可作些許之更動與潤飾，因此本發明之保護，圍虽視後附之中請專利範圍所界定者為準。【圖式簡單說明】圖1-1的步驟（a)、（b)是示意性表示半導體元件的 30 201200634 來作為應用本發明方法的-實施態樣的製二的步_面® _財發财法的-實施態樣的步驟（e)、（f)是示意性表示半導體元件的步二面圖二來作為應用本發明方法的-實施態樣的 4的步驟⑷是示意性表示半賴元件的製造過 :圖二)來作為應用本發明方法的一實施態樣的步驟剖 •疋對經過切割步驟的一般半導體基板的金屬膜的腐蝕（侵蝕）的狀態進行說明的剖面圖。【主要元件符號說明】 1、2:層間絕緣層 3:矽氧化膜 4 :鈍化膜 5、5’ ：襯墊 6 :通道 7、8:配線圖案 51、 53 :密著膜 52、 52’ ：銘-銅合金（Al-Cu)膜 55 :金屬膜表面 6卜71、81 :障壁金屬膜 31 201200634 62 :鎢膜 72、82 :鋁（A1)膜 c:孔蝕（黑點） Η :開口部 Ρ :純態膜 ζ :殘渣 32Black spot on AlCu 0.5% with or without C <<< C < c Anti-mildew, anti-bacterial test Easicult TTC cn ΓΠ mmm cn CN mmmmm cn m 1-H Easicult Μ CO ΓΟ m ro m CO cn ro ( N mmm cn m CO mm CN 00 q 〇\ 〇vd CN 〇6 VO od inch od Os vd oo CN OO VO oo mv〇vd \〇anti-album, anti-bacterial agent (wt%) c> O uo O H 1 ID 〇• 1 <z> 卜o yn cn dm 〇Ό) r·^ <N 1 1 1 c ω h-1 ω PQ ω ω s 1 < ω 1 ffi ω EM U ω « Q mow ω ω Ph W 1 1 1 carboxylic acid compound (D) (wt%) 1 1 1 1 1 vH 1 1 1 00 o 1 inch d 1 1 <Ti »—H 1 rH 1 1 1 1 1 1 co 1 1 1 DGA 1 1 < 1 MLA 1 < CO 1 Basic Compound (C) MEA DGAm KOH DEA TEA TMAH TMAH | BTMAH | DGAm | MEA | DGAm DGAm TEA DEA MEA TEA TBAH TEA KOH Tank Compound (B) (wt% ) 1-H ” Brick Oh CN Oh <N Ph 〇4 K, 5: K, Oh <N Ph Oh CN Ph 5: K, a: < 201 202 203 204 CN 206 | 207 | 208 209 | l2i 〇J 211 212 | 213 | 214 215 216 | 217 (N CN CO real 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 Example 15 Example 16 Example 17 Sister Reference Example 2 201200634 • Scaled compounds, organic compounds, and acid For the abbreviations of the compounds, refer to the notes in Table 1. (Moldproof, antibacterial agents) EA: 2-Methyl-4-isothiazolin-3-one EB: 1,2-Benzoisothiazolin-3-one EC. 5-Gas 2_Mercapto-4-iso-β-Sermine-3-酉 with ED: o-phenylphenolphthalein: p-oxophenol EF: 3-mercapto-4-chlorophenol EG : 2_ Pyrithione-1-oxide sodium EH. Hexahydro-1,3,5-triethyl-homogeneous EI: p-nonylbenzene acid 2,4,6-trimethyl 0 ratio bite EJ : 4 -(2-nitrobutyl)morphine 4 · 4,4'-(2-ethyl-2-decyltriindolyl) lanolin EL: gasified tetradecyl ammonium EM: gasified dodecane According to the above results, according to the above preferred results, the production of mold or bacteria is appropriately suppressed, and a high antioxidant effect is obtained even after a predetermined period of storage in the atmosphere. The present invention has been disclosed in the above preferred embodiments, but it is not intended to be used in the present invention. Any person skilled in the art can make some changes and refinements in the spirit of the present invention. The protection of the invention shall be subject to the definition of the scope of the patent as attached. BRIEF DESCRIPTION OF THE DRAWINGS Steps (a) and (b) of FIG. 1-1 are diagrams schematically showing a semiconductor device 30 201200634 as a method of applying the method of the present invention. The steps (e) and (f) of the financial method - schematically represent the step 2 of the semiconductor device. The step (4) of the embodiment 4 of the method of the present invention is schematically represented. Fig. 2 is a cross-sectional view showing a state in which corrosion (erosion) of a metal film of a general semiconductor substrate subjected to a dicing step is performed as a step of applying an embodiment of the method of the present invention. [Description of main component symbols] 1, 2: interlayer insulating layer 3: tantalum oxide film 4: passivation film 5, 5': spacer 6: channels 7, 8: wiring patterns 51, 53: adhesion film 52, 52': Ming-copper alloy (Al-Cu) film 55: metal film surface 6b 71, 81: barrier metal film 31 201200634 62: tungsten film 72, 82: aluminum (A1) film c: pitting (black spots) Η: opening Department: Pure Membrane: Residue 32

Claims

201200634 Λ. VII. Patent application scope: The anti-oxidation method for the surface of L metal film is characterized in that: when the surface of the metal film of the semiconductor substrate is treated with an anti-oxidation liquid, the water is used to contain at least a compound containing the filler and the test property. A compound having a pH adjusted to 6 to 1 Torr was used as the above antioxidant liquid. 2. The method for controlling oxidation of a surface of a metal film according to the invention of claim 2, wherein the anti-oxidation solution contains a mildew-proof and antibacterial agent. 3. The anti-oxidation method of the surface of the metal film according to claim 2, wherein the anti-mold and antibacterial agent comprises a phenol structure, a pyridine structure, a triazine structure, a morpholine structure, and an isothiazoline structure. A compound of any one of a pyridine rust structure and a quaternary ammonium structure. >4. The antioxidant method of the surface of the metal film according to the first or second aspect of the invention, wherein the male-containing compound is an inorganic scale compound or an organic phosphorus compound. >5. The oxidation resistance of the surface of the metal film as described in the first or second aspect of the patent application; the above-mentioned peach-containing compound is a hetero compound. The method of controlling the surface of a metal film according to the first or second aspect of the invention, wherein the antioxidant liquid further comprises an organic phthalic acid compound. The method for controlling the surface of a metal film according to claim 1 or 2, wherein the above-mentioned test compound is selected from the group consisting of a quaternary amine compound or an alcohol amine compound. At least t compounds. 8. The antioxidant method of the metal film surface 33 201200634., wherein the organic carboxylic acid compound is selected from the group consisting of citric acid, lactic acid, acetic acid, propionic acid, malic acid, and tartaric acid. , malonic acid, oxalic acid, succinic acid, gluconic acid, glycolic acid, diglycolic acid, maleic acid, benzoic acid, o-dicarboxylic acid, salicylic acid, salicylic acid And at least one compound of the group consisting of phthalhydroxamic acid. 9. The method of controlling the surface of a metal film according to claim 1 or 2, wherein the treatment with the above antioxidant is carried out before the cutting step. 10. The metal film name=antioxidation method according to the scope of claim 2 or 2, wherein after the cleaning step, the button using the right liquid is applied, and the above-mentioned clearing is _ into a half (four) substrate On the deposit 'synthesis of the residual / check and / or ashing; check for cleaning, and the above-mentioned electric smashing name is smear the money is to the plasma of the above-mentioned semi-conducting county plate to shape the shape = or to the above semiconductor The photoresist on the substrate is ashed by the name of the metal _ steel according to the second item, which consists of 4; the metal film is selected from the group of Ming, copper, and sho The surface of the metal film is adjusted to the pH value, and the gas 6 contains water, a Wei compound and an organic compound, and the antioxidant liquid is as described in item 12 of the profit range. An antioxidant solution according to the invention of claim 12 or 13, which further comprises an organic carboxylic acid compound. 15. The antioxidant solution according to claim 12 or 13, wherein the pH is set to 6 to 8. 35