DE4111559C1 - Currentless bath for chemical deposition of copper@ (alloy) - contains polyethyleneimine deriv. and is formaldehyde-free - Google Patents
Currentless bath for chemical deposition of copper@ (alloy) - contains polyethyleneimine deriv. and is formaldehyde-freeInfo
- Publication number
- DE4111559C1 DE4111559C1 DE19914111559 DE4111559A DE4111559C1 DE 4111559 C1 DE4111559 C1 DE 4111559C1 DE 19914111559 DE19914111559 DE 19914111559 DE 4111559 A DE4111559 A DE 4111559A DE 4111559 C1 DE4111559 C1 DE 4111559C1
- Authority
- DE
- Germany
- Prior art keywords
- copper
- bath
- free
- formaldehyde
- chemical deposition
- 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.)
- Expired - Lifetime
Links
- 229920002873 Polyethylenimine Polymers 0.000 title claims abstract description 10
- 238000005234 chemical deposition Methods 0.000 title claims abstract description 5
- 229910052802 copper Inorganic materials 0.000 title claims description 19
- 239000000956 alloy Substances 0.000 title abstract 2
- 229910045601 alloy Inorganic materials 0.000 title abstract 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims abstract description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims abstract description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 19
- 239000010949 copper Substances 0.000 claims description 19
- 239000004615 ingredient Substances 0.000 claims description 9
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 239000003638 chemical reducing agent Substances 0.000 abstract description 5
- 238000000576 coating method Methods 0.000 abstract description 5
- 230000007935 neutral effect Effects 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract 1
- 238000010979 pH adjustment Methods 0.000 description 13
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 11
- 229910052708 sodium Inorganic materials 0.000 description 11
- 239000011734 sodium Substances 0.000 description 11
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 10
- 238000000151 deposition Methods 0.000 description 10
- 230000008021 deposition Effects 0.000 description 10
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 7
- 239000004327 boric acid Substances 0.000 description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000008139 complexing agent Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 3
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 3
- 239000001488 sodium phosphate Substances 0.000 description 3
- 229910000162 sodium phosphate Inorganic materials 0.000 description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 3
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- HFDWIMBEIXDNQS-UHFFFAOYSA-L copper;diformate Chemical compound [Cu+2].[O-]C=O.[O-]C=O HFDWIMBEIXDNQS-UHFFFAOYSA-L 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- -1 for example Chemical class 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- WSANZYFPFILJKZ-UHFFFAOYSA-N 1-[2-[bis(2-hydroxypentyl)amino]ethyl-(2-hydroxypentyl)amino]pentan-2-ol Chemical compound CCCC(O)CN(CC(O)CCC)CCN(CC(O)CCC)CC(O)CCC WSANZYFPFILJKZ-UHFFFAOYSA-N 0.000 description 1
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- AQQVTZBWWYVEGR-UHFFFAOYSA-N [NH4+].[O-][PH2]=O Chemical compound [NH4+].[O-][PH2]=O AQQVTZBWWYVEGR-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 229910002065 alloy metal Inorganic materials 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- UORVGPXVDQYIDP-BJUDXGSMSA-N borane Chemical class [10BH3] UORVGPXVDQYIDP-BJUDXGSMSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-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
- HUQOFZLCQISTTJ-UHFFFAOYSA-N diethylaminoboron Chemical compound CCN([B])CC HUQOFZLCQISTTJ-UHFFFAOYSA-N 0.000 description 1
- YPTUAQWMBNZZRN-UHFFFAOYSA-N dimethylaminoboron Chemical compound [B]N(C)C YPTUAQWMBNZZRN-UHFFFAOYSA-N 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- PQTCMBYFWMFIGM-UHFFFAOYSA-N gold silver Chemical compound [Ag].[Au] PQTCMBYFWMFIGM-UHFFFAOYSA-N 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- NPFOYSMITVOQOS-UHFFFAOYSA-K iron(III) citrate Chemical compound [Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NPFOYSMITVOQOS-UHFFFAOYSA-K 0.000 description 1
- FEWJPZIEWOKRBE-LWMBPPNESA-N levotartaric acid Chemical compound OC(=O)[C@@H](O)[C@H](O)C(O)=O FEWJPZIEWOKRBE-LWMBPPNESA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- SDWBRBLWPQDUQP-UHFFFAOYSA-N n-boranyl-n-methylmethanamine Chemical compound BN(C)C SDWBRBLWPQDUQP-UHFFFAOYSA-N 0.000 description 1
- KERBAAIBDHEFDD-UHFFFAOYSA-N n-ethylformamide Chemical compound CCNC=O KERBAAIBDHEFDD-UHFFFAOYSA-N 0.000 description 1
- ATHHXGZTWNVVOU-VQEHIDDOSA-N n-methylformamide Chemical group CN[13CH]=O ATHHXGZTWNVVOU-VQEHIDDOSA-N 0.000 description 1
- IYRGXJIJGHOCFS-UHFFFAOYSA-N neocuproine Chemical compound C1=C(C)N=C2C3=NC(C)=CC=C3C=CC2=C1 IYRGXJIJGHOCFS-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- SIGUVTURIMRFDD-UHFFFAOYSA-M sodium dioxidophosphanium Chemical compound [Na+].[O-][PH2]=O SIGUVTURIMRFDD-UHFFFAOYSA-M 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- YPPQYORGOMWNMX-UHFFFAOYSA-L sodium phosphonate pentahydrate Chemical compound [Na+].[Na+].[O-]P([O-])=O YPPQYORGOMWNMX-UHFFFAOYSA-L 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
- C23C18/40—Coating with copper using reducing agents
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
Description
Die Erfindung betrifft ein Verfahren von Polyethyleniminen als Inhaltsstoffe in Bäder zur chemischen Abscheidung von Kupfer.The invention relates to a method of polyethyleneimines as ingredients in baths for chemical deposition of copper.
Aus dem Stand der Technik sind bereits formaldehydfreie Bäder zur stromlosen Abscheidung von Kupfer bekannt, die stickstoffhaltige Badinhaltsstoffe enthalten. Als stickstoffhaltige Badinhaltsstoffe solcher Bäder werden EDTP oder EDTA (US-PS 46 17 205), Triethylendiamin (US-PS 41 43 186) und Polyalkylenpolyamine (US-PS 37 93 038) bereits beschrieben.Formaldehyde-free baths for electroless deposition are already known from the prior art of copper containing nitrogen-containing bath ingredients. As nitrogenous Bath ingredients of such baths are EDTP or EDTA (US-PS 46 17 205), Triethylenediamine (US-PS 41 43 186) and polyalkylenepolyamines (US-PS 37 93 038) already described.
Das Betreiben dieser Bäder ist ausgesprochen aufwendig, da ein großer Überwachungsaufwand aufgewendet werden muß. Teilweise müssen bis zu 4 Regenerierlösungen verwendet werden, um beim Einhalten der Sollwerte der Badinhaltsstoffe zu einer befriedigenden Kupferabscheidung zu gelangen.The operation of these baths is extremely complicated, since a large monitoring effort must be spent. In some cases, up to 4 replenishment solutions must be used in order to keep the target values of the bath ingredients to a satisfactory level Copper deposition to arrive.
Festgestellt werden kann, daß sich aus dem Stand der Technik für die bisher bekannten stromlosen formaldehydfreien Kupferbäder die folgenden Nachteile zeigen:It can be determined that from the prior art for the previously known electroless formaldehyde-free copper baths show the following disadvantages:
- a) stark alkalische Bäder,a) strongly alkaline baths,
- b) zu verbessernde Qualität der Kupferüberzüge undb) to improve the quality of the copper coatings and
- c) hoher Überwachungsaufwand der Bäder.c) high monitoring effort of the baths.
Die vorliegende Erfindung beinhaltet die Aufgabe, ein formalinfreies, stromloses, überwachungsarmes Bad zur Abscheidung von Kupfer oder Kupferlegierung unter Einsatz eines umweltfreundlicheren Reduktionsmittels, im sauren oder neutralen Bereich arbeitet und unter Erhalt von Kupferüberzügen mit verbesserter Qualität, bereitzustellen.The present invention has the object of providing a formaline-free, electroless, low-maintenance bath for the deposition of copper or copper alloy with use a more environmentally friendly reducing agent, working in the acidic or neutral range and to obtain copper coatings of improved quality.
Diese Aufgabe wird durch das erfindungsgemäße Bad, gemäß Patentansprüchen, unter Verwendung von Polyethyleniminen der allgemeinen Formel IThis object is achieved by the bath according to the invention, according to claims, under Use of polyethyleneimines of the general formula I
H₂N-[(CH₂)n-NH]xH (I)H₂N - [(CH₂) n -NH] x H (I)
in der n=2, 3, 4; vorzugsweise für n=2, und x eine positive Zahl ist, vorzugsweise für X=30-1.500 steht, oder leiten sich von diesen ab; und besonders unter Verwendung von Polyethyleniminen der allgemeinen Formel IIin the n = 2, 3, 4; preferably for n = 2, and x is a positive number, preferably for X = 30-1,500 stands or derives from them; and especially using Polyethyleneimines of the general formula II
Y₂N-[(CH₂)n-N-Q]x-Z (II)Y₂N - [(CH₂) n -NQ] x -Z (II)
worin n und x die o. g. Bedeutung haben und
Y, Q und Z=Wasserstoff, Methyl, Ethyl, Propyl und/oder Butyl bedeuten, gelöst.where n and x have the above meaning and
Y, Q and Z = hydrogen, methyl, ethyl, propyl and / or butyl, dissolved.
Die Polyethylenimine oder deren Derivate (z. B. bekannt aus der DE-OS 37 43 744, US-PS 41 21 982) zeigen sich überraschenderweise als sehr gute Komplexbildner im sauren, neutralen und alkalischen Bereich. Es lassen sich damit alle bekannten Reduktionsmittel, die allgemein zur stromlosen Abscheidung geeignet sind, zur Abscheidung von Kupfer verwenden. Dabei erfolgt die Reduktion von Kupfer-(II)-ionen zum Kupfermetall.The polyethyleneimines or their derivatives (for example, known from DE-OS 37 43 744, US-PS 41 21 982) are surprisingly found to be very good complexing agents in the acidic, neutral and alkaline range. It can thus be all known reducing agents, the generally suitable for electroless deposition, use for the deposition of copper. The reduction of copper (II) ions to copper metal.
Polyethylenimine sind bekannte großtechnische Produkte; innerhalb der Galvanotechnik haben diese bereits als Glanzbildner bei der Abscheidung Gold-Silber Bedeutung erlangt (DE-OS 24 13 736); ebenso bei der galvanischen Zinkabscheidung.Polyethyleneimines are well known large scale products; within the electroplating industry these already acquired significance as brighteners in the gold-silver deposition (DE-OS 24 13 736); also in the galvanic zinc deposition.
Die Polyethylenimine sind keine einheitlichen Verbindungen, sondern es liegen Gemische mit den unterschiedlichsten Molekulargewichten vor. Erhalten werden diese Gemische durch Polymerisation von Aziridin. Festzustellen ist, daß sowohl die niedermolekularen, als auch die hochmolekularen, die linearen oder die verzweigten, die primären, sekundären oder tertiären Typen allein oder im Gemisch mit anderen Komplexbildnern anderer Klassen zur reduktiven Kupferabscheidung verwendet werden können.The polyethyleneimines are not uniform compounds, but there are mixtures with the most different molecular weights. These mixtures are obtained by Polymerization of aziridine. It should be noted that both the low molecular weight, as well the high molecular weight, the linear or the branched, the primary, secondary or tertiary types alone or in admixture with other complexing agents of other classes reductive copper deposition can be used.
Die Anwendung der erfindungsgemäßen Bäder ist auch für die Abscheidung von Kupferlegierungen möglich. Als Gemische von Metallsalzen können beispielsweise Sulfate, Nitrate, Oxide, Hydroxide, Carbonate oder Acetate der Metalle Kupfer, Nickel, Cobalt, Eisen oder Mangan verwendet werden. Diese metallischen Verbindungen bilden mit den erfindungsgemäßen Komplexbildnern Komplexverbindungen, die sich zur Abscheidung von Kupfer oder Kupferlegierungen eignen. The application of the baths according to the invention is also for the separation of Copper alloys possible. As mixtures of metal salts, for example, sulfates, Nitrates, oxides, hydroxides, carbonates or acetates of the metals copper, nickel, cobalt, iron or manganese can be used. These metallic compounds form with the complexing agents according to the invention complex compounds which are used for the deposition of Copper or copper alloys are suitable.
Als Reduktionsmittel finden in den erfindungsgemäßen Bädern beispielsweise Diethylaminoboran, Dimethylaminoboran, Natriumborhydrid, Ammoniumphosphinat, Natriumphosphinat, Phosphinsäure oder Hydrazin Anwendung. Vorzugsweise wird die Phosphinsäure oder ihre Salze zur Abscheidung verwendet. Das Aufbringen dicker Kupferschichten gelingt hier, ohne eine Passivierung oder Instabilität der verwendeten Bäder festzustellen. Als Reduktionsmittel kann auch die Methansäure oder deren Salze oder deren Derivate verwendet werden. Als geeignete Methansäurederivate sind beispielsweise zu nennen der Methyl- oder Ethylester, das N-Methyl oder Ethylformamid, das N,N-Dimethyl- und N,N- Diethylformamid, Ethylen- und Propylenkarbonat.As a reducing agent find in the baths according to the invention, for example Diethylaminoborane, dimethylaminoborane, sodium borohydride, ammonium phosphinate, Sodium phosphinate, phosphinic acid or hydrazine application. Preferably, the Phosphinic acid or its salts used for deposition. The application of thicker Copper layers succeed here without a passivation or instability of the baths used determine. As a reducing agent and the methanoic acid or its salts or their Derivatives are used. As suitable methanoic acid derivatives are mentioned, for example the methyl or ethyl ester, N-methyl or ethylformamide, N, N-dimethyl and N, N- Diethylformamide, ethylene and propylene carbonate.
Badzusätze beispielsweise von Nickel, Cobalt, Eisen oder Mangan dienen als echte Legierungsmetalle und destabilisieren nicht das reduktive Kupferbad. Bei einer Verwendung von Phosphinsäure oder deren Salzen und einer Verwendung von Borwasserstoffverbindungen werden auch Phosphor und Bor als Legierungsbestandteile in das System eingebaut. Damit vergrößert sich vorteilhaft das Anwendungsgebiet der abgeschiedenen Kupferlegierungen.Bath additives such as nickel, cobalt, iron or manganese serve as real Alloy metals and do not destabilize the reductive copper bath. When used of phosphinic acid or its salts and use of borane compounds Also, phosphorus and boron are incorporated as alloying ingredients in the system. In order to Advantageously, the field of application of the deposited copper alloys increases.
Als Puffersubstanzen können die in der Galvanotechnik üblichen Verbindungen verwendet werden.As buffer substances, the compounds customary in electroplating can be used become.
Eine Verbesserung der Qualität der Kupferüberzüge kann erreicht werden, wenn die erfindungsgemäßen Bäder Tenside und gegebenenfalls weitere, bekannte Zusätze enthalten.An improvement in the quality of the copper coatings can be achieved if the Baths according to the invention contain surfactants and optionally other known additives.
Mit dem erfindungsgemäß beschriebenen, formalinfreien Kupferbad lassen sich reine duktile Kupferüberzüge nach einem äußerst wirtschaftlichen und umweltfreundlichen Verfahren herstellen. With the formalin-free copper bath according to the invention can be pure ductile Copper coatings after a very economical and environmentally friendly process produce.
Die folgenden Beispiele sollen die Erfindung erläutern:The following examples are intended to illustrate the invention:
Quadrol® = N,N,N′,N′-Tetrakis-(2-hydroxyptopyl)-ethylendiamin.
Polyimin = Handelsname der Fa. Bayer für Verbindungen der
allgemeinen Formeln I und II.
Golpanol = Handelsname der Fa. BASF für Verbindungen der
allgemeinen Formeln I und II.Quadrol® = N, N, N ', N'-tetrakis- (2-hydroxy-pentyl) -ethylenediamine.
Polyimine = trade name of Bayer for compounds of general formulas I and II.
Golpanol = trade name of BASF for compounds of general formulas I and II.
Claims (2)
n=2, 3, 4 und
x=30-1.500
bedeuten
als Inhaltsstoff oder Inhaltsstoffe in wäßrigen, formaldehydfreien Bädern zur chemischen Abscheidung von Kupfer oder Kupferlegierung.1. Use of polyethyleneimines of the general formula I H₂N - [(CH₂) n -NH] x H (I) in the
n = 2, 3, 4 and
x = 30-1500
mean
as an ingredient or ingredients in aqueous, formaldehyde-free baths for chemical deposition of copper or copper alloy.
n=2, 3, 4
x=30-1.500 und
Y, Q und Z=Wasserstoff, Methyl, Ethyl, Propyl und/oder Butyl
bedeuten,
als Inhaltsstoff oder Inhaltsstoffe in wäßrigen, formaldehydfreien Bädern zur chemischen Abscheidung von Kupfer oder Kupferlegierung.2. Use of polyethyleneimines of the general formula II Y₂N - [(CH₂) n -NQ] x Z (II) in the
n = 2, 3, 4
x = 30-1,500 and
Y, Q and Z = hydrogen, methyl, ethyl, propyl and / or butyl
mean,
as an ingredient or ingredients in aqueous, formaldehyde-free baths for chemical deposition of copper or copper alloy.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19914111559 DE4111559C1 (en) | 1991-04-05 | 1991-04-05 | Currentless bath for chemical deposition of copper@ (alloy) - contains polyethyleneimine deriv. and is formaldehyde-free |
| PCT/DE1992/000284 WO1992017624A1 (en) | 1991-04-05 | 1992-04-06 | Formaldehyde-free bath for the currentless deposition of copper, process and the use of polyethylene imines in formaldehyde-free baths |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19914111559 DE4111559C1 (en) | 1991-04-05 | 1991-04-05 | Currentless bath for chemical deposition of copper@ (alloy) - contains polyethyleneimine deriv. and is formaldehyde-free |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE4111559C1 true DE4111559C1 (en) | 1992-04-30 |
Family
ID=6429198
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19914111559 Expired - Lifetime DE4111559C1 (en) | 1991-04-05 | 1991-04-05 | Currentless bath for chemical deposition of copper@ (alloy) - contains polyethyleneimine deriv. and is formaldehyde-free |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE4111559C1 (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3793038A (en) * | 1973-01-02 | 1974-02-19 | Crown City Plating Co | Process for electroless plating |
| DE2413736A1 (en) * | 1973-03-26 | 1974-10-10 | Technic | ELECTROLYTE BATH AND METHOD FOR GALVANIC DEPOSITION OF GOLD AND GOLD ALLOYS |
| US4121982A (en) * | 1978-02-03 | 1978-10-24 | American Chemical & Refining Company Incorporated | Gold alloy plating bath and method |
| US4143186A (en) * | 1976-09-20 | 1979-03-06 | Amp Incorporated | Process for electroless copper deposition from an acidic bath |
| US4617205A (en) * | 1984-12-21 | 1986-10-14 | Omi International Corporation | Formaldehyde-free autocatalytic electroless copper plating |
| US4695505A (en) * | 1985-10-25 | 1987-09-22 | Shipley Company Inc. | Ductile electroless copper |
| DE3743744A1 (en) * | 1987-12-23 | 1989-07-06 | Basf Ag | Polymeric conditioning agents for the pretreatment of nonmetallic surfaces for a chemical metallization |
-
1991
- 1991-04-05 DE DE19914111559 patent/DE4111559C1/en not_active Expired - Lifetime
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3793038A (en) * | 1973-01-02 | 1974-02-19 | Crown City Plating Co | Process for electroless plating |
| DE2413736A1 (en) * | 1973-03-26 | 1974-10-10 | Technic | ELECTROLYTE BATH AND METHOD FOR GALVANIC DEPOSITION OF GOLD AND GOLD ALLOYS |
| US4143186A (en) * | 1976-09-20 | 1979-03-06 | Amp Incorporated | Process for electroless copper deposition from an acidic bath |
| US4121982A (en) * | 1978-02-03 | 1978-10-24 | American Chemical & Refining Company Incorporated | Gold alloy plating bath and method |
| US4617205A (en) * | 1984-12-21 | 1986-10-14 | Omi International Corporation | Formaldehyde-free autocatalytic electroless copper plating |
| US4695505A (en) * | 1985-10-25 | 1987-09-22 | Shipley Company Inc. | Ductile electroless copper |
| DE3743744A1 (en) * | 1987-12-23 | 1989-07-06 | Basf Ag | Polymeric conditioning agents for the pretreatment of nonmetallic surfaces for a chemical metallization |
Non-Patent Citations (1)
| Title |
|---|
| DE-Z: Galvanotechnik 80(1989), S. 406 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP1114206B1 (en) | Cyanide-free aqueous alkaline bath used for the galvanic application of zinc or zinc-alloy coatings | |
| DE19538419C2 (en) | Use of a bath-soluble polymer in an aqueous alkaline bath for the galvanic deposition of zinc and zinc alloys | |
| DE2920766C2 (en) | ||
| DE4202409C2 (en) | Use of an additive for a zincate bath | |
| DE4105272C2 (en) | ||
| DE112016000145T5 (en) | Electrodeposition process, electrodeposition bath and process for producing a rare earth permanent magnet material by electrodeposition | |
| DE2845439A1 (en) | PROCESS FOR STABILIZING GALVANIC BAEDER IN THE PRODUCTION OF COATING FROM TIN OR TIN ALLOYS | |
| DE2049061A1 (en) | Electroless deposition of ductile copper | |
| DE2730322A1 (en) | PREPARATION OF SOLUTIONS CONTAINING HEAVY METALS AND COMPLEX FORMERS | |
| EP0037535B1 (en) | Plating bath for depositing coatings of gold and gold alloys | |
| DE10052960C5 (en) | Lead-free nickel alloy | |
| DE4111559C1 (en) | Currentless bath for chemical deposition of copper@ (alloy) - contains polyethyleneimine deriv. and is formaldehyde-free | |
| DE3712511C3 (en) | Alkaline cyanide-free electroplating bath and use of this bath | |
| DE2334813C2 (en) | Bath for the electrolytic deposition of white gold alloys | |
| DE4428966C2 (en) | Process for depositing a white palladium metal coating | |
| EP2435600B1 (en) | Method for depositing a palladium layer suitable for wire bonding on conductors of a printed circuit board and palladium bath for use in said method | |
| DE3329958A1 (en) | A METHOD AND SOLUTION FOR DEFLECTED COPPER DEPOSITION ON A SUBSTRATE | |
| DE3319772C2 (en) | ||
| DE2352970A1 (en) | CORROSION-RESISTANT METAL COATINGS CONTAINING ELECTRICALLY DEPOSITED NICKEL AND MICROPOROUS CHROME | |
| DE3129129C2 (en) | ||
| EP0346740A1 (en) | Alcaline aqueous bath for the galvanic deposition of zinc-iron alloys | |
| DE1270920B (en) | Bath for dip tinning aluminum or aluminum alloys | |
| DE2023304C3 (en) | Cyanide-free electroplating bath | |
| DE2839360C2 (en) | Aqueous bath for the galvanic deposition of shiny coatings made of palladium or its alloys | |
| DE4111558C1 (en) | Formaldehyde-free bath for electroless deposition of copper - contains copper salt complexing agent, and formic acid (salts) or addn. prods. as reducing agent |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 8100 | Publication of the examined application without publication of unexamined application | ||
| D1 | Grant (no unexamined application published) patent law 81 | ||
| 8364 | No opposition during term of opposition | ||
| 8327 | Change in the person/name/address of the patent owner |
Owner name: ATOTECH DEUTSCHLAND GMBH, 10553 BERLIN, DE |
|
| 8339 | Ceased/non-payment of the annual fee |