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WO2005100642A1 - Procede de depot electrochimique et dispositif obtenu par ce procede - Google Patents

Procede de depot electrochimique et dispositif obtenu par ce procede Download PDF

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Publication number
WO2005100642A1
WO2005100642A1 PCT/IL2005/000393 IL2005000393W WO2005100642A1 WO 2005100642 A1 WO2005100642 A1 WO 2005100642A1 IL 2005000393 W IL2005000393 W IL 2005000393W WO 2005100642 A1 WO2005100642 A1 WO 2005100642A1
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Prior art keywords
sol
metal
gel
conductive surface
conductive
Prior art date
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Ceased
Application number
PCT/IL2005/000393
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English (en)
Inventor
Ronen Shacham
David Avnir
Daniel Mandler
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Yissum Research Development Co of Hebrew University of Jerusalem
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Yissum Research Development Co of Hebrew University of Jerusalem
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Publication of WO2005100642A1 publication Critical patent/WO2005100642A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical 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
    • C25D9/00—Electrolytic coating other than with metals
    • C25D9/04—Electrolytic coating other than with metals with inorganic materials

Definitions

  • This invention relates to a method for the electrochemical deposition and devices obtained by such process.
  • Electrophoretic methods employ micrometric-size particles which are not suitable for sub-micrometric- size shapes. Furthermore, the coated products have rather rough coating. Another drawback of electrophoretic methods is the use of high voltage which may damage the sample undergoing a coating procedure. These drawbacks worsen as the geometry of the structure becomes more complex and are miniaturized. Using a sol-gel process for coating metals with metal alkoxides is known
  • the inventors of the present invention have developed a method for coating of a conducting material by eLectrodeposition of a sol gel film of silicon oxide originating from methyltrimethoxysilane (Shacham, R, et al. (1999) Adv. Mater. 11, 384-388).
  • the mechanism of the electrochemical sol-gel coating described in this reference involves the alteration of the local pH next to the conducting surface resulting in an enhancement of the deposition of the desired coating film specifically on the desired surface.
  • This technique is suitable for sol-gel coating of flat surfaces utilizing a basic pH above 8.2 by introducing a basic material.
  • the present invention is directed to an electrochemical method for depositing a thin film comprising metal- or transition metal- oxides or silicon oxides on a conductive surface comprising: (i) providing a conductive surface; (ii) immersing the conducting surface in a solution comprising sol-gel precursor which is comprised of monomers or prepolymers comprising metal, transition metal or Si compounds; alcohol; a determined amount of water and an inert soluble salt; (iii) carrying out an electrodeposition process by applying substantially low voltages to create negative or positive potential for a predetermined period of time to induce sol-gel reaction at the conductive surface, thereby obtaining conductive surface coated with a thin film having desired thickness and comprising oxides of silicon and/or metal and/or transition metal formed by said sol-gel reaction
  • the novel low-voltage electrochemical technique is capable of differentiating between conducting and non conducting surfaces.
  • the technique consists of subjecting a non-conductive substrate, carrying a conductive region or patterned with a plurality of spaced-apart conductive regions, to an electrochemical potential while immersed in a solution, thus selectively coating only the conductive region(s) while not coating the non-conductive surface o-f the substrate. Accordingly, conductive material present on a non-conductive material can selectively be coated with a thin film, where the thickness of the film is controlled. The selective coating is done by an electrochemically induced sol-gel process.
  • the present invention is further directed to a method accordin-g to claim 1 for depositing the thin film on the conductive surface carried by a non- conductive substrate, the method comprising: (i) providing a non-conductive substrate carrying a pattern formed by at least one conductive surface region on said substrate;
  • the sol-gel precursor is selected from metal, transition metal or silicon alkoxide monomers or ester monomers or monomers of the formula M(R) n (P) m , wherein M is a metallic or semi metallic element or Si, R is a hydrolyzable substituent, n is an integer from 1 to 4, P is a non polymerizable substituent and m is an integer from 0 to 3, or partially hydrolyzed and partially condensed polymer thereof, or any mixture thereof.
  • the sol-gel metal and transition metal are selected from zirconia, titania, alumina, iron, vanadium, cobalt nickel, tungsten and combinations thereof.
  • the coating material is a metal oxide derived from the respective metal alkoxide.
  • the sol-gel precursors may also be pre-polymers, being short polymers composed of a few units of monomers.
  • the thickness of the formed film is controlled through duration of the sol-gel reaction and/or applied voltage and may have a thickness of from a few monolayers to about a micron, preferably from about lOnm to about lOOOnm.
  • the duration of the applied potential is preferably less than one hour, more preferably from about 5 minutes to about 45 minutes.
  • the present invention can be used for example in the manufacture of capacitors by fabricating dielectric spacer between the capacitor plates utilizing the selective coating of the present invention.
  • Another possible application of the present invention is the manufacture of integrated electronic devices, such as optical devices utilizing a stack of materials with different optical properties.
  • the technique of the present invention provides for selectively coating with a material of a desired refractive index, and moreover provides for varying the refractive index during the coating procedure.
  • the present invention can further be used in the manufacture of flat panel displays, by selectively coating by electrodeposition cathode elements (tips) that are typically arranged in a spaced-apart relationship on a non-conductive substrate, with a photosensitive material. Since the technique of the present invention is not limited to the critical dimensions of the conventional lithography, and keeping in mind that growing of nanotip-cathodes is already known, the selective coating of the present invention provides for reducing the pixel size into a nanoscale. The present invention can also be used for manufacturing the pixel array of a photodetector.
  • the technique of the present invention can also be used in the manufacture of printed circuit boards. It is known (for example from WO 03/018871) that a pattern formed by spaced-apart conductive regions on a non-conductive structure can be obtained by irradiating with a focused laser beam the spaced-apart regions of a substrate comprising one or more thermally degradable compounds, thus resulting in local deposition of carbon within said regions. By selectively coating only the conductive carbon-containing regions with a material of an electrical conductivity higher than that of carbon (which by itself might not provide sufficient conductivity for an electronic circuit), the pattern of desired conductors on the non-conductive substrate can be created.
  • the selective coating process of the present invention may further be employed to the manufacture of materials having spatially non-homogenous microstructures and properties by coating spatially different layers.
  • Such blended layers of coatings form a functionalized graded material where the coating consists of at least two layers where each of them has a different ratio of metal to metal oxide in the layer. This is due to the fact that the technique of the present invention enables to timely vary the electrochemically negative or positive potential during the coating process, where the variation of potential results in a different ratio of metal to metal oxide in the coated layer.
  • Figs. 1A-1D illustrate in a schematic manner various possible devices obtainable by the novel electrochemical deposition of the present invention.
  • Fig. 2. shows a High Resolution Scanning Electron Microscope (HR- SEM) image of a gold mesh coated with Ti0 2 .
  • HR- SEM High Resolution Scanning Electron Microscope
  • FIG. 3 shows an Electron Diffraction Spectroscopy (EDS) map of a gold mesh coated with Ti0 2 .
  • EDS Electron Diffraction Spectroscopy
  • Fig. 7 shows the effect of added water on the thickness of the electrodeposited Zr0 2 films after applying a voltage (a) -1.2 V and (b) +2.5 V.
  • Fig. 8 shows the rate of Zr0 2 film buildup on ITO surface applying a voltage of -1.2 V (open circles) or +2.5 V (filled circles).
  • Fig. 9 shows the initial current densities and current decay profile as a function of the initially applied negative potential on ITO (a-d) and gold (e) electrodes; (a) -1.0 V (b) -1.2 V; (c) -1.4 V; (d) -1.5 V; and (e) -1.4 V.
  • Fig. 10 shows the chemical reactions occurring during the electrochemical process of the invention employing Zr(OR) as the sol-gel precursor. Applying either a negative or positive potential produces OH " or ET 1" species, respectively, which in turn cause the formation of the desired Zr0 2 (Zr-O-Zr sol-gel film) on the conducted surface serving as one
  • Figs. 1A-1D schematically illustrate various devices obtainable by the novel electrochemical deposition. To facilitate understanding, the same reference numbers are used for identifying components that are common in all the examples.
  • Fig. 1A shows a device 10 formed by a conductive structure (surface) 12 situated on a non-conducting substrate 14 and coated with a thin film 16 resulting from an electrochemically induced sol-gel process where a low-voltage is applied for a predetermined time period. This time period defines the thickness of the film.
  • the substrate 14 with the conductive surface 12 thereon was immersed in a solution including sol-gel precursor monomers, including metal, transition metal or Si compounds, alcohol, a determined amount of water and an inert soluble salt; and then an electrodeposition process was carried out by applying substantially low voltages (substantially not exceeding a few voltages in absolute values) to create negative or positive potential during the predetermined period of time to thereby induce a sol-gel reaction at the conductive surface 12.
  • substantially low voltages substantially not exceeding a few voltages in absolute values
  • the film 16 includes oxides of silicon and/or metal and/or transition metal formed in the sol-gel reaction.
  • the conductive surface 12 is any conductive material on the substrate 14 having dimensionality such as thickness and a minimal surface area.
  • Fig. IB illustrates a device 100 in the form of a patterned structure, such as a printed circuit board, display device (pixel array defined by the cathode/anode array, etc).
  • the device 100 includes a electrically non-conductive substrate 14 having a pattern Pi on its surface formed by an array of electrically conductive regions, generally at 12, and a pattern P 2 formed by the same array of thin film regions, generally at 16, each on top of a corresponding one of the regions 12.
  • the thin film regions resulted from the selective electro-deposition carried out when the substrate with pattern Pi is immersed in a solution 18 (as described above).
  • FIG. 1C shows a device 200 including an electrically conductive layer 12, which may or may not be carried by a non-conductive substrate 14 (shown in the figured in dashed lines as its provisional is optional); and at least two thin films (two such films 16A and 16B in the present example) stacked on the conductive layer 12.
  • the films are obtained by immersing the conductive layer 12 in a solution 18 (as described above) and carrying out an electro-deposition process with timely varying value of the applied voltage (low voltage) and possibly also varying dopants to sequentially cause the formation of the thin films 16A and 16B.
  • the device may an array of spaced-apart stacks, each formed by the conductive layer 12 with two or more thin films 16A, 16B thereon, all carried by the non-conductive substrate 14.
  • Fig. ID illustrates a device 300 configured as a capacitor or an array of capacitors, each formed by two electrodes Ei and E 2 spaced by a dielectric spacer D.
  • an electrically conductive layer 12 is formed either as a continuous layer or as a patterned layer (spaced-apart regions on a substrate 14), presenting a single electrode Ei or an array of such electrodes. Then the conductive layer (or a patterned conductive layer on a non-conductive substrate) is immersed in a solution 18 prepared to enable formation of a thin film dielectric film 16 (presenting a dielectric spacer D) as a result of electro-deposition using appropriate negative or positive voltage (vs. the reference voltage). Then the second electrode E 2 (or an array of such electrodes) is deposited on the dielectric layer (or dielectric layer regions). It is important to note that employing the process of the invention is facile and does not require a mask for the patterning purposes.
  • the present invention utilizes low voltages (e.g., -2.0 V to + 2.6 V), compared with a voltage up to 50V in electrophoretic processes.
  • the electrochemical process of the invention utilizes the direct use of monomers, thus saving the step of particles formation.
  • the process of the present invention is a controlled process with regards to the specificity of the coating as well as the thickness of the applied coating.
  • the present invention provides for an electrochemical process of coating of a conducting surface which may be either a reduction or an oxidation process.
  • the present invention provides coating of a conducting surface at both acidic and basic conditions where the acidic and basic conditions are formed as a result of the electrochemical process (formation of either H " or OH " species in solution) and therefore does not require balancing of the solution to a preplanned pH.
  • Conducting the process at a negative potential creates basic conditions (formation of OH " species) where conducting the reaction at a positive potential creates acidic conditions (formation of IT 1" species).
  • the process of sol-gel coating via an electrochemical mechanism of curved surfaces or surfaces having a surface relief is not simple. Such complex patterns (surface relieves) may include holes, steps, kinks which are present on the surface.
  • the technique of the present invention overcomes typical problems in coating of metal grids, porous objects, and inner surfaces of tubes, associated with effects of diffusion, fluidity and surface tension. These effects require careful control of the applied potential in order to obtain a controlled process with regards to specificity of coating and thickness of the coating film. Furthermore, the present invention demonstrates that the coating material may be single silicon or metal oxide coating or a combination of the two or more including a combination of two or more metal oxides.
  • Metals employed in sol-gel processes are either metals or transition metals, hence according to the present invention a layer comprising any mixture of the three components: silicon, metal and transition metal may easily be obtained.
  • the precursors of the sol-gel coating are compounds of the general formula M(R) n (P) m in the form of a monomer or in the form of a pre-polymer.
  • M represents a metallic or semi metallic element or Si. Any metal or transition metal may be used where non limiting examples of metals and transition metal elements are zirconium, aluminum, titanium, iron, tungsten, nickel, vanadium or cobalt.
  • R is a hydrolyzable substituents, n is an integer from 1 to 4.
  • P is a non polymerizable substituent and m is an integer from 0 to 3.
  • the R and P may also vary with the same M.
  • Non limiting examples of non polymerizable substituents are alkyl, amine, aklylamine or aryl moieties which may be substituted with thiol or amine.
  • the reaction requires the presence of an alcohol and an inert soluble salt.
  • the alcohol is a C C alcohol preferably, methanol, ethanol, propanol, isopropanol or butanol.
  • Non limiting examples of inert soluble salts are salts of alkali metals, preferably of Na, K and Li such as NaCl, NaBr, KC1, KBr, LiC10 4 , KN0 3 , KBF 4 and the like.
  • the coated metal oxide or combinations of metal oxides may be materials having different dielectric constants thus forming a surface having a controllable and variable dielectric constant from low-K and up.
  • Different sol-gel monomers have different chemical and physical properties enabling the formation of a tailored made surface.
  • Non limiting examples may be water hydrophobic (repellent) or hydrophilic, acid resistance, light reflection.
  • the metal oxide may further comprise functional doped materials for use as markers or for altering the coated layer resulting in tailored made functional surface.
  • the coated film according to the present invention may comprise colors, electroactive components, metal-nanoparticles, dopants suitable for sensing, biochemicals or luminescent molecules.
  • the present invention facilitates the formation of functionalized graded materials. In such materials where thin nanostructured layers of coating are applied on a substrate, rather than obtaining homogenity (one homogenous layer) it is desired to obtain non-homogenous layers. Such materials with spatially non-homogenous layers impart properties utilized in many applications. Ceramic coatings and film technology are two fields greatly benefiting from such non-homogenous coatings.
  • graded materials may easily be obtained according to the present invention by conducting the electrochemical sol-gel process with a solution having desired dopants. Conducting the electrochemical process at varying voltage results in the deposition of non homogenous layers where at each different voltage there is deposited a layer having a different ration between the dopant and the sol-gel. In case metal ions are the dopants, the resulting coated film will have non homogenous layers varying in the ratio of metal to metal oxide in each layer.
  • the dopant is a colored entity or optically active molecules the resulting process carried by varying the potential during the reaction will result in non- homogenous layers with regards to color or optical properties.
  • the dopants within the sol-gel precursor may further be organic, inorganic or bioorganic catalysts, chemical and biochemical sensors.
  • the selective sol-gel coating on conducting surfaces aided by electrodeposition of the present invention is a selective method for coating complex submicrometric-size particles. Such submicron-size patterns may be printed chips or inner microscopic tubes where selective and specific coating is desired.
  • the possibility of selectively engineering the microstructure enables the formation of capacitors and specifically minicapacitors, integrated and printed circuit boards, and flat panel displays.
  • the coating according to the present invention is specific, where only conducting surfaces are coated.
  • the thickness of a surface obtained by dip coating is random and usually is several tens of nanometer, whereas according to the present invention, the thickness of the coating film is controllable and may be up to several hundreds of nanometer.
  • Fig. 2 and Fig. 3 show high resolution scanning electron microscopy (HR-SEM) images and electron diffraction spectroscopy (EDS), respectively, of a gold mesh coated with Ti0 2 . Comparative coating was done by dip coating and by the method of the present invention. Comparing 2(b) to 2(c) of the HR-SEM as well as 3(b) and 3(c) to 3(d) and 3(e) of the EDS demonstrates the difference in thickness of coating achieved by the two techniques.
  • Figs 4 and 5 demonstrate such selectivity where an aluminum pattern sputtered on a silicon wafer is selectively coated with Zr0 2 and Ti0 2 , respectively.
  • Fig. 4(a) shows the HR-SEM of aluminum coated wafer. The aluminum complex pattern is demonstrated. Dip coating the silicone wafer in a Zr0 2 solution results in a non specific coating of the entire wafer as shown in the EDS image at Fig 4(d). Contrary to the non specific coating achieved by dip coating, employing the electrodeposition of the present invention yields selective coating only of the aluminum surface as shown in the EDS image at Fig 4(g).
  • Dip coating results in smoothening of the surface reducing the roughness value to 0.615 nm and the average kinks height is reduced (visually seen in Fig. 6(b)).
  • Using the elctrodeposition method of the present invention further reduces the roughness values to either 0.568 or 0.522 mn depending on the applied voltage (-0.9 V and -1.4 V, respectively). Furthermore, the average height of the kinks is further reduced (visually seen in Figs. 6(c) and 6(d)).
  • the result of smoothening of a rough surface by the electrodeposition according to the present invention further to what is achieved in a dip coating method may be attributed to the fact that the submicrometric size particles or clusters involved in the process are driven more specifically to fill the rough contours.
  • the voltage range which may be employed varies depending on the nature of the coated metal. Taking an ITO plate, the upper value is about +2.5 V versus Ag/AgBr, because considerable oxygen evolution occurs above this voltage. The negative voltage in such a plate is limited to up to -1.6 V where at higher negative voltage values there occurs considerable hydrogen evolution. Water must be present in order to achieve effective coating and its presence is required both in acidic or basic conditions (Fig. 7). Apparently, the results in Fig.
  • Film thickness obtained by simple dip coating is about 55 nm.
  • Film thickness using the electrodeposition coating of the present invention may be from several tens of nm to several hundreds on nm by variation of gthe applied potential. Film coating rapidly builds up during the first 15 minutes after the voltage is applied after which an almost constant thickness is reached (Fig. 8). This time-dependence behavior of the film coating is explained by measuring the decrease in current as a function of the applied potential (negative or positive) shown in Fig. 9. Fig.
  • the electrochemical sol-gel process according to the present invention enables to carry the deposition of the transition metals either using positive potentials or negative potentials, where the former process is an acid catalyzed polymerization process and the latter process is a base catalyzed polymerization process.
  • the possibility of the coating reaction to be a basic or acidic catalyzed reaction is demonstrated with regards to a precursor Zr(OR) forming a coating of Zr0 2 .
  • the conductive surface is immersed in a solution comprising the sol-gel precursor Zr(OR) 4 , the alcohol ROH and trace (several hundreds of ppm) of water.
  • the electrode which is the conducting surface is subjected to either a negative or to a positive potential.
  • solvated H + species are formed which catalyze the acidic chemical transformation of Zr(OR) to Zr0 2 on the electrode e.g. conducting surface.
  • solvated OH- species Upon application of a negative potential of up to (-1.8 V) relative to AgBr/Ag electrode, solvated OH- species are formed which catalyze the basic chemical transformation of Zr(OPr) 4 to Zr0 2 on the electrode e.g. conducting surface.
  • the electrochemical process generates both H* and OH " even in the absence of water.
  • water is crucial for the coating process implying that water is involved not only in the electrochemical process but also in the coating process.
  • Example 1 Coating a gold mesh with Ti0 2 thin film. Titania (Ti0 2 ) deposition solution was prepared by adding 16.15 mL of dry 2-PrOH that was wetted with 160 ppm water and 0.1 M LiC10 to 0.95 mL Ti(OPr) under vigorous stirring (monomer concentration was ca. 0.2 M). During the electrochemical deposition, a potential of -1.4 V vs.
  • Example 2 Coating aluminum sputtered on a silicone with Ti0 2 film The same titania solution of Example 1 was used and a potential of -1.4 V vs. Ag/AgBr was applied for duration of 15 min while stirring the solution.
  • Example 3 Coating aluminum sputtered on a silicone with Zr0 2 film
  • the Zr-deposition solution was prepared by adding 5 mL of dry 2-PrOH that was wetted with 900 ppm water and 0.1 M LiC10 4 to 5 mL Zr(OPr) 4 under vigorous stirring (monomer concentration was ca. 1.12 M). Dip coating was performed by pulling the substrate at a rate of 50 ⁇ m ' sec "1 from the deposition solution while stirring. During the electrochemical deposition, a potential of -1.4
  • V vs. Ag/AgBr was applied for duration of 30 min, while stirring the solution.
  • HR-SEM High resolution scanning electron microscope
  • FEI Company FEI Company
  • EDS Energy Dispersive X-ray Spectroscopy

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

L'invention porte sur un procédé de dépôt électrochimique d'une fine couche d'oxydes métalliques ou de silicium sur une surface conductrice placée sur un substrat non conducteur par électrodéposition sélective de précurseurs de sol-gel sur une surface conductrice. Lesdits précurseurs pouvant en outre comprendre différents dopants permettant de tracer des motifs sur la couche conductrice.
PCT/IL2005/000393 2004-04-13 2005-04-13 Procede de depot electrochimique et dispositif obtenu par ce procede Ceased WO2005100642A1 (fr)

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US60/561,547 2004-04-13

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Cited By (9)

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Publication number Priority date Publication date Assignee Title
WO2008038293A3 (fr) * 2006-09-27 2008-06-19 Yissum Res Dev Co Codéposition électrochimique de films sol-gel
US7470466B2 (en) 2005-12-23 2008-12-30 Boston Scientific Scimed, Inc. Nanoparticle structures and composite materials comprising a silicon-containing compound having a chemical linker that forms a non-covalent bond with a polymer
EP2261400A1 (fr) * 2009-06-09 2010-12-15 Tyco Electronics Corporation Ensemble composite pour connecteur électrique et procédé de fabrication de l'ensemble composite
US8455088B2 (en) 2005-12-23 2013-06-04 Boston Scientific Scimed, Inc. Spun nanofiber, medical devices, and methods
US8784147B2 (en) 2009-06-09 2014-07-22 Tyco Electronics Corporation Composite assembly for an electrical connector and method of manufacturing the composite assembly
US8790144B2 (en) 2010-06-07 2014-07-29 Tyco Electronics Corporation Contact assembly for an electrical connector and method of manufacturing the contact assembly
CN104439231A (zh) * 2014-11-15 2015-03-25 吉林大学 一种Au修饰Zn/ZnO微纳米材料的制备方法
CN106894071A (zh) * 2017-03-10 2017-06-27 国家开发投资公司 一种铝合金表面耐腐蚀处理方法
US11352292B2 (en) 2019-01-30 2022-06-07 Ppg Industries Ohio, Inc. Method for preparing optical articles with multi-layer antireflective coatings

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US5925228A (en) * 1997-01-09 1999-07-20 Sandia Corporation Electrophoretically active sol-gel processes to backfill, seal, and/or densify porous, flawed, and/or cracked coatings on electrically conductive material

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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7470466B2 (en) 2005-12-23 2008-12-30 Boston Scientific Scimed, Inc. Nanoparticle structures and composite materials comprising a silicon-containing compound having a chemical linker that forms a non-covalent bond with a polymer
US7799426B2 (en) 2005-12-23 2010-09-21 Boston Scientific Scimed, Inc. Nanoparticle structures comprising silicon oxide-based polymer, and composite materials
US8481643B2 (en) 2005-12-23 2013-07-09 Boston Scientific Scimed, Inc. Nanoparticle precursor structures, nanoparticle structures, and composite materials
US8455088B2 (en) 2005-12-23 2013-06-04 Boston Scientific Scimed, Inc. Spun nanofiber, medical devices, and methods
WO2008038293A3 (fr) * 2006-09-27 2008-06-19 Yissum Res Dev Co Codéposition électrochimique de films sol-gel
US20100078328A1 (en) * 2006-09-27 2010-04-01 Yissum Research Development Company Of The Hebrew University Of Jerusalem Electrochemical co-deposition of sol-gel films
US8216006B2 (en) 2009-06-09 2012-07-10 Tyco Electronics Corporation Composite assembly for an electrical connector and method of manufacturing the composite assembly
CN101944675A (zh) * 2009-06-09 2011-01-12 泰科电子公司 电连接器的复合组件及制造该复合组件的方法
EP2261400A1 (fr) * 2009-06-09 2010-12-15 Tyco Electronics Corporation Ensemble composite pour connecteur électrique et procédé de fabrication de l'ensemble composite
US8784147B2 (en) 2009-06-09 2014-07-22 Tyco Electronics Corporation Composite assembly for an electrical connector and method of manufacturing the composite assembly
US8790144B2 (en) 2010-06-07 2014-07-29 Tyco Electronics Corporation Contact assembly for an electrical connector and method of manufacturing the contact assembly
CN104439231A (zh) * 2014-11-15 2015-03-25 吉林大学 一种Au修饰Zn/ZnO微纳米材料的制备方法
CN106894071A (zh) * 2017-03-10 2017-06-27 国家开发投资公司 一种铝合金表面耐腐蚀处理方法
US11352292B2 (en) 2019-01-30 2022-06-07 Ppg Industries Ohio, Inc. Method for preparing optical articles with multi-layer antireflective coatings

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