TWI565834B - 銅或銅合金用之蝕刻液 - Google Patents

銅或銅合金用之蝕刻液 Download PDF

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Publication number
TWI565834B
TWI565834B TW100129156A TW100129156A TWI565834B TW I565834 B TWI565834 B TW I565834B TW 100129156 A TW100129156 A TW 100129156A TW 100129156 A TW100129156 A TW 100129156A TW I565834 B TWI565834 B TW I565834B
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Taiwan
Prior art keywords
acid
solution
copper
molecule
group
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TW100129156A
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English (en)
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TW201213613A (en
Inventor
吉田裕
小路祐吉
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美商恩特葛瑞斯股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/16—Acidic compositions
    • C23F1/18—Acidic compositions for etching copper or alloys thereof
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/02—Local etching
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/44—Compositions for etching metallic material from a metallic material substrate of different composition
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Description

銅或銅合金用之蝕刻液 [交叉參考相關申請案]
本案主張日本專利申請案第2010-181485號申請於2010年8月16日及名稱為「銅或銅合金用之蝕刻液」，及日本專利申請案第2011-175477號申請於2010年8月11日及名稱為「銅或銅合金用之蝕刻液」之優先權，二案全文皆係以引用方式併入此處。
本發明係有關於一種從一微電子基板蝕刻銅或銅合金之溶液，及更明確言之係有關於一種從具有由銅或銅合金及鎳所製成之電極例如凸塊之一微電子基板選擇性地蝕刻銅或銅合金之溶液。
於微電子裝置中，元件的微縮化與高度集積化已進展為改良其效能及伴以縮小其尺寸。不利地，微電子裝置的微縮化技術逐漸地趨近其極限。雖然具有三度空間結構之裝置諸如打線接合、覆晶、凸塊等的使用日增，但仍然期望有更高度的集積。
已經發展出藉由形成貫穿矽之細小通孔，及以傳導材料諸如銅填補通孔而形成電極之一項技術(TSV技術)。通常，於銅係用作為TSV技術之電極的情況下，於矽基板(1)設置一開口，及然後氧化矽層(2)(亦即低k介電層)及鈦、鉭等之障壁金屬層(3)係形成於開口內壁上。隨後，藉金屬有機化學氣相沉積法或物理氣相沉積法形成銅晶種層(4)(圖1)。其次，以抗蝕劑樹脂(5)形成保護性薄膜於銅晶種層上之形成電極部分以外之部分上(圖2)。金屬諸如銅(6)係埋設入其中未形成保護性薄膜的部分內部而形成一凸塊。不利地，若銅未經保護，則連結可靠度因表面氧化現象而減低。如此，通常鎳層(7)及金或錫與銀之合金之焊接層(8)係各自積層(圖3)。然後，藉由去除抗蝕劑樹脂而形成凸塊(9)(圖4)。
銅晶種層及障壁金屬層不僅係形成於矽基板之開口內部，同時也形成於矽基板之表面上，及甚至在抗蝕劑已經去除之後仍然保有。因此理由故，剩餘的銅晶種層及障壁金屬層必須藉蝕刻液去除(圖5及6)。其中至於濕蝕刻銅晶種層之方法，廣泛使用採用由酸及氧化劑所組成之蝕刻液，亦即硫酸與過氧化氫之混合液之方法(日本專利申請公開案第2000-286531及2009-120870號)。也廣泛已知使用含氯化銅或氯化鐵之蝕刻液之方法(日本專利申請公開案第2008-285720號)。不利地，此等蝕刻方法不僅只蝕刻形成於電子基板的銅晶種層，同時也造成凸塊變形，原因在於其也蝕刻用來形成凸塊的鎳。
據此，技藝界仍然需要有一種溶液其可從同時包括銅或銅合金及含鎳材料之微電子裝置，相對於含鎳材料而選擇性地蝕刻銅或銅合金。
大致上本發明係有關於一種溶液，其可在從包括銅或銅合金及含鎳材料之微電子基板蝕刻銅或銅合金之步驟選擇性地蝕刻銅或銅合金。
於一個態樣中，描述一種從同時包括銅或銅合金及含鎳材料之一微電子裝置選擇性地蝕刻銅或銅合金用之溶液，該溶液包含分子內具有酸基之螯合劑(A)、過氧化氫(B)、及分子內具有氧基伸乙基鏈之界面活性劑(C)。溶液可進一步包含選自於由至少一個溶劑(D)、至少一個耐腐蝕組分(E)、至少一個抗氧化劑(F)、及至少一個鹼性化合物(G)所組成之組群中之至少一個組分。
於另一態樣中，描述一種製造一微電子裝置之方法，該方法包含使用一溶液從該微電子裝置選擇性地蝕刻銅或銅合金，其中該裝置同時包括銅或銅合金及含鎳材料，其中該溶液包含分子內具有酸基之螯合劑(A)、過氧化氫(B)、及分子內具有氧基伸乙基鏈之界面活性劑(C)。溶液可進一步包含選自於由至少一個溶劑(D)、至少一個耐腐蝕組分(E)、至少一個抗氧化劑(F)、及至少一個鹼性化合物(G)所組成之組群中之至少一個組分。
本發明之其它態樣、特徵及具體例將從後文揭示及隨附之申請專利範圍更為彰顯。
此處描述一種從微電子裝置選擇性地蝕刻銅或銅合金之溶液，其中該銅或銅合金係相對於含鎳材料而選擇性地去除。又復，描述一種使用該溶液來從微電子裝置實質上去除銅或銅合金之方法，其中該銅或銅合金係相對於同時存在之含鎳材料選擇性地去除。
為了容易參照，「微電子裝置」係相對應於半導體基板、平板顯示器、相變記憶體、太陽能面板及其它產品包括太陽能基板、光伏電池及微機電系統(MEMS)製造供微電子、積體電路、或電腦晶片應用等用途。須了解「微電子裝置」一詞絕非表示限制性，及包括最終將變成微電子裝置或微電子總成之任一種基板。
如此處所述，「銅或銅合金」係相對應於銅(0)或銅與至少一種額外組分例如鋅、錫、鋁、矽、鎳、磷、鐵、錳、鈹、鈷、鉛、及其組合之混合物(合金)。熟諳技藝人士須了解已經進行某種表面反應例如氧化反應之銅或銅合金仍然視為針對本發明之目的之銅或銅合金。銅之實例包括藉化學氣相沉積法(CVD方法)、物理氣相沉積法(PVD方法)、原子層沉積法(ALD方法)、及鍍覆所形成之該等銅。
如此處使用，「障蔽金屬層」一詞相對應於技藝界用來密封金屬線路例如銅互連體來減少該等金屬例如銅擴散入介電材料之任一種材料。較佳障蔽層材料包括鉭、鈦、釕、鉿、鎢、及其它耐火金屬及其氮化物及矽化物。
如此處定義，「低k介電材料」相對應於用在層狀微電子裝置作為介電材料之任一種材料，其中該材料具有小於約3.5之介電常數。較佳低k介電材料包括低極性材料諸如含矽有機聚合物、含矽混成有機/無機材料、有機矽酸鹽玻璃(OSG)、四乙氧基矽烷(TEOS)、氟化矽酸鹽玻璃(FSG)、二氧化矽及摻碳氧化物(CDO)玻璃。須了解低k介電材料可具有不同密度及不同孔隙度。
「實質上不含」於此處係定義為低於2 wt.%，較佳低於1 wt.%，更佳低於0.5 wt.%，及最佳低於0.1 wt.%。
如此處使用，「約」一詞意圖相對應於陳述值之±5%。
如此處使用，「相對於含鎳材料選擇性地蝕刻銅或銅合金」係相對應於銅或銅合金相對於含鎳材料之去除率至少為100：1，更佳至少1000：1，又更佳至少10000：1，及最佳至少100000：1。
如此處定義，「實質上不含」相對應於以該組成物之總重為基準，低於該組成物之約2 wt.%，更佳低於約1 wt.%，又更佳低於0.1 wt.%，及最佳0 wt.%。
此處所述組成物可於寬廣多種特定配方具體實現，如本文中完整描述。
於全部此等組成物中，其中組成物之特定組分係參照重量百分比範圍包括零下限而討論，須了解此等組分可存在或不存在於多種特定組成物之具體例，例如當此等組分存在時，以其中採用此等組分之組成物總重為基準，其存在濃度可低至0.001重量百分比。
於一個態樣中，描述一種溶液，該溶液從其上具有銅或銅合金之微電子裝置蝕刻銅或銅合金材料，其中該溶液相對於含鎳材料選擇性地蝕刻銅或銅合金。該溶液可包含、其組成為、或其主要組成為至少一種分子內具有酸基之螯合劑(A)、過氧化氫(B)、及至少一種分子內具有氧基伸乙基鏈之界面活性劑(C)。於另一個具體例中，該溶液可包含、其組成為、或其主要組成為至少一種分子內具有酸基之螯合劑(A)、過氧化氫(B)、至少一種分子內具有氧基伸乙基鏈之界面活性劑(C)、及至少一種溶劑(D)。於另一個具體例中，該溶液可包含、其組成為、或其主要組成為至少一種分子內具有酸基之螯合劑(A)、過氧化氫(B)、至少一種分子內具有氧基伸乙基鏈之界面活性劑(C)、至少一種溶劑(D)、及至少一種耐腐蝕組分(E)。於另一個具體例中，該溶液可包含、其組成為、或其主要組成為至少一種分子內具有酸基之螯合劑(A)、過氧化氫(B)、至少一種分子內具有氧基伸乙基鏈之界面活性劑(C)、至少一種溶劑(D)、及至少一種抗氧化劑(F)。於又另一個具體例中，該溶液可包含、其組成為、或其主要組成為至少一種分子內具有酸基之螯合劑(A)、過氧化氫(B)、至少一種分子內具有氧基伸乙基鏈之界面活性劑(C)、至少一種溶劑(D)、至少一種抗腐蝕組分(E)、及至少一種抗氧化劑(F)。於又另一個具體例中，該溶液可包含、其組成為、或其主要組成為至少一種分子內具有酸基之螯合劑(A)、過氧化氫(B)、至少一種分子內具有氧基伸乙基鏈之界面活性劑(C)、至少一種溶劑(D)、及至少一種鹼性化合物(G)。於另一個具體例中，該溶液可包含、其組成為、或其主要組成為至少一種分子內具有酸基之螯合劑(A)、過氧化氫(B)、至少一種分子內具有氧基伸乙基鏈之界面活性劑(C)、至少一種溶劑(D)、至少一種抗腐蝕組分(E)、及至少一種鹼性化合物(G)。於又另一個具體例中，該溶液可包含、其組成為、或其主要組成為至少一種分子內具有酸基之螯合劑(A)、過氧化氫(B)、至少一種分子內具有氧基伸乙基鏈之界面活性劑(C)、至少一種溶劑(D)、至少一種抗氧化劑(F)、及至少一種鹼性化合物(G)。於又另一個具體例中，該溶液可包含、其組成為、或其主要組成為至少一種分子內具有酸基之螯合劑(A)、過氧化氫(B)、至少一種分子內具有氧基伸乙基鏈之界面活性劑(C)、至少一種溶劑(D)、至少一種抗腐蝕組分(E)、至少一種抗氧化劑(F)、及至少一種鹼性或酸性化合物(G)。
如此處描述，分子內有酸基之螯合劑(A)或其鹽，係添加來提高銅或銅合金之蝕刻率。較佳分子內具有酸基之螯合劑(A)具有二或更多個官能基，其中至少一個官能基為酸基。意圖涵蓋之其它官能基包括中性羥基或酚系羥基。螯合劑(A)中之酸基實例包括羧基、膦酸基、磺酸基、磷酸基、硫酸基、硝酸基及硼酸基。例如，螯合劑(A)可包括含2或更多個羧基作為酸基之有機酸或其鹽(A1)；包括含2或更多個膦酸基作為酸基之有機酸或其鹽(A2)；包括含2或更多個磺酸基作為酸基之有機酸或其鹽(A3)；及含一或多個羧基及一或多個膦酸基作為酸基之有機酸或其鹽(A4)。螯合劑(A)可以是只含一個羧基、一個膦酸基、或一個磺酸基作為酸基之螯合劑(A5)，只要螯合劑在分子內具有顯示螯合效果之羧基即可。須了解若存在有多於一個螯合劑，則意圖涵蓋A1、A2、A3、A4及A5螯合劑之任一種組合。
此處涵蓋之A1螯合劑包括但非限於伸乙基二胺四乙酸、二伸乙基三胺五乙酸、三伸乙基四胺六乙酸、羥基乙基伸乙基二胺三乙酸、二羥基乙基伸乙基二胺四乙酸、氮三乙酸、羥基乙基亞胺基二乙酸、β-丙胺酸二乙酸、天冬酸二乙酸、甲基甘胺酸二乙酸、亞胺基二丁二酸、絲胺酸二乙酸、羥基亞胺基二丁二酸、酒石酸、檸檬酸、苯均四酸、苯并多羧酸、環戊烷四羧酸、其鹽類及其組合物。
A2螯合劑包括但非限於甲基二膦酸、胺基三(亞甲基膦酸)、1-羥基亞乙基-1,1-二膦酸(HEDP)、伸乙基二胺四(亞甲基膦酸)、六亞甲基二胺四(亞甲基膦酸)、伸丙基二胺四(亞甲基膦酸)、二伸乙基三胺五(亞甲基膦酸)、三伸乙基四胺六(亞甲基膦酸)、三胺基三乙基胺六(亞甲基膦酸)、反-1,2-環己烷二胺四(亞甲基膦酸)、甘醇醚二胺四(亞甲基膦酸)、四伸乙基五胺七(亞甲基膦酸)、其鹽類及其組合物。
A3螯合劑包括但非限於甲烷二磺酸、乙烷二磺酸、酚二磺酸、萘二磺酸、哌-1,4-貳(2-乙烷磺酸)、其鹽類及其組合物。
A4螯合劑包括但非限於膦基乙酸、2-羥基-2-膦基乙酸、羧基膦酸、3-膦基丙酸、4-(3-膦基丙基)-2-哌羧酸、其鹽類及其組合物。
A5螯合劑包括但非限於乳酸、水楊酸、五倍子酸、2-羥基乙基膦酸、2-羥基乙烷磺酸、其鹽類及其組合物。
螯合劑最佳為得自A1、A2或A3者，最佳為得自A2者。分子內具有酸基之螯合劑(A)之含量以溶液總重為基準較佳為約0.1至約50%重量比，更佳為約0.5至約30%重量比，及最佳為約1至約20%重量比。
過氧化氫(B)係含括來提高銅或銅合金之蝕刻率。過氧化氫水溶液可用作為過氧化氫(B)。以純度表示其含量以溶液總重為基準，較佳為約0.05至約20%重量比，更佳為約0.1至約10%重量比，及最佳為約0.2至約5%重量比。
分子內具有氧基伸乙基鏈之界面活性劑(C)包括非離子性界面活性劑諸如烷基胺之環氧乙烷(EO)加合物(C1)、一羥基醇之EO加合物(C2)、多羥基醇之EO加合物(C3)、環氧乙烷環氧丙烷共聚物(C4)、烷基酚之EO加合物(C5)、及脂肪酸之EO加合物(C6)、經由改性烷基醇之EO加合物之端基所製備之陰離子性界面活性劑(C7)、經由改性烷基酚之EO加合物之端基所製備之陰離子性界面活性劑(C8)、及其任一種組合。烷基胺之EO加合物(C1)包括辛基胺之EO加合物及月桂基胺之EO加合物。一羥基醇(C2)之EO加合物實例包括多氧基伸乙基辛基醚、多氧基伸乙基月桂基醚、及多氧基伸乙基硬脂基醚之EO加合物。多羥基醇之EO加合物(C3)之實例包括蔗糖之EO加合物、甘露糖醇之EO加合物、季戊四醇之EO加合物及一月桂酸山梨糖醇酯之EO加合物。環氧乙烷-環氧丙烷共聚物(C4)之實例包括多氧基伸丙基二醇之環氧乙烷加合物及多氧基伸乙基二醇之環氧丙烷加合物。欲添加之環氧乙烷莫耳數為1至300，及欲添加之環氧丙烷莫耳數為1至300。使用環氧乙烷-環氧丙烷共聚物(C4)作為組分(C)特別有用，原因在於其具有作為消泡劑的效果。烷基酚之EO加合物(C5)之實例包括聚氧基伸乙基壬基苯基醚及聚氧基伸乙基辛基苯基醚。脂肪酸之EO加合物(C6)之實例包括一硬脂酸多乙二醇酯、二硬脂酸多乙二醇酯、一油酸多乙二醇酯、及二油酸多乙二醇酯。經由改性烷基醇之EO加合物之端基所製備之陰離子性界面活性劑(C7)之實例包括經由以有機酸改性一羥基醇之EO加合物(C2)所製備之陰離子性界面活性劑，諸如聚氧基伸乙基辛基醚乙酸(鹽)、聚氧基伸乙基月桂基醚乙酸(鹽)、聚氧基伸乙基辛基醚磺基丁二酸(鹽)、聚氧基伸乙基月桂基醚磺基丁二酸(鹽)、聚氧基伸乙基辛基醚硫酸酯(鹽)、及聚氧基伸乙基月桂基醚硫酸酯(鹽)。經由改性烷基酚之EO加合物之端基所製備之陰離子性界面活性劑(C8)之實例包括經由以有機酸改性烷基酚之EO加合物(C5)所製備之陰離子性界面活性劑，諸如聚氧基伸乙基壬基苯基醚硫酸酯(鹽)及聚氧基伸乙基辛基苯基醚硫酸酯(鹽)。較佳分子內具有氧基伸乙基鏈之界面活性劑(C)中存在的EO莫耳數為1至20，及較佳2至15。分子內具有氧基伸乙基鏈之界面活性劑(C)中，從銅或銅合金相對於含鎳材料之蝕刻率之比及晶圓之高度濕潤性觀點，較佳為烷基胺之EO加合物(C1)、環氧乙烷-環氧丙烷共聚物(C4)、及經由改性烷基醚之EO加合物之端基所製備之陰離子性界面活性劑(C7)。由金屬雜質含量小之觀點，更佳為烷基胺之EO加合物(C1)。從消泡效果之觀點，更佳為環氧乙烷-環氧丙烷共聚物(C4)。
從銅或銅合金之蝕刻率觀點，分子內具有酸基之螯合劑(A)重量對過氧化氫(B)之重量之比(A)/(B)較佳為1至30，更佳為2至20，及特佳為3至10。此外，分子內具有酸基之螯合劑(A)重量對界面活性劑(C)重量之比(A)/(C)較佳為1至100，更佳為2至50，及特佳為5至30。
溶劑(D)包括但非限於水、醇類、二醇醚類、醚類、酯類、酮類、碳酸酯類、醯胺類及其組合物。醇類之實施例包括甲醇、乙醇、異丙醇、正丙醇、正己醇、正辛醇、2-乙基己醇、環己醇、乙二醇、丙二醇、1,4-丁二醇、1,6-己二醇、四氫糠醇、及甘油。二醇醚類之實例包括丙二醇一甲基醚、乙酸丙二醇一甲基醚、乙二醇一甲基醚、乙酸乙二醇一甲基醚、丙酸乙二醚一甲基醚、乙二醇一丁基醚、及乙酸乙二醇一丁基醚。醚類之實例包括乙醚、二異丙基醚、二丁基醚、四氫呋喃、及1,4-二。醚類之實例包括乳酸乙酯、3-甲氧基丙酸甲酯、乙酸甲酯、乙酸乙酯、乙酸丙酯、及γ-丁內酯。酮類之實例包括丙酮、甲基乙基甲酮、甲基異丙基甲酮、甲基異丁基甲酮、甲基戊基甲酮、環戊酮及環己酮。碳酸酯類之實例包括碳酸二甲酯、碳酸二乙酯、碳酸伸乙酯及碳酸伸丙酯。醯胺類之實例包括N,N-二甲基乙醯胺及N,N-二甲基甲醯胺。以水為較佳溶劑。
為了保護佈線金屬，需要時可添加至少一種耐腐蝕組分(E)如三唑類、咪唑類、硫醇化合物、及糖醇類至該溶液。三唑類之實例包括苯并三唑、鄰-甲苯基三唑、間-甲苯基三唑、對-甲苯基三唑、羧基苯并三唑、1-羥基苯并三唑、硝基苯并三唑及二羥丙基苯并三唑。咪唑類之實例包括咪唑、苯并咪唑、苯并咪唑羧酸、咪唑-2-羧酸、咪唑-4-羧酸、咪唑-2-羧醛、咪唑-4-羧醛、及4-咪唑二硫羧酸。硫醇化合物之實例包括巰噻唑、巰乙醇及硫甘油。糖醇類之實例包括赤藻糖醇、蘇糖醇、阿拉伯糖醇、木糖醇、核糖醇、甘露糖醇、山梨糖醇、麥芽糖醇、及肌糖醇。
為了保護佈線金屬，需要時可添加抗氧化劑(F)至溶液。抗氧化劑之實例包括酚類諸如兒茶素、生育酚、兒茶酚、甲基兒茶酚、乙基兒茶酚、第三丁基兒茶酚、五倍子酸、五倍子酸甲酯、及五倍子酸丙酯、3-羥基黃酮及抗壞血酸。
鹼性或酸性化合物(G)視需要可添加至溶液作為pH調節劑。鹼性化合物可包括氨、胺類、氫氧化四烷基銨、及含氮雜環化合物。胺類之實例包括脂肪胺類、烷基胺類、伸烷基胺類、多伸烷基多胺類、芳香族胺類、環脂族胺類、及胍。脂肪胺類之實例包括甲基胺、乙基胺、丙基胺、異丙基胺、丁基胺、己基胺、二甲基胺、乙基甲基胺、丙基甲基胺、丁基甲基胺、二乙基胺、丙基乙基胺、二異丙基胺、三甲基胺、乙基二甲基胺、二乙基甲基胺、三乙基胺、三-正丙基胺、及三-正丁基胺。烷醇胺類之實例包括一乙醇胺、二乙醇胺、三乙醇胺、二甲基胺基乙醇、二乙基胺基乙醇、2-胺基-2-甲基-1-丙醇、N-(胺基乙基)乙醇胺、N,N-二甲基-2-胺基乙醇、及2-(2-胺基乙氧基)乙醇。伸烷基二胺類之實例包括伸乙基二胺、伸丙基二胺、三亞甲基二胺、四亞甲基二胺及六亞甲基二胺。多伸烷基多胺類之實例包括二伸乙基三胺、三伸乙基四胺、四伸乙基五胺、六亞甲基七胺、亞胺基貳丙基胺、貳(六亞甲基)三胺、及五伸乙基六胺。芳香族胺類之實例包括苯胺、伸苯基二胺、伸甲苯基二胺、伸二甲苯基二胺、亞甲基二苯胺、二苯基醚二胺、萘二胺及蒽二胺。環脂族胺類之實例包括異佛爾酮二胺、伸環己基二胺、哌、N-胺基乙基哌、及1,4-二胺基乙基哌。氫氧化四烷基銨之實例包括氫氧化四甲基銨、氫氧化四乙基銨、及膽鹼。含氮雜環系化合物之實例包括吡咯、咪唑、吡唑、唑、噻唑、吡啶、嘧啶、嗒、吡、聯吡啶、及菲繞啉。
酸性化合物可以是無機酸諸如硫酸、鹽酸、硝酸及氫氟酸；及有機酸諸如乙酸。為了穩定蝕刻率，添加無機酸或其鹽也有效。
於較佳具體例中，pH係於約0至約5，更佳約1至約4，及最佳約2至約3之範圍。
當需要時可添加消泡劑至溶液。消泡劑之實例包括聚矽氧消泡劑、長鏈醇消泡劑、脂肪酸酯消泡劑、及金屬皂消泡劑。前述環氧乙烷-環氧丙烷共聚物(C4)可用作為消泡劑。
此處所述溶液可用於下列用途包括但非限於銅或銅合金之去除，較佳相對於含鎳材料選擇性去除銅或銅合金。此外，預期此處所述溶液可用於金屬(例如含銅)產物之清潔及保護，包括但非限於微電子裝置、裝飾性金屬、金屬打線接合、印刷電路板及其它使用金屬或金屬合金之電子封裝。
於特佳具體例中，溶液包含、其組成為、或其主要組成為HEDP、月桂基胺之EO加合物、過氧化氫及水。
於又另一個較佳具體例中，此處所述溶液進一步包括銅。銅可溶解及/或懸浮於溶液。
本發明之溶液實質上不含磨蝕材料、氟陰離子來源、氟化碳化合物、雙胍化合物、絲胺酸、組胺酸及天冬酸、及其任一種組合。又復，溶液無法使用此處所述組分濃度形成含樹脂材料或聚合物材料。
溶液藉單純的添加個別成分及混合成均質條件而調配。此外，溶液容易配方成單一包裝配方或多份式配方，其在使用點或在使用點前混合，例如多份式配方之個別部分可於工具混合或於工具上游之儲存槽混合。相對成分之濃度係以溶液之特定倍數廣泛變化，亦即更稀或更濃，須了解此處所述溶液可個別包含或另外包含、其組成為或其主要組成為符合此處揭示之各成分之任一種組合。
如此，另一態樣係有關一種套件組包括，於一或多個容器內含有一種或多種適合形成此處所述溶液之組分。該套件組於一或多個容器內包含至少一種分子內具有酸基之螯合劑(A)、過氧化氫(B)、至少一種分子內具有氧基伸乙基鏈之界面活性劑(C)、選擇性地至少一種溶劑(D)、選擇性地至少一種抗腐蝕組分(E)、選擇性地至少一種抗氧化劑(F)、及選擇性地至少一種鹼性或酸性化合物(G)，用以於工廠或於使用點與溶劑組合。另外，套件組可於第一容器含有至少一種分子內具有酸基之螯合劑(A)、至少一種分子內具有氧基伸乙基鏈之界面活性劑(C)、選擇性地至少一種溶劑(D)、選擇性地至少一種抗腐蝕組分(E)、選擇性地至少一種抗氧化劑(F)、及選擇性地至少一種鹼性或酸性化合物(G)；及於第二容器含有過氧化氫(B)用來於工廠或於使用點彼此組合及與額外溶劑組合。套件組之容器適合用於儲存及運送該溶液例如NOWPak容器(Advanced Technology Materials,Inc.，美國，康乃狄格州，丹伯里)。
於此處所述用來從其中具有銅或銅合金之微電子裝置選擇性去除銅或銅合金之溶液之使用中，該溶液典型地係於約10℃至約100℃，較佳約20℃至約80℃範圍之溫度接觸裝置經歷約30秒至約10分鐘之較佳時間。此種接觸時間及溫度為說明性，任何其它適當時間及溫度條件皆可採用，於該方法之寬廣實務範圍內可有效地選擇相對於含鎳材料可選擇性地蝕刻銅或銅合金之適當時間及溫度。
於蝕刻之應用，溶液係以任一種適當方式施用至具有銅或銅合金於其上之微電子裝置表面，施用方式例如藉將溶液噴灑於裝置表面，藉將含銅或銅合金之裝置浸泡於或浸沒於(於靜態量或動態量之溶液內)於該溶液，經由該裝置接觸另一材料例如襯墊、或纖維狀吸收性施用器元件其上吸收有溶液，經由含銅或銅合金之裝置接觸循環溶液，或經由任何其它適當裝置、方式或技術，藉此溶液接觸其上具有銅或銅合金之微電子裝置。用於動態或靜態清潔施用可於批次裝置或單晶圓裝置。優異地，由於此處所述溶液對銅或銅合金材料相對於可能存在於微電子結構上的且暴露於溶液的其它含鎳材料具有選擇性，故此處所述溶液可以高度有效且高度選擇性方式達成銅或銅合金的去除。
於期望的蝕刻作用達成後，如本發明溶液之給定最終使用用途之期望及功效，該溶液方便從先前施用溶液之微電子裝置去除，例如藉清洗、洗滌或其它去除步驟去除。舉例言之，裝置可使用包括去離子水之清洗溶液清洗及/或乾燥(例如旋乾、氮氣、蒸氣乾燥等)。
另一態樣係有關一種包含清潔液、微電子裝置晶圓、銅或銅合金材料及含鎳材料之製造物件，其中該溶液包含至少一種分子內具有酸基之螯合劑(A)、過氧化氫(B)、至少一種分子內具有氧基伸乙基鏈之界面活性劑(C)、選擇性地至少一種溶劑(D)、選擇性地至少一種抗腐蝕組分(E)、選擇性地至少一種抗氧化劑(F)、選擇性地及至少一種鹼性或酸性化合物(G)。
藉後文討論之說明例將更完整顯示其特徵及優點。
[實施例1]
此處所述溶液及比較性溶液係經由於聚丙烯製成之容器內混合表1所示螯合劑(A)、過氧化氫(B)、界面活性劑(C)及水(D)而獲得。
表1符號相對應於下列化合物：
HEDP：60%1-羥基亞乙基-1,1-二膦酸水溶液
EDA：1,2-乙烷二磺酸二水合物
NTMPA：腈基參亞甲基膦酸
(C-1)：8莫耳月桂基胺之EO加合物
(C-2)：2.5莫耳月桂基醇之EO加合物之硫酸酯鈉鹽
(C-3)：聚氧基伸丙基二醇之EO加合物(約10至約50莫耳環氧丙烷，較佳約31莫耳環氧丙烷；約30至約60莫耳環氧丙烷，較佳約45莫耳環氧丙烷)
(C’-1)：氯化硬脂基三甲基銨
至於效能之評估，銅之蝕刻時間及鎳之蝕刻效能(蝕刻量)係藉下列方法評估。
銅之蝕刻時間係藉下列方法評估：
(1)圖4所示藉加工處理矽基板所製成的晶圓(銅晶種層厚度為1微米)切成15毫米見方來製備試驗件。使用掃描電子顯微鏡(SEM；日立高科技公司(Hitachi High-Technologies Corporation)，S-4800)經由將晶圓切成1厘米見方觀察得所製備的試驗件剖面。凸塊寬度約為30微米，凸塊高度約為8微米。銅晶種層厚度為1微米。
(2)實施例1至7及比較例1至5所製備之蝕刻液各自放置於聚丙烯製成的溶液內及攪拌。試驗件分別浸沒於蝕刻液內。
(3)浸沒於蝕刻液之試驗件表面經目測觀察，測量直到銅晶種層全體表面上的銅光澤消失為止的時間(例如圖5之(3)：直至可觀察得鈦層的全體表面)。
較佳直至銅光澤消失時間係不多於10分鐘。至於60分鐘後光澤仍未消失的試驗件，60分鐘後停止浸泡，於表1中之評估顯示為「>60」。
欲蝕刻之鎳數量係依據下述方法測定。使用SEM在蝕刻銅晶種層之前及蝕刻銅晶種層之後拍攝試驗件側表面之相片，使得可測定欲腐蝕之鎳層程度及欲腐蝕之寬度。由相片影像，於銅晶種層蝕刻前試驗件之鎳層寬度A1(微米)(圖4之7)及蝕刻後試驗件之鎳層寬度A2(微米)(圖7之7)經測量。若蝕刻前與後之鎳層寬度間之差A1-A2係小於1.0微米，則以○表示；若差異不小於1.0微米，則以×表示。
如表1可知，於實施例1至5中，銅晶種層快速地蝕刻，而未觀察得鎳部分之蝕刻。換言之，於銅晶種層去除期間，可形成期望之凸塊而不會降級。
另一方面，於此處所述不包括分子內具有氧基伸乙基鏈之界面活性劑(C)之比較例1及比較例2中，銅晶種層快速被蝕刻，但鎳也被蝕刻，結果導致形成變形的凸塊。結果該晶圓無法使用。又，於使用硫酸替代螯合劑(A)之比較例3中，銅晶種層快速被蝕刻但鎳也被蝕刻，結果導致變形的凸塊。結果該晶圓無法使用。於不包括螯合劑(A)之比較例4中，銅晶種層及鎳皆未被蝕刻。於不包括過氧化氫(B)之比較例5中，銅晶種層及鎳皆未被蝕刻。
雖然已經參考具體實施例及其特徵以各方面揭示本發明，但熟諳技藝人士基於此處揭示將了解前文描述之具體例及特徵絕非限制本發明，其它變化例、修改例及其它具體例將顯然自明。因此，本發明須廣義地解譯為涵蓋落入於後文陳述之申請專利範圍之精髓及範圍內之全部此等變化例、修改例及其它具體例。
1．．．矽基板
2．．．氧化矽層
3．．．障壁金屬層
4．．．銅晶種層
5．．．抗蝕劑樹脂
6．．．銅
7．．．鎳層
8．．．金或錫與銀之合金之焊接層
9．．．凸塊
圖1為具有一開口之矽基板(1)之剖面圖，其中氧化矽層(2)、障壁金屬層(3)、及銅晶種層(4)係積層在該開口之內壁上。
圖2為在施用抗蝕劑樹脂(5)及保護性薄膜形成在圖1之矽基板上後的矽基板之剖面圖。
圖3為在銅(6)、鎳(7)及金(8)之金屬進一步積層在圖2之矽基板上後的矽基板之剖面圖。
圖4為從圖3之矽基板去除抗蝕劑樹脂後的矽基板之剖面圖。
圖5為從圖4之矽基板去除銅晶種層後的矽基板之剖面圖。
圖6為從圖5之矽基板去除障壁金屬層後的矽基板之剖面圖。

Claims (18)

  1. 一種用於從同時包括銅或銅合金及含鎳材料之微電子裝置選擇性地蝕刻銅或銅合金之溶液，該溶液包含至少一個分子內具有酸基之螯合劑、過氧化氫、及至少一個分子內具有氧基伸乙基鏈之界面活性劑，其中，pH係介於0至5之範圍，及其中，該至少一個界面活性劑包含烷基胺之環氧乙烷加合物、烷基酚之環氧乙烷加合物、脂肪酸之環氧乙烷加合物及其組合。
  2. 如申請專利範圍第1項之溶液，其中，該至少一個螯合劑包含分子內具有至少兩個膦酸基、羧基或磺酸基之有機酸。
  3. 如申請專利範圍第1項之溶液，其中，該至少一個螯合劑包含分子內具有至少一個羧基及至少一個膦酸基之有機酸。
  4. 如申請專利範圍第1項之溶液，其中，該至少一個界面活性劑包含烷基胺之環氧乙烷加合物。
  5. 如申請專利範圍第1至4項中任一項之溶液，其中，該至少一個螯合劑之重量對過氧化氫之重量比為1至30。
  6. 如申請專利範圍第1至4項中任一項之溶液，其中，該至少一個螯合劑之重量對該至少一個界面活性劑之重量比為1至100。
  7. 如申請專利範圍第1至4項中任一項之溶液，其係進一 步包含至少一個溶劑。
  8. 如申請專利範圍第1至4項中任一項之溶液，其係進一步包含選自於由至少一個耐腐蝕組分、至少一個抗氧化劑、及至少一個鹼性化合物所組成之組群中之至少一個組分。
  9. 一種製造一微電子裝置之方法，該方法包含使用一溶液從該微電子裝置選擇性地蝕刻銅或銅合金，其中，該裝置同時包括銅或銅合金及含鎳材料，其中該溶液包含至少一個分子內具有酸基之螯合劑、過氧化氫、及至少一個分子內具有氧基伸乙基鏈之界面活性劑，其中，pH係介於0至5之範圍，及其中，該至少一個界面活性劑包含烷基胺之環氧乙烷加合物、烷基酚之環氧乙烷加合物、脂肪酸之環氧乙烷加合物及其組合。
  10. 如申請專利範圍第9項之方法，其係進一步包含至少一個溶劑。
  11. 如申請專利範圍第9或10項之方法，其係進一步包含選自於由至少一個耐腐蝕組分、至少一個抗氧化劑、及至少一個鹼性化合物所組成之組群中之至少一個組分。
  12. 如申請專利範圍第2項之溶液，其中，該至少一個螯合劑包含選自於由下列所組成群組之物質：伸乙基二胺四乙酸、二伸乙基三胺五乙酸、三伸乙基四胺六乙酸、羥基乙基伸乙基二胺三乙酸、二羥基乙基伸乙基二胺四乙酸、氮三乙酸、羥基乙基亞胺基二乙酸、β-丙胺酸二乙酸、天冬酸二乙 酸、甲基甘胺酸二乙酸、亞胺基二丁二酸、絲胺酸二乙酸、羥基亞胺基二丁二酸、酒石酸、檸檬酸、苯均四酸、苯并多羧酸、環戊烷四羧酸、甲基二膦酸、胺基三(亞甲基膦酸)、1-羥基亞乙基-1,1-二膦酸(HEDP)、伸乙基二胺四(亞甲基膦酸)、六亞甲基二胺四(亞甲基膦酸)、伸丙基二胺四(亞甲基膦酸)、二伸乙基三胺五(亞甲基膦酸)、三伸乙基四胺六(亞甲基膦酸)、三胺基三乙基胺六(亞甲基膦酸)、反-1,2-環己烷二胺四(亞甲基膦酸)、甘醇醚二胺四(亞甲基膦酸)、四伸乙基五胺七(亞甲基膦酸)、其鹽類及其組合。
  13. 如申請專利範圍第3項之溶液，其中，該至少一個螯合劑包含選自於由下列所組成群組之物質：膦基乙酸、2-羥基-2-膦基乙酸、羧基膦酸、3-膦基丙酸、4-(3-膦基丙基)-2-哌羧酸、其鹽類及其組合。
  14. 如申請專利範圍第4項之溶液，其中，該至少一個界面活性劑包含辛基胺之環氧乙烷加合物、月桂基胺之環氧乙烷加合物及其組合。
  15. 如申請專利範圍第1項之溶液，其中，該分子內具有氧基伸乙基鏈之界面活性劑中存在的環氧乙烷莫耳數為1至20。
  16. 如申請專利範圍第7項之溶液，其中，該至少一個溶劑包含選自於由下列所組成群組之物質：水、甲醇、乙醇、異丙醇、正丙醇、正己醇、正辛醇、2-乙基己醇、環己醇、 乙二醇、丙二醇、1,4-丁二醇、1,6-己二醇、四氫糠醇、甘油、丙二醇一甲基醚、乙酸丙二醇一甲基醚、乙二醇一甲基醚、乙酸乙二醇一甲基醚、丙酸乙二醇一甲基醚、乙二醇一丁基醚、乙酸乙二醇一丁基醚、乙醚、二異丙基醚、二丁基醚、四氫呋喃、1,4-二、乳酸乙酯、3-甲氧基丙酸甲酯、乙酸甲酯、乙酸乙酯、乙酸丙酯、γ-丁內酯、丙酮、甲基乙基甲酮、甲基異丙基甲酮、甲基異丁基甲酮、甲基戊基甲酮、環戊酮、環己酮、碳酸二甲酯、碳酸二乙酯、碳酸伸乙酯、碳酸伸丙酯、N,N-二甲基乙醯胺、N,N-二甲基甲醯胺及其組合。
  17. 如申請專利範圍第7項之溶液，其中，該至少一個溶劑包含水。
  18. 如申請專利範圍第1項之溶液，其包含1-羥基亞乙基-1,1-二膦酸(HEDP)、月桂基胺之環氧乙烷加合物、過氧化氫及水。
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