CN101416283B - Method of removing conductive metal oxide thin-film and apparatus thereof - Google Patents
Method of removing conductive metal oxide thin-film and apparatus thereof Download PDFInfo
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- CN101416283B CN101416283B CN2006800542174A CN200680054217A CN101416283B CN 101416283 B CN101416283 B CN 101416283B CN 2006800542174 A CN2006800542174 A CN 2006800542174A CN 200680054217 A CN200680054217 A CN 200680054217A CN 101416283 B CN101416283 B CN 101416283B
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- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 120
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 120
- 239000010409 thin film Substances 0.000 title claims abstract description 116
- 238000000034 method Methods 0.000 title claims abstract description 29
- 239000000463 material Substances 0.000 claims abstract description 32
- 239000000758 substrate Substances 0.000 claims abstract description 26
- 239000003792 electrolyte Substances 0.000 claims description 36
- 238000006722 reduction reaction Methods 0.000 claims description 13
- 239000011521 glass Substances 0.000 abstract description 8
- 230000008929 regeneration Effects 0.000 abstract description 3
- 238000011069 regeneration method Methods 0.000 abstract description 3
- 238000006073 displacement reaction Methods 0.000 abstract 1
- 239000008151 electrolyte solution Substances 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 description 14
- 239000002184 metal Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000010408 film Substances 0.000 description 7
- 239000002253 acid Substances 0.000 description 4
- 238000003486 chemical etching Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 239000010808 liquid waste Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 101100165177 Caenorhabditis elegans bath-15 gene Proteins 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
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- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
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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
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- 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
- H01L21/321—After treatment
- H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
- H01L21/32133—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only
- H01L21/32134—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by liquid etching only
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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
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- 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
- H01L21/321—After treatment
- H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
- C03C17/23—Oxides
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C23/00—Other surface treatment of glass not in the form of fibres or filaments
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D1/00—Electroforming
- C25D1/04—Wires; Strips; Foils
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
- C25F3/00—Electrolytic etching or polishing
- C25F3/02—Etching
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
- C25F7/00—Constructional parts, or assemblies thereof, of cells for electrolytic removal of material from objects; Servicing or operating
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/21—Oxides
- C03C2217/23—Mixtures
- C03C2217/231—In2O3/SnO2
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/30—Aspects of methods for coating glass not covered above
- C03C2218/32—After-treatment
- C03C2218/328—Partly or completely removing a coating
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Abstract
The invention provides a method and apparatus for removing conductive metal oxide thin-film until the end has non residual. Opposed to conductive metal oxide thin-film (12) lying on a surface of basematerial (11), positive electrode (13) and first negative electrode (14) are disposed in parallel in a non contact state. Between the positive electrode (13) and the first negative electrode (14), there are disposed multiple second negative electrodes (17) arranged in a contact state in the direction of width of conductive metal oxide thin-film (12). While electrolytic solution lies in the interspaces of conductive metal oxide thin-film (12) and electrodes (13), (14) and (17), a voltage is exerted to the electrodes (13), (14) and (17), relative displacement of the base material (11) is carriedout so that the conductive metal oxide thin-film (12) first passes the negative electrodes (14) and (17) and thereafter passes the positive electrode (13). The invention can effectively remove conductive metal oxide thin-film until the terminal section without generating flaw or stress deformation, and can realize the regeneration use of expensive functional glass substrate.
Description
Technical field
The conductive metal oxide thin film that the present invention relates to will be for example to be formed at base material by sputter evaporation etc. is removed, is made its method that can be reused and implements the device of this method.
Background technology
For example, the high functional glass substrate that is formed with ITO (oxide of indium and tin has the film of transparent conductivity) has good optical performance (transmissivity etc.) and mechanical performance (flatness etc.), is used to for example flat-panel monitor.But, because the price height of this high functional glass substrate when therefore the ITO that forms on its surface can't satisfy quality control standard, by this ITO is removed, reduces cost so that be used to again.
As the method for removing conductive metal oxide thin films such as this ITO, have by machinery and rub method of removing or the method for removing of wiping by chemical etching.Wherein, preceding a kind of method as shown in figure 11, the conductive metal oxide thin film 1a that utilizes abrasive brush 2 will be formed at the surface of machined object 1 removes by rubbing to wipe.
In addition, a kind of method in back as shown in figure 12, machined object 1 be impregnated in by chemical reaction can make in the chemical reagent 3 of conductive metal oxide thin film 1a dissolving, remove the conductive metal oxide thin film 1a (for example, with reference to patent documentation 1,2) on the surface that is formed at machined object 1 by this.
Patent documentation 1: Japanese patent laid-open 6-321581 communique
Patent documentation 2: Japanese patent laid-open 9-86968 communique
The announcement of invention
But, rub by machinery and to wipe the method remove owing to be to rub wiping with abrasive brush, therefore stay on the surface of machined object sometimes and rub scratch mark (flaw) or produce stress deformation.Stayed when rubbing the scratch mark and just can't utilize again.In addition, when being flat-panel monitor,, therefore, utilizing the machinery of the way of contact to rub to wipe to have and produce broken possibility because the thickness of glass of glass substrate is about 0.5mm as the machined object of object.So, must carry out the pressure adjustment of fine abrasive brush, peeling off fully needs the long period.
On the other hand, therefore the method for removing by chemical etching, produces chemical stress at substrate surface sometimes owing to used strong acid or the such chemical reagent of highly basic, generates metamorphic layer at substrate surface.In addition, want attention very during processing, not only operability is poor, and must carry out liquid waste processing to the electrolyte after using.In addition,, must extract operation in addition in order to reclaim rare metal, therefore very uneconomical.
The problem to be solved in the present invention is, rubbing by machinery in the method for wiping, because of generation is rubbed the scratch mark or stress deformation can't utilize base material again, and must carry out the fine pressure adjustment of abrasive brush, and peel off fully needs problems such as long-time; By in the method for chemical etching, substrate surface generates metamorphic layer sometimes, and operability variation not only, and must carry out liquid waste processing to the electrolyte after using in order to reclaim rare metal, also will be extracted operation and problem such as uneconomical in addition.
In order as far as possible not rub scratch mark and stress deformation etc. in that base material is residual, and do not use the such chemical reagent of strong acid or highly basic just the conductive metal oxide thin film of base material can be removed effectively, even reach the degree that does not also have residual film in the end of base material, the method for removing of conductive metal oxide thin film of the present invention has following topmost feature:
With positive electrode and the 1st negative electrode be formed at the conductive metal oxide thin film subtend of substrate surface and be arranged side by side with contactless state, while is at leading portion or back segment or the leading portion and the back segment of described the 1st negative electrode, with the 2nd negative electrode be formed at the conductive metal oxide thin film subtend of substrate surface and be provided with a plurality of at the Width of described conductive metal oxide thin film with contact condition, then, with at described positive electrode, the 1st negative electrode, the state that has electrolyte between the 2nd negative electrode and described conductive metal oxide thin film, to described positive electrode, the 1st negative electrode, the 2nd negative electrode applies voltage, make the conductive metal oxide thin film that is formed at substrate surface with respect to described positive electrode, the 1st negative electrode, the 2nd negative electrode moves, make conductive metal oxide thin film pass through the 1st negative electrode, by positive electrode, utilize reduction reaction to remove the conductive metal oxide thin film of described substrate surface by this behind the 2nd negative electrode.
Removing in the method for described conductive metal oxide thin film of the present invention, between positive electrode and the 1st negative electrode, the 2nd negative electrode is a plurality of with the contact condition configuration at the Width of described conductive metal oxide thin film, the conductive metal oxide thin film that is formed at substrate surface can be removed by this, even reach the degree that does not also have residual film in the end of base material.
Removing in the method for described conductive metal oxide thin film of the present invention as described positive electrode and the 1st negative electrode, also can be used the electrode that be configured to zigzag (staggered configuration) narrower than the wide cut of conductive metal oxide thin film.
Removing in the method for described conductive metal oxide thin film of the present invention is 10 by using resistivity
2Ω cm～10
6The electrolyte of Ω cm can be removed the conductive metal oxide thin film that is formed at substrate surface effectively.
But the device of the method for removing the application of the invention of conductive metal oxide thin film of the present invention is implemented.This device possesses: with the conductive metal oxide thin film subtend that is formed at substrate surface and be positive electrode and the 1st negative electrode that contactless state is arranged side by side; At leading portion or back segment or the leading portion and the back segment of described the 1st negative electrode, with described conductive metal oxide thin film subtend and at the Width of conductive metal oxide thin film with the 2nd a plurality of negative electrode of contact condition configuration; Store the electrolytic bath of the electrolyte between the conductive metal oxide thin film of supplying with described positive electrode, the 1st negative electrode, the 2nd negative electrode and being formed at described substrate surface, described positive electrode, the 1st negative electrode, the 2nd negative electrode and base material be impregnated in the electrolyte; Described positive electrode and the 1st negative electrode, the 2nd negative electrode are applied the power supply of voltage; And the conductive metal oxide thin film that is formed at substrate surface is moved with respect to described positive electrode, the 1st negative electrode, the 2nd negative electrode and make conductive metal oxide thin film by the travel mechanism by positive electrode behind the 1st negative electrode, the 2nd negative electrode.
Removing in the device of described conductive metal oxide thin film of the present invention, described positive electrode and the 1st negative electrode can be than the wide cut of conductive metal oxide thin film narrow be configured to continuously jagged electrode or than the wide cut of conductive metal oxide thin film narrow be configured to forniciform electrode continuously.
Among the present invention; 1) by leading portion or back segment or leading portion and back segment at the 1st negative electrode; Width at described conductive metal oxide thin film disposes a plurality of the 2nd negative electrodes with contact condition, can be does not rub scratch mark or stress deformation and only conductive metal oxide thin film is removed effectively in that base material is residual.
2) by Width at conductive metal oxide thin film, described positive electrode and the 1st negative electrode are configured to continuously than narrow zigzag of the wide cut of conductive metal oxide thin film or the bending narrower than the wide cut of conductive metal oxide, can effectively remove the conductive metal oxide thin film that is formed at substrate surface, even reach the degree that does not also have residual film in the end of base material.
In addition, owing to do not use strong acid or the such chemical reagent of highly basic,, can realize with the base material being the resources circulation of rare metal etc. of representative, help reducing cost so also can reduce environmental pollution.
The simple declaration of accompanying drawing
The figure of Fig. 1 (a) for basic principle of the present invention is described, (b) figure for problem is described.
The schematic diagram of Fig. 2 for example 1 of the present invention is described (a) is end view, (b) is vertical view.
Fig. 3 is the figure of the relation of translational speed in the expression example 1 of the present invention and electroreduction electric current.
The figure that Fig. 4 describes for the reducing condition when excessive with respect to translational speed electroreduction electric current.
The schematic top plan view of Fig. 5 for example 2 of the present invention is described.
The figure of Fig. 6 for describing in the example of the present invention 2 shown in Figure 5, to the reducible situation in final end of conductive metal oxide thin film.
The schematic top plan view of Fig. 7 for example 3 of the present invention is described.
The figure of Fig. 8 for describing in the example of the present invention 3 shown in Figure 7, to the reducible situation in final end of conductive metal oxide thin film.
The schematic side view of Fig. 9 for example 4 of the present invention is described.
Figure 10 has carried out the figure of an example of the retracting device after electroreduction is handled to conductive metal oxide thin film by the present invention for expression.
Figure 11 is for to rubbing the figure that the method for wiping metallic film describes by machinery.
The figure of Figure 12 for the method for removing metallic film by chemical etching is described.
Label declaration: 11 base materials, 12 conductive metal oxide thin films, 12a conductive metal, 13 positive electrodes, 14 the 1st negative electrodes, 15 electrolyte, 16 power supplys, 17 the 2nd negative electrodes.
The best mode that carries out an invention
The present invention is after utilizing non-contacting electrolysis wash-out to weaken adhesive force, when removing the conductive metal that is formed at base material, between positive electrode and the 1st negative electrode, Width at described conductive metal oxide thin film disposes a plurality of the 2nd negative electrodes with contact condition, and the conductive metal oxide thin film that can realize effectively removing base material does not by this have the purpose of any residual films yet until the end of base material.
Embodiment
Below, with Fig. 1 basic principle of the present invention is described after, describe in detail with Fig. 2～Figure 10 and to be used to implement best mode of the present invention and various form.
The present invention is as much as possible not in the processing method of residual flaw of base material or stress deformation etc., and is the method for removing of not using the conductive metal oxide thin film of strong acid or highly basic.
Promptly, the present invention is shown in Fig. 1 (a), formed on the surface insulant of conductive metal oxide thin film 12 or conducting objects etc. base material 11 above, for example with contactless state and row arrangement positive electrode 13 and the negative electrode (hereinafter referred to as 1st negative electrode) 14 wideer than the wide cut of described conductive metal oxide thin film 12.
Then, for example described positive electrode 13 and the 1st negative electrode 14 are flooded in the electrolyte 15 that is disposed in the electrolytic bath, apply direct voltage or pulse voltage by power supply 16, base material 11 is moved, make conductive metal oxide thin film 12 pass through positive electrode 13 by the 1st negative electrode 14 backs.
So just formed the closed circuit of power supply 16 (+)-positive electrode 13-electrolyte 15-conductive metal oxide thin film 12-electrolyte 15-the 1st negative electrode 14-power supply 16 (-), near the surface generation H of the conductive metal oxide thin film 12 the positive electrode 13
2Micro air bubble.
At this moment, near the H of the surface of the conductive metal oxide thin film positive electrode 13 12 generation
2Become reducing agent, play the O that removes in the conductive metal oxide thin film 12
2Effect.In addition, because this H
2Be to produce, so this reaction is effective reduction reaction at the interface of conductive metal oxide thin film 12.
Do not have and utilize O
2The conductive metal oxide thin film 12 that carries out combination becomes and only has metallic element, exists with the state that adhesion weakens on the surface of base material 11.The conductive metal 12a that weakens with combining of base material 11 for example uses flexibility objects such as rotation foams by the wiping of rubbing of weak stress, can positively be removed from base material 11.
But, shown in Fig. 1 (a), if positive electrode 13 and the 1st negative electrode 14 are in contactless state with conductive metal oxide thin film 12, the electrolyte 15 that then is present in 12 of described positive electrode 13 and the 1st negative electrode 14 and conductive metal oxide thin films becomes resistance, can't effectively conductive metal oxide thin film 12 be removed.On the contrary, if positive electrode 13 and the 1st negative electrode 14 are in contact condition with conductive metal oxide thin film 12, then a large amount of bubbles (hydrogen and oxygen) are attached to two electrodes 13,14, the current density of electrode 13,14 descends, cause the effect of removing of conductive metal oxide thin film 12 to reduce, can't remove fully.
In addition, in the electrode configuration of Fig. 1 (a), if the 1st negative electrode is by the final end of conductive metal oxide thin film 12, then the interval of conductive metal oxide thin film 12 and the 1st negative electrode 14 enlarges, therefore the magnitude of current that flows through conductive metal oxide thin film 12 sharply descends, and can't flow through the necessary electric current of reduction.
That is, in the electrode of Fig. 1 (a) configuration, the rearward end of conductive metal oxide thin film 12 is shown in Fig. 1 (b), and only the interval X part of 14 of positive electrode 13 and the 1st negative electrodes is not reduced.In addition, in the configuration of the electrode of Fig. 1 (a),, increase so flow through the voltage of the necessary electric current of reduction owing to the resistance of the electrolyte 15 that has 12 of the 1st negative electrode 14 and conductive metal oxide thin films.
Therefore, among the present invention, for example positive electrode 13 in the electrolyte in impregnated in electrolytic bath 15 and the 1st negative electrode are 14, as shown in Figure 2, dispose a plurality of the 2nd negative electrodes 17 at the Width of conductive metal oxide thin film 12 with contact condition.Among Fig. 2 18 compresses mechanism for spring that the 2nd negative electrode 17 and conductive metal oxide thin film 12 are compressed etc.
Among the present invention, described the 2nd negative electrode 17 interval L each other is preferably below 10 times of interval X (mm) (with reference to Fig. 2 (b)) of 14 of positive electrode 13 and the 1st negative electrodes more than or equal to the interval X (mm) of 14 of positive electrode 13 and the 1st negative electrodes.
If the 2nd negative electrode 17 interval L each other is less than the interval X (mm) of 14 of positive electrode 13 and the 1st negative electrodes, then, a large amount of bubbles (hydrogen) cause the current density of electrode descend (conductive metal oxide thin film 12 takes place remove the not exclusively situation of (inhomogeneous)) owing to being attached to the 2nd negative electrode 14.On the contrary, if surpass 10 times of interval X (mm) of 14 of positive electrode 13 and the 1st negative electrodes, then the effect that produced of the efficient of reduction current and additional contact electrode all descends.
Among the present invention, the necessary current value I (A) of reducing is preferably more than 0.003 times of the value that multiplies each other of the electrode width Y (cm) of the relative moving speed (cm/ minute) of positive electrode the 13, the 1st negative electrode the 14, the 2nd negative electrode 17 and base material 11 and positive electrode 13, (with reference to Fig. 3) below 0.01 times.
This be because, if less than described 0.003 times, then reduction is not enough, only the surface element of conductive metal oxide thin film 12 is reducible removes.
If above 0.01 times, then conductive metal oxide thin film 12 is by over reduction, conductive metal oxide thin film 12 is peeled off from base material 11 in reduction, the interval that positive electrode 13 and conductive metal oxide thin film are 12 enlarges, the electric current that flows through conductive metal oxide thin film 12 sharply descends, and is difficult to flow through the required electric current of reduction.
If positive electrode 13 then can reduce once more by released part, after this situation repeats to take place then as shown in Figure 4, the residual not reduction part that narrow strip is arranged.
The present invention according to this formation, utilization is set at the leading portion of the 1st negative electrode 14 or the 2nd negative electrode 17 of back segment or leading portion and back segment, the resistance that is present in the electrolyte 15 of 12 of described the 1st negative electrode 14 and conductive metal oxide thin films disappears, the efficient of removing of conductive metal oxide thin film 12 can be improved, the required electric current of reduction can be reduced simultaneously.In addition, by dispose a plurality of the 2nd negative electrodes 17 with interval L, can reduce the decline that is attached to the current density of the electrode that electrode 13,14,17 causes because of a large amount of bubbles.
Also can substitute the present invention shown in Figure 2 with formation shown in Figure 5.
In the example shown in Figure 5, positive electrode shown in Figure 2 13 and the 1st negative electrode 14 at the Width of conductive metal oxide thin film 12, are configured to the zigzag narrower than the wide cut of conductive metal oxide thin film 12 side by side.
By positive electrode 13 and the 1st negative electrode 14 are configured to zigzag, as shown in Figure 6, electroreduction, reducible final end to conductive metal oxide thin film 12 take place at adjacent positive electrode 13 and the 1st negative electrode 14 (parts of representing with hacures among Fig. 6).
In addition, example with Fig. 7 substitutes example shown in Figure 5, as shown in Figure 7, positive electrode 13 and the 1st negative electrode 14 also can be configured to the bending narrower than the wide cut of conductive metal oxide thin film 12 continuously at the Width of conductive metal oxide thin film 12, can obtain same action effect at the dashed area generation electroreduction of Fig. 8.
In addition, also can be as shown in Figure 9, described the 2nd negative electrode 17 is disposed with the final end state of contact with conductive metal oxide thin film 12, for example when base material 11 (conductive metal oxide thin film 12) is mobile, can make the 2nd negative electrode 17 and base material 11 same moved further, keep relative position relation with the final end of conductive metal oxide thin film 12.
Among above the present invention, conductive metal oxide thin film 12 owing to carry out micronize (0.1 μ m is following) as metal solid, therefore as shown in figure 10, can utilize water flow jet 20 to peel off the reducing metal after electroreduction is handled.Figure 10 shows that and with the mechanical stripping of flexibility material 21 example as supplementary means.
Then, utilize electrolyte catch tray 22 that electrolyte and the reducing metal of removing are lodged in accumulator tank 23 together, utilize micro air bubble generator 24 to sneak into micro air bubble.By this, because micro air bubble forms nuclear, make metal particle form bulk, available filter reclaims, and therefore, reclaims the reducing metal by filter 25.Among Figure 10 26 represents pump.
As mentioned above, the present invention is not that the electrolysis wash-out of usually implementing, machined object is applied positive voltage removes dereaction, but machined object is applied the processing method that negative voltage is a feature.
The cell reaction here is owing to be to produce H in the minimum zone at conductive metal oxide thin film interface
2Reaction, therefore need electric current hardly.
Thereby, used electrolyte 15 can be neutral salt solution, running water, river course water of using always or the electrolyte of having sneaked into neutral salt solution in running water or river course water etc., when base material 11 does not contact with positive electrode 13, negative electrode 14, as previously mentioned, preferably resistivity is adjusted into 10
2Ω cm～10
6Ω cm is more preferably and is adjusted into 10
3Ω cm～10
4Ω cm.
This be because, among the present invention, when positive electrode the 13, the 1st negative electrode 14 does not contact with base material 11, for resistivity less than 10
2The electrolyte 15 that the conductivity of Ω cm is high, because the voltage that puts on 13,14 at two electrodes is not by conductive metal oxide thin film 12, and form conducting state by electrolyte 15 between described two electrodes 13,14, so the efficient of removing of conductive metal oxide thin film 12 reduces.In addition, if resistivity surpasses 10
6Ω cm then must apply high voltage, is unfavorable for cost control.
Like this,, therefore can use in the past the running water that should not use as electrolyte 15 or river course water etc., consider more satisfactory from cost-effectivenes and fail safe aspect because the present invention is suitable for resistivity than higher electrolyte 15.
Subsidiary mentioning uses running water as electrolyte, will be formed with thickness 1500 * 10 on glass substrate
-10The machined object of 100mm * 100mm of the ITO of m impregnated in the aforementioned electrolyte as shown in Figure 2.
In same electrolyte, flooded Cu system positive electrode and the 1st negative electrode, (width of positive electrode and the 1st negative electrode all is 120mm to the 2nd negative electrode, and two interelectrode interval X are 10mm.In addition, the 2nd negative electricity is very 2).
Between described positive electrode and the 1st negative electrode, the 2nd negative electrode, apply the direct voltage (electric current of 150V; 6A), machined material was moved with 1m/ minute.By behind the conductive metal oxide thin film, described moving stopped 60 seconds at the 1st negative electrode, the final end of reduction conductive metal oxide thin film.
After implementing above the present invention, ITO is removed the final end until conductive metal oxide thin film, can realize the regeneration of glass substrate.
In addition, the positive electrode of above-mentioned experimental example and the 1st negative electrode are divided into 12 parts at the Width of machined object to be disposed with zigzag, each the 1st negative electrode that gets cutting apart is provided with 1 the 2nd negative electrode, and in addition, other all condition is identical with above-mentioned experimental example to experimentize.As a result, ITO is removed the final end until conductive metal oxide thin film, and glass substrate can be realized regeneration.
The ITO that will remove by above-mentioned experimental example is by the described retracting device of Figure 10 (mesh of filter: 1 μ m, accumulator tank capacity: 50 liters, micro air bubble generating capacity: 2 liters/minute, to the discharge rate of filter: 10 liters/minute) reclaim after, In and Sn can be used as metal solid and are recovered.In addition, micro air bubble is sneaked into after 1 minute and begin filter is spued.
With X-ray microanalyzer described recovery metal is carried out confirming after the constituent analysis, as the In of ITO composition and Sn with In: Sn=9: 1 ratio is detected, and ITO can this component ratio be recovered.
The present invention is not limited to described example, the example that electrolyte is supplied with at for example available necessary position to base material or electrode waits to substitute and makes base material or electrode impregnated in example in the electrolyte, in the scope of the technological thought that each claim item is put down in writing, but certain appropriate change execution mode.In addition, the recovery of sneaking into the reducing metal in the electrolyte also is not limited to method shown in Figure 10.
Claims (7)
1. the method for removing of conductive metal oxide thin film, it is characterized in that, with positive electrode and the 1st negative electrode be formed at the conductive metal oxide thin film subtend of substrate surface and be arranged side by side with contactless state, while is at leading portion or back segment or the leading portion and the back segment of described the 1st negative electrode, with contact condition be provided with a plurality of at the Width of described conductive metal oxide thin film the 2nd negative electrode, then, with at these positive electrodes, the 1st negative electrode, the state that has electrolyte between the 2nd negative electrode and described conductive metal oxide thin film, to described positive electrode, the 1st negative electrode, the 2nd negative electrode applies voltage, make the conductive metal oxide thin film that is formed at substrate surface with respect to described positive electrode, the 1st negative electrode, the 2nd negative electrode moves, make conductive metal oxide thin film pass through the 1st negative electrode, by positive electrode, utilize reduction reaction to remove the conductive metal oxide thin film of described substrate surface by this behind the 2nd negative electrode.
2. the method for removing of conductive metal oxide thin film as claimed in claim 1, it is characterized in that, interval between the 2nd negative electrode of described a plurality of configurations is more than the interval between described positive electrode and the 1st negative electrode, and below 10 times of the interval between described positive electrode and the 1st negative electrode.
3. the method for removing on conductive metal oxide as claimed in claim 1 or 2 surface is characterized in that, described positive electrode and the 1st negative electrode are that positive electrode and 1st negative electrode narrower than the wide cut of conductive metal oxide thin film are configured to jagged electrode.
4. the method for removing on conductive metal oxide as claimed in claim 1 or 2 surface is characterized in that, it is 10 that described electrolyte uses resistivity
2Ω cm～10
6The electrolyte of Ω cm.
5. the method for removing on conductive metal oxide as claimed in claim 3 surface is characterized in that, it is 10 that described electrolyte uses resistivity
2Ω cm～10
6The electrolyte of Ω cm.
6. conductive metal oxide thin film removes device, it is a device of implementing the method for removing of the described conductive metal oxide thin film of claim 1, it is characterized in that possessing: with the conductive metal oxide thin film subtend that is formed at substrate surface and be positive electrode and the 1st negative electrode that contactless state is arranged side by side; At leading portion or back segment or the leading portion and the back segment of described the 1st negative electrode, with described conductive metal oxide thin film subtend and at the Width of conductive metal oxide thin film with the 2nd a plurality of negative electrode of contact condition configuration; Supply with electrolyte to described positive electrode, the 1st negative electrode, the 2nd negative electrode be formed at mechanism between the conductive metal oxide thin film of described substrate surface, perhaps store the electrolytic bath that makes described positive electrode, the 1st negative electrode, the 2nd negative electrode and base material impregnated in the electrolyte in the electrolyte; Described positive electrode and the 1st negative electrode, the 2nd negative electrode are applied the power supply of voltage; And the conductive metal oxide thin film that is formed at substrate surface is moved with respect to described positive electrode, the 1st negative electrode, the 2nd negative electrode and make conductive metal oxide thin film by the travel mechanism by positive electrode behind the 1st negative electrode, the 2nd negative electrode.
7. conductive metal oxide thin film as claimed in claim 6 removes device, it is characterized in that described positive electrode and the 1st negative electrode are maybe positive electrode and 1st negative electrode narrower than the wide cut of conductive metal oxide thin film to be configured to forniciform electrode continuously with being configured to jagged electrode continuously than the narrow positive electrode of the wide cut of conductive metal oxide thin film and the 1st negative electrode.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP110170/2006 | 2006-04-12 | ||
| JP2006110170 | 2006-04-12 | ||
| PCT/JP2006/318968 WO2007122752A1 (en) | 2006-04-12 | 2006-09-25 | Method of removing conductive metal oxide thin-film and apparatus therefor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101416283A CN101416283A (en) | 2009-04-22 |
| CN101416283B true CN101416283B (en) | 2010-05-19 |
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|---|---|---|---|
| CN2006800542174A Expired - Fee Related CN101416283B (en) | 2006-04-12 | 2006-09-25 | Method of removing conductive metal oxide thin-film and apparatus thereof |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP5055269B2 (en) |
| KR (1) | KR20090010980A (en) |
| CN (1) | CN101416283B (en) |
| TW (1) | TW200738917A (en) |
| WO (1) | WO2007122752A1 (en) |
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| CN103046108B (en) * | 2012-12-24 | 2017-03-29 | 上海申和热磁电子有限公司 | Application of the electrolysis process in ito film is cleaned |
| KR101864368B1 (en) * | 2016-08-19 | 2018-06-29 | 나노하 | Apparatus for converting image to sound |
| KR102344878B1 (en) * | 2017-07-10 | 2021-12-30 | 삼성디스플레이 주식회사 | Cleaning apparatus for removing oxide and method of cleaning using the same |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP3353075B2 (en) * | 1994-01-18 | 2002-12-03 | 西山ステンレスケミカル株式会社 | Glass plate recycling method and apparatus |
| JP3659597B2 (en) * | 1994-11-28 | 2005-06-15 | 旭電化工業株式会社 | Method and apparatus for etching tin oxide film |
| FR2821862B1 (en) * | 2001-03-07 | 2003-11-14 | Saint Gobain | METHOD OF ENGRAVING LAYERS DEPOSITED ON TRANSPARENT SUBSTRATES OF THE GLASS SUBSTRATE TYPE |
-
2006
- 2006-09-25 JP JP2008511938A patent/JP5055269B2/en not_active Expired - Fee Related
- 2006-09-25 CN CN2006800542174A patent/CN101416283B/en not_active Expired - Fee Related
- 2006-09-25 KR KR1020087027604A patent/KR20090010980A/en not_active Application Discontinuation
- 2006-09-25 WO PCT/JP2006/318968 patent/WO2007122752A1/en active Application Filing
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Also Published As
| Publication number | Publication date |
|---|---|
| JP5055269B2 (en) | 2012-10-24 |
| TW200738917A (en) | 2007-10-16 |
| CN101416283A (en) | 2009-04-22 |
| KR20090010980A (en) | 2009-01-30 |
| WO2007122752A1 (en) | 2007-11-01 |
| JPWO2007122752A1 (en) | 2009-08-27 |
| TWI316098B (en) | 2009-10-21 |
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