CN101466869A - Electroless plating NiP adhering and/or covering layer for copper wiring layer - Google Patents
Electroless plating NiP adhering and/or covering layer for copper wiring layer Download PDFInfo
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- CN101466869A CN101466869A CNA200680055001XA CN200680055001A CN101466869A CN 101466869 A CN101466869 A CN 101466869A CN A200680055001X A CNA200680055001X A CN A200680055001XA CN 200680055001 A CN200680055001 A CN 200680055001A CN 101466869 A CN101466869 A CN 101466869A
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- 239000010949 copper Substances 0.000 title claims abstract description 68
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 44
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000007772 electroless plating Methods 0.000 title description 4
- 239000000758 substrate Substances 0.000 claims abstract description 75
- 238000007747 plating Methods 0.000 claims abstract description 52
- 239000011521 glass Substances 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 16
- 230000003750 conditioning effect Effects 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 238000004140 cleaning Methods 0.000 claims abstract description 7
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 6
- 239000002243 precursor Substances 0.000 claims abstract description 5
- 230000003197 catalytic effect Effects 0.000 claims description 16
- 230000008021 deposition Effects 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- 230000036541 health Effects 0.000 claims description 2
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 claims 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims 1
- 238000000151 deposition Methods 0.000 abstract description 11
- 238000005530 etching Methods 0.000 abstract description 3
- 230000001143 conditioned effect Effects 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 87
- 239000000243 solution Substances 0.000 description 46
- 230000000052 comparative effect Effects 0.000 description 16
- 101150003085 Pdcl gene Proteins 0.000 description 13
- 239000011159 matrix material Substances 0.000 description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000010408 film Substances 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 230000004888 barrier function Effects 0.000 description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 6
- 230000002829 reductive effect Effects 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000004973 liquid crystal related substance Substances 0.000 description 5
- 239000010409 thin film Substances 0.000 description 5
- 101710134784 Agnoprotein Proteins 0.000 description 4
- FEWJPZIEWOKRBE-JCYAYHJZSA-L L-tartrate(2-) Chemical compound [O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O FEWJPZIEWOKRBE-JCYAYHJZSA-L 0.000 description 4
- 241000080590 Niso Species 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 229940095064 tartrate Drugs 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 3
- -1 carboxyl organic compound Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000008139 complexing agent Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000011010 flushing procedure Methods 0.000 description 3
- 239000004310 lactic acid Substances 0.000 description 3
- 235000014655 lactic acid Nutrition 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 2
- 229910000085 borane Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000013016 damping Methods 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 150000002611 lead compounds Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical group CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 239000008351 acetate buffer Substances 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 150000001299 aldehydes Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000004411 aluminium Substances 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
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 239000012769 display material Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 description 1
- 150000002343 gold Chemical class 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229940046892 lead acetate Drugs 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 235000011006 sodium potassium tartrate Nutrition 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000005846 sugar alcohols Chemical class 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
- C23C18/40—Coating with copper using reducing agents
- C23C18/405—Formaldehyde
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1646—Characteristics of the product obtained
- C23C18/165—Multilayered product
- C23C18/1651—Two or more layers only obtained by electroless plating
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
- C23C18/1872—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment
- C23C18/1886—Multistep pretreatment
- C23C18/1889—Multistep pretreatment with use of metal first
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
- C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
- C23C18/36—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- 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
- H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
- H01L21/288—Deposition of conductive or insulating materials for electrodes conducting electric current from a liquid, e.g. electrolytic deposition
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- Electrodes Of Semiconductors (AREA)
Abstract
A method of depositing a copper interconnection layer on a substrate such on a glass substrate for use e.g. in TFT-LCD flat panel interconnection system. The method according to the invention comprising the steps of: a) optionally cleaning the substrate, b) optionally micro-etching the substrate, c) depositing a catalyzation layer on the substrate to obtain a catalyzed substrate, d) conditioning the catalyzed substrate with a conditioning solution to obtain a conditioned catalyzed substrate, e) plating the catalyzed substrate with a NiP layer by contacting said substrate or at least a portion thereof with a wet bath mixture comprising precursors of Ni and P, f) depositing a copper catalyst layer onto the plated NiP layer, depositing a Cu layer on said copper catalyst layer.
Description
Technical field
The present invention relates to go up the settled layer copper interconnection layer to be used for for example method of TFT-LCD flat panel interconnection system in substrate (for example substrate of glass).More specifically, the present invention relates to make the method for TFT-LCD two-d display panel, this panel comprises the copper-connection bus, and it is used for being electrically connected with the signal electrode bus and the scan electrode bus of display panels (LCD) or plasma body or similar display panel by thin film transistor (TFT) each pixel with picture element matrix.
Background technology
The ultimate principle that can be used as the TFT-LCD of computer screen or television indicator is known.These for example are described in detail in KTK Scientific publishers Tokyo, chap.7, in 1987 by " lcd tv display: the principle of liquid crystal and application " that E.Kaneko showed.
In typical two-d display panel, for example in LCD or plasma panel, display material, for example liquid crystal or discharge gas (respectively) itself are clipped between the substrate of glass of two electrical isolations.Electrical interconnection line or bus arrangement apply voltage with counter electrode on a surface of at least one substrate of glass, have liquid crystal or discharge gas between electrode.
For example, in activity matrix LCD system, during the matrix form that has is arranged, a plurality of signals or data electrode wire or bus and a plurality of grid or scan electrode bus are arranged on a surface of a substrate of glass.
When data electrode and grid intersect mutually, at least one thin film transistor as switch (on-off) and pixel electrode is arranged, each line of matrix is activated in order so that the TFT switch cuts out, and with its corresponding data line connection of each pixel electrode in this line, provide signal information with the suitable color at the related pixel electrode, this and traditional C RT system class are seemingly.
When the size of display panel increased, the frequency of actuate signal needed to increase, thereby the stray capacitance of these lines is increased, and this transmission that means actuate signal again produces delay.
In order to reduce these delay phenomenons, for example at the 498-501 page or leaf of Japan Display ' 89, the article that is entitled as " the low resistance copper address wire that is used for TFT-LCD " proposes, because the resistivity of copper is much smaller than the resistivity of aluminium, thus use copper with substitution of Al as the grid material of thin film transistor and relevant matrix interconnection line or bus.This copper layer deposits by sputtering method, but because its ability that is attached to glass surface is not good, thereby tantalum layer in the middle of needing.
Know a kind of method of making this metal interconnecting layer on the glass surface of TFT-LCD display panel by US-B 6413845, it uses the Ni film that is deposited on glass surface by electroless plating, covers photic etching reagent film then so that this metal deposition is formed pattern.Then, deposited gold film on the Ni film is at last by electroless plating (wet deposition method) method depositing copper film on this gold layer, with the suitable copper-connection system of final acquisition.Yet the use of photic etching reagent has increased the cost of this method.
Those skilled in the art are also known, and copper tends at its sedimentary material layer internal diffusion, therefore, must provide a barrier layer in this substrate before being deposited on the copper layer in the substrate.Aforesaid method at Journal of the electronic society, among the 149-11-2002, is entitled as by people such as for example Osaka that " the nothing electricity nickel ternary that is applied to diffused barrier layer in the copper interconnection technology is along SiO
2And deposit " article in describe.Yet these films that are disclosed in this document can't be attached on the substrate of glass, and have bad thickness evenness under the disclosed condition in this article.
Therefore, still having now needs a kind of method of design, and this method can not be increased in sedimentary cost on the diffused barrier layer, and the good adhesion with substrate of glass is provided, and preferably also can be applicable to the cap layer deposition process of copper layer.
According to the present invention, found that sedimentary under certain conditions no electric NiP layer can be used for making adhering to tectum and all has good Cu resistance barrier ability.The homogeneity of also finding the roughness of these layers and thickness is satisfactory.
The interconnection and/or the grid structure that are made of Cu/NiP/ glass are made by no electric NiP and Cu plating.NiP layer plating is on substrate of glass, and so that adhering to and hindering barrier of Cu to be provided, and Cu layer plating is on NiP, as for example gate material.Find that the NiP layer has good adhesion property on substrate of glass, and the good barrier layer with respect performance that can avoid the copper diffusion.Find that also the roughness and the thickness evenness of NiP layer are satisfactory.X-ray analysis demonstration NiP is an amorphous, and has good thermostability.This NiP adhesion layer is an individual layer, and therefore, it realizes easily than the described lamination of US-B6413845, thereby compares with the method for other wet/dry and to have reduced production cost.
Summary of the invention
According to the present invention, deposition for example is used for that the method for the copper interconnection layer of TFT-LCD flat panel interconnection system may further comprise the steps in the substrate of for example substrate of glass:
A) randomly, with the substrate cleaning,
B) randomly, with the substrate microetch,
C) go up deposition Catalytic Layer (101) in substrate (100), with acquisition catalytic substrate (100,101),
D) nurse one's health this catalytic substrate with conditioning solution, with the catalytic substrate (100,101,102) of acquisition through conditioning,
E) by this substrate or its at least a portion are contacted with the wet bath mixture of the precursor of precursor that comprises Ni and P, plating does not have electric NiP layer (103) on this catalytic substrate, thereby obtains the catalytic substrate (100,101,102,103) through conditioning of plating NiP,
F) deposited copper catalyst layer (104) on this plating NiP layer, and
G) go up copper layer (105) at described copper catalyst layer (104).
Preferably, the step of this method (f) is undertaken by using silver or palladium salt deposition of thin silver layer (104) on described NiP layer, and copper layer (105) is then by using mantoquita such as CuSO
4Carry out plating and deposit.
The invention still further relates to base material, certain part covers Catalytic Layer, conditioning layer, NiP layer, copper catalyst layer and copper layer in order at least thereon.
The accompanying drawing summary
Describe the present invention with reference to the accompanying drawings in detail, as an example, these accompanying drawings are represented:
Fig. 1 represents the schematic top plan view of TFT-LCD display panel.
Fig. 2 is the synoptic diagram of switch matrix configuration.
Fig. 3 is the detail drawing of interconnection line between between TFT and electrode.
Fig. 4 illustration according to the present invention on a substrate of glass sectional view of copper layer.
Embodiment
Display panels system is made of a plurality of pixels that are arranged to matrix in substrate, and is covered by the thin layer of glass substrate, and it covers all pixels together.
Each pixel can be considered the square-shaped electrode system, and it has bottom and top transparent electrode, and is liquid crystal layer betwixt.It above transparency electrode the substrate of glass that is coated with polarization layer.
In order to have and structure like the traditional C RT system class, wherein covering shady shielding harness system combines with color dot and electron beam, be arranged to have by the matrix of the top of screen to the continuous horizontal sweep trace of bottom, this pixel system system arranges in a similar manner, and each line of pixel is activated (being scanned) in order, and each pixel in the line that has started receives the proportional electronic signal of pixel required color therewith at the apex electrode place.Therefore, each pixel needs one by sweep signal (line) switch driven, and it can be connected to the top electrodes of each pixel suitable voltage (signal source is usually via electrical condenser) when being activated.At present, suitable switch is thin film transistor (TFT), and it makes according to the MOS technology usually.
In order to make such TFT-FDP screen, thereby need make at interval with fixed, thin film transistor (MOS type) has drain electrode, source electrode and grid.
The drain electrode of each TFT is connected to the transparent pixels electrode usually, and source electrode is linked in the signal electrode bus that is made of copper at present, and grid is connected to the scan electrode bus.
On behalf of this, Fig. 1 line up 10,11 respectively ... 12; 20,21 ... 22; 30,31 ... 32; 40,41 ... the synoptic diagram of a plurality of pixels of 42.Switch S
10, S
11... S
12And S separately
40, S
41... S
41Be connected to sweep trace L via its gate separately
1, L
2, L
3... L
4, simultaneously, the source electrode separately of switch is connected to signal rows C
1, C
2... C
4, and the drain electrode of each TFT is connected to its pixel electrode separately.
Fig. 2 schematically illustrates the fundamental principle (duplicate numbers is indicated identical cognation) of switch matrix circuit.
Fig. 2 a represents basic TFT switch matrix, wherein every line L
1, L
2, L
3Be connected to the gate of MOS transistor, and each signal electrode line C
1, C
2, C
3Be connected to transistorized source electrode, this transistor drain then is connected to liquid crystal pixel electrodes, and other electrode is ground connection then.
The matrix arrangements that Fig. 2 b explanation is identical, different is the parallel pixel 10,11 that is connected in, the electrical condenser F of 12 electrode
1, F
2, F
3This system can apply voltage always between the electrode of pixel, and can change this voltage (that is color of color dot) when each line sweep.
Fig. 3 is the synoptic diagram of an interconnection system, in order to the matrix form interconnection system on the crossover location that is implemented in adjacent threads L and row C." scanning " interconnection line L has the small-sized extension 62 of the gate 63 that is linked to TFT66, and line L and TFT are deposited on the clear glass substrate.Interconnection line L produces electrical isolation via insulation layer 60 with signal (OK) line C (line C and interconnection line L intersect).Yet signal wire C is electrically connected with the source electrode 65 of TFT, drains simultaneously 64 to be electrically connected with pixel electrode 61.
The present invention relates to the mode (when they are made and be deposited on the substrate of glass by copper) of the copper grid of making TFT switch and scanning interconnection line L (and signal interconnection line C) basically.
Fig. 4 illustration according to the sectional view that is deposited on the copper layer of substrate of glass of the present invention.Substrate of glass 100 is coated with Catalytic Layer 101, conditioning layer 102, NiP layer 103, copper catalyst layer 104 and copper layer 105.
Hereinafter obtain the method for this interlayer with the way of example explanation.
According to preferred embodiment above-mentioned each step is described below.
Step (a): the cleaning of glass surface:
Use ultraviolet ray, ozone solution and/or skim soln, for example NaOH, Na
2CO
3, Na
3PO
4Mixture, lip-deep organic impurity is removed.When the surface is enough clean, if or this processing mode may damage substrate or cause the chemical reaction of unexpected property the time, can omit this step.For UV and/or ozonize, this step is preferably carried out 10 seconds to 10 minutes time, more preferably 30 seconds to 3 minutes.When using skim soln, this cleaning carries out time of preferred 30 seconds and 10 minutes 30 ℃ to 100 ℃ temperature, more preferably carries out 1 minute to 5 minutes at 50 ℃ to 90 ℃.Then, clean this substrate with the deionization pure water.
Step (b): the microetch of glass surface:
The purpose of this step is to produce little anchor on glass surface, is attached to suprabasil effect to strengthen the NiP layer.Can provide tack if this glass surface is enough coarse, if or this processing mode may on glass surface, cause deleterious reaction the time, can omit this step.Usually, this step comprises the HF (NH that also can comprise 10g/L to 100g/L of 0.1 volume % to 5 volume % by immersion
4F) in the aqueous solution 10 seconds to 5 minutes and carry out, or immerse usually and comprise the HF of 0.3 volume % to 3 volume % and the NH of 30g/L to 60g/L
4In the aqueous solution of F 30 seconds to 3 minutes.
Step (c): the Catalytic Layer of NiP:
Available SnCl
2And PdCl
2Solution carries out this step, to produce palladium layer as thin as a wafer on glass basic surface.For this reason, SnCl is immersed in substrate
2In the solution, with the flushing of D.I. water, afterwards it is immersed PdCl then
2In the solution.Preferred SnCl2 solution is for comprising 0.1 volume % to 10 volume %HCl and 0.1g/L to 50g/L SnCl
2The aqueous solution.PdCl
2Solution is by HCl that contains 0.01 volume % to 5 volume % and the PdCl of 0.01g/L to 5g/L
2The aqueous solution make.More preferably, SnCl
2Solution comprises the SnCl that is dissolved in the 1g/L to 20g/L in 0.5% to the 5%HCl solution
2, and PdCl
2Solution then comprises the PdCl that is dissolved in the 0.1g/L to 2g/L in 0.05% to the 1%HCl solution
2Following chemical reaction: Sn may take place in expectation on glass surface
2++ Pd
2+ 
Sn
4++ Pd.
Step (d): conditioning:
Usually use the aqueous solution that comprises reductive agent to carry out this step.Found that this step is for obtaining the steps necessary of even NiP plating layer.The reducible lip-deep oxidisability Sn of this step
4+, and promote reductibility NiP electroplating chemical.This step is undertaken by immerse forming to be similar to used solution in the following step (e) but not comprise in the solution of Ni salt.Use comprises 5g/L to 50g/L NaH
2PO
2Solution.This program was carried out 10 seconds to 3 minutes usually.
Step (e): NiP plating:
Use NiSO
4And NaH
2PO
2Source as Ni and P.NaH
2PO
2Also as reductive agent.Complexing agent is selected from the have carboxyl organic compound and composition thereof of (COOX:X is H, metal, alkyl).More typically, it is selected from acetate, tartrate, oxyacetic acid, lactic acid and composition thereof.If necessary, adjust the pH value of solution with the pH damping fluid.In a specific examples, use the NiSO that comprises 10g/L to 45g/L
47H
2The NaH of O, 3g/L to 50g/L
2PO
2H
2O, 5mL/L to 50mL/L oxyacetic acid (70%) and the tartaric solution of 3g/L, and with the substrate immersion wherein.The lead compound that can add 0.5ppm to 10ppm is as stablizer.Temperature that plating is bathed and pH value respectively in 50 ℃ to 90 ℃ and 2 to 9 scope, more typically, in 70 ℃ to 90 ℃ and 2 to 6 scope.The time of plating can determine according to the speed of plating and desired thickness, usually, be 30 seconds to 1 minute under the situation that is the NiP layer.At last, with D.I. water washing substrate.
Step (f): the catalysis of Cu:
Substrate of glass is dipped in AgNO
3At NH
4Among the OH, PdCl
2In HCl or Pd (NH
3)
4Cl
2At NH
4Solution among the OH is to make silver or palladium layer as thin as a wafer on the NiP surface.More generally use 0.1g/L to 10g/L AgNO
30.01% to 1%NH
4Solution among the OH.This step is carried out 10 seconds to 5 minute usually, more preferably 30 seconds to 1 minute.As for the palladium layer, use in 0.01% to 5% HCl, to contain 0.01g/L to 5g/L PdCl
2Solution.More preferably, the PdCl of 0.1g/L to 2g/L
2Be dissolved in 0.05% to the 1%HCl solution.In other specific examples, use 0.1g/L to 10g/L Pd (NH
3)
4Cl is at 0.1% to 5% NH
4Solution among the OH.Then, if the non-conformity of quality of plating Cu closes when requiring, also can carry out reduction step.Usually the HCHO solution of use 0.1% to 5% is 10 seconds to 5 minutes, more generally uses 0.5% to 3% HCHO solution.Usually can use DMAB (dimethyamine borane) solution 30 seconds to 5 minutes of 0.1g/L to 5g/L to replace HCHO solution, more generally use the DMAB solution 1 minute to 3 minutes of 0.5g/L to 3g/L.
Step (g): plating Cu:
The copper plating solution comprises copper source, complexing agent, reductive agent and pH damping fluid.Usually use the CuSO of 2g/L to 15g/L
4As the Cu source.Complexing agent is selected from EDTAS, tartrate, Citrate trianion, diamines, sugar alcohol and composition thereof.In a specific examples, use 20g/L to 60g/L Seignette salt.Reductive agent is selected from aldehyde, amine, diamine, amido borine, oxoethanoic acid, xitix, hypophosphite and composition thereof.In specific examples, use 0.05% to 1% HCHO.Can add the Ni compound in case of necessity (is the NiCl of 0.1g/L to 10g/L
2) to promote the Cu plating.The sulphur compound that can add 0.1ppm to 2ppm is as stablizer.The available for example NaOH of the pH value of solution is adjusted at 9 to 13 scope.The time of plating is according to the speed of plating and desired thickness and determine; For the Cu layer of hundreds of nanometers, be generally 1 minute to 60 minutes, be more typically 5 minutes to 40 minutes.
According to another specific examples of the present invention, can on the Cu layer, deposit the NiP layer as covering or protective layer by repeating step (c) to (e) (in the preceding cleaning that can carry out copper of step (c)) preferably.
Understand the present invention better by following embodiment and Comparative Examples.
Embodiment 1
Substrate of glass is comprised NaH, Na 80 ℃ of immersions
2CO
3, Na
3PO
4Skim soln in 3 minutes, so that the organic impurity on it is removed.Behind deionized water rinsing, it is immersed rare HF/NH
4In the HF solution 1 minute, on this surface, to make little anchor.With after the D.I. water flushing, it is immersed in comprises 10g/L SnCl in the 1%HCl solution
2SnCl
2In the solution, be immersed in then in the 0.1% HCl solution and comprise 0.3g/L PdCl
2PdCl
2In (solution), in these two kinds of solution, respectively immersed 2 minutes.After washing this substrate with D.I. water, its immersion is contained in the conditioning solution of reductive agent 30 seconds.Then, it is immersed in the NiP plating solution.Table 1 has shown composition and the plating condition that plating is bathed.
Table 1
| Form | Condition |
| NiSO 4·7H 2O：30g/L | Be adjusted to pH5 with acetate buffer |
| NaH 2PO 2·H 2O：30g/L | Temperature: 70 ℃ |
| Lactic acid: 15mL/L | |
| Tartrate: 15g/L | |
| Lead acetate 3H 2O：1.5ppm |
After the flushing of D.I. water, this substrate is immersed in 0.3% NH
4Contain 1.5g/LAgNO in the OH solution
3AgNO
3In the solution 45 seconds.After washing this substrate with D.I. water, it is immersed in the Cu plating solution, this plating solution and corresponding plating condition thereof are as shown in table 2:
Table 2
| Form | Condition |
| CuSO 4·5H 2O：7g/L | Be adjusted to |
| C 4H 4NaO 6·5H 2O：34g/L | Room temperature |
| Na 2CO 3：3g/L | |
| NiCl 2：1g/L | |
| HCHO(37％)：13g/L | |
| Thiocarbamide: 0.2ppm |
Confirm that by carrying out " adhesive tape " test (nothing is peeled off) the Cu/NiP layer of plating has excellent tack for substrate of glass.Two-layer roughness and thickness evenness meet the requirements (be respectively be lower than 5nm and in 5%).The NiP film is made of the Ni of 91 weight % and the P of 9 weight %.X-ray analysis shows that NiP is an amorphous.The copper layer of plating on the NiP layer has low resistivity (2.6 μ Ω cm).X-ray analysis shows that also these two NiP and Cu layer have good thermal resistance, be 400 ℃ following 1 hour, and the copper that diffuses to the NiP layer behind thin heating steps can be ignored.
Comparative Examples 1
On same glass substrate,, but do not comprise the step of deposition NiP layer with the plating coating copper layer in steps of employed institute among the embodiment 1.The copper layer that is obtained demonstrates tack bad on substrate of glass, and it easily is stripped from.
Comparative Examples 2
As carry out the deposition of NiP and Cu layer as described in the embodiment 1 in the mode that is similar to embodiment 1, different is not carry out step (a), or the solution temperature of step (a) is lower than 30 ℃.Coating demonstrates the not good and shortage reproducibility of homogeneity, because the not enough cleaning in surface.
Comparative Examples 3
Carry out among the embodiment 1 except step (b) institute in steps.Many NiP layers show bad to the tack of substrate.
Comparative Examples 4
On substrate of glass, carry out embodiment 1 described step (a) and (b).Omit step (c), then as tentatively carrying out step (d) and (e) as described in the embodiment 1.Yet no NiP is deposited on this substrate of glass.
Comparative Examples 5
Carry out various Comparative Examples according to embodiment 1, the SnCl that different is in step (c)
2Concentration or be lower than 0.1g/L or be higher than 50g/L, perhaps PdCl
2Concentration or be lower than 0.01g/L or be higher than 5g/L.In all these examples, no NiP layer plating is in this substrate, and perhaps, when plating, the NiP layer demonstrates not good homogeneity, bad tack and/or lacks reproducibility.
Comparative Examples 6
In on substrate of glass, carry out step 1 institute in steps, different is not carry out step (d), perhaps NaH
2PO
2The employed concentration of solution or be lower than 5g/L or be higher than 50g/L.In all these different situations, no NiP layer plating is in this substrate, even perhaps on the plating, this NiP layer also demonstrates not good thickness evenness, bad tack and/or lacks reproducibility.
Comparative Examples 7
Carry out each example according to embodiment 1, that different is NiSO
47H
2O, NaH
2PO
2H
2The concentration of O, lactic acid, oxyacetic acid, tartrate and lead compound is not in each scope that above-mentioned steps (e) is defined.No NiP layer plating is in this substrate, even perhaps promptly be on the plating, this NiP layer also demonstrates not good homogeneity, bad tack and/or lacks reproducibility.
Comparative Examples 8
Carry out various examples to be similar to embodiment 1 described mode, temperature that the NiP plating bathes that different is is lower than 50 ℃ or be higher than 90 ℃.In some cases, no NiP layer plating is in this substrate, and perhaps when on the plating, this NiP layer demonstrates not good thickness evenness and/or lacks reproducibility.
Comparative Examples 9
Carry out various examples according to embodiment 1, pH value that the NiP plating bathes that different is is adjusted at and is lower than 2 or be higher than 9.In all these different instances, no NiP layer plating is in this substrate, and perhaps when on the plating, this NiP layer demonstrates not good homogeneity, bad tack and/or lacks reproducibility.
Comparative Examples 10
Carry out each step of embodiment 1, but do not carry out step (f), in the case, no Cu layer plating is on the NiP layer.
Comparative Examples 11
Carry out various examples similar to Example 1, that different is AgNO in step (f)
3Concentration is lower than 0.1g/L or is higher than beyond the 10g/L.Do not have Cu layer on the plating, even perhaps plating, the copper layer also demonstrates not good thickness evenness, bad tack, resistivity and/or lacks reproducibility.
Comparative Examples 12
Carry out various examples according to embodiment 1, different is to use PdCl in step (f)
2Solution in HCl or Pd (NH
3)
4Cl
2At NH
4Solution among the OH replaces AgNO
3At NH
4Solution among the OH.This step is used 0.3g/L PdCl
2In 0.1%HCl or 0.25g/LPd (NH
3)
4Cl
2At 2% NH
4Solution impregnation among the OH 3 minutes and finishing.The Cu layer of plating demonstrates thickness evenness, tack, resistivity and the reproducibility suitable with embodiment 1.
Comparative Examples 13
Carry out various examples similar to Example 1, that different is CuSO
45H
2O, C
4H
4KNNaO
65H
2In the scope separately that the concentration of O, Ni compound, HCHO and/or sulphur compound is not defined in above-mentioned steps (g) respectively.No Cu layer plating perhaps, demonstrates not good homogeneity, bad tack, high resistivity and/or lacks reproducibility when time on the plating in this substrate.
Comparative Examples 14
Carry out various examples similar to Example 1, the pH value that different is bathes the Cu plating is adjusted at and is lower than 9 or be higher than 13.
No Cu layer plating also demonstrates not good homogeneity, bad tack, high resistivity and/or lacks reproducibility even perhaps plate in substrate.
Claims (4)
1, a kind of in substrate, for example on substrate of glass, deposition is used for for example method of the copper interconnection layer of TFT-LCD flat panel interconnection system, and it may further comprise the steps:
A) randomly, with the substrate cleaning,
B) randomly, with the substrate microetch,
C) go up deposition Catalytic Layer (101) in substrate (100), with acquisition catalytic substrate (100,101),
D) nurse one's health this catalytic substrate with conditioning solution, with the catalytic substrate (100,101,102) of acquisition through conditioning,
E) by this substrate or its at least a portion are contacted with the wet bath mixture of the precursor of precursor that comprises Ni and P, plating does not have electric NiP layer (103) on this catalytic substrate, thereby obtains the catalytic substrate (100,101,102,103) through conditioning of plating NiP,
F) deposited copper catalyst layer (104) on this plating NiP layer, and
G) go up copper layer (105) at described copper catalyst layer (104).
2, according to the process of claim 1 wherein that described step f) undertaken by using silver salt deposition of thin silver layer (104) on described NiP layer.
3, according to the method for claim 1 or 2, wherein said Cu layer (105) is to use mantoquita, for example CuSO
4, sedimentary by plating.
4, a kind of base material (100), certain part covers Catalytic Layer (101), conditioning layer (102), NiP layer (103), copper catalyst layer (104) and copper layer (105) in regular turn at least thereon.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/EP2006/063286 WO2007144026A1 (en) | 2006-06-16 | 2006-06-16 | Electroless nip adhesion and/or capping layer for copper interconnexion layer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101466869A true CN101466869A (en) | 2009-06-24 |
Family
ID=36809611
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA200680055001XA Pending CN101466869A (en) | 2006-06-16 | 2006-06-16 | Electroless plating NiP adhering and/or covering layer for copper wiring layer |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP2009540585A (en) |
| CN (1) | CN101466869A (en) |
| TW (1) | TWI417948B (en) |
| WO (1) | WO2007144026A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101967630B (en) * | 2009-07-28 | 2012-07-25 | 中国科学院金属研究所 | Method for preparing catalyst layer on surface of magnesium and magnesium alloy by chemical plating of nickel and nickel-phosphorus alloy |
| CN105706222A (en) * | 2013-11-21 | 2016-06-22 | 株式会社尼康 | Wiring-pattern manufacturing method and transistor manufacturing method |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8938627B2 (en) | 2009-07-07 | 2015-01-20 | International Business Machines Corporation | Multilayer securing structure and method thereof for the protection of cryptographic keys and code |
| CN102776495B (en) * | 2012-07-13 | 2014-05-07 | 南京航空航天大学 | Chemical nickel-plating method for capacitive touch screen indium tin oxide (ITO) wiring |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US6835895B1 (en) * | 1996-12-19 | 2004-12-28 | Ibiden Co., Ltd. | Printed wiring board and method for manufacturing the same |
| JP2000357671A (en) * | 1999-04-13 | 2000-12-26 | Sharp Corp | Method of manufacturing metal wiring |
| JP4613271B2 (en) * | 2000-02-29 | 2011-01-12 | シャープ株式会社 | METAL WIRING, MANUFACTURING METHOD THEREOF, AND THIN FILM TRANSISTOR AND DISPLAY DEVICE USING THE METAL WIRING |
| JP3707394B2 (en) * | 2001-04-06 | 2005-10-19 | ソニー株式会社 | Electroless plating method |
| JP3808037B2 (en) * | 2001-05-15 | 2006-08-09 | インターナショナル・ビジネス・マシーンズ・コーポレーション | Method for electroless deposition and patterning of metal on a substrate |
| JP2003264159A (en) * | 2002-03-11 | 2003-09-19 | Ebara Corp | Catalyst treatment method and catalyst treatment solution |
-
2006
- 2006-06-16 CN CNA200680055001XA patent/CN101466869A/en active Pending
- 2006-06-16 WO PCT/EP2006/063286 patent/WO2007144026A1/en active Application Filing
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101967630B (en) * | 2009-07-28 | 2012-07-25 | 中国科学院金属研究所 | Method for preparing catalyst layer on surface of magnesium and magnesium alloy by chemical plating of nickel and nickel-phosphorus alloy |
| CN105706222A (en) * | 2013-11-21 | 2016-06-22 | 株式会社尼康 | Wiring-pattern manufacturing method and transistor manufacturing method |
| CN105706222B (en) * | 2013-11-21 | 2018-11-23 | 株式会社尼康 | The manufacturing method of wiring pattern and the manufacturing method of transistor |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2009540585A (en) | 2009-11-19 |
| TWI417948B (en) | 2013-12-01 |
| WO2007144026A1 (en) | 2007-12-21 |
| TW200816291A (en) | 2008-04-01 |
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