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
• • 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
  • H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
  • H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
  • H10K30/152—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2 the wide bandgap semiconductor comprising zinc oxide, e.g. ZnO
• • 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
  • H10K30/20—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising organic-organic junctions, e.g. donor-acceptor junctions
• • 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
  • H10K30/30—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
• • 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
  • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
  • H10K85/1135—Polyethylene dioxythiophene [PEDOT]; Derivatives thereof
• • 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
• • 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
  • H10K30/30—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
  • H10K30/35—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains comprising inorganic nanostructures, e.g. CdSe nanoparticles
• • 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
• • 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
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
  • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

• the invention relates generally to the production of photovoltaic cells, and in particular of organic photovoltaic cells (usually designated by the acronym OPC for "Organic Photovoltaic Cells").
• organic photovoltaic cell is meant, within the meaning of the present invention, photovoltaic cells of which at least the active layer consists of organic molecules.
• Organic cells represent a real interest in the field of photovoltaics. Indeed, the possibility of replacing the organic semiconductors generally used in photovoltaic cells makes it possible to increase the number of feasible systems and therefore the possibilities of use. The development of organic photovoltaic cells, and even more the development of marketable organic photovoltaic cells currently represent a major challenge.
• the PEDOT: PSS layer is placed on the ITO (English acronym for “Indium Tin Oxide”: indium tin oxide) and under the active layer, for example based on P 3 HT: PCBM (as illustrated in Figure 1), while in reverse structure photovoltaic cells, the layer of PEDOT: PSS is printed on the active layer and under the upper electrode serving as anode.
• Photovoltaic cells with reverse structure have the advantage of having better air stability than cells with conventional structure, and in addition of having higher conversion yields.
• conversion efficiency of a photovoltaic cell is meant, within the meaning of the present invention, the ratio of the maximum electric power delivered by the cell to the incident light power, for a spectral distribution and a given intensity.
• the applicant has developed a method for manufacturing a photovoltaic cell, in which all the layers applied to the substrate coated with a transparent electrode are applied by jet printing. ink, which makes it possible to customize the layers thus applied. It is already known to use inkjet printing to produce certain layers of organic photovoltaic cells.
• the present invention relates to a photovoltaic cell comprising:
• a first interfacial layer of zinc oxide or zinc oxide doped with aluminum said first interfacial layer covering said cathode
• a second interfacial layer comprising a polymer mixture of poly (3, 4-ethylenedioxythiophene) and sodium poly (styrene-sulfonate), said second interfacial layer covering said active photovoltaic layer;
• said cell being characterized in that said second interfacial layer is continuous, has an organic fibrous structure and an average thickness of between 30 nm and 120 nm.
• the organic fibrous structure of the second interfacial layer may preferably be an amorphous crystal structure defined by the presence of micrometric organic fibers based on poly (3,4-ethylenedioxythiophene) and poly (styrene-sulfonate) ) of sodium which can be observed using an atomic force microscope for example.
• the second interfacial layer can have an electrical conductivity of between 100 D / D and 600 D / D.
• the second interfacial layer may have a roughness Ra equal to or less than 5 nm.
• the active photovoltaic layer may comprise a mixture of polymers with a small gap comprising [6, 6] -phenyl-C7i-methyl butanoate (for example marketed by Nano-C® under the trade name
• PC70BM associated with poly (thienol [3, 4-b] -thiophene (for example marketed under the trade names PTB7-Th by 1- Materials and PV2000 by Raynergy Tek®).
• the support of the photovoltaic cell according to the invention can advantageously be flexible.
• the present invention also relates to the use of the photovoltaic cell according to the invention on products such as light sports equipment, stroller, packaging (packaging, bottles, cork), in particular luxury goods, luggage, leather goods, interior decoration, electronics.
• products such as light sports equipment, stroller, packaging (packaging, bottles, cork), in particular luxury goods, luggage, leather goods, interior decoration, electronics.
• IoT Internet of Connected Objects or in English "Internet of Things” (designated by the acronym IoT), BLE tag (acronym for "Bluetooth Low Energy”: Bluetooth low energy), Logistics sensor), advertising panel on point of sale, personal protective equipment, glove, toy and educational leisure, furniture, parasol, textile, cycle, automobile.
• the present invention also relates to a method for manufacturing a photovoltaic cell according to the invention, comprising the following steps:
• steps c) to f) are each carried out by depositing ink compositions by digital ink jet printing, followed by heat treatment, said ink composition used in step e) comprising a polymer mixture of poly (3,4-ethylenedioxythiophene) and sodium poly (styrene sulfonate) and said ink composition used in step f) comprising silver nanoparticles.
• steps d) and e) it is possible, between steps d) and e), to clean the photovoltaic active layer using a solvent chosen from ethanol, butanol, methanol and ethylene glycol.
• This cleaning can in particular be carried out by soaking in an alcohol such as isopropanol or ethylene glycol, then drying under argon or nitrogen or heating on a hot plate. The purpose of this cleaning is to eliminate dust and contamination of the active layer.
• steps c) to f) can be carried out as follows:
• a second ink composition of [6, 6] -phenyl-C 7i methyl butanoate (for example, sold by Nano-C® as trade name PC70BM) associated
• e) deposit by digital inkjet printing on the active photovoltaic layer of a third ink composition
• a third ink composition comprising a polymer mixture of poly (3, 4-ethylenedioxythiophene) and sodium poly (styrene-sulfonate) (this mixture typically in the form of a colloidal solution is usually designated by the acronym PEDOT: PSS), then heat treatment, to form a second interfacial layer;
• the heat treatments of steps c) to e) may be annealing treatments carried out at a temperature between 70 ° C and 130 ° C, for a period of between 1 and 5 minutes
• the heat treatment of the step f) can be an annealing treatment carried out at a temperature between 120 ° C and 145 ° C, for a period between 2 and 5 minutes.
• the heat treatment in step c) can be carried out on a hot plate at a temperature of 85 ° C for 3 minutes, while the heat treatment in step d) can be carried out on a hot plate at a temperature of 85 ° C for 2 minutes, that of step e) can be carried out on a hot plate at a temperature of 120 ° C for 1 to 5 minutes; and the heat treatment of step f) is an annealing treatment carried out at a temperature of 135 ° C for 3 minutes.
• step b) of the indium-tin oxide layer can be carried out by vacuum deposition.
• steps a) and b) are replaced by a step a ') of providing a glass support coated with a layer of indium tin oxide.
• the third ink composition can have a viscosity equal to or less than 10 mPa.s at 20 ° C. and comprise:
• FIG. 1 shows a schematic sectional view of a photovoltaic cell of conventional structure.
• FIG. 2 shows a schematic sectional view of a photovoltaic cell according to the invention.
• the PV2000 polymer of the E21 mixture or the PTB7-Th polymer of the E22 mixture are present in these second ink compositions at a rate of 10 mg / ml.
• the mass ratio between the PV2000 polymer of the E21 blend or the PTB7-Th polymer of the E22 blend and the PC70BM is 1: 1.5
• the volume ratio between the O-xylene solvent and the Tetralin additive is 97: 3 in these second compositions .
• a second ink composition is produced by adding the solvent and the additive to the polymer mixture E21 or E22 and maintaining this mixture for 24 hours with stirring on a hot plate at 80 ° C. at a speed of 700 RPM.
• PEDOT PSS marketed by Agfa® under the trade name IJ1005 or PEDOT: PSS marketed by Agfa® under the trade name ORGACON S315;
• o glycerol (1, 2, 3-Propanetriol or glycerin, of formula HOCH2CH (OH) CH20H) marketed by Merck®; o Deionized water, produced in the laboratory or sold by the company PURELAB® classic under the brand ELGA® for water.
• the thickness of the printed layers is measured using a DektakXT branded tip profilometer marketed by BRUKER from a scratch made with a cutter blade (a channel having the thickness of the deposit is thus created) .
• It is a contact profilometer which measures variations in relief thanks to the vertical displacement of a stylus with a point which scans the surface by applying a constant contact force and reveals all the differences in level.
• the sample is placed on a tray which allows it to move with a given speed and over a chosen distance.
• the thickness values presented in the present patent application correspond to the average of five measurements carried out at six different points on the same step of a sample. Before making the measurements, the length of the scanned area, its duration, the stylus support force and the measurement range must be defined.
• This measurement is carried out using the 4-point technique, as follows: - the 4 points aligned are placed far from the edges of the layer to be characterized.
• the viscosity of a fluid is manifested by its resistance to deformation or to the relative sliding of its layers.
• the speed of the molecules (v) is maximum in the axis of the tube and decreases until it vanishes at the wall while between the layers develops a relative slip; hence the appearance of tangential friction forces. Tangential forces in fluids depend on the nature of the fluid considered and the flow regime.
• the viscometer used is of the Ubbelhode type, it is placed in a thermostat maintained at constant temperature (25 ° C in our case study).
• the flow time of a constant volume V defined by two reference lines (Ml and M2) located on either side of a small reservoir surmounting the capillary is measured.
• AFM International acronym for “Atomic Force Microscope” measurements to reproduce surface topography
• TEM International acronym for “Transmission Electron Microscopy”: to validate the crystalline character of the materials as well as the sizes of nanoparticles present at the level of the layers.
• the conversion efficiency is the ratio of the power generated and the power of the incident solar radiation which is normalized to 100 mW / cm 2 for an AMI spectrum .5.
• EXAMPLE 1 Obtaining a First Example of a First Eli Ink Composition for First Interfacial Layer
• this large flask is fixed in an oil (or water) bath with stirring and under argon at 60 ° C. on a hot plate and with stirring.
• the KOH is dissolved in an ultrasonic bath to then add it drop by drop into this flask. We will see a color change from transparent to opaque. After a few minutes, the solution becomes transparent again. The mixture is then further stirred for 3 hours, at the end of which a white suspension of ZnO has formed.
• the zinc oxide ZnO obtained at the end of the Polyol technique at the end of Example 1.1 is cooled in a cold bath and the ZnO particles are separated by centrifugation (12 min and 7800 rpm) then dispersed in the butanol using ethylene glycol as a surfactant.
• An Eli ink of ZnO particles is obtained having a nanoparticle concentration of 4 mg / ml.
• the Eli ink is previously filtered with a 0.45 micrometer filter in cellulose acetate (AC).
• EXAMPLE 2 obtaining a second example of a first composition of ink E12 for the first interfacial layer
• the ink of aluminum doped Zinc oxide nanoparticles (AZO) sold by the company GENES 'INK® is used in the following manner: before printing by ink jet, the ink is first put in an ultrasonic bath for 2 minutes at room temperature, then filtered with a 0.45 micron filter of cellulose acetate. E12 ink is obtained.
• AZO aluminum doped Zinc oxide nanoparticles
• EXAMPLE 3 Obtaining a Third Example of First Composition of Ink E13 for First Interfacial Layer
• Zinc acetate, aluminum isopropylate and distilled water are introduced into a flask containing anhydrous ethanol.
• AZO NCs nanoparticles (English acronym for: “Aluminum Doped Zinc Oxide nano-crystals”) at Al doping levels ranging from 0% (undoped reference) to 0.8 at% were produced in varying the initial ratio of the aluminum isopropylate precursor to zinc acetate, and keeping all the other parameters constant.
• the AZO obtained at the end of the Polyol technique at the end of Example 3.1 is cooled in a cold bath and the AZO particles are separated by centrifugation (12 min and 7800 rpm) then dispersed in butanol using ethylene glycol as a surfactant.
• An E12 ink of AZO particles is obtained having a nanoparticle concentration of 2 mg / ml. Before printing by ink jet, the E12 ink is previously filtered with a 0.45 micron filter of cellulose acetate.
• EXAMPLE 4 obtaining second E21 and E22 ink for active photovoltaic layer
• the ink compositions E21 and E22 are obtained respectively, the compositions of which are detailed in Table 1 below:
• the ink composition E21 is obtained as follows:
• the mixture is stirred magnetically on a hot plate at 80 ° C for 24 hours.
• the ink Before printing, the ink is filtered beforehand with a 0.45 micron AC filter.
• the printed layers are then heat annealed on a hot plate at 85 ° C for 2 minutes.
• the ink composition E22 is obtained as follows: 10 mg PV2000 mixed with 15 mg of PC70BM (corresponding to a mass ratio 1: 1.5) in 1 milliliter of o-xylene and 60 microliters of tetralin.
• the mixture is stirred magnetically on a hot plate at 80 ° C for 24 hours.
• the E22 ink is filtered with a 0.45 micron AC filter.
• active photovoltaic layers are obtained which, once printed, are subjected to thermal annealing on a hot plate at 85 ° C for 2 minutes.
• EXAMPLE 5 obtaining third compositions of E31 ink and
• the PEDOT: PSS initially filtered is mixed with the mixture thus obtained after stirring, in the following proportions: 30 m ⁇ of mixture of the 3 additives in deionized water for 1 ml of PEDOT: PSS; the resulting mixture is put (with PEDOT: PSS) under magnetic stirring on a hot plate at room temperature for at least 1 hour; and
• OPV cells are produced in accordance with the invention according to the following method: Case of rigid substrates: • Cleaning of the rigid glass substrate with structured ITO layer by successive soaking in 4 different cleaning baths:
• o Bath 2 Acetone at 20-40 ° C for 10-15 minutes
• o Bath 3 Ethanol at 20-40 ° C for 10-15 minutes
• o Bath 4 Isopropanol at 20-40 ° C for 10-15 minutes ;
• the ITO / PET substrate is protected by two plastic films on both sides:
• this substrate is glued with double-sided tape on a glass slide having the same dimension; o The plastic film covering the ITO side of the substrate is then removed;
• OPV cells in accordance with the prior art / controls are produced according to the following method:
• ITO substrates purchased from Lumtec®, 15 Ohm sq-1
• IPA isopropanol
• PTB7-Th or PV2000
• PC70BM are mixed with a mass ratio of 1: 1.5 in o-xylene as solvent and tetralin as additive with a concentration of 10 mg / ml of polymer (the ratio between solvent and additive is 97: 3 v / v).
• a layer having a nominal thickness of 90-100 nm was deposited by centrifugation (or "spin coating") at 2,700 rpm for 2 min;
• a thin layer of poly (3,4-PEDOT: PSS) (S315) was deposited by centrifugation (or “spin coating") on the organic layer at the speed of 3000 rpm for 60 s, then heated on a hot plate at 120 ° C for 5 minutes;
• the OPV cells according to the invention C2 to C16 show that the problem of printing the ETL layer (acronym for “electron transport layer”) of PEDOT-PSS material, of a photovoltaic cell is solved: is able to produce a cell, or an organic module composed of 4 layers printed on a first transparent conductive electrode present on the flexible plastic or rigid glass substrate, or composed of 5 layers printed on a flexible plastic or rigid glass substrate of all materials.
• the invention consists in formulating a solution of PEDOT-PSS compatible with the inkjet printing process.
• This formulation allows us to advantageously implement a PEDOT-PSS of high conductivity conventionally used as a layer.
• HTL (English acronym for "hole transport layer"), to obtain an ETL.
• the inkjet printing process combined with this formulation allows us to control the thickness of the printed layer, to optimize the electrical and optical characteristics of the material, but also of the structure of the second interfacial layer with the production of a organic fibrous amorphous crystal structure, in particular having organic fibers essentially oriented substantially vertically to favor the transport of the loads.
• the conversion yields of the modules produced using the present invention remain unique to date. It is thus possible to produce a series of 10 modules of 6 interconnected cells, each module composed of 4 layers printed on a first layer of structured ITO, representing 3.5 cm 2 of active layer in total, with an average conversion yield. 5.7% and a maximum of 6.2% under 1 SUN AM 1.5.

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• Physics & Mathematics (AREA)
• Electromagnetism (AREA)
• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Inorganic Chemistry (AREA)
• Manufacturing & Machinery (AREA)
• Materials Engineering (AREA)
• Inks, Pencil-Leads, Or Crayons (AREA)
• Photovoltaic Devices (AREA)

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• 2018
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