WO2011080827A1 - 配線構造及びその形成方法 - Google Patents
配線構造及びその形成方法 Download PDFInfo
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- WO2011080827A1 WO2011080827A1 PCT/JP2009/071777 JP2009071777W WO2011080827A1 WO 2011080827 A1 WO2011080827 A1 WO 2011080827A1 JP 2009071777 W JP2009071777 W JP 2009071777W WO 2011080827 A1 WO2011080827 A1 WO 2011080827A1
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- WIPO (PCT)
- Prior art keywords
- copper wiring
- wiring
- forming
- copper
- barrier layer
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 77
- 239000010949 copper Substances 0.000 claims abstract description 215
- 229910052802 copper Inorganic materials 0.000 claims abstract description 191
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 190
- 230000004888 barrier function Effects 0.000 claims abstract description 66
- 239000000758 substrate Substances 0.000 claims abstract description 51
- 239000012964 benzotriazole Substances 0.000 claims abstract description 32
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000004140 cleaning Methods 0.000 claims abstract description 26
- 238000007772 electroless plating Methods 0.000 claims abstract description 8
- 125000000962 organic group Chemical group 0.000 claims abstract description 5
- 229910052751 metal Inorganic materials 0.000 claims description 20
- 239000002184 metal Substances 0.000 claims description 20
- 239000007864 aqueous solution Substances 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 12
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 7
- 239000000654 additive Substances 0.000 claims description 6
- 150000002894 organic compounds Chemical class 0.000 claims description 5
- -1 imidazole organic compound Chemical class 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 150000002736 metal compounds Chemical class 0.000 claims 2
- 238000000151 deposition Methods 0.000 claims 1
- 230000001681 protective effect Effects 0.000 abstract description 39
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- 239000002253 acid Substances 0.000 abstract description 9
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- 230000008569 process Effects 0.000 description 21
- 230000015572 biosynthetic process Effects 0.000 description 14
- 238000001994 activation Methods 0.000 description 13
- 238000005260 corrosion Methods 0.000 description 13
- 230000007797 corrosion Effects 0.000 description 13
- 239000000243 solution Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 238000001000 micrograph Methods 0.000 description 11
- 229920002120 photoresistant polymer Polymers 0.000 description 11
- 239000011253 protective coating Substances 0.000 description 11
- 230000004913 activation Effects 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 238000009792 diffusion process Methods 0.000 description 9
- 239000011229 interlayer Substances 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 230000001133 acceleration Effects 0.000 description 8
- 239000002585 base Substances 0.000 description 8
- 238000005530 etching Methods 0.000 description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 7
- 239000010703 silicon Substances 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 7
- 238000005259 measurement Methods 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- 238000009713 electroplating Methods 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910001431 copper ion Inorganic materials 0.000 description 4
- 229910052814 silicon oxide Inorganic materials 0.000 description 4
- 238000004544 sputter deposition Methods 0.000 description 4
- 239000012670 alkaline solution Substances 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000000206 photolithography Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 125000003354 benzotriazolyl group Chemical group N1N=NC2=C1C=CC=C2* 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000012212 insulator Substances 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 238000004949 mass spectrometry Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
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- 239000011800 void material Substances 0.000 description 2
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating 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
- 238000006664 bond formation reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
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- 150000002739 metals Chemical class 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
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- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
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- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
- H01L21/76877—Filling of holes, grooves or trenches, e.g. vias, with conductive material
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
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- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
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- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
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- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
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- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
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- H01L21/76801—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing
- H01L21/76829—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing characterised by the formation of thin functional dielectric layers, e.g. dielectric etch-stop, barrier, capping or liner layers
- H01L21/76834—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing characterised by the formation of thin functional dielectric layers, e.g. dielectric etch-stop, barrier, capping or liner layers formation of thin insulating films on the sidewalls or on top of conductors
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- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
- H01L21/76841—Barrier, adhesion or liner layers
- H01L21/7685—Barrier, adhesion or liner layers the layer covering a conductive structure
- H01L21/76852—Barrier, adhesion or liner layers the layer covering a conductive structure the layer also covering the sidewalls of the conductive structure
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- H01L21/76841—Barrier, adhesion or liner layers
- H01L21/76871—Layers specifically deposited to enhance or enable the nucleation of further layers, i.e. seed layers
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- H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
- H01L21/76885—By forming conductive members before deposition of protective insulating material, e.g. pillars, studs
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- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/52—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames
- H01L23/522—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body
- H01L23/532—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body characterised by the materials
- H01L23/53204—Conductive materials
- H01L23/53209—Conductive materials based on metals, e.g. alloys, metal silicides
- H01L23/53228—Conductive materials based on metals, e.g. alloys, metal silicides the principal metal being copper
- H01L23/53238—Additional layers associated with copper layers, e.g. adhesion, barrier, cladding layers
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- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
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- 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
- H05K3/22—Secondary treatment of printed circuits
- H05K3/24—Reinforcing the conductive pattern
Definitions
- the present invention relates to a wiring structure having copper wiring and a method for forming the same.
- circuit boards on which semiconductor devices are mounted such as package boards and silicon interposers.
- copper (Cu) or a copper alloy (hereinafter simply referred to as “copper” includes a copper alloy) is used as a wiring material for these circuit boards because of its low electrical resistance.
- a subtractive method, a semi-additive method, and the like are known as a method for forming copper wiring on these circuit boards. It is said that the semi-additive method is more suitable than the subtractive method for forming narrow pitch copper wirings such as package substrates and silicon interposers.
- a substrate, a copper wiring formed above the substrate, an insulating layer covering the copper wiring, and a barrier layer formed between the copper wiring and the insulating layer are provided. Then, a wiring structure having a Cu—N—R bond (where R is an organic group) at a grain boundary portion on the surface of the copper wiring is provided.
- the Cu—N—R bond is provided at the grain boundary portion on the surface of the copper wiring, the generation of voids is suppressed and the electromigration resistance is improved.
- a barrier layer is provided around the copper wiring, it is possible to prevent diffusion of metal atoms from the copper wiring to the insulating film and to prevent oxidation of the copper wiring due to moisture or oxygen in the insulating film. This avoids an increase in leakage current and an increase in wiring resistance.
- FIG. 1 is a diagram (part 1) illustrating an example of a method of forming a copper wiring by a semi-additive method.
- FIG. 2 is a diagram (part 2) illustrating an example of a method of forming a copper wiring by a semi-additive method.
- FIG. 3 is a cross-sectional view (part 1) illustrating the method for forming the wiring structure according to the first embodiment.
- FIG. 4 is a cross-sectional view (part 2) illustrating the method for forming the wiring structure according to the first embodiment.
- FIG. 5 is a cross-sectional view (part 3) illustrating the method for forming the wiring structure according to the first embodiment.
- FIG. 6 is a diagram showing a flow from the formation of the copper wiring to the formation of the barrier layer.
- FIGS. 1 is a diagram (part 1) illustrating an example of a method of forming a copper wiring by a semi-additive method.
- FIG. 2 is a diagram (part 2) illustrating an example of a
- FIGS. 7A to 7C are diagrams schematically showing the process from the step of forming the protective film to the step of forming the barrier layer.
- FIGS. 8A and 8B are schematic views showing the process of forming a Cu—N—R bond.
- FIG. 9 is a schematic diagram showing a corrosion current measuring method.
- FIG. 10 is a diagram showing the measurement results of the corrosion current density.
- FIG. 11 is a diagram showing the results of mass spectrometry of the surface of a copper wiring that has been performed up to the alkali cleaning step by TOF-SIMS.
- FIG. 12 is a view showing a binarized processing of a micrograph of the surface of the copper wiring after the protective coating is removed.
- FIG. 13 is a diagram showing a micrograph of the surface of the copper wiring after the formation of the barrier layer after binarization.
- FIG. 14A is a diagram showing a binarized cross-sectional micrograph of the sample of Example 1 using NiP as the barrier layer
- FIG. 14B is Example 1 using CoWP as the barrier layer. It is a figure which carries out the binarization process and shows the cross-sectional microscope picture of this sample.
- FIG. 15A is a diagram showing a binarized cross-sectional micrograph of a comparative example sample using NiP as a barrier layer
- FIG. 15B is a comparative sample using CoWP as a barrier layer. It is a figure which carries out the binarization process and shows the cross-sectional micrograph of this.
- FIG. 14A is a diagram showing a binarized cross-sectional micrograph of the sample of Example 1 using NiP as the barrier layer
- FIG. 14B is Example 1 using CoWP as the barrier layer. It is a figure
- FIG. 16 is a diagram showing a binarized cross-sectional micrograph of the sample of Example 2 using CoWP as the barrier layer.
- FIG. 17 is a cross-sectional view (part 1) illustrating the method for forming a wiring structure according to the second embodiment.
- FIG. 18 is a cross-sectional view (part 2) illustrating the method for forming the wiring structure according to the second embodiment.
- FIG. 19 is a cross-sectional view (part 3) illustrating the method for forming the wiring structure according to the second embodiment.
- FIG. 20 is a cross-sectional view (part 4) illustrating the method for forming the wiring structure according to the second embodiment.
- FIG. 21 is a cross-sectional view (part 1) illustrating the method for forming a wiring structure according to the third embodiment.
- FIG. 22 is a cross-sectional view (part 2) illustrating the method for forming the wiring structure according to the third embodiment.
- FIG. 23 is a cross-sectional view (part 3) illustrating the method for forming
- FIGS. 1 and 2 are diagrams showing an example of a method for forming a copper wiring by a semi-additive method.
- a base insulating film 12 is formed on a silicon (Si) substrate 11, and an adhesion layer 13 is further formed thereon by using, for example, Ti.
- the adhesion layer 13 has a function of firmly bonding the copper wiring formed on the adhesion layer 13 and the base insulating film 12 in a process to be described later, and diffusion of metal atoms (Cu) from the copper wiring to the base insulating film 12. And a function as a barrier layer for preventing the above.
- a plating seed layer 14 is formed thinly on the adhesion layer 13.
- a photoresist film 15 is formed on the plating seed layer 14, and exposure and development processing are performed to form openings 15a in which the plating seed layer 14 is exposed in a desired pattern. Form with.
- copper is plated on the plating seed layer 14 inside the opening 15a by an electrolytic plating method or an electroless plating method to form a copper wiring 16.
- the photoresist film 15 is removed.
- portions of the plating seed layer 14 and the adhesion layer 13 that are not covered with the copper wiring 16 are removed by etching.
- an insulating material is deposited on the entire upper surface of the substrate 11 to form an insulating film 17 that covers the copper wiring 16. In this way, a wiring structure is formed.
- the side surface and the upper surface of the copper wiring 16 are in direct contact with the insulating film 17. For this reason, the side surfaces and the upper surface of the copper wiring 16 are oxidized by moisture and oxygen contained in the insulating film 17. Further, it has been confirmed that metal atoms (Cu) diffuse from the copper wiring 16 into the insulating film 17 in a high temperature accelerated test (reliability test) for testing long-term reliability in a high temperature environment.
- a barrier layer so as to cover the side surface and upper surface of the copper wiring.
- a plating layer made of a metal such as NiP so as to cover the side surface and the upper surface of the copper wiring as a barrier layer, oxidation of the copper wiring and diffusion of metal atoms can be avoided.
- Electromigration relates to voids (voids) generated in the wiring, and it can be said that the electromigration resistance is lower as voids are more likely to be generated.
- voids are mainly generated at the grain boundary part (including the grain boundary triple point part: the same applies hereinafter) on the surface of the copper wiring.
- the reason why voids are generated in the grain boundary part can be considered as follows.
- the inventors of the present application conducted various experiments and research in order to avoid the generation of voids.
- R represents an organic group.
- N replaces O and bonds with Cu at the grain boundary portion on the surface of the copper wiring to prevent copper ionization.
- the movement of copper ions is eliminated, so that it is difficult for vacancies to gather at the grain boundary portion, and as a result, generation of voids is avoided and electromigration resistance is increased.
- FIGS. 3 to 5 are cross-sectional views showing a method of forming a wiring structure according to a first embodiment in the order of steps.
- a base insulating film 22 is formed on a substrate 21.
- a silicon substrate is used as the substrate 21, but a substrate made of resin or ceramic can also be used.
- the base insulating film 22 may be a thermal oxide film formed by thermally oxidizing the surface of the silicon substrate 21 or an insulating film formed by a CVD (Chemical Vapor Deposition) method or the like.
- an adhesion layer 23 made of a metal such as Ti (titanium) or a compound thereof is formed on the base insulating film 22 to a thickness of 5 nm to 20 nm, for example.
- the adhesion layer 23 has a function of firmly bonding a copper wiring 26 (see FIG. 2D), which will be described later, and the base insulating film 22, and diffusion of metal atoms (Cu) from the copper wiring 26 to the base insulating film 22. And a function as a barrier layer for preventing the above.
- a plating seed layer 24 made of copper is formed on the adhesion layer 23 to a thickness of 10 nm to 200 nm by, for example, sputtering.
- a photoresist film 25 is formed on the plating seed layer 24, and the photoresist film 25 is exposed and developed to open an opening where the plating seed layer 24 is exposed.
- 25a is formed in a desired pattern (wiring pattern).
- the width of the opening 25a that is, the width of the wiring to be formed is about 2 ⁇ m.
- the plating seed layer 24 and the adhesion layer 23 which are not covered with the copper wiring 26 are removed by etching.
- the plating seed layer 24 is etched using, for example, fluidized potassium. In this etching process, the copper wiring 26 is also etched. However, since the thickness of the copper wiring 26 is sufficiently thicker than that of the seed layer 24 and the adhesion layer 25, the decrease in the thickness of the copper wiring 26 is slight. In consideration of the reduction in film thickness due to this etching, the width of the opening 25a and the plating thickness when the copper wiring 26 is formed are set in advance.
- the adhesion layer 23 is etched using, for example, ammonium fluoride.
- the surface (upper surface and side surface) of the copper wiring 26 is acid cleaned using, for example, an H 2 SO 4 (sulfuric acid) aqueous solution or the like. By this acid cleaning, the surface of the copper wiring 26 is activated. Then, the board
- the substrate 21 on which the protective film 27 is formed is cleaned with an alkaline cleaning liquid (for example, KOH aqueous solution) whose pH is adjusted within the range of 8.0 to 10.0, as shown in FIG.
- the protective film 27 is removed. After the protective film 27 is removed, Cu—N—R bonds remain in the grain boundary portion on the surface of the copper wiring 26.
- the substrate 21 is immersed in an activation treatment liquid containing Pd (palladium) (for example, an acidic liquid containing palladium chloride as a main component).
- an activation treatment liquid containing Pd (palladium) for example, an acidic liquid containing palladium chloride as a main component.
- a metal such as CoWP or NiP is deposited on the side surface and the upper surface of the copper wiring 26 by an electroless plating method to form a barrier layer 28 as shown in FIG.
- the thickness of the barrier layer 28 is, for example, 20 nm to 200 nm.
- the barrier layer 28 is formed of a metal that has high adhesion to the copper wiring 26 and can prevent the intrusion of moisture and oxygen and the diffusion of Cu. Suitable metals for the barrier layer 28 include CoWB, CoP, CoB, NiWP, NiB, and NiWB in addition to the aforementioned CoWP and NiP.
- an insulating film 29 is formed on the entire upper surface of the substrate 21 to a thickness of 5 ⁇ m, for example, and the copper wiring 26 is covered with the insulating film 29.
- the insulating film 29 may be formed of an organic insulator such as resin, or may be formed of an inorganic insulator such as silicon oxide. In this way, the wiring structure according to this embodiment is completed.
- FIG. 6 is a diagram showing a flow from the formation of the copper wiring to the formation of the barrier layer.
- 7A to 7C are diagrams schematically showing a process from the step of forming the protective film 27 to the step of forming the barrier layer 28.
- FIG. 6 is a diagram showing a flow from the formation of the copper wiring to the formation of the barrier layer.
- 7A to 7C are diagrams schematically showing a process from the step of forming the protective film 27 to the step of forming the barrier layer 28.
- step S11 after forming the copper wiring 26 (step S11), acid cleaning is performed to activate the surface of the copper wiring (step S12). Then, the substrate 21 is immersed in the BTA aqueous solution to form the protective film 27, and Cu—N—R bonds are formed at the grain boundary portion on the surface of the copper wiring 26 (step S13).
- FIG. 7A schematically shows a state in which the substrate 21 on which the copper wiring 26 is formed is immersed in a BTA aqueous solution and a protective film 27 is formed on the surface of the copper wiring 26.
- the copper wiring 26 includes a large number of grain boundaries.
- the protective film 27 has Cu—N—R bonds 27 a at the grain boundary portion on the surface of the copper wiring 26.
- the protective film 27 is removed as shown in FIG. 7B, but the Cu—N—R bonds 27a at the grain boundary portion on the surface of the copper wiring 26 remain.
- the surface of the copper wiring 26 is activated with an activation treatment liquid containing Pd (step S15), and then a barrier layer 28 is formed to cover the surface of the copper wiring 26 as shown in FIG. S16).
- oxygen (O) bonded to copper (Cu) exists also in a portion other than the grain boundary on the surface of the copper wiring 26.
- Cu—N is also present in the portion other than the grain boundary.
- -R bond is possible.
- the number is small, and when the protective film 27 is removed by alkali cleaning, most of the Cu—N—R bonds existing in parts other than the grain boundaries are removed.
- the protective coating 27 does not disturb. Therefore, the activation process cannot be performed, and the barrier layer 28 is difficult to be formed. Even if the barrier layer 28 can be formed on the protective film 27, the adhesion of the barrier layer 28 cannot be ensured due to the protective film 27. Therefore, in order to form the barrier layer 28 with high adhesion, a step of removing the protective film 27 is necessary.
- the formation of voids is prevented by forming Cu—N—R bonds 27 a at the grain boundary portions on the surface of the copper wiring 26. Then, as shown in FIGS. 7B and 7C, the protective film 27 is removed, and the surface of the copper wiring 26 is activated to ensure the adhesion between the copper wiring 26 and the barrier layer 28.
- FIGS. 8A and 8B are schematic views showing the formation process of the Cu—N—R bond.
- BTA has a nitrogen (N) double bond.
- N nitrogen
- FIG. 8B N is replaced with O
- BTA and Cu are bonded.
- an imidazole organic compound or an organic compound having a benzene ring and an NH bond can be considered. It is also considered that a chelating agent that chelates Cu has the same effect.
- BTA bonded to Cu at the grain boundary is also removed. If BTA is present on the surface of the copper wiring after alkali cleaning, it should show good corrosion resistance. Therefore, by measuring the corrosion current, it can be determined whether BTA is present on the surface of the copper wiring after the alkali cleaning.
- FIG. 9 is a schematic diagram showing a corrosion current measuring method.
- an Ag / AgCl electrode was used as the reference electrode (RE) 42 of the corrosion current measuring instrument (Potentio Galvano Stat) 40, and a Pt electrode was used as the counter electrode (CE) 41.
- a substrate having a Cu film washed with an alkaline solution having a pH of 8 to 13 after BTA was adsorbed as a measurement sample (WE) 43 was used. Further, an aqueous citric acid solution was used as a measurement solution. Then, the corrosion current density was measured by changing the potential of the measurement sample 43 (Sweep). In this case, if the corrosion current density is low even if the potential of the measurement sample 43 is increased, it can be said that the corrosion resistance is excellent.
- FIG. 10 is a diagram showing the measurement results of the corrosion current density.
- the corrosion current density is 0.5 mA / cm 2 or less, and the corrosion resistance is good. Was recognized. This shows that BTA exists on the surface of the copper wiring even after alkali cleaning.
- the Cu film washed with an alkaline solution having a pH exceeding 10.0 has low corrosion resistance. From this, it is considered that even when the pH of the alkaline cleaning solution exceeds 10, the Cu—N—R bond at the grain boundary is removed. For this reason, it is preferable that the pH of the alkaline cleaning liquid used when removing the protective coating 27 is 10.0 or less. However, if the pH of the alkaline cleaning liquid is lower than 8.0, the protective film 27 cannot be sufficiently removed. Accordingly, the pH of the alkaline cleaning liquid is preferably within the range of 8.0 to 10.0.
- FIG. 11 is a diagram showing the result of mass spectrometry of the surface of the copper wiring that has been performed up to the alkali cleaning step using a TOF-SIMS (Time-of-Flight mass-spectrometer).
- FIG. 11 also shows that BTA exists on the surface of the copper wiring after the alkali cleaning.
- the wiring structure according to this embodiment is highly reliable because it avoids disconnection, current leakage, and increase in electrical resistance even when used for a long period of time.
- the formation of the Cu—N—R bond and the cleaning of the surface of the copper wiring 26 are performed in separate processes. However, these processes can be performed simultaneously. For example, when a BTA aqueous solution having a concentration of 0.5 wt% to 1.0 wt% adjusted to pH 8.0 to 10.0 with KOH is used, Cu—N—R bond formation and the surface of the copper wiring 26 Can be simultaneously performed.
- Example 1 First, the surface of the silicon substrate 21 was thermally oxidized to form a base insulating film 22 having a thickness of about 100 nm to 1000 nm. Thereafter, Ti is formed to a thickness of 5 nm to 20 nm on the base insulating film 22 by sputtering to form an adhesion layer 23, and copper is further formed to a thickness of 10 nm to 200 nm on the adhesion layer 23 by sputtering. Thus, a plating seed layer 24 was obtained (see FIG. 3B).
- a photoresist film 25 was formed on the plating seed layer 24, exposed and developed, and openings 25a were opened in the photoresist film 25 in a predetermined pattern. Thereafter, copper was plated on the plating seed layer 24 inside the opening 25a by electrolytic plating to form a copper wiring 26 having a thickness of about 2 ⁇ m and a width of about 2 ⁇ m (see FIG. 3D).
- the substrate 21 on which the copper wiring 26 was formed was immersed in an aqueous H 2 SO 4 solution having a concentration of 10 wt% for 5 to 60 seconds.
- the temperature of the H 2 SO 4 aqueous solution was room temperature.
- the substrate 21 was immersed in a BTA aqueous solution having a concentration of 0.5 wt% to 1.0 wt% for 60 seconds to 300 seconds to form a protective film 27 covering the upper surface and side surfaces of the copper wiring 26 (FIG. 4C). reference).
- the temperature of the BTA aqueous solution was room temperature.
- FIG. 12 is a view showing a binarized processing of a micrograph of the surface of the copper wiring after the protective coating is removed. From FIG. 12, it can be seen that Cu—N—R bonds are formed at the grain boundary portions of the copper wiring (the white streaks in FIG. 12).
- FIG. 5A is a diagram showing a micrograph of the surface of the copper wiring after the formation of the barrier layer after binarization.
- an insulating film 29 having a thickness of, for example, 5 ⁇ m was formed on the entire upper surface of the substrate 21 with a phenol resin (see FIG. 5B).
- each water washing is implemented for 1 minute.
- FIG. 14A is a diagram showing a cross-sectional micrograph of the sample of Example 1 using NiP as the barrier layer 28, and FIG. 14B is an example using CoWP as the barrier layer 28.
- FIG. It is a figure which carries out the binarization process and shows the cross-sectional microscope picture of the sample of Example 1. 14A and 14B, it can be seen that almost no void is generated at the interface between the copper wiring and the barrier layer.
- Example 2 As a comparative example, a copper wiring structure was formed in the same manner as in Example 1 except that the barrier layer 28 was formed directly on the surface of the copper wiring 26 without forming the protective film 27.
- FIG. 15A is a diagram showing a cross-sectional micrograph of a sample of a comparative example using NiP as the barrier layer 28, and FIG. 15B is a comparative example using CoWP as the barrier layer 28.
- FIG. It is a figure which carries out the binarization process and shows the cross-sectional microscope picture of this sample. As shown in FIGS. 15A and 15B, many voids are generated at the interface between the copper wiring and the barrier layer in the comparative example.
- Example 2 As Example 2, a copper wiring structure was formed in the same manner as in Example 1 except that the formation of Cu—N—R bonds and the cleaning treatment of the surface of the copper wiring 26 were simultaneously performed.
- a BTA aqueous solution having a pH adjusted within the range of 8.0 to 10.0 with KOH and having a concentration of 0.5 wt% to 1.0 wt% It was used.
- the temperature of the BTA aqueous solution was room temperature, and the treatment time was 300 seconds.
- FIG. 16 is a diagram showing a binarized processing of a cross-sectional micrograph of the sample of Example 2 using CoWP as the barrier layer 28.
- Example 2 slightly more voids are generated at the interface between the copper wiring and the barrier layer than in Example 1 (FIG. 14), but less voids are generated than in the comparative example (FIG. 15).
- FIGS. 17 to 20 are sectional views showing a method of forming a wiring structure according to a second embodiment in the order of steps. In the present embodiment, a method for forming a multilayer wiring structure will be described. 17 to 20, the same components as those in FIGS. 3 to 5 are denoted by the same reference numerals.
- a first wiring layer (a copper wiring 26, an insulating film 29, etc.) is formed on the substrate 21 by the method described in the first embodiment.
- a first wiring layer (a copper wiring 26, an insulating film 29, etc.) is formed on the substrate 21 by the method described in the first embodiment.
- an adhesion layer 31 made of a metal such as Ti is formed on the entire upper surface of the substrate 21;
- a plating seed layer 32 made of copper is sequentially formed.
- a photoresist film 33 is formed on the plating seed layer 32, and the photoresist film 33 is exposed and developed to open an opening through which the plating seed layer 32 a is exposed. 33a is formed in a desired pattern.
- FIG. 18 (a) copper is plated to a thickness of 2 ⁇ m, for example, on the plating seed layer 32 inside the opening 33a to form a copper wiring.
- FIG. 18B after the photoresist film 33 is removed, the plating seed layer 32 and the adhesion layer 31 that are not covered with the copper wiring 34 are etched as shown in FIG. 18C. Remove with.
- the substrate 21 on which the copper wiring 34 is formed is immersed in a BTA aqueous solution, and as shown in FIG. And the protective film 35 which covers an upper surface is formed.
- the protective coating 35 contains BTA (Cu—N—R) bonded to Cu at the grain boundary portion on the surface of the copper wiring 34.
- the substrate 21 on which the protective coating 35 is formed is washed with an alkaline aqueous solution whose pH is adjusted to a range of 8.0 to 10.0, and the protective coating 35 is removed as shown in FIG. . Even after the protective coating 35 is removed, BTA bonded to Cu remains in the grain boundary portion on the surface of the copper wiring 34.
- the surface of the copper wiring 34 is activated by immersing the substrate 21 in the activation treatment liquid. Thereafter, a barrier layer 36 is formed by electroless plating or the like to cover the side and top surfaces of the copper wiring 34 as shown in FIG.
- an insulating film 37 is formed on the entire upper surface of the substrate 21, and the copper wiring 34 is covered with the insulating film 36. Thereby, the second wiring layer is completed. Thereafter, if necessary, the third wiring layer, the fourth wiring layer,... Are formed in the same manner as the second wiring layer. In this way, the wiring structure (multilayer wiring structure) according to this embodiment is completed.
- the adhesion layers 23 and 31 and the barrier layers 28 and 36 prevent the copper wirings 26 and 34 from being oxidized by moisture and oxygen contained in the insulating films 22, 29 and 37. Therefore, the wiring structure according to the present embodiment is highly reliable because it avoids disconnection, current leakage, and increase in electrical resistance even when used for a long period of time.
- FIGS. 21 to 23 are cross-sectional views showing a method of forming a wiring structure according to a third embodiment in the order of steps.
- the present embodiment shows an example applied to an LSI wiring structure.
- an element isolation film 52 and a transistor 53 are formed on a semiconductor (silicon) substrate 51 by a known method. Thereafter, an interlayer insulating film 54 covering the element isolation film 52 and the transistor 53 and a protective film 55 thereon are formed.
- the interlayer insulating film 54 is made of silicon oxide and has a thickness of 300 nm.
- the protective film 55 is made of SiOC and has a thickness of 50 nm.
- a via hole reaching the transistor 53 from the upper surface of the protective film 55 is formed using a known photolithography method and etching method.
- a barrier layer 56 made of TiN is formed to a thickness of 25 nm on the entire upper surface of the substrate 51 by sputtering, for example, and the inside of the via hole is covered with the barrier layer 56.
- a W (tungsten) film is formed on the entire upper surface of the substrate 51 by CVD or the like, and W is buried in the via hole to form a W plug 57.
- the W film and the barrier layer 56 on the protective film 55 are removed by, for example, CMP (Chemical-Mechanical-Polishing) method until the protective film 55 is exposed. In this way, the structure shown in FIG.
- an interlayer insulating film 58 is formed on the protective film 55 and the W plug 57 with a thickness of, for example, 300 nm using silicon oxide or the like. Then, a wiring groove is formed in a desired pattern in the interlayer insulating film 58 by using a photolithography method and an etching method. Thereafter, a barrier layer 59 is formed on the entire upper surface of the substrate 51 with Ta, for example, to a thickness of 5 nm to 20 nm, for example, and a plating seed layer (not shown) made of Cu is formed thereon with a thickness of 50 nm to 200 nm. To do.
- a copper film is formed on the plating seed layer by electrolytic plating, and copper is embedded in the wiring groove to form the copper wiring 60.
- the copper film, the plating seed layer, and the barrier layer 59 on the interlayer insulating film 58 are removed by CMP until the interlayer insulating film 58 is exposed.
- the upper surface of the copper wiring 60 is subjected to an acid activation process using, for example, an aqueous H 2 So 4 solution having a concentration of 10 wt%.
- the substrate 51 is immersed in an aqueous BTA solution to form a protective film (BTA film) 61 on the copper wiring 60 as shown in FIG.
- the protective film 61 has Cu—N—R bonds at the grain boundary portion on the upper surface of the copper wiring 61.
- the surface of the copper wiring 60 is alkali washed with a KOH aqueous solution or the like to remove the protective coating 61. Even when the protective coating 61 is removed, Cu—N—R bonds remain at the grain boundary portions of the copper wiring 61. Then, the board
- an interlayer insulating film 63, a stopper film 64, an interlayer insulating film 65, and a stopper film 66 are sequentially formed on the entire upper surface of the substrate 51.
- the interlayer insulating films 63 and 65 are made of silicon oxide
- the stopper films 64 and 66 are made of silicon nitride.
- a wiring groove 65a having a depth reaching the stopper film 64 from the upper surface of the stopper film 66 and a via hole reaching the copper wiring 60 (barrier layer 62) from the upper surface of the stopper film 64 are used. 63a.
- a barrier layer 67 made of, for example, NiP or CoWP and a plating seed layer (not shown) made of copper are sequentially formed on the entire upper surface of the substrate 51.
- a copper film is formed on the plating seed layer by electrolytic plating, and copper is embedded in the via hole 63a and the wiring groove 65a.
- the second copper wiring 69 and the via contact 68 that electrically connects the first copper wiring 60 and the second copper wiring 69 are formed.
- the copper film, the plating seed layer, and the barrier layer 67 on the stopper layer 65 are removed by CMP until the stopper layer 65 is exposed.
- the upper surface of the copper wiring 69 is subjected to an acid activation treatment with, for example, an aqueous H 2 SO 4 solution having a concentration of 10 wt%. Thereafter, the substrate 51 is immersed in an aqueous BTA solution to form a protective film (not shown) on the copper wiring 69.
- This protective film has Cu—N—R bonds at the grain boundary portion on the upper surface of the copper wiring 69.
- the surface of the copper wiring 69 is alkali washed with a KOH aqueous solution or the like to remove the protective film.
- the substrate 51 is immersed in an activation treatment solution containing Pd to activate the surface of the copper wiring 69, and then NiP or CoWP is electrolessly plated on the copper wiring 69 to form a barrier layer (metal cap). Layer) 70 is formed.
- an activation treatment solution containing Pd to activate the surface of the copper wiring 69
- NiP or CoWP is electrolessly plated on the copper wiring 69 to form a barrier layer (metal cap).
- Layer 70 is formed.
- the wiring structure according to the present embodiment is highly reliable because it avoids disconnection, current leakage, and increase in electrical terms even when used for a long period of time.
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Abstract
Description
図3~図5は、第1の実施形態に係る配線構造の形成方法を工程順に示す断面図である。
まず、シリコン基板21の表面を熱酸化させて、厚さが100nm~1000nm程度の下地絶縁膜22を形成した。その後、スパッタ法により下地絶縁膜22の上にTiを5nm~20nmの厚さに形成して密着層23とし、更にスパッタ法により密着層23の上に銅を10nm~200nmの厚さに形成してめっきシード層24とした(図3(b)参照)。
比較例として、保護被膜27を形成することなく銅配線26の表面に直接バリア層28を形成すること以外は実施例1と同様にして、銅配線構造を形成した。
実施例2として、Cu-N-R結合の形成と銅配線26の表面の洗浄処理とを同時に行うこと以外は実施例1と同様にして、銅配線構造を形成した。Cu-N-R結合の形成及び銅配線26の表面の洗浄には、KOHによりpHを8.0~10.0の範囲内に調整した濃度が0.5wt%~1.0wt%のBTA水溶液を使用した。BTA水溶液の温度は室温とし、処理時間は300秒間とした。
図17~図20は、第2の実施形態に係る配線構造の形成方法を工程順に示す断面図である。本実施形態では、多層配線構造の形成方法について説明する。また、図17~図20において、図3~図5と同一物には同一符号を付している。
図21~図23は、第3の実施形態に係る配線構造の形成方法を工程順に示す断面図である。本実施形態は、LSIの配線構造に適用した例を示している。
Claims (11)
- 基板と、
前記基板の上方に形成された銅配線と、
前記銅配線を被覆する絶縁層と、
前記銅配線と前記絶縁層との間に形成されたバリア層とを具備し、
前記銅配線の表面の粒界の部分にCu-N-R結合(但し、Rは有機基)を有することを特徴とする配線構造。 - 前記基板と前記銅配線との間に、下地絶縁膜と、該下地絶縁膜と前記銅配線との密着性を確保する密着層とが設けられていることを特徴とする請求項1に記載の配線構造。
- 前記バリア層が、CoWP、CoWB、CoP、CoB、NiP、NiWP、NiB及びNiWBのうちのいずれか1種の金属化合物を主成分とすることを特徴とする請求項1に記載の配線構造。
- 基板の上方に銅配線を形成する工程と、
前記銅配線を有機化合物に接触させて前記銅配線の表面の粒界部分にCu-N-R結合(但し、Rは有機基)を形成する工程と、
洗浄液により前記銅配線の表面を洗浄する工程と、
前記洗浄後の前記銅配線の表面に金属を被着させてバリア層を形成する工程と、
前記基板の上方に、前記銅配線及び前記バリア層を覆う絶縁膜を形成する工程と
を有することを特徴とする配線構造の形成方法。 - 前記有機化合物が、イミダゾール系有機化合物、又はベンゼン環とNーH結合とを有する有機化合物のいずれかであることを特徴とする請求項4に記載の配線構造の形成方法。
- 前記洗浄液のpHが8.0から10.0の範囲内であることを特徴とする請求項4に記載の配線構造の形成方法。
- 前記バリア層を、無電解めっきにより形成することを特徴とする請求項4に記載の配線構造の形成方法。
- 前記バリア層が、CoWP、CoWB、CoP、CoB、NiP、NiWP、NiB及びNiWBのうちの1種の金属化合物を主成分とすることを特徴とする請求項4に記載の配線構造の形成方法。
- 前記Cu-N-R結合を形成する工程及び前記銅配線の表面を洗浄する工程は、pHを8.0から10.0の範囲内に調整したBTA(Benzo triazole)水溶液を使用して同時に行うことを特徴とする請求項4に記載の配線構造の形成方法。
- 前記銅配線を、セミアディティブ法により形成することを特徴とする請求項4に記載の配線構造の形成方法。
- 前記銅配線を形成する工程の前に、前記基板上に下地絶縁膜を形成する工程と、前記下地絶縁膜の上に金属からなる密着層を形成する工程とを有し、
前記銅配線を形成する工程と前記Cu-N-R結合を形成する工程との間に、前記銅配線に覆われていない部分の前記密着層を除去する工程を有することを特徴とする請求項4に記載の配線構造の形成方法。
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JP2011547210A JP5387695B2 (ja) | 2009-12-28 | 2009-12-28 | 配線構造の形成方法 |
PCT/JP2009/071777 WO2011080827A1 (ja) | 2009-12-28 | 2009-12-28 | 配線構造及びその形成方法 |
EP09852805.2A EP2521165B1 (en) | 2009-12-28 | 2009-12-28 | Method for forming a wiring structure |
KR1020127009191A KR101315173B1 (ko) | 2009-12-28 | 2009-12-28 | 배선 구조 및 그 형성 방법 |
US13/431,127 US20120181070A1 (en) | 2009-12-28 | 2012-03-27 | Interconnection structure and method of forming the same |
US14/706,764 US9263326B2 (en) | 2009-12-28 | 2015-05-07 | Interconnection structure and method of forming the same |
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EP (1) | EP2521165B1 (ja) |
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US20150243555A1 (en) | 2015-08-27 |
JPWO2011080827A1 (ja) | 2013-05-09 |
JP5387695B2 (ja) | 2014-01-15 |
KR101315173B1 (ko) | 2013-10-08 |
EP2521165A4 (en) | 2014-08-06 |
KR20120052414A (ko) | 2012-05-23 |
US20120181070A1 (en) | 2012-07-19 |
US9263326B2 (en) | 2016-02-16 |
EP2521165A1 (en) | 2012-11-07 |
EP2521165B1 (en) | 2018-09-12 |
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