US20050126919A1 - Plating method, plating apparatus and a method of forming fine circuit wiring - Google Patents
Plating method, plating apparatus and a method of forming fine circuit wiring Download PDFInfo
- Publication number
- US20050126919A1 US20050126919A1 US10/980,320 US98032004A US2005126919A1 US 20050126919 A1 US20050126919 A1 US 20050126919A1 US 98032004 A US98032004 A US 98032004A US 2005126919 A1 US2005126919 A1 US 2005126919A1
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- United States
- Prior art keywords
- plating
- leveler
- copper
- phosphorus
- plating solution
- Prior art date
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- Abandoned
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- 238000007747 plating Methods 0.000 title claims abstract description 235
- 238000000034 method Methods 0.000 title claims abstract description 36
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 105
- 229910052802 copper Inorganic materials 0.000 claims abstract description 104
- 239000010949 copper Substances 0.000 claims abstract description 104
- 239000000758 substrate Substances 0.000 claims abstract description 35
- 150000001875 compounds Chemical class 0.000 claims abstract description 21
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 20
- 230000000382 dechlorinating effect Effects 0.000 claims abstract description 14
- 238000009713 electroplating Methods 0.000 claims abstract description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 11
- 230000004888 barrier function Effects 0.000 claims abstract description 9
- -1 phosphorus compound Chemical class 0.000 claims description 52
- 239000000460 chlorine Substances 0.000 claims description 40
- 229910052801 chlorine Inorganic materials 0.000 claims description 39
- 229910052698 phosphorus Inorganic materials 0.000 claims description 23
- 239000011574 phosphorus Substances 0.000 claims description 23
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 21
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 16
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 14
- 239000000654 additive Substances 0.000 claims description 11
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 11
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 11
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 9
- 238000006298 dechlorination reaction Methods 0.000 claims description 4
- 239000000470 constituent Substances 0.000 claims description 3
- 238000005868 electrolysis reaction Methods 0.000 claims description 3
- 238000005259 measurement Methods 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 238000004062 sedimentation Methods 0.000 claims description 3
- 229910001392 phosphorus oxide Inorganic materials 0.000 claims description 2
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 claims 1
- 239000000243 solution Substances 0.000 description 98
- 235000012431 wafers Nutrition 0.000 description 38
- 239000010410 layer Substances 0.000 description 28
- 239000004065 semiconductor Substances 0.000 description 12
- 239000004094 surface-active agent Substances 0.000 description 11
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 9
- 238000010586 diagram Methods 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 6
- 238000000151 deposition Methods 0.000 description 6
- 230000008021 deposition Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 5
- 239000003637 basic solution Substances 0.000 description 5
- 229910001431 copper ion Inorganic materials 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920002717 polyvinylpyridine Polymers 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 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 3
- 238000004090 dissolution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000012086 standard solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 150000003840 hydrochlorides Chemical class 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000006259 organic additive Substances 0.000 description 2
- 238000010587 phase diagram Methods 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- LMPMFQXUJXPWSL-UHFFFAOYSA-N 3-(3-sulfopropyldisulfanyl)propane-1-sulfonic acid Chemical compound OS(=O)(=O)CCCSSCCCS(O)(=O)=O LMPMFQXUJXPWSL-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910017888 Cu—P Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001409 amidines Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- LUXYLEKXHLMESQ-UHFFFAOYSA-N iridium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ir+3].[Ir+3] LUXYLEKXHLMESQ-UHFFFAOYSA-N 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
- LFGREXWGYUGZLY-UHFFFAOYSA-N phosphoryl Chemical class [P]=O LFGREXWGYUGZLY-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920000083 poly(allylamine) Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/12—Process control or regulation
- C25D21/14—Controlled addition of electrolyte components
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/40—Forming printed elements for providing electric connections to or between printed circuits
- H05K3/42—Plated through-holes or plated via connections
- H05K3/423—Plated through-holes or plated via connections characterised by electroplating method
Definitions
- This invention relates to a copper plating method and more particularly to a copper plating method employing a dechlorinated leveler and the leveler and plating apparatus employed therefor.
- This invention relates also to a method of forming fine circuit wiring by plating on a substrate having a fine circuit pattern, such as a semiconductor or a printed wiring board, and particularly to a method of forming fine circuit wiring in which phosphorus-doped copper plating is relied upon for preventing the electromigration of the fine circuit wiring as formed, and a plating solution and a plating apparatus therefor.
- Aluminum or an aluminum alloy has hitherto been used as a material for forming a wiring circuit on a semiconductor wafer.
- An improved degree of integration has, however, created a demand for a material of higher electric conductivity. Copper has drawn attention as a material satisfying such a demand and has come to be used for plating a substrate.
- additives such as a surface active agent, an unsaturated organic compound and chlorine ions
- chlorine ions are necessary for assisting the dissolution of the anode and the action of a brightener ( Handbook of Plating , Society for the Study of Electroplating, The Nikkan Kogyo Shinbun, Ltd., page 76).
- the additives also include a leveler so called, since it is used for leveling the growth of a plating film, and a nitrogen-containing high molecular compound is usually used as the leveler.
- the nitrogen-containing high molecular compound is often supplied in the form of a hydrochloride as a tertiary or quaternary nitrogen salt and therefore, the leveler often contains chlorine ions.
- fine copper wiring is, for example, formed on a semiconductor wafer by forming first a wiring pattern by via or other holes and trenches and then plating the wafer with copper to fill the holes and trenches with the copper to thereby form copper wiring.
- Electromigration is likely to cause the formation of voids in copper wiring or its insulation and thereby exert a serious effect on electronic devices. Moreover, electromigration causes stress migration as a secondary phenomenon and is likely to increase the frequency of occurrence of the serious effect as stated above.
- a copper plating film forming copper wiring is required to have a high degree of electromigration resistance.
- the inventors of this invention have discovered that the chlorine ions incorporated in a plating film are not the chlorine ions added intentionally to a plating solution, but a small amount of chlorine ions which a leveler contains. This invention is based on our discovery.
- a method of copper plating using a leveler containing a nitrogen-containing high molecular compound wherein the leveler is dechlorinated prior to its use for plating.
- a leveler for copper plating containing a nitrogen-containing high molecular compound, the leveler having a chlorine ion content of 0.1 g or less per gram of nitrogen-containing high molecular compound.
- a plating apparatus comprising a tank for preparing a plating solution, a device for dechlorinating a leveler, a leveler supply station for supplying the dechlorinated leveler to the tank and a plating station.
- a plating apparatus for forming a metal film on a seed layer on a substrate surface by electroplating, the apparatus comprising a loading and unloading station, a substrate conveying device, a cleansing unit, a plating tank, a tank for preparing a plating solution and supplying it to the plating tank, a station for measuring the concentrations of additives, a device for dechlorinating a leveler and a leveler supply station for supplying the dechlorinated leveler to the plating solution, the concentration measuring station measuring the concentration of the leveler in the plating solution and in accordance with the result of the measurement, the leveler supply station adding the dechlorinated leveler to the plating solution.
- a method of forming fine circuit wiring comprising forming a circuit with a layer of phosphorus-doped copper plating on a substrate for an electronic circuit having a fine circuit pattern, a barrier layer and any necessary seed layer formed thereon.
- a phosphorus-doped copper plating solution containing 1 ⁇ 10 ⁇ 6 to 50% by weight of elemental phosphorus in the form of a phosphorus compound in a copper sulfate plating solution containing copper sulfate, sulfuric acid and chlorine ions.
- a plating apparatus having an anode plate and a substrate to be plated which are positioned opposite each other in a plating tank containing a phosphorus-doped copper plating solution for electroplating the surface of the substrate by supplying an electric current between the anode plate and the substrate from a power source, the apparatus having at least a device for supplying a solution containing a phosphorus compound as a device for supplying a constituent composing the plating solution.
- any copper plating method, leveler or plating apparatus makes it possible to reduce the amount of the chlorine ions incorporated in any copper plating film and thereby the possibility of corrosion and deterioration of any copper-plated wiring.
- the fine circuit wiring formed by phosphorus-doped copper in accordance with this invention has a higher level of electromigration resistance than that of any wiring formed by copper alone, allows an electric current to pass therethrough at a higher current density and therefore copes with a demand for finer and higher density circuit wiring.
- FIGS. 1A to 1 C are a series of sectional views showing an example of plating processes
- FIG. 2 is a diagram showing a plating apparatus embodying this invention
- FIG. 3 is a diagram showing a dechlorinating device and a raw leveler tank in the apparatus embodying this invention
- FIG. 4 is a diagram showing a plating station in the apparatus embodying this invention.
- FIG. 5 is a diagram showing another form of plating station
- FIGS. 6A to 6 D are a series of views showing the steps of a method embodying this invention.
- FIG. 7 is a phase diagram of copper and phosphorus.
- FIG. 8 is a diagram showing another form of plating apparatus embodying this invention.
- a leveler used in copper plating is usually employed for leveling the growth of a plating film and contains a nitrogen-containing high molecular compound.
- the nitrogen-containing high molecular compound used herein may be any high molecular compound containing a nitrogen element in its molecule, for example, poly(dialkylaminoethyl acrylate), poly(diallyl dimethyl ammonium), polyethyleneimine, polyvinyl pyridine, polyvinyl amidine, polyallylamine or polyaminesulfonic acid.
- the nitrogen-containing high molecular compound is used in the form of a hydrochloride as a tertiary or quaternary nitrogen salt so that its solubility in water may be improved. Accordingly, the leveler contains a nitrogen-containing high molecular compound and chlorine ions.
- the leveler is usually provided in the form of an aqueous solution containing, say, 5 to 20 g of nitrogen-containing high molecular compound and 3 to 10 g of chlorine ions per liter.
- the leveler is added to a plating solution to the extent that the plating solution usually contains 5 to 20 mg of nitrogen-containing high molecular compound per liter.
- the chlorine ions which the leveler contains are carried over into the plating solution and the plating solution usually contains several milligrams of chlorine ions per liter.
- chlorine ions are usually added in the amount of 40 to 80 mg per liter, as it is said that they are necessary for assisting the dissolution of the anode and the action of a brightener.
- the dechlorination of the leveler by sedimentation may, for example, be carried out by adding to it a substance forming a hardly soluble salt with chlorine ions, e.g. silver nitrate, as shown by expression I: AgNO 3 +Cl ⁇ ⁇ AgCl ⁇ +NO 3 ⁇ (I)
- the dechlorination by electrolysis may, for example, be carried out by removing chlorine gas at the anode, as shown by expression II: 2Cl ⁇ ⁇ Cl 2 ⁇ +2e ⁇ (II)
- the dechlorinated leveler used in accordance with this invention preferably has a chlorine ion content of 0.1 g or less, more preferably 0.05 g or less and still more preferably 0.01 g or less per gram of nitrogen-containing high molecular compound. If its chlorine ion content exceeds 0.1 g per gram of nitrogen-containing high molecular compound, it is likely that an undesirably large amount of chlorine ions may be incorporated into a plating film.
- the dechlorinated leveler used in accordance with this invention preferably has a chlorine ion content of 1 g or less per liter. If it is exceeded, it is likely that an undesirably large amount of chlorine ions may be incorporated into a plating film.
- the plating method, leveler for plating and plating apparatus according to this invention are mainly used for forming copper layers of wiring by electroplating on the surface of a semiconductor wafer to be plated. Reference is first made to FIGS. 1A to 1 C showing an example of plating processes.
- a semiconductor wafer W has a conductive layer la formed on a substrate 1 having a semiconductor device formed thereon, an insulating film 2 of SiO 2 deposited thereon, a contact hole 3 and a wiring trench 4 formed therein by lithography and etching, a barrier layer 5 formed thereon from e.g. TiN and a seed layer 7 formed thereon as a feed layer for electrolytic plating, as shown in FIG. 1A .
- the semiconductor wafer W has its surface plated with copper, so that a copper layer 6 maybe deposited on the insulating film 2 , while the contact hole 3 and trench 4 of the substrate 1 are filled with copper, as shown in FIG. 1B . Then, the copper layer 6 on the insulating film 2 is removed by chemical mechanical polishing (CMP), so that the copper layer 6 filling the contact hole 3 and wiring trench 4 may have a surface substantially flush with the surface of the insulating film 2 . As a result, wiring is formed by the copper layer 6 , as shown in FIG. 1C .
- CMP chemical mechanical polishing
- FIG. 2 is a diagram showing a plating apparatus 10 embodying this invention.
- the plating apparatus 10 of this invention has a plating solution tank 12 for preparing and holding a plating solution 14 , a concentration measuring station 16 , a carrier supply station 40 , a surface active agent supply station 50 and a leveler supply station 30 connected to the plating solution tank 12 by pipelines 15 , 48 , 58 and 38 , respectively, a dechlorinating device 60 connected to the leveler supply station 30 by a pipeline 67 , a raw leveler tank 90 connected to the dechlorinating device 60 by a pipeline 94 , a control station 18 connected to all of the concentration measuring station 16 , leveler supply station 30 , carrier supply station 40 and surface active agent supply station 50 , and a plating station 70 connected to the plating solution tank 12 by a pipeline 100 , a pump 102 , a filter 104 , a pipeline 108 and a pump 106 , as shown in FIG. 2 .
- the leveler supply station 30 has a leveler tank 32 holding a dechlorinated leveler 34 and a pump 36 connected to the control station 18
- the carrier supply station 40 has a carrier tank 42 holding a carrier 44 and a pump 46 connected to the control station 18
- the surface active agent supply station 50 has a surface active agent tank 52 holding a surface active agent 54 and a pump 56 connected to the control station 18 , as shown in FIG. 2 .
- FIG. 3 is a diagram showing details of the dechlorinating device 60 and raw leveler tank 90 by example.
- the de-chlorinating device 60 has a dechlorinating tank 62 , a cathode 64 , an anode 65 and a stirrer 66 , as shown in FIG. 3 .
- the raw leveler tank 90 holds a raw leveler 92 and is connected to the dechlorinating tank 62 by the pipeline 94 with a pump 96 .
- FIG. 4 is a diagram showing details of the plating station 70 by example.
- a plating tank 76 connected to the pipelines 100 and 108 holds a plating solution 14 in which a wafer W mounted on a jig and an anode 72 are disposed opposite each other, while a power source 74 is connected between the wafer W and the anode 72 , as shown in FIG. 4 .
- FIG. 5 is a top plan view of another form of plating station 70 .
- the plating station 70 has four loading and unloading units 80 holding a plurality of substrates W therein, four plating units 82 for performing plating and auxiliary treatment, two conveying robots 84 and 85 for conveying the substrates W between the loading and unloading units 80 and the plating units 82 , two bevel and rear surface cleansing units 86 , a film thickness measuring device 87 and a temporary wafer support 88 , as shown in FIG. 5 .
- the plating units 82 are all connected to the pipelines 100 and 108 , though they are only partly shown.
- the conveying robots 84 and 85 constitute s substrate conveying device according to this invention.
- All the equipment shown in FIG. 2 for preparing the plating solution may be installed within the plating station shown in FIG. 5 so as to form an integral part thereof.
- the raw leveler 92 held in the raw leveler tank 90 and still to be dechlorinated is drawn by the pump 96 through the pipeline 94 into the dechlorinating device 60 , whereby it is dechlorinated.
- the raw leveler 92 pumped into the dechlorinating tank 62 is uniformly stirred by the stirrer 66 .
- the reaction shown by the expression II occurs at the anode 65 and chlorine gas (Cl 2 ) emerges. This indicates the dechlorination of the leveler.
- the dechlorinated leveler 34 is transferred by the pump 69 through the pipeline 67 into the leveler tank 32 in the leveler supply station 30 .
- the plating solution 14 held in the plating solution tank 12 is transferred to the concentration measuring station 16 , in which the concentrations of the leveler, carrier and surface active agent in the solution are measured.
- the results of the measurements are sent to the control station 18 and if the concentration of any of those additives is lower than the pre-set control range, the dechlorinated leveler 34 , carrier 44 or surface active agent 54 is supplied by the pump 36 , 46 or 56 from the leveler supply station 30 , carrier supply station 40 , or surface active agent supply station 50 to the plating solution tank 12 through the pipeline 38 , 48 or 58 , so that the concentration of each additive may be kept within the control range by the control station 18 .
- the plating solution 14 having its additives controlled in concentration as described is drawn by the pump 102 through the pipeline 100 and the filter 104 into the plating station 70 and used for plating the substrate or substrates W in the plating tank 76 or the plating units 82 .
- the plating solution having lowered concentrations of surface active agent, carrier and leveler as a result of their consumption by plating is returned by the pump 106 into the plating solution tank 12 through the pipeline 108 .
- the plating solution 14 having its additives controlled in concentration is supplied by the pump 102 through the pipeline 100 and the filter 104 into the plating tank 76 .
- a voltage is applied between the anode 72 and the wafer W by the power source 74 , whereby the wafer W has its surface plated with copper.
- the plating solution is returned by the pump 106 into the plating solution tank 12 through the pipeline 108 .
- a wafer W to be plated is taken out by the conveying robot 84 from a wafer cassette installed in any of the loading and unloading stations 80 and is conveyed to the film thickness measuring device 87 in which the thickness of a plating film for the wafer W to be plated is measured. Then, the wafer W is taken out by the robot 84 from the film thickness measuring device 87 and mounted on the temporary wafer support 88 . Then, the wafer W on the temporary wafer support 88 is taken by the hands of the other conveying robot 85 and charged into any of the plating units 82 through its wafer charge and discharge opening, while its surface to be plated is held upside.
- the plating solution 14 having its additives controlled in concentration is supplied from the plating solution tank 12 by the pump 102 through the pipeline 100 and the filter 104 into the plating unit 82 to plate the wafer. After plating, the plating solution is returned by the pump 106 through the pipeline 108 into the plating solution tank 12 .
- the wafer W is discharged from the plating unit 82 by the robot 85 .
- the wafer W as discharged is conveyed to one of the bevel and rear surface cleansing units 86 and after its cleansing and drying, it is mounted on the temporary wafer support 88 by the robot 85 and is, then, conveyed by the robot 84 to the film thickness measuring device 87 , in which the thickness of the plating film formed on the wafer W is measured, and it is conveyed by the robot 84 into the wafer cassette installed in any of the loading and unloading stations 80 . This is the end of the whole process of plating a single wafer W.
- the method of this invention is carried out by, for example, employing a substrate for an electronic circuit having a fine circuit pattern formed thereon as shown in FIG. 6A , forming a barrier layer on the substrate as shown in FIG. 6B , forming a seed or catalyst layer thereon as shown in FIG. 6C and forming a phosphorus-doped copper plating layer thereon to fill the fine holes and trenches defining the fine circuit pattern as shown FIG. 6D .
- 201 and 203 denote interlayer insulating layers formed on the substrate, 202 a conductive layer, 204 the barrier layer, 205 the seed or catalyst layer, and 206 the phosphorus-doped copper plating layer.
- the substrate on which fine circuit wiring is formed by the method of this invention is a semiconductor wafer, or printed circuit substrate having a fine circuit pattern formed on its surface.
- a pattern is, for example, formed by fine trenches and holes, such as via holes, and the trenches and holes are filled with phosphorus-doped copper to form circuit wiring.
- the method of forming fine circuit wiring according to this invention is carried out after the substrate is pre-treated by a customary method.
- the pretreatment of, for example, a silicon substrate such as a silicon wafer is done to form a barrier layer of, for example, Ta, TaN, TiN, WN, SiTiN, CoWP or CoWB ( FIG. 6B ).
- a barrier layer of, for example, Ta, TaN, TiN, WN, SiTiN, CoWP or CoWB
- a copper seed layer serving as a power feed layer is formed by e.g. PVD as pretreatment after the formation of a barrier layer.
- pretreatment is done to form a catalytic layer ( FIG. 6C ).
- the substrate pretreated as described has a phosphorus-doped copper plating layer formed thereon ( FIG. 6D ). This plating is so done as to fill the whole fine trenches and holes forming a fine circuit pattern. Finally, the phosphorus-doped copper film deposited on any other surface than the area of the circuit wiring is removed by e.g. CMP, leaving a fine circuit wiring formed by the phosphorus-doped copper film.
- the phosphorus-doped copper plating solution used to form a phosphorus-doped copper film in accordance with this invention contains, for example, the following constituents: Copper sulfate pentahydrate 150 to 250 g/l Sulfuric acid 10 to 100 g/l Chlorine ion 30 to 90 mg/l Phosphorus compound 100 to 10,000 mg/l (as phosphoric acid ion) Polymer component 10 to 40 ml/l Carrier component 1 to 20 ml/l Leveler component 1 to 20 ml/l
- electrolytic copper sulfate plating When electrolytic copper sulfate plating is employed to fill wiring trenches and holes in the surface of e.g. a semiconductor wafer, it is often the case to add three kinds of organic additives called the polymer, carrier and leveler components to the basic components, copper sulfate (CuSO 4 .5 H 2 O), sulfuric acid (H 2 SO 4 ) and chlorine (Cl), in order to make it possible to form a plating film of improved quality and fill the trenches and holes in an improved way.
- the polymer, carrier and leveler components to the basic components, copper sulfate (CuSO 4 .5 H 2 O), sulfuric acid (H 2 SO 4 ) and chlorine (Cl), in order to make it possible to form a plating film of improved quality and fill the trenches and holes in an improved way.
- the polymer component is a component added to suppress the deposition of adsorbed copper ions on the cathode surface to thereby increase activation polarization and improve uniformity of electrodeposition, and also called a suppressor or carrier.
- a surface active agent such as polyethylene glycol (PEG) or polypropylene glycol (PPG), is usually employed.
- the carrier component is a component added to improve the density and brightness of a plating film and also called a brightener.
- a sulfur compound such as mercapto-alkylsulfonic acid or HS—C n H 2n —SO 3 , is usually employed. It is in the form of anions in the plating solution, inhibits the deposition of copper ions and thereby promotes the formation of a finer deposit.
- the leveler component is a compound containing nitrogen, such as polyamine. It is in the form of cations in the plating solution.
- the adsorption of the leveler is more likely to occur in a place having a high current density and in the place where the adsorption of the leveler is more likely to occur, activation overvoltage increases and the deposition of copper is suppressed.
- the adsorption of the leveler is less likely to occur and the deposition of copper is predominant.
- Examples of the phosphorus compounds in the phosphorus-doped copper plating solution are, for example, phosphoric acid, copper sulfate and phosphorus oxides such as phosphorus pentoxide.
- the above plating solution When used to form a phosphorus-doped copper plating film, it may have a temperature of, say, 15° C. to 40° C. and a current density of, say, 0.3 to 30 mA/cm 2 may be employed.
- an insoluble substance such as platinum (Pt) or iridium oxide (Ir 2 O 3 ), as the anode instead of metallic copper and add a solution of the component to be deposited.
- the phosphorus-doped copper plating film formed as described is a film of copper containing a very small amount of phosphorus or a phosphorus compound incorporated therein.
- the phase in which phosphorus or a compound thereof is present in copper is not clearly known, it is obvious from the Cu—P phase diagram in FIG. 7 that when copper has a temperature of 300° C. or below, for example, 0.6 atm % or less of phosphorus may be incorporated in the crystal grain boundary of copper, or its crystal and form a solid solution with it, and its presence in such a phase is, therefore, possible. It is considered that phosphorus provides an improved electro-migration resistance, as it inhibits the diffusion of copper atoms. The same is true with a phosphorus compound.
- FIG. 8 shows an example of plating apparatus which can be employed to form fine circuit wiring by a phosphorus-doped copper film in accordance with this invention.
- FIG. 8 is a diagram showing the layout of the plating apparatus by example, which includes a plating tank 210 holding a phosphorus-doped copper plating solution Q, in which an anode plate 211 and a substrate 212 to be plated are disposed opposite each other, and if a plating current is supplied between the anode 211 and the substrate 212 from a power source E, the substrate 212 has its surface plated electrolytically.
- a plating solution preparing tank for preparing a phosphorus-doped copper plating solution is a plating solution preparing tank for preparing a phosphorus-doped copper plating solution.
- a standard copper sulfate plating solution Q 1 (basic solution), an additional solution Q 2 obtained by adding the polymer component to the basic solution, an additional solution Q 3 obtained by adding the carrier component to the basic solution, an additional solution Q 4 obtained by adding the leveler component to the basic solution, sulfuric acid (H 2 SO 4 ) Q 5 and hydrochloric acid (HCl) Q 6 can be supplied to the plating solution preparing tank 213 from a standard solution tank 214 through a pump P 1 and a valve V 1 , from an additional solution tank 215 through a pump P 2 and a valve V 2 , from an additional solution tank 216 through a pump P 3 and a valve V 3 , from an additional solution tank 217 through a pump P 4 and a valve V 4 , from a sulfuric acid tank 218 through a pump
- the phosphorus-doped copper plating solution Q 8 prepared in the plating solution preparing tank 213 is supplied by a pump P 8 to the plating tank 210 through a filter 220 .
- the plating solution Q exceeding a predetermined surface level in the plating tank 210 is returned to the plating solution preparing tank 213 .
- the plating solution is circulated between the plating solution preparing tank 213 and the plating tank 210 .
- 221 is a sampling device for taking a sample of the phosphorus-doped copper plating solution Q 8 supplied to the plating solution 210 and 222 is an automatic analyzing device for analyzing automatically the composition of the sample of the plating solution Q 8 taken by the sampling device 221 .
- 223 is a waste solution tank
- 224 is a level sensor for measuring the surface level of the plating solution Q 8 in the plating solution preparing tank 213
- 225 is a control unit.
- the composition of the plating solution Q 8 as analyzed by the automatic analyzing device 222 and the level of the plating solution Q 8 as measured by the level sensor 224 are inputted to the control unit 225 .
- the control unit 225 controls the pumps P 1 to P 7 and the valves V 1 to V 7 to control the standard solution Q 1 supplied from the standard solution tank 214 , the additional solution Q 2 supplied from the additional solution tank 215 , the additional solution Q 3 supplied from the additional solution tank 216 , the additional solution Q 4 supplied from the additional solution tank 217 , sulfuric acid Q 5 supplied from the sulfuric acid tank 218 , hydrochloric acid Q 6 supplied from the hydrochloric acid tank 219 and phosphoric acid Q 7 and thereby regulate the composition of the plating solution Q 8 in the plating solution preparing tank 213 .
- a test was conducted to ascertain that chlorine ions incorporated into a plating film were of a leveler.
- One liter of a plating solution was so prepared as to contain 200 g of CuSO 4 .5H 2 O, 10 g of H 2 SO 4 , 60 mg of chlorine ions, 200 mg of polyethylene glycol having a molecular weight of about 3000 and 5 mg of bis(3-sulfopropyl)disulfide.
- a quaternary ammonium hydrochloride salt of polyvinyl pyridine yet to be dechlorinated was employed as a leveler and was so added to the plating solution that the plating solution might contain 10 mg of polyvinyl pyridine per liter.
- the leveler yet to be dechlorinated contained 16 g of polyvinyl pyridine and 4 g of chlorine ions per liter.
- the plating solution was used for the copper plating of a silicon wafer.
- the plating solution to which no leveler had been added was also used for the copper plating of a silicon wafer.
- the copper-plated silicon wafers were examined by a secondary ion mass spectrometer (SIMS) for the chlorine ions incorporated in their copper plating films. As a result, it was confirmed that the amount of chlorine ions in the copper plating film formed by using the leveler containing chlorine ions was about 10 times larger than in the plating film formed without using any leveler.
- SIMS secondary ion mass spectrometer
- the leveler used in Example 1 was dechlorinated to prepare a leveler having a chlorine ion concentration reduced to 1 g/l.
- the dechlorinated leveler and the same plating solution as in Example 1 were used for the copper plating of a silicon wafer.
- Example 1 The examination of the wafer by SIMS as in Example 1 can confirm a reduction in the amount of chlorine ions incorporated in its copper plating film.
- a phosphorus-doped copper plating solution was prepared by adding 5 ml of 50% phosphoric acid to one liter of a copper sulfate plating solution (basic solution) having the composition shown below.
- the plating solution was used for one minute of phosphorus-doped copper plating at a temperature of 25° C. and a current density of 30 mA/cm 2 on a semiconductor wafer in which via holes having a width of 150 nm and an aspect ratio of 5 had been formed.
- the semiconduct or wafer had a barrier and a seed layer formed by customary methods.
- Copper Sulfate Plating Solution Copper sulfate pentahydrate 200 g/l Sulfuric acid 50 g/l Chlorine ion 50 mg/l Phosphorus compound 100 mg/l (as phosphoric acid ion) Polymer component 30 ml/l Carrier component 10 ml/l Leveler component 10 ml/l
- the plating method, plating apparatus and leveler according to this invention make it possible to reduce the amount of chlorine ions incorporated in a plating film.
- the phosphorus-doped copper plating film formed in accordance with this invention can form copper wiring having a higher level of electromigration resistance than that of any ordinary copper plating film.
- the phosphorus-doped copper wiring is widely useful as wiring for a smaller and more highly integrated substrate for an electronic circuit, such as a semiconductor wafer.
Abstract
Description
- 1. Field of the Invention
- This invention relates to a copper plating method and more particularly to a copper plating method employing a dechlorinated leveler and the leveler and plating apparatus employed therefor.
- This invention relates also to a method of forming fine circuit wiring by plating on a substrate having a fine circuit pattern, such as a semiconductor or a printed wiring board, and particularly to a method of forming fine circuit wiring in which phosphorus-doped copper plating is relied upon for preventing the electromigration of the fine circuit wiring as formed, and a plating solution and a plating apparatus therefor.
- 2. Description of the Related Art
- Aluminum or an aluminum alloy has hitherto been used as a material for forming a wiring circuit on a semiconductor wafer. An improved degree of integration has, however, created a demand for a material of higher electric conductivity. Copper has drawn attention as a material satisfying such a demand and has come to be used for plating a substrate.
- Various additives, such as a surface active agent, an unsaturated organic compound and chlorine ions, are used in copper plating to form a uniform plating film. Among these additives, it is said that chlorine ions are necessary for assisting the dissolution of the anode and the action of a brightener (Handbook of Plating, Society for the Study of Electroplating, The Nikkan Kogyo Shinbun, Ltd., page 76). The additives also include a leveler so called, since it is used for leveling the growth of a plating film, and a nitrogen-containing high molecular compound is usually used as the leveler. The nitrogen-containing high molecular compound is often supplied in the form of a hydrochloride as a tertiary or quaternary nitrogen salt and therefore, the leveler often contains chlorine ions.
- While the chlorine ions play an important role in a plating solution as stated above, it has been a problem that the chlorine ions incorporated in a copper plating film lower its electric conductivity. Another problem has been due to the corrosiveness of chlorine ions, as they cause the corrosion and deterioration of plated wiring.
- On the other hand, copper is used as a material for wiring on an LSI or printed circuit board owing to its low electric resistivity. Fine copper wiring is, for example, formed on a semiconductor wafer by forming first a wiring pattern by via or other holes and trenches and then plating the wafer with copper to fill the holes and trenches with the copper to thereby form copper wiring.
- There has recently been growing a strong demand for still smaller, higher capacity and faster LSI devices and printed circuit boards calling for finer and more highly integrated copper wiring. Accordingly, copper wiring has come to be required to allow a steady flow of an electric current at a higher current density, but has come to present a problem of electromigration.
- When an electric current is passed through copper wiring, the copper ions (electrons) in the wiring are subjected to a coulomb force from an electrical field and a force of bombardment with the flowing electrons. At a high current, a balance between those forces is lost and the migration (diffusion) of copper ions occurs, which is a phenomenon known as electromigration. Electromigration is likely to cause the formation of voids in copper wiring or its insulation and thereby exert a serious effect on electronic devices. Moreover, electromigration causes stress migration as a secondary phenomenon and is likely to increase the frequency of occurrence of the serious effect as stated above.
- Accordingly, a copper plating film forming copper wiring is required to have a high degree of electromigration resistance.
- There are, however, only a few reports made so far in respect of methods of imparting electromigration resistance to copper, including a method in which tin is added to copper. As tin is a metal which is electrochemically baser than copper, it has been difficult to form a deposited copper film containing tin uniformly by electroplating, since copper is deposited more actively than tin. Accordingly, there has been no effective way to form copper wiring having a high level of electromigration resistance by copper plating.
- It is, therefore, an object of this invention to provide a method of forming a plating film containing less chlorine ions.
- It is another object of this invention to provide a method of forming circuit wiring having a high level of electromigration resistance by electroplating.
- We, the inventors of this invention, have discovered that the chlorine ions incorporated in a plating film are not the chlorine ions added intentionally to a plating solution, but a small amount of chlorine ions which a leveler contains. This invention is based on our discovery.
- According to one aspect of this invention, therefore, there is provided a method of copper plating using a leveler containing a nitrogen-containing high molecular compound, wherein the leveler is dechlorinated prior to its use for plating.
- According to another aspect of this invention, there is provided a leveler for copper plating containing a nitrogen-containing high molecular compound, the leveler having a chlorine ion content of 0.1 g or less per gram of nitrogen-containing high molecular compound.
- According to still another aspect of this invention, there is provided a plating apparatus comprising a tank for preparing a plating solution, a device for dechlorinating a leveler, a leveler supply station for supplying the dechlorinated leveler to the tank and a plating station.
- According to a further aspect of this invention, there is provided a plating apparatus for forming a metal film on a seed layer on a substrate surface by electroplating, the apparatus comprising a loading and unloading station, a substrate conveying device, a cleansing unit, a plating tank, a tank for preparing a plating solution and supplying it to the plating tank, a station for measuring the concentrations of additives, a device for dechlorinating a leveler and a leveler supply station for supplying the dechlorinated leveler to the plating solution, the concentration measuring station measuring the concentration of the leveler in the plating solution and in accordance with the result of the measurement, the leveler supply station adding the dechlorinated leveler to the plating solution.
- We have studied various possibilities of forming copper wiring having a high level of electromigration resistance by copper plating, and discovered that a phosphorus-doped copper plating film deposited by using a copper plating solution containing phosphorus or phosphoric acid ions in addition to copper ions has a higher level of electromigration resistance than that of an ordinary copper plating film. We have found that the use of such a plating solution makes it possible to form copper wiring having a high level of electromigration resistance on a semiconductor wafer, or the like, and we have made this invention.
- According to a still further aspect of this invention, therefore, there is provided a method of forming fine circuit wiring, comprising forming a circuit with a layer of phosphorus-doped copper plating on a substrate for an electronic circuit having a fine circuit pattern, a barrier layer and any necessary seed layer formed thereon.
- According to a still further aspect of this invention, there is provided a phosphorus-doped copper plating solution containing 1×10−6 to 50% by weight of elemental phosphorus in the form of a phosphorus compound in a copper sulfate plating solution containing copper sulfate, sulfuric acid and chlorine ions.
- According to a still further aspect of this invention, there is provided a plating apparatus having an anode plate and a substrate to be plated which are positioned opposite each other in a plating tank containing a phosphorus-doped copper plating solution for electroplating the surface of the substrate by supplying an electric current between the anode plate and the substrate from a power source, the apparatus having at least a device for supplying a solution containing a phosphorus compound as a device for supplying a constituent composing the plating solution.
- The use of any copper plating method, leveler or plating apparatus according to this invention makes it possible to reduce the amount of the chlorine ions incorporated in any copper plating film and thereby the possibility of corrosion and deterioration of any copper-plated wiring.
- The fine circuit wiring formed by phosphorus-doped copper in accordance with this invention has a higher level of electromigration resistance than that of any wiring formed by copper alone, allows an electric current to pass therethrough at a higher current density and therefore copes with a demand for finer and higher density circuit wiring.
-
FIGS. 1A to 1C are a series of sectional views showing an example of plating processes; -
FIG. 2 is a diagram showing a plating apparatus embodying this invention; -
FIG. 3 is a diagram showing a dechlorinating device and a raw leveler tank in the apparatus embodying this invention; -
FIG. 4 is a diagram showing a plating station in the apparatus embodying this invention; -
FIG. 5 is a diagram showing another form of plating station; -
FIGS. 6A to 6D are a series of views showing the steps of a method embodying this invention; -
FIG. 7 is a phase diagram of copper and phosphorus; and -
FIG. 8 is a diagram showing another form of plating apparatus embodying this invention. - A leveler used in copper plating is usually employed for leveling the growth of a plating film and contains a nitrogen-containing high molecular compound. The nitrogen-containing high molecular compound used herein may be any high molecular compound containing a nitrogen element in its molecule, for example, poly(dialkylaminoethyl acrylate), poly(diallyl dimethyl ammonium), polyethyleneimine, polyvinyl pyridine, polyvinyl amidine, polyallylamine or polyaminesulfonic acid. The nitrogen-containing high molecular compound is used in the form of a hydrochloride as a tertiary or quaternary nitrogen salt so that its solubility in water may be improved. Accordingly, the leveler contains a nitrogen-containing high molecular compound and chlorine ions.
- The leveler is usually provided in the form of an aqueous solution containing, say, 5 to 20 g of nitrogen-containing high molecular compound and 3 to 10 g of chlorine ions per liter.
- The leveler is added to a plating solution to the extent that the plating solution usually contains 5 to 20 mg of nitrogen-containing high molecular compound per liter. When the leveler is added to the plating solution, the chlorine ions which the leveler contains are carried over into the plating solution and the plating solution usually contains several milligrams of chlorine ions per liter.
- Other additives used in a copper plating solution include chlorine ions. The chlorine ions are usually added in the amount of 40 to 80 mg per liter, as it is said that they are necessary for assisting the dissolution of the anode and the action of a brightener.
- As the amount of the chlorine ions carried over from the leveler into the plating solution is by far smaller than that of the chlorine ions added to the plating solution for assisting the dissolution of the anode and the action of the brightener, it has been considered that the chlorine ions which are carried over from the leveler do not exert any effect on plating.
- Our study has, however, ascertained that the chlorine ions carried over from the leveler into the plating solution are incorporated predominantly into a plating film, as will become obvious from the description of examples. Accordingly, the chlorine ions contained in the leveler are dechlorinated to reduce the amount of chlorine ions incorporated into a plating film.
- While any method can be employed for dechlorinating the leveler in accordance with this invention if it can reduce the amount of chlorine ions, a method relying upon sedimentation or electrolysis is preferred.
- The dechlorination of the leveler by sedimentation may, for example, be carried out by adding to it a substance forming a hardly soluble salt with chlorine ions, e.g. silver nitrate, as shown by expression I:
AgNO3+Cl−→AgCl↓+NO3 − (I)
The dechlorination by electrolysis may, for example, be carried out by removing chlorine gas at the anode, as shown by expression II:
2Cl−→Cl2↑+2e− (II) - The dechlorinated leveler used in accordance with this invention preferably has a chlorine ion content of 0.1 g or less, more preferably 0.05 g or less and still more preferably 0.01 g or less per gram of nitrogen-containing high molecular compound. If its chlorine ion content exceeds 0.1 g per gram of nitrogen-containing high molecular compound, it is likely that an undesirably large amount of chlorine ions may be incorporated into a plating film.
- Moreover, the dechlorinated leveler used in accordance with this invention preferably has a chlorine ion content of 1 g or less per liter. If it is exceeded, it is likely that an undesirably large amount of chlorine ions may be incorporated into a plating film.
- The invention will now be described in further detail with reference to the drawings, though the drawings are not intended for limiting the scope of this invention.
- The plating method, leveler for plating and plating apparatus according to this invention are mainly used for forming copper layers of wiring by electroplating on the surface of a semiconductor wafer to be plated. Reference is first made to
FIGS. 1A to 1C showing an example of plating processes. - A semiconductor wafer W has a conductive layer la formed on a
substrate 1 having a semiconductor device formed thereon, an insulatingfilm 2 of SiO2 deposited thereon, acontact hole 3 and awiring trench 4 formed therein by lithography and etching, abarrier layer 5 formed thereon from e.g. TiN and aseed layer 7 formed thereon as a feed layer for electrolytic plating, as shown inFIG. 1A . - The semiconductor wafer W has its surface plated with copper, so that a
copper layer 6 maybe deposited on the insulatingfilm 2, while thecontact hole 3 andtrench 4 of thesubstrate 1 are filled with copper, as shown inFIG. 1B . Then, thecopper layer 6 on the insulatingfilm 2 is removed by chemical mechanical polishing (CMP), so that thecopper layer 6 filling thecontact hole 3 andwiring trench 4 may have a surface substantially flush with the surface of the insulatingfilm 2. As a result, wiring is formed by thecopper layer 6, as shown inFIG. 1C . -
FIG. 2 is a diagram showing aplating apparatus 10 embodying this invention. Theplating apparatus 10 of this invention has aplating solution tank 12 for preparing and holding aplating solution 14, aconcentration measuring station 16, acarrier supply station 40, a surface activeagent supply station 50 and aleveler supply station 30 connected to theplating solution tank 12 bypipelines dechlorinating device 60 connected to theleveler supply station 30 by apipeline 67, araw leveler tank 90 connected to thedechlorinating device 60 by apipeline 94, acontrol station 18 connected to all of theconcentration measuring station 16,leveler supply station 30,carrier supply station 40 and surface activeagent supply station 50, and aplating station 70 connected to theplating solution tank 12 by apipeline 100, apump 102, afilter 104, apipeline 108 and apump 106, as shown inFIG. 2 . - The
leveler supply station 30 has aleveler tank 32 holding adechlorinated leveler 34 and apump 36 connected to thecontrol station 18, thecarrier supply station 40 has acarrier tank 42 holding acarrier 44 and apump 46 connected to thecontrol station 18 and the surface activeagent supply station 50 has a surfaceactive agent tank 52 holding a surfaceactive agent 54 and apump 56 connected to thecontrol station 18, as shown inFIG. 2 . -
FIG. 3 is a diagram showing details of thedechlorinating device 60 andraw leveler tank 90 by example. Thede-chlorinating device 60 has adechlorinating tank 62, acathode 64, ananode 65 and astirrer 66, as shown inFIG. 3 . Theraw leveler tank 90 holds araw leveler 92 and is connected to thedechlorinating tank 62 by thepipeline 94 with apump 96. -
FIG. 4 is a diagram showing details of theplating station 70 by example. Aplating tank 76 connected to thepipelines plating solution 14 in which a wafer W mounted on a jig and ananode 72 are disposed opposite each other, while apower source 74 is connected between the wafer W and theanode 72, as shown inFIG. 4 . -
FIG. 5 is a top plan view of another form of platingstation 70. Theplating station 70 has four loading and unloadingunits 80 holding a plurality of substrates W therein, four platingunits 82 for performing plating and auxiliary treatment, two conveyingrobots units 80 and the platingunits 82, two bevel and rearsurface cleansing units 86, a filmthickness measuring device 87 and atemporary wafer support 88, as shown inFIG. 5 . The platingunits 82 are all connected to thepipelines FIG. 5 , the conveyingrobots - All the equipment shown in
FIG. 2 for preparing the plating solution may be installed within the plating station shown inFIG. 5 so as to form an integral part thereof. - Description will now be made of the operation of the plating apparatus of this invention constructed as described above. The
raw leveler 92 held in theraw leveler tank 90 and still to be dechlorinated is drawn by thepump 96 through thepipeline 94 into thedechlorinating device 60, whereby it is dechlorinated. Theraw leveler 92 pumped into thedechlorinating tank 62 is uniformly stirred by thestirrer 66. Upon application of a voltage to theanode 65 andcathode 64, the reaction shown by the expression II occurs at theanode 65 and chlorine gas (Cl2) emerges. This indicates the dechlorination of the leveler. Thedechlorinated leveler 34 is transferred by thepump 69 through thepipeline 67 into theleveler tank 32 in theleveler supply station 30.
2Cl−→Cl2↑+2e− (III) - The
plating solution 14 held in theplating solution tank 12 is transferred to theconcentration measuring station 16, in which the concentrations of the leveler, carrier and surface active agent in the solution are measured. The results of the measurements are sent to thecontrol station 18 and if the concentration of any of those additives is lower than the pre-set control range, thedechlorinated leveler 34,carrier 44 or surfaceactive agent 54 is supplied by thepump leveler supply station 30,carrier supply station 40, or surface activeagent supply station 50 to theplating solution tank 12 through thepipeline control station 18. - The
plating solution 14 having its additives controlled in concentration as described is drawn by thepump 102 through thepipeline 100 and thefilter 104 into theplating station 70 and used for plating the substrate or substrates W in theplating tank 76 or theplating units 82. The plating solution having lowered concentrations of surface active agent, carrier and leveler as a result of their consumption by plating is returned by thepump 106 into theplating solution tank 12 through thepipeline 108. - Description will now be made of the operation of the
plating station 70. Referring first to one form of platingstation 70 as shown inFIG. 4 , theplating solution 14 having its additives controlled in concentration is supplied by thepump 102 through thepipeline 100 and thefilter 104 into theplating tank 76. A voltage is applied between theanode 72 and the wafer W by thepower source 74, whereby the wafer W has its surface plated with copper. After plating, the plating solution is returned by thepump 106 into theplating solution tank 12 through thepipeline 108. - Referring now to another form of plating
station 70 as shown inFIG. 5 , a wafer W to be plated is taken out by the conveyingrobot 84 from a wafer cassette installed in any of the loading and unloadingstations 80 and is conveyed to the filmthickness measuring device 87 in which the thickness of a plating film for the wafer W to be plated is measured. Then, the wafer W is taken out by therobot 84 from the filmthickness measuring device 87 and mounted on thetemporary wafer support 88. Then, the wafer W on thetemporary wafer support 88 is taken by the hands of the other conveyingrobot 85 and charged into any of the platingunits 82 through its wafer charge and discharge opening, while its surface to be plated is held upside. Theplating solution 14 having its additives controlled in concentration is supplied from theplating solution tank 12 by thepump 102 through thepipeline 100 and thefilter 104 into theplating unit 82 to plate the wafer. After plating, the plating solution is returned by thepump 106 through thepipeline 108 into theplating solution tank 12. - After its plating, the wafer W is discharged from the
plating unit 82 by therobot 85. The wafer W as discharged is conveyed to one of the bevel and rearsurface cleansing units 86 and after its cleansing and drying, it is mounted on thetemporary wafer support 88 by therobot 85 and is, then, conveyed by therobot 84 to the filmthickness measuring device 87, in which the thickness of the plating film formed on the wafer W is measured, and it is conveyed by therobot 84 into the wafer cassette installed in any of the loading and unloadingstations 80. This is the end of the whole process of plating a single wafer W. - The method of this invention is carried out by, for example, employing a substrate for an electronic circuit having a fine circuit pattern formed thereon as shown in
FIG. 6A , forming a barrier layer on the substrate as shown inFIG. 6B , forming a seed or catalyst layer thereon as shown inFIG. 6C and forming a phosphorus-doped copper plating layer thereon to fill the fine holes and trenches defining the fine circuit pattern as shownFIG. 6D . InFIGS. 6A to 6D, 201 and 203 denote interlayer insulating layers formed on the substrate, 202 a conductive layer, 204 the barrier layer, 205 the seed or catalyst layer, and 206 the phosphorus-doped copper plating layer. - The substrate on which fine circuit wiring is formed by the method of this invention is a semiconductor wafer, or printed circuit substrate having a fine circuit pattern formed on its surface. Such a pattern is, for example, formed by fine trenches and holes, such as via holes, and the trenches and holes are filled with phosphorus-doped copper to form circuit wiring.
- The method of forming fine circuit wiring according to this invention is carried out after the substrate is pre-treated by a customary method. The pretreatment of, for example, a silicon substrate such as a silicon wafer is done to form a barrier layer of, for example, Ta, TaN, TiN, WN, SiTiN, CoWP or CoWB (
FIG. 6B ). If electroplating is thereafter carried out, a copper seed layer serving as a power feed layer is formed by e.g. PVD as pretreatment after the formation of a barrier layer. If electroless plating is carried out, pretreatment is done to form a catalytic layer (FIG. 6C ). - The substrate pretreated as described has a phosphorus-doped copper plating layer formed thereon (
FIG. 6D ). This plating is so done as to fill the whole fine trenches and holes forming a fine circuit pattern. Finally, the phosphorus-doped copper film deposited on any other surface than the area of the circuit wiring is removed by e.g. CMP, leaving a fine circuit wiring formed by the phosphorus-doped copper film. - The phosphorus-doped copper plating solution used to form a phosphorus-doped copper film in accordance with this invention, which has been discovered by us, the inventors of this invention, contains, for example, the following constituents:
Copper sulfate pentahydrate 150 to 250 g/ l Sulfuric acid 10 to 100 g/ l Chlorine ion 30 to 90 mg/ l Phosphorus compound 100 to 10,000 mg/l (as phosphoric acid ion) Polymer component 10 to 40 ml/ l Carrier component 1 to 20 ml/ l Leveler component 1 to 20 ml/l - When electrolytic copper sulfate plating is employed to fill wiring trenches and holes in the surface of e.g. a semiconductor wafer, it is often the case to add three kinds of organic additives called the polymer, carrier and leveler components to the basic components, copper sulfate (CuSO4.5 H2O), sulfuric acid (H2SO4) and chlorine (Cl), in order to make it possible to form a plating film of improved quality and fill the trenches and holes in an improved way.
- Firstly, the polymer component is a component added to suppress the deposition of adsorbed copper ions on the cathode surface to thereby increase activation polarization and improve uniformity of electrodeposition, and also called a suppressor or carrier. A surface active agent, such as polyethylene glycol (PEG) or polypropylene glycol (PPG), is usually employed.
- Secondly, the carrier component is a component added to improve the density and brightness of a plating film and also called a brightener. A sulfur compound, such as mercapto-alkylsulfonic acid or HS—CnH2n—SO3, is usually employed. It is in the form of anions in the plating solution, inhibits the deposition of copper ions and thereby promotes the formation of a finer deposit.
- Thirdly, the leveler component is a compound containing nitrogen, such as polyamine. It is in the form of cations in the plating solution. The adsorption of the leveler is more likely to occur in a place having a high current density and in the place where the adsorption of the leveler is more likely to occur, activation overvoltage increases and the deposition of copper is suppressed. At the bottom of any fine trench or hole, on the other hand, the adsorption of the leveler is less likely to occur and the deposition of copper is predominant.
- Examples of the phosphorus compounds in the phosphorus-doped copper plating solution are, for example, phosphoric acid, copper sulfate and phosphorus oxides such as phosphorus pentoxide.
- In order to have a phosphorus-doped copper film deposited from the above plating solution, it is desirable to control the deposition potentials of copper and phosphorus so that they may be close to each other. Moreover, it is possible to add to the plating solution any organic additive known as used in any known acidic copper plating solution, such as a deposition inhibitor or accelerator, if required.
- When the above plating solution is used to form a phosphorus-doped copper plating film, it may have a temperature of, say, 15° C. to 40° C. and a current density of, say, 0.3 to 30 mA/cm2 may be employed. In order to form a phosphorus-doped copper film which is stable in composition, it is desirable to use an insoluble substance, such as platinum (Pt) or iridium oxide (Ir2O3), as the anode instead of metallic copper and add a solution of the component to be deposited.
- The phosphorus-doped copper plating film formed as described is a film of copper containing a very small amount of phosphorus or a phosphorus compound incorporated therein. Although the phase in which phosphorus or a compound thereof is present in copper is not clearly known, it is obvious from the Cu—P phase diagram in
FIG. 7 that when copper has a temperature of 300° C. or below, for example, 0.6 atm % or less of phosphorus may be incorporated in the crystal grain boundary of copper, or its crystal and form a solid solution with it, and its presence in such a phase is, therefore, possible. It is considered that phosphorus provides an improved electro-migration resistance, as it inhibits the diffusion of copper atoms. The same is true with a phosphorus compound. -
FIG. 8 shows an example of plating apparatus which can be employed to form fine circuit wiring by a phosphorus-doped copper film in accordance with this invention. -
FIG. 8 is a diagram showing the layout of the plating apparatus by example, which includes aplating tank 210 holding a phosphorus-doped copper plating solution Q, in which ananode plate 211 and asubstrate 212 to be plated are disposed opposite each other, and if a plating current is supplied between theanode 211 and thesubstrate 212 from a power source E, thesubstrate 212 has its surface plated electrolytically. - 213 is a plating solution preparing tank for preparing a phosphorus-doped copper plating solution. A standard copper sulfate plating solution Q1 (basic solution), an additional solution Q2 obtained by adding the polymer component to the basic solution, an additional solution Q3 obtained by adding the carrier component to the basic solution, an additional solution Q4 obtained by adding the leveler component to the basic solution, sulfuric acid (H2SO4) Q5 and hydrochloric acid (HCl) Q6 can be supplied to the plating
solution preparing tank 213 from astandard solution tank 214 through a pump P1 and a valve V1, from anadditional solution tank 215 through a pump P2 and a valve V2, from anadditional solution tank 216 through a pump P3 and a valve V3, from anadditional solution tank 217 through a pump P4 and a valve V4, from asulfuric acid tank 218 through a pump P5 and a valve V5 and from ahydrochloric acid tank 219 through a pump P6 and a valve V6, respectively. Phosphoric acid (H3PO4) Q7 can be supplied from aphosphoric acid tank 226 through a pump P7 and a valve V7. - The phosphorus-doped copper plating solution Q8 prepared in the plating
solution preparing tank 213 is supplied by a pump P8 to theplating tank 210 through afilter 220. The plating solution Q exceeding a predetermined surface level in theplating tank 210 is returned to the platingsolution preparing tank 213. Thus, the plating solution is circulated between the platingsolution preparing tank 213 and theplating tank 210. 221 is a sampling device for taking a sample of the phosphorus-doped copper plating solution Q8 supplied to theplating solution sampling device 221. 223 is a waste solution tank, 224 is a level sensor for measuring the surface level of the plating solution Q8 in the platingsolution preparing tank - The composition of the plating solution Q8 as analyzed by the
automatic analyzing device 222 and the level of the plating solution Q8 as measured by thelevel sensor 224 are inputted to thecontrol unit 225. In accordance with the results of analysis of the plating solution Q8 by theautomatic analyzing device 222, thecontrol unit 225 controls the pumps P1 to P7 and the valves V1 to V7 to control the standard solution Q1 supplied from thestandard solution tank 214, the additional solution Q2 supplied from theadditional solution tank 215, the additional solution Q3 supplied from theadditional solution tank 216, the additional solution Q4 supplied from theadditional solution tank 217, sulfuric acid Q5 supplied from thesulfuric acid tank 218, hydrochloric acid Q6 supplied from thehydrochloric acid tank 219 and phosphoric acid Q7 and thereby regulate the composition of the plating solution Q8 in the platingsolution preparing tank 213. - The invention will now be described in further detail by examples, though these examples are not supposed at all to limit the scope of this invention.
- A test was conducted to ascertain that chlorine ions incorporated into a plating film were of a leveler.
- One liter of a plating solution was so prepared as to contain 200 g of CuSO4.5H2O, 10 g of H2SO4, 60 mg of chlorine ions, 200 mg of polyethylene glycol having a molecular weight of about 3000 and 5 mg of bis(3-sulfopropyl)disulfide.
- A quaternary ammonium hydrochloride salt of polyvinyl pyridine yet to be dechlorinated was employed as a leveler and was so added to the plating solution that the plating solution might contain 10 mg of polyvinyl pyridine per liter. The leveler yet to be dechlorinated contained 16 g of polyvinyl pyridine and 4 g of chlorine ions per liter. The plating solution was used for the copper plating of a silicon wafer. The plating solution to which no leveler had been added was also used for the copper plating of a silicon wafer.
- The copper-plated silicon wafers were examined by a secondary ion mass spectrometer (SIMS) for the chlorine ions incorporated in their copper plating films. As a result, it was confirmed that the amount of chlorine ions in the copper plating film formed by using the leveler containing chlorine ions was about 10 times larger than in the plating film formed without using any leveler.
- It is, therefore, obvious that the chlorine ions carried over from the leveler into the plating solution are predominantly incorporated into the plating film.
- The leveler used in Example 1 was dechlorinated to prepare a leveler having a chlorine ion concentration reduced to 1 g/l.
- The dechlorinated leveler and the same plating solution as in Example 1 were used for the copper plating of a silicon wafer.
- The examination of the wafer by SIMS as in Example 1 can confirm a reduction in the amount of chlorine ions incorporated in its copper plating film.
- A phosphorus-doped copper plating solution was prepared by adding 5 ml of 50% phosphoric acid to one liter of a copper sulfate plating solution (basic solution) having the composition shown below. The plating solution was used for one minute of phosphorus-doped copper plating at a temperature of 25° C. and a current density of 30 mA/cm2 on a semiconductor wafer in which via holes having a width of 150 nm and an aspect ratio of 5 had been formed. The semiconduct or wafer had a barrier and a seed layer formed by customary methods.
- Composition of the Copper Sulfate Plating Solution:
Copper sulfate pentahydrate 200 g/l Sulfuric acid 50 g/ l Chlorine ion 50 mg/l Phosphorus compound 100 mg/l (as phosphoric acid ion) Polymer component 30 ml/ l Carrier component 10 ml/ l Leveler component 10 ml/l - There was obtained a phosphorus -doped copper plating film having a phosphorus content of 1×10−6 atom % or more along its depth. Its examination by a scanning electron microscope did not reveal any void in any of the via holes in the substrate. Its electromigration resistance was higher than that of any copper plating film not containing phosphorus.
- As is obvious from the foregoing, the plating method, plating apparatus and leveler according to this invention make it possible to reduce the amount of chlorine ions incorporated in a plating film.
- The phosphorus-doped copper plating film formed in accordance with this invention can form copper wiring having a higher level of electromigration resistance than that of any ordinary copper plating film.
- The phosphorus-doped copper wiring is widely useful as wiring for a smaller and more highly integrated substrate for an electronic circuit, such as a semiconductor wafer.
Claims (16)
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JP2003-377719 | 2003-11-07 | ||
JP2003377719A JP2005139516A (en) | 2003-11-07 | 2003-11-07 | Plating method and plating device |
JP2003380831A JP4226994B2 (en) | 2003-11-11 | 2003-11-11 | Method for forming fine circuit wiring and plating solution and plating apparatus used therefor |
JP2003-380831 | 2003-11-11 |
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US10/980,320 Abandoned US20050126919A1 (en) | 2003-11-07 | 2004-11-04 | Plating method, plating apparatus and a method of forming fine circuit wiring |
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Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20060070885A1 (en) * | 1999-09-17 | 2006-04-06 | Uzoh Cyprian E | Chip interconnect and packaging deposition methods and structures |
US20070084732A1 (en) * | 2005-09-30 | 2007-04-19 | Rohm And Haas Electronic Materials Llc | Leveler compounds |
US20080029891A1 (en) * | 2006-08-03 | 2008-02-07 | Joo Sung J | Semiconductor Device and Method for Fabricating the Same |
US20090166213A1 (en) * | 2005-10-31 | 2009-07-02 | Mitsui Mining & Smelting Co., Ltd. | Production method of electro-deposited copper foil, electro-deposited copper foil obtained by the production method, surface-treated copper foil obtained by using the electro-deposited copper foil and copper-clad laminate obtained by using the electro-deposited copper foil or the surface-treated copper foil |
US20090280243A1 (en) * | 2006-07-21 | 2009-11-12 | Novellus Systems, Inc. | Photoresist-free metal deposition |
EP2161355A1 (en) * | 2007-05-21 | 2010-03-10 | C. Uyemura & Co., Ltd. | Copper electroplating bath |
US20100224501A1 (en) * | 2000-08-10 | 2010-09-09 | Novellus Systems, Inc. | Plating methods for low aspect ratio cavities |
CN110740579A (en) * | 2018-07-18 | 2020-01-31 | 住友金属矿山株式会社 | Copper-clad laminated board |
Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2707323A (en) * | 1955-05-03 | Method of producing copper clad steel | ||
US5368715A (en) * | 1993-02-23 | 1994-11-29 | Enthone-Omi, Inc. | Method and system for controlling plating bath parameters |
US5801100A (en) * | 1997-03-07 | 1998-09-01 | Industrial Technology Research Institute | Electroless copper plating method for forming integrated circuit structures |
US6254760B1 (en) * | 1999-03-05 | 2001-07-03 | Applied Materials, Inc. | Electro-chemical deposition system and method |
US6352467B1 (en) * | 1997-11-10 | 2002-03-05 | Applied Materials, Inc. | Integrated electrodeposition and chemical mechanical polishing tool |
US6503375B1 (en) * | 2000-02-11 | 2003-01-07 | Applied Materials, Inc | Electroplating apparatus using a perforated phosphorus doped consumable anode |
US20030106802A1 (en) * | 2001-05-09 | 2003-06-12 | Hideki Hagiwara | Copper plating bath and plating method for substrate using the copper plating bath |
US6679983B2 (en) * | 2000-10-13 | 2004-01-20 | Shipley Company, L.L.C. | Method of electrodepositing copper |
US20040026122A1 (en) * | 2001-04-06 | 2004-02-12 | Katsuhiko Hayashi | Printed circuit board and production method therefor, and laminated printed circuit board |
US20050173256A1 (en) * | 2002-10-21 | 2005-08-11 | Masashi Kumagai | Copper electrolytic solution containing organic sulfur compound and quaternary amine compound of specified skeleton as additives and electrolytic copper foil produced therewith |
-
2004
- 2004-11-04 US US10/980,320 patent/US20050126919A1/en not_active Abandoned
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2707323A (en) * | 1955-05-03 | Method of producing copper clad steel | ||
US5368715A (en) * | 1993-02-23 | 1994-11-29 | Enthone-Omi, Inc. | Method and system for controlling plating bath parameters |
US5801100A (en) * | 1997-03-07 | 1998-09-01 | Industrial Technology Research Institute | Electroless copper plating method for forming integrated circuit structures |
US6352467B1 (en) * | 1997-11-10 | 2002-03-05 | Applied Materials, Inc. | Integrated electrodeposition and chemical mechanical polishing tool |
US6254760B1 (en) * | 1999-03-05 | 2001-07-03 | Applied Materials, Inc. | Electro-chemical deposition system and method |
US6503375B1 (en) * | 2000-02-11 | 2003-01-07 | Applied Materials, Inc | Electroplating apparatus using a perforated phosphorus doped consumable anode |
US6679983B2 (en) * | 2000-10-13 | 2004-01-20 | Shipley Company, L.L.C. | Method of electrodepositing copper |
US20040026122A1 (en) * | 2001-04-06 | 2004-02-12 | Katsuhiko Hayashi | Printed circuit board and production method therefor, and laminated printed circuit board |
US20030106802A1 (en) * | 2001-05-09 | 2003-06-12 | Hideki Hagiwara | Copper plating bath and plating method for substrate using the copper plating bath |
US20050173256A1 (en) * | 2002-10-21 | 2005-08-11 | Masashi Kumagai | Copper electrolytic solution containing organic sulfur compound and quaternary amine compound of specified skeleton as additives and electrolytic copper foil produced therewith |
Cited By (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20060070885A1 (en) * | 1999-09-17 | 2006-04-06 | Uzoh Cyprian E | Chip interconnect and packaging deposition methods and structures |
US20100224501A1 (en) * | 2000-08-10 | 2010-09-09 | Novellus Systems, Inc. | Plating methods for low aspect ratio cavities |
US8236160B2 (en) | 2000-08-10 | 2012-08-07 | Novellus Systems, Inc. | Plating methods for low aspect ratio cavities |
US20070084732A1 (en) * | 2005-09-30 | 2007-04-19 | Rohm And Haas Electronic Materials Llc | Leveler compounds |
US8506788B2 (en) | 2005-09-30 | 2013-08-13 | Rohm And Haas Electronic Materials Llc | Leveler compounds |
US8262891B2 (en) | 2005-09-30 | 2012-09-11 | Rohm And Haas Electronic Materials Llc | Leveler compounds |
US20090166213A1 (en) * | 2005-10-31 | 2009-07-02 | Mitsui Mining & Smelting Co., Ltd. | Production method of electro-deposited copper foil, electro-deposited copper foil obtained by the production method, surface-treated copper foil obtained by using the electro-deposited copper foil and copper-clad laminate obtained by using the electro-deposited copper foil or the surface-treated copper foil |
US20090277801A1 (en) * | 2006-07-21 | 2009-11-12 | Novellus Systems, Inc. | Photoresist-free metal deposition |
US7947163B2 (en) * | 2006-07-21 | 2011-05-24 | Novellus Systems, Inc. | Photoresist-free metal deposition |
US20090280243A1 (en) * | 2006-07-21 | 2009-11-12 | Novellus Systems, Inc. | Photoresist-free metal deposition |
US8500985B2 (en) | 2006-07-21 | 2013-08-06 | Novellus Systems, Inc. | Photoresist-free metal deposition |
US7482691B2 (en) * | 2006-08-03 | 2009-01-27 | Dongbu Hitek Co., Ltd. | Semiconductor device and method for fabricating the same |
US20080029891A1 (en) * | 2006-08-03 | 2008-02-07 | Joo Sung J | Semiconductor Device and Method for Fabricating the Same |
EP2161355A1 (en) * | 2007-05-21 | 2010-03-10 | C. Uyemura & Co., Ltd. | Copper electroplating bath |
US20100219081A1 (en) * | 2007-05-21 | 2010-09-02 | C. Uyemura & Co., Ltd. | Copper electroplating bath |
EP2161355A4 (en) * | 2007-05-21 | 2012-01-25 | Uyemura C & Co Ltd | Copper electroplating bath |
US8679317B2 (en) * | 2007-05-21 | 2014-03-25 | C. Uyemura & Co., Ltd. | Copper electroplating bath |
CN110740579A (en) * | 2018-07-18 | 2020-01-31 | 住友金属矿山株式会社 | Copper-clad laminated board |
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