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Definitions

• the present invention relates to the field of inorganic semiconductor compounds, in particular 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
• 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, or at a very low level, 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, even not to use this type of anions.
• One of the objects of the present invention is a new material comprising at least one compound of formula (I):
• M is a member or a mixture of elements selected from the group (A) consisting of Pb, Sn, Hg, Ca, Sr, Ba, Sb, In, Tl, Mg, rare earths,
• M ' is a member or a mixture of elements selected from the group (B) consisting of Ag, Ti, V, Cr, Mn, Fe, Co, Ni, Zn, Ga, Mg, Al, Cd,
• x, y and z are numbers less than 1, in particular less than 0.6, especially less than 0.5, for example less than 0.2,
• the elements M, M 'and M are generally substitution elements occupying respectively the place of the element Bi, of the element Cu and S element.
• material comprising at least one compound of formula (I) is meant a solid, generally in divided form (powder, dispersion) or in the form of a coating or a continuous or discontinuous layer on a support, and which comprises, or even consists of, a compound of formula (I).
• Ring earth means the elements of the group constituted by yttrium and scandium and the elements of the periodic classification of atomic number inclusive between 57 and 71.
• the element M may preferably be chosen from Sb, Pb, Ba and rare earth elements.
• the element M may for example be lutetium.
• the element M ' may preferably be chosen from the elements Ag, Zn, Mn.
• the element M ' may for example be the element Ag.
• the element M can in particular be the element I.
• the compound of formula (I) according to the invention corresponds to the following formula: Bi 1-x M x Cui - £ OS (l a), where x ⁇ 0, ⁇ is a number null or non-zero and M is an element or a mixture of elements selected from the group (A) consisting of Pb, Sn, Hg, Ca, Sr, Ba, Sb, In, Tl, Mg, rare earths.
• M is an element or a mixture of elements chosen from rare earths.
• the compound of formula (I) according to the invention corresponds to the following formula: -Y- BiCui £ M 'y OS (l b), where y ⁇ 0, ⁇ is a number zero or non-zero and M 'is a member or a mixture of elements selected from the group (B) consisting of Ag, Ti, V, Cr, Mn, Fe, Co, Ni, Zn, Ga, Mg, Al, Cd.
• M ' is an element or a mixture of elements chosen from the Ag and Zn elements.
• the compound of formula (I) according to the invention corresponds to the following formula: M z BiCuOS "1-z (l c), where z ⁇ 0, ⁇ is a number zero or non-zero and M" is a halogen.
• the invention also relates to different access routes to the material according to the invention.
• the subject of the invention is a first process for preparing the material according to the invention comprising a step of solid grinding of a mixture comprising at least inorganic compounds of bismuth and copper, and optionally at least one oxide, sulfide, oxysulfide, halide or oxyhalide of at least one element selected from Bi and the elements of group (A) consisting of Pb, Sn, Hg, Ca, Sr, Ba, Sb, In, Tl, Mg, the earths rare, and
• group (B) consisting of Ag, Ti, V, Cr, Mn, Fe, Co, Ni, Zn, Ga, Mg, Al, Cd.
• a solid form mixture comprising at least inorganic compounds of bismuth and copper is ground.
• the inorganic compounds of bismuth and copper present in the mixture are at least the compounds Bi 2 O 3 , Bi 2 S 3 and Cu 2 S.
• This grinding can be done according to any known means.
• This mixture can in particular be placed in an agate mortar.
• the grinding may for example be carried out with a planetary mill.
• grinding balls which consist for example of stainless steel balls, special chromium steel balls, agate balls, tungsten carbide balls , balls made of zirconium oxide.
• the grinding time can be adjusted according to the desired product. It may especially be between 20 minutes and 96 hours, in particular between 1 hour and 72 hours.
• the particle sizes referred to here can typically be measured by scanning electron microscopy (SEM).
• the subject of the invention is a second method for preparing the material according to the invention by carrying out a precipitation reaction comprising the following steps:
• step (e) filtration, and washing if necessary, of the compound of formula (I) obtained at the end of step (d).
• This method consists in carrying out a precipitation reaction by using soluble metal precursors in order to obtain a homogeneous mixture of the substitution elements in the material comprising the compound of formula (I).
• the different precursor solutions are prepared separately and then mixed together, whereby a homogeneous mixture and submicron particle sizes are obtained.
• the precipitation can be carried out by raising the temperature in particular to obtain a better crystallization.
• a precipitation can be carried out as follows: (a) - (b) providing a solution of the soluble metal precursors.
• a basic pH solution can be prepared in which:
• the elements Bi and of the group (A) are stabilized by complexation with a highly complexing polycarboxylate anion such as citrate, lactate, tartrate ...
• the copper is stabilized in the form of copper (I) by adding an excess of reducing agent (such as, for example, sodium thiosulfate, hydrazine, etc.),
• reducing agent such as, for example, sodium thiosulfate, hydrazine, etc.
• the copper and the elements of the group (B) can be kept soluble in basic medium either by the action of the basic pH (Al, Zn) or stabilized in basic medium by addition of ligands complexing the ion such as amine ligands (ammonia ethylene diamine, organic amine ).
• the subject of the invention is a third method for preparing the material according to the invention, comprising the following steps:
• a deagglomeration step can be carried out, for example, by means of an ultrasound probe.
• the inorganic bismuth and copper compounds provided in the mixture of step (a ') are at least Bi 2 O 3 and Cu 2 O.
• step (b') is advantageously carried out in the presence of a source of oxygen, such as water, nitrates or even carbonates.
• the source of sulfur employed in step (a ') may be chosen from sulfur, hydrogen sulphide H 2 S and its salts, an organic sulfur compound (thiol, thioether, thioamide, etc.), preferably a anhydrous or hydrated sodium sulphide.
• the oxides in the dispersed state are employed in step (a ') in the form of particles, typically in the form of powders, having a particle size of less than 10 ⁇ , in particular lower than at 5 ⁇ , preferably less than 1 ⁇ .
• This particle size can for example be obtained by prior grinding of the oxides (separately, or more advantageously in the case of oxide mixtures, this grinding can be carried out on the oxide mixture), for example, using a Micronizer type device or wet ball mill.
• step (b ') the dissolution is carried out in "hydrothermal conditions".
• hydrothermal conditions in the sense of the present description is meant that the step is conducted at a temperature above 180 ° C under the saturated vapor pressure of water.
• the temperature of step (b ') may be less than 240 ° C, or even less than 210 ° C, for example between 180 ° C and 200 ° C.
• step (b ') can be carried out without preliminary grinding, in which case it is however preferable to carry out the step at a temperature greater than 240 ° C., preferably greater than 250 ° C.
• step (b ') the mixture is placed in water at a temperature below the hydrothermal conditions (typically at a temperature at room temperature and under atmospheric pressure), then the temperature is slowly raised, advantageously at a rate of less than 10 ° C./min, for example between 0.5 and 5 ° C./min, typically 2.5 ° C./min, in typically operating in a closed environment (using a device such as a hydrothermal bomb, in particular a Parr bomb) until the operating temperature is reached.
• a temperature below the hydrothermal conditions typically at a temperature at room temperature and under atmospheric pressure
• the temperature is slowly raised, advantageously at a rate of less than 10 ° C./min, for example between 0.5 and 5 ° C./min, typically 2.5 ° C./min, in typically operating in a closed environment (using a device such as a hydrothermal bomb, in particular a Parr bomb) until the operating temperature is reached.
• step (b ') 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).
• the temperature is maintained at at least 190 ° C for at least 12 hours, for example for 48 hours, or even 7 days.
• the solution obtained is, in step (c), typically reduced to an ambient temperature or more generally to a temperature of between 10 and 30 ° C. cooling, for example by decreasing the temperature by at least 1 ° C / min, preferably by a faster cooling, with a reduction typically of at least 3 ° C / min, for example from 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 material according to the invention is obtained by the first solid grinding process described above.
• the present invention further relates to the use of a material comprising at least one compound of formula (I):
• M is a member or a mixture of elements selected from the group (A) consisting of Pb, Sn, Hg, Ca, Sr, Ba, Sb, In, Tl, Mg, rare earths,
• M ' is an element or a mixture of elements selected from group (B) consisting of by Ag, Ti, V, Cr, Mn, Fe, Co, Ni, Zn, Ga, Mg, Al, Cd,
• x, y and z are numbers less than 1, in particular less than 0.6, especially less than 0.5, for example less than 0.2,
• the compound that is present in the semiconductor material is a substituted inorganic material, in particular of the p type.
• substitutions such as the substitution of the element Bi by rare earths or by the element Sb or alternatively the substitution of the element Cu by the element Ag
• these substitutions can, in particular by modifying the parameters and / or by changing the extension of the orbitals and their energy position, thus causing changes in the gap (valence band - conduction band).
• the aliovalent substitutions modify the degree of oxidation of the element Cu.
• the introduction of substituents in the structure of the semiconductor may, as the case may be, cause a reduction or an increase in the number of charge carriers.
• the substituted materials may in particular have a higher conductivity, which induces an improved conduction capacity, compared to its unsubstituted form, or conversely a lower conductivity.
• the inventors have now demonstrated that the materials corresponding to the above formula (I), in particular, when they are p-type, are capable of providing a photocurrent when they are irradiated under a wavelength greater than their gap (namely 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” (Ie the electron gap) being free to move to generate a current).
• the inventors have now demonstrated that the materials of the invention prove to be suitable for ensuring a photovoltaic effect.
• 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, which is also specifically of the p type, in contact with a semiconductor n-type between two electrodes, in direct contact 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.
• a material based on a semiconductor of formula (I) above which is also specifically of the p type, in contact with a semiconductor n-type between two electrodes, in direct contact 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.
• an additional coating for example a charge collection coating
• the present invention relates to photovoltaic devices comprising, between a hole-conducting material and an electron-conducting material, a layer based on a compound of formula (I) of type p 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 n-type semiconductor layer is in proximity to 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 electrical 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 ZnS.
• the hole-conducting material used in the photovoltaic devices according to the invention may be, for example, a suitable metal, such as gold, tungsten, or molybdenum; or a metal deposited on a support, or in contact with an electrolyte, 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 suitable metal such as gold, tungsten, or molybdenum
• Pt / FTO platinum deposited
• 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 at least one material. partially transparent that allows to pass the electromagnetic radiation used.
• 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
• n-type conductor n-type conductor.
• the layer based on an n-type semiconductor which is in contact with the layer based on a compound of formula (I) of type p 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) employed 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 ⁇ , preferentially 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 ⁇ .
• These particles are preferably obtained according to one of the preparation methods of the invention.
• 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 typically having dimensions remaining less than 5 ⁇ . , (preferably less than 1 ⁇ , more preferably less than 500 nm), with a thickness which 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 of formula (I) p type according to the invention can thus, for example play the role of a photoactive electrode for a photoelectrochemical device that 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:
• the electrochemical device can comprise:
• 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 conductor and will enter the external electrical circuit.
• 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 an average diameter such as as measured by laser granulometry (for example, by means of a Malvern type laser particle size)
• 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.
• 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 ⁇ and typically greater than 500 nm.
• 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 p-type compound of formula (I) according to this particular variant of the invention is typically placed in the vicinity of a n-type semiconductor layer between a hole conductive material. and an electron conducting material for forming 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 ZnS.
• 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 typically comprises at least 95% by weight, or even at least 98% by weight, more preferably at least 99% by weight. by mass of the compound of formula (I).
• the continuous layer based on a compound of formula (I) employed according to this embodiment can take several forms.
• the continuous layer may in particular comprise 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 the 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 the 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.
• Figure 1 is a schematic sectional representation of a photoelectrochemical cell used in Example 4 described below;
• FIG. 2 is a diagrammatic representation in section of a photodetector device
• Figure 3 is a schematic sectional representation of a photovoltaic device
• FIG. 4 is a schematic sectional representation of a photovoltaic device according to the invention, not exemplified.
• 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 ⁇ m particle-based order 14 of a compound of formula (I) according to the invention, the particles 14 were previously dispersed in terpineol and then deposited by coating ("Doctor Blade Coating" in English) on the conductive glass plate 1 1.
• the three electrodes 11, 15 and 16 are immersed in an electrolyte 17 of KCI at 1 M.
• the three electrodes are connected by a potentiostat 18.
• FIG. 2 a photodetector device 20 which comprises particles 21 of a compound of formula (I) according to the invention.
• This device comprises a layer 22 FTO of thickness of the order of 500 nm on which is electrodeposited a layer 23 of thickness of order 1 ⁇ ZnO based.
• the layer 24 with a thickness of the order of 1 ⁇ based on the particles 21 of a compound of formula (I) according to the invention is deposited on the surface of the layer 23 by depositing drops from a suspension of particles of a compound of formula (I) according to the invention at 25-30% by weight in ethanol.
• FIG. 3 is shown the photovoltaic device 30 which comprises particles 31 of a compound of formula (I) according to the invention.
• This device comprises a layer 32 FTO of thickness of the order of 500 nm on which is electrodeposited a layer 33 of thickness of order 1 ⁇ ZnO based.
• the layer 34 of thickness of about 1 m based on the particles 31 of a compound of formula (I) according to the invention is deposited on the surface of the layer 33 by depositing the drops from a suspension of particles of formula (I) according to the invention at 25-30% by weight in ethanol.
• FIG. 4 shows photovoltaic device 40 which comprises a layer 41 based on particles of a compound of formula (I) according to the invention deposited on a layer 42 based on ZnO by coating, layer 42 based on ZnO being prepared by the sol-gel deposition, the layer 41 being in contact with a layer 43 of gold and the layer 42 based on the ZnO being in contact with an FTO layer 44.
• a compound of formula (I) according to the invention Contacting a compound of formula (I) according to the invention with a n-type ZnO semiconductor forms a pn junction.
• the electrons generated go into the ZnO and the holes generated remain in the compound of formula (I) according to the invention.
• ZnO is in contact with FTO (electron conductor) to extract the electrons and the compound of formula (I) according to the invention is in contact with gold (conductor holes) to extract the holes.
• FTO electron conductor
• gold conductor holes
• a powder of BiCuo.sAgo.sOS was prepared by reactive grinding at room temperature, according to the following protocol:
• the mortar is then covered and placed in a Fritsch No. 6 planetary mill with a rotation speed of the order of 500 rpm. The grinding is continued for 120 min until a pure phase is obtained.
• a powder of BiCuOSo.slo.s was prepared by reactive grinding at room temperature, according to the following protocol:
• a powder of BiCu 0.7 Zn 0.3 OS was prepared by reactive grinding at room temperature, according to the following protocol:
• the mortar is then covered and placed in a Fritsch type planetary mill
• the mixture is heated moderately (50 ° C) for four hours. A colorless solution is obtained. It is preferable to use closed containers to avoid the oxidation of copper (I).
• the cation solution (Bi, Cu, Zn) is added to the Na 2 S solution. A black precipitate forms immediately. The solution is stirred at 90 ° C for four hours. It is then filtered, washed with distilled water and dried at 80 ° C. in an oven.
• the device described in FIG. 1 was used, polarizing the working electrode at a potential of -0.8 V vs. Ag / AgCl.
• the system is irradiated under an incandescent lamp (whose color temperature is 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 each of the compounds Ci to C 3 to generate a photocurrent.
• This photocurrent is cathodic (i.e., negative) which is consistent with the fact that each of these compounds C 1 to C 3 is a p-type semiconductor.

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• 2014
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