TW555886B - Electrochemical etch for high tin solder bumps - Google Patents

Electrochemical etch for high tin solder bumps Download PDF

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Publication number
TW555886B
TW555886B TW090126212A TW90126212A TW555886B TW 555886 B TW555886 B TW 555886B TW 090126212 A TW090126212 A TW 090126212A TW 90126212 A TW90126212 A TW 90126212A TW 555886 B TW555886 B TW 555886B
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Taiwan
Prior art keywords
tin
content
concentration
metals
scope
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Application number
TW090126212A
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English (en)
Inventor
Lisa A Fanti
John Michael Cotte
David Ely Eichstadt
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Ibm
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Publication of TW555886B publication Critical patent/TW555886B/zh

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F3/00—Electrolytic etching or polishing
    • C25F3/02—Etching
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    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
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    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
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    • H01L21/32133—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only
    • H01L21/32134—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by liquid etching only
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555886 五、 經濟部智慧財產局員工消費合作社印製 A7 B7 發明說明（） fag領域： 本發明涉及金屬的選擇性腐蝕。更具體而言，本發明 係涉各種焊球存在的條件下對金屬進行的電化學腐蝕。 1¾背景： C4是一種先進的微電子晶片的包裝和連接技術。”C4，， 代表可控塌陷晶片連接（Controlled Collapse Chip Connection)。C4 也叫"焊球（solder bump)"、”焊料球，，及” 覆晶（flip chip)"，而且這些術語也可共稱之，如稱作”C4 焊球π。 C4的基本思想是將晶片（半導體器件）、晶片封組或這 類的其它單元連接起來，它是通過這些單元的兩表面之間 的一些焊球來完成的。這些導電焊料的細小隆起將把連接 單元上的相應兩金屬墊之間的間隙跨接起來。每塊金屬聲 都在另一單元的表面上有一金屬墊與之對應；該等金屬塾 的排列都呈鏡像。當將這些單元壓在一起並加熱時，該第 一單元的金屬墊上的焊球就會與該第二單元上的相應導 電金屬塾（沒有焊球）接觸並被軟溶，就會使該焊球局部塌 陷並在相應金屬墊之間形成一些連接。 在C4中該等烊球被直接做在—個單元的那些金屬整 上。這些金屬塾與其它零件之間被每塊金屬塾周圍的絕緣 基片電絕緣。該基片可以是矽（Si)，★ π σ ^ )也可是某種其它的材 料。該金屬墊的底部是與該晶片電路 W电連接的。 片與载體或封組連結夫 第4頁 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公f ) , I I---------—訂·-------- (請先閱讀背面之注意事項再填寫本頁) C4的主要應用是將 555886 A7 五、發明說明（） 來。晶片通常都是以矩形陣列的形式做在被稱作"晶片，，的 單晶矽片上。在每塊晶片上制做很多晶片，然後將該晶片 分裂成一些單個的晶片並將這些晶片"封裝”在一些足夠 大的單元中，以便操作處理。將該等C4焊球放置在這些 晶片上，同時還將它們連接在晶片中。 將晶片做得盡可能大，以便減少為製備一定數目的晶 片所必須處理的晶片數。為了同樣的理由，（其中）還將這 些晶片做得盡可能小。這樣，最好的C4製備系統就是能 在一大面積上製備成千的很小的、間隔很近的，每個都是 精確地安放的焊球的系統。 當將兩表面按壓在一起時，C4的焊球應該被機械地很 好地固定在它們的金屬塾上，否則它們就可被撕扯開。一 般皆知一複雜的裝置，如電腦可以具有幾十個晶片和成百 上千個C4的焊料球連接點，只要有一個這種隆起失靈則 會使整個裝置播用。該C4隆起的連接需要審慎的設計方 得為之。 形成焊球的-種方法利用了賤射或真空沈積技術。在 這種方法中，焊料金屬在真空腔中被汽化。該金屬蒸氣會 使該真空腔中的每件東西上覆蓋一層該蒸發金屬的薄 膜。為了在基片上形成焊球，可使該蒸氣通過固定在該基 片上的金屬遮罩中的孔。通過這些孔的烊料蒸汽就在該冷 表面上凝結成一些焊球。這種方法需要一高真空腔來容納 該基片、遮罩、和閃蒸器。 製備焊球的另一技術為電化學覆鍍或電鍍。這種方法 第5頁 1 —k^w ^ (請先閱讀背面之注意事項再填寫本頁) 訂--- #丨 經濟部智慧財產局員工消費合作社印製 555886 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明（ 也使用遮罩並只在所選擇的位冒、 、_ ]彳罝上形成焊球，但該技術與 該蒸發法是很不相同的。 電解形成C4焊球過程的第一步是在擬形成隆起的該 晶片上沈積-連續的金屬薄膜的叠層(，。這就是所謂 的"種子層"’它起著雙重作用。首先，它在焊球的電解沈 積過程中提供了一電流的導電通路。第二，它保留在焊球 的下面，形成C4的球形限制冶金（bau⑽⑴叫
Metallurgy)(BLM)的基礎。因而，為了在該晶片的整個橫 向跨度上说進行均勻的電沈積，必須至少有一層是足夠導 電的。該底層必須很好地粘附在下面的半導體器件上以便 鈍化，而頂層必須與該焊料進行充分的相互作用以便形成 可靠的連接。Λ外，肖BLM可以包含一些阻擋層，以避 免焊料與下面的器件組分發生有害的相互作用。最後，由 混合堆疊（composite stack)所產生的應力應足夠小，以便 在各種熱學和機械應力範圍上維持該C4連接的可靠性。 考慮到所有這些因素，種子層通常由一種以上的金屬層組 成，而且這些不同的層必須在處理過程中的某一時刻從 C4之間被腐蚀掉，以便各互連點電絕緣。 在敷設種子層之後，第二步就是用光刻法形成一遮 罩。在該種子層上敷設一層光刻膠，並使它曝光。未曝光 的光刻膠（如一負性光刻膠）那時就可被洗去以便將固化 的光刻膠留下作遮罩。該遮罩具有一些孔列，焊球就將沈 積在這些孔所在的位置上。 第三步是將焊料電沈積（電鍍）到上述遮罩孔中。 第6頁 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 裝--------訂--------- (請先閱讀背面之注意事項再填寫本頁) 555886 A7 _-__B7 經濟部智慧財產局員工消費合作社印製 五、發明說明（） 在上述焊球形成之後，就將固化的光刻膠的遮罩除 去。這時該基片就被連續的種子層和大量的焊球所覆蓋。 然後’通過適當的濕浸蚀和/或電腐蚀工藝將該焊球之間 的種子層除去以便使它們電絕緣。 典型地用於C4焊球的焊料為97wt%的Pb和3wt°/〇的 Sn。典型的種子層總是包括一 Tiw層、一形成過渡相的 Cr/Cu 層（phased Cr/Cu layer)或 Cr/Cu 合金、和一 Cu 層。 用來同時除去該Cr/Cu和Cu層的方法是電腐蝕方法，它 包括一種含有甘油和硫酸鉀的水溶液，就如在Datta等的 美國專利5,486,282中所公開者一般，該公開内容併入本 案中，以作為參考。該甘油用作潤濕劑，而硫酸鉀的目的 則是雙重的。第一，該硫酸鉀賦予該溶液電解導電率。第 二’自由的硫酸根離子易於與高Pb的焊球絡合，形成一 保護外殼’在電腐蝕過程中這外殼能防止焊球被溶解。然 後利用濕浸蚀方法對該Tiw層進行腐蝕，該濕浸蝕方法包 括含有過氧化氫、EDTA、和硫酸钟的含水腐蝕水溶液， 就如在Datta等的美國專利5,462,63 8和Fanti等的美國專 利6，0 1 5，5 0 5所公開者一般，該公開内容被併入本案中 以作為參考。該焊球上的"外殼”在緊接著的清洗過程中被 除去。 更近的一些應用利用了一低熔點的焊料作C4 9隆起 以便能進行低溫的晶片連接。這樣的一種低熔點焊料可〆 是包括63wt%的Sn和37wt%的Pb的鉛/錫焊料。 Cotte等的美國專利5,8〇〇,726提出 !水/合硬以便 第7頁 本紙張尺度適用中國國豕標準（CNS)A4規格（21〇 X 997公餐） (請先閱讀背面之注意事 ,φ 項再填 裝---- 寫本頁) 訂--------- 555886 五、 經濟部智慧財產局員工消費合作社印製 發明說明（） 在存在有易溶焊料的情況下齊久 链 ^ r野各種金屬，如Tiw，的濕浸
餘，該專利内容被併入本案φ，” μ t A 菜中，以供作參考。這種溶液包 括磷酸鉀、過氧化氫、EDTA、以及草酸。 本案發明人已認識到，翊咕AA & & 現時的電腐蝕方法對於高Sn 焊球並非有效的。理由是s n粗、λ + △ 、 疋n對於硫酸根離子並不是很活 潑的，因而現行技術的電腐妯 、 电腐蚀〉谷视，如上述Datta等的美 國專利5，486,282中所公開杏 ^者’並不能在電腐蝕過程中在 烊球上形成保護外殼。不良的 艮的〜果疋從孩焊球浸出大量的
Sn。此外，該溶解下來的 n曰自由地重新沈積在TiW上 並與Tiw絡合，使得該Tiw w層對於傳統的濕浸蝕來說是 不可滲透的。 分層的焊料結構使問題# & Ί題更加複雜。例如，在這種分層 、、、口構中’低溶點的高Sn、焊跋雜 干衣4被沈積在一高熔點的高pb 焊球上。 這樣，本發明者們就認識到，需要一種這樣的腐触工 ，它要既能有效地電腐蚀金屬而又 包含有高Pn的焊料的焊球。 因此’本發明的目的在 ;對具有一些有待電腐蝕的金 屬和不擬腐蚀的高Sn的焊球的基片進行電腐触。 本發明的另一目的在於對具有一些有待電腐触的金 屬和不想被腐蚀的包本右合 G η有同Sn焊球和高Pb焊球的焊 層結構的基片進行電腐蚀。 本發明的這些和袁令μ 、勺目的從下面的描述並結合附 圖來看將曰變得更加明顯。 第8頁 本紙張尺度適用中國國家標準（CNS)^^^ · ϋ I ί ι>1 一。、I H ϋ H ϋ ϋ ϋ I (請先閱讀背面之注意事項再填寫本頁) x 297 公 f ) δδΟ
五、發明說明（ 壁L明目6<?及概诚：_ 本發明的目的已由下述方 被腐蝕的金屬的情況 在存在有一或多種不想 (請先閱讀背面之注意事項再填寫本頁) 卜’本發明的裳 電化學腐蝕水溶液，田七 吊—態樣中，提供一種 斤J來對—些金 溶液至少包括： —“臂進行腐蝕，該腐蝕水 甘油，其濃度為1.30-Uom; 硫酸鹽化合物，其 磁妨胳几人仏 雕卞/晨度為〇—0·:5Μ ; 舞酸鹽化合物，其 六从“丹螂酸鹽離子濃度為〇·1- 0.5Μ。 .ΤΊΓ ^從 有一或多種不想被溶解的金屬的情 、、 一心樣中，棱供了一種用來選擇性地 溶解一或多種擬溶解 0金屬的，該万法至少包括下述步 驟· 用種腐蝕水/谷液對想要溶解的金屬進行電化學腐 ^ ό水腐蚀水落液包括：甘油，其濃度為^ 3 〇 一 K7〇M;硫酸M化合物，其硫酸根離子濃度為〇- 〇·5Μ; 以及鱗酸鹽化合物，其磷酸根離子濃度為0.1 — 0.5M。 按照本發明的第三態樣，提供了 一種用來選擇性地腐 蚀一物件的方法’該方法至少包括下述步驟： 經濟部智慧財產局員工消費合作社印製 提供一物件，該物件具有一或多種想要溶解的金屬， 同時還存在有一或多種不想被溶解的金屬； 用一種腐蝕水溶液對想要溶解的金屬進行電化學腐 蚀’該含水腐蝕水溶液包括：甘油，其濃度為丨.30 — 1·7〇Μ ;硫酸鹽化合物，其硫酸根離子濃度為〇一 〇 5M ; 以及磷酸鹽化合物，其磷酸根離子濃度為0.1 — 0.5Μ。 第9頁 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） A7 B7
555886 五、發明說明（） 圖式簡單說明：_ 被認為是本發明的一些新穎特點和本發明的一些特 徵的要素都被詳細陳述於後附之申請專利範園中。所有附 圖都僅供圖示說明用，故皆未按比例繪出。但是，透過參 考後文的詳述及這些附圖的配合說明，本發明本身之妗構 和操作方法得以得到最佳的理解，其中： 第1圖是一晶片的側視圖，它表示該種子層和第一種焊料 分層結構，該結構僅包含有主要是gj η的焊料。 第2圖是一晶片的側視圖，它表示出該種子層和第二種焊 料分層結構，該結構包含有高Sn的焊料和高pb的 焊料。 第3圖是在利用現行技術的腐蝕水溶液進行電腐蚀之後 弟2圖晶片的側視圖。 第4圖是為了除去該種子層的最後一層而進行濕侵蝕之 後的弟3圖晶片的側視圖。 第5圖是第4圖所示晶片的表面圖示，它表示出該種子層 的不完全腐蝕。 第6圖是在用本發明所述的腐蝕水溶液進行電腐蚀之後 的第2圖晶片的側視圖。 第7圖是為了除去該種子層的最後一層而進行濕侵蝕之 後的第6圖晶片的側視圖。 第8圖是第7圖所示晶片的表面圖示，它表示出該種子層 的完全腐蚀。 第10頁 本紙張尺度適用中國國家標準（CNS)A4規格（21〇 X 297公餐） I I I I I ·11111111 ^»^^1 (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 555886 A7 B7 五、 發明說明（ 對照說明 10 14 18 24 32 36 39 42 第一晶片 種子層 第二層 焊球 焊球 焊料 錫 表面 12 半導體材料 16 第一層 2〇 第三層 30 第二晶片 34 焊料 38 保護性外殼 4〇 第一層之部份區域 璧L明詳細說明 經濟部智慧財產局員工消費合作社印製 詳細參考附圖，特別是參考第丨圖，該圖表示出第一 晶片10,它由半導體材料12、種子層14和焊球24構成。 如早先所指出的那樣，該種子層14實際上是一多層結 構。為了圖示而非限制的目的，一種典型的層組合的第一 層16為TiW合金（例如，1〇wt%的Ti和9〇wt%的w)，第 一層18為形成過渡相的Cr/Cu(phased心/以彡或Cr/Cu合 金’第二層20為Cu。還可有，例如，一鎳的阻擋層22。 在晶片10上的焊球24主要包含Sn的焊料。這樣的 焊料可以由適度的Sn含量，如6〇wt%或更多的Sn和 4〇Wt%或更少的Pb構成，也可由高&含量，如95wt%或 更多的Sn和保持平衡的Pb含量構成。而且，該坪料還可 包括主要是含Sn的一些無^合金，如Sn/Ag、Sn/Cu、 Sn/Ag/Cu、以及Sn/Bi合金，這裏僅列舉了幾個。 第11頁 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公餐） I ^ ί— --------I Ί --------訂--I--------* (請先閱讀背面之注意事項再填寫本頁) 555886 A7
現在參考第2圖，該圖表示出第二晶彳30,它是由半 和焊球32構成。種子層14可 導體材料12、種子層14、 與第1圖所示的種子. . 層相问，也可不同，這取決於具體應 弟一晶片30也可具有阻擋層22。第二晶片3〇 含有：些焊球32。但是，在這種情形，焊球32卻包括由 較同熔化/皿度的烊料34和一較低熔化溫度的焊料％組 成的-烊料分層結構。第2圖所示的該烊料分層結構僅只 是為了圖示的目的；如果需要，還可有另外一些焊料層。 較鬲溶化溫度的焊料34可以是高Pb的焊料，具有95 一 97Wt%的Pb’餘下的是Sn。較低溶化溫度的焊料“可 以是上面提及的任何中度的Sn含量、高Sn含量或無Μ 的合金。 餘下的討論將集中在第二晶片3〇上，但應明白本發 明同樣適用於第一晶片1 〇。 現在來參看第3圖，第二晶片30已被包括甘油和硫 酸鉀的傳統的含水腐蝕水溶液電腐蝕過了。這種腐蝕水溶 液的組成為1.5Μ的甘油和〇·35Μ的K2S〇4(硫酸鉀）。電 池電壓為14.0伏特，工件與電極之間的間隔為3.〇mm， 脈衝保持時間與間隙之比為2〇0/〇。 如從第3圖所能見者，在電腐蝕過程中，較高熔化溫 度的悍料34已被一保護性外殼所保護起來，而較低熔化 溫度的焊料36卻被腐蝕了，這就導致了的有害的sn的損 失和隨之而來的焊球3 2中成分的變化。而且，來自較低 溶化溫度焊料36的一些錫39已重新沈積在該種子層的第 第12頁 本紙張尺度適用中國國家標準（CNS)A4規格（21〇 X 297公釐） 裝--------訂--------- (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 A7
555886 五、發明說明（） 一層16上，而且甚至可與之絡合。 緊接著，將第二晶片3 0在傳統的含水腐蝕水溶液中 進行了濕浸蚀，所用腐蝕水溶液包括3〇wt%的過氧化氣、 7.8g/lK—EDTA以及1.1M的硫酸鉀，其腐蝕周期為33〇 秒。該腐蚀槽的溫度設定為50。(：。濕浸蚀後的結果圖示 在第4圖和第5圖中，圖中可以看到第一層16已被基本 除去’留下第二晶片30的表面42大部分沒有該第一層 16。另一方面，Sn的沈積物39(如第3圖所示）妨礙了第 一層16的某些區域的腐蝕，因而留下了一些沒有被腐蝕 掉的第一層16的一些區域40。 如第3圖至第5圖所示晶片結構是不希望的，而且可 能導致尚的產率損失。如一般所知，在晶片處理的這個階 段的任何產率損失都是代價很高的。 現在來參看第6圖，第二晶片3 0按照本發明被含水 腐蚀水溶液所腐蚀。 本發明所用的該電化學腐蝕水溶液的組成至少包 括 ：1.3 0 — 1.70M (以 1.5M 為更佳）的甘油 (H0CH2(0H)CH20H)，0 — 0.5M(以 0.35M 為更佳）的硫酸根 離子濃度和0.1 — 0.5M(以0.15M為更佳）磷酸根離子濃 度。該含水腐蝕水溶液的pH值應為4 — 9(標稱值為5)， 該電池電壓應為13 — 17伏特（標稱為14.5)，電極間隔為 3.0mm，以及占空因數（duty cycle)為10 — 30%(以20%為更 佳）。 該硫酸根離子和磷酸根離子都可從任意相應的鹽類 第13頁 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐) ---------*--裝--------訂-----------r (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 555886 A7
五、發明說明（） 產生。硫酸抑和磷酸鉀都屬於這些鹽類，而硫酸鈉或磷酸 納也可用於本發明的這些目的。 (請先閱讀背面之注意事項再填寫本頁) 硫酸根和嶙酸根離子的相對含量應根據存在的高Pb 和南Sn焊料的量來調節。如果高pb和高Sll焊料兩者都 存在’則為了保護這些焊料就必須存在硫酸根和磷酸根兩 種離子。如果不存在高pl)焊料，則就不需存在硫酸根離 子。作為最小值來說，硫酸根離子和磷酸根離子必須提供 一足夠南的溶液電導率以便在合理的電壓下進行電腐 蚀。 在焊球存在的情況下可被腐蝕的金屬包括鈦、鎢、 路、銅、鎳、以及它們的合金。在焊球存在的情況下可被 電腐蚀的金屬包括各種金屬疊層（meUl stack)，包括Cu、
Cr/Cu、Cu/Ni、和 Cr/Cu/Ni 等合金。 作為本發明的一種優選腐蝕水溶液的例子，用於第二 晶片30電腐蚀的腐蝕水溶液包含1 5M的甘油、〇 35M的 K2S04(硫酸鉀）、〇·15Μ的K3p〇4(磷酸鉀）。用磷酸將pH 值調到5.0。電池電壓為μ 〇伏特，電極間隔為3 〇mm， 以及占空因數為20%。由硬殼3 5保護各個焊球。第二和 經濟部智慧財產局員工消費合作社印製 第三層18、20分別都被除去，而且沒有殘留物留在該第 一層1 6上。 然後’將第二晶片3 0放在傳統的含水腐蚀水溶液中 進行濕浸蚀，該腐蝕水溶液包括30wt%的過氧化氫、 7.8§/11(："~^〇丁八、和1.1%的硫酸鉀，腐蝕周期為330秒。 該腐触槽的溫度被設定為5〇°c。結果被圖示於第7圖和 第14頁 本紙張尺度適用中國國家標準（CNS)A4規格（21〇 X 297公f ) 555886
五、 發明說明（ 第8圖中，在圖中可看到該第一層16已完全被除去，留 下的第二晶片30的表面42上沒有任何的殘留物。 在濕浸蝕後保護性外殼3 8仍保留在適當的地方，在 濕、浸蝕完成後再用甲磺酸將其除去。 已發現，本發明的使用大大地提高了電腐蝕過移的虞 率。 對於與本公開有關的技術領域的業内人士來說，顯然 可以對本發明進行一些超出此處所具體描述的那痤實施 例的其它改進，而並不偏離本發明的精神。因此，遠呰改 進都被$忍為不脫離本發明之範圍。 ----------—裝--------tr--------- (請先閱讀背面之注意亊頊存填寫本貢) 經濟部智慧財產局員工消費合作社印製 頁 5 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）

Claims (1)

  1. 5 變86告本 B8 C8 D8 利範圍 $二朁換本^ a 經濟部智慧財產局員工消费合作社印製 i.一種電牝學腐蝕水溶液，在存在有一或多種不擬腐蝕的 金屬的情況下用來對一些金屬進行腐蝕，該腐餘水溶 液至少包括： 甘油，濃度為1.30 — 1.70M ; 硫酸鹽化合物，硫酸鹽離子濃度為〇 一 〇. 5 M ; 磷酸鹽化合物，磷酸鹽離子濃度為〇1 一 〇.5M。 2·如申請專利範圍第1項所述之電化學腐蝕.水溶液，其特 徵在於：該腐飯水溶液的pH值為4— 9。 3·如申請專利範圍第.1所述之電化學腐蝕水溶液，其特徵 在於：該不擬腐蝕的一或多種金屬是從由鉛、錫、以及 它們的合金構成的組群中選出的。 4·如申請專利範圍第丨項所述之電化學腐蝕水溶液，其特 徵在於：該不擬腐蝕的一或多種金屬是從由下列的一此 焊料構成的組群中選出的：高鉛/錫焊料，其錯含量的 重量百分比大於95,錫的含量為其平衡數；中等比率 的錯/錫焊料，其鉛含量的重量百分比 、’賜的含 量為其平衡數；高錫/低鉛焊料，其錫含量的重量百八 比大於95，鉛的含量為其平衡數；無鉛焊料，其锡= 量的重量百分比大於95 ;以及它們的組合。 S 5.如申請專利範圍帛i項所述之電化學腐钱水 再特 本紙張尺度適用中關家標準（CNS)A4規格（210 X 29^ (請先·Μ讀背面之注意事項再填寫本頁) -線· 555886 六 、申請專利範圍 經 濟 部 智 慧 財 產 局 消 費 合 作 社 印製 徵在於：擬腐蝕的那些金屬是從由鉻、鋼、鎳、以及它 們的合金構成的組群中選出的。 6.如申請專利範圍第1項所述之電化學腐蝕水溶液，其特 徵在於：該硫酸鹽化合物的濃度為〇·2— 〇·5Μ。 7·如申請專利範圍第1項所述之電化學腐蝕水溶液，其特 徵在於：.該甘油的濃度為1 ·4Μ，該硫酸鹽的濃度為 〇·3 5Μ ’而該磷酸鹽的濃度為〇.15]Μ。 8· 一種在一物件中在存有一或多不擬溶解的金屬的情況 下用來選擇性地溶解一或多種擬溶解的金屬的方法，該 方法至少包括下述步驟： 用一種腐蝕水溶液對擬溶解的金屬進行電化學腐 蝕，該含水腐蝕水溶液包括：甘油，其濃度為13〇〜 1.70Μ，硫酸鹽化合物，其硫酸根離子濃度為〇〜〇 ; 以及磷酸鹽化合物，其構酸根離子濃度為〇 i〜n 9.如申請專利範圍帛8項所述之方法，其特徵在於··該腐 钱水溶液的pH值為4— 9。 !〇•如申請專利範圍第8項所述之方法，其特徵在於. 不擬腐蝕的-或多種金屬是從由錯、錫、以及它們的 金構成的組群中選出的。 該合 閱 再 訂 本紙張尺度適用中國國家標準(CNS)A4規格 555886
    11.如申請專利範圍第8項所述之方法，其特徵在於：該 不擬腐蝕的一或多種金屬是從由下列的一些焊料構成 的組群中選出的：高鉛/錫焊料，其鉛含量的重量百分 比大於95，錫的含量為其平衡數；中等比率的鉛/錫^ 料’其鉛含量的重量百分比小於40，錫的含量為其平 衡數；高錫/低鉛焊料，其錫含量的重量百分比大於9 $ 船的含量為其平衡數·，無鉛焊料，其錫含量的重量百 分比大於· 95 ;以及它們的組合。 12·如申請專利範圍第8項所述之方法，其特徵在於：擬 腐餘的那些金屬是從由鉻、銅、鎳、以及它們的合金 構成的組群中選出的。 13·如申請專利範圍第8項所述之方法，其特徵在於：該 硫酸鹽化合物的濃度為〇·2— 0.5M。 經濟部智慧財產局員工消費合作社印製 14.如申請專利範圍第8項所述之方法，其特徵在於：該 甘油的濃度為1.4M，該硫酸鹽的濃度為〇·35Μ，而碟 酸鹽的濃度為0.15Μ。 1 5· —種用來選擇性地腐蝕一物件的方法，該方法至少包 括下述步驟： 供一物件’該物件具有一或多種擬溶解的金屬， 同時還存在有一或多種不擬溶解的金屬； 本紙張尺度適帛中國國家群(CNS)A4規格(21G X 297¾¾ ) 555886 B8 C8 D8 六、申請專利範圍 用一種腐蝕水溶液對擬溶解的金屬進行電化學腐 蝕，該含水腐蝕水溶液包括：甘油，其濃度為— uom•，硫酸鹽化合物，其硫酸根離子濃度為m 以及磷酸鹽化合物，其磷酸根離子濃度為〇m 經濟部智慧財產局員工消費合作社印製 16·如申請專利範圍第15項所 貝所遂之方法，其特徵在於： 該腐蝕水溶液的pH值為4— 9。 17·如申請專利範圍第15項所诫夕古、土 ^ 唄所述之方法，其特徵在於： 該不擬腐蝕的一或多種金屬是從由鉛、錫、以及它們 的合金構成的組群中選出的。 18·如申請專利範圍第！5項所述之方法，以寺徵在於： 該不擬腐蝕的一或多種金屬是從由下列的一些焊料構 成的組群中選出的：高鉛/錫焊料，其鉛含量的重量百 分比大於95，錫的含量爲其平衡數；中等比率的鉛/锡 焊料’其船含量的重量百分比小力4〇，锡的含量為其 平衡數；高錫/低鉛焊料，其錫含量的重量百分比大於 95，鉛的含量為其平衡數；無鉛焊料，其錫含量的重 量百分比大於95 ;以及它們的組合。 19·如申請專利範圍第15項所述之方法，其特徵在於： 擬腐蝕的那些金屬是從由鉻、鋼、鎳、以及它們的合 金構成的組群中選出的。
    ,-------------L (請先-S3讀背面之注意事項再填¾.本頁) - Β8 C8 D8 555886 六、申請專利範圍 20.如申請專利範圍第15項所述之方法，其特徵在於： 該硫酸鹽化合物的濃度為0.2 — 0.5M。 2 1 ·如申請專利範圍第1 5項所述之方法，其特徵在於： 該甘油的濃度為1.4M，該硫酸鹽的濃度為0.35M，而 該磷酸鹽的濃度為0.1 5 Μ。 ----a.--------—l· <請先朋讀背面之注意事項再填寫本頁) · 線- 經濟部智慧財產局員工消費合作社印製 10 2 /V 格 規 4 )Α S) Ν (C 準 標 家 國 國 中 用 適 度 尺 張 紙 本 J
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