Classifications

• • 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
  • H10K71/10—Deposition of organic active material
  • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
  • H10K71/13—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen printing
  • H10K71/135—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen printing using ink-jet printing
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05C—APPARATUS FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05C5/00—Apparatus in which liquid or other fluent material is projected, poured or allowed to flow on to the surface of the work
  • B05C5/02—Apparatus in which liquid or other fluent material is projected, poured or allowed to flow on to the surface of the work the liquid or other fluent material being discharged through an outlet orifice by pressure, e.g. from an outlet device in contact or almost in contact, with the work
  • B05C5/0254—Coating heads with slot-shaped outlet
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/02—Printing inks
  • C09D11/10—Printing inks based on artificial resins
  • C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/52—Electrically conductive inks
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K39/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic radiation-sensitive element covered by group H10K30/00
  • H10K39/30—Devices controlled by radiation
  • H10K39/32—Organic image sensors
• • 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
  • H10K71/10—Deposition of organic active material
  • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
  • H10K71/15—Deposition of organic active material using liquid deposition, e.g. spin coating characterised by the solvent used
• • 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
  • H10K71/40—Thermal treatment, e.g. annealing in the presence of a solvent vapour
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K39/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic radiation-sensitive element covered by group H10K30/00
  • H10K39/30—Devices controlled by radiation
• • 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
  • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
  • H10K50/17—Carrier injection layers
• • 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
  • H10K71/10—Deposition of organic active material
  • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
  • H10K85/10—Organic polymers or oligomers
  • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
  • H10K85/10—Organic polymers or oligomers
  • H10K85/141—Organic polymers or oligomers comprising aliphatic or olefinic chains, e.g. poly N-vinylcarbazol, PVC or PTFE

Definitions

• the present description relates generally to inks for optoelectronic components and more particularly to the deposition methods of these inks.
• Inks based on polyethylenesimine (PEI) and ethoxylated polyethylenesimine (PEIE) are used in particular in image sensors and more particularly on the surface of the electrodes of such sensors in order to modify the output work of said electrodes .
• One embodiment provides a method for producing a layer, from an ink, on a substrate, comprising the following steps: depositing a volume of ink with a die coating device; first drying; and second drying.
• the substrate is an electrode.
• the first drying is carried out in a vacuum chamber.
• the method comprises, before the deposition step, a step of surface treatment of the substrate by atmospheric plasma, by vacuum plasma, by etching by reactive ions or by corona.
• the ink comprises a solvent and a polymer.
• the solvent is chosen from butanol, ethylene glycol, propylene glycol methyl ether acetate and dimethylsulfoxide.
• the polymer is chosen from a polyethylene imine, an ethoxylated polyethylene imine, a perfluoroanthracene and one or more conjugated thiols.
• the polymer has a volume concentration in the ink of between 0.001% and 0.1%, preferably of between 0.01% and 0.04%.
• the polymer has a molar mass of between 1 kg / mol and 1000 kg / mol, preferably between 20 kg / mol and 200 kg / mol.
• the layer has a thickness, called wet, at the end of the deposition step of between 7 ⁇ m and 45 ⁇ m.
• the layer has a thickness, called dry, at the end of the second drying of between 1 nm and 3 nm, preferably equal to approximately 1.5 nm
• FIG. 1 represents, in a partial and schematic sectional view, an exemplary embodiment of a user interface device with transparent electrodes
• FIG. 2 represents, in a partial and diagrammatic sectional view, a step of an embodiment of a method for producing a layer
• FIG. 3 represents, in a partial and schematic sectional view, another step of an embodiment of a method for producing a layer
• FIG. 4 represents, in a partial and schematic sectional view, yet another step of an embodiment of a method for producing a layer
• FIG. 5 represents, in a partial and schematic sectional view, yet another step of an embodiment of a method for producing a layer
• FIG. 6 represents, in a partial and schematic sectional view, yet another step of an embodiment of a method for producing a layer.
• a layer or a film is said to be opaque to radiation when the transmittance of the radiation through the layer or the film is less than 10%.
• a layer or a film is said to be transparent to radiation when the transmittance of the radiation through the layer or the film is greater than 10%, preferably greater than 50%.
• all the elements of the optical system which are opaque to radiation have a transmittance which is less than half, preferably less than the fifth, more preferably less. to tenth, the lowest transmittance of the elements of the optical system transparent to said radiation.
• the electromagnetic radiation passing through the optical system in operation is called “useful radiation”.
• Figure 1 shows a partial and schematic sectional view of an embodiment of a user interface device 1 with transparent electrodes.
• the device 1 comprises a matrix of photon sensors, called photo-detectors 21 (a photo-detector 21 is symbolized by dotted lines in FIG. 1), preferably suitable for detecting variations of the shadow or of the image of an actuating member, for example a finger 23.
• the photo-detectors 21 are formed on a substrate 25 of a transparent or translucent dielectric material, for example glass or plastic.
• the substrate 25 is an array of read circuits comprising, for example, thin film transistors (TFT, Thin-Film Transistors).
• TFT thin film transistors
• Thin-Film Transistors Thin-Film Transistors
• Each photo-detector 21 comprises a stack, comprising, from bottom to top:
• TCO material Transparent Conductive Oxide
• TCO Transparent Conductive Oxide
• indium oxide doped with tin zinc oxide doped with gallium
• tin oxide doped tin oxide fluorine (FTO, Fluorine-doped Tin Oxide)
• FTO Fluorine-doped Tin Oxide
• zinc oxide zinc oxide doped with aluminum
• a metal for example, gold, silver, lead, palladium, copper, nickel, tungsten or chromium
• an electron injecting layer 134 EIL Electron injecting Layer
• the active layer 27 may comprise an ambipolar semiconductor material, or a mixture of an N-type semiconductor material and a P-type semiconductor material, for example in the form of superimposed layers or an intimate mixture at the nanometric scale so as to form a heteroj unction by volume.
• the thickness of the active layer 27 may be between 50 nm and 2 ⁇ m, for example of the order of 200 nm;
• HIL Hole Injection Layer
• an electrode 31 constituting a cathode common to all the photodetectors made from a polymer of the PEDOT: PSS type or from a TCO, such as for example ITO (indium-tin oxide).
• P-type semiconductor polymers suitable for producing the active layer 27 are poly (3-hexylthiophene) (P3HT), poly [N-9 ′ -heptadecanyl-
• PCDTBT poly [(4, 8-bis- ( 2-ethylhexyloxy) -benzo [1, 2-b; 4, 5-b '] dithiophene) -2, 6-diyl- ait- (4- (2-ethylhexanoyl) -thieno [3, 4-b] thiophene)) -2, 6-diyl]
• PBDTTT-C poly [2-methoxy-5- (2-ethyl-hexyloxy ) -1, 4-phenylene-vinylene] (MEH-PPV) or poly [2, 6- (4, 4-bis- (2-ethylhexyl) -4ff-cyclopenta [2, lb; 3,4-b ' ] dithiophene) -alt-
• N-type semiconductor materials suitable for making the active layer 27 are fullerenes, in particular C 6CL, [6, 6] -phenyl-C61-butanoate ([60] PCBM) and Methyl [6, 6] -phenyl-C7i-butanoate ([70] PCBM).
• the photoactive layer 27 of the photo-detectors 21 is here intended to be illuminated through an encapsulation layer 33 and through the electrode 31 and the layer 29.
• the light radiation is schematically represented by arrows 35.
• the layers 29 can be structured during, for example, a step of photolithography not shown.
• the matrix of photo-detectors 21 can be a passive matrix or an active matrix.
• the transparent electrodes 31 can correspond to rectilinear and parallel bands, each band being able to be connected to all the photo-detectors 21 of the same row.
• the transparent electrodes 31 may correspond to a continuous layer in contact with all the photo-detectors 21 of the matrix.
• the transparent electrodes 31 can be isolated from one another, the photo-detectors 21 being in this case independent from one another.
• Figures 2 to 6 illustrate steps of an embodiment of a method of producing the layer 134 on the surface of the electrode 11. More generally, Figures 2 to 6 illustrate steps of '' a mode of implementation of a method of producing the layer 134 on the surface of a substrate 11 'which may be, for example, different from an electrode.
• FIG. 2 represents, in a partial and diagrammatic sectional view, a step of an embodiment of a method for producing the layer 134.
• FIG. 2 illustrates a starting structure of the process.
• the starting structure comprises the substrate 11 '(for example the electrode 11 of FIG. 1).
• the substrate 11 ' is made of a metal oxide, chosen from: zinc oxides ZnO x , indium-tin oxide ITO, zinc-tin oxide ZTO, the zinc-aluminum oxide AZO, titanium oxides TiO x , molybdenum oxides MoO x , nickel oxides NiO x , chromium oxides CrO x , copper oxides CuO x , cobalt oxides CoO x , iron oxides FeO x , manganese oxides MnO x , or a mixture of at least two of these oxides.
• a metal oxide chosen from: zinc oxides ZnO x , indium-tin oxide ITO, zinc-tin oxide ZTO, the zinc-aluminum oxide AZO, titanium oxides TiO x , molybdenum oxides MoO x , nickel oxides NiO x , chromium oxides CrO x , copper oxides CuO x , cobal
• the substrate 11 ' is made of metal or of a metal alloy, chosen from the list: gold, copper, silver, molybdenum-tantalum, molybdenum-copper.
• the substrate 11 ' is made of a ceramic material, that is to say, for example, of a carbide, such as titanium carbide (TiC), a boride, a nitride such as titanium nitride (TiN), aluminum nitride (AIN), etc.
• a carbide such as titanium carbide (TiC)
• a boride such as titanium nitride (TiN)
• AIN aluminum nitride
• the substrate 11 ′ is first treated by plasma at atmospheric pressure.
• the plasma treatment is, for example, used in order to make the surface of the substrate 11 ′ hydrophilic.
• the plasma treatment is, moreover, used to functionalize (revealing hydroxyl and carbonyl functions) the surface of the substrate 11 ′ and to increase the surface energy of the substrate 11 ′.
• the surface of the substrate 11 ' is treated by vacuum plasma, by etching by reactive ions (RIE, Reactive Ion Etching) or by corona.
• RIE reactive ions
• FIG. 3 represents, in a partial and diagrammatic sectional view, another step of an embodiment of a method for producing the layer 134.
• FIG. 3 illustrates a step of depositing a volume of a solution or ink 13 on the surface of the substrate 11 'to form a layer 131.
• Solution 13 is preferably formulated and composed of a polymer and a solvent.
• the solvent used in the composition of solution 13 is preferably a solvent capable of uniformly dissolving or dispersing the polymer.
• the solvent is, for example, a solvent having a boiling point greater than about 110 ° C.
• the solvent is preferably butanol, ethylene glycol, propylene glycol methyl ether acetate (PGMEA), dimethyl sulfoxide (DMSO) or a combination of these solvents.
• the polymer is, for example, chosen from a polyethylene imine (PEI), an ethoxylated polyethylene imine (PEIE), a conjugated thiol or a perfluoroanthracene.
• PEI polyethylene imine
• PEIE ethoxylated polyethylene imine
• conjugated thiol a conjugated thiol or a perfluoroanthracene.
• the polymer is preferably a polyethylene imine.
• the polymer has a molar mass of, for example, between 1 kg / mol and 1000 kg / mol, preferably between 20 kg / mol and 200 kg / mol.
• the molar masses of the polymers are measured, for example, by gel penetration chromatography (GPC, Gel Permeation Chromatography) coupled in particular to a light scattering detector.
• GPC Gel penetration chromatography
• This technique consists of separating the molecules, here polymers, according to their sizes by pumping them into different columns. Light scattered at a very low angle allows the weight average molecular mass to be known.
• the molar masses used in the present description are average molar masses by weight.
• the polymer at a volume concentration in solution 13 of between 0.001% and 0.1%, preferably between 0.01% and 0.04%.
• the deposition of the solution 13 is carried out with a die coating device (slot-die).
• the die coating device consists in providing a uniform solution on a given surface. It is composed in particular of a head 15 provided with a slot 151.
• the solution or coating material is deposited on said surface after having passed through the slot in the head.
• the substrate is generally set in motion, preferably rectilinear, so that the solution is deposited over the whole of a selected area.
• the die coating device is generally provided with four subsystems:
• a sub-system for positioning the head with respect to said surface a distribution subsystem which ensures a uniform distribution of the solution over the entire width of said surface
• the thickness of the deposited layer is thus a function of:
• the deposition of the layer 131 is made full plate. That is to say, the layer 131 covers the entire upper face of the substrate 11 '.
• the polymer is adsorbed, by physisorption or chemisorption depending on the polymers, on the surface of the substrate 11 ', forming a mono-molecular sublayer.
• the solvent is deposited in one or more successive sublayers.
• PEIE and PEI generate a physisorption mechanism at the surface of the substrate 11 ′, while perfluoroanthracene and the conjugated thiols generate a chemisorption mechanism.
• the speed of movement of the head 15 relative to the substrate 11 ' is approximately equal to 70 mm / sec.
• the flow rate of the solution 13 at the outlet of the slot 151 is approximately equal to 300 pL / sec.
• a thickness A which is substantially constant over the entire surface of the substrate 11 ′.
• the thickness A is, for example, equal to a value between 7 ⁇ m and 45 ⁇ m.
• FIG. 4 represents, in a partial and schematic sectional view, yet another step of an embodiment of a method for producing the layer 134.
• FIG. 4 illustrates a first drying step allowing partial evaporation of the solvent, illustrated in FIG. 4 by vapors 17, present in the layer 131 of the structure obtained at the end of the steps of FIGS. 2 and 3.
• the step illustrated in FIG. 4 further allows the fixing of the polymer to the surface of the substrate 11 '.
• the structure illustrated in FIG. 4 comprises the substrate 11 'and a layer 132, derived from the layer 131 of FIG. 3.
• the layer 132 is a layer whose composition changes during the step illustrated in FIG. 4.
• the layer 132 corresponds to the layer 131.
• the evaporation of the solvent present in the layer 132 generates a decrease in the percentage of the solvent in the composition of the layer 132.
• the percentage of the solvent in the composition of the layer 132 decreases by several tens of percent.
• the percentage of the solvent in the composition of the layer 132 is, for example, less than 10%, preferably less than 5%.
• the percentage of the solvent in the composition of the layer 132 at the end of the first drying is, more preferably, less than 1%.
• the thickness of the layer 132 is much less than that of the layer 131 illustrated in FIG. 3.
• the layer 132 thus has a thickness of, for example, between a few nanometers and a few tens of nanometers.
• the first drying is carried out in a vacuum chamber (VCD, Vaccum Chamber Dryer). Drying has, for example, a duration of about 2 minutes.
• VCD vacuum chamber
• Vaccum Chamber Dryer Vaccum Chamber Dryer
• the chamber may or may not be heated.
• the steps of Figures 3 and 4 are preferably consecutive.
• the time between these two steps is, for example, between 10 seconds and 20 seconds.
• FIG. 5 represents, in a partial and schematic sectional view, yet another step of an embodiment of a method for producing the layer 134.
• FIG. 5 illustrates a second drying step making it possible to continue the evaporation of the solvent present in the layer 132 of the structure obtained at the end of the steps of FIGS. 2 to 4.
• the second drying is, for example, carried out in an oven 19 at a temperature, for example, between 50 ° C and 200 ° C, preferably between 50 ° C and 150 ° C.
• the temperature of the second drying is, more preferably, equal to approximately 100 ° C.
• the second drying has a duration, for example, between 1 minute and 120 minutes, preferably, between 5 minutes and 20 minutes.
• the duration of the second drying is, more preferably, equal to approximately 10 minutes.
• the structure illustrated in FIG. 5 comprises the substrate 11 ′ and a layer 133 resulting from the layer 132 of FIG. 4.
• the layer 133 is a layer whose composition changes during the step illustrated in FIG. 5.
• the layer 133 corresponds to the layer 132.
• the continued evaporation of the solvent present in the layer 133 generates a decrease in the percentage of the solvent in the composition of the layer 133.
• the percentage of the solvent in the composition of the layer 133 decreases by a few percent.
• the percentage of the solvent in the composition of the layer 133 is, for example, less than 1%, preferably less than 0.1%.
• the percentage of the solvent in the composition of the layer 133 at the end of the second drying is, more preferably, less than 0.01%.
• FIG. 6 represents, in a partial and schematic sectional view, yet another step of an embodiment of a method for producing the layer 134.
• FIG. 6 illustrates the final structure obtained at the end of the steps of FIGS. 2 to 5.
• the structure illustrated in Figure 6 comprises the substrate 11 'and the layer 134 resulting from the layer 133 of Figure 5.
• the layer 134 corresponds to the layer 133 at the end of the step illustrated in Figure 5.
• Layer 134 composed of the polymer and traces of solvent, has a thickness B, called dry, approximately uniform, preferably uniform, over the entire substrate
• the thickness B of the layer 134 is, for example equal to a value between 0.5 nm and 10 nm.
• the thickness B of the layer 134 is preferably between 1 nm and 3 nm.
• the variation in thickness of the layer 134 over the whole of the substrate 11 ′ is less than 0.3 nm, preferably less than 0.1 nm.
• An advantage of the embodiments and implementation described is the control of the thickness of the polymer deposits (of PEI or PEIE in the preferred embodiments) on a substrate 11 'such as, for example, an electrode a sensor.
• Another advantage of the embodiments and implementation described is that they allow the production of a very thin layer, which makes it possible to increase the performance of the sensors.
• Yet another advantage of the embodiments and implementation described is that they make it possible to ensure uniformity (of the order of a tenth of a nanometer) of the thickness of the layer over the entire surface. surface of the substrate.

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• Wood Science & Technology (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Laminated Bodies (AREA)
• Electroluminescent Light Sources (AREA)
• Light Receiving Elements (AREA)

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• 2020
  • 2020-07-08 CN CN202080052317.3A patent/CN114127977A/zh active Pending
  • 2020-07-08 WO PCT/EP2020/069179 patent/WO2021013537A1/fr unknown
  • 2020-07-08 KR KR1020227002866A patent/KR20220034803A/ko not_active Application Discontinuation
  • 2020-07-08 US US17/628,031 patent/US20220246849A1/en active Pending
  • 2020-07-08 EP EP20737016.4A patent/EP3999597A1/fr not_active Withdrawn
  • 2020-07-08 JP JP2022503879A patent/JP2022541306A/ja active Pending

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