(2) 6 sy om en @ 6s) oy (2) 68) 6) United States Patent Bernards et al. METHOD AND COMPOSITION FOR SELECTIVELY STRIPPING NICKI SUBSTRATE Inventors: Roger Assignee: OMG Electronic Chemicals, Ine. South Plainfield, NJ (US) Notice: Subject to any disclaimer, the team ofthis pateat is extended of adjusted under 35 USC. 154(b) by 176 days. Appl. No 11/416,729 Filed: May 3, 2006 Prior Publication Data S 2007)0257010A1 Nov. 8, 2007 Incl. Hoi 1300 (2006.01) us.cl. eld of Class 26/21; 216/13, 216/13, 216/21, 108 See application file for complete search history. References Cited sation Search USS, PATENT DOCUMENTS 3365401 A /1968 Sabet sa A'SSKO A LLID85 Bestenbeck 4oir392 A "41987 Cook 4520932 811988 Colley ©523169 BL 112001 Abeta 638297 BL 122001 Coley (6642199 B2 11-2003, Humplieys etal ‘US007S91956B2 (10) Patent No. 4s) Date of Patent: US 7,591,956 B2 Sep. 22, 2009 sagas me 20020188048 AL 92004 Har eta 4102002, Humphreys eal FOREIGN PATENT DOCUMENTS BP ssiousi a * Wo wo2007-130282 1980 112007 (OTHER PUBLICATIONS PCTUSO7(0977 lmmational Sexrch Report, Nov. 9, 2007 Intemational Preliminary Report on Patentability comesponting to Intrmational Applicaton Seal No. PCT'US2009 009797 nme Now 13,2008, 5 pages. * cited by examiner Roberts Culbert ‘MeAndres, Held & Malloy Primary Examiner (74) Atiorney, Agent, oF Firm Li. 6 ABSTRACT A method of stripping nickel fom a printed wiring boant comprises providing a printed wiring board with a nickel ‘deposit on a surface and contacting the nickel deposit with phosphate ions and an oxidizer, An aqueous solution com- prises ammonium ions, phosphate ions and an oxidizing ‘agent preset in amounts elfective io srip nickel. An aqueous solution comprises abort 19% to about 10% by weight hydro- ‘gen peroxide and about 5% to about 30% by weight of an fammonivim phosphate, method of pre-cating @ copper substrate comprises providing a printed Wiring board having 4 copper substrate and contocting the copper substrate with phosphate ions, and an oxidizer A method of neutralizing permanganate on a printed wiring board comprises providing ‘printed wiriny board with a permanganate residue on the prints wiring board and contacting the permanganate res- ‘due with phosphate jos, and an oxidizer 1€ 5, No DrawUS 7,591,956 B2 1 METHOD AND COMPOSITION FOR SELECTIVELY STRIPPING NICKEL FROM A, SUBSTRATE RELATED APPLICATIONS, [Not Applicable] FIELD OF THE INVENTION ‘he present technology generally relates to stripping nickel from a substrate. For example, the present technology Jncludes method and composition for sieipping aickel Irom printed wiring boand. Te present technology is particularly usefl for removing High Phosphorous Fleiroless Nickel BACKGROUND OF THE INVENTION Printed wiring boards are formed from a layer of eonduc- tive material (commonly, copper or copper plated with solder ‘or gold) caried ona layer of insulating material (commonly Blass-fiberteinforced epoxy resin) A printed wiring board having two conductive surfaces positioned on opposite sides ‘ofasingle insulating layeris nownasa “double-sided circuit board” To accommodate even more circuits on a single board, several copper layers are sandwiches! between boards ‘orother layers of insulating material to produce a muli-layer ‘wiring board. ‘The copper or other condoctive material ean be plated, clad for otherwise deposited onto the insulating board and then, ‘etched into the desired formations, During mantifactoring, nickel can be deposited onto the copper or ober conductive substrate. This ean bedone, fr example sing the electroless nickel part of an electroless nicke/immersion gold (ENIG) technique. The process reslts ina layer af electoless nickel being deposited on the conductive substrate. ‘Depositing an electroless nickel finish onto the conductive substrate has a number of advantages. It prevents copper ‘oxidation, facilitates solderability and prevents defects dar- ing the assembly process Despite these many benefits, sometimes it would be desir. able to selectively remove the deposited electroless nickel from the conductive substrate, For example, in order 0 re- work the eopper on a faulty wiring boant it would fist be desirable to remove the deposited nickel. It would be impor. tant that no significant amount of copper be removed daring the deposited nickel removal. Ideally’ the copper should remain bright, uniform and unvetched, This would allow for the best re-working surfice. Previously, the deposited electroless nickel could not be selectively removed Irom faulty boards, Faulty boards had to be thrown away becaine it was impossible to remove the nickel wihoutalso removing or damaging the copper. Repro- ‘essing of faully boards was impossible, Attempis have been made using chemicals to selectively remove deposited nickel while lewving the substrate unal- fected, Vanous degrees of suocess have been obtained. US. Pat. No. 454,089 (Bastenbeck) deseribesa solution stated to be useful for stripping electrolyte nickel and low phosphorous electroless nickel Irom a ferrous metal substrate tha ies slfamate ons, nitrate ions, ehloridefons andan iron ‘complexing agent However, this sofution isnot intended for the removal of elsetroles nickel from copper on printed Wiring boards. is more difficult selectively remove nickel fom copper than from a ferrous metal. The printed wiring boardindustry requires. high deyseeof precision when selec- 0 o 2 tively removing nickel trom copper. This believed to achieve the required precision, USS. Pat, No, 4.720.332 (Colley) discloses a nickel strip ping bath tat is stated to utilize soluble nitrobenzene com- pounds, zwitterions (as chelating agents), sulfide producing ‘compounds, carbonstes and a reverse current to remove the nickel deposit. This method is believed to microscopically ctch in high current density aeas, which dlls the substrate surface. This method also requires an electrical contact with the substrate. A pane that hae already been selectively etched js not coatactable with eleceic cureent because the etching creates gaps inthe conductive material (for example opp. ‘These gaps prevent electric current from flowing othe nickel coated surfaces and stripping the nickel. Tis process would also etch copper along with the nickel US. Pat. No. 6,323,169 (Abe) deseribes 2 composition said 0 be useful 8s a resist stripping agent containing. an oxidizing agent, a chelating agent (Selected from the group of aminopolyearboxylie acids, the salts of aminopolycarboxylie ‘acids, phosphonic chelating agents, condensed phospharie ‘acids andl salts of condensed phosphoric acids) and a water soluble Muorine compound. However, this isa resist stripping ‘cthod and is nt disclosed to selectively strip nickel Irom copper. USS. Pat, No, 6:332,970 (Coffey) describes an lectolti method said tobe useful fr stripping electroless nickel ro iron, cast iron, steel alloy, stainless steel, aluminum, elect plated nickel, ast nickel, ion niekeV/eobalt ally, sulfamste fickel or titanium. Coffey discloses immersing the substrate {no an eletrotytie bath containing an oxeacid, oxoacidl salt fora combination thereof and hytlrgen peroxide. As with astenbeck, this method isnot direted to removing eletro- less nickel from a copper substrate fr sein printed wiring boards. Furthermore, an electrolyte method may not be suit ahleto remove electroless nickel from a printed wiring board. As previously stated, panel that hs already been selectively ftchod is not contactable with electric cunent because the etching reates zaps inthe conductive material (for example ‘opper) These gaps prevent electric current fom flowing to the nickel coated surfaces and stripping the nickel This pro- cess wotld also etch copper along with the nickel. USS. Pat. No. 6,682,199 (Humphreys) deseribes @ nickel stripping composition containing an oxidizing agent, an ‘amine and an organic or borie acid. The composition in Fum- hey is said to quire a pH of ereaer than 65 in order for stripping to take place. highly alkaline formula such as the ‘one described in the "199 patent can ruin the soldermask om a srinted wiring board, US. Pat. No. 6,797,682 (Hara) deseribes a resist stipper made up of hydrogen peroxide, quaternary ammonium salt, ‘water and a water soluble onganic solvent. However, this is ‘understood to be aresist stripping method ands not dielosed to selectively strip nickel trom copper Furthermore, this ‘method is not effective on printed wiring boards because the highly alkane formula can ruin the soldermask “Accordingly, it would be desirable to providea method and composition for selectively stripping nickel from a printed ‘wiring board without removing 2 significant amount of the ‘underlying substrate I also would be desirable to provide a ‘method o stripping nickol such that the underlying substate is bright, uniform, not significantly etehed and fit for ne ‘working after the nickel i stripped. pethod is not SUMMARY OF THE INVENTION ‘The current method of stripping nickel from a printed Wiring board comprises providing. printed wiring bosed withUS 7,591,956 B2 3 ‘nickel depositon surface and contacting the nickel deposit ‘with phosphate ions and an oxidizer under conditions eflec- tive 0 remove at least a portion ofthe nickel deposit, "The current aqueous solution comprises ammonium ions, phosphate fons and an oxidizing agent present in amounts ‘effective to strip nickel TInone embodiment the aqueous solution comprises 1% t0 10% by weight hydrogen peroxide and 5% 1o 30% by weight ‘of an ammonium phosphate The current method of pre-treating a copper substratecom- prises providing «printed wiring board having a copper sub- te and contacting the copper substrate with phosphate fons, and an oxidizer under conditions effective to brighten the copper subsea The current method of neutralizing permanganate on 2 printed wiring board comprises providing a printed wiring board with @ permanganate reside on the printed wiring board and contacting the pemmanganate residue with phos phate ions, and an oxidizer under conditions effective 10 neutralize the permanganate DETAILED DESCRIPTION ‘Thecurtent iselosure relates to amethod! and composition Jor selectively stripping nickel fom a printed wiring board or other subsirate without removing a significant amount ofthe ‘underlying substrate. The current disclosure alsa relate to @ method and composition for pretreating a copper substrate anda method and composition for neullizing pemaanganate ‘ona printed wiring board. The embodiments disclosed herein ‘are intended to be illusirave and should not be read as limitations to the disclosed inventions. “The method of stripping aickel {rom printed wiring board (or other substrate) hepins with providing a printed wiring board (or other substrate) comprising a nickel deposit on a surface. surface on which nickel can be deposited is con- templated for use herein. A common printed wiring board surface is ade of copper, although other contemplated mate- rials include brass, do, in-lead, Bismuth alloys and gold, The sutface can have an exposed dielectric such aan epoxy panel ‘orsoldermask. Methods of depositing nickel on asurlace are known to those familie with the technology: The nickel ‘deposit is commonly the electroless nickel deposited by the fist part of an ENIG process (that is before the immersion old layer is applied), The current technology is particularly ‘useful emoving electroplated nickel and electroless nickel ‘of various phosphorous levels. However, oer deposits of nickel or nickel alloy can be removed using this method “The nickel deposit is then contacted with phosphate ions ‘and an oxidizer trier conditions effective to remove at least 1 portion of the nickel deposit, Contemplated oxidizers include peroxides (such as hydrogen peroxide), persulfates, nitri acid, and other oxidizers capable of oxidizing nickel ‘metal Some contemplated sources of phosphate ions include ‘ammonium phosphate monobasic and sodium phosphate ‘monobasic, which ean be formed by combining ammonium chloride or trisodium phosphate with phosphor ack, Other ‘contemplated sources of phosphate ions inelude ammonium Phosphate dibasic, ammonium phosphate ribasic,potassinm Phosphate monobasic, potassium phosphate dibasic, potas- sium phosphate tribasic, phosphoric acid, or other soluble phosphate sali, Othee combinations of chemicals providing the recited ions in solution or dispersion are also conten- plated, The phosphate fons and oxidizer can be applied to the nickel deposit ins single soliton Tn one embodiment ammonium ions ean also be contacted with te nickel deposit, Contemplated sourees of ammonium 0 o 4 fons include without limitation ammonium phosphate ‘monobasic, ammonium phosphate dibasic, ammonium phos- phate tibasic, ammonium hydroxide, ammonium ehloride, ammonium carbonate, ammonium sulfate or other soluble ‘ammonium salts. The ammonium fons are sometimes added Jnconjunetion with thephosphate ions as with the ammoninm phosphates. The ammonium fons ean be contacted 10 the fickel deposit in separate salution or ina single solution with the phosphate ions and oxidizer. ‘Conditions that can allect aickel removal andthe quality of the underlying surface include the eonceateatons of phos- phate ions and oxidizer. la one embodiment the phosphite jonsare provided in an aqueous solution ata concentration of sore thin about 10 pi, allematvely over bout 100 g/L oF altematively mote than about 150 g/L (measured as g of PO,” per liter), Oxidizer can be provided in an aqueous soliton at a concentration of about 15 to about 100 g/L, allematively about 20 to about 30 gL or alternatively about 25 g/L (measured as g of oxidizer molecules per liter). If persulfate is used as an oxidizer the concentration should be bout 15 to about 200 g/L alternatively about 125 to about 175 iL or altematively about 150 pL (measured as g of 8,0,°° molectiles per liter. If ammonium ions are ade they ean be prvidedinan aqueous solution ataconceatration ‘of about 110 about 100 g/L altematvely about Sto about 30 iL or alternatively about 25 g/L. (measured as g of NEL,” molecules per liter). ‘Another condition that ean alfet nickel removal and the quality of the underlying surface isthe pHi ofthe treatment solution(), When a single solution is employed the solution fn operate at a pl of about 2 to abort 12. An altemative pl range is about 2.3 1 about 50, oF about 2.5 to about 40, Alternatively the pl ofthe solution can be about 3.2. These pil ranges ae also contemplate foreach treatment solution, Jn embodiments in which more than one treatment solution is used, "The temperature at which the nickel deposit is contacted «ean also affect nickel removal and the quality of the underly ing surface. In one embodiment the nickel is contacted at a temperature between about Dan about 10°C. Alternatively, contacting ean occur between about 21 and about $5° Cor between about 38 and about 45°C. Alternatively, contacting can oecur at about 41°C. ‘The time of contacting also may affect nickel removal and the qulity ofthe underlying surface. In some embodiments the time of contacting can offer a large operating window. A \iring board (or other substrate) contacted for to 4 days ean show no significant attack on the underlying surface, Thus, the contemplated contact time ranges between about S and bout 600 minutes. Altematively, the nickel deposit can be ‘contacted with a treatment solution for a time sullicient to remove at least substantially all the nickel contacted by the solution, and short enough oleae the underlying substrateia condition for redepostion of nickel "The method describe herein can be carried ont by placing the nickel deposit in a bath ofthe treatment sofution, When using a bath the phosphate ions and oxidizer can be combined in an aqueous solution. The nickel deposit can then be immersed ino a bath of this aqueous solution. Inone embod ‘ment, ammonium ions can also beaded othe bath prior 19 jmmersion ofthe nickel deposit Tn certain embodiments the conltions are such that all or substantially all of the nickel deposit is removed and the underlying surface is bright, uniform and not significantly etched after the contacting step. This allows for e-working, Specifically, it allows anew layer of nickel or other metal to be deposited onto the surface. In other embodiments, as 10US 7,591,956 B2 5 partially etch niekel, leaving a nickel surfce, less than all of the nickel deposit can be removed. It may be desirable to remove less than all of the nickel in order to speed up the nickel removal process none embodiment the wiring board can be removed fom ‘contact with the treatment solution or solutions prior to removal of al or substantially all ofthe nickel, Without fim- iting the broadest scope of the invention to the following ‘explanation, the inventors theorize thatthe nickel stripping process is two stage dissolution. First the nickel reacts with the stripping solution to form nickel oxide. The nickel oxide then resets to form Ni? Since the Ni is extremely soluble ‘teanthenbe rinsed of: inthis embodiment, the wiring board (or other substrate removed from the treatment solution or solutions after most of the nick has been removed and only 4 small amount of nickel oxide remains, At this pont, the nickel oxide ean typically be rubbed off with light pressure, such a fom finger, Persons knowledgeable in the ld will know when mostof the nickel has been removed such that ‘oly a small amount of nickel oxide remains. fle removal the board goes though a miero-etching process, During the micro-etehing the wiring boar (or other substrate) is con- tacted with standard ciching solution, A micro-ctching pro- ‘cess Known inthe printed wiring board field can be used. A few examples include a peroxide'sulfurie method, a cupric chloride method, a persulfate method, a carboxylic acid method and antec acid method. This process speeds up the nickel removal process by removing the bostd from contact ‘withthe treatment solution affer a shorter contacting period, 1 also results in a brighter underlying surface because it removes insoluble blue crystal rescue that remains alter the cantaet with the treatment solution or solutions ‘Where all or substantially all of the nickel is removed, the printed wiring board can still be put through a micro-tching process as outlined above. This will remove at leat some of the insoluble blue erystal that remains alter the contact with the treatment solution or stations. ‘One embodiment relates to an aqueous solution. The sole tion s made up of phosphate ion and an oxidizing agent and ‘can be employed atthe same temperature, pl and eoncenta- tion levels. previously described, Possible oxidizing agents include peroxides (such as hydrogen peroxide), persllates, nitric acid or other oxidizers capable of oxidizing nickel metal, Contemplated sources of phosphate ions include ‘ammosium phosphate monobasic’ or sodium phosphate monobasic, which ean be formed by combining ammonium ‘chloride or trisodium phosphate with phosphoric acid, Other ‘contemplated sources of phosphate ions include ammonium phosphate dibasic, ammonium phosphate tribasic, potassinm Phosphate monobasic, potassium phosphate dibasic, potas- sium phosphate tribasic, phosphoric acid, or other soluble Phosphate salts. Other combination ot chemicals providing the recited ions in solution or dispersion are also conten- plated, "Ammonium ions can also beaded tothe aqueous solution, Possible sources of ammonium ions inckide ammonium phosphate monobasic, ammonium phosphate dibasic, ammo- rium phosphate tribasic, ammonium hydroxide, ammonium chloride, mmoninm carbonate, ammonium sulfate of other solubleammoniunsals.The ammonium ions are sometimes ‘added in conjunction withthe phosphate ions as with the ‘ammonium phosphates, “The current aqueous soltion can effectively strip nickel fom a printed wiring board or other substrate ws described ‘hove. The conditions (that is temperature, pl, concentra tion, ete.) described above are also applicabic to the aqueous solution When used to strip nickel. The eorreet pH and salt 0 o 6 shosphate ion concentration ean also be obisined by mixing Phosphoric acid with a base such as sodium hydroxide, ‘ammonium hydroxide or potasium hydroxide ‘The current solution is also an effective substrate pro- treatment, Inthe printed wiring board industry the subseate undergoes processing prior 10 application of nickel in the [ENIG process. This processing can include processes that ‘make the substrate surface dll and uneven, such as pulse plating and application ofthe soldermask. When the under- Jing substrates dll and uneven, there ia greater likelihood of problems with the nickel application during the ENIG process TInthese situations the current scfutioncan be applied othe substrate prior to application ofthe nickel. This is eontem- plated to avoid a need to strip the nickel at a later point. When Using the cureat solution as a substrate pre-treatment the conditions and variations described above can be used (lor ‘example temperature, pH, concentration, etc). However, the contacting time ean be from about 1 to about 60 minutes or altematively about { to about 15 minutes. ‘The agus solution is also an effective permanganate neutralizer. During the printed wiring board manufacturing process, holes are drilled through the board far interconnce- tions between inner and outer layers. The holes are thea cleaned using pemanganate baths in a process called des- ‘mearing. Aer desmearing, the permanganate residues the ‘board must be neutralized. Traditional neutralizer are either expensive ike hydroxyl amine sulfate, or they tend to etch too mach copper and dull the surface of the copper, like sulfrieaeid/peroxide mixtures. "The current soltion improvesthe appearance ofthe copper ‘while simultaneously neutralizing the permanganate residues left after desmearing the holes, When the current soliton is used to neutralize permanganate, the various conditions and ‘composition variations discussed above are applicable. Flow ever, thecontaeting time can beabout 10 seconds to about 100 ‘minutes of altematvely about 10 seconds to about 10 min- utes, Theoxidizer coneentrationcan be abent 10 about 10% by weight of oxidizer, or alternatively shout 2 to about 4Y6by ‘weight of oxidizer. ‘One embodiment of the aqueous solution for stripping nickel is made up of about 1% to about 10% by weight of hydrogen peroxide and from sbout $% to about 30% by ‘Weight ofan ammonium phosphate. The aqueous solution of {his embodiment ea be employed atthe same temperature, pH and concentration levels as previously described. EXAMPLE 1 none non-limiting embodiment a bath at pl 3.2 contain we 250 g/L ammonium dihydrogen phosphate and 25 lnydrogen peroxide, is prepared. printed wiring board including & copper eircit race with an electroless nickel depositapplied aoeording to te fest part of an ENIG process is contacted with the bath by immersing it for 90 minutes at arc After being contacted with the bath, the nickel is found 10 be selectively removed from the printed wiring board. The copper remains bright aod not significantly etched. The cop- per surface is ready for e-working. EXAMPLE2 In another non-limiting embodiment a bath as deseribed in Example [is prepared. The copper substrate with an electro- Jess nickel deposit applied according to the frst part of an [ENIG process contacted with the bath for 304 days at 41° ©.US 7,591,956 B2 7 Affe being contacted with the bath, the nickel is found ro be selectively removed from the printed wiring board. The ‘copper remains bright andl not significantly etched. The cop= per surface is ready for re-working. EXAMPLES Insnother non-limiting embodiment bath as describe in Example | is prepared. The copper substrate is copper foil ‘with an electroless nickel deposit applied according to the first part of an ENIG process. The copper fil is contacted ‘withthe ath for 90 minites at 41° C. ‘After being contacted with the bath, the nickel is found 10 be selectively removed from the printed wiring boand. The ‘copper remains bright and not significantly etched. The cop= per surface is ready for re-working EXAMPLES In one non-timiting embodiment a bath at pH13.9 contain ing 25 g/L ammonium dlsydrogen phosphate, 200 g/L. potas- sium phosphate and 4% by weight of peroxide is prepared. A Printed wiring board including s copper circuit trace witha ‘elecioless nickel deposit applied according tothe fist part of fan ENIG process is contacted withthe bath by immersing it ‘overnight at 41°C, ‘After being contacted with the bath, the nickel is found to be selectively removed from the printed wiring board. The ‘copper remains bright andl not significantly etched. The cop= per surface is ready for re-working, EXAMPLES none non-limiting embodiment a bath at pH3.84 contain ing 50 g/L ammonium dltydrogen phosphate, 200 g/L. potas- sum phosphate and 4% by weight of peroxide, is prepared. Printed wiring board including s copper cireit trace with an ‘electroless nickel deposit applied according to the first partof fn ENIG process is contacted withthe bath by immersing it ‘ovemight at 41°C. ‘Afler being contacted with the bath, the nickel is found 10 be selectively removed ffom the printed wiring board. The ‘copper remains bright andl not significantly etched. The cop= per surface is ready for re-working. EXAMPLE6 none non-limiting embodiment a bath at pH 3.77 contain= ing 100 g/1. ammonium dihydrogen phosphate, 100 gi Polassiu phosphate and 4% by weight of peroide, is pre- pared. A printed wiring board including « copper circuit ace with an electroless nickel deposit applicd according to the fist part of an ENIG process is contacted with the bath by immersing i overnight at 41°C. ‘After being contacted with the bath, the nickel is found to be selectively removed from the printed wiring board. The ‘copper remains bright and not significantly etched. The cop= per surface is ready for re-working. EXAMPLET Inone non-limiting embodiment a bath at pH3.77 contain- ing 100 g/l. ammonium dihydrogen phosphate, 200 g/l potassium phosphate and 4% by weight of peroxide, is pre- pared, A printed wiring board inchiding a copper circuit trace with an electroless nickel deposit applied acconting to the 0 o 8 first part of an ENIG process is contacted Jmmersing it overnight at 41°C. After being contacted with the hath the nickel is found to be selectively removed from the printed wiring board. The copper remains bright aod not significantly etched. The eop- per surface is ready for re-working. the bath by EXAMPLE 8. Inonenon-limiting embodiment a bath at pH13.2S eontain- ing 50 g/- ammonium dihydrogen phosphate, 200 g/L. potss- sium phosphate and 4% by weight of peroxide, is prepared. A Printed wiring board including w copper circuit ince with an electroless nickel deposit applied according othe first part of ‘an ENIG process is contoeted with the bath by immersing it ‘overnight a 41°C. ‘After being contacted with de bath the nickel is found to be selectively removed from the printed wiring board. The copper remains bright and not significantly etched, The cop- per surface is ready for re-working. EXAMPLE 9 Inonenoa-timiting embodiment a bath at pH13.2S contain ing 100 g/L. ammonium dihydrogen phosphate, 100 g/. potassium phosphate and 49% by weight of peroxide, is pre- pared. A printed wiring board inching a copper eiruit trace ‘with an electroless nickel deposit applied according to the fist part of an ENIG process is contacted with the bath by immersing it overnight at 41°C. ‘After being contacted with the hath, the nickel is found to be selectively removed from the printed wiring board. The copper remains bright aod not significantly etched. The cop- per surface is ready for e-working. EXAMPLE 10 Inonenos-limiting embodiment a bath a pH13.25 contain. ing 100 gL ammonium dihydrogen phosphate, 200 g/l. potassium phosphate and 4% by weight of peroxide, is pre- ‘pared. A printed wiring board including « copper eieuit race ‘with an electroless nickel deposit applied according to the fist part of an ENIG process is eontacted with the bath by ‘immersing i overnight at 41°C. ‘After being contacted with de bath, the nickel is found 10 be sclectively removed fom the printed wiring board. The copper remains bright and not significantly etched. The eop- pet surface is ready for re-working. EXAMPLE 11 none non-limiting embodiment a bath at pH 3.2 contain ing 250 g/l. ammonium dihydrogen phosphate and 25 g/. hydrogen peroxide is prepared. A copper substrate is eon- ‘acted with the bath by immersing it for 15 minutes at 41°C. ‘After being contacted with the bath, the copper is bright ‘and not sigilicantly etched, Electroless nickel is then depos- ited on the copper surface according t0 the fst part of an ENIG process. EXAMPLE 12 none non-limiting embodiment a bath at pH 3.2 contain ing 250 g/l. ammonium dihydrogen phosphate and 5% by ‘weight of hyemgen peroxide is prepared. A printed wiring ‘oar including a circuit trace having permanganate residuesUS 7,591,956 B2 fio immersing t for 5 minutes a 41°C. ‘Affer being contacted with the bath the permanganate is neutralized. The copper remsins bright and is not signifi ‘cantly etched, The panel snow: eady for through hole (andor micro via) metallization. ‘While particular elements, embodiments and applications ‘ofthe disclose inventions have heen shown and described, it ‘will be understood, of course, that the iaventions are not limited thereto since modification can be made by those skilled in the art without departing from the scope of the present disclosure particularly i ight ot the foregoing teach- ings, ‘What is claimed is 1. A method of stripping nickel ftom a printed wiring board, comprising: providing a printed wiring board comprising @ nickel ‘deposit om 8 copper surface: ad contetng the nickel deposit with phosphate ions, and an oxidizer, ‘wherein said contacting step occurs at pH between about 23 and about 50 and tinder conditions effective to ‘remove at least a portion of the nickel deposit from the copper surface without damaging a sokdermask on the ‘printed Wiring board, 2. The method of claim 1 wherein said copper sutiee is bright after sad contacting step, 3. The method of elsim 1 wherein said copper surface is uniform after said contacting step. 4. The method of elaim 1 wherein said copper surface is ready for re-working after stid contacting step. 'S. The method of claim 1 wherein said nickel deposit ‘comprises electroless nickel 6. The method of claim 1 further comprising subsequently “depositing nickel on said eopper surface, 7. Themethod of claim | wherein std copper surfaceisnot significantly etched after sai contacting step, 8. The method of claim 1 further comprising contacting sai nickel deposit with ammonium ions 9, The method of claim 1 witercin said phosphate ions are provided in an aqueous solution ata concentration of at least about 10 gL. 10, The method of claim 1 wherein suid oxidizer is pro- vided in an aqueous solution ata concentration of about 1510 about 100 a acted with the bath by 10 11, The method of claim 1 wherein said contacting step ‘occurs at temperature between about O and about 100! C. 12, The method of claim 1 wherein the duration of said ccnteting step is fom about 5 to about 600 mines 13. The method of claim 1 wherein said phosphate ions, and oxidizer are provided in the form ofa single solution, 14. The method of elaim 1 wherein said contacting step is carried out by forming a bath of phosphate ions and peroxide ‘in aqueous sofution and immersing said nickel deposit in said bath 15, The method of claim 1 wherein said conditions are effective to remove substantially all of said nickel deposit {rom at least portion of said copper surface 16, The method claim oF 15 further comprising contacting said copper surface with an etching solution, 17. Themethodof claim 1 wherein said oxidizer is selected from the group consisting of peroxides, persulates and nitric acid. 18, A method of pre-ceating a copper substrate compris- ing: Providing prin wring ad compsing onrerh- ‘cantocting the copper substrate with phosphate fons, and anoxidizer, ‘wherein said contacting step occurs at a pH between about 23 and about 5.0 and under conditions effective to brighten the copper substrate without damaging a sol- ‘dermask on the printed wiring board, 19, The method of claim 18 further comprising contacting sid copper substrate with ammonium ions, 20. A method of neutralizing permanganate on a printed wiring board comprising: providing # printed wiring board with a pera ‘residue onthe printed wiring board; and contacting the penmanganate residue with phosphate fons, and anoxidizer, ‘wherein sid contacting step occurs at a pl hetween about 2:3 and about $0 and under conditions effective to net tralize the permanganate without damaging « solder: mask on the printed witing hoard 21, The method of claim 20 funkier comprising contacting sid permanganate residve with ammonium ions ngamateUNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION PATENT NO. 7,591,956 B2 Page I of 1 APPLICATION NO. : 11/416729 DATED September 22, 2009 INVENTOR(S) Bemards etal. It is cotitied that error appears in the above-identiied patent and that said Letters Patent is hereby corrected as shown below: On the Title Page: ‘The first or sole Notice should read — Subject to any disclaimer, the term of this patent is extended or adjusted under 35 U.S.C. 154(b) by 318 days. Signed and Sealed this ‘Twenty-first Day of September, 2010 Lewd D: Cappes David J. Kappos Director ofthe United States Patent and Trademark Offce