CN102388437A - Solution based non-vacuum method and apparatus for preparing oxide materials - Google Patents
Solution based non-vacuum method and apparatus for preparing oxide materials Download PDFInfo
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- CN102388437A CN102388437A CN2010800163297A CN201080016329A CN102388437A CN 102388437 A CN102388437 A CN 102388437A CN 2010800163297 A CN2010800163297 A CN 2010800163297A CN 201080016329 A CN201080016329 A CN 201080016329A CN 102388437 A CN102388437 A CN 102388437A
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- 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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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/18—Electroplating using modulated, pulsed or reversing current
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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
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/20—Electroplating using ultrasonics, vibrations
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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
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- C25D17/10—Electrodes, e.g. composition, counter electrode
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/10—Agitating of electrolytes; Moving of racks
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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
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/12—Process control or regulation
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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
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/60—Electroplating characterised by the structure or texture of the layers
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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
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
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- C—CHEMISTRY; METALLURGY
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- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
- C25D9/08—Electrolytic coating other than with metals with inorganic materials by cathodic processes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
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- C—CHEMISTRY; METALLURGY
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- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
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- C25D5/34—Pretreatment of metallic surfaces to be electroplated
- C25D5/36—Pretreatment of metallic surfaces to be electroplated of iron or steel
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- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Physics & Mathematics (AREA)
- Automation & Control Theory (AREA)
- Manufacturing & Machinery (AREA)
- Electromagnetism (AREA)
- Photovoltaic Devices (AREA)
- Physical Vapour Deposition (AREA)
- Electrodes Of Semiconductors (AREA)
Abstract
A high quality, highly adherent layer of a metal and oxygen material such as a transparent electrically conductive oxide material is electro deposited onto a substrate in a solution deposition process. The substrate is activated prior to the electro deposition of the metal and oxygen material thereonto by contacting it with a multidentate activating agent which promotes the adhesion of the metal and oxygen material to the substrate. Use of the activation agent eliminates the need to pre-deposit a "seed" layer of the metal and oxygen material onto the substrate by a vacuum deposition process.; Process parameters are controlled so as to result in the deposition of a high quality layer of material which is suitable for use in a back reflector structure of a high efficiency photovoltaic device In particular instances the activation method may be implemented in a continuous, roll-to-roll process. Further disclosed are semiconductor devices and components of semiconductor devices made by the present process, as well as apparatus for carrying out the process.
Description
The cross reference of related application
Present patent application is the part continuation application that the name of submission on February 11st, 2009 is called the U.S. Patent Application Serial Number 12/369,045 of " method and apparatus of the high-quality oxidation material of solution deposition (Method and Apparatus for the Solution Deposition of High Quality Oxide Material) ".At this its full content is incorporated herein by reference.
The explanation of government's rights and interests
The present invention accomplishes down at least partially in the contract number DE-FC36-07G017053 of United States Department of Energy.Government can enjoy rights to the present invention.
Invention field
The present invention relates in general to the electro-deposition of transparent conductive oxides material, is specifically related to the deposition of the transparent conductive metal oxide material relevant with the manufacturing of semiconductor device, Optical devices and similar device.Particularly, the present invention relates to the method and apparatus based on solution, wherein the high-quality layers of metal oxide materials is deposited over without in the pretreated substrate of vacuum deposition process.
Background of invention
Multiple electronic installation has been introduced one or more layers transparent conductivity material therein.These devices include but not limited to semiconductor device, like electronic storage device, electrooptical device, optical sensor, other photoresponse device, display unit and similar device.These layers are generally processed by transparent conductive metal oxide (TCO) material; And, comprise a kind of special TCO material based on the material of zinc oxide.The transparent conductivity zinc oxide material is impure on stoichiometry usually, and generally introduces like materials such as protoxide, hydroxide, ionic species, dopants, and it can work to strengthen electronic installation conductivity.Therefore, in context of the present disclosure, it being understood that " metal oxygen material (metal and oxygen materials) " means the material that comprises based on it, and also can comprise protoxide, hydroxide and other material.For example, the material (being called as " zinc oxide " or " zinc oxide material " sometimes) based on zinc and oxygen also can comprise the protoxide of zinc, the hydroxide such as the Zn (OH) of zinc
2, Zn
2+Ion (being generally the form of zinc salt) and other this type material.Equally, other metal oxygen material like the material based on tin and indium, can comprise oxide, protoxide, hydroxide and ionic species.It being understood that equally that in context of the present disclosure metal oxygen material also can comprise dopant or modifier such as boron, it can play the conductivity and/or the control sedimentary deposit physical aspect of oxide material (for example ZnO) layer of adjustment deposition.
Zinc oxide material refers to a kind of metal oxygen material, and its back reflector construction package as the efficiency light electric installation has important function, and the present invention will describe to these materials; But it being understood that principle of the present invention can be used for depositing other metal oxygen material.Back reflector is the significant components of electrooptical device.Part as support base as the one of which is deposited on the device back side, and has the not absorption photon reflection that makes the photoelectric activity semiconductor layer that passes covering and change direction and return and wear this layer to absorb again.General back reflector structure comprises the highly reflective metal level, like silver or aluminium lamination, deposits the microstructure layer of transparent conductivity zinc oxide material on it.The effect of the architectural characteristic of zinc oxide material is to make to pass stacked photoelectric material for the first time and do not have the scattering of absorbed reflection of incident light photon, thereby it is absorbed when passing said solar cell for the second time subsequently.
For making the maximizing efficiency of electrooptical device, electronics, optics and the physical property of the controlled oxidation of taking every caution against error Zinc material.Zinc oxide material must have good electrical conductivity because the photoelectric current that semiconductor layer produced that covers must pass zinc oxide material, with below be able to collect in the basal electrode.Therefore, the resistivity of oxide material is represented the parasitic drain of electrooptical device.Equally; This material must have the good optical transparency; Because the reflection photon can repeatedly pass this layer (depending on the absorption characteristic of electrooptical device semi-conducting material and the scattering properties of zinc oxide and back reflector layer), and any optical absorption also will be represented the loss of unit efficiency.At last, the microstructure of this layer need be controlled optimizing the scattering of reflection photon, thereby maximizes the chance that semiconductor layer that those photons are capped absorbs.Therefore, the controllable deposition of high-quality zinc oxide material is important for making the efficiency light electric installation.
Prior art general using vacuum deposition process is like sputter, with the depositing zinc oxide material.But this technology is that equipment is intensive in essence, and deposition rate is slow relatively, and the Capital expenditure cost is high, and high material cost and high operating cost have adverse effect to the cost of making electrooptical device.In addition, this depositing operation is slow in essence, and has represented the bottleneck in the electrooptical device depositing operation.Therefore, if attempt a large amount depositing operation, the back reflector manufacturing platform must be extremely huge and expensive.
Because with the relevant problem of this material vacuum moulding machine, prior art has been attempted through the low-cost electrodeposition technology depositing zinc oxide of high speed material, wherein zinc oxide material is electroplated onto in the substrate in water-bath.For example, in United States Patent (USP) 6,133,061; 6,224,736; 6,238,808; With 6,379, some this technologies are disclosed in 521.Although carried out multiple trial, prior art so far can't be reliably and the such zinc oxide material of electro-deposition repeatedly: its electricity, optics and physical characteristic make its effect maximization in the back reflector structure of efficiency light electric installation.Consistency problem when in addition, prior art processes has run into this type material and is deposited in the concrete substrate.
The problem that type prior art depositing operation of addressing in the United States Patent (USP) that preceding text are quoted has met with is an adhesion problem.The metal oxygen material of having found electro-deposition in many cases as zinc oxide material and multiple device manufacturing process are used substrate bonding very a little less than.For example, in the manufacturing of electrooptical device, the back reflection layer of aluminium, silver or silver alloy is deposited in the substrate, and zinc oxide or other this metalloid oxygen material layer depositions are on it then.The oxide material of having found electro-deposition with aluminize, the substrate of silver or silver alloy bonding can be very a little less than.To this problem, prior art is found, and---like the technology of sputter, evaporation, chemical vapour deposition or its combination---" seed " layer of plated metal oxygen material makes the material bodies of electro-deposition subsequently bonding through vacuum deposition process.But,, then utilize motivation and the advantage forfeiture or the minimizing of electrodeposition technology if this arts demand is made substrate in advance through utilizing the vacuum coated step.Obviously;, high adherence metal oxygen material high-quality to making with complete method based on solution is deposited on suprabasil technology and has demand, and said complete technology based on solution deposits " seed " layer or makes or handle substrate in addition without any need for the technology of using in advance based on vacuum.
Like what hereinafter specified, the invention provides and to make the method and apparatus that need not use any kind in polytype substrate that high-quality zinc oxide and other transparent conductive oxide material electro-deposition use to the efficiency light electric installation based on this substrate of technology preliminary treatment of vacuum.In addition, the invention provides the method and apparatus that can the deposition of zinc oxide and other transparent conductive oxide material be limited to the base part of preliminary election.At last, the invention provides and high speed, volume to volume (roll-to-roll) manufacturing large tracts of land, the compatible method and apparatus of high efficiency electrooptical device.These and other advantage of the present invention from following accompanying drawing, explanation and discussion with being tangible.
The invention summary
Disclose suprabasil method has been arrived in the electro-deposition of metal oxygen material layer, be limited with depositional plane in this substrate.According to the present invention, the depositional plane and the multiple tooth activator with a plurality of functional groups (multidentate activating agent) of substrate coiled material contacted, thereby generate activated face.Thereafter, with the electro-deposition of metal oxygen material layer on activated face.Be noted that substrate is characterised in that its vacuum-deposited metal oxygen " Seed Layer " material without any need for type is present on the depositional plane.
In embodiment of the present invention, utilize multiple tooth activator with the form of the solution such as the aqueous solution, and this agent can comprise in boric acid, phosphoric acid or polybasic carboxylic acid and their salt, ester and other this type material one or more.In other instance, multiple tooth activator can comprise ethylenediamine tetra-acetic acid and salt or some other this type chelating agents.Can be used for concrete polybasic carboxylic acids more of the present invention and comprise phthalic acid, fumaric acid, malic acid and lactic acid.In some instances, can before the electro-deposition of metal oxygen material layer is on base material, wash base material.In instantiation, deposit aluminium, silver or silver alloy layer of reflective material on the depositional plane of base material body, and metal oxygen material is a zinc oxide material in some instances.
Method of the present invention can be carried out on static substrate with batch process, and this static substrate is moved in the processing platform of adjacent series in succession; Or more preferably, the present invention can carry out with continuous processing, and wherein the base material coiled material is advanced continuously and passes the processing platform of said series.First processing platform is the activation platform, and wherein the depositional plane of base material coiled material contacts with multiple tooth activator.The coiled material that has activated face subsequently gets into the coating platform, wherein metal oxygen material layer by electro-deposition on the activated face of coiled material.Randomly, can arrange the flushing platform, so that be coated with before and/or wash afterwards coiled material in electro-deposition.The system that implements this method is also disclosed.
The present invention on the other hand; With following technology metal oxygen material is electroplated onto in the substrate: first's layer thickness is deposited in the substrate with first deposition rate; Thereafter the second portion layer thickness is deposited on first's thickness with second deposition rate, said second deposition rate is different with said first deposition rate.In instantiation, second deposition rate is slower than first deposition rate.
Also have the present invention on the other hand, with following technology with the electro-deposition of metal oxygen material to substrate: part substrate crested element (masking member) covers at least, and said shadowing elements prevents that metal oxygen material from depositing in its that part of substrate that adheres to.Shadowing elements can adhere to substrate through magnetic force in some instances.In instantiation, electrodeposition technology is implemented on elongated base material coiled material, and this base material coiled material is advanced past the depositing system that comprises deposition platform continuously, and in this deposition platform, metal oxygen material is deposited in the substrate.In this embodiment of the invention, when base members is in deposition platform and when metal oxygen material just is being deposited on the base material coiled material front surface, the masking material of shoestring is contacted with the back side of base members.In some instantiations, depositing system can comprise biased element such as pressing plate (platen) or roller series, and it can impel the masking material strip to contact with substrate.
Also have the present invention on the other hand, base members keeps anti-orientation of particles (partiphobic orientation) when metal oxygen material just is being deposited on the base members, mixes in the metal oxygen material sedimentary deposit so that at least partly suppress granular materials.
Also have another aspect of the present invention, metal oxygen material layer is electroplated onto in the substrate, and this substrate is arranged in the electrolyte, is spaced relationship with electrode.In this technology, power supply can be operated when energize and set up electric current, through electrode, electrolyte and substrate, thereby makes metal oxygen material layer depositions in substrate.In this technology, implement at least two in the following step: when metal oxygen material layer is just depositing in the substrate, import ultrasonic energy to electrolyte in the part-time at least; , metal oxygen material layer periodically interrupts the electric current between electrode, electrolyte and substrate when just depositing; , metal oxygen material layer keep substrate to be anti-orientation of particles when just depositing in the substrate; Make the gas bubbling pass through electrolyte; With when first's metal oxygen material just is being deposited in the substrate, make power supply with the first horizontal energize; So that first deposits with first deposition rate; Thereafter the second portion at layer is just depositing to the last chien shih power supply of first with the second horizontal energize, so that second portion deposits with second deposition rate.In instantiation, second deposition rate is less than first deposition rate.In some instantiations, implement at least three in the above-mentioned steps.In the present invention's other execution mode in this respect, at least one step below implementing again: the composition of monitoring bath; Dopant level in the metal oxygen material of monitoring deposition; Use the electrode of dimensionally stable; Use is constructed to the electrode of hollow cage (hollow basket), comprises metallic particles in this hollow cage; With use filter guard electrode.
The present invention can implement by multiple continuous processing, and in instantiation, can be used for making the back reflector structure of efficiency light electric installation.
The present invention also comprises substrate, according to the metal oxygen material that has deposition in above-mentioned said this substrate.Substrate of the present invention can be used as the back reflector structure of electrooptical device.In instantiation; The present invention relates to substrate, it comprises deposition highly reflective metal such as aluminium or silver layer on it, and has electro-deposition high adherence metal oxygen layer on it; Like zinc oxygen layer; Wherein these substrates are characterised in that they do not comprise any vacuum moulding machine metal oxygen material Seed Layer on it, and therefore in according to electrodeposition technology of the present invention, all metal oxygen materials that are deposited on reflective metal or the alloy are deposited by solution.
The present invention also relates to implement said method and the equipment of making said products.
The accompanying drawing summary
Fig. 1 shows the electrooptical device cross-sectional view that comprises the back reflector structure of the zinc oxide material of deposition according to the present invention;
Fig. 2 is the cross-sectional view that can be used for the schematic electroplating device of embodiment of the present invention method;
Fig. 3 is a flow chart of describing an embodiment of the invention;
Fig. 4 is the schematic description with the equipment of continuous processing embodiment of the present invention method;
Fig. 5 is the enlarged drawing of equipment deposition platform shown in Figure 4 part, better example masking system; With
Fig. 6 is overall similar but comprise the description of the deposition platform of bias voltage pressing plate with deposition platform shown in Figure 5.
Detailed Description Of The Invention
Will present invention is described together with the manufacturing of efficiency light electric installation back reflector structure with reference to the deposition of metal oxide such as zinc oxide material.Yet, it being understood that principle of the present invention can easily extend to any application with the high-quality metal oxide materials of high speed a large amount technology electro-deposition.As stated, these application can comprise the manufacturing of display unit, sensor device, light emitting devices and similar device.
Refer now to Fig. 1, shown the cross-sectional view of general (generalized) efficiency light electric installation 10.Device comprises substrate 12, and it is used for the remainder of bracing or strutting arrangement, and is used to device base, current acquisition, electrode are provided.In example, substrate 12 is made up of two independent layers.Ground floor 14 is body of stainless steel.Be furnished with the thinner layer 16 of highly reflective metal such as aluminium, silver or its alloy on it.This layer 16 defines back civilian so-called substrate " depositional plane ".In some instances, the thinner layer of another kind of material such as titanium or molybdenum layer (not shown) can be inserted between ground floor 14 and the reflective metal 16.In other execution mode of electrooptical device, substrate can be made up of the body of electrical insulating material such as polymer, glass, pottery or analog, and condition is to be furnished with one or more layers conductive material on it.
Be arranged in the substrate 12 be transparent, conductive metal oxide material---being zinc oxide material in the exemplary embodiment---layer 18.As stated, this layer mainly is made up of ZnO, but also can comprise other material and dopant and analog based on zinc.The material of forming zinc oxide film 18 is a crystal at least partly, and therefore the surface of this layer can have the quality that is equivalent to the material crystals characteristic.Generally speaking, the preferred crystal characteristic has the magnitude range of about 200-1000 nanometer, so that make the visible light scattering maximization from it.Layer 18 has good electrical conductivity and good optical transparency.
Be arranged on the zinc oxide film 18 is photoelectric semiconductor material body 20.The active semiconductor layer of this body 20 is used to absorb charge carrier that incident photon and generation device electrode gathered to (carrier pairs).As known in the art, this body 20 can be made up of a plurality of semiconductor material layers with different arranged.In a concrete execution mode; Semiconductor bulk 20 is made up of the silane alloy material; Therefore can comprise one or more tlv triple of piling up (triads), each tlv triple is made up of following: intrinsic basically semiconductor material layer inserts between the semiconductor layer of that p-mixes and n-doping.
Being arranged on the photoconductive body 20 is top electrode layer 22, and it is processed by optical clear conductive material such as ZnO or another kind of TCO material in the instance of the concrete structure of this device.As known in the art, current acquisition structure such as bus, grid and analog can be arranged on the top electrodes 22.
In the electrooptical device running, photon passes top electrode layer 22 accesss to plant, and is absorbed by photoconductive body 20, and wherein they generate electron-hole pair.The intrinsic built-in electric field of photoconductive body 20 makes the right photohole of these charge carriers separate with electronics, and they are collected by top electrodes 22 and substrate 12 respectively.The photon that is not absorbed by photoconductive body 20 passes zinc oxide film 18, and layer 16 reflection that are reflected.The reticulate pattern property of zinc oxide film 18 (textured nature) makes the photon scattering of reflection, so that they return and to wear the one-tenth angle approach of photoconductive body 20 and compare with the photon of scattering not and increase.And in some embodiments, reflector 16 also will comprise dictyonitic structure, also help to make the photon scattering of reflection.
Refer now to Fig. 2, shown general-purpose system 30, it can be used for deposition according to zinc oxide material of the present invention.System 30 comprises jar 32, and this jar is set up and can operates the electrolyte material 34 to keep certain volume therein.Equipment further comprises the electrode platform, and this electrode platform has the depositing electrode 36 that is supported in wherein.As shown in Figure 2, electrode 36 is configured to pole plate (plate), mainly is made up of metal material such as metallic zinc.It being understood that equipment shown in Figure 2 is general, and electrode can be configured to grid (mesh) and/or bulk non-planar in some instances.In one embodiment, electrode is the porous body of hollow cage shape, and it is made up of the material that depositing operation is had inertia such as Ti, Pt, Pd, Au or similar material.The zinc particle of bullet (shot) or similar type is arranged in the ducted body.In another embodiment, it is neighbouring with guard electrode that filter is placed in electrode, and prevent that particle from arriving the substrate surface that deposition takes place.In one embodiment, filter is the form of porous polyethylene filter bag, and it is arranged to around electrode.In another embodiment, electrode is the dimensionally stable electrode of inertia, and it is processed by inert material such as titanium.As known in the art, in such electroplating technology, all metal ions that forms plated metal oxygen layer provides by electrolyte.In some instances, such inert electrode system can comprise remote platform (remote station), and wherein the tenor of electrolyte is electrochemically replenished by the metallic object that wherein keeps.Remote platform can be communicated with other segment fluid flow of system, or it can separate with other part of system.As further be appreciated that, the electrode platform also can comprise retaining element, like anchor clamps, support and analog, with the supporting electrode body.Equally, discuss further like hereinafter, the electrode platform can comprise a plurality of dispersive electrodes in some instances.
System shown in Figure 2 is supported in substrate 38 in the electrolyte material body 34.As stated, substrate 38 can comprise single layer structure or sandwich construction.
Electrode 36 and substrate 38 all with the power supply platform electric connection, this power supply platform comprises power supply 40, this power supply 40 and then controlled by controller 42.Power supply 40 is DC power supplys, and electrode 36 is communicated with the positive terminal of power supply 40, and the negative pole end electric connection of substrate and power supply 40.The execution mode of Fig. 2 example comprises a power supply 40; But it being understood that in other embodiments power supply platform can comprise a plurality of power supplys, it can operate the power of supplying with a plurality of dispersive electrode energy and/or varying level being provided.
Like further institute example, system 30 comprises heater 44, and it is arranged in jars 32.Heater 44 can be operated and keep electrolyte 34 to be in preselected temperature, and thus, heater 44 has coupled controller 46.Example as shown here, heater 44 is resistance heaters, though can use the heater of other type known in the art equally.
System 30 also preferably includes gas bubbler (bubbler) 48, and it is arranged in the jar.Bubbler 48 has coupled gas supply 50, and when activation, can operate and make gas such as air or nitrogen bubble pass electrolyte 34, thereby keeps electrolyte to be stirred.And the air bubbling is that electroplating reaction provides air or oxygen.Under depositing temperature, the dissolved oxygen in bathing in the electrodeposition process keeps constant oxygen content.
System also comprises ultrasonic transducer 52, and it is arranged in the jar.This transducer passes through controller 54 energizes, and when energize, can operate ultrasonic energy is introduced in the electrolyte material 34.Do not hope to receive supposition to retrain, the inventor supposes that ultrasonic energy can keep deposition substrate cleaning surfaces and/or sedimentary deposit cleaning through removing unnecessary material.
System of the present invention also can comprise monitoring platform, is used for measuring the composition of deposition process electrolyte, so that confirm the concentration of metal ion, dopant and other material.This monitoring is preferably carried out in position and in real time, and guarantees the uniformity and the consistency of deposition materials.Monitoring can be carried out through following technology: comprise potential measurement technology, chemical technology such as EDTA titration, spectral technique and similar techniques.Monitoring can with the agent delivery system Combination application with feedback model operation.Therefore, for example,, can add extra metal if the metal concentration of electrolyte is low excessively.Perhaps, if pH is too high, can add acid automatically.Equally, system can be based on level control of measuring in electrolyte and/or the sedimentary deposit and the level of regulating dopant.
In Fig. 2, shown on the surface of base material 38 with masking material body 56.Masking material is used for the guard section substrate, so that in technology, zinc oxide material can not deposit on the base part of those protection.This characteristic is chosen wantonly in practice of the present invention; But in many technologies and device construction, the deposition that has been found that such restriction zinc oxide material is useful.Masking material can dispose and adhere to substrate in many ways, and therefore can comprise polymer underseal (resist coating).But in an embodiment of the present invention, masking material 56 comprises the material piece of part at least that can invest a surface of substrate through magnetic force.Thus, masking material 56 can comprise the magnetizable metal sheet, or it can comprise the polymeric material body that wherein is dispersed with magnetized particles.In instantiation, masking material is an electric insulation, so that prevent deposition above that.
In the common technology according to depositing zinc oxide material of the present invention, electrolyte material 34 comprises about 0.03 mole of Zn (NO
3)
2Solution.In some embodiments, electrolyte also will comprise more a spot of short sticking material, like ethylenediamine tetra-acetic acid (EDTA).Can comprise other chelating material and/or short stick equally, like fumaric acid, malic acid, have various other compounds (multiple tooth material) of a plurality of functional groups and such as the compound of sucrose.These concentration of material are usually in the scope of 1-200ppm.Electrolyte material also can comprise one or more dopants or modifier, and they are used to strengthen the conductivity of the zinc oxide material of deposition.The used a kind of concrete alloy of the present invention comprises boron, and it can the boric acid form be present in the electrolyte, and concentration is in the scope of 0.01%-1.0% by weight.Electrolyte generally remains on the 50-100 ℃ of temperature in the scope in depositing operation, and in common instance, electrolyte is maintained at about 80 ℃ temperature.
In deposition those instances based on the material of tin and oxygen, electrolyte will comprise one or more pink salts, like stannic chloride, tin acetate, STANNOUS SULPHATE CRYSTALLINE and analog.Deposition based on the material of indium will be used such electrolyte: it comprises indium salt, like inidum chloride, indium nitrate, indium sulfate and analog.
Activating power is so that set up about 0.5 to 20 volt electromotive force between electrode 36 and substrate 38.This electromotive force will make zinc oxide material deposit in the substrate, and deposition rate will be proportional with suprabasil power density.Therefore, the control deposition power will make deposition rate controlled.In common deposition, suprabasil power density will be at 0.5-20mA/cm
2Scope in.
For improving the uniformity of the zinc oxide that deposits, at least periodically stir bath 34, and this can be through utilizing the circulating pump (not shown) and/or carrying out through making gas pass electrolyte by bubbler 48 bubblings.Have been found that in this technology air or nitrogen and can be used for this purpose; But, can use inertia equally or not in addition to disadvantageous other gas of depositing operation.
According to a further aspect of the invention, have been found that then the quality of depositing zinc oxide material is improved if at least periodically introduce ultrasonic energy to bath.For example, in one embodiment, make ultrasonic transducer 52 with about 500 watts power level energize.The structure of used ultrasonic energy system will depend on the others of the structure and the electro-deposition system of electric installation.
In the present invention on the other hand, have been found that with pulse mode operation power supply 40 to have advantage, wherein put on electrode 36 and substrate 38 DC current cycle property be interrupted.In common technology, the speed with 1 to 10Hz makes electric current produce pulse.Although do not hope to receive supposition to retrain, the applicant supposes to make with the pulse mode operation sedimentary condition balance of substrate surface, and therefore promotes the material with the best composition and form to be able to deposition.
According to another aspect of the invention, the inventor has been found that the deposition that in many deposition rates technology, can make very high-quality zinc oxide material.In this embodiment of the invention, initial depositing operation with relative high speed is coated with the ground floor zinc oxide material with substrate.High speed deposition can be realized through following: the control power supply, so that with high-caliber relatively power supply electrode 36 and substrate 38 energy.This causes comparatively fast depositing than the zinc oxide material body of thickness portion.Thereafter, power supply is with power supply electrode of reduced levels 36 and substrate 38 energy, so as with zinc oxide material with on the sedimentary deposit before being deposited on than low rate.According to thinking that this presents extraordinary crystal structure and the surface texturisation that makes the zinc oxide film performance optimization than the low rate material.Therefore, the Application and implementation of dual rate technology the benefit of high average sedimentation rate, produce zinc oxide material body simultaneously with excellent electricity, optics and physical property.In the further improvement of this technology, can three kinds or more kinds of deposition rate deposit said body.Also have, being noted that does not need the flip-flop deposition rate; And in the context of the present invention aspect this, can on continuous foundation, change deposition rate through changing current density so that material with non-step-wise manner or only the part step-wise manner by at a high speed to low speed or by low speed to the high speed transition.
In still another aspect of the invention, have been found that the material of superior quality is able to prepare when substrate 38 keeps following orientation: said orientation will make gravity inhibition particle pile up above that.Therefore can be substrate 38 is vertical orientated, as shown in Figure 2.But, also can use other orientation that suppresses particle packing.For example, can with the arranged in orientation substrate of down depositional plane level.In other instance, can with the angled relationship substrate of vertical axis, condition is a depositional plane towards having a down dip so that suppress particle packing.In context of the present disclosure, all these substrates orientation---wherein gravity (part at least) work to suppress particle on depositional plane, pile up---is called as " (partiphobic) that prevent particle ".
The zinc oxygen material that the present invention produces has extraordinary physics, optics and electronic property, and this makes them be ideally suited for the back reflector structure of electrooptical device.It is believed that this properties of combination is derived from least two, the perhaps more a plurality of the invention described above characteristics independence and/or the synergy of---being the application of pulse power, double-deck at least material---with the ultrasonic clean of sedimentary deposit and the use that prevents the anti-particle substrate orientation of particle inclusion in the deposition of different capacity level, the depositing operation.Can help the other factors of the material quality that this technology produces to comprise that the in-situ monitoring bath forms; The application of in-situ monitoring dopant composition and outward appearance; With above-mentioned electrode structure such as hollow cage shape, the electrode of dimensionally stable and/or the application of filter guard electrode.The common layer thickness of back reflector structure is about 0.1 to 3 micron, and compares with the method for carrying out the whole deposition of layer through vacuum technology, and the high speed character of depositing operation of the present invention has greatly improved the economy and the actual implementation of manufacturing process.
Though the invention provides the high speed electrochemical deposition of zinc oxide material, it being understood that in some instances the present invention can combine comprehensive manufacturing process to implement, wherein can be with the zinc oxide material of vacuum technology such as sputtering sedimentation some parts.For example, above comprising, the electrooptical device substrate of using always deposits the stainless steel of silver, silver alloy or aluminium reflectance coating.The reflector is quite thin, and usually through sputter or some other vacuum technology depositions.
According to the present invention, the inventor can be with the high-quality TCO material electro-deposition with very good adhesiveness and device operating parameter on various reflective substrate, and need not any vacuum-deposited Seed Layer, thereby have considerably reduced manufacturing cost.The elimination of Seed Layer also is even more important through electroplating in those instances that deposit in the reflector, because this allows whole atmospheric pressure technologies.Have been found that to comprise short stick such as EDTA in the electrolyte, make the bonding enhancing of deposition layer and reflective metal, thereby eliminated needs vacuum-deposited Seed Layer.In experimentalists and technicians, quite layer is good equally to find to scribble zinc oxide on the silver layer of zinc oxide seed layer to top vacuum with electro-deposition at least by the adhesiveness of the zinc oxide film of the direct electro-deposition of the bath that contains EDTA to the silver layer.If from bathe, remove short stick, then the adhesiveness of zinc oxide film under the non-existent situation of Seed Layer very a little less than.In these experimentalists and technicians, lift from (tape lift-off) method and circular cone bend test (cone bending test) measurement adhesiveness through adhesive tape.
According to a further aspect of the invention; Have been found that; Through also strengthening metal oxygen material layer with activator preliminary treatment base material depositional plane and having or do not have below substrate bonding of reflective metal or metal alloy compositions on it, said activator is the multiple tooth material of the above-mentioned type.Multiple tooth material comprises a plurality of independent avtive spots; Although and do not hope to receive supposition to retrain; The inventor supposes that multiple tooth activator is incorporated into the base material depositional plane through one in its active sites, and its remaining one or more active sites are lighted following effect: promote metal oxygen material bonding of deposition subsequently.Can be used for multiple tooth activator of the present invention and can comprise the inorganic acid that---as way of illustration but not limitation---has an above avtive spot.This acid includes but not limited to phosphoric acid and boric acid.Equally, multifunctional organic acid can use like polybasic carboxylic acid by this way.These acid comprise malic acid, fumaric acid and lactic acid and aromatic acid such as phthalic acid.All above-mentioned acid can also be used with the form of compound such as ester, salt, acid anhydrides and other this type material.In other instance, multiple tooth activator can be chelating agent such as ethylenediamine tetra-acetic acid or analog.Other multiple tooth activator will be tangible to those skilled in the art.
Usually use multiple tooth activator with the solution form, this solution is the aqueous solution in instantiation.In the solution concentration of activator will depend on activator itself character, institute's activation the surface and deposit to the material on the activated face.But in most instances, the concentration of activator is in the scope of per 1,000,000 1-1000 parts by weight.In instantiation, concentration is in the scope of per 1,000,000 1-100 parts, though other concentration range will be very tangible to those skilled in the art.
In general technology, the substrate depositional plane contacts with activator at least, and this can be through being ejected into activator solution on the depositional plane or through the substrate dipping is realized in activator solution.In using those instances of activator solution, usually this solution is remained on following temperature range: to about 100 ℃, particularly 5 ℃ to 50 ℃, the most particularly around room temperature from room temperature.In some instances, can stir or stir this solution.Also can import ultrasonic energy to promote activating process.
In some instances, can the steam form but not the solution form is used activator.This activation pattern is generally used in those instances that activator has higher vapor pressure.For example, activator can comprise low relatively polybasic carboxylic acid such as the lactic acid that boils, and activation can realize to generate steam and to make substrate pass through this chamber through heat-activated agent in the chamber.In view of the instruction that this paper proposes, activating process can be readily integrated in the various depositing systems.
The substrate of activation can directly be delivered to deposition platform, and metal oxygen material layer is electroplated onto on it in deposition platform.In other instance, can before plating, wash substrate.
Method of the present invention can easily be incorporated in the continuous processing of the above-mentioned type.Thus, can the activation platform be incorporated in the system.For example, the activation platform can comprise jar, and this jar is passed through in substrate before plating.Likewise, it can comprise the jet chamber that substrate is passed through.
In an exemplary activated technology of the present invention, the Ag coating stainless steel coiled material that rolls is loaded in unwrapping wire (pay-off) platform.At first coiled material is imported the surface active platform from the unwrapping wire platform, wherein Potassium Hydrogen Phthalate (phthalate) solution is injected into coiled material to form the surface active layer on its top surface.Find that about 21mg phthalate provides good adhesiveness and solar cell properties in 1 premium on currency.Used coiled material speed is about 30 centimetres of per minute.Solution temperature remains on room temperature.Then coiled material is moved in the electro-deposition platform, wherein ZnO is deposited on the activated face.In the flushing water cleaning platform, clean coiled material then, in obtaining (take-up) platform, be dried and roll then.Use other activator can implement similar activating process.Equally, this technology may be implemented in the discrete patch of base material.
In an embodiment of the present invention, substrate is the stainless steel layer of about 5 mil thick.To be sputtered in those instances on it in the reflector, the titanium adhesive layer of about 100 nanometer thickness is vacuum-deposited on the stainless steel.Subsequently, silver or aluminium reflector---thickness is in the 100-500 nanometer, in the scope of preferred 100-250 nanometer---be deposited in the substrate.Thereafter, through making the reflector contact above-mentioned multiple tooth activator and the activation reflector.The substrate of activation thus (or suprabasil reflector) is oxidized Zinc material layer coating in technology of the present invention.Depend on concrete application, the thickness of this multiple tooth layer is generally in the scope of 0.1-3 nanometer, preferably in the scope of an about molecular layer.
Refer now to Fig. 3, shown the generalized flow chart of describing one embodiment of the present invention of using many speed electrodeposition technology; But, it being understood that activating process of the present invention can use with the electrodeposition technology of other type.As shown in Figure 3, this technology utilization experiences the substrate of activating process as stated.In the first of depositing operation, zinc oxide material is deposited to high relatively deposition rate in the substrate of activation, this deposition rate is about 10nm/sec in some instances.The temperature of this embryo deposit in 50-100 ℃ of scope carried out under 80 ℃ temperature usually.Stir the electrolyte in the sedimentary deposit tank through activating the gas bubbler system; But, can randomly stir through pump, blender or similar device.After part layer (30-80% of its thickness, 50-70% in instantiation) has usually deposited, ultrasonic energy is input in the sedimentary deposit tank.Sedimentary condition is remained at a high speed down, and prolonged agitation is bathed.The effect of ultrasonic energy is to remove the solution particle of not expecting from sedimentary deposit.Owing to any plaque that the bonding loose material of removal stays is filled through the zinc oxide material of deposition.In the second stage of this technology, deposit the residual thickness of final zinc oxide film.
In the phase III of depositing operation, with the other part of low relatively deposition rate depositing zinc oxide material layer.In instantiation, this speed is in the scope of about 1-5nm/sec.Deposition bath keeps and preceding two roughly the same temperature of stage, and the stirring through utilizing bubbler or other device to keep electrolyte.
Can use other depositional model.In an example, embryo deposit can carry out under low speed, carries out high speed deposition then, then randomly carries out second low speed deposition.It is generally acknowledged that low speed deposition impels the layer that has than megacryst to form, should be used to promote optimal light scattering than megacryst.Equally, the low speed material can provide the adhesiveness good with lower floor.In addition, the low speed material can provide template for the high speed material that deposits subsequently, so that the crystal structure of high speed material is similar to the crystal structure of low speed material to a certain extent.
In case the gross thickness of zinc oxide material layer is deposited, then water washes substrate and carries out drying then.Drying utilizes atmosphere usually in baking oven or through using air blast to carry out.Drying is generally carried out under high-temperature, normally in 25-200 ℃ scope, carries out about 2 minutes time.The effect of drying steps is to remove moisture, and makes the zinc hydroxide material at least partly be converted into the zinc oxide material.Drying also can work to make anneal of material, thereby further increases its adhesiveness to substrate.In a concrete instance, drying/annealing was carried out under 250 ℃ 2 minutes; In another instantiation, it carried out under 275 ℃ 1 minute.After drying/annealing, this technology is accomplished, and substrate can be machined in the electrooptical device subsequently.
Technology of the present invention is easily being implemented in the volume to volume technology continuously, and with manufacturing photovoltaic substrate material, and a kind of such enforcement is presented among Fig. 4.What wherein describe is volume to volume depositing device 60, and it is used for zinc/elongated substrate coiled material of oxygen material coating.The system 60 of Fig. 4 comprises unwrapping wire platform 62, and it is supported the coiled material 38 of base material and sees the coiled material 38 of base material off from supplying with volume 64.As known in the art, the unwrapping wire platform can comprise live-rollers (turning roller), slewing rollers (steering roller), strainer (tensioning mechanism) and similar device.
Each deposition platform includes heater 44, and is noted that in this embodiment, and each deposition platform 66,68 and 70 includes two depositing electrodes.Thus, first platform comprises electrode 36a, 36b, and second platform comprises electrode 36c, 36d, and the 3rd platform comprises electrode 36e, 36f.Deposition process has been quickened in the use of bipolar electrode.Of Fig. 2, electrode 36 all is communicated with suitable power supply, and to be enough to the providing power level of expectation deposition rate to be supplied to energy.
As stated, often expectation comprises the masking material body, and it is used to prevent that zinc/oxygen material from depositing to the specific part of substrate.In the exemplary embodiment, each deposition platform includes masking system, and said masking system is made up of two parts 72a, 72b as institute's example.
Refer now to Fig. 5, shown the part enlarged drawing of Fig. 4 first deposition platform, with example masking system better.As described, part substrate coiled material 38 centers on live-rollers 76 through the first depositing electrode 36a, and through the second depositing electrode 36b.The first masking system 72a is arranged, and when being positioned at the first electrode 36a regional with convenient substrate 38 substrate 38 back sides is contacted with masking material body 78.That masking material 78 has is flexible, electrical insulating property and magnetic, therefore can comprise the wherein polymer of embedded magnetic material.Masking material 78 is configured to continuous coiled material, and it is supported by first roller 80 and second roller 82.In service in system, coiled material 38 advances through deposition platform, and is attached to its magnetic material 78 contacts.The coiled material of magnetic material 78 is advanced with substrate, through electrode 36a.The magnetic of masking material keeps it to contact with substrate.After the first region territory was left in substrate 38, second roller 82 was dragged masking material 78 away from substrate 38.The second masking system 72b arranges about the second electrode 36b, and to move with the similar mode of the first masking system 72a.
The substrate masking system can be configured to comprise roller, pressing plate and similar device, and it can help shadowing elements is biased in the substrate.Can be with the shadowing elements Combination application of these bias systems and magnetic force adhesion; Though in some instances, good contact the between the substrate of biasing force sufficient to guarantee and the biased element, thus need not use magnetic pull.Refer now to Fig. 6, shown an execution mode of bias system, this bias system is set to be used for Fig. 5 deposition platform of display type substantially; Thus, similar elements will be through similar reference number identification.The deposition platform of Fig. 6 comprises the first and second depositing electrode 36a, 36b, and this depositing electrode is set up and can operates the zinc oxide material layer electro-deposition to the process base material coiled material 38 of deposition platform.The deposition platform of Fig. 6 further comprises the first masking system 72a and the second masking system 72b, and it comprises masking material body 78 flexible, electric insulation as stated, and this masking material body 78 is supported by first roller 80 and second roller 82.The system of Fig. 6 further comprises crooked bias voltage pressing plate 84, and it is provided so that contact masking material strip 78, and impels this material near part substrate 38.Second such pressing plate 86 is relevant with the second masking system 72b.Bias voltage can be accomplished through the element that is provided with in addition.For example, bias voltage pressing plate 84,86 can be replaced by one or more rollers.Because the bias voltage pressing plate impels masking material to contact with substrate, though therefore can use magnetic, masking material need not to have magnetic.
Return Fig. 4 at present, can see, system 60 further comprises flushing platform 84, and it is arranged at the downstream of deposition platform 66,68 and 70.Flushing platform 84 comprises jar, and this jar is provided so that the substrate of coating through this jar, and wherein substrate is washed by water.Flushing platform 84 can further comprise agitator, blender or similar device, to strengthen flushing action.It can comprise that also circulation (flow-through) system is with continuous replacing flushing water.In some instances, the flushing platform can comprise the can,douche that two or more are discrete.
The downstream of flushing platform 84 are dry platforms 86, and wherein the coiled material of coating is dried as stated.Dry platform can comprise baking oven, drying tunnel or similar device, and can comprise pharoid, hot air blowers or similar device.After drying, base material is wound onto in obtaining platform 90 subsequently and obtains on the volume 88.
Also can implement the coating of zinc oxygen material with single continuous processing, wherein the reflector is electroplated onto on the stainless steel coiled material, is coated with zinc oxygen material thereafter.Thus, equipment can comprise first deposition platform, and wherein substrate is electroplated by silver or aluminium reflector.For example, can silver be electroplated onto on the stainless steel from bath, this bath comprises: 37.5g/l dimethyl hydantoin, 12.0g/l silver nitrate, 0.38g/l thiamine hydrochloride, 7.5g/l potassium chloride and 7g/l potassium hydroxide.Plating occurs in 60-90 ℃ temperature, utilizes current density to be about 3mA/cm
2Silver electrode, and with the deposited at rates highly reflective silver layer of about 2nm/sec.Aluminium also can be electroplated through technology known in the art.
The system of Fig. 4 produces the elongated web of base material, and this base material can be used for making the continuous processing of electrooptical device subsequently.Thus, the roller of material can be transferred to the photoelectricity depositing device.In other instance, the substrate coating system can be in line with the photoelectricity depositing device and place or incorporate in the photoelectricity depositing device.For example, can implement volume to volume technology, wherein silver or aluminium reflector at first are electroplated onto in the substrate, and zinc oxygen material layer is electroplated onto in the substrate in same equipment thereafter.The substrate of coating can be transported to a series of semiconductor deposition chamber that link to each other with same equipment then, or it can be transported to the semiconductor deposition chamber of independent setting subsequently.
The invention provides the method and apparatus of fast effective depositing metal oxide materials such as zinc oxide material high-quality layers.Invention has been described to the concrete equipment that is particularly suitable for making the substrate of efficiency light electric installation and concrete operations condition.But it being understood that principle of the present invention may extend to other method and apparatus and manufacturing and is used for device and the technology of material beyond the photovoltaic applications.Therefore, in view of the instruction that this paper provides, multiple modification of the present invention and variation will be tangible to those skilled in the art.It being understood that above-mentioned accompanying drawing, discuss and be described as the example of the specific embodiment of the invention, but not mean the restriction on its practical.What limit the scope of the invention is accompanying claims, comprises all equivalents.
Claims (6)
1. metal oxygen material layer is electroplated onto suprabasil method; Wherein said substrate is arranged in the electrolyte; Be spaced relationship with electrode, wherein power supply can be operated when energize and set up electric current, through said electrode, said electrolyte and said substrate; Thereby make said metal oxygen material layer depositions in said substrate, it is characterized in that said depositing operation comprises to be selected from least two following steps:
, said metal oxygen material layer imports ultrasonic energy to said electrolyte in the part-time at least when just depositing in the said substrate;
, said metal oxygen material layer periodically interrupts the electric current between said electrode, said electrolyte and said substrate when just depositing;
, said metal oxygen material layer keep said substrate to be anti-orientation of particles when just depositing in the said substrate;
Make the gas bubbling pass said electrolyte; With
Just be deposited in the first of said metal oxygen material and making said power supply in the said suprabasil time with the first horizontal energize; So that said first deposits with first deposition rate; Thereafter just depositing at the second portion of said layer makes said power supply with the second horizontal energize in the time in the said first; The power of wherein said second level is selected, so that the deposition rate of said second portion is less than the deposition rate of said first.
2. the described method of claim 1 is wherein improved and is comprised and implement said technology to utilize at least three in the said step.
3. the described method of claim 1 comprises the step that at least one is other, and said step is selected from as follows:
The composition of monitoring bath;
Monitor the dopant level in the metal oxygen material of said deposition;
Use the electrode of dimensionally stable;
Use is set to the electrode of hollow cage, comprises said metallic particles in the said hollow cage; With
Use the filter guard electrode.
4. the described method of claim 1, wherein said method can be operated zinc oxygen material layer depositions to said substrate.
5. implement the equipment of the said method of claim 1.
6. the zinc oxygen material layer of processing by the said method of claim 4.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US12/369,045 | 2009-02-11 | ||
| US12/369,045 US20100200408A1 (en) | 2009-02-11 | 2009-02-11 | Method and apparatus for the solution deposition of high quality oxide material |
| PCT/US2010/023878 WO2010093781A2 (en) | 2009-02-11 | 2010-02-11 | Solution based non-vacuum method and apparatus for preparing oxide materials |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102388437A true CN102388437A (en) | 2012-03-21 |
Family
ID=42539495
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010800163297A Pending CN102388437A (en) | 2009-02-11 | 2010-02-11 | Solution based non-vacuum method and apparatus for preparing oxide materials |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US20100200408A1 (en) |
| EP (1) | EP2396811A2 (en) |
| JP (1) | JP2012517532A (en) |
| KR (1) | KR20110127201A (en) |
| CN (1) | CN102388437A (en) |
| WO (1) | WO2010093781A2 (en) |
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| CN105229204A (en) * | 2013-03-15 | 2016-01-06 | 恩索恩公司 | The galvanic deposit of silver and fluoropolymer nanoparticle |
| CN113166963A (en) * | 2018-10-01 | 2021-07-23 | Rise技术有限责任公司 | Making multicomponent structures by dynamic meniscus |
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| US20130302578A1 (en) * | 2011-02-28 | 2013-11-14 | Michael Delpier | Coating particles |
| FR2974450B1 (en) * | 2011-04-19 | 2013-12-20 | Commissariat Energie Atomique | INTEGRATION OF A 2D METAL OXIDE LAYER ON A CONDUCTIVE PLASTIC SUBSTRATE |
| JP5888696B2 (en) * | 2012-04-04 | 2016-03-22 | 奥野製薬工業株式会社 | Method for preventing discoloration of silver-based materials |
| JP5303676B1 (en) * | 2012-04-26 | 2013-10-02 | 株式会社ムラタ | Electrolyte for forming protective film, protective film and method for forming the same |
| KR101992352B1 (en) * | 2012-09-25 | 2019-06-24 | 삼성전자주식회사 | Semicondctor devices |
| US9783901B2 (en) | 2014-03-11 | 2017-10-10 | Macdermid Acumen, Inc. | Electroplating of metals on conductive oxide substrates |
| WO2015177311A1 (en) * | 2014-05-23 | 2015-11-26 | Stamford Devices Limited | A method for producing an aperture plate |
| CN114540929B (en) * | 2020-11-26 | 2023-09-08 | 长鑫存储技术有限公司 | Electroplating method and electroplating device |
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Also Published As
| Publication number | Publication date |
|---|---|
| WO2010093781A2 (en) | 2010-08-19 |
| JP2012517532A (en) | 2012-08-02 |
| WO2010093781A3 (en) | 2010-11-18 |
| EP2396811A2 (en) | 2011-12-21 |
| KR20110127201A (en) | 2011-11-24 |
| US20100200408A1 (en) | 2010-08-12 |
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