TW201436888A - 用於無電鍍覆之方法及用於該方法之溶液 - Google Patents
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Abstract
本發明係提供一種在非導電性材料之表面選擇性施加無電金屬化之預處理方法及用於該預處理之溶液。此方法達成非導電性材料之表面上欲鍍覆區域的良好覆蓋,沒有漏鍍或溢鍍的情況。
Description
本發明係有關一種在非導電性材料之表面上無電銅鍍覆之預處理方法及用於該方法之溶液。更具體而言,本發明係有關一種在欲鍍覆區域內經化學地或物理地局部改質之非導電性材料之表面的選擇性無電鍍覆方法。
無電鍍覆已使用於許多應用(包含電子裝置製造)之各式各樣的基板。該些電子裝置的表面經常需要藉由金屬鍍覆形成導體圖案。近來,已發展雷射直接結構化方法(LDS)且用於模製塑膠材料之選擇性鍍覆,所謂的模製互連裝置(MID)。利用LDS,可能在複合3-維基板上實現高度功能之電路佈局。此方法基本涵蓋具有無機填充劑之添加劑掺雜之熱塑性塑料或熱固性塑料,其可藉由雷射活化,接著使用無電鍍覆金屬化形成電路佈線。藉由雷射束使含有掺入該塑料中之添加劑的金屬活化,使其變得活潑而作為欲鍍覆的塑料表面之經處理區域上之無電銅鍍覆的觸媒。除了活化外,雷射處理可產生顯微地粗糙表面,在
金屬化期間銅變得會牢牢地固定至此粗糙表面。
然而,基於本案發明人的研究,該些基板
並非總是可藉由其中在雷射處理後將零組件直接導入無電銅浴之沉積方法予以輕易地金屬化。為了確保在經雷射照射之所有區域上皆形成具有所需之銅厚度沉積物,經常需要高度反應性之無電銅浴(所謂的底浴)以形成薄且均勻之初始層,然後在另一個更安定之無電銅浴(完全建構浴)中增加銅層的厚度至所需之值。由於該底浴經常在導致較高消耗浴成分的條件及在比一般無電銅浴更高之溫度操作,故該鍍浴壽命較短,導致經常需要製備新底浴的不便利。
核發給Imura等人之US4,659,587揭露一種
在經雷射束處理之工件的表面上選擇性無電鍍覆方法。此專利揭露當雷射照射破壞基板時,可藉由將其直接浸泡在化學鍍浴中而在基板上選擇性形成鍍覆膜,無需預先活化處理。
核發給Naundorf等人之US7,060,421揭露一
種在包括尖晶石型之金屬氧化物的非導電性材料上製造導體軌道結構之方法。此文件所揭露之模製非導電性材料係藉由電磁輻射,如來自Nd:YAG雷射者,予以照射而使之瓦解而釋放出形成可被鍍覆之圖案之金屬核。經由處理,使經照射之材料在超音波清潔浴中以水沖洗之,之後進行銅鍍覆。
核發給Schildmann之US7,578,888揭露一種
處理雷射結構化之塑料表面之方法。此專利揭露在導入無
電鍍浴中之前,使雷射結構化之基板與適合作為除去非刻意沉積之金屬種之處理溶液接觸,以減少非經雷射處理之表面區域的偽鍍覆。
然而,當本案發明人嘗試這些美國專利所
揭露之方法且在經雷射照射之表面上以習知無電銅鍍覆浴進行鍍覆時,電路佈線區域上的銅沉積並不完全(漏鍍)。
當本案發明人在無電鍍覆前使用習知膠體觸媒溶液時,銅不但沉積在經雷射照射之區域上亦沉積在非經照射之區域,因此無法達成選擇性鍍覆(溢鍍)。因此,需要一種改良MID-LDS基板的選擇性無電金屬化之方法。
本案發明人研究許多種類的化學品及這些化學藥品的組合作為選擇性無電鍍覆之預處理溶液的成分,發現化學藥品的特定組合提供無電鍍覆之良好選擇性,亦即良好覆蓋,沒有漏鍍或溢鍍,及工業生產製程可接受之沉積速率。
本發明之目的係提供一種在非導電性材料之表面上選擇性金屬化之方法。
本發明之另一目的係提供一種用於此方法之溶液,包括催化性金屬離子,含有磺酸根基團之酸及氯離子,該溶液中該催化性金屬離子對該氯離子的重量比為1比10至1比1000之間。
第1圖係具有沉積銅之良好覆蓋之模製樹脂試樣的照片。
第2圖係具有輕微漏鍍之模製樹脂試樣的照片。
第3圖係沒有鍍覆之模製樹脂試樣的照片。
本說明書全文所使用之以下縮寫具有下列定義,除非文中另有明白指示:g=克;mg=毫克;L=升;m=米;min=分鐘;s=秒;h=小時;ppm=百萬分率;g/L=克/升。
本說明書全文中,係可交替地使用用語“沉積”,“鍍覆”及“金屬化”。本說明書全文中,係可交替地使用用語“溶液”及“浴”。溶液及浴係包括水,除非文中另有明白指示。
本發明之方法係有關非導電性材料之表面的選擇性金屬化。於具體本實施例中,‘選擇性金屬化’一詞係指僅在那些材料表面上意欲鍍覆之區域金屬化(鍍覆),且實質上不在意欲之區域以外的區域沉積。當該意欲鍍覆之區域的沉積不足(漏鍍)時,無法獲得所需之導電性能。當在非意欲鍍覆之區域實質沉積(溢鍍)時,該電路路徑結構的功能性劣化,因此由於短路而在電路上造成問題。此方法包括四個步驟。
此方法的第一步驟為(a)藉由化學地或物理地改質欲鍍覆之表面區域而準備非導電性材料之表面。
非導電性材料較佳為熱固性塑料或熱塑性
塑料。可使用作為非導電性材料之塑料的實例包含聚碳酸酯(PC),聚對苯二甲酸乙二酯(PET),聚對苯二甲酸丁二酯(PBT),聚丙烯酸酯(PA),液晶聚合物(LCP),聚鄰苯二甲醯胺(PPA),丙烯腈丁二烯苯乙烯共聚物(ABS)及其混合物。較佳之塑料為使用上述之熱塑性塑料所製造之模製塑料。
非導電性材料可視需要地含有習知使用之
一種或多種無機填充劑如氧化鋁,矽酸鹽,滑石或其衍生物。
非導電性材料視需要地含有一種或多種金
屬或金屬化合物。金屬化合物包含金屬氧化物,金屬矽酸鹽,金屬磷酸鹽及金屬螯合物。使金屬或金屬化合物與非導電性材料混合,在化學或物理改質後,這些化合物的一部份浮現在材料的表面上且變得活化以扮演金屬沉積的觸媒。金屬的實例包含,但不限於,貴金屬如鈀,過渡金屬如銅,鉻,鈷,鐵,鋅及其混合物。US 7,060,421揭露該些材料。
在欲鍍覆之區域化學地或物理地改質材
料。非導電性材料表面之化學改質的實例包含以鹼或酸溶液蝕刻。物理改質的實例包含以雷射如Nd:YAG雷射處理之。基於在材料的表面上形成導電佈線的要求選擇欲鍍覆之區域。化學或物理改質產生顯微地粗糙表面,可用於固定住沉積之金屬層。該些材料可自市面購得,如LPKF Laser and Electronic AG,德國出品者。
此方法的第二步驟為(b)使該非導電性材料
與包括調節劑及鹼材料之預處理溶液接觸。
預處理溶液係一種顯示選擇性地強化觸媒
材料在經雷射處理之表面上之吸收之性質的組成物。較佳之調節劑包含陰離子性界面活性劑及有機酸。本發明之陰離子性界面活性劑的較佳組成物包含聚氧伸烷基酚磷酸酯及聚醚磷酸酯。有機酸之較佳組成物的實例包含烷基磺酸或芳香族磺酸,如酚磺酸。調節劑的濃度視組成物的種類而定,但當使用陰離子性界面活性劑作為調節劑時,較佳之濃度通常為1至50g/L之間,更佳為2.5至15g/L。當使用磺酸,如芳香族磺酸作為調節劑時,較佳之濃度通常為1至50g/L,更佳為2.5至25g/L。
鹼材料通常係以鹼金屬氫氧化物添加。預
處理溶液中之鹼金屬氫氧化物的濃度通常為1至200g/L,較佳為10至90g/L。
預處理溶液視需要地含有多羥基化合物。
此成分之較佳濃度通常為0至100g/L,較佳為10至50g/L。此溶液之pH通常大於12,較佳為大於13。
使欲鍍覆之材料與此溶液接觸之方法可為
任何種類之方法,如浸漬或噴霧。使此材料與預處理溶液接觸的條件為,例如,使此材料在40至90℃之溶液中浸漬1至20分鐘。上述步驟較佳可接著水沖洗。
此方法的第三步驟為(c)使該非導電性材料
與包括催化性金屬離子、具有至少一個磺酸根基團之酸及
氯離子之觸媒溶液接觸。該催化性金屬離子較佳為貴金屬離子,如鈀離子。任何種類之鈀離子來源皆可使用於此溶液,只要該鈀離子來源在溶液中產生鈀離子即可。鈀離子來源的實例包括氯化鈀,硫酸鈀,乙酸鈀,溴化鈀及硝酸鈀。
具有至少一個磺酸根基團之酸包括有機酸
及無機酸兩者。有機酸的實例包含甲烷磺酸,無機酸的實例包含硫酸。較佳的酸為硫酸。
任何種類之氯離子來源皆可使用於此溶
液,只要該氯離子來源在溶液中提供氯離子即可。氯離子來源的實例包括氯化鈉,氫氯酸及氯化鉀。較佳之氯離子來源為氯化鈉。
以溶液之重量計,溶液中之各成分的較佳
用量通常為1至50ppm催化性金屬離子,50至150g/L硫酸,及0.1至10g/L氯離子。以溶液之重量計,溶液中之各成分的更佳用量為5至25ppm催化性金屬離子、75至125g/L硫酸,及0.5至5g/L氯離子。
溶液中該催化性金屬離子對該氯離子的比
率較佳於1比10至1比1000之間,更佳於1比20至1比500之間,又更佳於1比50至1比200之間。若氯離子的比率超過1000,則可觀察到漏鍍。若氯離子的比率小於10,則可觀察到溢鍍。
本發明之溶液可視需要地包括一種或多種
使用於無電鍍覆之預處理溶液之各式各樣的添加劑如界面
活性劑,錯合劑,pH調整劑,緩衝劑,安定劑,銅離子及加速劑。此溶液的pH通常為0.2至2,較佳為0.2至1。
使用於此溶液之較佳界面活性劑為陽離子性界面活性劑。
界面活性劑的用量視界面活性劑的種類而定,但以溶液之重量計,通常為0.1至10g/L。
與此溶液接觸之方法可為任何種類之方
法,如浸漬或噴霧。使此材料與觸媒溶液接觸的條件為,例如,使此材料在20至80℃,較佳為50至70℃之溶液中浸漬1至20分鐘,較佳為5至20分鐘。上述步驟較佳可接著水沖洗。
此方法的第四步驟為(d)無電地鍍覆非導電
性材料表面上之欲金屬化之區域。無電鍍覆方法及鍍覆銅之組成物係為習知技術。可使用習知方法及無電銅鍍覆浴。該種銅浴的實例包含1至5g/L銅離子,10至50g/L錯合劑,0.01至5g/L界面活性劑,5至10g/L氫氧化鈉及2至5g/L還原劑。可使用習知無電銅浴,如Dow Electronic Materials出品之CIRCUPOSITTM 71HS無電銅,CIRCUPOSITTM LDS 91無電銅。
無電鍍覆的條件為,例如,使此材料在20
至70℃,較佳為45至65℃之無電銅鍍覆浴中浸漬足以沉積所需之銅厚度的時間,例如20至300分鐘。上述步驟較佳可接著一次或多次水沖洗。
本發明之觸媒溶液可使用作為非導電性材
料之選擇性無電鍍覆之預處理溶液。此溶液的內容物與第
三步驟所述之溶液相同。溶液中該催化之金屬離子對該氯離子的重量比於1比10至1比1000之間。
本發明之方法能夠省略習知方法所用之無
電銅底浴。此方法能夠僅在非導電性材料之表面上欲鍍覆之特定區域內直接金屬化。
藉由本發明方法所獲得之材料僅在那些經
化學地或物理地改質之區域內選擇性地金屬化,亦即,具有良好覆蓋及均勻厚度,沒有溢鍍或漏鍍。此外,沉積速率係工業加工可以接受的。
實施例1
以雷射處理由PC與ABS(PC/ABS)樹脂之掺合物所製成之LDS基板試樣之欲鍍覆之區域(LPKF Laser and Electronic AG)。使基板試樣在70℃含有70g/L NaOH及5g/L陰離子性界面活性劑(聚酯磷酸酯,Dow Electronics Materials以TRITONTM QS-44界面活性劑供應之)之預處理溶液中浸漬5分鐘。此溶液的pH為大約14。以去離子水沖洗後,使基板試樣在69℃含有18.4mg/L硫酸鈀(9.5ppm鈀離子),60mL/L 98%硫酸及1.7g/L氯化鈉之觸媒溶液中浸漬10分鐘。然後以去離子水沖洗基板試樣,再於56℃無電地鍍覆120分鐘(CIRCUPOSITTM 71HS無電銅,Dow Electronic Materials)。以水沖洗經鍍覆之基板試樣,然後以下述標準予以分級。藉由X-光螢光(XRF)測得銅層的厚度為9微米且沉積品質的等級為5-5。第1圖係顯示經雷
射處理之表面上完全之銅沉積物。
等級
使用光學顯微鏡觀察銅的沉積並在經雷射處理之區域及未經處理之區域兩者內從1至5予以分級。第一數字表示經雷射處理之區域內的性能,而第二數字表示未經處理之區域的性能。在經雷射處理之區域中,“1”表示沒有沉積及“5”表示完全之銅覆蓋沒有漏鍍。“3”之等級表示銅的覆蓋不完全。其他等級數字表示界於這些定義等級間之性能。在未經雷射處理之區域中,“5”表示在該區域沒有沉積(無溢鍍)及“1”表示觀察到大量之過度鍍覆(嚴重溢鍍)。5-5的等級表示最佳整體效果。
實施例2
重複實施例1的程序,但以含有39g/L NaOH及17g/L酚磺酸之預處理溶液取代含有70g/L NaOH及5g/L陰離子性界面活性劑之預處理溶液,且預處理溶液的浸漬時間從5分鐘改成10分鐘。銅層的厚度為8.4微米且沉積品質的等級為4-5。
實施例3
重複實施例1的程序,但以含有30g/L NaOH,8.7g/L酚磺酸及36.8g/L丙三醇之預處理溶液取代含有70g/L NaOH及5g/L陰離子性界面活性劑之預處理溶液,且預處理溶液的浸漬時間從5分鐘改成10分鐘。銅層的厚度為8.8微米且沉積品質的等級為4.5-5。第2圖係顯示在平坦之經雷射處理之表面上完全之銅覆蓋,但在孔洞區域中具
有輕微漏鍍。
比較例1
重複實施例1的程序,但以含有5g/L陰離子性界面活性劑之預處理溶液取代含有70g/L NaOH及5g/L陰離子性界面活性劑之預處理溶液。銅層的厚度為8.4微米且沉積品質的等級為3-5。
比較例2
重複實施例1的程序,但以含有18.4mg/L硫酸鈀及60mL/L 98%硫酸之觸媒溶液取代含有18.4mg/L硫酸鈀,60mL/L 98%硫酸及1.7g/L氯化鈉之觸媒溶液。銅層的厚度為3.0微米且沉積品質的等級為1-5。第3圖係顯示在經
雷射處理之表面上沒有鍍覆。
由於本案的圖為結果照片,並非本案的代表圖。故本案無指定代表圖。
Claims (6)
- 一種選擇性金屬化之方法,包括下述步驟:(a)準備非導電性材料之表面,係藉由化學地或物理地改質欲鍍覆之區域內的該表面;(b)使該非導電性材料與包括調節劑及鹼性材料之預處理溶液接觸;(c)使該非導電性材料與包括催化性金屬離子、具有至少一個磺酸根基團之酸及氯離子之觸媒溶液接觸;以及(d)無電地鍍覆該非導電性材料之表面上的那些欲鍍覆之區域。
- 如申請專利範圍第1項所述之方法,其中,該預處理溶液中之該調節劑係選自陰離子性界面活性劑及有機酸所組成之群組者。
- 如申請專利範圍第1項所述之方法,其中,該觸媒溶液中該催化性金屬離子對該氯離子的重量比為1比10至1比1000之間。
- 如申請專利範圍第1項所述之方法,其中,以該溶液之重量計,該觸媒溶液包括1至50ppm催化性金屬離子。
- 如申請專利範圍第1項所述之方法,其中,以該溶液之重量計,該觸媒溶液包括50至150g/L硫酸。
- 一種用於如申請專利範圍第1項所述之方法中之觸媒溶液之溶液,係包括1至50ppm催化性金屬離子、具 有至少一個磺酸根基團之酸及氯離子,其中,該觸媒溶液中之該催化性金屬離子對該氯離子的重量比於1比10至1比1000之間。
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US11174402B2 (en) | 2016-05-18 | 2021-11-16 | Sumitomo Bakelite Co., Ltd. | Thermosetting resin composition for LDS, resin molded article, and three-dimensional molded interconnect device |
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IT201700055942A1 (it) | 2017-05-23 | 2018-11-23 | St Microelectronics Srl | Procedimento per fabbricare dispositivi a semiconduttore, dispositivo e circuito corrispondenti |
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US4659587A (en) | 1984-10-11 | 1987-04-21 | Hitachi, Ltd. | Electroless plating process and process for producing multilayer wiring board |
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