EP4710095A1 - Photoelectrochemical electrochemiluminescence method, systems and device - Google Patents

Photoelectrochemical electrochemiluminescence method, systems and device

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Publication number
EP4710095A1
EP4710095A1 EP24723574.0A EP24723574A EP4710095A1 EP 4710095 A1 EP4710095 A1 EP 4710095A1 EP 24723574 A EP24723574 A EP 24723574A EP 4710095 A1 EP4710095 A1 EP 4710095A1
Authority
EP
European Patent Office
Prior art keywords
electrode
junction
series
junctions
pole
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP24723574.0A
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German (de)
French (fr)
Inventor
Gabriel Loget
Neso Sojic
Yiran ZHAO
Julie DESCAMPS
Yoan Leger
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Centre National de la Recherche Scientifique CNRS
Universite de Rennes 1
Institut National des Sciences Appliquees de Rennes
Ecole Nationale Superieure de Chimie de Rennes
Universite de Bordeaux
Institut Polytechnique de Bordeaux
Original Assignee
Centre National de la Recherche Scientifique CNRS
Universite de Rennes 1
Institut National des Sciences Appliquees de Rennes
Ecole Nationale Superieure de Chimie de Rennes
Universite de Bordeaux
Institut Polytechnique de Bordeaux
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Application filed by Centre National de la Recherche Scientifique CNRS, Universite de Rennes 1, Institut National des Sciences Appliquees de Rennes, Ecole Nationale Superieure de Chimie de Rennes, Universite de Bordeaux, Institut Polytechnique de Bordeaux filed Critical Centre National de la Recherche Scientifique CNRS
Publication of EP4710095A1 publication Critical patent/EP4710095A1/en
Pending legal-status Critical Current

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Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/76—Chemiluminescence; Bioluminescence
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/66—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light electrically excited, e.g. electroluminescence
    • G01N21/69—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light electrically excited, e.g. electroluminescence specially adapted for fluids, e.g. molten metal
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F55/00—Radiation-sensitive semiconductor devices covered by groups H10F10/00, H10F19/00 or H10F30/00 being structurally associated with electric light sources and electrically or optically coupled thereto
    • H10F55/10—Radiation-sensitive semiconductor devices covered by groups H10F10/00, H10F19/00 or H10F30/00 being structurally associated with electric light sources and electrically or optically coupled thereto wherein the radiation-sensitive semiconductor devices control the electric light source, e.g. image converters, image amplifiers or image storage devices
    • H10F55/17—Radiation-sensitive semiconductor devices covered by groups H10F10/00, H10F19/00 or H10F30/00 being structurally associated with electric light sources and electrically or optically coupled thereto wherein the radiation-sensitive semiconductor devices control the electric light source, e.g. image converters, image amplifiers or image storage devices wherein the radiation-sensitive semiconductor devices have potential barriers
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/48—Biological material, e.g. blood, urine; Haemocytometers
    • G01N33/50—Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing
    • G01N33/58—Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing involving labelled substances
    • G01N33/582—Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing involving labelled substances with fluorescent label
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/48—Biological material, e.g. blood, urine; Haemocytometers
    • G01N33/50—Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing
    • G01N33/58—Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing involving labelled substances
    • G01N33/585—Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing involving labelled substances with a particulate label, e.g. coloured latex
    • G01N33/587—Nanoparticles

Definitions

  • the present invention relates to photoelectrochemical devices, devices that absorb light and create electron-hole pairs, then emit light using an electrochemiluminescent reaction involving the electron-hole pairs.
  • Electrochemiluminescence is a powerful and sensitive analytical technique that is widely employed for immunoassays, clinical diagnosis and imaging. It consists of the generation of light triggered by an electrochemical reaction at an electrode surface. This process requires an electrolyte containing a dissolved luminophore that is electrochemically promoted to an excited state and relaxes through the emission of a photon.
  • ECL devices require an electric power source to induce ECL-light emission. Therefore, analytical devices relying on ECL always use potentiostats or similar electronic devices.
  • US patent application US2019/296162 discloses a photovoltaic device, produced under lighting to obtain specific electrodes, but fails to address light emission and in particular electrochemiluminescence.
  • the object of the invention is to design an electrochemiluminescent device comprising a photovoltaic element, which can convert external light into electric power, as well as photoelectrochemical electrochemiluminescent systems and methods.
  • This disclosure thus relates to a photoelectrochemical electrochemiluminescent (PECL) device comprising:
  • a photovoltaic element in which light absorption generates an electron/hole pair said photovoltaic element having a first pole and a second pole; said generated holes moving towards the first pole; and said generated electrons moving towards the second pole;
  • a second electrode connected to the second pole of the photovoltaic element; said PECL device emitting light at an electrode when said electrode is immersed in an electrolyte comprising:
  • This disclosure also relates to a bio-chemical determination method using a photoelectrochemical electrochemiluminescent (PECL) device as disclosed hereabove.
  • PECL photoelectrochemical electrochemiluminescent
  • this disclosure relates to a photoelectrochemical electrochemiluminescent, PECL-ox, system comprising:
  • a photovoltaic element in which light absorption generates an electron/hole pair said photovoltaic element having a first pole and a second pole; said generated holes moving towards the first pole; and said generated electrons moving towards the second pole;
  • a first electrode connected to the first pole of the photovoltaic element
  • a second electrode connected to the second pole of the photovoltaic element; an electrolyte in which said first electrode and said second electrode are immersed, said electrolyte comprising a luminophore undergoing oxidation at the first electrode and simultaneously emitting light at the first electrode; and an oxidant undergoing reduction at the second electrode; wherein PECL-ox system is passive.
  • this disclosure relates to a photoelectrochemical electrochemiluminescent, PECL-red, system comprising:
  • a photovoltaic element in which light absorption generates an electron/hole pair said photovoltaic element having a first pole and a second pole; said generated holes moving towards the first pole; and said generated electrons moving towards the second pole;
  • a first electrode connected to the first pole of the photovoltaic element
  • this disclosure also relates to photoelectrochemical electrochemiluminescence, PECL, method comprising the following steps: immersing in an electrolyte a first electrode and a second electrode of a device comprising: i.
  • a photovoltaic element in which light absorption generates an electron/hole pair; said photovoltaic element having a first pole and a second pole; said generated holes moving towards the first pole; and said generated electrons moving towards the second pole; ii. the first electrode connected to the first pole of the photovoltaic element; iii. the second electrode connected to the second pole of the photovoltaic element; illuminating the device with external light, preferably infrared light; emitting light by i. oxidation of a luminophore at the first electrode thereby emitting light; and reduction of an oxidant at the second electrode; or ii. reduction of a luminophore at the second electrode thereby emitting light; and oxidation of a reducing agent at the second electrode; and wherein the photoelectrochemical electrochemiluminescence method does not comprise an electric source.
  • PECL devices may be combined with one or more of the following features, taken in isolation from one another or in any technically acceptable combination with one another:
  • an electric circuit comprising the photovoltaic element, the first electrode and the second electrode is closed only by the electrolyte in which it is immersed;
  • the photovoltaic element is selected from the group consisting of: semiconductor junctions, CIGS junction, DSSC junction, perovskite junction, organic junction, Schottky junctions, tandem cells; metal oxides; binary metal oxides such as TiCh, ZnO, WO3, Fe2Os, CuO, or CU2O; ternary metal oxides such as BiVC , CuWCU or TaON; III-V semiconductors such as GaAs or InAs; II- VI semiconductors such as CdS, CdSe or CdTe;
  • the electrodes are made of metal such as Pt, Au, Sn, Cu, Ag, their mixtures, or their oxides; carbon-based materials; alloys such as stainless steel; transparent conductive materials such as ITO and FTO; or two- dimensional inorganic compounds;
  • the PECL device further comprises an insulating layer between the photovoltaic element and one electrode; preferably the insulating layer is made of SiO2, non-stoichiometric silica SiO x , TiO2, AI2O3, HfO2, or SnO2;
  • the first electrode is on the first pole of the photovoltaic element and the second electrode is on the second pole of the photovoltaic element;
  • the electrolyte further comprises a co-reactant enabling formation of an excited state of the luminophore during oxidation at the first electrode or during reduction at the second electrode;
  • the electrolyte is a water-based electrolyte.
  • the luminophore is selected from the group consisting of organometallic complexes such as Iridium-based organometallic complexes or Ruthenium-based organometallic complexes; 5-amino-2,3-dihydro-l,4-phtalazinedione and their derivatives; 8-amino-5-chloro-7-phenyl-pyrido[3,4-d]pyridazine- l,4(2H,3H)dione and their derivatives; and nanoparticles such as quantum dots, carbon dots, luminophore-doped particles, luminophore-doped zeolites or luminophore-doped Metal Organic Frameworks, more specifically, the electrolyte comprises Ru(bpy)3 2+ as luminophore, tripropylamine as co
  • the PECL device (1) comprises a photovoltaic element (10), a first electrode (20) and a second electrode (30).
  • the photovoltaic element (10) is intrinsically able to absorb light.
  • light refers to light that may be encountered in natural conditions, from ultraviolet-A light - wavelength from 280 nm to 380 nm - to visible light - wavelength from 380 nm to 780 nm - to near infrared light - wavelength from 780 nm to 3000 nm.
  • the absorption range of the photovoltaic element (10) is determined by its bandgap energy. Upon absorption of a photon, the photovoltaic element (10) generates an electron/hole pair. The electron then moves towards a first pole of the photovoltaic element (10), while the hole moves towards a second pole of the photovoltaic element (10).
  • the photovoltaic element (10) may be of any-type.
  • the photovoltaic element (10) may be selected from the group of semiconductor junctions, CIGS junction, DSSC junction, perovskite junction, organic junction, Schottky junctions - all junction being either homojunction or heterojunctions -, tandem cells, metal oxides, or semiconductor materials.
  • Suitable semiconductor junctions for the photovoltaic element (10) are p-n semiconductor junctions, p-i-n junctions, or heterojunctions where p stands for a p-type semiconductor; z stands for an intrinsic semiconductor, z.e., with a very low concentration of dopant; and n stands for n- type semiconductor.
  • a high level of dopant may be noted n + or n ++ , as it is well-known in the semiconductor domain.
  • Heterojunctions are junctions composed of different semiconductor materials, p-n, p-i-n or heterojunction junctions are especially suitable because of their commercial availability, their high photocurrent density and their high photovoltage.
  • Schottky junctions are photovoltaic elements (10) comprising a semiconductor, a metal coating and optionally an interlayer - for instance, silicon oxide. Schottky junctions are especially suitable because of their simple fabrication. Multijunctions are also suitable photovoltaic elements (10) comprising several similar junctions associated serially. For instance, several p-i-n junctions are juxtaposed in such a way that the n-p junction between two successive p-i-n junctions behaves as a tunnel junction.
  • Tandem cells are photovoltaic elements (10) comprising several junctions of different semiconductors - for instance: tandem Si-Perovskite. Tandem junctions are especially suitable because of their light conversion efficiency.
  • Suitable metal oxides for the photovoltaic element (10) may be selected from binary oxides such as TiCh, ZnO, WO3, Fe2Os, CuO, or CU2O; or ternary oxides such as Bi VO4, CuW04 or TaON. Metal oxides are especially suitable because of their improved stability.
  • Suitable semiconductor materials for the photovoltaic element (10) may be III-V semiconductors such as GaAs or InAs; or II- VI semiconductors such as CdS or CdSe or CdTe. Semiconductor materials are especially suitable because of their tunable bandgap.
  • Suitable junctions are known under the generic CIGS junction acronym, standing for copper indium gallium selenide alloy. These junctions are I-III-VI2 semi-conductor materials under the form of a solid solution of copper indium selenide and copper gallium selenide, with a chemical formula of CuIn x Ga(i- x )Se2, where the value of x may vary from 1 (pure copper indium selenide) to 0 (pure copper gallium selenide)
  • Suitable junctions are known under the generic DSSC junction acronym, standing for dye-sensitized solar cell.
  • Suitable junctions are known under the generic perovskite junction name, where the light absorbing material is a perovskite, in particular a hybrid organic-inorganic lead or tin halide-based material.
  • Suitable junctions are organic junctions comprising organic molecules as light absorbers, such as multilayer photovoltaic cells or bulk heterojunction cells.
  • the photovoltaic element (10) comprises at least two elements selected from the group of semiconductor junctions, CIGS junction, DSSC junction, perovskite junction, organic junction, Schottky junctions, tandem cells, metal oxides, or semiconductor materials; these elements being associated serially.
  • the first electrode (20) is connected to the first pole the photovoltaic element (10). In an embodiment, the first electrode (20) is on the first pole of the photovoltaic element (10), in direct contact. In another embodiment, the first electrode (20) may be separated from the photovoltaic element (10) by an intermediate layer, preferably an insulating layer, for instance made of SiO 2 , non- stoichiometric silica SiO x , TiO 2 , AI2O3, HfO 2 , or SnO 2 .
  • an intermediate layer preferably an insulating layer, for instance made of SiO 2 , non- stoichiometric silica SiO x , TiO 2 , AI2O3, HfO 2 , or SnO 2 .
  • the second electrode (30) is connected to the second pole of the photovoltaic element (10).
  • the second electrode (20) is on the second pole of the photovoltaic element (10), in direct contact.
  • the second electrode (30) may be separated from the photovoltaic element (10) by an intermediate layer.
  • the intermediate layer may be a conductive layer, for instance made of highly n- doped or p-doped silicon; or an insulating layer, for instance made of silica SiO 2 , non- stoichiometric silica SiO x , TiO 2 , A1 2 O3, HfO 2 , or SnO 2 .
  • the first electrode (20) may be connected to the photovoltaic element (10) by a wire (14) or any similar electrical connection means. This last embodiment allows to have the first electrode (20) immersed in the electrolyte (2) while the other parts of the PECL device (1) are not immersed.
  • the second electrode (30) may be connected to the photovoltaic element (10) by a wire (14) or any similar electrical connection means. This last embodiment allows to have the second electrode (30) immersed in the electrolyte (2) while the other parts of the PECL device (1) are not immersed.
  • a specific embodiment, illustrated in figure 4 shows a photovoltaic element (10) connected to both electrodes (20, 30) by wires (14). Electrodes (20,30) are immersed in the electrolyte (2), but not the photovoltaic element (10).
  • the electrodes (20, 30) may be made of the same material or of different materials. Each electrode (20, 30) may be selected in the group of metals, metal oxides, alloys, carbon-based materials, transparent conductive materials, two-dimensional inorganic compounds, or semiconductor layers.
  • Suitable metals for electrodes (20, 30) may be selected from the group of platinum (Pt), Gold (Au), Tin (Sn), copper (Cu) or Silver (Ag), as well as their mixtures or their oxides. Some alloys such as stainless steel are also suitable.
  • Suitable carbon-based materials for electrodes (20, 30) may be selected from the group of graphite, graphene, glassy carbon, toray paper, or carbon nanotubes (CNT) structures.
  • Electrodes (20, 30) may be transparent conductive materials, such as Indium Tin oxide (ITO) or Fluorine doped Tin oxide (FTO)
  • Suitable two-dimensional inorganic compounds may be selected form the group of transition metal dichalcogenides such as M0S2 or WSe2.
  • Suitable semiconductor layers for electrodes (20, 30) may be selected from the group of TiO 2 , ZnO, NiO, CuO, and Cu 2 O.
  • metal electrodes and carbon-based electrodes are especially adapted because of their good conductivity and electrochemical properties.
  • the PECL device (1) emits light when immersed in an electrolyte (2) or when electrodes (20, 30) are immersed in an electrolyte (2).
  • the electrolyte (2) comprises a luminophore, a molecule able to reach an excited state, then relaxing into a ground state by emission of a photon. Excitation of the luminophore occurs at an electrode (20, 30) in a redox reaction. Another compound undergoes another redox reaction at the other electrode (30, 20) to maintain electric neutrality.
  • the luminophore undergoes oxidation at the first electrode (20) and simultaneously emits light; and an oxidant undergoes reduction at the second electrode (30).
  • the luminophore undergoes reduction at the second electrode (30) and simultaneously emits light; and a reducing agent undergoes oxidation at the second electrode (20).
  • the PECL (1) device is passive.
  • “passive” refers to usual electric concept of passive component or circuit, in which no power source is present.
  • the PECL device (1) does not comprise an electric source - potentiostat, generator or similar power sources - nor a battery.
  • the PECL device (1) considered as a system receives energy from absorption of light and chemical reactions at the electrodes and releases energy by emission of light. It is noteworthy that in certain conditions, the energy of emitted light may be higher than the energy of absorbed light - phenomenon known as upconversion - thanks to chemical energy released during luminophore redox reaction.
  • the electric circuit comprising the photovoltaic element (10), the first electrode (20) and the second electrode (30) is closed only by the electrolyte (2) in which it is immersed.
  • This set-up may be named “wireless”.
  • the electrolyte (2) further comprises a co-reactant. Said co-reactant enables formation of the excited state of the luminophore during oxidation at the first electrode (20) or during reduction at the second electrode (30).
  • Various electrolytes (2) may be used to immerse a PECL device (1) or electrodes (20, 30) of a PECL device (1) disclosed herein, leading to light emission.
  • suitable system type of photovoltaic element (10) - defining the potential developed between the poles after absorption of a photon nature of electrodes (20, 30) - allowing to trigger redox reactions at lower potentials type of luminophore and optionally co-reactant; is not always straightforward. But a large variety of systems can be designed, as exemplified hereafter.
  • the PECL device (1) is named WB-PECL, and light emission is obtained when the electrolyte (2) is water-based.
  • Suitable luminophore for WB-PECL devices may be selected from the group of organometallic complexes, organic compounds, or nanoparticles.
  • Suitable organometallic complexes may be Iridium-based organometallic complexes or Ruthenium-based organometallic complexes generally noted [M(CAN)2(LAX)], where M stands for Iridium (Ir) or Ruthenium (Ru); CAN stands for organic ligands - including cyclometalated ligands -, LAX stands for ligands such as picolinate, acetylacetonate, 2,2'-bipyridine or phenylphenanthridine.
  • [Ir(ppy)2(bpy)]PF6 and their derivatives, Ru(bpy)3 2+ - as Chloride salt - and their derivatives are suitable.
  • ppyH is 2-phenylpyridine
  • bpy is 2,2'-bipyridine
  • PFe is hexafluorophosphate anion.
  • Other suitable organometallic complexes are tris(l,10- phenanthroline) ruthenium, bis(2, 2 '-bipyridine) (2,2'-bipyridine-biotine) ruthenium, bis(2,2'-bipyridine) (2,2'-bipyridine-streptavidine) ruthenium, tris(2, 2 '-bipyridine) ruthenium - NHS ester, tris(2, 2 '-bipyridine) ruthenium - phosphoramadite, tris(2,2’- bipyrazine) ruthenium, tris(2,2'-bipyridine) iridium, tris(l,10-phenanthroline) iridium, tris(2-phenylpyridine)iridium, bis(2,2
  • a particularly suitable electrolyte (2) comprises Ru(bpy)3 2+ - Cl’ salt - as luminophore with tripropylamine (0.1 M) as co-reactant and O2 as oxidant - note that water or even solvated protons may be oxidant as well.
  • the electrolyte has a pH of about 7.4.
  • a first WB-PECL device comprising three p-i-n junction connected in series (BPW34 from Vishay), with a carbon-based electrode (carbon paint DAG-T-502 from Ted Pella) connected to the first pole of the first p-i-n junction connected in series - the -sidc of the junction here - and a platinum electrode connected to the second pole of the third p-i-n junction connected in series - the n-side of the junction here - immersed in said electrolyte leads to spontaneous emission of visible light of wavelength 630 nm at the carbon electrode, when illuminated with infrared light of 850 nm.
  • BPW34 carbon paint DAG-T-502 from Ted Pella
  • Suitable organic compounds may be 5-amino-2,3-dihydro-l,4-phtalazinedione (also known as luminol) and their derivatives; or 8-amino-5-chloro-7-phenyl- pyrido[3,4-d]pyridazine-l,4(2H,3H)dione (also known as L-012) and their derivatives.
  • a particularly suitable electrolyte (2) - referred to as “luminol electrolyte” hereafter - comprises 5-amino-2,3-dihydro-l,4-phtalazinedione (10 mM) as luminophore with hydrogen peroxide H2O2 (33 mM) as co-reactant. Hydrogen peroxide is also the oxidant reacting at the second electrode here.
  • the electrolyte also contains 0.1 M potassium hydroxide KOH, leading to a pH of about 12.8.
  • a second WB-PECL device - illustrated in figure 1 - comprising a p-i-n junction (BPW34 from Vishay), with a carbon-based electrode (carbon paint DAG-T-502 from Ted Pella) connected to the first pole - the -sidc of the junction here - and a platinum electrode connected to the second pole - the n-side of the junction here - immersed in “luminol electrolyte” leads to spontaneous emission of IR light of wavelength 440 nm at the carbon electrode, when illuminated with infrared light of 850 nm. At the other electrode made of platinum, oxidant H2O2 is reduced in water.
  • a third WB-PECL device - illustrated in figure 2 - comprising a p-n-n ++ junction was prepared: on a photovoltaic p-n junction (p layer 11, n layer 12), a highly doped n ++ layer (13) is deposited on the n side of the junction then a 16 nm-thick platinum layer is deposited on the n ++ layer to form the second electrode (30).
  • This structure ensures the establishment of a Ohmic contact and optimal charge collection at the platinum electrode.
  • the p side of the junction is structured with 190 nm high pillars, on which gold nanoparticles are deposited to form the first electrode (20).
  • the gold electrode has a diameter of 280 nm and a thickness of 75 nm.
  • a fourth WB-PECL device - illustrated in figure 1 - comprising a p-i-n junction (BPW34 from Vishay), with a carbon-based electrode (carbon paint DAG-T-502 from Ted Pella) connected to the first pole - the -sidc of the junction here - and a platinum electrode connected to the second pole - the n-side of the junction here - immersed in “luminol electrolyte” leads to spontaneous emission of IR light of wavelength 440 nm at the carbon electrode, when illuminated with a solar simulator constituted of a Xe lamp equipped with an AM 1.5 G filter. At the other electrode made of platinum, oxidant H2O2 is reduced in water.
  • Suitable nanoparticles used as luminophores may be nanoparticles that are intrinsically luminophores, like quantum dots (QDs) or carbon dots.
  • QDs quantum dots
  • Various QDs - e.g., II- VI, III-V and IV- VI - with different sizes and shapes are suitable, in particular Cd- based QDs such as CdS, CdSe or CdSe/ZnS core-shell particles, germanium based QDs, lead based QDs such as PbS, perovskite QDs, molybdenum (Mo)/tungsten (W)/tin (Sn)- based QDs, MXene-derived QDs - i.e., QDs modified with layered transition metal (M) carbides, nitrides, or carbonitrides -, sulfur QDs.
  • Carbon dots such as carbon NPs, aromatic hydrocarbon-NPs, carbon nitrides NPS with different sizes
  • nanoparticles may be host of luminophores - for instance organometallic complexes or organic compounds as listed hereabove, especially Iridium and Ruthenium organometallic complexes - such as luminophore-doped nanoparticles - for instance silica nanoparticles - luminophore-doped zeolites, or luminophore-doped Metal Organic Frameworks.
  • Nanoparticles may be either dispersed in the electrolyte (2) or linked to the electrodes (20, 30), for instance by absorption on the electrodes (20 ,30).
  • Absorption of nanoparticles may be direct on the electrodes (20, 30) or obtained via grafting of organic molecules or via biomolecules such as proteins, nucleic acids or functional molecules leading to molecular interactions resulting in anchoring of nanoparticles at the electrode (20, 30).
  • Some systems are designed to work in a solvent-based electrolyte (2) - solvent excluding water-based as usually acknowledged in the domain of electrochemistry.
  • the PECL device (1) is named SB-PECL, and light emission is obtained when the electrolyte (2) is solvent-based.
  • the electrolyte still needs to be electrically conductive. Therefore, ionic liquids are suitable solvents.
  • Solvent may comprise ionic species - typically quaternary amines - to achieve electric conductivity.
  • a particularly suitable solvent-based electrolyte (2) comprises Ru(bpy)3 2+ as luminophore with benzoyl peroxide (0.01 M) as co-reactant and O2 as oxidant in acetonitrile. Tetrabutylammonium hexafluorophosphate salt is added in acetonitrile to provide sufficient electric conductivity.
  • PECL-ox device with electrolyte and luminophore undergoing oxidation.
  • This disclosure also relates to a photoelectrochemical electrochemiluminescent, PECL-ox, system.
  • the PECL-ox system comprises a photovoltaic element (10), a first electrode (20), a second electrode (30) and an electrolyte (2) in which said first electrode (20) and said second electrode (30) are immersed.
  • the system comprises the device (1) disclosed hereabove with first electrode (20 and second electrode (30) immersed in the electrolyte (2).
  • the electrolyte (2) comprises a luminophore undergoing oxidation at the first electrode (20) and simultaneously emitting light at the first electrode (20); and an oxidant undergoing reduction at the second electrode (30).
  • the PECL-ox system is passive, which means that no power source is present. In particular, the PECL-ox system does not comprise an electric source - potentiostat, generator or similar power sources - nor a battery.
  • the luminophore is a luminescent Ruthenium(II) complex - Ru(II) - and the electrolyte (2) further comprises hydrazine or an aliphatic amine as co-reactant.
  • Suitable luminescent Ru(II) complex may be selected from the group consisting of tris(2,2'-bipyridine) ruthenium, tris(l,10-phenanthroline) ruthenium, bis(2,2'- bipyridine) (2,2'-bipyridine-biotine) ruthenium, bis(2, 2 '-bipyridine) (2,2'-bipyridine- streptavidine) ruthenium, tris(2, 2 '-bipyridine) ruthenium - NHS ester, tris(2,2'- bipyridine) ruthenium - phosphoramadite, tris(2, 2’ -bipyrazine) ruthenium, their derivatives or mixtures.
  • Suitable aliphatic amines may be selected from the group consisting of tripropylamine, triethanolamine, 2-(dibutylamino) ethanol, nicotinamide adenine dinucleotide.
  • the photovoltaic element (10) may be selected from the group consisting of an Si homojunction, a series of Si homojunctions, an Si heterojunction, a series of Si heterojunctions, a CdTe junction, a series of CdTe junctions, a CIGS junction, a series of CIGS junctions, a DSSC junction, a series of DSSC junctions, a III-V junction, a series of III-V junctions, an organic junction, a series of organic junctions, a perovskite junction, a series of perovskite junctions, a III-V multijunction, or a Si/perovskite tandem junction.
  • the luminophore is a luminescent Ruthenium(II) complex - Ru(II) - and the electrolyte (2) further comprises a peroxide as co-reactant.
  • Suitable luminescent Ru(II) complex may be selected from the group consisting of tris(2,2'-bipyridine) ruthenium, tris(l,10-phenanthroline) ruthenium, bis(2,2'- bipyridine) (2,2'-bipyridine-biotine) ruthenium, bis(2, 2 '-bipyridine) (2,2'-bipyridine- streptavidine) ruthenium, tris(2, 2 '-bipyridine) ruthenium - NHS ester, tris(2,2'- bipyridine) ruthenium - phosphoramadite, tris(2, 2’ -bipyrazine) ruthenium, their derivatives or mixtures.
  • Suitable peroxide may be selected from the group consisting of benzoyl peroxide, and hydrogen peroxide.
  • the photovoltaic element (10) may be selected from the group consisting of an Si homojunction, a series of Si homojunctions, an Si heterojunction, a series of Si heterojunctions, a CdTe junction, a series of CdTe junctions, a CIGS junction, a series of CIGS junctions, a DSSC junction, a series of DSSC junctions, a III-V junction, a series of III-V junctions, an organic junction, a series of organic junctions, a perovskite junction, a series of perovskite junctions, a III-V multijunction, or a Si/perovskite tandem junction.
  • the luminophore is a luminescent Ruthenium(II) complex - Ru(II) - and the electrolyte (2) further comprises oxalate or peroxodisulfate as co-reactant.
  • Suitable luminescent Ru(II) complex may be selected from the group consisting of tris(2,2'-bipyridine) ruthenium, tris(l,10-phenanthroline) ruthenium, bis(2,2'- bipyridine) (2,2'-bipyridine-biotine) ruthenium, bis(2, 2 '-bipyridine) (2,2'-bipyridine- streptavidine) ruthenium, tris(2, 2 '-bipyridine) ruthenium - NHS ester, tris(2,2'- bipyridine) ruthenium - phosphoramadite, tris(2, 2’ -bipyrazine) ruthenium, their derivatives or mixtures.
  • the photovoltaic element (10) may be selected from the group consisting of an Si homojunction, a series of Si homojunctions, an Si heterojunction, a series of Si heterojunctions, a CdTe junction, a series of CdTe junctions, a CIGS junction, a series of CIGS junctions, a DSSC junction, a series of DSSC junctions, a III-V junction, a series of III-V junctions, an organic junction, a series of organic junctions, a perovskite junction, a series of perovskite junctions, a III-V multijunction, or a Si/perovskite tandem junction.
  • the luminophore is a luminescent Iridium(III) complex - IR(III) - and the electrolyte (2) further comprises hydrazine or an aliphatic amine as co-reactant.
  • Suitable luminescent Ir(III) complex may be selected from the group consisting of tris(2,2'-bipyridine) iridium, tris(l,10-phenanthroline) iridium, tris(2- phenylpyridinejiridium, bis(2,2'-bipyridine) (2,2'-bipyridine-biotine) iridium, bis(2,2'- bipyridine) (2,2'-bipyridine- streptavidine) iridium, their derivatives or mixtures.
  • Suitable aliphatic amines may be selected from the group consisting of tripropylamine, triethanolamine, 2-(dibutylamino) ethanol, nicotinamide adenine dinucleotide.
  • the photovoltaic element (10) may be selected from the group consisting of an Si homojunction, a series of Si homojunctions, an Si heterojunction, a series of Si heterojunctions, a CdTe junction, a series of CdTe junctions, a CIGS junction, a series of CIGS junctions, a DSSC junction, a series of DSSC junctions, a III-V junction, a series of III-V junctions, an organic junction, a series of organic junctions, a perovskite junction, a series of perovskite junctions, a III-V multijunction, or a Si/perovskite tandem junction.
  • the luminophore is luminol or a luminol derivative and the electrolyte (2) further comprises hydrogen peroxide - H2O2 - as coreactant.
  • the photovoltaic element (10) may be selected from the group consisting of an Si homojunction, a series of Si homojunctions, an Si heterojunction, a series of Si heterojunctions, a CdTe junction, a series of CdTe junctions, a CIGS junction, a series of CIGS junctions, a DSSC junction, a series of DSSC junctions, a III-V junction, a series of III-V junctions, an organic junction, a series of organic junctions, a perovskite junction, a series of perovskite junctions, a III-V multijunction, or a Si/perovskite tandem junction.
  • the luminophore is luminol or a luminol derivative and the electrolyte (2) further comprises dioxygen - O2 - as co-reactant.
  • the photovoltaic element (10) is a Schottky junction.
  • PECL-red device with electrolyte and luminophore undergoing reduction.
  • This disclosure also relates to another photoelectrochemical electrochemiluminescent, PECL-red, system.
  • the PECL-red system comprises a photovoltaic element (10), a first electrode (20), a second electrode (30) and an electrolyte (2) in which said first electrode (20) and said second electrode (30) are immersed.
  • the system comprises the device (1) disclosed hereabove with first electrode (20 and second electrode (30) immersed in the electrolyte (2).
  • the electrolyte (2) comprises a luminophore undergoing reduction at the second electrode (30) and simultaneously emitting light at the second electrode (30); and a reducing agent undergoing oxidation at the first electrode (20).
  • the PECL-red system is passive, which means that no power source is present.
  • the PECL-red system does not comprise an electric source - potentiostat, generator or similar power sources - nor a battery.
  • the luminophore is a luminescent Ruthenium(II) complex - Ru(II) - and the electrolyte (2) further comprises benzoyl peroxide as co-reactant.
  • a reducing agent is also provided in the electrolyte (2).
  • This disclosure also relates to a photoelectrochemical electrochemiluminescence method comprising the following steps: immersing in an electrolyte (2) a first electrode (20) and a second electrode (30) of a device (1) comprising: i. a photovoltaic element (10) in which light absorption generates an electron/hole pair; said photovoltaic element (10) having a first pole and a second pole; said generated holes moving towards the first pole; and said generated electrons moving towards the second pole; ii. the first electrode (20) connected to the first pole of the photovoltaic element (10); iii.
  • the second electrode (30) connected to the second pole of the photovoltaic element (10); illuminating the device (2) with external light, preferably infrared light; emitting light at the first electrode (20) or second electrode (30) by i. oxidation of a luminophore at the first electrode (20) thereby emitting light; and reduction of an oxidant at the second electrode (30); or ii. reduction of a luminophore at the second electrode (30) thereby emitting light; and oxidation of a reducing agent at the second electrode (20); and wherein the photoelectrochemical electrochemiluminescence method does not use an electric source.
  • All embodiments and variants of the PECL system - encompassing the device (1) whose electrodes (20, 30) are immersed in the electrolyte (2) - may be used in the method.
  • This disclosure also relates to a bio-chemical determination method using a PECL device (1) or PECL-ox system or PECL-red system as disclosed hereabove. In other words, the disclosure relates to the use of a PECL device (1) or PECL-ox system or PECL-red system as disclosed hereabove in a bio-chemical determination method.
  • Figure 1 is a graph showing a PECL device (1) immersed in an electrolyte (2) - thus forming a PECL system - according to an embodiment.
  • FIG 2 is a graph showing a PECL device (1) according to an embodiment.
  • the photovoltaic element (10) is a p-n-n ++ junction.
  • the first electrode (20) on the first pole of the photovoltaic element (10) is a Gold layer (Au).
  • the second electrode (30) on the second pole of the photovoltaic element (10) is a Platinum layer (Pt).
  • Figure 3 is an enlarged view of the first electrode (20) of figure 2, showing the reactional scheme involving luminol - luminophore - and H2O2 - co-reactant - interacting with a hole (h + ) at the first electrode (20) to promote an excited state of luminol, then relaxing through the emission of a photon of wavelength 440 nm.
  • FIG 4 is a graph showing a PECL device (1) according to an embodiment in which the photovoltaic element (10) is connected to electrodes (20, 30) by wires (14).
  • PECL photoelectrochemical electrochemiluminescent

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Abstract

The present invention relates to a passive photoelectrochemical electrochemiluminescent device, systems and methods comprising a photovoltaic element and two electrodes.

Description

PHOTOELECTROCHEMICAL ELECTROCHEMILUMINESCENCE METHOD, SYSTEMS AND DEVICE
FIELD OF INVENTION
[0001] The present invention relates to photoelectrochemical devices, devices that absorb light and create electron-hole pairs, then emit light using an electrochemiluminescent reaction involving the electron-hole pairs.
BACKGROUND OF INVENTION
[0002] Electrochemiluminescence (ECL) is a powerful and sensitive analytical technique that is widely employed for immunoassays, clinical diagnosis and imaging. It consists of the generation of light triggered by an electrochemical reaction at an electrode surface. This process requires an electrolyte containing a dissolved luminophore that is electrochemically promoted to an excited state and relaxes through the emission of a photon. However, ECL devices require an electric power source to induce ECL-light emission. Therefore, analytical devices relying on ECL always use potentiostats or similar electronic devices.
[0003] It is highly desirable to design an electrochemiluminescence system which would not require electric power source. Indeed, such an ECL device could be used in point of care approach, in remote areas, as a portable device and in electrochemiluminescence microscopy.
[0004] In the publication "Metal-Insulator-Semiconductor Anodes for Ultrastable and Site- Selective Upconversion Photoinduced Elecrochemiluminescence", Angewandte Chemie International Edition, Vol. 61, n°20 - 2022-03-16 - DOI:
10.1002/anie.202201865, authors disclose a photoinduced elecrochemiluminescence device and method, using a potentiostat as electric power element.
[0005] In the publication "Anti-Stockes photoinduced electrochemiluminescence at a photocathode", Chemical communications, Vol. 58, n° 47 - 2022-05-19 - DOI: 10.1039/D2CC01804G, authors also disclose a photoinduced electrochemiluminescence device and method, using a potentiostat as electric power element. [0006] Chinese patent application CN104132978 discloses a device based on bipolar electrodes to show electrochemiluminescence. This device works with an external power source.
[0007] US patent application US2019/296162 discloses a photovoltaic device, produced under lighting to obtain specific electrodes, but fails to address light emission and in particular electrochemiluminescence.
[0008] The object of the invention is to design an electrochemiluminescent device comprising a photovoltaic element, which can convert external light into electric power, as well as photoelectrochemical electrochemiluminescent systems and methods.
SUMMARY
[0009] This disclosure thus relates to a photoelectrochemical electrochemiluminescent (PECL) device comprising:
- A photovoltaic element in which light absorption generates an electron/hole pair; said photovoltaic element having a first pole and a second pole; said generated holes moving towards the first pole; and said generated electrons moving towards the second pole;
- A first electrode connected to the first pole of the photovoltaic element;
- A second electrode connected to the second pole of the photovoltaic element; said PECL device emitting light at an electrode when said electrode is immersed in an electrolyte comprising:
- A luminophore undergoing oxidation at the first electrode and simultaneously emitting light; and an oxidant undergoing reduction at the second electrode; or
- A luminophore undergoing reduction at the second electrode and simultaneously emitting light; and a reducing agent undergoing oxidation at the second electrode; wherein PECL device is passive. [0010] This disclosure also relates to a bio-chemical determination method using a photoelectrochemical electrochemiluminescent (PECL) device as disclosed hereabove.
[0011] Besides, this disclosure relates to a photoelectrochemical electrochemiluminescent, PECL-ox, system comprising:
A photovoltaic element in which light absorption generates an electron/hole pair; said photovoltaic element having a first pole and a second pole; said generated holes moving towards the first pole; and said generated electrons moving towards the second pole;
A first electrode connected to the first pole of the photovoltaic element;
A second electrode connected to the second pole of the photovoltaic element; an electrolyte in which said first electrode and said second electrode are immersed, said electrolyte comprising a luminophore undergoing oxidation at the first electrode and simultaneously emitting light at the first electrode; and an oxidant undergoing reduction at the second electrode; wherein PECL-ox system is passive.
[0012] In addition, this disclosure relates to a photoelectrochemical electrochemiluminescent, PECL-red, system comprising:
A photovoltaic element in which light absorption generates an electron/hole pair; said photovoltaic element having a first pole and a second pole; said generated holes moving towards the first pole; and said generated electrons moving towards the second pole;
A first electrode connected to the first pole of the photovoltaic element;
A second electrode connected to the second pole of the photovoltaic element; an electrolyte in which said first electrode and said second electrode are immersed, said electrolyte comprising a luminophore undergoing reduction at the second electrode and simultaneously emitting light; and a reducing agent undergoing oxidation at the second electrode; wherein PECL-red system is passive. [0013] Last, this disclosure also relates to photoelectrochemical electrochemiluminescence, PECL, method comprising the following steps: immersing in an electrolyte a first electrode and a second electrode of a device comprising: i. a photovoltaic element in which light absorption generates an electron/hole pair; said photovoltaic element having a first pole and a second pole; said generated holes moving towards the first pole; and said generated electrons moving towards the second pole; ii. the first electrode connected to the first pole of the photovoltaic element; iii. the second electrode connected to the second pole of the photovoltaic element; illuminating the device with external light, preferably infrared light; emitting light by i. oxidation of a luminophore at the first electrode thereby emitting light; and reduction of an oxidant at the second electrode; or ii. reduction of a luminophore at the second electrode thereby emitting light; and oxidation of a reducing agent at the second electrode; and wherein the photoelectrochemical electrochemiluminescence method does not comprise an electric source.
[0014] The various PECL devices, PECL-ox and PECL-red systems and the PECL method disclosed hereabove may be combined with one or more of the following features, taken in isolation from one another or in any technically acceptable combination with one another:
- an electric circuit comprising the photovoltaic element, the first electrode and the second electrode is closed only by the electrolyte in which it is immersed;
- the photovoltaic element is selected from the group consisting of: semiconductor junctions, CIGS junction, DSSC junction, perovskite junction, organic junction, Schottky junctions, tandem cells; metal oxides; binary metal oxides such as TiCh, ZnO, WO3, Fe2Os, CuO, or CU2O; ternary metal oxides such as BiVC , CuWCU or TaON; III-V semiconductors such as GaAs or InAs; II- VI semiconductors such as CdS, CdSe or CdTe;
- the electrodes are made of metal such as Pt, Au, Sn, Cu, Ag, their mixtures, or their oxides; carbon-based materials; alloys such as stainless steel; transparent conductive materials such as ITO and FTO; or two- dimensional inorganic compounds;
- the PECL device further comprises an insulating layer between the photovoltaic element and one electrode; preferably the insulating layer is made of SiO2, non-stoichiometric silica SiOx, TiO2, AI2O3, HfO2, or SnO2;
- the first electrode is on the first pole of the photovoltaic element and the second electrode is on the second pole of the photovoltaic element;
- the electrolyte further comprises a co-reactant enabling formation of an excited state of the luminophore during oxidation at the first electrode or during reduction at the second electrode;
- light emission is obtained in a water-based electrolyte. In other words, the electrolyte is a water-based electrolyte. In particular the luminophore is selected from the group consisting of organometallic complexes such as Iridium-based organometallic complexes or Ruthenium-based organometallic complexes; 5-amino-2,3-dihydro-l,4-phtalazinedione and their derivatives; 8-amino-5-chloro-7-phenyl-pyrido[3,4-d]pyridazine- l,4(2H,3H)dione and their derivatives; and nanoparticles such as quantum dots, carbon dots, luminophore-doped particles, luminophore-doped zeolites or luminophore-doped Metal Organic Frameworks, more specifically, the electrolyte comprises Ru(bpy)32+ as luminophore, tripropylamine as co-reactant, and dioxygen (O2) as oxidant; or the electrolyte comprises 5-amino-2,3-dihydro-l,4-phtalazinedione as luminophore, H2O2 as co-reactant, H2O2 as oxidant, and potassium hydroxide; light emission is obtained in a solvent-based electrolyte. In other words, the electrolyte is a solvent-based electrolyte.
DETAILED DESCRIPTION
PECL device principle
[0015] This disclosure relates to a photoelectrochemical electrochemiluminescent (PECL) device (1). The PECL device (1) comprises a photovoltaic element (10), a first electrode (20) and a second electrode (30).
[0016] The photovoltaic element (10) is intrinsically able to absorb light. In this disclosure, light refers to light that may be encountered in natural conditions, from ultraviolet-A light - wavelength from 280 nm to 380 nm - to visible light - wavelength from 380 nm to 780 nm - to near infrared light - wavelength from 780 nm to 3000 nm. The absorption range of the photovoltaic element (10) is determined by its bandgap energy. Upon absorption of a photon, the photovoltaic element (10) generates an electron/hole pair. The electron then moves towards a first pole of the photovoltaic element (10), while the hole moves towards a second pole of the photovoltaic element (10).
[0017] The photovoltaic element (10) may be of any-type. In particular, the photovoltaic element (10) may be selected from the group of semiconductor junctions, CIGS junction, DSSC junction, perovskite junction, organic junction, Schottky junctions - all junction being either homojunction or heterojunctions -, tandem cells, metal oxides, or semiconductor materials.
[0018] Suitable semiconductor junctions for the photovoltaic element (10) are p-n semiconductor junctions, p-i-n junctions, or heterojunctions where p stands for a p-type semiconductor; z stands for an intrinsic semiconductor, z.e., with a very low concentration of dopant; and n stands for n- type semiconductor. A high level of dopant may be noted n+ or n++, as it is well-known in the semiconductor domain. Heterojunctions are junctions composed of different semiconductor materials, p-n, p-i-n or heterojunction junctions are especially suitable because of their commercial availability, their high photocurrent density and their high photovoltage.
[0019] Schottky junctions are photovoltaic elements (10) comprising a semiconductor, a metal coating and optionally an interlayer - for instance, silicon oxide. Schottky junctions are especially suitable because of their simple fabrication. Multijunctions are also suitable photovoltaic elements (10) comprising several similar junctions associated serially. For instance, several p-i-n junctions are juxtaposed in such a way that the n-p junction between two successive p-i-n junctions behaves as a tunnel junction.
[0020] Tandem cells are photovoltaic elements (10) comprising several junctions of different semiconductors - for instance: tandem Si-Perovskite. Tandem junctions are especially suitable because of their light conversion efficiency.
[0021] Suitable metal oxides for the photovoltaic element (10) may be selected from binary oxides such as TiCh, ZnO, WO3, Fe2Os, CuO, or CU2O; or ternary oxides such as Bi VO4, CuW04 or TaON. Metal oxides are especially suitable because of their improved stability.
[0022] Suitable semiconductor materials for the photovoltaic element (10) may be III-V semiconductors such as GaAs or InAs; or II- VI semiconductors such as CdS or CdSe or CdTe. Semiconductor materials are especially suitable because of their tunable bandgap.
[0023] Suitable junctions are known under the generic CIGS junction acronym, standing for copper indium gallium selenide alloy. These junctions are I-III-VI2 semi-conductor materials under the form of a solid solution of copper indium selenide and copper gallium selenide, with a chemical formula of CuInxGa(i-x)Se2, where the value of x may vary from 1 (pure copper indium selenide) to 0 (pure copper gallium selenide)
[0024] Suitable junctions are known under the generic DSSC junction acronym, standing for dye-sensitized solar cell.
[0025] Suitable junctions are known under the generic perovskite junction name, where the light absorbing material is a perovskite, in particular a hybrid organic-inorganic lead or tin halide-based material. [0026] Suitable junctions are organic junctions comprising organic molecules as light absorbers, such as multilayer photovoltaic cells or bulk heterojunction cells.
[0027] In an embodiment, the photovoltaic element (10) comprises at least two elements selected from the group of semiconductor junctions, CIGS junction, DSSC junction, perovskite junction, organic junction, Schottky junctions, tandem cells, metal oxides, or semiconductor materials; these elements being associated serially.
[0028] The first electrode (20) is connected to the first pole the photovoltaic element (10). In an embodiment, the first electrode (20) is on the first pole of the photovoltaic element (10), in direct contact. In another embodiment, the first electrode (20) may be separated from the photovoltaic element (10) by an intermediate layer, preferably an insulating layer, for instance made of SiO2, non- stoichiometric silica SiOx, TiO2, AI2O3, HfO2, or SnO2.
[0029] The second electrode (30) is connected to the second pole of the photovoltaic element (10). In an embodiment, the second electrode (20) is on the second pole of the photovoltaic element (10), in direct contact. In another embodiment, the second electrode (30) may be separated from the photovoltaic element (10) by an intermediate layer. The intermediate layer may be a conductive layer, for instance made of highly n- doped or p-doped silicon; or an insulating layer, for instance made of silica SiO2, non- stoichiometric silica SiOx, TiO2, A12O3, HfO2, or SnO2.
[0030] In an embodiment, the first electrode (20) may be connected to the photovoltaic element (10) by a wire (14) or any similar electrical connection means. This last embodiment allows to have the first electrode (20) immersed in the electrolyte (2) while the other parts of the PECL device (1) are not immersed.
[0031] In an embodiment, the second electrode (30) may be connected to the photovoltaic element (10) by a wire (14) or any similar electrical connection means. This last embodiment allows to have the second electrode (30) immersed in the electrolyte (2) while the other parts of the PECL device (1) are not immersed. [0032] A specific embodiment, illustrated in figure 4 shows a photovoltaic element (10) connected to both electrodes (20, 30) by wires (14). Electrodes (20,30) are immersed in the electrolyte (2), but not the photovoltaic element (10).
[0033] The direct contact between an electrode (20, 30) and a pole of the photovoltaic element (10) allows to reduce the size of the PECL device (1) and can enable the establishment of a Schottky junction or an Ohmic contact.
[0034] The presence of a conducting intermediate layer between an electrode (20, 30) and a pole of the photovoltaic element (10) allows to ensure the establishment of a Ohmic contact and optimal charge collection at the electrode (20,30).
[0035] The presence of an insulating intermediate layer between an electrode (20, 30) and a pole of the photovoltaic element (10) allows to improve the stability and the pho to voltage of the junction.
[0036] The electrodes (20, 30) may be made of the same material or of different materials. Each electrode (20, 30) may be selected in the group of metals, metal oxides, alloys, carbon-based materials, transparent conductive materials, two-dimensional inorganic compounds, or semiconductor layers.
[0037] Suitable metals for electrodes (20, 30) may be selected from the group of platinum (Pt), Gold (Au), Tin (Sn), copper (Cu) or Silver (Ag), as well as their mixtures or their oxides. Some alloys such as stainless steel are also suitable.
[0038] Suitable carbon-based materials for electrodes (20, 30) may be selected from the group of graphite, graphene, glassy carbon, toray paper, or carbon nanotubes (CNT) structures.
[0039] Electrodes (20, 30) may be transparent conductive materials, such as Indium Tin oxide (ITO) or Fluorine doped Tin oxide (FTO)
[0040] Suitable two-dimensional inorganic compounds may be selected form the group of transition metal dichalcogenides such as M0S2 or WSe2. [0041] Suitable semiconductor layers for electrodes (20, 30) may be selected from the group of TiO2, ZnO, NiO, CuO, and Cu2O.
[0042] Among all electrodes (20, 30), metal electrodes and carbon-based electrodes are especially adapted because of their good conductivity and electrochemical properties.
[0043] In this disclosure, the PECL device (1) emits light when immersed in an electrolyte (2) or when electrodes (20, 30) are immersed in an electrolyte (2). The electrolyte (2) comprises a luminophore, a molecule able to reach an excited state, then relaxing into a ground state by emission of a photon. Excitation of the luminophore occurs at an electrode (20, 30) in a redox reaction. Another compound undergoes another redox reaction at the other electrode (30, 20) to maintain electric neutrality.
[0044] In an embodiment, the luminophore undergoes oxidation at the first electrode (20) and simultaneously emits light; and an oxidant undergoes reduction at the second electrode (30).
[0045] Alternatively, the luminophore undergoes reduction at the second electrode (30) and simultaneously emits light; and a reducing agent undergoes oxidation at the second electrode (20).
[0046] Last, the PECL (1) device is passive. In this disclosure, “passive” refers to usual electric concept of passive component or circuit, in which no power source is present. In particular, the PECL device (1) does not comprise an electric source - potentiostat, generator or similar power sources - nor a battery. From a thermodynamic point of view, the PECL device (1) considered as a system receives energy from absorption of light and chemical reactions at the electrodes and releases energy by emission of light. It is noteworthy that in certain conditions, the energy of emitted light may be higher than the energy of absorbed light - phenomenon known as upconversion - thanks to chemical energy released during luminophore redox reaction.
[0047] In an embodiment, the electric circuit comprising the photovoltaic element (10), the first electrode (20) and the second electrode (30) is closed only by the electrolyte (2) in which it is immersed. This set-up may be named “wireless”. [0048] In an embodiment, the electrolyte (2) further comprises a co-reactant. Said co-reactant enables formation of the excited state of the luminophore during oxidation at the first electrode (20) or during reduction at the second electrode (30).
[0049] Various electrolytes (2) may be used to immerse a PECL device (1) or electrodes (20, 30) of a PECL device (1) disclosed herein, leading to light emission. The selection of suitable system: type of photovoltaic element (10) - defining the potential developed between the poles after absorption of a photon nature of electrodes (20, 30) - allowing to trigger redox reactions at lower potentials type of luminophore and optionally co-reactant; is not always straightforward. But a large variety of systems can be designed, as exemplified hereafter.
[0050] Some systems are designed to work in a water-based electrolyte (2). In this situation, the PECL device (1) is named WB-PECL, and light emission is obtained when the electrolyte (2) is water-based.
[0051] Suitable luminophore for WB-PECL devices may be selected from the group of organometallic complexes, organic compounds, or nanoparticles.
[0052] Suitable organometallic complexes may be Iridium-based organometallic complexes or Ruthenium-based organometallic complexes generally noted [M(CAN)2(LAX)], where M stands for Iridium (Ir) or Ruthenium (Ru); CAN stands for organic ligands - including cyclometalated ligands -, LAX stands for ligands such as picolinate, acetylacetonate, 2,2'-bipyridine or phenylphenanthridine. In particular, [Ir(ppy)2(bpy)]PF6 and their derivatives, Ru(bpy)32+ - as Chloride salt - and their derivatives are suitable. Here ppyH is 2-phenylpyridine; bpy is 2,2'-bipyridine; and PFe" is hexafluorophosphate anion. Other suitable organometallic complexes are tris(l,10- phenanthroline) ruthenium, bis(2, 2 '-bipyridine) (2,2'-bipyridine-biotine) ruthenium, bis(2,2'-bipyridine) (2,2'-bipyridine-streptavidine) ruthenium, tris(2, 2 '-bipyridine) ruthenium - NHS ester, tris(2, 2 '-bipyridine) ruthenium - phosphoramadite, tris(2,2’- bipyrazine) ruthenium, tris(2,2'-bipyridine) iridium, tris(l,10-phenanthroline) iridium, tris(2-phenylpyridine)iridium, bis(2,2'-bipyridine) (2,2'-bipyridine-biotine) iridium, bis(2,2'-bipyridine) (2,2'-bipyridine- streptavidine) iridium, their derivatives or mixtures. [0053] A particularly suitable electrolyte (2) comprises Ru(bpy)32+ - Cl’ salt - as luminophore with tripropylamine (0.1 M) as co-reactant and O2 as oxidant - note that water or even solvated protons may be oxidant as well. The electrolyte has a pH of about 7.4. A first WB-PECL device comprising three p-i-n junction connected in series (BPW34 from Vishay), with a carbon-based electrode (carbon paint DAG-T-502 from Ted Pella) connected to the first pole of the first p-i-n junction connected in series - the -sidc of the junction here - and a platinum electrode connected to the second pole of the third p-i-n junction connected in series - the n-side of the junction here - immersed in said electrolyte leads to spontaneous emission of visible light of wavelength 630 nm at the carbon electrode, when illuminated with infrared light of 850 nm.
[0054] Suitable organic compounds may be 5-amino-2,3-dihydro-l,4-phtalazinedione (also known as luminol) and their derivatives; or 8-amino-5-chloro-7-phenyl- pyrido[3,4-d]pyridazine-l,4(2H,3H)dione (also known as L-012) and their derivatives.
[0055] A particularly suitable electrolyte (2) - referred to as “luminol electrolyte” hereafter - comprises 5-amino-2,3-dihydro-l,4-phtalazinedione (10 mM) as luminophore with hydrogen peroxide H2O2 (33 mM) as co-reactant. Hydrogen peroxide is also the oxidant reacting at the second electrode here. The electrolyte also contains 0.1 M potassium hydroxide KOH, leading to a pH of about 12.8.
[0056] A second WB-PECL device - illustrated in figure 1 - comprising a p-i-n junction (BPW34 from Vishay), with a carbon-based electrode (carbon paint DAG-T-502 from Ted Pella) connected to the first pole - the -sidc of the junction here - and a platinum electrode connected to the second pole - the n-side of the junction here - immersed in “luminol electrolyte” leads to spontaneous emission of IR light of wavelength 440 nm at the carbon electrode, when illuminated with infrared light of 850 nm. At the other electrode made of platinum, oxidant H2O2 is reduced in water.
[0057] A third WB-PECL device - illustrated in figure 2 - comprising a p-n-n++ junction was prepared: on a photovoltaic p-n junction (p layer 11, n layer 12), a highly doped n++ layer (13) is deposited on the n side of the junction then a 16 nm-thick platinum layer is deposited on the n++ layer to form the second electrode (30). This structure ensures the establishment of a Ohmic contact and optimal charge collection at the platinum electrode. The p side of the junction is structured with 190 nm high pillars, on which gold nanoparticles are deposited to form the first electrode (20). The gold electrode has a diameter of 280 nm and a thickness of 75 nm. When immersed in the “luminol electrolyte” under illumination with an infrared light of 1050 nm or 850 nm or a visible light of 733 nm or 633 nm, a spontaneous emission of blue light of wavelength 440 nm is observed at the first electrode (20) made of gold nanoparticles. The reaction scheme is illustrated in figure 3. At the second electrode (30) made of platinum, oxidant H2O2 is reduced in water.
[0058] A fourth WB-PECL device - illustrated in figure 1 - comprising a p-i-n junction (BPW34 from Vishay), with a carbon-based electrode (carbon paint DAG-T-502 from Ted Pella) connected to the first pole - the -sidc of the junction here - and a platinum electrode connected to the second pole - the n-side of the junction here - immersed in “luminol electrolyte” leads to spontaneous emission of IR light of wavelength 440 nm at the carbon electrode, when illuminated with a solar simulator constituted of a Xe lamp equipped with an AM 1.5 G filter. At the other electrode made of platinum, oxidant H2O2 is reduced in water.
[0059] Suitable nanoparticles used as luminophores may be nanoparticles that are intrinsically luminophores, like quantum dots (QDs) or carbon dots. Various QDs - e.g., II- VI, III-V and IV- VI - with different sizes and shapes are suitable, in particular Cd- based QDs such as CdS, CdSe or CdSe/ZnS core-shell particles, germanium based QDs, lead based QDs such as PbS, perovskite QDs, molybdenum (Mo)/tungsten (W)/tin (Sn)- based QDs, MXene-derived QDs - i.e., QDs modified with layered transition metal (M) carbides, nitrides, or carbonitrides -, sulfur QDs. Carbon dots such as carbon NPs, aromatic hydrocarbon-NPs, carbon nitrides NPS with different sizes, shapes and compositions are suitable.
[0060] Alternatively, nanoparticles may be host of luminophores - for instance organometallic complexes or organic compounds as listed hereabove, especially Iridium and Ruthenium organometallic complexes - such as luminophore-doped nanoparticles - for instance silica nanoparticles - luminophore-doped zeolites, or luminophore-doped Metal Organic Frameworks. Nanoparticles may be either dispersed in the electrolyte (2) or linked to the electrodes (20, 30), for instance by absorption on the electrodes (20 ,30). Absorption of nanoparticles may be direct on the electrodes (20, 30) or obtained via grafting of organic molecules or via biomolecules such as proteins, nucleic acids or functional molecules leading to molecular interactions resulting in anchoring of nanoparticles at the electrode (20, 30).
[0061] Some systems are designed to work in a solvent-based electrolyte (2) - solvent excluding water-based as usually acknowledged in the domain of electrochemistry. In this situation, the PECL device (1) is named SB-PECL, and light emission is obtained when the electrolyte (2) is solvent-based. Of course, the electrolyte still needs to be electrically conductive. Therefore, ionic liquids are suitable solvents. Solvent may comprise ionic species - typically quaternary amines - to achieve electric conductivity.
[0062] A particularly suitable solvent-based electrolyte (2) comprises Ru(bpy)32+ as luminophore with benzoyl peroxide (0.01 M) as co-reactant and O2 as oxidant in acetonitrile. Tetrabutylammonium hexafluorophosphate salt is added in acetonitrile to provide sufficient electric conductivity.
PECL-ox device with electrolyte and luminophore undergoing oxidation.
[0063] This disclosure also relates to a photoelectrochemical electrochemiluminescent, PECL-ox, system. The PECL-ox system comprises a photovoltaic element (10), a first electrode (20), a second electrode (30) and an electrolyte (2) in which said first electrode (20) and said second electrode (30) are immersed. In other words, the system comprises the device (1) disclosed hereabove with first electrode (20 and second electrode (30) immersed in the electrolyte (2).
[0064] Here, the electrolyte (2) comprises a luminophore undergoing oxidation at the first electrode (20) and simultaneously emitting light at the first electrode (20); and an oxidant undergoing reduction at the second electrode (30). [0065] The PECL-ox system is passive, which means that no power source is present. In particular, the PECL-ox system does not comprise an electric source - potentiostat, generator or similar power sources - nor a battery.
[0066] All embodiments and variants of the device (1) disclosed hereabove may apply in the PECL-ox system.
[0067] All embodiments and variants of the electrolyte (2) disclosed hereabove may apply in the PECL-ox system.
[0068] In a specific embodiment, the luminophore is a luminescent Ruthenium(II) complex - Ru(II) - and the electrolyte (2) further comprises hydrazine or an aliphatic amine as co-reactant.
[0069] Suitable luminescent Ru(II) complex may be selected from the group consisting of tris(2,2'-bipyridine) ruthenium, tris(l,10-phenanthroline) ruthenium, bis(2,2'- bipyridine) (2,2'-bipyridine-biotine) ruthenium, bis(2, 2 '-bipyridine) (2,2'-bipyridine- streptavidine) ruthenium, tris(2, 2 '-bipyridine) ruthenium - NHS ester, tris(2,2'- bipyridine) ruthenium - phosphoramadite, tris(2, 2’ -bipyrazine) ruthenium, their derivatives or mixtures.
[0070] Suitable aliphatic amines may be selected from the group consisting of tripropylamine, triethanolamine, 2-(dibutylamino) ethanol, nicotinamide adenine dinucleotide.
[0071] In this specific embodiment the photovoltaic element (10) may be selected from the group consisting of an Si homojunction, a series of Si homojunctions, an Si heterojunction, a series of Si heterojunctions, a CdTe junction, a series of CdTe junctions, a CIGS junction, a series of CIGS junctions, a DSSC junction, a series of DSSC junctions, a III-V junction, a series of III-V junctions, an organic junction, a series of organic junctions, a perovskite junction, a series of perovskite junctions, a III-V multijunction, or a Si/perovskite tandem junction.
[0072] In another specific embodiment, the luminophore is a luminescent Ruthenium(II) complex - Ru(II) - and the electrolyte (2) further comprises a peroxide as co-reactant. [0073] Suitable luminescent Ru(II) complex may be selected from the group consisting of tris(2,2'-bipyridine) ruthenium, tris(l,10-phenanthroline) ruthenium, bis(2,2'- bipyridine) (2,2'-bipyridine-biotine) ruthenium, bis(2, 2 '-bipyridine) (2,2'-bipyridine- streptavidine) ruthenium, tris(2, 2 '-bipyridine) ruthenium - NHS ester, tris(2,2'- bipyridine) ruthenium - phosphoramadite, tris(2, 2’ -bipyrazine) ruthenium, their derivatives or mixtures.
[0074] Suitable peroxide may be selected from the group consisting of benzoyl peroxide, and hydrogen peroxide.
[0075] In this specific embodiment the photovoltaic element (10) may be selected from the group consisting of an Si homojunction, a series of Si homojunctions, an Si heterojunction, a series of Si heterojunctions, a CdTe junction, a series of CdTe junctions, a CIGS junction, a series of CIGS junctions, a DSSC junction, a series of DSSC junctions, a III-V junction, a series of III-V junctions, an organic junction, a series of organic junctions, a perovskite junction, a series of perovskite junctions, a III-V multijunction, or a Si/perovskite tandem junction.
[0076] In another specific embodiment, the luminophore is a luminescent Ruthenium(II) complex - Ru(II) - and the electrolyte (2) further comprises oxalate or peroxodisulfate as co-reactant.
[0077] Suitable luminescent Ru(II) complex may be selected from the group consisting of tris(2,2'-bipyridine) ruthenium, tris(l,10-phenanthroline) ruthenium, bis(2,2'- bipyridine) (2,2'-bipyridine-biotine) ruthenium, bis(2, 2 '-bipyridine) (2,2'-bipyridine- streptavidine) ruthenium, tris(2, 2 '-bipyridine) ruthenium - NHS ester, tris(2,2'- bipyridine) ruthenium - phosphoramadite, tris(2, 2’ -bipyrazine) ruthenium, their derivatives or mixtures.
[0078] In this specific embodiment the photovoltaic element (10) may be selected from the group consisting of an Si homojunction, a series of Si homojunctions, an Si heterojunction, a series of Si heterojunctions, a CdTe junction, a series of CdTe junctions, a CIGS junction, a series of CIGS junctions, a DSSC junction, a series of DSSC junctions, a III-V junction, a series of III-V junctions, an organic junction, a series of organic junctions, a perovskite junction, a series of perovskite junctions, a III-V multijunction, or a Si/perovskite tandem junction.
[0079] In another specific embodiment, the luminophore is a luminescent Iridium(III) complex - IR(III) - and the electrolyte (2) further comprises hydrazine or an aliphatic amine as co-reactant.
[0080] Suitable luminescent Ir(III) complex may be selected from the group consisting of tris(2,2'-bipyridine) iridium, tris(l,10-phenanthroline) iridium, tris(2- phenylpyridinejiridium, bis(2,2'-bipyridine) (2,2'-bipyridine-biotine) iridium, bis(2,2'- bipyridine) (2,2'-bipyridine- streptavidine) iridium, their derivatives or mixtures.
[0081] Suitable aliphatic amines may be selected from the group consisting of tripropylamine, triethanolamine, 2-(dibutylamino) ethanol, nicotinamide adenine dinucleotide.
[0082] In this specific embodiment the photovoltaic element (10) may be selected from the group consisting of an Si homojunction, a series of Si homojunctions, an Si heterojunction, a series of Si heterojunctions, a CdTe junction, a series of CdTe junctions, a CIGS junction, a series of CIGS junctions, a DSSC junction, a series of DSSC junctions, a III-V junction, a series of III-V junctions, an organic junction, a series of organic junctions, a perovskite junction, a series of perovskite junctions, a III-V multijunction, or a Si/perovskite tandem junction.
[0083] In another specific embodiment, the luminophore is luminol or a luminol derivative and the electrolyte (2) further comprises hydrogen peroxide - H2O2 - as coreactant.
[0084] In this specific embodiment the photovoltaic element (10) may be selected from the group consisting of an Si homojunction, a series of Si homojunctions, an Si heterojunction, a series of Si heterojunctions, a CdTe junction, a series of CdTe junctions, a CIGS junction, a series of CIGS junctions, a DSSC junction, a series of DSSC junctions, a III-V junction, a series of III-V junctions, an organic junction, a series of organic junctions, a perovskite junction, a series of perovskite junctions, a III-V multijunction, or a Si/perovskite tandem junction.
[0085] In another specific embodiment, the luminophore is luminol or a luminol derivative and the electrolyte (2) further comprises dioxygen - O2 - as co-reactant. In this specific embodiment the photovoltaic element (10) is a Schottky junction.
PECL-red device with electrolyte and luminophore undergoing reduction.
[0086] This disclosure also relates to another photoelectrochemical electrochemiluminescent, PECL-red, system. The PECL-red system comprises a photovoltaic element (10), a first electrode (20), a second electrode (30) and an electrolyte (2) in which said first electrode (20) and said second electrode (30) are immersed. In other words, the system comprises the device (1) disclosed hereabove with first electrode (20 and second electrode (30) immersed in the electrolyte (2).
[0087] Here, the electrolyte (2) comprises a luminophore undergoing reduction at the second electrode (30) and simultaneously emitting light at the second electrode (30); and a reducing agent undergoing oxidation at the first electrode (20).
[0088] The PECL-red system is passive, which means that no power source is present. In particular, the PECL-red system does not comprise an electric source - potentiostat, generator or similar power sources - nor a battery.
[0089] All embodiments and variants of the device (1) disclosed hereabove may apply in the PECL-red system.
[0090] All embodiments and variants of the electrolyte (2) disclosed hereabove may apply in the PECL-red system.
[0091] In a specific embodiment, the luminophore is a luminescent Ruthenium(II) complex - Ru(II) - and the electrolyte (2) further comprises benzoyl peroxide as co-reactant. A reducing agent is also provided in the electrolyte (2).
PECL method [0092] This disclosure also relates to a photoelectrochemical electrochemiluminescence method comprising the following steps: immersing in an electrolyte (2) a first electrode (20) and a second electrode (30) of a device (1) comprising: i. a photovoltaic element (10) in which light absorption generates an electron/hole pair; said photovoltaic element (10) having a first pole and a second pole; said generated holes moving towards the first pole; and said generated electrons moving towards the second pole; ii. the first electrode (20) connected to the first pole of the photovoltaic element (10); iii. the second electrode (30) connected to the second pole of the photovoltaic element (10); illuminating the device (2) with external light, preferably infrared light; emitting light at the first electrode (20) or second electrode (30) by i. oxidation of a luminophore at the first electrode (20) thereby emitting light; and reduction of an oxidant at the second electrode (30); or ii. reduction of a luminophore at the second electrode (30) thereby emitting light; and oxidation of a reducing agent at the second electrode (20); and wherein the photoelectrochemical electrochemiluminescence method does not use an electric source.
[0093] All embodiments and variants of the device (1) disclosed hereabove may apply to the device (1) used in the method.
[0094] All embodiments and variants of the electrolyte (2) disclosed hereabove may apply to the electrolyte (2) used in the method.
[0095] All embodiments and variants of the PECL system - encompassing the device (1) whose electrodes (20, 30) are immersed in the electrolyte (2) - may be used in the method. [0096] This disclosure also relates to a bio-chemical determination method using a PECL device (1) or PECL-ox system or PECL-red system as disclosed hereabove. In other words, the disclosure relates to the use of a PECL device (1) or PECL-ox system or PECL-red system as disclosed hereabove in a bio-chemical determination method.
BRIEF DESCRIPTION OF THE DRAWINGS
[0097] Figure 1 is a graph showing a PECL device (1) immersed in an electrolyte (2) - thus forming a PECL system - according to an embodiment.
[0098] Figure 2 is a graph showing a PECL device (1) according to an embodiment. Here the photovoltaic element (10) is a p-n-n++ junction. The first electrode (20) on the first pole of the photovoltaic element (10) is a Gold layer (Au). The second electrode (30) on the second pole of the photovoltaic element (10) is a Platinum layer (Pt).
[0099] Figure 3 is an enlarged view of the first electrode (20) of figure 2, showing the reactional scheme involving luminol - luminophore - and H2O2 - co-reactant - interacting with a hole (h+) at the first electrode (20) to promote an excited state of luminol, then relaxing through the emission of a photon of wavelength 440 nm.
[0100] Figure 4 is a graph showing a PECL device (1) according to an embodiment in which the photovoltaic element (10) is connected to electrodes (20, 30) by wires (14).
Numeric references:
1 - photoelectrochemical electrochemiluminescent (PECL) device 111 - electrolyte // 10 - photovoltaic element // l l - p-doped silicon layer // 12 - n-doped silicon layer // 13 - n++-doped silicon layer // 14 - wires // 20 - first electrode // 30- second electrode // e“ - electron // h+ - hole

Claims

1. A photoelectrochemical electrochemiluminescence method comprising the following steps:
- immersing in an electrolyte (2) a first electrode (20) and a second electrode (30) of a device (1) comprising: i. a photovoltaic element (10) in which light absorption generates an electron/hole pair; said photovoltaic element (10) having a first pole and a second pole; said generated holes moving towards the first pole; and said generated electrons moving towards the second pole; ii. the first electrode (20) connected to the first pole of the photovoltaic element (10); iii. the second electrode (30) connected to the second pole of the photovoltaic element (10);
- illuminating the device (2) with external light, preferably infrared light;
- emitting light at the first electrode (20) or second electrode (30) by i. oxidation of a luminophore at the first electrode (20) thereby emitting light; and reduction of an oxidant at the second electrode (30); or ii. reduction of a luminophore at the second electrode (30) thereby emitting light; and oxidation of a reducing agent at the second electrode (20); and wherein the photoelectrochemical electrochemiluminescence method does not use an electric source.
2. The photoelectrochemical electrochemiluminescence method according to claim 1, wherein an electric circuit comprising the photovoltaic element (10), the first electrode (20) and the second electrode (30) is closed only by the electrolyte (2) in which it is immersed.
3. The photoelectrochemical electrochemiluminescence method according to claim 1 or claim 2, wherein the photovoltaic element (10) is selected from the group consisting of: semiconductor junctions, CIGS junction, DSSC junction, perovskite junction, organic junction, Schottky junctions, tandem cells; metal oxides; binary metal oxides such as TiCh, ZnO, WO3, Fe2O3, CuO, or CU2O; ternary metal oxides such as BiVC , CuWC or TaON; III-V semiconductors such as GaAs or InAs; II- VI semiconductors such as CdS, CdSe or CdTe.
4. The photoelectrochemical electrochemiluminescence method according to any one of claims 1 or 3, wherein the electrodes (20, 30) are made of metal such as Pt, Au, Sn, Cu, Ag, their mixtures, or their oxides; carbon-based materials; alloys such as stainless steel; transparent conductive materials such as ITO and FTO; or two- dimensional inorganic compounds.
5. The photoelectrochemical electrochemiluminescence method according to any one of claims 1 to 4, further comprising an insulating layer between the photovoltaic element and one electrode (20, 30); preferably the insulating layer is made of SiO2, non- stoichiometric silica SiOx, TiO2, AI2O3, HfO2, or SnO2.
6. The photoelectrochemical electrochemiluminescence method according to any one of claims 1 to 5, wherein the first electrode (20) is on the first pole of the photovoltaic element (10) and the second electrode (30) is on the second pole of the photovoltaic element (10).
7. The photoelectrochemical electrochemiluminescence method according to any one of claims 1 to 6, wherein the electrolyte (2) further comprises a co-reactant enabling formation of an excited state of the luminophore during oxidation at the first electrode (20) or during reduction at the second electrode (30).
8. The photoelectrochemical electrochemiluminescence method according to any one of claims 1 to 7, wherein the electrolyte (2) is a water-based electrolyte (2).
9. The photoelectrochemical electrochemiluminescence method according to claim 8, wherein the luminophore is selected from the group consisting of organometallic complexes such as Iridium-based organometallic complexes or Ruthenium-based organometallic complexes; 5-amino-2,3-dihydro-l,4-phtalazinedione and their derivatives; 8-amino-5-chloro-7-phenyl-pyrido[3,4-d]pyridazine-l,4(2H,3H)dione and their derivatives; and nanoparticles such as quantum dots, carbon dots, luminophore-doped particles, luminophore-doped zeolites or luminophore-doped Metal Organic Frameworks.
10. The photoelectrochemical electrochemiluminescence method according to claim 8, wherein the electrolyte (2) comprises Ru(bpy)32+ as luminophore, tripropylamine as co-reactant, and dioxygen as oxidant.
11. The photoelectrochemical electrochemiluminescence method according to claim 8, wherein the electrolyte (2) comprises 5-amino-2,3-dihydro-l,4-phtalazinedione as luminophore, H2O2 as co-reactant, H2O2 as oxidant, and potassium hydroxide.
12. The photoelectrochemical electrochemiluminescence method according to any one of claims 1 to 7, wherein the electrolyte (2) is a solvent-based electrolyte (2).
13. A photoelectrochemical electrochemiluminescent, PECL-ox, system comprising:
- A photovoltaic element (10) in which light absorption generates an electron/hole pair; said photovoltaic element (10) having a first pole and a second pole; said generated holes moving towards the first pole; and said generated electrons moving towards the second pole;
- A first electrode (20) connected to the first pole of the photovoltaic element (10);
- A second electrode (30) connected to the second pole of the photovoltaic element (10);
- an electrolyte (2) in which said first electrode (20) and said second electrode (30) are immersed, said electrolyte (2) comprising a luminophore undergoing oxidation at the first electrode (20) and simultaneously emitting light at the first electrode (20); and an oxidant undergoing reduction at the second electrode (30); wherein PECL-ox system is passive.
14. A PECL-ox system according to claim 13, wherein: - the luminophore is a luminescent Ru(II) complex;
- the electrolyte (2) further comprises hydrazine or an aliphatic amine as co-reactant;
- the photovoltaic element (10) is selected from the group consisting of an Si homojunction, a series of Si homojunctions, an Si heterojunction, a series of Si heterojunctions, a CdTe junction, a series of CdTe junctions, a CIGS junction, a series of CIGS junctions, a DSSC junction, a series of DSSC junctions, a III-V junction, a series of III-V junctions, an organic junction, a series of organic junctions, a perovskite junction, a series of perovskite junctions, a III-V multijunction, or a Si/perovskite tandem junction.
15. A PECL-ox system according to claim 13, wherein:
- the luminophore is a luminescent Ru(II) complex;
- the electrolyte (2) further comprises a peroxide, preferably benzoyl peroxide, as co-reactant;
- the photovoltaic element (10) is selected from the group consisting of an Si homojunction, a series of Si homojunctions, an Si heterojunction, a series of Si heterojunctions, a CdTe junction, a series of CdTe junctions, a CIGS junction, a series of CIGS junctions, a DSSC junction, a series of DSSC junctions, a III-V junction, a series of III-V junctions, an organic junction, a series of organic junctions, a perovskite junction, a series of perovskite junctions, a III-V multijunction, or a Si/perovskite tandem junction.
16. A PECL-ox system according to claim 13, wherein:
- the luminophore is a luminescent Ru(II) complex;
- the electrolyte (2) further comprises oxalate or peroxodisulfate as coreactant;
- the photovoltaic element (10) is selected from the group consisting an Si homojunction, a series of Si homojunctions, an Si heterojunction, a series of Si heterojunctions, a CdTe junction, a series of CdTe junctions, a CIGS junction, a series of CIGS junctions, a DSSC junction, a series of DSSC junctions, a III- V junction, a series of III- V junctions, an organic junction, a series of organic junctions, a perovskite junction, a series of perovskite junctions, a III-V multijunction, or a Si/perovskite tandem junction.
17. A PECL-ox system according to claim 13, wherein:
- the luminophore is a luminescent Ir(III) complex;
- the electrolyte (2) further comprises hydrazine or an aliphatic amine as co-reactant;
- the photovoltaic element (10) is selected from the group consisting of an Si homojunction, a series of Si homojunctions, an Si heterojunction, a series of Si heterojunctions, a CdTe junction, a series of CdTe junctions, a CIGS junction, a series of CIGS junctions, a DSSC junction, a series of DSSC junctions, a III-V junction, a series of III-V junctions, an organic junction, a series of organic junctions, a perovskite junction, a series of perovskite junctions, a III-V multijunction, or a Si/perovskite tandem junction.
18. A PECL-ox system according to claim 13, wherein the luminophore is luminol or a luminol derivative and
- the electrolyte (2) further comprises hydrogen peroxide as co-reactant; and the photovoltaic element (10) is selected from the group consisting of an Si homojunction, a series of Si homojunctions, an Si heterojunction, a series of Si heterojunctions, a CdTe junction, a series of CdTe junctions, a CIGS junction, a series of CIGS junctions, a DSSC junction, a series of DSSC junctions, a III-V junction, a series of III-V junctions, an organic junction, a series of organic junctions, a perovskite junction, a series of perovskite junctions, a III-V multijunction, a Schottky junction or a Si/perovskite tandem junction; or
- the electrolyte (2) further comprises dioxygen as co-reactant and the photovoltaic element (10) is a Schottky junction.
19. A photoelectrochemical electrochemiluminescent, PECL-red, system comprising: - A photovoltaic element (10) in which light absorption generates an electron/hole pair; said photovoltaic element (10) having a first pole and a second pole; said generated holes moving towards the first pole; and said generated electrons moving towards the second pole;
- A first electrode (20) connected to the first pole of the photovoltaic element (10);
- A second electrode (30) connected to the second pole of the photovoltaic element (10);
- an electrolyte (2) in which said first electrode (20) and said second electrode (30) are immersed, said electrolyte (2) comprising a luminophore undergoing reduction at the second electrode (30) and simultaneously emitting light; and a reducing agent undergoing oxidation at the second electrode (20); wherein PECL-red system is passive.
20. A photoelectrochemical electrochemiluminescent, PECL, device (1) comprising:
- A photovoltaic element (10) in which light absorption generates an electron/hole pair; said photovoltaic element (10) having a first pole and a second pole; said generated holes moving towards the first pole; and said generated electrons moving towards the second pole;
- A first electrode (20) connected to the first pole of the photovoltaic element (10);
- A second electrode (30) connected to the second pole of the photovoltaic element (10); said PECL device (1) emitting light at the first electrode (20) or the second electrode (30) when said first electrode (20) or said second electrode (30) is immersed in an electrolyte (2) comprising:
A luminophore undergoing oxidation at the first electrode (20) and simultaneously emitting light; and an oxidant undergoing reduction at the second electrode (30); or - A luminophore undergoing reduction at the second electrode (30) and simultaneously emitting light; and a reducing agent undergoing oxidation at the second electrode (20); wherein PECL device (1) is passive.
EP24723574.0A 2023-05-12 2024-05-07 Photoelectrochemical electrochemiluminescence method, systems and device Pending EP4710095A1 (en)

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