WO2018109724A1 - Fabrication d'électrodes transparentes à motifs pour applications d'éclairage de type delo - Google Patents

Fabrication d'électrodes transparentes à motifs pour applications d'éclairage de type delo Download PDF

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Publication number
WO2018109724A1
WO2018109724A1 PCT/IB2017/057965 IB2017057965W WO2018109724A1 WO 2018109724 A1 WO2018109724 A1 WO 2018109724A1 IB 2017057965 W IB2017057965 W IB 2017057965W WO 2018109724 A1 WO2018109724 A1 WO 2018109724A1
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Prior art keywords
substrate
conductive film
donor film
metal nanowires
nanowires
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PCT/IB2017/057965
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English (en)
Inventor
Sang Hoon Kim
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Sabic Global Technologies B.V.
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Publication of WO2018109724A1 publication Critical patent/WO2018109724A1/fr

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/50—Forming devices by joining two substrates together, e.g. lamination techniques
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/621—Providing a shape to conductive layers, e.g. patterning or selective deposition
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/80—Manufacture or treatment specially adapted for the organic devices covered by this subclass using temporary substrates
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • H10K30/81—Electrodes
    • H10K30/82—Transparent electrodes, e.g. indium tin oxide [ITO] electrodes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/805—Electrodes
    • H10K50/81—Anodes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/805—Electrodes
    • H10K50/82—Cathodes
    • H10K50/828—Transparent cathodes, e.g. comprising thin metal layers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • the present disclosure relates to patterned conductive electrodes and processes for fabricating the same. More particularly, the disclosure relates to a fabrication process that includes depositing nanowire electrode material on a donor film; patterning the electrode material; and laminating that film with the patterned electrode to a substrate containing a transfer resin to embed the nanowires within the transfer resin.
  • OLEDs organic light emitting diodes
  • OLEDs typically have a stacked structure composed of one or more organic layers positioned between two electrodes. At least one of the two electrodes, either the anode or the cathode electrode is formed from a transparent conductive material, which enables the light emitted from the OLED to be visible.
  • the transparent conductive material used as an electrode should possess certain properties such as low resistivity and high optical transmittance to produce an OLED device with desirable performance.
  • Indium tin oxide (ITO) is a transparent electrode material that is useful in OLED applications due to its high transparency in the visible wavelength range.
  • ITO is commonly used in many liquid crystal display (LCD) applications.
  • Transparent conductive oxides, such as ITO are problematic for flexible OLED devices because they are brittle and prone to cracking under stress. The cracking reduces the conductivity of the electrode and ultimately may degrade the OLED. As a result, this particular drawback has limited the use of ITO in flexible OLEDs.
  • electrodes formed using silver nanowires suffer from, challenges associated with higher surface roughness. For example, when silver nanowires are deposited on a surface the nanowires overlap each other creating protrusions and causing surface roughness. While these portions of overlapping nanowires increase the conductivity of the electrode, higher surface roughness lowers the efficiency and the stability of the overall device. Therefore, it is important that surface characteristics of electrodes formed using silver nanowire are improved to allow for stable and efficient devices.
  • PEDOT:PSS tends to negatively affect the properties of the silver nanowire and the device stability. Electrodes formed using hybrid solutions that combine silver nanowires and PEDOT:PSS have also been tested and produce similar results. Another approach to improving surface roughness involves welding to fill in the existing gaps in a deposited layer of silver nanowire. The welding process may improve surface roughness, but it significantly increases the production costs and complexity of fabrication. Furthermore, none of these approaches addresses the need to fabricate a patterned electrode using silver nanowires.
  • a process for fabricating a patterned conductive film on a substrate includes (a) depositing a plurality of metal nanowires on a donor film; (b) coating the metal nanowires with a curable resin; (c) patterning the donor film with a selected pixel pattern; (d) applying a transfer resin to the donor film; (e) laminating the donor film with a substrate; (f) curing the transfer resin; and (g) detaching the substrate from the donor film.
  • the disclosure further relates to a conductive electrode prepared by a process.
  • the process can comprise: (a) depositing a plurality of metal nanowires on a donor film; (b) patterning the donor film with a selected pixel pattern; (c) applying a transfer resin to a substrate; (d) laminating the donor film with the substrate to embed the metal nanowires in the transfer resin; (e) curing the transfer resin; and (f) detaching the donor film.
  • the present disclosure relates to a conductive film that can be formed by a process comprising: depositing a plurality of metal nanowires at a donor film; patterning the donor film with a selected pattern; applying a transfer resin to a substrate; laminating the donor film with the substrate to embed the metal nanowires in the transfer resin; curing the transfer resin; and detaching the donor film.
  • the conductive film can exhibit a power efficiency greater than a substantially similar conductive film formed in the absence of a plurality of metal nanowires and formed according to a non-transfer process when tested according to current density-voltage-luminance assessment, and wherein the conductive film exhibits a current efficiency greater than a substantially similar conductive film formed in the absence of a plurality of metal nanowires and formed according to a non-transfer process when tested according to current density-voltage-luminance.
  • FIG. 1 is an edge view of the conductive patterned film on a substrate according to one example of the present disclosure.
  • FIG. 2A is a schematic illustration of a step of depositing electrode material on a donor film according to one example of the present disclosure.
  • FIG. 2B is a schematic illustration of patterning the electrode coated donor film.
  • FIG. 2C is a schematic illustration of laminating the electrode coated donor film with a substrate carrying a transfer resin to embed the metal nanowires in the transfer resin according to one example of the present disclosure.
  • FIG. 2D is a schematic illustration of curing the transfer resin according to one example of the present disclosure.
  • FIG. 2E is a schematic illustration of delaminating the transfer resin according to one example of the present disclosure.
  • FIG. 2F is a schematic illustration of a patterned electrode after the donor film has been removed according to one example of the present disclosure.
  • FIG. 3 is an image of a patterned conductive film according to an example of the present disclosure with an enlarged portion showing further detail of the nanowires embedded in the transfer resin.
  • FIG. 4 is a schematic illustration of a roll-to-roll process for laminating the donor film and substrate to embed the nanowires within the transfer resin according to an example of the present disclosure.
  • FIG. 5 presents current and efficiency curves for patterned conductive films at different thicknesses (#12, #16, and #18 Mayer rods) compared to a conventional ITO electrode/film.
  • FIG. 6 presents surface roughness data for patterned conductive films at different thicknesses (#12, #16, and #18 Mayer rods) compared to bare (non-coated) polyimide.
  • FIG. 7 presents sheet resistance data and percent uniformity for patterned conductive films formed at different Mayer rod thicknesses (#12, #16, and #18 Mayer rods).
  • the present disclosure provides a process for producing a patterned conductive film composed of metal nanowires, such as silver nanowires.
  • the process includes a patterned electrode fabrication method by transfer process. Surface roughness coming from overlapping silver nanowire is improved by the transfer process by patterning a donor film before transfer of the nanowires.
  • metal nanowires are coated on a donor film, the donor film is patterned to have a selected pixel pattern. Transfer resin is applied to the metal nanowire coated donor film, and then the film is laminated with a substrate, such as a plastic substrate. Afterwards, the structure is cured causing the transfer resin to transfer to the substrate. The donor film is then detached leaving the nanowires embedded in the transfer resin decreasing the surface roughness of the metal nanowires.
  • FIG. 1 illustrates a patterned conductive film 100 or electrode formed using the process according to one example of the present disclosure.
  • the patterned conductive film 100 may have a stacked layered structure.
  • the patterned conductive film 100 includes a substrate 1 10 and a transparent conductive layer 120 disposed on the substrate 110.
  • the transparent conductive layer 120 includes of a curable resin coating 130 and a plurality of metal nanowires 140.
  • the transparent conductive layer 120 is patterned at 150.
  • FIGS, 2A-2F illustrate examples of the various process steps that may be used to fabricate a patterned conductive film 100.
  • the patterned conductive film 100 may be used as an electrode, including an anode electrode or a cathode electrode. In one example, the patterned conductive film 100 may be transparent.
  • the patterned conductive film 100 may be used to form OLED lighting, solar cell, touch display, flexible electronics, or other photovoltaic device. Other uses for the patterned conductive film 100, however, are contemplated and the present disclosure is not limited in this regard.
  • metal nanowires are coated onto a donor film 105.
  • nanowires 140 are bar coated on to donor film 1 5 using a Mayer bar or rod 115. It will be understood that other coating methods may be used including but not limited to slot die coating, micro gravure coating, screen printing, spray coating, inkjet printing, and the like.
  • Nanowires may be any metal nanowire, metal mesh, metal particle, or other configuration suitable for the desired application.
  • the metal nanowires 140 may also include metal nanorods, nanostrands, nanowires, or a mixture thereof. As used herein, the term nanowire is meant to collectively refer to nanorods, nanostrands, nanoparticles, and nanowires.
  • the metal nanowires 140 may comprise at least one of silver, gold, copper. nickel, rhodium, palladium, platinum, aluminum, and/or alloys thereof. These metals may generally be preferred because of their strong conductive properties. Metals used for the metal nanowires 140 may include, but are not limited to, copper, silver, aluminum and alloys thereof. In one example of the disclosure, the metal nanowires 140 are silver nanowires (Ag- NW). In the example, silver nanowires may be used to form a patterned conductive Saver 120 on a flexible substrate 110 (see, e.g., FIG. 2C).
  • the metal nanowires 140 may be arranged randomly such that the orientation of each individual nanowire is random. This random arrangement may form a network of overlapping metal nanowires 140 on the curable resin coating 130. The contact between the nanowires improves the overall conductivity of the metal nanowire network. There may also be gaps or spaces between the metal nanowires 140.
  • the metal nanowires 140 may have varying example ratios.
  • the metal nanowires 140 may be sized to provide the desired electrical properties, such as conductivity.
  • the deposited layer of metal nanowires 140 formed on the curable resin coating may be at least 2 microns, at least 5 microns, at least 10 microns.
  • the deposited layer of metal nanowires 140 formed on the curable resin coating 130 may range from 10 nanometers (nm) to 500 nm. In general, adjusting the concentration of the metal nanowires 140 and/or the amount of the solution containing the metal nanowires 140 may increase or decrease the conductivity achieved.
  • the metal nanowires 140 may be deposited on donor film 105 as shown in FIG. 2B.
  • a solution containing the metal nanowires 140 may be initially prepared .
  • the solution may be applied to the curable resin coating 130 using suitable solution coating methods known in the art.
  • the solution may include the metal nanowires 140 and an aqueous solvent.
  • the aqueous solvent may include alcohol and/or other organic solvents.
  • the solution may further include a polymer binder.
  • the polymeric binder may be a curable resin similar to the composition of the curable resin coating 130 described below.
  • suitable polymenc binders may include poiyurethane, acrylic resin, acrylic copolymers, polyethers, polyesters, epoxy containing polymers, and mixtures thereof.
  • the solution may include 0.001 weight percent (wt%) to 5 wt% metal nanowires 140. in another example of the disclosure, the solution may include 0.005 wt% to 2 wt% metal nanowires 140. Other concentrations of metal nanowires 140, however, are also contemplated.
  • a silver nanowire is used.
  • additional metal nanowires including but not limited to indium tin oxide (ITO,) zinc oxide (ZnO), and tin oxide (SnO) can be deposited such that they are transferred with the silver nanowire, as described more completely below.
  • ITO indium tin oxide
  • ZnO zinc oxide
  • SnO tin oxide
  • other metals such as copper Cu, nickel i, aluminum Al , silver Ag and platinum Pt can be deposited after the silver nanowire, and transferred with the silver nanowire.
  • the donor film 105 may be any suitable substrate material for supporting the nanowires.
  • Suitable substrate materials for the donor film may include, but are not limited to, glass, plastics, semiconductor materials such as silicon, and ceramics.
  • Specific examples of the substrate material for the donor film may include, but are not limited to a film made of plastic such as polyethylene terephthalate (PET), poly methyl aciylate (PMA), poly methyl methacrylate (PMMA), poly acryiate copolymer, polyurethane (PU), polyurethane copolymer, cellulose acetate, polystyrene (PS), polystyrene co-polymer, poly imide (PI) and the like.
  • PET polyethylene terephthalate
  • PMA poly methyl aciylate
  • PMMA poly methyl methacrylate
  • PU polyurethane
  • PS polyurethane copolymer
  • cellulose acetate polystyrene
  • PS polystyrene co-pol
  • the film 105 is configured to form a selected pattern, for example, an OLED pixel pattern or other pattern suitable for the desired application.
  • the pattern 150 may be applied according to variety of available methods including but not limited to photolithography, laser patterning, and the like.
  • Transfer resin 130 is applied to the nanowire coated donor film 105.
  • Transfer resin generally may be a curable polymer.
  • the transfer resin 130 may be an ultraviolet (UV) sensitive curing polymer, thermal curing polymer or mixture thereof.
  • Any suitable transfer resin may be used including but not limited to polyvinyl alcohol (PVA) including a UV sensitive functional group such as a diazo compound, styryl pyridinium and photo polymerization polymer such as polyester aciylate, epoxy acryiate, urethane acryiate, silicone resin aciylate including photo initiator.
  • PVA polyvinyl alcohol
  • photo polymerization polymer such as polyester aciylate, epoxy acryiate, urethane acryiate, silicone resin aciylate including photo initiator.
  • resin could be ester polymer, acrylic polymer, urethane base polymer, acryl copolymer, urethane base copolymer (reactivity high molecular compound), silane coupl ing agent (reactivity small molecular compound) and synthetic rubbers including UV sensitive functional group and thermal sensitive functional group.
  • transfer resin is NOA 63 from noisy.
  • the curable resin composition may be applied to the electrode coated donor film 105 fay spraymg, dipping, roll-coating or roll-to-roll coating the curable resin material onto the electrode coated donor film 105.
  • the curable resin coating is applied to the electrode by applying a thin layer of the resin material by any well- known methods such as spraying, dipping, roll-coating and the like. A sufficient amount of the resin material should be applied to the substrate to provide a thickness suitable for embedding the metal nanowires 140.
  • the curable resin coating 130 may be applied to the substrate 110 using a roii-to-roll coating process.
  • the curable resin coating (transfer resin) 130 may be dried and rinsed once the curable resin coating 130 has been applied to the substrate.
  • the curable resin coating 130 thickness is not limited. The thickness of the curable resin coating 130, however, should be sufficient to embed the silver nanowires 140 into the resin coating to reduce the surface roughness.
  • the curable resin coating 130 may be at least 50 micrometers (microns, ⁇ ) thick.
  • Application methods may be repeated to form thicker curable resin coatings 130 if needed.
  • a solution may be prepared by dissolving the curable resin polymer composition in one or more solvents.
  • the curable resin composition may then be applied to the substrate i 10 surface.
  • the solvent(s) may be removed by evaporating or drying the curable resin composition resulting in the curable resin coating 130.
  • the curable resin coating 130 may also be possible to prepare a solution of monomers that may be polymerized to form, the curable resin coating 130.
  • the monomer solution may then be used to coat the substrate 110 surface. Polymerization of the monomer solutions may occur by applying heat and/or light to the monomer solution.
  • the transfer resin material is generally film forming and able to sufficiently adhere to the substrate 1 10 during lamination, as discussed below.
  • the resin material may also be a thermoplastic or a thermosetting polymer.
  • the curable resin coating may be ultraviolet sensitive such that the resin material may cure when exposed to ultraviolet light.
  • the photopolymer may be capable of absorbing light in a wavelength in the range from 180 nanometers (nm) to 500 nm.
  • the photopolymer may be capable of absorbing light in a wavelength in the range from 320 nm to 400 nm.
  • transfer resm material may include a photopolymer, in particular an ultraviolet sensitive photopolymer.
  • the resin material may include other polymers in addition to other polymers.
  • the resin material may consist essentially of a photopolymer.
  • the resin material may include a polymer binder and a photoinitiator.
  • the photoinitiator may be ultraviolet light sensitive.
  • the photopolymer may include for example a polymer having diazo functional groups or styryl functional groups.
  • the photopolymer may include a styryl pyridinium or a styryl pyridinium derivative.
  • the photopolymer may also include poly(vinyl pyridine).
  • the photopolymer may also be a polyvinyl alcohol based photopolymer.
  • the curable resin material in transfer resin 130 may include a polymer binder and a photoinitiator.
  • Suitable examples of the polymer binder in the resin material may include, but are not limited to, silicone resins, epoxy resins, polyallylate resins, polyethylene terephthalate (PET) modified polyallylate resins, polycarbonate resins (PC), cyclic olefins, PET resms, polymethylmethacrylate resins (PMMA) and mixtures thereof.
  • the polymer binder may include a polyester acrylate, an epoxy acrylate, a urethane acrylate, a silicone resin acrylate or mixtures thereof.
  • the electrode coated donor film 105 is laminated to a substrate 1 10 (also shown in FIG. 2C), such as, for example, a plastic substrate.
  • the substrate 1 10 may be laminated by a roller, roll-to-roll process, or other suitable lamination process that contacts substrate 110 to donor film as shown to form a layered structure comprising donor film coated with a patterned electrode covered by substrate 1 10.
  • a roll-to-roll process is schematically shown.
  • a laminating assembly 400 includes a first roil 401 and a second roll 402 that define a nip 403 there between.
  • the (electrode coated) donor film 105 is routed over a first roll 401 and substrate 110 containing the transfer resm 130 is routed over second roll 402.
  • the materials are respectively routed such that the exposed nanowires on donor film 105 contact the transfer resin 130 on substrate 110 to embed the nanowires within transfer resin as they pass through nip 403.
  • Suitable polymeric materials for the substrate 110 include, but are not limited to polyethylene terephthalate (PET), poly methylacrylate (PMA), polymethyl methacrylate (PMMA), polyacrylate copolymer, polyurethane (PU), polyurethane copolymer, cellulose acetate, polystyrene, polystyrene copolymer, polyimide (PI) and mixtures thereof.
  • PET polyethylene terephthalate
  • PMA poly methylacrylate
  • PMMA polymethyl methacrylate
  • PU polyurethane
  • PU polyurethane copolymer
  • cellulose acetate polystyrene
  • polystyrene copolymer polyimide (PI) and mixtures thereof.
  • PI polyimide
  • the thickness of the substrate 110 is not particularly limited.
  • the substrate 1 10 thickness may be 300 micrometers ( ⁇ ) or less, more preferably 200 ⁇ or less, and even more preferably 100 ⁇ or less.
  • the substrate 1 0 thickness may range from 100 ⁇ to 50 ⁇ .
  • the substrate 1 10 thickness may range from 10 ⁇ to 50 ⁇ .
  • the substrate 1 10 is flexible. Polymeric materials that are generally transparent as well as flexible may be used to form the substrate 110. A transparent flexible substrate 110 may be particularly useful for OLED lighting applications or touch screen displays such that light generated by the OLED may pass through the OLED.
  • polyethylene terephthaiate is used to form the substrate 110. The polyethylene terephthaiate substrate 110 may be used to form a patterned conductive film 100.
  • a curing step is shown.
  • heat, light, or a combination thereof may be used to cure the layered substrate.
  • a suitable curing assembly generally indicated at 200, is provided with at least one of a heat and light source, 212 to perform curing .
  • an ultraviolet light source is used within curing assembly 200.
  • the curable resin coating 130 may cure i.e., cross-link, upon exposure to the ultraviolet light source.
  • the type of light source and level of penetration may be selected according to the resin material.
  • an ultraviolet light source (up to about 400 nm, e.g., from 280 nm to 400 nm) was used to irradiate at 365 nm.
  • This example was for a PET material and should not be considered limiting.
  • Curing may be performed for a time period based on the type of resin selected. The time period is not limiting in this regard, in the example shown, a PET resin was used and curing occurred at room temperature for a time period of 30 seconds or about 30 seconds to 10 minutes or about 10 minutes. In some examples, the curing may occur for about 10 minutes.
  • transfer resin 130 is transferred to the substrate 1 10 thereby embedding the patterned nanowires within transfer resin 130 (such as a curable resin coating).
  • the donor film 105 is removed leaving a layered structure comprising substrate 1 10 and transfer resin with an embedded pattern of nanowire electrodes therein to form a patterned electrode (patterned conductive film) 100 as schematically depicted in FIG. 1.
  • FIG. 3 shows a more detailed view or image of a patterned electrode 300 formed according to the disclosure. As shown, the pattern 350 may have any shape or configuration as needed for a particular application or created for purposes of ornamentation.
  • FIG. 3 An enlarged portion is shown in FIG. 3 to illustrate the embedding of the nanowire within the pattern and improvement in surface characteristics of the patterned electrode 300.
  • the nanowires 340 are embedded within transfer resin 130 in the desired pattern reducing machining operations needed to remove material to form the pattern in other fabrication techniques.
  • applying the pattern before the transfer resin is applied allows greater flexibility in forming the pattern using techniques such as photolithography and laser patterning rather than masks used to form the pattern during a curing process and remove excess material with solvents, in the process shown, the nanowires are embedded within the transfer resin reducing the surface roughness attributable to the nanowires compared to other fabrication techniques, in the example shown in FIGS. 2A-2F, the embedded nanowire pattern 150 had a surface roughness suitable for applying an OLED panel.
  • a conductive film formed by according to the processes disclosed herein can exhibit certain improved properties with respect to current and power efficiencies, surface morphology, and sheet resistance.
  • the conductive film can exhibit a power efficiency greater than a substantially similar conductive film (a) formed in the absence of a plurality of metal nanowires and (b) formed according to a non-transfer process when tested according to current density -voltage-luminance assessment.
  • the conductive film can exhibit a current efficiency greater than a substantially similar conductive film formed in the absence of a plurality of metal nanowires and formed according to a non-transfer process when tested according to a current density-voltage-iuminance assessment.
  • the conductive film can exhibit a sheet resistance vasity of greater than 5% when the patterning of the donor film is performed via Mayer rod coating using a #12, #16, or #18 Mayer rod. Films formed according to the present disclosure can also be sufficiently flexible making them useful for applications in flexible OLED devices (compared to conventional ITO glass based OLED devices which can be non-flexible).
  • Mayer rod refers to a stainless steel rod that is wound tightly with stainless steel wire of varying diameter.
  • the rod may be used to adjust (doctor) excess coating solution and control coating weight.
  • the wet thickness after doctoring may be controlled by the diameter of the wire used to wind the roll and may be approximately 0.1 times the wire diameter.
  • Rods are available in a wide variety of wire sizes to provide a range of coating weights. Theoretical coating amount may depend on wire rod size (generally, grams dry per square meter).
  • Exemplary Mayer rod numbers are #12 (1.2 wet mils thickness, 30.5 microns thickness), #16 (1.6 wit mils thickness, 40.6 microns thickness), and #18 (1.8 wet mils thickness, 45.7 microns thickness). Dry thickness may be determined by the solids concentration of the respective coating solutions.
  • a substantially similar (conductive) film formed in the absence of a plurality of metal nanowires and formed according to a non-transfer process is described herein.
  • the substantially similar conductive film has been formed without a plurality of metal nanowires.
  • the substantially similar film is also not formed according to the transfer process described herein.
  • the substantially similar film may be formed according to conventional methods of forming a conductive film.
  • the substantially similar film is a conventional ITO glass based film.
  • Ranges can be expressed herein as from one value (first value) to another value (second value). When such a range is expressed, the range includes in some aspects one or both of the first value and the second value. Similarly, when values are expressed as approximations, by use of the antecedent 'about,' it will be understood that the particular value forms another example. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint. It is also understood that there are a number of values disclosed herein, and that each value is also herein disclosed as "about” that particular value in addition to the value itself. For example, if the value "10" is disclosed, then “about 10" is also disclosed. It is also understood that each unit between two particular units are also disclosed. For example, if 10 and 15 are disclosed, then 11, 12, 13, and 14 are also disclosed.
  • the terms “about” and “at or about” mean that the amount or value in question can be the designated value, approximately the designated value, or about the same as the designated value. It is generally understood, as used herein, that it is the nominal value indicated ⁇ 5% variation unless otherwise indicated or inferred. The term is intended to convey that similar values promote equivalent results or effects recited in the claims. That is, it is understood that amounts, sizes, formulations, parameters, and other quantities and characteristics are not and need not be exact, but can be approximate and/or larger or smaller, as desired, reflecting tolerances, conversion factors, rounding off, measurement error and the like, and other factors known to those of skill in the art.
  • an amount, size, formulation, parameter or other quantity or characteristic is “about” or “approximate” whether or not expressly stated to be such. It is understood that where "about” is used before a quantitative value, the parameter also includes the specific quantitative value itself, unless specifically stated otherwise. [0059] Disclosed are the components to be used to prepare the compositions of the disclosure as well as the compositions themselves to be used within the methods disclosed herein.
  • the term "light” means electromagnetic radiation including ultraviolet, visible or infrared radiation.
  • photopolymer refers to a polymeric composition that undergoes polymerization, cross-linking, any hardening or curing reactions or otherwise undergoes structural and property changes upon exposure to light.
  • photoinitiator refers to a composition that generates a reactive species such as free radicals, cations, ions, when exposed to radiation (UV or visible).
  • the term “transparent” means that the level of transmittance for a disclosed composition is greater than 50%. In some embodiments, the transmittance can be at least 60%, 70%, 80%, 85%, 90%, or 95%, or any range of transmittance values derived from the above exemplified values. In the definition of "transparent”, the term
  • transmittance refers to the amount of incident light that passes through a sample measured in accordance with ASTM D1003 at a thickness of 3.2 millimeters.
  • patterned may describe an orientation of the metal nanowires throughout, or at, a film, or film surface, for example.
  • the application of a pattern may be random, or substantially random.
  • the patterned electrode may comprise a repeating pattern, in one aspect, the metal nanowires are random such that the donor film is randomly patterned.
  • the metal nanowires are random such that the donor film is randomly patterned.
  • the present disclosure comprises at least the following aspects.
  • a process for fabricating a patterned conductive film on a substrate comprising:
  • a process for fabricating a patterned conductive film on a substrate consisting essentially of:
  • a process for fabricating a patterned conductive film on a substrate consisting of:
  • Aspect 2 The process of any of aspects 1A-1C, wherein patterning includes at least one of photolithography and laser patterning.
  • Aspect 3 The process of any one of aspects 1A-2, wherein the curing includes applying ultraviolet light selected at a wavelength between 280 nm and 400 nm.
  • Aspect 4 The process of any one of aspects 1A-2, wherein the curing includes applying ultraviolet light at 365 nm or at about 365 nm.
  • Aspect 5 The process of aspect 3 or 4, wherein curing includes applying the ultraviolet light for from about 30 seconds to about 10 minutes.
  • Aspect 6 The process of aspect 3 or 4, wherein curing includes applying the ultraviolet light for 10 minutes or for about 10 minutes.
  • Aspect 7 The process of any one of aspects 1A-6, wherein the substrate is a transparent plastic.
  • Aspect 8 The process of any one of aspects 1A-7, wherein applying the transfer resin on the substrate includes (a) preparing a curable resin composition and (b) applying the curable resin composition to the substrate by at least one of spraying, dipping, roll-coating or roll-to-roll coating the curable resin material onto at least a portion of the surface of the subsiraie.
  • Aspect 9 The process of any one of aspects 1A-8, wherein the laminating includes roll-to-roll lamination, where the donor film is provided on a first roll and the substrate is provided on a second roll, where the nanowires face the transfer resin as they enter a nip formed between the first and second roll.
  • Aspect 10 The process of any one of aspects 1A-9, wherein the plurality of metal nanowires comprises at least one of silver, gold, tin, copper or platinum.
  • Aspect 11 The process of any one of aspects 1A-9, wherein the plurality of metal nanowires comprises silver.
  • Aspect 12 The process of any one of aspects lA-11, wherein the transfer resin is at least one of a polyvinyl alcohol including a ultraviolet sensitive functional group, a photo polymerization polymer such as polyester acrylate, epoxy acrylate, urethane acrylate, silicone resin acrylate including photo initiator, an ester polymer, an acrylic polymer, a urethane base polymer, an acryl copolymer, a urethane base copolymer, a silane coupling agent, and synthetic rubbers including at least one of an ultraviolet sensitive functional group and a thermal sensitive functional group.
  • a photo polymerization polymer such as polyester acrylate, epoxy acrylate, urethane acrylate, silicone resin acrylate including photo initiator, an ester polymer, an acrylic polymer, a urethane base polymer, an acryl copolymer, a urethane base copolymer, a silane coupling agent, and synthetic rubbers including at least one of an ultraviolet sensitive functional group and
  • Aspect 13 The process of aspect 12, wherein the polyvinyl alcohol based polymer comprises one or more diazo-functional groups or one or more styryl functional groups.
  • Aspect 14 The process of any one of aspects 1A-13, wherein the plurality of nanowires is configured as at least one of a wire, a rod, a mesh, and a particle.
  • Aspect 15 The process of any one of aspects 1A-14, wherein the step of depositing a plurality of nanowires includes coating the donor film with a silver nanowire, and subsequently applying at least one of a metal oxide and a metal, wherein the metal oxide includes at least one of an indium tin oxide, a zinc oxide, and a tin oxide, and wherein the metal includes at least one of a copper, nickel, aluminum, silver, gold and platinum.
  • Aspect 16 The process of any of aspects 1A-15, wherein the donor film is at least one of a polyethylene terephthalate, poly methyl acrylate, poly methyl methacrylate, poly acrylate co-polymer, polyurethane, polyurethane co-polymer, cellulose acetate, polystyrene, polystyrene co-polymer, and poly imide.
  • Aspect 17 The process of any of aspects 1A-16, wherein depositing the nanowires includes at least one of roll coating, Mayer rod coating, slot die coating, micro gravure coating, screen printing, spray coating, and inkjet printing.
  • a solar cell comprising: a conductive film prepared by the process of any one of aspects 1A-1C.
  • Aspect 19 An OLED comprising: a conductive film prepared by the process of any one of aspects lA-lc.
  • a touch display comprising: a conductive film prepared by the process of any one of aspects 1A-1C.
  • Aspect 21 A flexible electronic comprising: a conductive film prepared by the process of any of aspects 1A-1C.
  • a conductive film formed by a process comprising: depositing a plurality of metal nanowires at a donor film; patterning the donor film with a selected pattern; applying a transfer resin to a substrate; laminating the donor film with the substrate to embed the metal nanowires in the transfer resin; curing the transfer resin; and detaching the donor film.
  • Aspect 23B A conductive film formed by a process consisting essentially of:
  • Aspect 24 The conductive film of any of aspects 23A-23C, wherein the conductive film exhibits a power efficiency greater than a substantially similar conductive film formed in the absence of a plurality of metal nanowires and formed according to a non-transfer process when tested according to current density-voltage-luminance assessment, and wherein the conductive film exhibits a current efficiency greater than a substantially similar conductive film formed in the absence of a plurality of metal nanowires and formed according to a non- transfer process when tested according to current density-voltage-luminance.
  • a conductive film formed by a process comprising: depositing a plurality of metal nanowires at a donor film; patterning the donor film with a selected pattern; applying a transfer resin to a substrate; laminating the donor film with the substrate to embed the metal nanowires in the transfer resin; curing the transfer resin; and detaching the donor film, wherein the conductive film exhibits a power efficiency greater than a substantially similar conductive film formed in the absence of a plurality of metal nanowires and formed according to a non-transfer process when tested according to current density-voltage- luminance assessment, and wherein the conductive film exhibits a current efficiency greater than a substantially similar conductive film formed in the absence of a plurality of metal nanowires and formed according to a non-transfer process when tested according to current density-voltage -luminance .
  • the conductive film exhibits a power efficiency greater than a substantially similar conductive film formed in the absence of a plurality of metal nanowires and formed according to a non-transfer process when tested according to current density-voltage -luminance assessment, and wherein the conductive film exhibits a current efficiency greater than a substantially similar conductive film formed in the absence of a plurality of metal nanowires and formed according to a non-transfer process when tested according to current density -voltage-luminance.
  • a solar cell comprising the conductive film of any one of aspects 23 A- 25C.
  • Aspect 27 An OLED comprising the conductive film of any one of aspects 23A- 25C .
  • a touch display comprising the conductive film of any one of aspects 23A-25C.
  • a flexible electronic device comprising the conductive film of any one of aspects 23A-25C.
  • a touch display comprising the conductive film of any one of aspects
  • reaction conditions e.g., component concentrations, desired solvents, solvent mixtures, temperatures, pressures and other reaction ranges and conditions that can be used to optimize the product purity and yield obtained from the described process. Only reasonable and routine experimentation will be required to optimize such process conditions.
  • J-V-L or J-V and L-V characteristics were performed on patterned conductive films according to the present disclosure (at thicknesses of #12, #16, and #18 Mayer rods) and on a conventional ITO glass based OLED for comparison.
  • the J-V and L-V characteristics were simultaneously analyzed by a Keithley 2400 and by photodiodes.
  • the electroluminescence (EL) spectrum was recorded with a colorimeter.
  • the transmittances were measured by spectrophotometer. All measurements were performed at room temperature in ambient air.
  • the J-V-L curves are shown in FIG. 6.
  • Optical imaging integrated in the AFM was used to select a cross-section area of interest for imaging in the AFM.
  • Surface roughness is quantitatively presented as RRMS which is the Root Mean Square of a surface's measured microscopic peaks and valleys. Peak to valley roughness (RPV) was also observed. Results are presented in FIG. 6.Values for RRMS and RPV increase significantly before embedding. After transfer of the silver nanowire, the values for both significantly decrease and approach the bare PI levels.
  • the patterned nanowire film exhibited good sheet resistance in that each sample had a uniformity of greater than 85%. Elevated values for sheet resistance may result in voltage drop in certain applications, which is related to device failure.
  • Method examples described herein can be machine or computer-implemented at least in part. Some examples can include a computer-readable medium or machine-readable medium encoded with instructions operable to configure an electronic device to perform methods as described in the above examples.
  • An implementation of such methods can include code, such as microcode, assembly language code, a higher-level language code, or the like. Such code can include computer readable instructions for performing various methods. The code may form portions of computer program products. Further, in an example, the code can be tangibly stored on one or more volatile, non-transitory, or nonvolatile tangible computer-readable media, such as during execution or at other times.
  • Examples of these tangible computer-readable media can include, but are not limited to, hard disks, removable magnetic disks, removable optical disks (e.g., compact disks and digital video disks), magnetic cassettes, memory cards or sticks, random access memories (RAMs), read only memories (ROMs), and the like.

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  • Manufacturing & Machinery (AREA)
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Abstract

L'invention concerne un processus de fabrication d'un film conducteur à motifs sur un substrat, le processus comprenant le dépôt d'une pluralité de nanofils métalliques sur un film donneur ; la formation de motifs sur le film donneur selon un motif de pixel sélectionné ; l'application d'une résine de transfert sur un substrat ; la stratification du film donneur avec le substrat pour incorporer les nanofils métalliques dans la résine de transfert ; le durcissement de la résine de transfert ; et le détachement du film donneur.
PCT/IB2017/057965 2016-12-14 2017-12-14 Fabrication d'électrodes transparentes à motifs pour applications d'éclairage de type delo WO2018109724A1 (fr)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2701468C1 (ru) * 2018-12-25 2019-09-26 федеральное государственное автономное образовательное учреждение высшего образования "Санкт-Петербургский национальный исследовательский университет информационных технологий, механики и оптики" (Университет ИТМО) Прозрачный проводящий оксид с наночастицами золота
RU2701467C1 (ru) * 2018-12-25 2019-09-26 федеральное государственное автономное образовательное учреждение высшего образования "Санкт-Петербургский национальный исследовательский университет информационных технологий, механики и оптики" (Университет ИТМО) Прозрачный проводящий оксид
CN110429202A (zh) * 2019-07-18 2019-11-08 武汉华星光电半导体显示技术有限公司 一种柔性oled显示面板、制作方法及智能穿戴设备
WO2021007962A1 (fr) * 2019-07-18 2021-01-21 武汉华星光电半导体显示技术有限公司 Panneau d'affichage à oled flexible, son procédé de fabrication et dispositif portatif intelligent
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CN111588372A (zh) * 2020-04-20 2020-08-28 北京邮电大学 一种制备柔性心电（ecg）电极的方法

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