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  • C01B19/00—Selenium; Tellurium; Compounds thereof
  • C01B19/002—Compounds containing, besides selenium or tellurium, more than one other element, with -O- and -OH not being considered as anions
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• • H—ELECTRICITY
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  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
  • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
  • H01G9/20—Light-sensitive devices
  • H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
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  • H10F10/00—Individual photovoltaic cells, e.g. solar cells
  • H10F10/10—Individual photovoltaic cells, e.g. solar cells having potential barriers
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  • H10F77/00—Constructional details of devices covered by this subclass
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  • H10F77/00—Constructional details of devices covered by this subclass
  • H10F77/10—Semiconductor bodies
  • H10F77/12—Active materials
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  • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
  • H10P14/20—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials
  • H10P14/26—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials using liquid deposition
  • H10P14/265—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials using liquid deposition using solutions
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  • H10P14/20—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials
  • H10P14/32—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials characterised by intermediate layers between substrates and deposited layers
  • H10P14/3202—Materials thereof
  • H10P14/3224—Materials thereof being Group IIB-VIA semiconductors
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  • H10P14/20—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials
  • H10P14/34—Deposited materials, e.g. layers
  • H10P14/3402—Deposited materials, e.g. layers characterised by the chemical composition
  • H10P14/3434—Deposited materials, e.g. layers characterised by the chemical composition being oxide semiconductor materials
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  • H10P14/20—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials
  • H10P14/34—Deposited materials, e.g. layers
  • H10P14/3402—Deposited materials, e.g. layers characterised by the chemical composition
  • H10P14/3436—Deposited materials, e.g. layers characterised by the chemical composition being chalcogenide semiconductor materials not being oxides, e.g. ternary compounds
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  • H10P14/20—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials
  • H10P14/34—Deposited materials, e.g. layers
  • H10P14/3451—Structure
  • H10P14/3452—Microstructure
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  • C01P2006/00—Physical properties of inorganic compounds
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  • H10P14/20—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials
  • H10P14/203—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials using transformation of metal, e.g. oxidation or nitridation
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  • H10P14/20—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials
  • H10P14/22—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials using physical deposition, e.g. vacuum deposition or sputtering
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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  • Y02E10/00—Energy generation through renewable energy sources
  • Y02E10/50—Photovoltaic [PV] energy
  • Y02E10/542—Dye sensitized solar cells

Definitions

• the present invention relates to the field of inorganic compounds intended to provide a photocurrent, in particular by photovoltaic effect.
• photovoltaic technologies using inorganic compounds are mainly based on silicon technologies (over 80% of the market) and on thin film technologies (mainly CdTe and CIGS (Copper Indium Gallium Selenium), representing 20% of the market).
• CdTe and CIGS Copper Indium Gallium Selenium
• CZTS Cu 2 ZnSnSe 4
• An object of the present invention is precisely to provide inorganic compounds alternative to those used in current photovoltaic technologies, which make it possible to avoid the aforementioned problems.
• the present invention proposes to use a new family of inorganic materials, whose inventors have now shown that, unexpectedly, they prove to have good efficiency, and that they have the advantage of not having to use rare or toxic metals of the type In, Te, Cd mentioned above, and furthermore offer the possibility of using anions, such as Se or Te, in a reduced content, or even not to use this type of anion.
• the subject of the present invention is the use of a material comprising at least one compound of formula (I):
• 0 ⁇ z ⁇ 0.2 for example, 0 ⁇ z ⁇ 0.1
• 0 ⁇ a ⁇ 2; 0 ⁇ b ⁇ 2; 0 ⁇ c ⁇ 2; 0 ⁇ d ⁇ 2; and a + b + c + d 2; as a p-type semiconductor, to provide a photocurrent.
• the materials of formula (I) above are capable of providing a photocurrent when irradiated at a wavelength greater than their gap (ie the generation of an electron-hole pair within the material under the effect of an incident photon of sufficient energy, the charged species formed (the electron and the "hole", namely the electron gap) being free to move to generate a current).
• the materials of the invention prove to be suitable for ensuring a photovoltaic effect.
• a photovoltaic effect is obtained by the joint implementation of two different type of semiconductor compounds, namely:
• These compounds are placed close to each other in a manner known per se (ie in direct contact or at least at a sufficiently small distance to ensure the photovoltaic effect) to form a p-n type junction.
• the electron-hole pairs created by light absorption are dissociated at the pn junction and the excited electrons can be conveyed by the n-type semiconductor towards the anode, the holes being led towards the cathode via the p-type semiconductor.
• the photovoltaic effect is typically obtained by placing a material based on a semiconductor of formula (I) above in contact with an n-type semiconductor between two electrodes, in direct contact with each other. or optionally connected to at least one of the electrodes via an additional coating, for example a charge collection coating; and irradiating the photovoltaic device thus produced with adequate electromagnetic radiation, typically by the light of the solar spectrum. To do this, it is preferable that one of the electrodes passes the electromagnetic radiation used.
• the subject of the present invention is photovoltaic devices comprising, between a hole-conducting material and an electron-conducting material, a layer based on a compound of formula (I), in particular based on BiCuOS. , and a layer based on an n-type semiconductor, where:
• the layer based on the compound of formula (I) is in contact with the layer based on the n-type semiconductor;
• the layer based on the compound of formula (I) is close to the hole-conducting material
• the layer based on the n-type semiconductor is in the vicinity of the electron-conducting material.
• the term "hole-conducting material” means a material which is capable of ensuring a flow of current between the p-type semiconductor and the electric circuit.
• the n-type semiconductor employed in the photovoltaic devices according to the invention may be chosen from any semiconductor which exhibits an electron acceptor character which is more marked than the compound of formula (I) or a compound promoting the evacuation of electrons.
• the n-type semiconductor may be an oxide, for example ZnO, or TiO 2 , or a sulphide, for example CdS.
• the hole-conducting material used in the photovoltaic devices according to the invention may be for example a metal, such as gold, tungsten, or molybdenum; or a metal deposited on a support, such as Pt / FTO (platinum deposited on fluorine-doped tin dioxide); or a conductive oxide such as ⁇ (tin-doped indium oxide), for example, deposited on glass; or a p-type conductive polymer.
• a metal such as gold, tungsten, or molybdenum
• a metal deposited on a support such as Pt / FTO (platinum deposited on fluorine-doped tin dioxide); or a conductive oxide such as ⁇ (tin-doped indium oxide), for example, deposited on glass; or a p-type conductive polymer.
• the hole-conducting material may comprise a hole-conducting material of the aforementioned type and a redox mediator, for example an electrolyte containing the ⁇ 2 / pair, in which case the hole-conducting material is typically Pt. / OTF.
• the electron-conducting material may be, for example, FTO, or AZO (aluminum-doped zinc oxide), or an n-type semiconductor.
• the holes generated at the p-n junction are extracted via the hole-conducting material and the electrons are extracted via the electron-conducting material of the aforementioned type.
• the hole-conducting material and / or the electron-conducting material is an at least partially transparent material that allows the electromagnetic radiation to be passed through.
• the at least partially transparent material is advantageously placed between the source of the incident electromagnetic radiation and the p-type semiconductor.
• the hole-conducting material may for example be a material chosen from a metal or a conductive glass.
• the electron-conducting material may be at least partially transparent, and is then chosen, for example, from FTO (fluorine-doped tin dioxide), or AZO (aluminum-doped zinc oxide), or a semiconductor.
• FTO fluorine-doped tin dioxide
• AZO aluminum-doped zinc oxide
• the layer based on an n-type semiconductor which is in contact with the layer based on a compound of formula (I) may also be at least partially transparent.
• partially transparent material is meant here a material that passes at least part of the incident electromagnetic radiation, useful for providing the photocurrent, and which can be:
• the compound of formula (I), in particular BiCuOS, used according to the present invention is advantageously used in the form of isotropic or anisotropic objects having at least one dimension less than 50 ⁇ , preferably less than 20 ⁇ , typically less than 10 ⁇ preferably less than 5 ⁇ , generally less than 1 ⁇ , more preferably less than 500 nm, for example less than 200 nm, or even 100 nm.
• the dimension less than 50 ⁇ can be:
• the objects based on a compound of formula (I) are particles, typically having dimensions less than 10 ⁇ . This mode is particularly advantageous when the compound of formula (I) is BiCuOS.
• particles is meant here isotropic or anisotropic objects, which may be individual particles, or aggregates.
• the particle sizes referred to herein can typically be measured by scanning electron microscopy (SEM).
• the compound of formula (I) is in the form of platelet-type anisotropic particles, or agglomerates of a few tens to a few hundreds of particles of this type, these platelet-type particles having typically dimensions remaining less than 5 ⁇ , (preferably less than 1 ⁇ , more preferably less than 500 nm), with a thickness that typically remains less than 500 nm, for example less than 100 nm.
• Particles of the type described according to the first variant can typically be employed in the state deposited on an n-type conductive or semiconductor support.
• a plate of ITO or metal covered with particles according to the invention can thus for example act as a photoactive electrode for a photoelectrochemical device which can be used in particular as a photodetector.
• a photoelectrochemical type device implementing a photoactive electrode of the aforementioned type comprises an electrolyte which is generally a salt solution, for example a KCl solution, typically having a concentration of the order of 1 M, in which are immersed:
• these three electrodes being interconnected, typically by a potentiostat.
• the electrochemical device can comprise:
• a photoactive electrode a support (such as an ITO plate) coated with BiCuOS particles;
• a reference electrode for example, an Ag / AgCl electrode
• a counter-electrode for example, a platinum wire
• these three electrodes being interconnected, typically by a potentiostat.
• the electrolyte is an aqueous solution, which is most often the case, the water in the electrolyte is reduced to close to the photoactive electrode by the generated electrons, producing hydrogen and OH-ions ".
• OH "ions so produced will migrate to the against-electrode via the electrolyte; and the holes of the compound of formula (I) will be extracted via the ITO-type conductor and will enter the electrical circuit external.
• the oxidation of the OH " is carried out by means of the holes near the counter-electrode producing oxygen .
• the setting in movement of these charges (holes and electrons), induced by the absorption of the light of the compound of formula (I) generates a photocurrent.
• the device can in particular be used as a photodetector, the photocurrent being generated only when the device is illuminated.
• a photoactive electrode as described above can in particular be carried out by employing a suspension comprising the particles of a compound of formula (I) of the aforementioned type dispersed in a solvent, and by depositing this suspension on a support, for example a glass plate covered with ITO or a metal plate, by the wet method or any coating method, for example, by drop-casting, centrifugation ("spin-coating” in English) ), dipping ("dip-coating” in English), inkjet or serigraphy.
• a support for example a glass plate covered with ITO or a metal plate
• the wet method or any coating method for example, by drop-casting, centrifugation ("spin-coating" in English) ), dipping ("dip-coating” in English), inkjet or serigraphy.
• the particles based on a compound of formula (I) which are present in the suspension have a mean diameter as measured by laser particle size (for example, by means of a laser granulometry Malvern type) which
• the particles of compound of formula (I) may be previously dispersed in a solvent, for example, terpineol or ethanol.
• the suspension containing the particles of compound of formula (I) may be deposited on a support, for example a conductive oxide coated plate.
• Particles of BiCi 2 -z O a S b Se c Te d for example of BiCuOS, well adapted to the implementation of the invention can typically be obtained according to a process comprising a heat treatment of a mixture of inorganic compounds with the dissolved, dispersed or divided state (typically in the form of a solution or a powder), comprising:
• a source of oxygen preferably including at least one bismuth or copper oxide
• a sulfur source and optionally a source of selenium, which leads to compounds where c> 0
• a source of oxygen preferably including at least one bismuth or copper oxide
• a sulfur source and optionally a source of selenium, which leads to compounds where c> 0
• forming particles BiCui -z Oas B c Te d which are generally recovered after a cooling following the heat treatment.
• the dissolution being able to be carried out during the hydrothermal treatment for all or part of the inorganic compounds and / or prior to the hydrothermal treatment for all or part of the organic compounds;
• BiCui -z O a S b for example BiCuOS, of dimensions less than 5 pm well adapted to the implementation of the invention can typically be obtained according to a process comprising the following steps:
• particles of BiCui -z OaS b Se c Te d of formula (I) of dimensions less than 5 m well suited to the implementation of the invention can typically be obtained according to a process comprising the following steps:
• the aqueous medium used in steps (a) and (a ') can in particular be a solvent, for example a mixture of ethylene glycol or a refluxing ionic liquid.
• step (c) or (c ') it is possible to perform a disagglomeration step, for example, with an ultrasonic probe.
• the inorganic bismuth and copper compounds provided in the mixture of step (a) or (a ') are, for example, Bi 2 O 3 and Cu 2 O. According to another possible embodiment, soluble salts may be used. of bismuth and copper.
• step (b) (and respectively (b')) is advantageously carried out in the presence of a source of oxygen, such as water, nitrates or even carbonate.
• the inorganic tellurium compound in the mixture of step (a ') is, for example, tellurium, tellurium oxide or a tellurium salt.
• the source of sulfur employed in steps (a) and (a ') may be chosen from sulfur, hydrogen sulphide H 2 S and its salts, an organic sulfur compound (thiol, thioether, thioamide, etc.), preferably an anhydrous or hydrated sodium sulphide.
• the source of selenium used in step (a ') may be chosen from selenium, selenium oxide or a selenium salt, for example Na 2 Se.
• the oxides in the dispersed state are employed in steps (a) and (a ') in the form of particles, typically in the form of powders, having a particle size of less than 5 ⁇ , typically less than 1 ⁇ , preferably less than 500 nm.
• This particle size may for example be obtained by prior grinding of the oxides (separately, or more advantageously in the case of oxide mixtures, this grinding may be carried out on the oxide mixture), by for example, using a micronizer type device or wet ball mill.
• steps (b) and (b ') the dissolution is carried out in "hydrothermal conditions".
• the step is conducted at a temperature above 180 ° C under the saturated vapor pressure of water.
• the temperature of step (b) or (b ') may be less than 240 ° C, or even less than 210 ° C, for example between 180 ° C and 200 ° C.
• step (b) or (b ') can be carried out without preliminary grinding, in which case it is however preferable to conduct the step at a temperature greater than 240 ° C., preferably greater than 250 ° C.
• the mixture is placed in water at a temperature below the hydrothermal conditions (typically at room temperature and at atmospheric pressure), then the temperature is slowly raised, preferably at room temperature. less than 10 ° C / min, for example between 0.5 and 5 ° C / min, typically 2.5 ° C / min, typically operating in a closed environment (using a device such as hydrothermal bomb, in particular Parr bomb) until reaching the operating temperature.
• a temperature below the hydrothermal conditions typically at room temperature and at atmospheric pressure
• the temperature is slowly raised, preferably at room temperature. less than 10 ° C / min, for example between 0.5 and 5 ° C / min, typically 2.5 ° C / min, typically operating in a closed environment (using a device such as hydrothermal bomb, in particular Parr bomb) until reaching the operating temperature.
• the dissolution is specifically carried out with stirring.
• This agitation can be carried out in particular by magnetic stirring, for example by placing the hydrothermal bomb, on a magnetic stirrer, the assembly being placed in a heating chamber (such as an oven).
• Steps (b) and (b ') are conducted for a time sufficient to obtain dissolution.
• the temperature is maintained at least 190 ° C for at least 12h, for example for 48h or 7 days.
• the solution obtained is typically brought to room temperature or more generally to a temperature of between 10 and 30 ° C by cooling, for example by decreasing the temperature by at least 1 ° C / min, preferably by a faster cooling, with a decrease typically of at least 3 ° C / min, for example 3 to 5 ° C / min.
• This type of cooling typically leads to particles having a length of between 50 nm and 5 ⁇ , typically between 100 nm and 1 ⁇ , and a thickness of 50 nm.
• the aforementioned high cooling rates generally lead to very low levels of impurities (Cu 2 S, Bi 2 O 3 and Cu 3 BiS 3 , in particular).
• particles of BiCui -z OaS b Se c Te d of formula (I) of dimensions less than 5 ⁇ well adapted to the implementation of the invention can be obtained according to a process comprising the following steps: an aqueous solution of inorganic compounds comprising:
• a source of oxygen preferably including at least one bismuth or copper oxide
• a sulfur source and optionally a source of selenium, which leads to compounds where c> 0
• hydrothermal preferably with stirring
• Another method that can be envisaged which leads to particles of BiCi 2 -z OaS b Se c Te d of formula (I) well adapted to the implementation of the invention, typically of dimensions less than 5 ⁇ , comprises the following steps: providing a solid mixture of inorganic compounds in the divided state (typically in powder form) comprising:
• a source of oxygen preferably including at least one bismuth or copper oxide
• a sulfur source and optionally a source of selenium, which leads to compounds where c> 0
• treatment of the solid mixture at a temperature of at least 500 ° C (preferably in the range from 520 to 600 ° C, for example about 550 ° C), whereby it forms particles of BiCui -z Oas B c Te d ( typically recovered after cooling).
• the compound of formula (I) is in the form of a continuous layer based on the compound of formula (I), the thickness of which is less than 50 ⁇ , preferably less than 20 ⁇ , more preferably less than 10 ⁇ , for example less than 5 m and typically greater than 500 nm.
• the compound of formula (I) can in particular be BiCuOS.
• continuous layer is meant here a homogeneous deposit made on a support and covering said support, not obtained by simply depositing a dispersion of particles on the support.
• the continuous layer based on a compound of formula (I) according to this particular variant of the invention is typically placed in the vicinity of a layer of an n-type semiconductor between a hole-conducting material and a conductive material. electrons, to form a photovoltaic device for providing a photovoltaic effect.
• An n-type semiconductor in the use according to the invention may be a conductive oxide, for example ZnO, or TiO 2 , or a sulphide, for example CdS.
• layer based on the compound of formula (I) means a layer comprising the compound of formula (I), preferably at least 50% by weight, or even at least 75% by weight. % by mass.
• the continuous layer according to the second variant consists essentially of the compound of formula (I), and it typically comprises at least 95% by weight, or even at least 98% by weight, more preferably at least
• the continuous layer based on a compound of formula (I) employed according to this embodiment can take several forms:
• Variant 1 the continuous layer is a continuous layer based on a compound of formula (I) deposited on a support.
• the layer consists essentially of the layer of formula (I).
• the continuous layer can typically be obtained:
• the electrochemical deposition comprises the following steps:
• the support is immersed (as a cathode) in an electrolyte bath containing copper and bismuth ions and optionally tellurium, and a counter-electrode (as anode) and, by passage of an electric current between the two electrodes is induced deposition of an alloy based on Bi and Cu, and optionally Te, on the support;
• step (1b) the support coated with the alloy obtained at the end of step (1a) is reacted under an atmosphere containing an oxygen source, and / or a source of sulfur and / or a source of selenium.
• the thickness of the layer obtained on the support can be very easily controlled, namely, by simple modulation of the duration of the electrodeposition operation (the more the current is allowed to circulate, the greater the thickness of the layer) .
• physical deposition in particular by cathodic sputtering or magnetron sputtering:
• sputtering or magnetron sputtering deposition comprises the following steps:
• a potential difference is applied between one or more targets containing Bi and Cu and optionally tellurium, and the walls of the reactor, where a plasma created bombardes the target whose elements are ejected and condense on the support to form an alloy based on Bi and Cu, and optionally Te;
• step (2c) the support coated with the alloy obtained at the end of step (2b) is reacted under an atmosphere containing an oxygen source, and / or a source of sulfur and / or a source of selenium.
• the thickness of the layer can be controlled by the deposition time, the longer the deposition time, the greater the thickness of the layer. . by co-evaporation:
• co-evaporation deposition comprises the following steps: (3a) simultaneously evaporating under vacuum simultaneously copper and bismuth metal elements and optionally Te on a support to form an alloy based on Bi and Cu, and optionally Te;
• step (3b) the support coated with the alloy obtained at the end of step (3a) is reacted under an atmosphere containing an oxygen source, and / or a source of sulfur and / or a source of selenium.
• the thickness of the layer can be controlled by the evaporation time, ie the longer the deposition time, the greater the thickness of the layer.
• the source of sulfur, used in step (1b) or (2c) or (3b) may be chosen from sulfur, hydrogen sulphide H 2 S and its salts, an organic sulfur compound (thiol, thioether , thioamide ).
• the source of selenium used in steps (1b), (2c) and (3b) may be selected from selenium, selenium oxide or a selenium salt, for example Na 2 Se.
• the support on which the compound of formula (I) of the above-mentioned layer type according to the invention is deposited may for example be an n-type conductive or semiconductor material.
• Variant 2 the continuous layer comprises a polymer matrix and, dispersed within this matrix, particles based on a compound of formula (I), typically of dimensions less than 10 ⁇ , or even less than 5 ⁇ , especially of type of those used in the first embodiment of the invention.
• a compound of formula (I) typically of dimensions less than 10 ⁇ , or even less than 5 ⁇ , especially of type of those used in the first embodiment of the invention.
• the polymer matrix comprises a p-type conductive polymer, which may especially be chosen from polythiophene derivatives, more particularly from poly (3,4-ethylenedioxythiophene) derivatives: poly (styrenesulfonate) (PEDOT: PSS).
• polythiophene derivatives more particularly from poly (3,4-ethylenedioxythiophene) derivatives: poly (styrenesulfonate) (PEDOT: PSS).
• the particles based on the compound of formula (I) present in the polymer matrix preferably have dimensions of less than 5 ⁇ , which can in particular be determined by SEM.
• the dispersion of the particles in the polymer matrix allows a size analysis by laser granulometry, where appropriate, the average particle diameter is generally less than 5 ⁇ .
• Figure 1 is a schematic sectional representation of a photoelectrochemical cell used in Example 2 described below;
• Figure 2 is a schematic sectional representation of the photodetector device used in Example 3;
• FIG. 3 is a schematic sectional representation of the photovoltaic device used in Example 4.
• Figure 4 is a schematic sectional representation of a photovoltaic device according to the invention, not exemplified.
• FIG. 1 there is shown a photoelectrochemical cell 10 which comprises:
• a photoactive electrode 11 consisting of a support 12 based on a glass covered with a 2 cm ⁇ 1 cm ITO conductive layer on which a layer 13 of thickness of the entire surface has been deposited over the entire surface; 1 order of 1 ⁇ based on BiCuOS particles 14 prepared according to the protocol of Example 1 described below, the particles 14 BiCuOS were previously dispersed in terpineol and then deposited by coating ("Doctor Blade Coating" in English) on the conductive glass plate 1 1.
• FIG. 2 a photodetector device 20 which comprises particles 21 of BiCuOS prepared in the conditions of Example 1 described below.
• This device comprises a layer 22 FTO of thickness of the order of 500 nm on which is deposited a layer 23 of the order of 1 ⁇ thickness based on ZnO.
• the layer 24 of thickness of the order of 1 ⁇ m based on the particles 21 of BiCuOS is deposited on the surface of the layer 23 by depositing the drops from a suspension of BiCuOS at 25.degree. 30% by weight in ethanol.
• FIG 3 is shown the photovoltaic device 30 which comprises particles 31 BiCuOS prepared under the conditions of Example 1 described below.
• This device comprises a layer 32 FTO of thickness of the order of 500 nm on which is deposited a layer 33 of thickness of the order 1 ⁇ ZnO based.
• the layer 34 with a thickness of around 1 ⁇ m based on the BiCuOS particles 31 is deposited on the surface of the layer 33 by depositing the drops from a suspension of BiCuOS at 25-30% by weight in the water. ethanol.
• An electrolyte containing the torque ⁇ 2/35 serving as redox mediator is deposited by deposition of drops on the surface of the layer 34, and on which a gold layer 36 having a thickness of about 1 ⁇ being deposited by evaporation.
• FIG. 4 shows the photovoltaic device which comprises a layer 41 based on BiCuOS deposited on a layer 42 based on ZnO by coating, the layer 42 based on ZnO being prepared by the sol-gel deposition, the layer 41 with base of the BiCuOS being in contact with a layer 43 of gold and the layer 42 based on ZnO being in contact with a layer FTO 44.
• BiCuOS Contacting the BiCuOS with a n-type ZnO semiconductor forms a pn junction.
• the electrons generated go into the ZnO and the generated holes remain in the BiCuOS.
• ZnO is in contact with FTO (electron conductor) to extract the electrons and the BiCuOS is in contact with gold (conductor holes) to extract the holes.
• FTO electron conductor
• Au conductor holes
• ground oxides are introduced into a teflon jacket with 75 ml of water (milliQ quality);
• the Teflon jacket is placed in a 125 ml Parr bomb and the assembly is placed in a heating chamber;
• the temperature of the chamber is raised from 25 ° C. to 190 ° C. at a rate of 2.5 ° C./min;
• the temperature is left at 190 ° C. for 2 days;
• the system is then brought back to ambient temperature at a rate of 3 ° C./min, whereby a suspension is obtained.
• the suspension obtained is filtered, washed with 3 times 100 ml of water (MilliQ quality) then with 3 times 50 ml of a solution of 4% by weight hydrochloric acid and then washed again with 3 times 100 ml of water. water (MilliQ quality).
• the solid obtained is dried at 80 ° C. in an oven for 2 hours.
• BiCuOS powder was hydrothermally prepared by dissolving the inorganic precursors in the form of an S solution prior to the hydrothermal treatment, according to the following protocol:
• Bismuth nitrate is solubilized at 0.2 M in an aqueous solution of HN0 3 5% by weight. 50 ml of the solution obtained is slowly added in 50 ml of a solution containing 15 g of NaOH and 0.2 M of tartaric acid, whereby a solution S1 is obtained.
• the Teflon jacket is placed in a 125 ml Parr bomb and the assembly is placed in a heating chamber;
• the temperature of the chamber is raised from 25 ° C. to 240 ° C. at a rate of 2.5 ° C./min;
• the temperature is left at 240 ° C. for 2 days;
• the system is then brought back to ambient temperature at a rate of 3 ° C./min, whereby a suspension is obtained.
• the suspension obtained is filtered, washed with 3 times 100 ml of water (MilliQ quality) then with 3 times 50 ml of a solution of 4% by weight hydrochloric acid and then washed again with 3 times 100 ml of water. water (MilliQ quality).
• the mixture is then introduced into a silica tube of a volume of 200 cm 3 , the tube is evacuated and sealed, and then introduced into an oven at 550 ° C. for 2 days (calcination).
• BiCuOS of Example 1 Use of the BiCuOS of Example 1 in a photoelectrochemical device
• the device described in FIG. 1 was used, polarizing the working electrode to a potential of -0.8 V vs Ag / AgCl.
• the system is irradiated under an incandescent lamp (color temperature of 2700 K) alternating periods of darkness and periods of light.
• the intensity of the current increased when the system was placed in the light. It is a photocurrent confirming the ability of BiCuOS to generate a photocurrent.
• This photocurrent is cathodic (that is to say negative) which is consistent with the fact that BiCuOS is a p-type semiconductor.
• BiCuOS of Example 1 Use of the BiCuOS of Example 1 in a photovoltaic device
• the device described in FIG. 3 irradiated under an incandescent lamp (color temperature of 2700 K) was used.
• the redox couple ⁇ 2 / is used as a redox mediator to transport the holes.
• the counter electrode is platinum.

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• 2012
  • 2012-09-28 FR FR1202589A patent/FR2996355B1/fr not_active Expired - Fee Related
• 2013
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