TW201816191A - Nickel plating solution - Google Patents
Nickel plating solution Download PDFInfo
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- TW201816191A TW201816191A TW106134778A TW106134778A TW201816191A TW 201816191 A TW201816191 A TW 201816191A TW 106134778 A TW106134778 A TW 106134778A TW 106134778 A TW106134778 A TW 106134778A TW 201816191 A TW201816191 A TW 201816191A
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- nickel
- electroplating composition
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 261
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 132
- 238000007747 plating Methods 0.000 title claims abstract description 58
- 239000000203 mixture Substances 0.000 claims abstract description 74
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000004327 boric acid Substances 0.000 claims abstract description 21
- -1 halogen ion Chemical class 0.000 claims description 55
- 238000009713 electroplating Methods 0.000 claims description 45
- 239000004065 semiconductor Substances 0.000 claims description 18
- 150000001735 carboxylic acids Chemical class 0.000 claims description 17
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 claims description 17
- 229910001453 nickel ion Inorganic materials 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 10
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 229910052736 halogen Inorganic materials 0.000 claims description 7
- QDWYPRSFEZRKDK-UHFFFAOYSA-M sodium;sulfamate Chemical compound [Na+].NS([O-])(=O)=O QDWYPRSFEZRKDK-UHFFFAOYSA-M 0.000 claims description 6
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical group Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 5
- 239000004094 surface-active agent Substances 0.000 claims description 5
- BTAAXEFROUUDIL-UHFFFAOYSA-M potassium;sulfamate Chemical compound [K+].NS([O-])(=O)=O BTAAXEFROUUDIL-UHFFFAOYSA-M 0.000 claims description 4
- 239000000080 wetting agent Substances 0.000 claims description 4
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- 239000003002 pH adjusting agent Substances 0.000 claims description 2
- 229960002645 boric acid Drugs 0.000 abstract 1
- 235000010338 boric acid Nutrition 0.000 abstract 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract 1
- 235000012431 wafers Nutrition 0.000 description 16
- 229910052751 metal Inorganic materials 0.000 description 13
- 239000002184 metal Substances 0.000 description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 229910052802 copper Inorganic materials 0.000 description 7
- 239000010949 copper Substances 0.000 description 7
- 239000006174 pH buffer Substances 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000012776 electronic material Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- GEHMBYLTCISYNY-UHFFFAOYSA-N Ammonium sulfamate Chemical compound [NH4+].NS([O-])(=O)=O GEHMBYLTCISYNY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000013475 authorization Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910021585 Nickel(II) bromide Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 150000004820 halides Chemical group 0.000 description 1
- 239000003906 humectant Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- IPLJNQFXJUCRNH-UHFFFAOYSA-L nickel(2+);dibromide Chemical compound [Ni+2].[Br-].[Br-] IPLJNQFXJUCRNH-UHFFFAOYSA-L 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/12—Semiconductors
- C25D7/123—Semiconductors first coated with a seed layer or a conductive layer
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
Description
本發明係關於一種不包含有機羧酸但具有高浴pH穩定性之無硼酸鎳鍍敷組合物。所述鎳鍍敷組合物提供適用於電子材料之鎳鍍敷膜，所述電子材料諸如凸塊下金屬（UBM）。This invention relates to a nickel borate-free plating composition that does not contain an organic carboxylic acid but has high bath pH stability. The nickel plating composition provides a nickel plating film suitable for electronic materials such as under bump metal (UBM).
由於鎳電鍍之所得膜有良好的諸如抗腐蝕及導電性之特性，因此鎳電鍍已習知地用於電子材料。習知之鎳鍍敷組合物包括硼酸作為pH緩衝液，以將鎳鍍敷浴之pH值維持在約3至5。然而，硼酸被視為一種對環境有害之化學品。舉例而言，硼酸在日本被列為水污染防治行動（Water Pollution Prevention Act）之受控化學品，以及在歐洲被列為化學品登記、評估、授權及限制（Registration, Evaluation, Authorization and Restriction of Chemicals，REACH）之潛在化學品。因此，無硼酸鎳電鍍組合物為所期望的。Nickel plating has been conventionally used for electronic materials because the resulting film of nickel plating has good properties such as corrosion resistance and electrical conductivity. Conventional nickel plating compositions include boric acid as a pH buffer to maintain the pH of the nickel plating bath at about 3 to 5. However, boric acid is considered a chemical that is harmful to the environment. For example, boric acid is listed as a controlled chemical in the Water Pollution Prevention Act in Japan and as a chemical registration, evaluation, authorization and restriction in Europe (Registration, Evaluation, Authorization and Restriction of Potential chemicals in Chemicals, REACH). Therefore, a nickel borate-free plating composition is desirable.
舉例而言，JP2012126951A、JP2004265253A、JP2001172790A及JP2010267208A揭示了一些無硼酸鎳電鍍浴。然而，此等專利文獻中所揭示之鎳電鍍組合物包含諸如檸檬酸或葡糖酸之有機羧酸或其他有機化合物作為pH緩衝液。For example, JP2012126951A, JP2004265253A, JP2001172790A, and JP2010267208A disclose some nickel borate-free electroplating baths. However, the nickel electroplating compositions disclosed in these patent documents contain an organic carboxylic acid such as citric acid or gluconic acid or other organic compound as a pH buffer.
已知包括有機羧酸之無硼酸鎳鍍敷浴之pH值在使用所述浴的鍍敷製程期間容易增加（亦即浴pH不穩定）。此外，當在鎳鍍敷組合物中包含此等有機羧酸時，由鎳鍍敷組合物形成之鎳鍍敷膜之內應力增加。因此，仍期望具有良好的浴pH穩定性及良好的鎳鍍敷膜特性之無硼酸鎳電鍍組合物。It is known that the pH of a nickel borate-free plating bath comprising an organic carboxylic acid is easily increased during the plating process using the bath (i.e., the bath pH is unstable). Further, when such an organic carboxylic acid is contained in the nickel plating composition, the internal stress of the nickel plating film formed of the nickel plating composition is increased. Therefore, a nickel borate-free plating composition having good bath pH stability and good nickel plating film characteristics is still desired.
本發明人發現當在鎳電鍍組合物中使用胺基磺酸或其鹽而非硼酸時，使用所述組合物之鎳電鍍浴具有良好的pH穩定性。此外，由具有胺基磺酸或其鹽之鎳電鍍組合物形成之鎳鍍敷膜與由包括硼酸之習知鎳電鍍組合物形成之膜具有類似內應力。其意指由包括胺基磺酸或其鹽之組合物形成之鎳鍍敷膜可為用於電子材料之習知鎳電鍍組合物的替代物。The inventors have found that when an aminosulfonic acid or a salt thereof is used instead of boric acid in a nickel electroplating composition, the nickel electroplating bath using the composition has good pH stability. Further, a nickel plating film formed of a nickel plating composition having an aminosulfonic acid or a salt thereof has a similar internal stress as a film formed of a conventional nickel plating composition including boric acid. It means that a nickel plating film formed from a composition comprising an amine sulfonic acid or a salt thereof can be an alternative to the conventional nickel plating composition for electronic materials.
因此，本發明之一個實施例為一種鎳電鍍組合物，其包括0.8至2.8 mol/L之鎳離子、0.06至1.5 mol/L之鹵素離子及1.6至5.1 mol/L之胺基磺酸根離子；胺基磺酸根離子及鹵素離子之呈mol/L形式的總量大於鎳離子之mol/L的兩倍；鎳電鍍組合物具有3至5之pH值且鎳電鍍組合物基本上不含硼酸及有機羧酸。Accordingly, one embodiment of the present invention is a nickel electroplating composition comprising 0.8 to 2.8 mol/L of nickel ions, 0.06 to 1.5 mol/L of halide ions, and 1.6 to 5.1 mol/L of amine sulfonate ions; The total amount of the amine sulfonate ion and the halogen ion in the mol/L form is greater than twice the mol/L of the nickel ion; the nickel plating composition has a pH of 3 to 5 and the nickel plating composition is substantially free of boric acid and Organic carboxylic acid.
本發明之另一實施例為一種由以下形成之鎳電鍍組合物：100 g/L至650 g/L之胺基磺酸鎳；2 g/L至100 g/L之鹵化鎳；5 g/L至130 g/L之選自胺基磺酸、胺基磺酸鈉、胺基磺酸鉀及胺基磺酸銨之胺基磺酸化合物；水以及視情況界面活性劑、pH調節劑、濕潤劑及晶粒細化劑；鎳電鍍組合物具有3至5之pH值且鎳電鍍組合物基本上不含硼酸及有機羧酸。Another embodiment of the present invention is a nickel electroplating composition formed from: 100 g/L to 650 g/L of nickel sulfonate; 2 g/L to 100 g/L of nickel halide; 5 g/ L to 130 g/L of an aminosulfonic acid compound selected from the group consisting of aminosulfonic acid, sodium aminosulfonate, potassium aminosulfonate and ammonium aminesulfonate; water and, optionally, surfactants, pH adjusters, A humectant and a grain refiner; the nickel electroplating composition has a pH of from 3 to 5 and the nickel electroplating composition is substantially free of boric acid and an organic carboxylic acid.
本發明之又一實施例為一種由以下組成之鎳電鍍組合物：一或多種鎳離子源；一或多種鹵素離子源；一或多種選自胺基磺酸、胺基磺酸鈉、胺基磺酸鉀及胺基磺酸銨之胺基磺酸根離子源；水以及一或多種選自界面活性劑、pH調節劑、濕潤劑及晶粒細化劑之視情況選用之化合物；鎳電鍍組合物具有3至5之pH值且其中鎳電鍍組合物基本上不含硼酸及有機羧酸。Yet another embodiment of the present invention is a nickel electroplating composition consisting of one or more nickel ion sources; one or more halogen ion sources; one or more selected from the group consisting of aminosulfonic acids, sodium aminosulfonates, and amine groups. a source of aminosulfonate ion of potassium sulfonate and ammonium aminesulfonate; water and one or more compounds selected from the group consisting of surfactants, pH adjusters, wetting agents and grain refiners; nickel plating combination The material has a pH of from 3 to 5 and wherein the nickel electroplating composition is substantially free of boric acid and organic carboxylic acids.
此外，本發明係關於一種將鎳層電鍍於半導體晶圓上之方法，其包括：提供包括複數種導電黏合特徵之半導體晶圓，使半導體晶圓與上文所揭示之任何組合物接觸，及施加足夠的電流密度以將鎳層沈積在導電黏合特徵上。Furthermore, the present invention is directed to a method of electroplating a nickel layer onto a semiconductor wafer, comprising: providing a semiconductor wafer comprising a plurality of conductive bonding features, contacting the semiconductor wafer with any of the compositions disclosed above, and A sufficient current density is applied to deposit a layer of nickel on the conductive bonding features.
此外，本發明係關於一種由上文所揭示中之任一種組合物形成之鎳凸塊下金屬。Furthermore, the present invention relates to a nickel under bump metal formed from any of the compositions disclosed above.
如本說明書通篇所使用，除非上下文另外明確指示，否則以下縮寫將具有以下含義：℃ =攝氏度；g =公克；mg =毫克；L =公升；ml = mL =毫升；cm =公分；mm =毫米；μm =微米（microns）=微米（micrometer）；Å =埃；A/dm2 = ASD =安培/平方公寸；AH/L=安培小時/公升；以及± =加或減。在整個本說明書中，術語「沈積」及「鍍敷」互換使用。除非另外指出，否則所有百分比按重量計。所有數值範圍為包含性的且可按任何順序組合，但邏輯上此類數值範圍被限制於總計共100%。As used throughout this specification, the following abbreviations will have the following meanings unless the context clearly indicates otherwise: °C = degrees Celsius; g = grams; mg = milligrams; L = liters; ml = mL = milliliters; cm = centimeters; mm = Mm; μm = microns = micrometer; Å = angstrom; A / dm 2 = ASD = ampere / square inch; AH / L = ampere hour / liter; and ± = plus or minus. Throughout this specification, the terms "depositing" and "plating" are used interchangeably. All percentages are by weight unless otherwise indicated. All numerical ranges are inclusive and can be combined in any order, but logically such numerical ranges are limited to a total of 100%.
本發明之鎳電鍍組合物基本上不含硼酸及有機羧酸，且包括胺基磺酸或其鹽以將浴pH值自3維持至5。較佳地，本發明之鎳電鍍組合物不含硼酸及有機羧酸，且包括胺基磺酸或其鹽以將浴pH值自3維持至5。The nickel electroplating composition of the present invention is substantially free of boric acid and organic carboxylic acids, and includes an amine sulfonic acid or a salt thereof to maintain the bath pH from 3 to 5. Preferably, the nickel electroplating composition of the present invention is free of boric acid and organic carboxylic acids, and includes an amine sulfonic acid or a salt thereof to maintain the bath pH from 3 to 5.
在本發明之一個態樣中，鎳電鍍組合物可由胺基磺酸鎳、鹵化鎳、胺基磺酸化合物、水以及視情況用於傳統鎳電鍍組合物之添加劑形成。In one aspect of the invention, the nickel electroplating composition can be formed from an amine sulfonate, a nickel halide, an amine sulfonic acid compound, water, and optionally an additive for a conventional nickel electroplating composition.
可使用可商購之胺基磺酸鎳。鎳電鍍組合物中胺基磺酸鎳的量為100至650 g/L，較佳200至500 g/L。在鎳電鍍組合物中胺基磺酸鎳形成鎳離子及胺基磺酸根離子。A commercially available nickel sulfonate can be used. The amount of nickel sulfonate in the nickel plating composition is from 100 to 650 g/L, preferably from 200 to 500 g/L. Nickel sulfonate is formed in the nickel electroplating composition to form nickel ions and amine sulfonate ions.
鹵化鎳之實例包含氯化鎳及溴化鎳。可使用可商購之鹵化鎳。較佳地，鹵化鎳為氯化鎳。鎳電鍍組合物中鹵化鎳的量為2至100 g/L，較佳5至50 g/L。當鹵化鎳為氯化鎳時，其較佳的量為4至20 g/L。在鎳電鍍組合物中鹵化鎳形成鎳離子及鹵素離子。鹵素離子有助於溶解鎳陽極。Examples of the nickel halide include nickel chloride and nickel bromide. A commercially available nickel halide can be used. Preferably, the nickel halide is nickel chloride. The amount of nickel halide in the nickel plating composition is from 2 to 100 g/L, preferably from 5 to 50 g/L. When the nickel halide is nickel chloride, the preferred amount is 4 to 20 g/L. Nickel halide forms nickel ions and halide ions in the nickel plating composition. Halogen ions help dissolve the nickel anode.
胺基磺酸化合物為在水溶液中形成胺基磺酸根離子之化合物。胺基磺酸化合物包括胺基磺酸及胺基磺酸鹽，諸如胺基磺酸鈉、胺基磺酸鉀及胺基磺酸銨。胺基磺酸鹽為水溶性的。較佳地，胺基磺酸化合物選自胺基磺酸、胺基磺酸鈉、胺基磺酸鉀及胺基磺酸銨。可使用胺基磺酸化合物中之兩者或更多者之組合。較佳地，胺基磺酸化合物為胺基磺酸與胺基磺酸鹽之混合物。當胺基磺酸化合物為胺基磺酸與胺基磺酸鹽之混合物時，胺基磺酸與胺基磺酸鹽之莫耳比為1:3至1:300。更佳地，胺基磺酸與胺基磺酸鹽之莫耳比為1:5至1:200。The aminosulfonic acid compound is a compound which forms an aminosulfonate ion in an aqueous solution. The aminosulfonic acid compound includes an aminosulfonic acid and an aminesulfonic acid salt such as sodium aminosulfonate, potassium aminosulfonate and ammonium aminosulfonate. The amino sulfonate is water soluble. Preferably, the aminosulfonic acid compound is selected from the group consisting of aminosulfonic acid, sodium aminosulfonate, potassium aminosulfonate and ammonium aminosulfonate. A combination of two or more of the aminosulfonic acid compounds can be used. Preferably, the aminosulfonic acid compound is a mixture of an aminosulfonic acid and an amine sulfonate. When the aminosulfonic acid compound is a mixture of an aminosulfonic acid and an aminosulfonate, the molar ratio of the aminosulfonic acid to the aminosulfonate is from 1:3 to 1:300. More preferably, the molar ratio of the aminosulfonic acid to the aminosulfonate is from 1:5 to 1:200.
鎳電鍍組合物中胺基磺酸化合物之量為5 g/L或更大，較佳10 g/L或更大，更佳20 g/L或更大。同時，鎳電鍍組合物中胺基磺酸化合物之量為600 g/L或更小，較佳300 g/L或更小，更佳200 g/L或更小，最佳130 g/L或更小。在鎳電鍍組合物中胺基磺酸化合物形成胺基磺酸根離子及抗衡陽離子。The amount of the aminosulfonic acid compound in the nickel plating composition is 5 g/L or more, preferably 10 g/L or more, more preferably 20 g/L or more. Meanwhile, the amount of the aminosulfonic acid compound in the nickel plating composition is 600 g/L or less, preferably 300 g/L or less, more preferably 200 g/L or less, and most preferably 130 g/L or smaller. The amine sulfonic acid compound forms an amine sulfonate ion and a counter cation in the nickel electroplating composition.
與習知鎳電鍍組合物相比，本發明之鎳電鍍組合物包括更大量之胺基磺酸根離子。鎳電鍍組合物中之胺基磺酸根離子來自胺基磺酸鎳及胺基磺酸鹽化合物。較佳地，鎳電鍍組合物包括0.5至3.0 mol/L之鎳離子、0.03至2.0 mol/L之鹵素離子及1.0至6.5 mol/L之胺基磺酸根離子。更佳地，本發明之鎳電鍍組合物包括0.8至2.8 mol/L之鎳離子、0.06至1.5 mol/L之鹵素離子及1.6至5.1 mol/L之胺基磺酸根離子。胺基磺酸根離子及氯離子之呈mol/L形式的總量大於鎳離子之量（以mol/L為單位）的兩倍。The nickel electroplating compositions of the present invention comprise a greater amount of amine sulfonate ions than conventional nickel electroplating compositions. The amine sulfonate ion in the nickel electroplating composition is derived from a nickel sulfonate and an amine sulfonate compound. Preferably, the nickel plating composition comprises 0.5 to 3.0 mol/L of nickel ions, 0.03 to 2.0 mol/L of halide ions, and 1.0 to 6.5 mol/L of amine sulfonate ions. More preferably, the nickel electroplating composition of the present invention comprises 0.8 to 2.8 mol/L of nickel ion, 0.06 to 1.5 mol/L of halogen ion, and 1.6 to 5.1 mol/L of amine sulfonate ion. The total amount of the amine sulfonate ion and the chloride ion in the form of mol/L is greater than twice the amount of nickel ion (in mol/L).
通常，鍍敷浴之pH值在其操作期間將逐漸增加。當鎳電鍍浴之pH值低於3時，鎳金屬之沈積速度將降低。當鎳電鍍浴之pH值高於5時，沈積後之鎳金屬之內應力將增加。因此，將鎳電鍍浴之pH值維持在3與5之間至關重要。Typically, the pH of the plating bath will gradually increase during its operation. When the pH of the nickel plating bath is below 3, the deposition rate of nickel metal will decrease. When the pH of the nickel plating bath is higher than 5, the internal stress of the deposited nickel metal will increase. Therefore, it is important to maintain the pH of the nickel plating bath between 3 and 5.
本發明人發現，在鎳電鍍浴中，特定量之胺基磺酸根離子類似於pH緩衝液起作用，以將鎳鍍敷浴之pH值維持在3至5之間。不受理論束縛，而是認為與浴中之硼酸一樣，胺基磺酸根離子藉由控制浴中氫氣之產生類似於pH緩衝液起作用。因此，本發明之鎳電鍍組合物具有高pH穩定性而不包含硼酸或有機羧酸。The inventors have found that in a nickel electroplating bath, a specific amount of the amine sulfonate ion acts similarly to the pH buffer to maintain the pH of the nickel plating bath between 3 and 5. Without being bound by theory, it is believed that, like boric acid in the bath, the amine sulfonate ion acts similar to the pH buffer by controlling the production of hydrogen in the bath. Therefore, the nickel electroplating composition of the present invention has high pH stability without containing boric acid or an organic carboxylic acid.
鎳電鍍組合物視情況包括界面活性劑、pH調節劑、濕潤劑及晶粒細化劑。此類視情況選用之添加劑為本領域中熟習此項技術者所熟知。然而，鎳電鍍組合物之添加劑不包含有機羧酸及硼酸，因為本發明之鎳電鍍組合物基本上不含硼酸及有機羧酸，且較佳地不含硼酸及有機羧酸。The nickel electroplating composition optionally includes a surfactant, a pH adjuster, a wetting agent, and a grain refiner. Such additives, as appropriate, are well known to those skilled in the art. However, the additive of the nickel electroplating composition does not contain an organic carboxylic acid and boric acid because the nickel electroplating composition of the present invention is substantially free of boric acid and organic carboxylic acid, and is preferably free of boric acid and organic carboxylic acid.
鎳電鍍組合物之溶劑通常為水。可使用自來水、去離子水或蒸餾水。The solvent for the nickel electroplating composition is typically water. Tap water, deionized water or distilled water can be used.
本發明之一個態樣為一種由以下組成之鎳電鍍組合物：一或多種鎳離子源；一或多種鹵素離子源；一或多種選自胺基磺酸、胺基磺酸鈉、胺基磺酸鉀及胺基磺酸銨之胺基磺酸根離子源；水以及一或多種選自界面活性劑、pH調節劑、濕潤劑及晶粒細化劑之視情況選用之化合物。如上文所揭示，鎳電鍍組合物具有3至5之pH值且鎳電鍍組合物基本上不含硼酸及有機羧酸。較佳地，鎳離子源為胺基磺酸鎳。較佳地，一或多種胺基磺酸根離子源之濃度係按5至130 g/L之量。此類鎳電鍍組合物不含硼酸及有機羧酸。One aspect of the present invention is a nickel electroplating composition consisting of one or more sources of nickel ions; one or more sources of halogen ions; one or more selected from the group consisting of aminosulfonic acids, sodium aminosulfonates, and amine sulfonates A source of the amine sulfonate ion of potassium acid and ammonium sulfonate; water and one or more compounds selected from the group consisting of surfactants, pH adjusters, wetting agents, and grain refiners. As disclosed above, the nickel electroplating composition has a pH of from 3 to 5 and the nickel electroplating composition is substantially free of boric acid and organic carboxylic acids. Preferably, the source of nickel ions is nickel sulfonate. Preferably, the concentration of the one or more aminosulfonate ion sources is in an amount from 5 to 130 g/L. Such nickel plating compositions are free of boric acid and organic carboxylic acids.
本發明之鎳電鍍組合物適用於電子材料。本發明之一個態樣係關於一種將鎳層電鍍於半導體晶圓上之方法，其包括：提供包括複數種導電黏合特徵之半導體晶圓，使半導體晶圓與上文所揭示之任何組合物接觸，及施加足夠的電流密度以將鎳層沈積於導電黏合特徵上。The nickel electroplating composition of the present invention is suitable for use in electronic materials. One aspect of the invention is directed to a method of electroplating a nickel layer onto a semiconductor wafer, comprising: providing a semiconductor wafer comprising a plurality of electrically conductive bonding features to contact the semiconductor wafer with any of the compositions disclosed above And applying sufficient current density to deposit a layer of nickel on the conductive bonding features.
半導體晶圓之實例包含但不限於矽晶圓、玻璃基板及有機基板。導電黏合特徵通常藉由以下步驟形成：在半導體晶圓之表面上形成導電層，在半導體晶圓之導電層上形成抗蝕劑層，接著移除至少一部分之抗蝕劑層以在導電層上形成開口。銅通常用作導電層。導電層可藉由任何已知方法諸如濺鍍或無電金屬鍍敷來形成。Examples of semiconductor wafers include, but are not limited to, germanium wafers, glass substrates, and organic substrates. The conductive bonding feature is generally formed by forming a conductive layer on the surface of the semiconductor wafer, forming a resist layer on the conductive layer of the semiconductor wafer, and then removing at least a portion of the resist layer on the conductive layer. An opening is formed. Copper is commonly used as a conductive layer. The conductive layer can be formed by any known method such as sputtering or electroless metal plating.
具有導電層之半導體晶圓藉由任何已知方法與上文所揭示之組合物接觸，以將鎳沈積於半導體晶圓之導電層上。通常，半導體晶圓浸沒於鎳鍍敷溶液中且施加電流。A semiconductor wafer having a conductive layer is contacted with the composition disclosed above by any known method to deposit nickel on the conductive layer of the semiconductor wafer. Typically, the semiconductor wafer is immersed in a nickel plating solution and an electrical current is applied.
鎳金屬可用作陽極，但在一些情形下可使用不溶電極，諸如鉑鍍敷之鈦板。電流密度在0.5至40 A/dm2 、較佳5至20 A/dm2 範圍內。鎳鍍敷組合物之溫度基本上為10至80℃，較佳30至65℃。鍍敷時間視電流密度及所需之鍍敷厚度而定。舉例而言，若電流密度為1 A/dm2 且所需之Ni層厚度為3微米，則鍍敷時間為約15分鐘。Nickel metal can be used as the anode, but in some cases an insoluble electrode such as a platinum plated titanium plate can be used. The current density is in the range of 0.5 to 40 A/dm 2 , preferably 5 to 20 A/dm 2 . The temperature of the nickel plating composition is substantially 10 to 80 ° C, preferably 30 to 65 ° C. The plating time depends on the current density and the required plating thickness. For example, if the current density is 1 A/dm 2 and the required Ni layer thickness is 3 microns, the plating time is about 15 minutes.
由本發明方法形成之鎳層具有40 MPa或更小之內應力。更佳地，內應力為30 MPa或更小，且最佳地，內應力為25 MPa或更小。內應力由沈積應力分析器來量測。由於由包括硼酸之習知鎳電鍍浴形成之內應力為約10至40 MPa，因此本發明之鎳電鍍組合物在與習知浴類似之內應力下提供鎳沈積。The nickel layer formed by the method of the present invention has an internal stress of 40 MPa or less. More preferably, the internal stress is 30 MPa or less, and optimally, the internal stress is 25 MPa or less. The internal stress is measured by a sedimentary stress analyzer. Since the internal stress formed by a conventional nickel plating bath including boric acid is about 10 to 40 MPa, the nickel plating composition of the present invention provides nickel deposition under internal stress similar to a conventional bath.
本發明之鎳鍍敷組合物可用來形成金鍍敷下層及銅表面之阻擋層。本發明之鎳鍍敷組合物亦適用於形成凸塊下金屬（UBM）。UBM為種子金屬（seed metal）（約2000Å之銅）與焊料之間的保護緩衝層。同樣，本發明之鎳鍍敷組合物可用來在基板上形成凸塊（支柱）以在基板與電子組件之間電性地連接。 實例 本發明實例1-3及比較實例1-3The nickel plating composition of the present invention can be used to form a barrier layer for a gold plating underlayer and a copper surface. The nickel plating composition of the present invention is also suitable for forming under bump metal (UBM). UBM is a protective buffer layer between seed metal (about 2000 Å copper) and solder. Also, the nickel plating composition of the present invention can be used to form bumps (pillars) on a substrate to electrically connect between the substrate and the electronic component. EXAMPLES Examples 1-3 and Comparative Examples 1-3 of the present invention
IMAT Co.所提供之矽晶圓用作測試樣品（測試樣品（Test Sample））。測試樣品為60 mm × 50 mm大小之矽晶圓，在矽晶圓之表面上具有鈦層（下層）及銅層（上層），接著在銅層上形成抗蝕劑層且具有75微米直徑之十個孔形成通過抗蝕劑層。藉由1,000Å鈦粒子濺鍍形成鈦層，同時藉由3,000Å銅粒子濺鍍形成銅層。將測試樣品浸沒於鎳鍍敷溶液（在下文揭示）中並電鍍。陽極為鎳金屬。電流密度為6 A/dm2 ，且鎳鍍敷溶液之溫度為60℃。鍍敷目標厚度為3 μm。接著用DI水洗滌測試樣品。之後，將抗蝕劑藉由在60℃下浸漬於Shipley BPR汽提器（可購自Rohm and has Electronic Materials，美國馬薩諸塞州馬波羅市（Marlborough, Massachusetts, USA））中5分鐘來移除。在測試樣品上之孔中形成十次鎳沈積（鎳凸塊下金屬）。藉由SEM觀測鎳沈積之表面。由Electrochemical co. ltd.所提供之沈積應力分析器量測鎳沈積之內應力。檢查浴pH穩定性且結果顯示於圖3中。 鎳鍍敷溶液 4-水合胺基磺酸鎳：500 g/L（作為鎳金屬為90 g/L） 6-水合氯化鎳：20 g/L（作為氯離子為6 g/L） pH緩衝液：揭示於表1及2中 剩餘部分：蒸餾水 藉由添加NaOH或H3 NSO3 將pH調節至約4The silicon wafer supplied by IMAT Co. is used as a test sample (Test Sample). The test sample is a 60 mm × 50 mm tantalum wafer having a titanium layer (lower layer) and a copper layer (upper layer) on the surface of the tantalum wafer, followed by a resist layer on the copper layer and having a diameter of 75 μm. Ten holes are formed through the resist layer. A titanium layer was formed by sputtering of 1,000 Å of titanium particles while a copper layer was formed by sputtering of 3,000 Å of copper particles. The test sample was immersed in a nickel plating solution (disclosed below) and electroplated. The anode is nickel metal. The current density was 6 A/dm 2 and the temperature of the nickel plating solution was 60 °C. The plating target has a thickness of 3 μm. The test sample was then washed with DI water. Thereafter, the resist was removed by immersion in a Shipley BPR stripper (available from Rohm and has Electronic Materials, Marlborough, Massachusetts, USA) at 60 ° C for 5 minutes. . Ten nickel deposits (metal under the nickel bump) were formed in the pores on the test sample. The surface of the nickel deposit was observed by SEM. The internal stress of nickel deposition was measured by a sedimentary stress analyzer provided by Electrochemical co. ltd. The bath pH stability was checked and the results are shown in Figure 3. Nickel plating solution Nickel 4-hydrated sulfonate: 500 g/L (90 g/L as nickel metal) 6-Hydrated nickel chloride: 20 g/L (6 g/L as chloride ion) pH buffer Liquid: Revealed in the remainder of Tables 1 and 2: Distilled water is adjusted to a pH of about 4 by the addition of NaOH or H 3 NSO 3
針對pH緩衝液，使用表1及2中寫入之化合物。 表1
藉由實例2獲得之UBM之SEM顯示於圖1（放大率為1500倍）中，且藉由實例3獲得之UBM之SEM照片顯示於圖2（放大率為1000倍）中。The SEM of the UBM obtained by Example 2 is shown in Figure 1 (magnification 1500 times), and the SEM photograph of the UBM obtained by Example 3 is shown in Figure 2 (magnification 1000 times).
無no
圖1為顯示藉由實例2獲得之鎳凸塊下金屬之掃描電子顯微照片（SEM）。 圖2為顯示藉由實例3獲得之鎳凸塊下金屬之SEM。 圖3為本發明實例1、比較實例1至3之浴pH穩定性測試結果。BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a scanning electron micrograph (SEM) showing the metal under the nickel bump obtained by Example 2. 2 is a SEM showing a metal under the nickel bump obtained by Example 3. Figure 3 is a graph showing the results of bath pH stability test of Example 1, Comparative Examples 1 to 3 of the present invention.
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