TWI335648B - Semiconductor packages; lead-containing solders and anodes; and methods of removing alpha-emitters from materials - Google Patents
Semiconductor packages; lead-containing solders and anodes; and methods of removing alpha-emitters from materials Download PDFInfo
- Publication number
- TWI335648B TWI335648B TW092127949A TW92127949A TWI335648B TW I335648 B TWI335648 B TW I335648B TW 092127949 A TW092127949 A TW 092127949A TW 92127949 A TW92127949 A TW 92127949A TW I335648 B TWI335648 B TW I335648B
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- Prior art keywords
- lead
- cts
- less
- alpha
- solder
- Prior art date
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- H—ELECTRICITY
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- H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
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- H01L24/10—Bump connectors ; Manufacturing methods related thereto
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
- B23K35/0222—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in soldering, brazing
- B23K35/0244—Powders, particles or spheres; Preforms made therefrom
- B23K35/025—Pastes, creams, slurries
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/18—Electrolytic production, recovery or refining of metals by electrolysis of solutions of lead
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- H01L23/488—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor consisting of soldered or bonded constructions
- H01L23/498—Leads, i.e. metallisations or lead-frames on insulating substrates, e.g. chip carriers
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- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
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- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
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- B23K35/268—Pb as the principal constituent
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
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- Manufacture And Refinement Of Metals (AREA)
Description
1335648 玖、發明說明: 【相關前案】 本發明與2002年10月8曰提出申請之| 吴國5s時申請案第 60/417,241 號有關。 【發明所屬之技術領域】 本發明係關於半導體包裝;含錯之焊料及陽極;及自讨 料移除α放射物之方法。 【先前技術】 焊料普遍4用在半導體裝置包裝中。若焊料·含有α粒子 放射物同位素(在此稱為α粒子放射物),所放射的α粒子讦 能導致包裝半導體裝置的損傷。據此,預期降低烊料中之 α粒子放射物濃度。 一示範的先前技藝半導體包裝在圖】中示為包裝5〇,與該 示範包裝一起呈現的是一覆晶結構。該包裝包含一半導體 構件12(例如一積體電路晶片該包裝也包含一用來支撐該 半導體構件12的板材14。複數個接觸焊墊38(只有其中的某 些被標記)係與晶片12接合,並且複數個接觸焊塾4〇 (只有 其中的某些被標記)係與板材14接合。錫球或凸塊39 (只有 其中的某些被標記)係經提供在焊墊38和40之間以形成銲 墊3 8和40間的電氣內連線。運用錫球或凸塊39連同銲塾38 和40的電氣連線可以併入所謂的晶圓凸塊技術。 可以如圖示般在該晶片12及基板14上提供適合的封膠 44。此外’及/或另外,可在該晶片丨2上提供例如散熱片(heat sinks)和熱分散器之傳熱裝置(未示出)。 88541 -6- 1335648 接觸焊墊30(只有其中的某些被標記)係位於該板材丨斗下 侧(即在板材14相反於緊鄰晶片12一側的側邊上>接觸銲墊 3〇通常包含銅、鎳和金的堆疊。錫球32(只有其中的某些被 標記)係經提供在該等接觸焊墊上,並用來形成該等接觸焊 墊30和其他位於該晶片包裝外部的電路(未示出)間的電氣 内連線。該等接觸焊墊40可以透過延伸通過板材14的電路 軌跡(未示出)來與該等焊墊3〇連接。 所不的包裝50具有來自錫球39,並且可能經由與焊墊 及/或焊墊40j|關的晶圓凸塊,之緊鄰晶片12的焊料。在包 裝5〇内可能有其他沒有特別示出的焊料應用。例如,—錫 霄(solder paste)可經提供在晶片12和多種傳熱裝置之間。 用在包裝50内的該等焊料可能會有問題,如上所討論 者,因為該等烊料可能包含α粒子放射物。α粒子對於半 導體裝置來說是有問題的,因為該等α粒子可以引起所謂 的軟錯誤(soft errors) ^將該等錯誤稱為「軟的」是因為該 等錯誤並非永久性。但是,該等錯誤通常會導致至少—個 位數(round)的錯誤計算。 ^^粒子有許多來源,包含由宇宙射線(cosmic rays)所導致 的反應。但是,對半導體裝置包裝來說,通常最有問題的 來源是用來形成關診半導體晶粒之多種内連線的焊料。例 如,晶圓凸塊技術在形成對於半導體晶粒之高密度内連線 上逐漸變得普遍。該等凸塊是形成在與一半導體晶粒包裝 相關的電子結點(electrical n〇des)上之焊料的部分。若用在 該等凸塊中的焊料具有α粒予放射物成分的話,該等α粒 88541 1335648 子常常在接近與該半導體晶粒相關的積體電路處放射。 偶爾’形成在該等電子結點上的焊料係呈大的拄狀物型 式。此種柱狀物常被稱為圓柱(column)。為了解釋本揭示, 應將「凸塊」一詞理解為包含形成在電子結點上之多種型 式的焊料,包含常稱為圓柱的型式。 許多焊料的典型成分是鉛。但是,鉛同位素的一種(明確 也0Pb)具有導致α粒子發生的衷變鍵(decay chain)。此 外’多種常見的鉛污染物會發射α粒子,包含,例如,鈾、 赵、鐳和針的同位素。 —^ 存在鉛中的該等α粒子放射物可以存在於最初精鍊鉛的 礦石中。α粒子放射物可以,此外,或另外,在製程及/或 使用鉛期間被引進。例如,磷酸和某些抗靜電系統包含α 粒予放射物;某些研磨和清潔劑可以將α粒子放射物引進 錯内;而商用鉛的精鍊可以引入鈾。 —存在錯内的峰子放射物的量通常是由^量測試來決 定,其結果係以每小時每單元之α粒子數來說明 (cts/cm/hi^在商業上取得具有從〇 〇〇2至〇 〇2此仏^心的 ,是可能的’但是非常難取得具有更低α流量的材料。但 疋半導月丑工業要求α流量特別低的材料,包含例如,具 有小於G.GGGl ets/em2/hi^ α流量的材料。 在與將一材料内之《流量放射物濃度降低至極低水準] 關的固難中的-個困難是測量流量水準低糾獨㈣心 的放射物濃度。除非可以測量濃度’否則監控-純化製; 來決足《粒予放射物是否已經移除是困難的。例如,在么 88541 -8- 1335648 化製程的任何階段決定〇:粒子放射物是否連同—材料或離 開該材料分餾可能是困難的。 雖然上面的討論集中在將α粒子放射物從含鉛坪料中移 除’需瞭解α粒子放射物在其他材料中也是有問題的。例 如’用來降低烊料中之《粒子放射物濃度的方法之一創造 出所謂的無鉛焊料。此種焊料含有少量’若有任何的話, 的錯,其從環境觀點來說是預期的。但是,該烊料可能仍 然具有不預期數量的粒子放射物存在其中。示範的無鉛 坪料是錫:3二5%銀;錫:4%銀:0.5%鋼;以及鉍:213% 銀’其中該百分比是重量百分比β 已用來降低含鉛焊料中之α粒子放射物數量的方法之— 是從具有非常少的放射物在其中的鉛材料開始。目前此種 材料有三種來源。該等來源是(1)非常古老的鉛,其中2l0pb 基本上已全部衰變;(2)某些特定的硫化鉛礦石體,其中具 有非常少的210Pb,並且已被謹慎地精鍊;以及(3)經受雷射 同位素分離以從鉛中移除的鉛。所有的來源皆存在多 種問題。例如,該第一來源使用非常古老的鉛,因此精鍊 通常很拙劣並因而含有多種放射性核素做為污染物。該第 一來源通常沒有足夠低的α粒子放射物濃度以符合半導體 工業最終預期的要求《該第三來源的形成是非常耗費能源 的,因此不是商業可行的。 【發明内容】 在一觀點中,本發明包含一種精鍊—材料的方法。該材 料取初成份係經提供。該最初成分具有大於或等於〇 〇〇2 88541 1335648 cts/cm2/hr的α流量。該材料係經純化以形成該材料之第二 成份。該第二成份具有小於0.001 cts/cm2/hr的α流量,較佳 地小於0.0005 cts/cm2/hr,更佳地小於0.0002 cts/cm2/hr,並 且甚至更佳地小於0.0001 cts/cm2/hr。該純化可以包含,例 如,電精鍊及/或化學精鍊。
在又另一個觀點中,本發明包含一半導體結構,其含有 <2流量小於0.001 cts/cm2/hr之焊料,較佳地小於0.0005 cts/cm2/hr,更佳地小於0.0002 cts/cm2/hr,並且甚至更佳地 小於 0.0001 cts/cm2/hr° —5= 在又另一個觀點中,本發明包含一含鉛陽極,其α流量 小於0.001 cts/cm2/hr,較佳地小於0.0005 cts/cm2/lir,更佳地 小於0.0002 cts/cm2/hr,並且甚至更佳地小於0.0001 cts/cm /hr °
在又另一個觀點中,本發明包含一含鉛烊料凸塊,其α 流量小於0.001 cts/cm2/hr,較佳地小於0.0005 cts/cm2/hr, 更佳地小於0.0002 cts/cm2/hr,並且甚至更佳地小於0.0001 cts/cm2/lir。該凸塊可以,在具體觀點中,是一圓柱形式。 在又另一個觀點中,本發明包含一含鉛錫膏,其α流量 小於0.001 cts/cm2/hr,較佳地小於0.0005 cts/cm2/hr,更佳地 小於0.0002 cts/cm2/hr,並且甚至更佳地小於0.0001 cts/cm2/hr。 【實施方式】 本發明之此揭示係為促進美國專利法「促進科學和實用 技藝的進展」(條款1,第8項)之憲法立意而提呈》 88541 -10· 1335648 本發明之一觀點係對於即使鉛同位素(2i〇Pb)是含有高濃 度α放射物的鉛之永久α放射物,但這不是含有低或非常 低濃度α放射物的鉛的情況之認知。為了解釋本揭示和隨 後的申請專利範圍,含有低濃度α放射物的鉛是α流量約 〇-〇2cts/cm2/hr的鉛,並且含有非常低濃度^放射物的鉛是 α 流< 量約 〇_〇〇2 cts/cm2/hr的船。 鈾同位素、鉦同位素、以及或許其他非鉛同位素被認為 是含有低或非常低濃度〇;放射物的鉛之主要α放射物。此 、. 吊 濃度0:粒子放射物之錯的α 流量對時間關係並不遵守從2i〇pb衰變預測的長期平衡曲線 的觀察。對於鉛之主要α放射物是非鉛同位素的認知導致 改良的用來降低最初含有低和非常低濃度α粒子放射物的 鉛之α放射物水準的方法。具體地,該α放射物水準可以 利用純化方法來降低,其從鉛移除微量非鉛污染物。根據 本發明之觀點所發展的示範方法是利用含有硝酸:水浴的 電精鍊(硝酸濃度從約2%至約50%,體積百分比 對於非鉛不純物是含有低或非常低濃度α放射物的鉛之 主要α放射物的認知也經由此種鉛之α流量隨著鉛之不純 物含量而提升的觀察得到證實。 雖然本發明在此缉常關於從鉛移除α粒子放射材料來敘 述,需瞭解的是本發明也可以用來純化鉛以外的其他材科 (例如金屬,例如錫、銀、銅、銦、鉍等常合併在無鉛焊料 中者)。α粒子的移除對於使用在半導體製造中的金屬特別 有利;例如,合併在晶圓凸塊烊料中的金屬。 88541 •11· 1335648 本發明之一觀點是在純化一原始材料期間間接追蹤至少 一種低濃度α粒子放射物的方法。該α粒子放射物係一污 染物,而非該材料的同位素。在具體觀點中,該材料可以 疋:li» ’並且該粒子放射物是杜和抽的同位素。存在於原 始材料内之一種或多種濃度比〇粒子放射物高的污染物係 經確認’並且在純化期間與該等放射物同樣做分餾。確認 的污染物較佳地是可以在純化期間輕易追蹤的物質。該等 污染物的分餾係關於污染物在純化製程期間餘留欲純化的 原始材料部之與從該原始材料分離出的部分之間的分類。 較佳地’分餾可以使基本上所有的污染物在純化製程期間 從該原始材料中分離。 污染物的分餾在純化期間被追蹤,並且從此追蹤的分餾 推論一種或多種QJ粒子放射物的分餾。據此,該α粒子放 射物的分館是推斷的,而非直接測量的。如此可避免與測 量一具有非常低濃度〇:粒子放射物之材料的α流量有關的 問題。低或非常低濃度的α粒子放射物產生通常與背景無 顯著差異的〇:流量,因此一般非常難以有高信賴度的測 量。因為α粒予放射物是污染物而非所純化之原始材料的 同位素’該α粒子放射物會與其他污染物一起分餾,若純 化使用的是非常明確地將原始材料與污染物質分館的方法 的話。具有適當的明確性之示範方法是電精鍊。也可以使 用化學精鍊,除了電精鍊之外或二擇—的。 欲純化的原始材料可以,如上所討論般,是鉛,並且在 純化之前最初可以包含重量百分比至少99.99%的鉛。據 88541 •12· 1335648 此,可將欲純化之原始材料視為基本上由,或由,鉛所構 成。在其他觀點中,欲純化的原始材料基本上可由,或由 銀、錫、銅、麵和銦所構成。在具體觀點中,欲純化的材 料最終可以用在一無鉛焊料中。 純化方法可以是任何適合的方法,包含,例如,化學精 鍊及/或電精鍊。在純化鉛之示範方法中,電精鍊係以包含 水以及硝酸、曱基磺酸、氟矽酸鹽和氟硼酸鹽之一種或多 種的水浴來使用。在本發明之明確觀點中,發現在含有或 基本上含有硝酸和水的水浴中之鉛的電精鍊(具有以重量 β 百分比濃度從約2%至約50%存在的硝酸)對於降低最初含 · 有低或非常低濃度α放射物的鉛之α流量來說是特別有效 的。在一硝酸浴中的鉛之電精鍊示範條件包含從約70 °F (21 °C )至約l〇〇°F(3 8°C )的硝酸浴溫度,從約幾小至約幾天的處 理時間,以及從約1安培/平方英尺(A/ft2)至約70 A/ft2的處 理電流密度。
與此揭示一起提供幾個圖式(標示為圖2-5),並且這些圖 式證實了一材料的α流量會隨著該材料中之不純物總量而 提升。據此,在純化製程期間的α放射粒子之分餾可以從 該純化製程期間其他不純物的分餾來推論。從銀純度 99.99%純化至銀純度99.999%使α活動從0.0162 ± 0.0017 cts/cm2/hr 降低至 0.0062 ± 0.0007 cts/cm2/hr。從錫純度 99.99%純化至錫純度99.999%使α活動從0.0066 ± 0.0005 cts/cm2/lir 降低至 0_0007±0.0008 cts/cm2/hr。 88541 -13 - 1335648 基本上可以從無船焊錫材料中移除α放射物(例如鉦和鈾 的同位素)。該等α放射污染物的移除可以利用測量樣品的 α流量來輕易確認,因為其通常以低於大部分分析方法之 偵測限度的量存在,例如輝光放電質譜儀(GDMS) ^但是類 似GDMS的分析方法可以用來追蹤以比該等α放射物高的 濃度存在並且在純化期間以與該等α放射物相似的速率移 除的非放射不純物的濃度。 順應法令,本發明已利用大約明確的方式關於結構和方 法特徵作表ft。但是應瞭解的是,本發明並不囿限於所示% 和所述的明確特徵,因為在此所述的方法包含使本發明產 生效用的較佳形式❶本發明,因此,主張任何在所附之根 據相同原理適當解釋之申請專利範圍的適當範圍内的形式 或調整。 【圖式簡單說明】 圖1係一先前技藝半導體包裝結構之概略剖面侧視圖。 圖2係根據本發明之觀點純化的材料之〇 c〇unts/cm2/hr 對於總不純杨之曲線圖。 · 圖3係根據本發明之觀點純化的材料之α c〇unts/cm2/hr 對於銅濃度之曲線圖。 圖4係根據本發%之觀點純化的材料之a counts/cm2/iir 對於總不純物之曲線圖。 圖5 Y系才艮 發明之觀點純化的材料之ύ: counts/cm2/hr 對於總銀濃度之曲線圖。 88541 -15- 1335648 【圖式代表符號說明】 12 半導體構件 14 基板 30、40 接觸銲墊 32、39 錫球 38、40 烊墊 44 封膠 50 包裝 88541
Claims (1)
- Ϊ335648 拾、申請專利範園: h —種半導體包裝’包含一 α流量小於〇 〇〇1總數/平方公分 /小時(cts/cm2/hr)的焊料。 2 其中該焊料主要包 其中該焊料主要包 其中該焊料主要包 其中該焊料基本上 其中該烊料係鉛重 其中該含鉛焊料具 其中該含鉛焊料具 其中該含鉛焊料具 如申請專利範園第1項之半導體包裝 含銀、叙、銅、鋼、錯或錫。 如申請專利範圍第1項之半導體包裝 含銀。 4 如申請專利範圍第1項之半導體包裝 含錫。 —* 如申請專利範圍第1項之半導體包裝 是無錯的。 6 如申請專利範圍第1項之半導體包裳 量百分比至少99°/❶的含錯焊料。 7 _如申請專利範園第6項之半導體包裝 有小於0.0005 (^/(;1112/111>的(^流量。 8‘如申請專利範圍第6項之半導體包裝 有小於0.00Ό2 cts/cm2/hr的α流量》 9 ·如申請專利範圍第6項之半導體包裝 有小於0.0001 «^/^112/111"的(^流量。 瓜一種CX流量小於0.001 cts/cm2/hl^含鉛陽極該含鉛陽名 包含重量百分比至少約5 0 %的錯。 11·如申請專利範圍第10項之含錯陽極’具有小於〇侧 cts/cm2/hr的 α 流量。 12.如申請專利範園第1()項之含㈣極,具有小於〇厕 88541 1335648 cts/cm2/hr的 α 流量。 13. 如申請專利範圍第10項之含鉛陽極,具有小於0.0001 cts/cm2/hr的 α 流量。 14. 一種α流量小於0.001 cts/cm2/hr的含鉛焊錫凸塊,該含鉛 焊錫凸塊包含重量百分比至少約50%的鉛。 15. 如申請專利範圍第14項之含鉛焊錫凸塊,具有小於0.0005 cts/cm2/hr的 α 流量。 16. 如申請專利範圍第14項之含鉛焊錫凸塊,具有小於0.0002 cts/cm2/hr的 α 流量。 ---- 17. 如申請專利範圍第14項之含鉛焊錫凸塊,具有小於0.0001 .cts/cm2/hr的 α 流量。 18_ —種α流量小於0.001 cts/cm2/hr的含鉛錫膏,該含鉛錫膏 包含重量百分比至少約50%的鉛。 19. 如申請專利範圍第18項之錫膏,具有小於0.0005 cts/cm2/hr的 α 流量。 20. 如申請專利範圍第18項之錫膏,具有小於0.0002 cts/cm2/lir的 α 流量。 21. 如申請專利範圍第18項之錫膏,具有小於0.0001 cts/cm2/hr的 α 流量。 22. —種精鍊含錯材料的方法,包含: 提供該含鉛材料的最初成份,該最初成份具有大於或 等於0.002 cts/cm2/hr的α流量;以及 純化該含鉛材料以形成該含鉛材料之第二成份,該第 二成分具有小於0.001 cts/cm2/hr的α流量。 88541 -2- 1335648 23. 如申請專利範圍第22項之方法,其中該純化包含一種或 多種電精鍊,區域精鍊和化學精鍊。 24. 如申請專利範圍第22項之方法,其中該純化包含利用含 有硝酸和水的水浴(bath)之電精鍊,具有以重量百分比濃 度從約2%至約50%存在的硝酸。 25. 如申請專利範圍第22項之方法,其中該純化包含利用主 要由硝酸和水構成的水浴之電精鍊,具有以重量百分比 濃度從約2%至約50%存在的硝酸。 26. 如申請專利範圍第22項之方法,其中該第二成份之含鉛 —,二 材料係重量百分比至少99.99%的鉛。 27. 如申請專利範園第22項之方法,其中該第二成份具有小 於0.0005 如/〇312/111^的〇:流量。 28. 如申請專利範圍第22項之方法,其中該第二成份具有小 於0.0002 cts./cm2/hr的 α 流量。 29. 如申請專利範圍第22項之方法,其中該第二成份具有小 KO.OOOlcts/cmVhr^atfu'l:0 88541
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- 2003-09-25 AU AU2003272790A patent/AU2003272790A1/en not_active Abandoned
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- 2003-10-08 TW TW099132853A patent/TWI482247B/zh not_active IP Right Cessation
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| US7521286B2 (en) | 2009-04-21 |
| WO2004034427B1 (en) | 2004-08-05 |
| TW200421581A (en) | 2004-10-16 |
| TWI482247B (zh) | 2015-04-21 |
| AU2003272790A8 (en) | 2004-05-04 |
| WO2004034427A3 (en) | 2004-06-17 |
| AU2003272790A1 (en) | 2004-05-04 |
| US9666547B2 (en) | 2017-05-30 |
| US20070045838A1 (en) | 2007-03-01 |
| US20100206133A1 (en) | 2010-08-19 |
| US20060201279A1 (en) | 2006-09-14 |
| US20040065954A1 (en) | 2004-04-08 |
| TW201123379A (en) | 2011-07-01 |
| US20070045842A1 (en) | 2007-03-01 |
| WO2004034427A2 (en) | 2004-04-22 |
| US20070045839A1 (en) | 2007-03-01 |
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