CN104801879A - Cu芯球、焊膏和焊料接头 - Google Patents
Cu芯球、焊膏和焊料接头 Download PDFInfo
- Publication number
- CN104801879A CN104801879A CN201510044092.8A CN201510044092A CN104801879A CN 104801879 A CN104801879 A CN 104801879A CN 201510044092 A CN201510044092 A CN 201510044092A CN 104801879 A CN104801879 A CN 104801879A
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- China
- Prior art keywords
- ball
- solder
- plating film
- solder plating
- core
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910000679 solder Inorganic materials 0.000 title claims abstract description 132
- 238000007747 plating Methods 0.000 claims abstract description 151
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 26
- 239000000956 alloy Substances 0.000 claims abstract description 26
- 230000003746 surface roughness Effects 0.000 claims abstract description 20
- 230000005260 alpha ray Effects 0.000 claims description 72
- 229910052770 Uranium Inorganic materials 0.000 claims description 15
- 238000005476 soldering Methods 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 238000003466 welding Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 42
- 239000012535 impurity Substances 0.000 abstract description 22
- 230000008569 process Effects 0.000 abstract description 12
- 239000010949 copper Substances 0.000 description 251
- 239000000463 material Substances 0.000 description 27
- 238000004519 manufacturing process Methods 0.000 description 20
- 238000002844 melting Methods 0.000 description 17
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 16
- 229910052776 Thorium Inorganic materials 0.000 description 16
- 230000008018 melting Effects 0.000 description 16
- 230000002285 radioactive effect Effects 0.000 description 16
- 229910052745 lead Inorganic materials 0.000 description 15
- 238000010438 heat treatment Methods 0.000 description 13
- 239000002245 particle Substances 0.000 description 12
- 239000007789 gas Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 239000003463 adsorbent Substances 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 10
- 229910052797 bismuth Inorganic materials 0.000 description 10
- 239000003792 electrolyte Substances 0.000 description 10
- 239000004065 semiconductor Substances 0.000 description 10
- 229910052718 tin Inorganic materials 0.000 description 9
- 229910017944 Ag—Cu Inorganic materials 0.000 description 8
- 238000009434 installation Methods 0.000 description 8
- 229940098779 methanesulfonic acid Drugs 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 7
- 229910052709 silver Inorganic materials 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- -1 pink salt Chemical class 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000008139 complexing agent Substances 0.000 description 5
- 230000005611 electricity Effects 0.000 description 5
- 238000005469 granulation Methods 0.000 description 5
- 230000003179 granulation Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 230000005855 radiation Effects 0.000 description 5
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 229910020220 Pb—Sn Inorganic materials 0.000 description 4
- 230000033228 biological regulation Effects 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 238000011900 installation process Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000004439 roughness measurement Methods 0.000 description 4
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052787 antimony Inorganic materials 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000009499 grossing Methods 0.000 description 3
- 238000009616 inductively coupled plasma Methods 0.000 description 3
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 3
- 238000005453 pelletization Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229910001432 tin ion Inorganic materials 0.000 description 3
- YYYOQURZQWIILK-UHFFFAOYSA-N 2-[(2-aminophenyl)disulfanyl]aniline Chemical compound NC1=CC=CC=C1SSC1=CC=CC=C1N YYYOQURZQWIILK-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910000967 As alloy Inorganic materials 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-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 2
- PWKSKIMOESPYIA-BYPYZUCNSA-N L-N-acetyl-Cysteine Chemical compound CC(=O)N[C@@H](CS)C(O)=O PWKSKIMOESPYIA-BYPYZUCNSA-N 0.000 description 2
- 229960004308 acetylcysteine Drugs 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
- 238000000889 atomisation Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 230000000994 depressogenic effect Effects 0.000 description 2
- 238000005553 drilling Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000012776 electronic material Substances 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000000174 gluconic acid Substances 0.000 description 2
- 235000012208 gluconic acid Nutrition 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 230000001939 inductive effect Effects 0.000 description 2
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 229910001923 silver oxide Inorganic materials 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- QPBYLOWPSRZOFX-UHFFFAOYSA-J tin(iv) iodide Chemical compound I[Sn](I)(I)I QPBYLOWPSRZOFX-UHFFFAOYSA-J 0.000 description 2
- XEFNPVOFXHNZFW-UHFFFAOYSA-N 2,3-dihydroxybutanedioic acid;tin Chemical compound [Sn].OC(=O)C(O)C(O)C(O)=O XEFNPVOFXHNZFW-UHFFFAOYSA-N 0.000 description 1
- DIZBQMTZXOUFTD-UHFFFAOYSA-N 2-(furan-2-yl)-3h-benzimidazole-5-carboxylic acid Chemical compound N1C2=CC(C(=O)O)=CC=C2N=C1C1=CC=CO1 DIZBQMTZXOUFTD-UHFFFAOYSA-N 0.000 description 1
- GEZAUFNYMZVOFV-UHFFFAOYSA-J 2-[(2-oxo-1,3,2$l^{5},4$l^{2}-dioxaphosphastannetan-2-yl)oxy]-1,3,2$l^{5},4$l^{2}-dioxaphosphastannetane 2-oxide Chemical compound [Sn+2].[Sn+2].[O-]P([O-])(=O)OP([O-])([O-])=O GEZAUFNYMZVOFV-UHFFFAOYSA-J 0.000 description 1
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 description 1
- IOVSQAQVXZOFTD-UHFFFAOYSA-N 2-hydroxypropane-1,2,3-tricarboxylic acid;tin Chemical compound [Sn].OC(=O)CC(O)(C(O)=O)CC(O)=O IOVSQAQVXZOFTD-UHFFFAOYSA-N 0.000 description 1
- OQXSRALAOPBHPM-UHFFFAOYSA-N 2-hydroxypropanoic acid;silver Chemical compound [Ag].CC(O)C(O)=O OQXSRALAOPBHPM-UHFFFAOYSA-N 0.000 description 1
- QJDGQRSDUWBFJB-UHFFFAOYSA-N 2-hydroxypropanoic acid;tin Chemical compound [Sn].CC(O)C(O)=O QJDGQRSDUWBFJB-UHFFFAOYSA-N 0.000 description 1
- OCUCCJIRFHNWBP-IYEMJOQQSA-L Copper gluconate Chemical compound [Cu+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O OCUCCJIRFHNWBP-IYEMJOQQSA-L 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910021612 Silver iodide Inorganic materials 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- 229910020836 Sn-Ag Inorganic materials 0.000 description 1
- 229910020888 Sn-Cu Inorganic materials 0.000 description 1
- 229910020988 Sn—Ag Inorganic materials 0.000 description 1
- 229910019204 Sn—Cu Inorganic materials 0.000 description 1
- 229910018956 Sn—In Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910021623 Tin(IV) bromide Inorganic materials 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- LPEHFRQCUXZVLR-UHFFFAOYSA-M [Ag]F.[B] Chemical compound [Ag]F.[B] LPEHFRQCUXZVLR-UHFFFAOYSA-M 0.000 description 1
- MJLTYHNYPWPXTI-UHFFFAOYSA-M [Ag]F.[Si] Chemical compound [Ag]F.[Si] MJLTYHNYPWPXTI-UHFFFAOYSA-M 0.000 description 1
- DEWYJFOUSNWBTE-UHFFFAOYSA-L [Cu](F)F.[B] Chemical compound [Cu](F)F.[B] DEWYJFOUSNWBTE-UHFFFAOYSA-L 0.000 description 1
- DFDYKCDUMMVROR-UHFFFAOYSA-L [Cu](F)F.[Si] Chemical compound [Cu](F)F.[Si] DFDYKCDUMMVROR-UHFFFAOYSA-L 0.000 description 1
- XPDKEDUCGIWKEL-UHFFFAOYSA-J [Sn](F)(F)(F)F.[B] Chemical compound [Sn](F)(F)(F)F.[B] XPDKEDUCGIWKEL-UHFFFAOYSA-J 0.000 description 1
- DEPTXYMLDSHYIQ-UHFFFAOYSA-J [Sn](F)(F)(F)F.[Si] Chemical compound [Sn](F)(F)(F)F.[Si] DEPTXYMLDSHYIQ-UHFFFAOYSA-J 0.000 description 1
- QYIJPFYCTROKTM-UHFFFAOYSA-N [Sn].P(O)(O)(O)=O Chemical compound [Sn].P(O)(O)(O)=O QYIJPFYCTROKTM-UHFFFAOYSA-N 0.000 description 1
- CWEZQDMMYKITLP-UHFFFAOYSA-N [Sn].S(N)(O)(=O)=O Chemical compound [Sn].S(N)(O)(=O)=O CWEZQDMMYKITLP-UHFFFAOYSA-N 0.000 description 1
- KKKAMDZVMJEEHQ-UHFFFAOYSA-N [Sn].[N+](=O)(O)[O-] Chemical compound [Sn].[N+](=O)(O)[O-] KKKAMDZVMJEEHQ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000005262 alpha decay Effects 0.000 description 1
- 238000005915 ammonolysis reaction Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000005255 beta decay Effects 0.000 description 1
- 238000005219 brazing Methods 0.000 description 1
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 description 1
- PQQMFTAUKPHVMV-UHFFFAOYSA-L butanedioate;tin(2+) Chemical compound [Sn+2].[O-]C(=O)CCC([O-])=O PQQMFTAUKPHVMV-UHFFFAOYSA-L 0.000 description 1
- MGIWDIMSTXWOCO-UHFFFAOYSA-N butanedioic acid;copper Chemical compound [Cu].OC(=O)CCC(O)=O MGIWDIMSTXWOCO-UHFFFAOYSA-N 0.000 description 1
- SHLCGTACJPPATG-UHFFFAOYSA-N butanedioic acid;silver Chemical compound [Ag].OC(=O)CCC(O)=O SHLCGTACJPPATG-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229940108925 copper gluconate Drugs 0.000 description 1
- HPAXFNMMMBLYJU-UHFFFAOYSA-N copper sulfamic acid Chemical compound [Cu].S(N)(O)(=O)=O HPAXFNMMMBLYJU-UHFFFAOYSA-N 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- GQDHEYWVLBJKBA-UHFFFAOYSA-H copper(ii) phosphate Chemical compound [Cu+2].[Cu+2].[Cu+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GQDHEYWVLBJKBA-UHFFFAOYSA-H 0.000 description 1
- RSJOBNMOMQFPKQ-ZVGUSBNCSA-L copper;(2r,3r)-2,3-dihydroxybutanedioate Chemical compound [Cu+2].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O RSJOBNMOMQFPKQ-ZVGUSBNCSA-L 0.000 description 1
- DYROSKSLMAPFBZ-UHFFFAOYSA-L copper;2-hydroxypropanoate Chemical compound [Cu+2].CC(O)C([O-])=O.CC(O)C([O-])=O DYROSKSLMAPFBZ-UHFFFAOYSA-L 0.000 description 1
- HFDWIMBEIXDNQS-UHFFFAOYSA-L copper;diformate Chemical compound [Cu+2].[O-]C=O.[O-]C=O HFDWIMBEIXDNQS-UHFFFAOYSA-L 0.000 description 1
- AEJIMXVJZFYIHN-UHFFFAOYSA-N copper;dihydrate Chemical compound O.O.[Cu] AEJIMXVJZFYIHN-UHFFFAOYSA-N 0.000 description 1
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- FWBOFUGDKHMVPI-UHFFFAOYSA-K dicopper;2-oxidopropane-1,2,3-tricarboxylate Chemical compound [Cu+2].[Cu+2].[O-]C(=O)CC([O-])(C([O-])=O)CC([O-])=O FWBOFUGDKHMVPI-UHFFFAOYSA-K 0.000 description 1
- PEVJCYPAFCUXEZ-UHFFFAOYSA-J dicopper;phosphonato phosphate Chemical compound [Cu+2].[Cu+2].[O-]P([O-])(=O)OP([O-])([O-])=O PEVJCYPAFCUXEZ-UHFFFAOYSA-J 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- ZUVOYUDQAUHLLG-OLXYHTOASA-L disilver;(2r,3r)-2,3-dihydroxybutanedioate Chemical compound [Ag+].[Ag+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O ZUVOYUDQAUHLLG-OLXYHTOASA-L 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- CCIVGXIOQKPBKL-UHFFFAOYSA-N ethanesulfonic acid Chemical compound CCS(O)(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-N 0.000 description 1
- PTSNAAXZLFGCNO-UHFFFAOYSA-N formic acid;tin Chemical compound [Sn].OC=O PTSNAAXZLFGCNO-UHFFFAOYSA-N 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 230000035784 germination Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000000918 plasma mass spectrometry Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- HNDXKIMMSFCCFW-UHFFFAOYSA-N propane-2-sulphonic acid Chemical compound CC(C)S(O)(=O)=O HNDXKIMMSFCCFW-UHFFFAOYSA-N 0.000 description 1
- 229910052704 radon Inorganic materials 0.000 description 1
- SYUHGPGVQRZVTB-UHFFFAOYSA-N radon atom Chemical compound [Rn] SYUHGPGVQRZVTB-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 description 1
- 229940071536 silver acetate Drugs 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- SDLBJIZEEMKQKY-UHFFFAOYSA-M silver chlorate Chemical compound [Ag+].[O-]Cl(=O)=O SDLBJIZEEMKQKY-UHFFFAOYSA-M 0.000 description 1
- 229940071575 silver citrate Drugs 0.000 description 1
- 229940045105 silver iodide Drugs 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- FJOLTQXXWSRAIX-UHFFFAOYSA-K silver phosphate Chemical compound [Ag+].[Ag+].[Ag+].[O-]P([O-])([O-])=O FJOLTQXXWSRAIX-UHFFFAOYSA-K 0.000 description 1
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 description 1
- 229910000367 silver sulfate Inorganic materials 0.000 description 1
- FTNNQMMAOFBTNJ-UHFFFAOYSA-M silver;formate Chemical compound [Ag+].[O-]C=O FTNNQMMAOFBTNJ-UHFFFAOYSA-M 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- VPKAOUKDMHJLAY-UHFFFAOYSA-J tetrasilver;phosphonato phosphate Chemical compound [Ag+].[Ag+].[Ag+].[Ag+].[O-]P([O-])(=O)OP([O-])([O-])=O VPKAOUKDMHJLAY-UHFFFAOYSA-J 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- LTSUHJWLSNQKIP-UHFFFAOYSA-J tin(iv) bromide Chemical compound Br[Sn](Br)(Br)Br LTSUHJWLSNQKIP-UHFFFAOYSA-J 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- YJGJRYWNNHUESM-UHFFFAOYSA-J triacetyloxystannyl acetate Chemical compound [Sn+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O YJGJRYWNNHUESM-UHFFFAOYSA-J 0.000 description 1
- QUTYHQJYVDNJJA-UHFFFAOYSA-K trisilver;2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Ag+].[Ag+].[Ag+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QUTYHQJYVDNJJA-UHFFFAOYSA-K 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 238000007601 warm air drying Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
本发明涉及Cu芯球、焊膏和焊料接头。提供抑制软错误的发生、设为安装处理中不成问题的表面粗糙度的低α射线量的Cu芯球。一种Cu球,作为核的Cu球的纯度为99.9%以上且99.995%以下,并且该Cu球中所含的杂质中Pb和/或Bi的总含量为1ppm以上,其球形度为0.95以上。覆盖于Cu球的焊料镀覆膜为Sn焊料镀覆膜或由以Sn作为主要成分的无铅焊料合金形成的焊料镀覆膜,U为5ppb以下的含量且Th为5ppb以下的含量。Cu球和焊料镀覆膜的综合的α射线量为0.0200cph/cm2以下,而且上述Cu芯球的表面粗糙度为0.3μm以下。
Description
技术领域
本发明涉及改善了表面粗糙度且α射线量少的Cu芯球、焊膏和焊料接头。
背景技术
近年来,由于小型信息设备的发展,所搭载的电子部件正在进行急速的小型化。对电子部件而言,为了应对小型化的要求所带来的连接端子的狭窄化、安装面积的缩小化,采用了将电极设置于背面的球栅阵列封装(以下称为“BGA”)。
对于在半导体封装体中应用BGA而得到的电子部件,具备电极的半导体芯片被树脂密封,而且在半导体芯片的电极上形成有焊料凸块。焊料凸块是将焊料球接合于半导体芯片的电极而成的,通过与印刷电路基板的导电性焊盘接合的方式安装于印刷电路基板。
近年来,为了应对进一步的高密度安装的要求,研究了半导体封装体在高度方向上堆叠的三维的高密度安装。
在三维高密度安装而成的半导体封装体中应用BGA时,由于半导体封装体的自重,焊料球有时会被压碎。如果发生这样的情况,还可以想到会发生焊料从电极露出、电极间的短路(short)。
为了消除这样的问题,研究了采用硬度高于焊料球的球。作为硬度高的球,研究了使用Cu球、Cu芯球而形成的焊料凸块。Cu芯球是指在Cu球的表面形成有焊料覆膜(焊料镀覆膜)的球。
Cu球、Cu芯球由于在焊料的熔点下不熔融,所以即使半导体封装体的重量施加于焊料凸块,安装处理时焊料凸块也不会被压碎,因此可以可靠地支撑半导体封装体。作为Cu球等的相关技术,例如可以列举出专利文献1。
然而,电子部件的小型化虽然使高密度安装成为可能,但高密度安装会引起软错误(soft error)之类的问题。软错误是指:存在α射线进入半导体集成电路(IC电路)的存储单元中而改写存储内容的可能性。
认为α射线是通过焊料合金中的U、Th、Po等放射性元素、Pb、Bi等中所含的放射性同位素经过β衰变并进行α衰变而放射的。
近年来,正在进行降低了放射性元素的含量的低α射线的焊料材料的开发。作为相关文献,例如可以列举出专利文献2。
另外,关于Cu芯球,在Cu球的表面形成有焊料镀覆膜,该焊料镀覆膜为均匀膜厚的镀层。另一方面,由于镀覆处理时的条件等而使晶体的生长变得不均匀,其结果,有时在表面会产生凹凸。对于在表面具有凹凸的Cu芯球,球的滚动变差,作为焊料凸块而将球接合时的接合位置精度变低。
另外,在凸块形成时被卷入凹凸面的有机成分在回流焊时熔融并汽化,其有时会在焊料镀覆膜中以空隙的形式残留。空隙残留时,其使接合的可靠性降低、或者自焊料镀覆膜中释放气体成分时引起焊料凸块的位置偏移的问题受到诟病。
作为尽量减轻焊料镀覆膜的凹凸的技术,已知有专利文献3等。
现有技术文献
专利文献
专利文献1:国际公开第95/24113号
专利文献2:日本特许第4472752号公报
专利文献3:日本特开2010-216004号公报
发明内容
发明要解决的问题
专利文献1中记载了球形度高的Cu球、Cu芯球。然而,专利文献1中完全没有考虑到降低Cu芯球的α射线量这样的课题。
另外,该文献中,关于构成焊料覆膜的焊料合金,仅仅作为背景技术的说明而唯一公开了Pb-Sn合金。关于α射线,在Sn中作为杂质而含有的Pb的同位素210Pb在以210Pb→210Bi→210Po→206Pb进行衰变的过程中,自210Po放射α射线。
该文献中唯一公开的Pb-Sn焊料合金由于大量含有Pb而被认为还含有放射性同位素210Pb。因此,即使将该焊料合金用于Cu芯球的焊料覆膜,也不能降低α射线量。
该文献中完全没有公开对Cu球进行Sn镀覆、在Cu球和电解液流动的状态下进行电镀的内容。
另外,在该文献所记载的电解精炼中,由于电解析出面不限定于单向,所以无法对Cu球这样的微小工件形成膜厚均匀的镀覆膜。
专利文献2中公开了α射线量低的Sn锭的技术方案,记载了如下技术方案:不单纯地进行电解精炼,而是使吸附剂悬浮于电解液中,从而吸附Pb、Bi使α射线量降低。
根据该文献,Pb、Bi的标准电极电位与Sn接近,因此,若仅仅通过一般的电解精炼而使Sn向平板电极上进行电解析出时难以降低α射线量。假设将该文献中记载的电解精炼应用于Cu球的镀覆膜的形成,使吸附剂悬浮于镀液地进行转筒滚镀时,镀液、工件被搅拌,同时吸附剂也被搅拌。上述情况下,存在吸附于吸附剂的Pb离子、Bi离子成为载体,与吸附剂一起被引入到焊料覆膜内的可能性。
引入了吸附剂的焊料覆膜放射较高的α射线。另外,吸附剂的粒径为亚微米水平,非常小,因此认为边使镀液流动边将悬浮后的吸附剂分离/回收是困难的。因此,难以使吸附有Pb、Bi的吸附剂不被引入到覆膜中。
此外,专利文献1中虽然公开了Pb-Sn焊料合金,但是公开了镀覆法、熔接法、铜焊法等作为等价的方法,因此反而记载了否定降低α射线量的内容。
专利文献1的课题在于制造球形度高的Cu芯球,另一方面,专利文献2中公开了为了解决降低α射线量的课题而在电解精炼中尽量去除Sn中的Pb。
因此,知晓专利文献1的本领域技术人员不会想到降低该文献中公开的Cu芯球的α射线量这样的课题,而且焊料的组成也截然相反,因此可以认为,如果想要想到降低α射线量的课题,进而想到从无数存在的焊料合金中采用Sn系焊料来代替构成焊料覆膜的Pb-Sn焊料合金,则需要无限次的反复试验。
即使对于本领域技术人员而言,使用该文献中公开的α射线量低的Sn锭制作镀液,利用专利文献1中公开的镀覆法形成Cu芯球也是极其困难的。
可见,采用专利文献1、专利文献2中记载的现有技术制造的Cu芯球被用于接头的形成时,Cu芯球的焊料覆膜中存在的放射性元素向接头的电极扩散并释放α射线的可能性高。因此,无法避免因高密度安装而成为新问题的软错误。
专利文献3中,为了消除焊料镀覆膜表面的粗糙,作为其平滑化处理,使焊料镀覆膜表面与研磨剂等介质接触来进行。作为介质,除如此以机械方式去除的物理方法之外还公开了酸洗等化学方法。
然而,这样的利用介质的平滑化处理中,为了获得安装处理中不成问题的表面粗糙度(Ra),需要花费相当长的处理时间。例如,直至作为上述表面粗糙度的算术平均粗糙度Ra达到0.3μm以下为止需要5~6小时的处理时间。这样的程度难以实用化。
因此,本发明提供抑制软错误的发生、设为安装处理中不成问题的表面粗糙度且低α射线量的Cu芯球、焊膏和焊料接头。
用于解决问题的方案
为了解决上述课题,本发明为由Cu球和覆盖于其表面的焊料镀覆膜构成的Cu芯球,如以下那样构成作为其核的Cu球和焊料镀覆膜。
Cu球使用以下的核球,即,所述核球的纯度为99.9%~99.995%,球形度为0.95以上,α射线量为0.0200cph/cm2以下,Cu球中所含的杂质成分中的包含放射性同位素的Pb和/或Bi的含量为1ppm以上,同样属于放射性元素的U、Th为5ppb以下、优选为2ppb以下。
焊料镀覆膜为Sn或以Sn作为主要成分的焊料合金,为焊料合金的情况下,Sn的含量选自40%以上。焊料镀覆膜的表面粗糙度以算术平均粗糙度Ra计为0.3μm以下、优选为0.2μm左右。
另外,在其他实施例中,Cu球使用纯度为99.9%~99.995%、且球形度为0.95以上的核球。
焊料镀覆膜为Sn或以Sn作为主要成分的焊料合金,作为放射性元素的U、Th为5ppb以下、优选为2ppb以下,Cu芯球的α射线量为0.0200cph/cm2以下,而且焊料镀覆膜的表面粗糙度以算术平均粗糙度Ra计为0.3μm以下、优选为0.2μm左右。
Cu芯球也可以作为焊料接头使用,还可以作为焊膏的粉末焊料使用。
为了得到这样的条件,本发明人等首先对Cu芯球中使用的Cu球进行选择。其结果发现,如果Cu球中不含有一定量的Pb和/或Bi,则Cu球的球形度降低,进行焊料镀覆时,对Cu球的焊料镀覆变得不均匀,结果所得Cu芯球的球形度降低。
通过在将Cu球造球时的加热处理温度设为1000℃以上的高温下进行,从而使Cu球中所含的杂质中的放射性元素挥发,实现Cu球的低α射线量化。
接着,为了降低构成Cu芯球的焊料覆膜的α射线量,着眼于使用镀覆法形成焊料镀覆膜的方面进行了深入研究。本发明人等为了减少镀液中的Pb、Bi、由这些元素中的放射性同位素的衰变而生成的Po而边使Cu球、镀液流动边在Cu球上形成镀覆膜时,预料之外地发现,即使不使吸附剂悬浮,这些Pb、Bi、Po元素也形成了盐。由此得到以下见解:由于该盐为电中性,所以这些放射性元素不会被引入到镀覆膜中,构成Cu芯球的镀覆膜的α射线量降低。
针对表面粗糙度的平滑化处理以在将Cu芯球浸渍于镀液的状态下照射超声波的方式来进行。通过该超声波照射,可以在短时间内达到目标表面粗糙度。
附图说明
图1为使用纯度为99.9%的Cu颗粒制造的Cu球的SEM照片。
图2为使用纯度为99.995%以下的Cu线制造的Cu球的SEM照片。
图3为使用纯度超过99.995%的Cu板制造的Cu球的SEM照片。
具体实施方式
更详细地对本发明做出以下说明。在本说明书中,与Cu芯球的焊料覆膜的组成相关的单位(ppm、ppb和%)只要没有特别指定就表示相对于焊料覆膜的质量的比例(质量ppm、质量ppb和质量%)。另外,与Cu球的组成相关的单位(ppm、ppb、和Wt%)只要没有特别指定就表示相对于Cu球的质量的比例(质量ppm、质量ppb和质量%)。
本发明的Cu芯球具备Cu球以及覆盖该Cu球的表面的焊料镀覆膜。以下,对作为Cu芯球的构成要素的Cu球和镀覆膜(焊料镀覆膜)进行详述。
1.关于Cu球
Cu球在用于焊料凸块时在焊接的温度下不会熔融,因此,从可以抑制焊料接头的高度的偏差出发,优选的是,Cu球的球形度高、直径的偏差少。
(1a)Cu球的纯度:99.9%以上且99.995%以下
Cu球的纯度优选为99.9%以上且99.995%以下。通过适当包含杂质,从而Cu球的球形度提高,可以在熔融Cu中确保充分的量的晶核。
制造Cu球时,形成为规定形状的小片的Cu材料通过在1000℃或其以上的温度下加热,从而熔融,熔融Cu因表面张力而成为球形,其发生凝固,形成Cu球。在熔融Cu自液体状态凝固的过程中,晶粒在球形的熔融Cu中生长。详细情况后述。
此时,如果杂质元素多,则该杂质元素成为晶核,抑制晶粒的生长。球形的熔融Cu利用生长受到抑制的微细晶粒而形成球形度高的Cu球。
另一方面,如果杂质元素少,则相应地成为晶核的杂质元素少,颗粒生长不受抑制地具有一定方向性地生长。其结果,球形的熔融Cu的表面的一部分突出并发生凝固,因此球形度低。由此,为了提高Cu球的球形度,必须含有一定水平的杂质。
作为杂质元素,如后述那样,可以想到Sn、Sb、Bi、Zn、As、Ag、Cd、Ni、Pb、Au、P、S、U、Th等。
对于Cu球的纯度,除了球形度的问题之外,从抑制后述α射线量、抑制由纯度降低导致的Cu球的电导率、热导率的劣化的观点出发,优选为99.9%以上且99.995%以下。
对于后述的焊料镀覆膜而言,纯度高时可以降低α射线量,而另一方面,对于Cu球而言,即使不将纯度提高至必要程度以上,也可以使α射线量降低。其理由如以下所述。
Cu的熔点高于Sn,因此Cu的造球时的加热温度高。制造Cu球时,如后述那样,进行以往不会进行的高温加热处理,所以在该加热处理过程中杂质中所含的210Po、210Pb、210Bi等放射性元素挥发。其结果,即使杂质中存在放射性元素,由其放射的α射线量也不会成为担心造成影响的水平的量。
另一方面,覆盖Cu球的镀覆膜也如后述那样往往包含Pb、Bi等中的放射性同位素。
焊料镀覆膜使用以Sn作为主要成分的焊料,焊料液中所含的放射性元素几乎不挥发而残留于镀液中。因此,在镀覆膜处理的情况下,无法期待α射线量的降低,所以需要如后述那样预先降低Pb、Bi等的杂质浓度来提高焊料镀覆膜的纯度。
(1b)α射线量:0.0200cph/cm2以下
自Cu球放射的α射线量优选为0.0200cph/cm2以下。该数值为在电子部件的高密度安装中软错误不会成为问题的水平的数值。
通过在为了制造Cu球而通常进行的加热处理工序的基础上再次实施加热处理,少量残留于Cu的原材料中的210Po也挥发,因此与Cu的原材料相比,Cu球的α射线量变得更低。α射线量从抑制软错误的观点出发更优选为0.0010cph/cm2以下较好。
(1c)Pb和/或Bi的含量总计为1ppm以上
Cu球中所含的杂质元素中,特别是Pb和/或Bi的含量总计为1ppm以上是优选的。
Pb、Bi中所含的210Pb和210Bi因β衰变而变为210Po。为了降低α射线量,优选的是,作为杂质元素的Pb和Bi的含量也尽量低,但是,由于这些放射性元素的含有率原本就较低,所以认为如上述那样通过在Cu球造球过程中的加热处理而将210Pb、210Bi去除。
另一方面,为了提高Cu球的球形度,杂质元素的含量高较好,因此从Cu球的硬度和球形度的均衡出发,优选的是,Pb和/或Bi的含量总计为1ppm以上。可以为1ppm以上,例如在抑制Cu球的电导率的劣化方面,可以含有至10~50ppm或其以上、例如1000ppm左右。
(1d)Cu球的球形度:0.95以上
如果Cu球的球形度小于0.95,则Cu球成为不规则形状,因此凸块形成时会形成高度不均匀的凸块,发生接合不良的可能性变高。这是因为,进一步对Cu球进行的焊料镀覆变得不均匀,将Cu芯球搭载于电极并进行回流焊时,Cu芯球发生位置偏移,自对准性(self-alignment property)也会恶化。因此,球形度为0.95以上、优选为0.990左右较好。
此处,球形度表示与完美球形的差距。球形度例如可以通过最小二乘中心法(LSC法)、最小区域中心法(MZC法)、最大内切中心法(MIC法)、最小外切中心法(MCC法)等各种方法来求出。
当然,优选的是,该球形度即使在镀覆膜覆盖于Cu球的状态下也保持上述值。
(1e)Cu球的直径:1~1000μm
构成本发明的Cu球的直径优选为1~1000μm。这是由于,处于该范围时,可以稳定地制造球状的Cu球,而且可以抑制端子间为窄间距的情况下的连接短路。
需要说明的是,直径为1~300μm左右时,虽然使用方式不同,但也可以以焊膏中的粉末的形式来配混。
作为Cu球的基底处理,也可以在形成焊料镀覆膜(后述)之前,预先用其他金属的镀层覆盖Cu球的表面。在Cu球表面覆盖有Ni镀层、Co镀层等时,可以减少Cu向焊料镀覆膜中的溶出,因此可以抑制Cu球的Cu侵蚀。
2.关于焊料镀覆膜
本发明的Cu芯球如下构成:在Cu球的表面以成为规定的厚度的方式覆盖焊料镀覆膜。
焊料镀覆膜主要是使作为工件的Cu球和镀液流动而形成的。已判明,通过镀液的流动,在镀液中Pb、Bi、Po等中的具有放射性同位素的元素形成盐并沉淀。一旦形成作为盐的析出物,则稳定地存在于镀液中。
因此,本发明的Cu芯球的析出物不会被引入到焊料镀覆膜中,由此可以降低焊料镀覆膜中所含的放射性元素的含量,作为其结果,可以大幅降低Cu芯球自身的α射线量。
(2a)焊料镀覆膜的组成
焊料镀覆膜的组成为Sn、或以Sn作为主要成分的无铅焊料合金的合金组成。作为合金组成,从落下冲击特性的观点出发,优选为Sn-3Ag-0.5Cu合金较好。
作为除此之外的合金组成,可以列举出:Sn-Ag合金、Sn-Cu合金、Sn-Ag-Cu合金、Sn-In合金、以及在它们中添加了规定的合金元素而成的合金。上述合金组成中Sn的含量均为40质量%以上。作为所添加的合金元素,例如有Ag、Cu、In、Ni、Co、Sb、Ge、P、Fe等。
对焊料镀覆膜的厚度没有特别限制,优选为100μm以下就足够。一般而言,为20~50μm即可。
(2b)U的含量:5ppb以下、Th:5ppb以下
U和Th为放射性元素,为了抑制软错误,必须抑制它们的含量。为了使焊料镀覆膜的α射线量为0.0200cph/cm2以下,U和Th的含量必须分别为5ppb以下。另外,从抑制目前或将来的高密度安装中的软错误的观点出发,U和Th的含量分别优选为2ppb以下。利用本发明使用的测定方法(ICP-MS)时,作为U和Th的含量而示出的数值2ppb为测定极限值。
(2c)α射线量:0.0200cph/cm2以下
自本发明的Cu芯球的表面放射的α射线量为0.0200cph/cm2以下。该数值为在电子部件的高密度安装中软错误不会成为问题的水平的α射线量。
焊料镀覆膜在100℃左右的温度下形成,因此很难认为U、Th、Po、Bi和Pb等中的放射性同位素会气化而含量降低。
边使镀液、Cu球流动边进行镀覆处理时,U、Th、Pb、Bi、210Po等中的放射性同位素在镀液中形成盐并沉淀。沉淀出的盐为电中性,即使镀液流动也不会混入到焊料镀覆膜中。盐保持沉淀了的状态,因此焊料镀覆膜中的放射性元素的含量显著降低。
为了可以显著降低焊料镀覆膜中的放射性元素的含量,本发明的Cu芯球的α射线量可以抑制为0.0200cph/cm2以下,优选可以抑制为0.0010cph/cm2以下。
需要说明的是,作为焊料镀覆膜组成使用Sn焊料时,焊料镀覆膜的纯度为焊料镀覆膜中的除Sn之外的杂质的总含量。焊料镀覆膜的合金组成为Sn-3Ag-0.5Cu的焊料合金时,焊料镀覆膜的纯度为焊料镀覆膜中的除Sn、Ag和Cu之外的杂质的含量的总和。
作为Sn焊料镀覆膜中所含的杂质,可以列举出Ag、Ni、Pb、Au、U、Th等。由Sn-Ag-Cu合金形成的焊料镀覆膜的情况下,作为杂质可以列举出Sb、Fe、As、In、Ni、Pb、Au、U、Th等。
这些杂质中,特别优选Bi的含量少。一般而言,Bi的原料中包含微量的放射性同位素210Bi。因此认为,通过降低Bi的含量,可以显著降低焊料镀覆膜的α射线量。Bi的含量优选为15ppm以下,更优选为10ppm以下,特别优选为0ppm。
3.Cu芯球的制造例
接着,如下说明上述Cu芯球的制造例。
(3a)关于Cu球
(i)将作为材料的Cu材料放置于陶瓷这样的耐热性的板(以下称为“耐热板”),与耐热板一起在炉中被加热。在耐热板上设有底部成为半球状的多个圆形的槽。
槽的直径、深度根据Cu球的粒径适当设定,例如直径为0.8mm,深度为0.88mm。另外,将切断Cu细线而得到的碎片形状的Cu材料(以下称为“碎片材料”)逐个投入到耐热板的槽内。
(ii)对于在槽内投入了碎片材料的耐热板,在填充有氨分解气体的炉内升温至1100~1300℃,进行30~60分钟的加热处理。此时炉内温度成为Cu的熔点以上时,碎片材料熔融而成为球状。之后,使炉内冷却,Cu球在耐热板的槽内成形。
(iii)冷却后,成形的Cu球在低于Cu的熔点的温度即800~1000℃下再次进行加热处理。再次的加热处理是为了使残留的放射性元素尽量挥发,从而实现α射线量的降低。
另外,作为其他造球方法,有以下的方法:将熔融Cu自设置于坩埚的底部的孔口滴下,将生成的液滴冷却,对Cu球进行造粒的雾化法;利用热等离子体,将Cu切割金属加热至1000℃以上进行造粒的方法。
可以对如此造粒而成的Cu球分别在800~1000℃的温度下实施30~60分钟的再加热处理。也可以在对Cu球造粒前将作为Cu球的原料的Cu材料在800~1000℃下进行加热处理。
作为Cu球的原料的Cu材料,可以使用颗粒、线、柱等。Cu材料的纯度从不过度降低Cu球的纯度的观点出发,可以为99.9~99.99%。进而,使用高纯度的Cu材料时,可以将熔融Cu的保持温度与目前同样地降低至1000℃左右,而不进行前述加热处理。
如此,前述加热处理可以根据Cu材料的纯度、α射线量而适当省略、变更。另外,制造出α射线量高的Cu球、异形的Cu球时,这些Cu球也可以作为原料而再利用,能够进一步降低α射线量。
(3b)焊料镀覆膜处理
将如上述那样制作的Cu球浸渍于镀液中,使镀液流动来形成镀覆膜。作为形成焊料镀覆膜的方法,有以下的方法等:公知的转筒滚镀等电镀法;连接于镀覆槽的泵在镀覆槽中使镀液产生高速紊流,利用镀液的紊流而在Cu球上形成镀覆膜的方法;在镀覆槽上设置振动板,以规定的频率使其振动,从而对镀液进行高速紊流搅拌,利用镀液的紊流而在Cu球上形成镀覆膜的方法。
以下示出在直径100μm的Cu球上形成膜厚20μm的Sn-Ag-Cu焊料镀覆膜,形成直径约140μm的Cu芯球的例子。
(3b-i)含Sn-Ag-Cu镀液在以水作为主体的介质中含有磺酸类和作为金属成分的Sn、Ag和Cu作为必须成分。
金属成分在镀液中以Sn离子(Sn2+和/或Sn4+)、Ag离子(Ag+)和Cu离子(Cu+/Cu2+)的形式存在。镀液通过将主要由水和磺酸类构成的镀覆母液与金属化合物混合而得到,为了金属离子的稳定性,优选含有有机络合剂。
作为镀液中的金属化合物,例如可以列举出以下的物质。
作为Sn化合物的具体例,可以列举出:甲磺酸、乙磺酸、2-丙磺酸、对苯酚磺酸等有机磺酸的锡盐、硫酸锡、氧化锡、硝酸锡、氯化锡、溴化锡、碘化锡、磷酸锡、焦磷酸锡、乙酸锡、甲酸锡、柠檬酸锡、葡萄糖酸锡、酒石酸锡、乳酸锡、琥珀酸锡、氨基磺酸锡、硼氟化锡、硅氟化锡等亚Sn化合物。这些Sn化合物可以单独使用一种或混合两种以上使用。
作为Cu化合物,可以列举出:上述有机磺酸的铜盐、硫酸铜、氧化铜、硝酸铜、氯化铜、溴化铜、碘化铜、磷酸铜、焦磷酸铜、乙酸铜、甲酸铜、柠檬酸铜、葡萄糖酸铜、酒石酸铜、乳酸铜、琥珀酸铜、氨基磺酸铜、硼氟化铜、硅氟化铜等。这些Cu化合物可以单独使用一种或混合两种以上使用。
作为Ag化合物,可以列举出:上述有机磺酸的银盐、硫酸银、氧化银、氯化银、硝酸银、溴化银、碘化银、磷酸银、焦磷酸银、乙酸银、甲酸银、柠檬酸银、葡萄糖酸银、酒石酸银、乳酸银、琥珀酸银、氨基磺酸银、硼氟化银、硅氟化银等。这些Ag化合物可以单独使用一种或混合两种以上使用。
对于镀液中的各金属的配混量,以Sn2+计为0.21~2mol/L、优选为0.25~1mol/L,以Ag+计为0.01~0.1mol/L、优选为0.02~0.05mol/L,以Cu2+计为0.002~0.02mol/L、优选为0.003~0.01mol/L。参与镀覆的是Sn2+,所以调整Sn2+的量即可。
相对于Cu离子浓度的Ag离子浓度(Ag/Cu摩尔比)优选为4.5~5.58的范围,如果为该范围,则可以形成Sn-3Ag-0.5Cu合金那样的熔点低的Sn-Ag-Cu镀覆膜。
(3b-ii)根据法拉第电解定律,利用下述式(1)估计期望的焊料镀覆的析出量,算出电量,以成为算出的电量的方式使电流对镀液进行通电,边使Cu球和镀液流动边进行镀覆处理。
在直径100μm的Cu球上形成膜厚20μm的Sn-Ag-Cu焊料镀覆膜时,需要约0.0108库仑的电量。
镀覆槽的容量可以根据Cu球和镀液的总投入量确定。
w(g)=(I×t×M)/(Z×F)···式(1)
式(1)中,w为电解析出量(g),I为电流(A),t为通电时间(秒),M为析出的元素的原子量(Sn的情况下为118.71),Z为化合价(Sn的情况下为2价),F为法拉第常数(96500库仑),电量Q(A·秒)用(I×t)表示。
在本发明中,边使Cu球和镀液流动边进行镀覆,但对流动的方法没有特别限定。例如,可以如筒式电镀法那样利用转筒的旋转而使Cu球和镀液流动。
(3b-iii)在镀覆处理后,在大气中、N2气氛中进行规定时间的干燥,从而可以得到本发明的Cu芯球。该焊料镀覆膜处理也可以用于以Cu为核的圆柱、柱、颗粒的形态。
为了测定本发明的Cu芯球的球形度和α射线量,制作以下那样的Cu芯球(试样)。在以下进行说明。
4.试样用Cu球的制作例
(4a)Cu球
调査球形度高的Cu球的制作条件。准备纯度为99.9%的Cu颗粒、纯度为99.995%以下的Cu线、以及纯度超过99.995%的Cu板。将其分别投入坩埚中,然后将坩埚的温度升温至1200℃,进行45分钟的加热处理,将熔融Cu自设置于坩埚底部的孔口滴下,将所生成的液滴冷却,从而对Cu球进行造粒。由此,制作平均粒径为250μm的Cu球。将制作好的Cu球的元素分析结果和球形度示于表1。以下,对球形度的测定方法进行详述。
(4b)Cu球的球形度
球形度利用CNC图像测定系统测定。
装置为Mitutoyo Corporation制造的ULTRA QUICK VISION、ULTRAQV350-PRO。球形度是指将500个Cu球的直径分别除以该Cu球的长径时算出的算术平均值,值越接近作为上限的1.00表示越接近完美球形。
本发明中的长径的长度和直径的长度是指分别通过Mitutoyo Corporation制造的ULTRA QUICK VISION、ULTRA QV350-PRO测定装置测定的长度。
另外,将制作好的各Cu球的SEM照片示于图1~3。图1为使用纯度为99.9%的Cu颗粒制造的Cu球的SEM照片。图2为使用纯度为99.995%以下的Cu线制造的Cu球的SEM照片。图3为使用纯度超过99.995%的Cu板制造的Cu球的SEM照片。SEM照片的倍率为100倍。
(4c)Cu球的α射线量
α射线量的测定使用气流正比计数器的α射线测定装置。测定样品是将Cu球铺满于300mm×300mm的平面浅底容器至使得看不到容器的底为止的样品。将该测定样品放入α射线测定装置内,在PR-10气流下放置24小时,然后测定α射线量。
测定中使用的PR-10气体(氩气90%-甲烷10%)是将PR-10气体填充于储气瓶中后经过了3周以上的气体。
使用经过了3周以上的储气瓶是为了遵守JEDEC(Joint Electron DeviceEngineering Council;电子器件工程联合委员会)中规定的JEDECSTANDARD-Alpha Radiation Measurement in Electronic Materials JESD221(JEDEC标准-电子材料中的阿尔法射线测量JESD221),使得进入到气体储气瓶的大气中的氡不产生α射线。
(4d)Cu球的元素分析
关于元素分析,对于U和Th,通过电感耦合等离子体质谱(ICP-MS分析)来进行,对于其他元素,通过电感耦合等离子体发光分光分析(ICP-AES分析)来进行。
将制作好的Cu球的元素分析结果、α射线量示于(表1)。
表1
*U、Th为质量ppb。其他元素为质量ppm。
如表1、图1和图2所示那样,使用纯度为99.9%的Cu颗粒得到的Cu球和使用纯度为99.995%以下的Cu线得到的Cu球的球形度均显示为0.990以上。另一方面,如表1和图3所示那样,使用纯度超过99.995%的Cu板的Cu球的球形度低于0.95。
因此,以下所示的例子均使用利用99.9%的Cu颗粒制造的Cu球制作而成的Cu芯球作为试样。
(试样1)
以下示出试样1的Cu芯球的制作例。
对于利用纯度99.9%的Cu颗粒制造的Cu球,在以下的条件下,形成Sn焊料镀覆膜,从而制作Cu芯球。
对于Cu芯球,以在直径250μm的Cu球上覆盖膜厚为50μm的Sn焊料镀覆的方式,将电量设为约0.17库仑,使用以下的镀液进行镀覆处理。通过SEM照片观察Cu芯球的截面,结果焊料镀覆膜的膜厚为50μm。处理后,在大气中进行干燥,得到Cu芯球。
(试样1中使用的焊料镀液)
在搅拌容器中,在调制镀液所需的水的1/3中加入全部的54重量%的甲磺酸水溶液,制成基液。接着,加入作为络合剂的硫醇化合物的一例即乙酰半胱氨酸,确认其溶解后,加入作为其他络合剂的芳香族氨基化合物的一例即2,2’-二硫代二苯胺。形成较淡的浅蓝色的凝胶状的液体后迅速加入甲磺酸亚锡。
接着,加入镀液所需的水的2/3,最后加入表面活性剂的一例即α-萘酚聚氧乙烯醚(EO10摩尔)3g/L,镀液的调制结束。制成了镀液中的甲磺酸的浓度为2.64mol/L、锡离子浓度为0.337mol/L的镀液。
本例中使用的甲磺酸亚锡是以下述Sn片材作为原料制备而成的。关于作为焊料镀液的原料的Sn片材的元素分析、以及形成于Cu芯球的表面的焊料镀覆膜的元素分析,对于U和Th,通过高频电感耦合等离子体质谱(ICP-MS分析)来进行,对于其他元素,通过高频电感耦合等离子体发光分光分析(ICP-AES分析)来进行。
对于Sn片材的α射线量,除了将Sn片材铺满于300mm×300mm的平面浅底容器之外,与Cu球同样地测定。Cu芯球的α射线量与前述Cu球同样地测定。另外,对于Cu芯球的球形度,也在与Cu球相同的条件下进行测定。将这些测定结果示于表2。
(试样2)
以下示出试样2的Cu芯球的制作例。
对于使用纯度99.9%的Cu颗粒制造的Cu球,形成膜厚为50μm的Sn-Ag-Cu焊料镀覆膜,从而制作Cu芯球。
(试样2中使用的焊料镀液)
焊料镀液为(Sn-Ag-Cu)镀液。
在搅拌容器中加入调制镀液所需的水的1/3、以及全部的54重量%的甲磺酸水溶液,制成基液。
接着,边搅拌边加入全部的所需量的氧化银,确认变得透明而完全没有黑色沉淀后迅速加入全部的氢氧化铜,完全溶解后,加入作为络合剂的硫醇化合物的一例即乙酰半胱氨酸,确认其溶解后,加入作为其他络合剂的芳香族氨基化合物的一例即2,2’-二硫代二苯胺。
形成较淡的浅蓝色的凝胶状的液体后迅速加入甲磺酸亚锡。液体变为黄色透明。接着,加入镀液所需的水的2/3,最后加入表面活性剂的一例即α-萘酚聚氧乙烯醚(EO10摩尔)3g/L,镀液的调制结束。制成了镀液中的甲磺酸的浓度为2.64mol/L、锡离子浓度为0.337mol/L、铜离子浓度为0.005mol/L、银离子浓度为0.0237mol/L的镀液。
如此制作镀液后,使用试样1中使用的α射线量为0.203cph/cm2的Sn片材、α射线量<0.0010cph/cm2且纯度为6N的Cu板材、以及α射线量<0.0010cph/cm2且纯度为5N的Ag碎片材料,除此之外,与试样1同样地制作镀液,制作Cu芯球,进行元素分析和α射线量、球形度的测定。将测定结果示于表2。
本例中,锡离子来自于上述Sn片材,对于银离子、铜离子,也分别来自于上述Ag碎片材料、Cu板材。
(比较试样)
对于利用纯度99.9%的Cu颗粒制造的Cu球,使用熔接法,在以下的条件下形成Sn焊料覆膜,从而制作Cu芯球。
具体而言,在难以焊接的铝板的规定的位置设置多个研钵状的凹陷部。另外,使用前述Sn片材,通过公知的雾化法,预先制作直径为300μm的Sn球。
在设置于铝基板的各凹陷部中逐个放入Cu球和Sn球,喷雾助焊剂。之后,将铝板在加热炉中加热至270℃,使Sn球熔融。熔融Sn在Cu球周围浸润,利用表面张力覆盖Cu球。
如此制作比较试样的Cu芯球。焊料覆膜的膜厚为50μm。对于制作好的比较试样,与试样1同样地,测定元素分析和α射线量、球形度。将测定结果示于表2。
表2
*U、Th为质量ppb。其他元素为质量ppm。
根据表2,试样1中显示α射线量小于0.0010cph/cm2。证实了以下结论,试样1的Cu芯球由于通过湿式镀覆法形成焊料镀覆膜,所以α射线量降低。
试样2中显示,将焊料镀覆膜的组成为Sn-2.95Ag-0.29Cu时的焊料α射线量小于0.0010cph/cm2。证实了以下结论,试样2的Cu芯球与试样1同样地通过镀覆法形成焊料镀覆膜,所以α射线量降低。试样1、2中制成的Cu芯球即使在制成后经过1年也没有观察到α射线上升。
另一方面,比较试样中显示,α射线量为0.183cph/cm2,显示出与Sn片材同等水平的α射线量。比较试样的Cu芯球无法降低至能够避免软错误的水平的α射线量。
Cu芯球的表面粗糙度的评价
作为表面粗糙度测定用的试样显然可以使用试样1、2中示出的Cu芯球,但此次重新制作表面粗糙度测定用的试样。
(5a)表面粗糙度测定用的试样
使用与(试样1)中使用的同样的Cu球(使用Cu材料,直径200μm、且纯度为99.9%以上且99.995%以下)。对该Cu球进行基底用的镀覆处理。该例中,进行2μm的镀Ni处理。
之后,对该Cu球实施Sn100%的镀覆处理,直至膜厚为48μm。因此,所得Cu芯球的直径成为250μm。
将该Cu芯球和镀液直接采集至300cc的烧杯中,安置于超声波机内照射超声波。超声波机使用市售的超声波清洗机(AS ONE Corporation制造的US-CLEANER),该例中以输出功率80W、40kHz的频率进行。经过规定时间后用离子交换水清洗,之后进行温风干燥,制成表面粗糙度测定用的试样。
表面粗糙度的评价(图像评价)使用KEYENCE株式会社制造的激光显微镜(型号VK-9510/符合JISB0601-1994)进行。评价面积优选为尽量窄的范围,该例中,由于使用直径为250μm的Cu芯球,所以以Cu芯球的顶点的最平坦的部分作为中心在25×25μm的范围内测定。z轴上的测定间距为0.1μm。
(5b)表面粗糙度的评价
在这样的条件下,作为Cu芯球的算术平均粗糙度Ra,测定任意的10个位置的表面粗糙度,使用它们的算术平均值作为真实的算术平均粗糙度。同时将改变超声波的照射时间(处理时间)并测定得到的结果示于(表3)。
表3
由(表3)的结果可以确认,通过照射50~60分钟左右的超声波,算术平均粗糙度Ra达到0.3μm以下,利用60分钟的照射而改善至0.22μm左右。需要说明的是,为了得到该水平的算术平均粗糙度Ra,专利文献3中需要5~6小时的处理时间。如果适当调整超声波的频率、输出功率水平,则可以得到更良好的结果。
如以上那样,本发明可以提供抑制软错误发生、设为安装处理中不成问题的表面粗糙度且低α射线量的Cu芯球。
本发明的Cu芯球无论在焊料接头用途、还是焊膏用途中均可以适用,这是毋庸讳言的。
Claims (7)
1.一种Cu芯球,其特征在于,具备作为核的Cu球、以及覆盖该Cu球的表面的焊料镀覆膜,
该Cu球是纯度为99.9%以上且99.995%以下、U为5ppb以下的含量且Th为5ppb以下的含量、Pb和或Bi的总含量为1ppm以上、球形度为0.95以上、α射线量为0.0200cph/cm2以下的Cu球,
所述焊料镀覆膜为Sn焊料镀覆膜或由以Sn作为主要成分的无铅焊料合金形成的焊料镀覆膜,
所述Cu芯球的算术平均表面粗糙度为0.3μm以下。
2.根据权利要求1所述的Cu芯球,其特征在于,所述焊料镀覆膜中,U为5ppb以下的含量且Th为5ppb以下的含量。
3.根据权利要求1或2中的任一项所述的Cu芯球,其特征在于,所述表面粗糙度为0.22μm以下。
4.根据权利要求1~3中的任一项所述的Cu芯球,其特征在于,所述Cu球在利用所述焊料镀覆膜进行覆盖之前预先利用由选自Ni和Co中的1种元素以上形成的镀层进行了覆盖。
5.根据权利要求1~4中的任一项所述的Cu芯球,其特征在于,α射线量为0.0200cph/cm2以下。
6.一种焊膏,其特征在于,使用权利要求1~5中的任一项所述的Cu芯球。
7.一种焊料接头,其特征在于,其是使用权利要求1~6中的任一项所述的Cu芯球而形成的。
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