TWI790929B - 含銀溶液與化學鍍中形成銀種子層的方法 - Google Patents
含銀溶液與化學鍍中形成銀種子層的方法 Download PDFInfo
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- TWI790929B TWI790929B TW111106315A TW111106315A TWI790929B TW I790929 B TWI790929 B TW I790929B TW 111106315 A TW111106315 A TW 111106315A TW 111106315 A TW111106315 A TW 111106315A TW I790929 B TWI790929 B TW I790929B
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- Prior art keywords
- silver
- seed layer
- containing solution
- ions
- molar concentration
- Prior art date
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- 229910052709 silver Inorganic materials 0.000 title claims abstract description 196
- 239000004332 silver Substances 0.000 title claims abstract description 196
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 135
- 238000000034 method Methods 0.000 title claims abstract description 22
- 238000007747 plating Methods 0.000 title abstract description 30
- 239000000126 substance Substances 0.000 title abstract description 4
- -1 silver ions Chemical class 0.000 claims abstract description 104
- 239000000758 substrate Substances 0.000 claims abstract description 39
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 11
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 69
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 66
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 51
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 claims description 44
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 40
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 33
- 235000019253 formic acid Nutrition 0.000 claims description 33
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 25
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 20
- 229910052802 copper Inorganic materials 0.000 claims description 20
- 239000010949 copper Substances 0.000 claims description 20
- 229910052759 nickel Inorganic materials 0.000 claims description 20
- 238000007772 electroless plating Methods 0.000 claims description 18
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims description 17
- 235000006408 oxalic acid Nutrition 0.000 claims description 17
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- 239000002270 dispersing agent Substances 0.000 claims description 9
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 5
- 235000011054 acetic acid Nutrition 0.000 claims description 5
- 150000001298 alcohols Chemical class 0.000 claims description 5
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 5
- 235000015165 citric acid Nutrition 0.000 claims description 5
- 239000001630 malic acid Substances 0.000 claims description 5
- 235000011090 malic acid Nutrition 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 3
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 3
- 229910001431 copper ion Inorganic materials 0.000 claims description 3
- 229910001453 nickel ion Inorganic materials 0.000 claims description 3
- 239000000243 solution Substances 0.000 description 77
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 64
- 239000007864 aqueous solution Substances 0.000 description 32
- 229910001961 silver nitrate Inorganic materials 0.000 description 32
- 238000001556 precipitation Methods 0.000 description 23
- 238000000411 transmission spectrum Methods 0.000 description 17
- 239000000203 mixture Substances 0.000 description 15
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 14
- 239000002244 precipitate Substances 0.000 description 14
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
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- 229910052763 palladium Inorganic materials 0.000 description 7
- 230000008569 process Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 229910000365 copper sulfate Inorganic materials 0.000 description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 3
- 229910021389 graphene Inorganic materials 0.000 description 3
- 238000007641 inkjet printing Methods 0.000 description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 3
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- 150000003378 silver Chemical class 0.000 description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 description 3
- 239000012279 sodium borohydride Substances 0.000 description 3
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 229920002873 Polyethylenimine Polymers 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
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- 229910052757 nitrogen Inorganic materials 0.000 description 2
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- 229920001223 polyethylene glycol Polymers 0.000 description 2
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- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
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- 238000001179 sorption measurement Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- PLKATZNSTYDYJW-UHFFFAOYSA-N azane silver Chemical class N.[Ag] PLKATZNSTYDYJW-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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- C—CHEMISTRY; METALLURGY
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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- Plasma & Fusion (AREA)
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- Inorganic Chemistry (AREA)
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Abstract
形成銀種子層的方法包括提供基材;施加含銀溶液於基材上;施加能量至含銀溶液,以形成銀種子層於基材上,其中含銀溶液包括:銀離子;二胺化合物;羧酸化合物;以及溶劑。此外,可將含有銀種子層於其上的基材浸入化學鍍液中,以形成金屬層於銀種子層上。
Description
本揭露關於在化學鍍製程中形成銀種子層的方法,更特別關於其採用的含銀溶液。
化學鍍廣泛使用金屬鈀作為觸發反應的種子,然而金屬鈀價格高昂,以其它材料取代一直是技術發展的趨勢。銀的催化活性與鈀相當,僅需極小的能量即可驅動,但價格卻比鈀便宜許多。然而銀對光有較高敏感性,容易伴隨著時間有不受控制的變化,不利於量產中品質的控制而不被採用。雖然硝酸銀在諸多的銀化合物中相對光敏感性較低,但仍然極易受光影響。如直接使用於噴墨的漿料,一旦受光催化析出沉澱,將產生堵塞噴頭的風險,嚴重影響產品的品質。
早期多有銀氨錯合物的研究,雖有改善然而穩定性多不理想,甚至有爆炸危險性。若以奈米銀膠體(colloid)溶液的形式取代,隨時間聚集成團影響效能或沉澱,仍然有可靠度的隱憂。近年來有研究提議用氧化石墨烯作為吸附的載體,但是缺點是石墨烯需在強酸的環境下經繁瑣並耗能的程序製得,價格不僅高昂,分離純化也產生大量的廢水廢酸,相較之下並不比鈀金屬經濟。另外有以聚多巴胺(polydopamine)作為還原吸附載體,價格較石墨烯便宜一些,然原料價格一來仍然相當昂貴,再者過程需高速離心以及透析純化,產生高比例量的廢棄物。
綜上所述,目前亟需改善製備銀種子層所用的含銀溶液之穩定性,以利化學鍍製程。
本揭露一實施例提供之含銀溶液包括:銀離子;二胺化合物;羧酸化合物;以及溶劑。
在一些實施例中,銀離子的濃度為0.01 M至10 M。
在一些實施例中,二胺化合物包括乙二胺、丙二胺、或上述之組合,且二胺化合物與銀離子的莫耳濃度比為2.5:1至200:1。
在一些實施例中,羧酸化合物包括甲酸、乙酸、檸檬酸、草酸、蘋果酸、或上述之組合,且羧酸化合物與銀離子的莫耳濃度比為0.1:1至1.2:1。
在一些實施例中,溶劑包括水、醇類、或上述之組合。
在一些實施例中,含銀溶液更包括分散劑。
本揭露一實施例提供化學鍍中形成銀種子層的方法,包括提供基材;施加含銀溶液於基材上;施加能量至含銀溶液,以形成銀種子層於基材上,其中含銀溶液包括:銀離子;二胺化合物;羧酸化合物;以及溶劑。
在一些實施例中,含銀溶液的銀離子濃度為0.01 M至10 M。
在一些實施例中,二胺化合物包括乙二胺、丙二胺、或上述之組合,且二胺化合物與銀離子的莫耳濃度比為2.5:1至200:1。
在一些實施例中,羧酸化合物包括甲酸、乙酸、檸檬酸、草酸、蘋果酸、或上述之組合,且羧酸化合物與銀離子的莫耳濃度比為0.1:1至1.2:1。
在一些實施例中,溶劑包括水、醇類、或上述之組合。
在一些實施例中,含銀溶液更包括分散劑。
在一些實施例中,能量包括電漿、脈衝光、紫外線、或雷射。
在一些實施例中,上述方法更包括將含有銀種子層於其上的基材浸入化學鍍液中,以形成金屬層於銀種子層上。
在一些實施例中,化學鍍液包括銅離子或鎳離子,且金屬層包括銅層或鎳層。
銀鹽具高光敏感性(light sensitive),一經光刺激即自發性析出銀奈米粒子,是作為觸媒可利用的手段。然而析出的銀奈米微粒自然團聚沉澱,造成應用上的困擾:如堵塞噴墨印刷噴頭或活性濃度不斷變化而難以掌握。為克服上述問題,本揭露將銀離子轉換為對環境光不敏感的錯合物,提高受光析出的臨界能障,使其在環境光下維持穩定。實際使用時施加超過臨界能障(活化能, energy barrier)的能量以立即快速析出銀奈米粒子,以活化利用其特徵的應用,如圖1所示。
本揭露一實施例提供化學鍍中形成銀種子層的方法,包括提供基材。在一些實施例中,基材可為玻璃基材、金屬基材、陶瓷基材、塑膠基材、或其他合適基材,且基材上可形成有其他材料層如介電層、半導體層、金屬層、或其他合適材料層。上述材料層可圖案化以形成裝置如半導體裝置、內連線結構、或其他電子裝置。換言之,本揭露的方法可用於形成電子裝置或其中間結構。
接著施加含銀溶液於基材上,且施加方法可為噴塗、旋轉塗佈、網印、噴墨印刷、浸塗、或其他合適的施加方法。接著可施加能量至含銀溶液,以形成銀種子層於基材上。能量可使含銀溶液中的銀離子還原成金屬銀。舉例來說,能量可為電漿、脈衝光、紫外線、雷射、或其他合適的能量。
在一些實施例中,含銀溶液包括:銀離子;二胺化合物;羧酸化合物;以及溶劑。舉例來說,在一些實施例中,含銀溶液的銀離子濃度為0.01 M至10 M。若銀離子的濃度過低,則無法形成足夠的銀種子層以助後續的化學鍍製程。若銀離子的濃度過高,則含銀溶液可能無法用於特殊製程如噴墨印刷。此外,若銀離子的濃度過高,可能無法長時間儲存。
在一些實施例中,二胺化合物包括乙二胺、丙二胺、或上述之組合,且二胺化合物與銀離子的莫耳濃度比為2.5:1至200:1。若二胺化合物的用量過低,則含銀溶液在一段短時間後即可能產生析出或沉澱,即無法長時間儲存。若二胺化合物的用量過高,則稀釋過度,不足以展現銀所期待的活性。
在一些實施例中,羧酸化合物包括甲酸、乙酸、檸檬酸、草酸、蘋果酸、或上述之組合,且羧酸化合物與銀離子的莫耳濃度比為0.1:1至1.2:1。若羧酸化合物的用量過低,則含銀溶液在一段短時間後即可能產生析出或沉澱,即無法長時間儲存。若羧酸化合物的用量過高,將會破壞銀與二胺錯合物的穩定性,直接造成還原析出的沉澱產生,反而不利於溶液澄清穩定性的維持。
在一些實施例中,溶劑包括水、醇類、或上述之組合。舉例來說,醇類可為甲醇、乙醇、異丙醇、丁醇、或上述之組合。
在一些實施例中,含銀溶液更包括分散劑。舉例來說,分散劑可高分子型分散劑如聚乙烯吡咯烷酮(PVP)、聚乙烯醇(PVA)、聚乙烯亞胺(PEI)、聚乙二醇(PEG)、或其他合適的高分子;或陽離子型分散劑如十二烷基硫酸鈉(SDS)、月桂基硫酸鈉(SLS)、或其他合適的陽離子型分散劑。
在一些實施例中,上述方法更包括將含有銀種子層於其上的基材浸入化學鍍液中,以形成金屬層於銀種子層上。舉例來說,化學鍍液可包含銅離子或鎳離子,且金屬層包括銅層或鎳層。在此實施例中,銀種子層作為化學鍍金屬層所用的種子層以觸發化學鍍。
綜上所述,本揭露開發錯合配方技術,通過適量的配比,可將銀的鹽類化合物轉化為相對穩定的水溶液,原料容易取得,混合程序簡單,具有很高的成本優勢(不含昂貴的鈀)。轉化後的錯合物受光催化析出的臨界能量被提高,環境光下不受影響。使用上僅需施加稍高的活化能即可激發活性,充分發揮出銀粒子高催化活性的原始特徵。
本案經試驗發現,在一定胺/銀莫耳比例(胺/銀2)的溶液中摻入少許的羧酸(羧酸/銀莫耳比例0.1),對於阻止銀粒子的受光析出,會有不同程度提升的效果,錯合溶液常溫下放置於不遮光的透明瓶中數天可維持清澈透明,不致發生析出沉澱的現象。
為讓本揭露之上述內容和其他目的、特徵、和優點能更明顯易懂,下文特舉出較佳實施例,並配合所附圖式,作詳細說明如下:
比較例1
將丙二胺加入1M的硝酸銀水溶液後混合,且丙二胺與銀離子的莫耳濃度比為2:1。將丙二胺加入另一1M的硝酸銀水溶液後混合,且丙二胺與銀離子的莫耳濃度為3:1。將丙二胺加入另一1M的
硝酸銀水溶液後混合,且丙二胺與銀離子的莫耳濃度為4:1。將硝酸銀水溶液與不同濃度的丙二胺的含銀溶液置於環境光、常溫、與常壓下不同時間,量測其穿透光譜,如圖2A至2D所示。硝酸銀水溶液在放置48小時後出現黑色沉澱物。丙二胺與銀離子的莫耳濃度為3:1或4:1的含銀溶液在放置7天後維持澄清且無沉澱,但穿透率下降。丙二胺與銀離子的莫耳濃度為2:1的含銀溶液在放置七天後出現大量的析出與沉澱。
實施例1
將乙二胺與檸檬酸加入1M的硝酸銀水溶液後混合,乙二胺與銀離子的莫耳濃度比為2:1,且檸檬酸與銀離子的莫耳濃度比為0.1:1。將乙二胺與檸檬酸加入另一1M的硝酸銀水溶液後混合,乙二胺與銀離子的莫耳濃度比為3:1,且檸檬酸與銀離子的莫耳濃度比為0.1:1。將乙二胺與檸檬酸加入另一1M的硝酸銀水溶液後混合,乙二胺與銀離子的莫耳濃度比為4:1,且檸檬酸與銀離子的莫耳濃度比為0.1:1。將硝酸銀水溶液以及不同濃度的乙二胺與檸檬酸的含銀溶液置於環境光、常溫、與常壓下不同時間,量測其穿透光譜,如圖3A至3D所示。硝酸銀水溶液在放置48小時後出現黑色沉澱物。檸檬酸可改善含銀溶液的穩定性,使其於48小時內不產生沉澱。乙二胺與銀離子的莫耳濃度為3:1的含銀溶液在放置15天後維持澄清、無沉澱、與高光穿透率。
實施例2
將乙二胺與檸檬酸加入1M的硝酸銀水溶液後混合,乙二胺與銀離子的莫耳濃度比為2:1,且檸檬酸與銀離子的莫耳濃度比為0.2:1。將乙二胺與檸檬酸加入另一1M的硝酸銀水溶液後混合,乙二胺與銀離子的莫耳濃度比為3:1,且檸檬酸與銀離子的莫耳濃度比為0.2:1。將乙二胺與檸檬酸加入另一1M的硝酸銀水溶液後混合,乙二胺與銀離子的莫耳濃度比為4:1,且檸檬酸與銀離子的莫耳濃度比為0.2:1。將硝酸銀水溶液以及不同濃度的乙二胺與檸檬酸的含銀溶液置於環境光、常溫、與常壓下不同時間,量測其穿透光譜,如圖4A至4D所示。硝酸銀水溶液在放置48小時後出現黑色沉澱物。檸檬酸可改善含銀溶液的穩定性,使其於48小時內不產生沉澱。乙二胺與銀離子的莫耳濃度為3:1與4:1的含銀溶液在放置15天後維持澄清、無沉澱、與高穿透率。與實施例1相較,實施例2中較高濃度的檸檬酸可進一步改善含銀溶液的穩定性。
實施例3
將丙二胺與草酸加入1M的硝酸銀水溶液後混合,丙二胺與銀離子的莫耳濃度比為2:1,且草酸與銀離子的莫耳濃度比為0.1:1。將丙二胺與草酸加入另一1M的硝酸銀水溶液後混合,丙二胺與銀離子的莫耳濃度比為3:1,且草酸與銀離子的莫耳濃度比為0.1:1。將丙二胺與草酸加入另一1M的硝酸銀水溶液後混合,丙二胺與銀離子的莫耳濃度比為4:1,且草酸與銀離子的莫耳濃度比為0.1:1。將硝酸銀水溶液以及不同濃度的丙二胺與草酸的含銀溶液置於環境
光、常溫、與常壓下不同時間,量測其穿透光譜,如圖5A至5D所示。硝酸銀水溶液在放置48小時後出現黑色沉澱物。與檸檬酸類似,草酸可改善含銀溶液的穩定性,使其於48小時內不產生沉澱。丙二胺與銀離子的莫耳濃度為3:1與4:1的含銀溶液在放置15天後維持澄清、無沉澱、與高光穿透率。
實施例4
將丙二胺與甲酸加入1M的硝酸銀水溶液後混合,丙二胺與銀離子的莫耳濃度比為2:1,且甲酸與銀離子的莫耳濃度比為0.1:1。將丙二胺與甲酸加入另一1M的硝酸銀水溶液後混合,丙二胺與銀離子的莫耳濃度比為3:1,且甲酸與銀離子的莫耳濃度比為0.1:1。將丙二胺與甲酸加入另一1M的硝酸銀水溶液後混合,丙二胺與銀離子的莫耳濃度比為4:1,且甲酸與銀離子的莫耳濃度比為0.1:1。將硝酸銀水溶液以及不同濃度的丙二胺與甲酸的含銀溶液置於環境光、常溫、與常壓下不同時間,量測其穿透光譜,如圖6A至6D所示。硝酸銀水溶液在放置48小時後出現黑色沉澱物。甲酸可改善含銀溶液的穩定性,使其於48小時內不產生沉澱。丙二胺與銀離子的莫耳濃度為2:1、3:1、與4:1的含銀溶液在放置15天後維持澄清、無沉澱、與高光穿透率。與實施例1至3相較,甲酸可進一步改善含銀溶液的穩定性。
實施例5
取表面粗化的玻璃載玻片作為基材。將實施例3中含有草酸與不同濃度的乙二胺的含銀溶液稀釋20倍後,塗佈於基材上並以氮氣電漿處理60秒,以形成銀種子層。將硫酸銅(2.5 g/mL)與甲醛(6 mL/L)混合形成溶液後,調整其pH值至約12.5,以形成化學鍍銅所用的銅鍍浴。將上述具有銀種子層於其上的基材置於加熱的銅鍍浴中(如55℃至60℃),30秒內即開始化學鍍銅。最終可形成銅層於銀種子層上。
取表面粗化的玻璃載玻片作為基材。將實施例3中含有草酸與不同濃度的乙二胺的含銀溶液稀釋20倍後,塗佈於基材上並以1.5 J/cm
2的紫外線照射,以形成銀種子層。將硫酸銅(2.5 g/mL)與甲醛(6 mL/L)混合形成溶液後,調整其pH值至約12.5,以形成化學鍍銅所用的銅鍍浴。將上述具有銀種子層於其上的基材置於加熱的銅鍍浴中(如55℃至60℃),30秒內即開始化學鍍銅。最終可形成銅層於銀種子層上。
取表面粗化的玻璃載玻片作為基材。將實施例4中含有甲酸與不同濃度的丙二胺的含銀溶液稀釋20倍後,塗佈於基材上並以1.5 J/cm
2的紫外線照射,以形成銀種子層。將硫酸銅(2.5 g/mL)與甲醛(6 mL/L)混合形成溶液後,調整其pH值至約12.5,以形成化學鍍銅所用的銅鍍浴。將上述具有銀種子層於其上的基材置於加熱的銅鍍浴中(如55℃至60℃),30秒內即開始化學鍍銅。最終可形成銅層於銀種子層上。
實施例6
取表面粗化的玻璃載玻片作為基材。將實施例3中含有草酸與不同濃度的乙二胺的含銀溶液稀釋20倍後,塗佈於基材上並以氮氣電漿處理60秒,以形成銀種子層。將硫酸鎳(7 g/mL)經錯合再與硼氫化鈉(5.5 g/L)混合形成溶液後,調整其pH值至約8.5,以形成化學鍍鎳所用的鎳鍍浴。將上述具有銀種子層於其上的基材置於加熱的鎳鍍浴中(如45℃至50℃),30秒內即開始化學鍍鎳。最終可形成鎳層於銀種子層上。
取表面粗化的玻璃載玻片作為基材。將實施例3中含有草酸與不同濃度的乙二胺的含銀溶液稀釋20倍後,塗佈於基材上並以1.5 J/cm
2的紫外線照射,以形成銀種子層。將硫酸鎳(7 g/mL)經錯合再與硼氫化鈉(5.5 g/L)混合形成溶液後,調整其pH值至約8.5,以形成化學鍍鎳所用的鎳鍍浴。將上述具有銀種子層於其上的基材置於加熱的鎳鍍浴中(如45℃至50℃),30秒內即開始化學鍍鎳。最終可形成鎳層於銀種子層上。
取表面粗化的玻璃載玻片作為基材。將實施例4中含有甲酸與不同濃度的丙二胺的含銀溶液稀釋20倍後,塗佈於基材上並以1.5 J/cm
2的紫外線照射,以形成銀種子層。將硫酸鎳(7 g/mL)經錯合再與硼氫化鈉(5.5 g/L)混合形成溶液後,調整其pH值至約8.5,以形成化學鍍鎳所用的鎳鍍浴。將上述具有銀種子層於其上的基材置於加熱的鎳鍍浴中(如45℃至50℃),30秒內即開始化學鍍鎳。最終可形成鎳層於銀種子層上。
綜上所述,本揭露實施例的含銀溶液可穩定存放長時間,且可在能量活化後形成銀種子層以用於後續化學鍍銅或化學鍍鎳。與化學鍍銅或化學鍍鎳所用的習知鈀種子層相較,上述銀種子層的成本較低。
比較例2 (二胺不足)
將丙二胺與甲酸加入1 M的硝酸銀水溶液後混合,丙二胺與銀離子的莫耳濃度比為1:1,且甲酸與銀離子的莫耳濃度比為0.1:1。含銀溶液配置完成後1小時之內即逐漸轉變為灰黑色,放置24小時後出現大量黑色析出物而吸附在容器壁上,導致樣品已近乎完全不透光,如圖7的穿透光譜所示。分別提高丙二胺與銀離子的莫耳濃度比至1.5:1與3:1,且甲酸與銀離子的莫耳濃度比仍維持0.1:1。將硝酸銀水溶液以及不同濃度的丙二胺與甲酸的含銀溶液置於環境光、常溫、與常壓下不同時間後,量測其穿透光譜,如圖7所示。硝酸銀水溶液在放置24小時後出現了些許黑色懸浮物。相較於丙二胺與銀離子的莫耳濃度比為3:1的含銀溶液靜置15天的樣品,丙二胺與銀離子的莫耳濃度比為1.5:1的含銀溶液的穿透率呈現相對快速下降的趨勢;然而相較於丙二胺與銀離子莫耳濃度比為1:1的含銀溶液快速析出黑化的情況,仍有所相當程度的改善。由上述證據顯示,當二胺化合物的用量不足,則無法有效改善含銀溶液的穩定性。
比較例3 (羧酸化合物不足)
將丙二胺與甲酸加入1 M的硝酸銀水溶液後混合,丙二胺與銀離子的莫耳濃度比為3:1,且甲酸與銀離子的莫耳濃度比為0.05:1。將硝酸銀水溶液以及丙二胺與甲酸的含銀溶液置於環境光、常溫、與常壓下不同時間,量測其穿透光譜,如圖8所示。含銀溶液在放置24小時後仍可維持澄清狀態;然持續靜置9天,則出現黑色懸浮粒子,穿透率下降。而另一方面,甲酸與銀離子的莫耳濃度比提升到0.1:1(甲酸:銀離子)的含銀溶液,在放置了15天之後,仍然保持著相當澄清的狀態,並未出現明顯的析出與沉澱。由上述可知,羧酸化合物的用量不足,無法長時間確保含銀溶液的穩定性。
比較例4 (羧酸化合物過多)
將丙二胺與甲酸加入1 M的硝酸銀水溶液後混合,丙二胺與銀離子的莫耳濃度比為3:1,以甲酸與銀離子的莫耳濃度比為0.1:1作為1X基準,過多的甲酸破壞銀離子與胺基形成穩定的錯合物,銀反而快速還原析出:例如當將甲酸的比例提高到了20倍,即甲酸與銀離子的莫耳濃度比為2:1(20X),幾乎是立即性地,溶液發生大規模析出懸浮物的現象,並於24小時內於杯底出現析出物的沉澱;將甲酸與銀離子的莫耳濃度比降為0.5:1(5X),配製完成的溶液初始狀態為澄清狀,並足以維持一段時間。10天的觀察下並無明顯的變化;甲酸的濃度比例甚至在10X以內,對銀錯合物的影響仍在可接受範圍;超過了12X的劑量,長時間靜置下(5天),仍有過剩甲酸的強還原性造成析出沉澱的疑慮。上述含銀溶液的穿透光譜如圖9所示。一般使用銀作為觸媒種子,原則上除銀以外,其餘不易分解物質的添加應當越少越好,避免銀的活性表面受到汙染或遮蓋。由上述可知,羧酸化合物的用量適量即可,過多並無助於改善含銀溶液的穩定性。
雖然本揭露已以數個較佳實施例揭露如上,然其並非用以限定本揭露,任何所屬技術領域中具有通常知識者,在不脫離本揭露之精神和範圍內,當可作任意之更動與潤飾,因此本揭露之保護範圍當視後附之申請專利範圍所界定者為準。
無。
圖1係本揭露一實施例中,銀鹽與銀錯合物形成銀奈米粒子的能障圖。
圖2A至2D係本揭露一實施例中,含銀溶液的穿透光譜。
圖3A至3D係本揭露一實施例中,含銀溶液的穿透光譜。
圖4A至4D係本揭露一實施例中,含銀溶液的穿透光譜。
圖5A至5D係本揭露一實施例中,含銀溶液的穿透光譜。
圖6A至6D係本揭露一實施例中,含銀溶液的穿透光譜。
圖7係本揭露一實施例中,含銀溶液的穿透光譜。
圖8係本揭露一實施例中,含銀溶液的穿透光譜。
圖9係本揭露一實施例中,含銀溶液的穿透光譜。
Claims (8)
- 一種含銀溶液,包括:多個銀離子;一二胺化合物;一羧酸化合物;以及一溶劑,其中該些銀離子的濃度為0.01M至10M,其中該二胺化合物包括乙二胺、丙二胺、或上述之組合,且該二胺化合物與該些銀離子的莫耳濃度比為2.5:1至200:1,其中該羧酸化合物包括甲酸、乙酸、檸檬酸、草酸、蘋果酸、或上述之組合,且該羧酸化合物與該些銀離子的莫耳濃度比為0.1:1至1.2:1。
- 如請求項1之含銀溶液,其中該溶劑包括水、醇類、或上述之組合。
- 如請求項1之含銀溶液,更包括一分散劑。
- 一種化學鍍中形成銀種子層的方法,包括:提供一基材;施加一含銀溶液於該基材上;施加一能量至該含銀溶液,以形成一銀種子層於該基材上;其中該含銀溶液包括:多個銀離子; 一二胺化合物;一羧酸化合物;以及一溶劑,其中該含銀溶液的銀離子濃度為0.01M至10M,其中該二胺化合物包括乙二胺、丙二胺、或上述之組合,且該二胺化合物與該些銀離子的莫耳濃度比為2.5:1至200:1,其中該羧酸化合物包括甲酸、乙酸、檸檬酸、草酸、蘋果酸、或上述之組合,且該羧酸化合物與該些銀離子的莫耳濃度比為0.1:1至1.2:1,其中該能量包括電漿、脈衝光、紫外線、或雷射。
- 如請求項4之化學鍍中形成銀種子層的方法,其中該溶劑包括水、醇類、或上述之組合。
- 如請求項4之化學鍍中形成銀種子層的方法,其中該含銀溶液更包括一分散劑。
- 如請求項4之化學鍍中形成銀種子層的方法,更包括將含有該銀種子層於其上的該基材浸入一化學鍍液中,以形成一金屬層於該銀種子層上。
- 如請求項7之化學鍍中形成銀種子層的方法,其中該化學鍍液包括多個銅離子或多個鎳離子,且該金屬層包括一銅層或一鎳層。
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