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  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B82—NANOTECHNOLOGY
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  • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
  • H01L31/0352—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions
  • H01L31/035209—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions comprising a quantum structures
  • H01L31/035218—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions comprising a quantum structures the quantum structure being quantum dots
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  • B82—NANOTECHNOLOGY
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  • B82Y15/00—Nanotechnology for interacting, sensing or actuating, e.g. quantum dots as markers in protein assays or molecular motors
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B82—NANOTECHNOLOGY
  • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
  • B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B82—NANOTECHNOLOGY
  • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
  • B82Y40/00—Manufacture or treatment of nanostructures
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  • C01—INORGANIC CHEMISTRY
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  • C01P2002/00—Crystal-structural characteristics
  • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
  • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
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  • C01P2002/00—Crystal-structural characteristics
  • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
  • C01P2002/76—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by a space-group or by other symmetry indications
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2004/00—Particle morphology
  • C01P2004/01—Particle morphology depicted by an image
  • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2004/00—Particle morphology
  • C01P2004/60—Particles characterised by their size
  • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
• • 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
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S977/00—Nanotechnology
  • Y10S977/70—Nanostructure
  • Y10S977/773—Nanoparticle, i.e. structure having three dimensions of 100 nm or less
• • 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
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S977/00—Nanotechnology
  • Y10S977/84—Manufacture, treatment, or detection of nanostructure
  • Y10S977/895—Manufacture, treatment, or detection of nanostructure having step or means utilizing chemical property
  • Y10S977/896—Chemical synthesis, e.g. chemical bonding or breaking
• • 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
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S977/00—Nanotechnology
  • Y10S977/902—Specified use of nanostructure
  • Y10S977/932—Specified use of nanostructure for electronic or optoelectronic application
• • 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
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S977/00—Nanotechnology
  • Y10S977/902—Specified use of nanostructure
  • Y10S977/932—Specified use of nanostructure for electronic or optoelectronic application
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• • 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
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S977/00—Nanotechnology
  • Y10S977/902—Specified use of nanostructure
  • Y10S977/932—Specified use of nanostructure for electronic or optoelectronic application
  • Y10S977/953—Detector using nanostructure

Definitions

• the present invention relates to the field of the manufacture of antimonide nanoparticle-based materials. More particularly, it relates to a novel process for preparing nanocrystals of semiconductor antimonides, in particular indium antimonide (InSb).
• semiconductor antimonides in particular indium antimonide (InSb).
• Antimonide nanocrystals can be used in many fields, for example in the development of photovoltaic cells, light-emitting diodes, photodetectors, gas sensors, thermoelectric devices or fluorescent markers in biology.
• nanocrystals In general, semiconductor nanocrystals, crystalline particles whose dimensions are typically between a few nanometers and a few tens of nanometers, have been the subject of numerous studies. Such nanocrystals have proved particularly interesting in view of the appearance of a phenomenon of "quantum confinement" in these particles when their size is smaller than the excitonic Bohr radius. This phenomenon is reflected in particular by a significant increase in the forbidden band energy, so ranges of wavelengths that can be absorbed or emitted by the nanocrystal, compared to the solid semiconductor. By acting only on the particle size of a given semiconductor material, it is thus possible to adjust its optical properties to meet the requirements of the intended application.
• colloidal chemical synthesis advantageously enables the production, at low cost and in large quantities, of particles having a small size dispersion.
• This technique gives very satisfactory results in the case of cadmium chalcogenides (CdS, CdSe and CdTe).
• CdS, CdSe and CdTe cadmium chalcogenides
• the European RoHS directive aims to outlaw the use of such substances for the construction of electronic devices marketed in Europe after July 2006. It therefore seems essential to turn to alternative materials that do not harm the health of living organisms.
• indium antimonium is an advantageous option, given, on the one hand, its innocuousness and, on the other hand, its particularly interesting intrinsic physical properties.
• the electron mobility values obtained for indium antimonide can reach 78,000 cm 2 / Vs (against 1 450 cm 2 / Vs in solid silicon).
• Indium antimonide therefore represents a prime candidate for the development of optical devices, provided that it makes good use of the strong quantum confinement phenomenon that can be exerted in this material if the particle sizes are sufficiently small.
• the lithography technique is generally used in the shaping processes of many devices based on semiconductor materials.
• the liquid deposition methods spin- or spray-coating for example
• printing or inkjet may sometimes advantageously replace lithography.
• the different modes of synthesis used to obtain inorganic nanocrystals are based on the use of liquid or gaseous phases.
• the particles obtained are polydisperse and strongly attached to the substrate. It is therefore difficult to detach them for use in an ink.
• this method is very expensive because it uses the use of specific substrates as well as constraining experimental conditions (working under high vacuum).
• Li et al. [7] implement a reaction of this type to obtain nanocrystals of InSb and GaSb.
• the main disadvantage of this approach lies in the fact that the nanocrystals thus obtained are relatively large and highly poly-dispersed (their diameter varies between 20 and 60 nm).
• the present invention relates to a method for preparing nanoparticles of antimonide element (s) metal (s), characterized in that it implements antimony trihydride as a of antimony source.
• the antimonide nanoparticles are more particularly obtained in the form of a colloidal solution.
• antimonide is meant the combination of antimony with one or more metallic element (s).
• Said metal element may be chosen especially from aluminum (Al), gallium (Ga), indium (In), thallium (Tl), zinc (Zn), cadmium (Cd), iron (Fe) ), cobalt (Co), nickel (Ni), bismuth (Bi), scandium (Se), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), copper (Cu), rubidium (Rb), strontium (Sr), yttrium (Y), zirconium (Zr), niobium (Nb), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), cesium (Cs), barium (Ba), hafnium (Hf), iridium (Ir), platinum (Pt), gold (Au), tin (Sn), lead (Pb), and mixtures thereof.
• antimony
• source of antimony is meant the precursor capable of providing the supply of Sb atoms necessary for the growth of nanoparticles antimonide.
• Antimony trihydride (SbH 3 ) is in the form of a gas at temperatures above -17 ° C. This compound is also more commonly referred to as “stibnite”. By “antimony trihydride” is meant for the purposes of the invention the compound in gaseous form.
• nanoparticle in particular, a particle of the nanocrystal type.
• the antimony trihydride may be more particularly formed and injected as it is formed, in a liquid medium, hereinafter referred to as a reaction medium, comprising at least one precursor of an element metal of which it is desired to form the antimonide.
• the antimonide nanoparticles obtained by the process of the invention have the desired characteristics, in particular in terms of composition, crystallinity, size dispersion and photoluminescence, for their integration into optoelectronic devices.
• the nanoparticles obtained according to the invention can be isolated, in other words they are not trapped in a matrix or attached to a substrate, which advantageously allows their implementation by a liquid route or else in an ink for inkjet in the development of optoelectronic devices.
• Such nanoparticles can thus be used in solar cells, in photodetectors, light converters, light-emitting diodes, transistors, as fluorescent markers or in chemical or optical sensors.
• the method of the invention makes it possible to produce discrete and globally spherical antimonide nanoparticles whose average diameter is preferably less than or equal to 30 nm.
• discrete particles is intended to denote particles that are not aggregated with each other, that is to say non-agglomerated and that can be isolated individually.
• the present invention relates to metal antimonide nanoparticles (s) that can be obtained according to the method of the invention.
• the nanoparticles may more particularly be used in the form of a colloidal solution in a solvent, in particular in an apolar solvent, such as, for example, hexane, toluene or chloroform.
• apolar solvent such as, for example, hexane, toluene or chloroform.
• the colloidal solutions formed from the nanoparticles of the invention have good stability properties.
• the present invention relates to a colloidal solution of indium antimonide nanoparticles, comprising nanocrystals crystallized according to the Ino i5 Sbo cubic phase, and nanocrystals crystallized according to the Ino phase i4 Sbo, 6, with said nanoparticles having a dispersion in size less than 30%.
• the present invention relates to a colloidal solution of nanoparticles obtained by suspending the nanoparticles as defined above in a solvent. According to yet another of its aspects, the present invention aims at the use of these nanoparticles or a colloidal solution as defined above in solar cells, photodetectors, light converters, light emitting diodes, transistors , as fluorescent markers or in chemical or optical sensors.
• the method of the invention is more particularly aimed at the formation of antimonide nanoparticles whose metallic element is chosen from aluminum (Al), gallium (Ga), indium (In), thallium (Tl), zinc (Zn), cadmium (Cd), iron (Fe), cobalt (Co), nickel (Ni), bismuth (Bi), scandium (Se), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), copper (Cu), rubidium (Rb), strontium (Sr), yttrium (Y), zirconium (Zr), niobium ( Nb), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), cesium (Cs), barium (Ba), hafhium (Hf), iridium ( Ir), platinum (Pt), gold (Au), tin (Sn), lead (Pb), and mixtures thereof.
• metallic element is chosen from aluminum
• the method of the invention allows the formation of antimonide nanoparticles whose metal element (s) is (are) chosen from aluminum, gallium , indium, thallium and mixtures thereof.
• the method of the invention makes it possible to form nanoparticles of indium antimonide (InSb).
• InSb indium antimonide
• the method of the invention more particularly comprises at least one step of placing antimony trihydride in contact with at least one precursor of a metal element under conditions conducive to the formation of said nanoparticles.
• the method of the invention comprises at least the steps of:
• reaction medium comprising at least one precursor of a metallic element whose antimonide and at least one solvent are to be formed
• Step (ii) more particularly comprises the injection of antimony trihydride into said reaction medium.
• Said precursor of the metal element may be the complex of said metal element with a fatty acid, in particular having a linear or branched carbon chain, saturated or unsaturated, having between 4 and 36 carbon atoms, preferably an alkyl chain linear comprising between 12 and 18 carbon atoms.
• Said fatty acid may be more particularly chosen from lauric acid, myristic acid, palmitic acid, stearic acid and oleic acid.
• an indium precursor may be indium myristate.
• said precursor of the metal element can be formed beforehand by reaction in a solvent, in particular under a primary vacuum, of an organic or inorganic salt of said metal element with a fatty acid with a chain linear or branched carbonaceous, saturated or unsaturated, having between 4 and 36 carbon atoms, preferably a linear alkyl chain having between 12 and 18 carbon atoms.
• organic or inorganic salt of said metal element is chosen in accordance with the general knowledge of those skilled in the art, and typically, for example, from acetates, acetylacetonates or metal halides.
• the solvent is an organic compound having a boiling point greater than 150 ° C., in particular chosen from saturated or unsaturated hydrocarbons, such as 1-octadecene.
• the precursor of the metal element may be present in a proportion of 1 to 100 millimoles per liter in the reaction medium.
• the formation reaction of said precursor of the metal element from the mixture of the salt of said metal element and the fatty acid may be more particularly carried out at a temperature ranging from 25 to 200 ° C., under vacuum or at ambient pressure.
• indium myristate can be obtained by reaction of indium acetate (In (Ac) 3 ) and myristic acid, in particular at a temperature of 220 ° C. under argon for fifteen minutes. minutes.
• the fatty acid or acids may be present in a proportion of 1 to 6 molar equivalents, relative to the organic or inorganic salt of the metal element.
• Said metal precursor may be generated, within the reaction medium, prior to the step (ii) of introduction of antimony trihydride.
• the reaction medium may further comprise one or more co-ligands.
• the presence of one or more co-ligands makes it possible to influence the size of the nanoparticles or to reduce their size dispersion.
• the said co-ligand (s) may be more particularly chosen from amines, in particular octylamine, decylamine, dodecylamine, tetradecylamine, hexadecylamine or oleylamine. Preferably, it is dodecylamine.
• the said co-ligand (s) may be present in the reaction medium in a proportion of 1 to 6 molar equivalents relative to the precursor of the metal element.
• the antimony trihydride can be produced from an aqueous solution of acidic pH (less than 7) of potassium tartrate and antimony, and potassium borohydride.
• the antimony trihydride can be generated by adding an acidic pH solution, for example sulfuric acid, with a mixture of tartrate of potassium and antimony and potassium borohydride, maintained at basic pH for example in a solution of potassium hydroxide.
• an acidic pH solution for example sulfuric acid
• a mixture of tartrate of potassium and antimony and potassium borohydride maintained at basic pH for example in a solution of potassium hydroxide.
• antimony trihydride is carried out under an inert atmosphere, for example under an argon or nitrogen atmosphere.
• antimony trihydride It is of course up to those skilled in the art to adjust the experimental conditions to form antimony trihydride.
• An example of a method for producing antimony trihydride is presented in the following examples.
• the antimony trihydride is formed simultaneously with its use in step (ii).
• the process of the invention may comprise the injection of antimony trihydride into the reaction medium as described above.
• the antimony trihydride is formed, for example according to the method described above, simultaneously with its introduction into said reaction medium.
• the method of the invention may thus comprise the following steps:
• step (b) contacting the antimony trihydride formed in step (a) with said reaction medium comprising at least one precursor of said metallic element, under conditions conducive to the formation of the antimonide nanoparticles,
• the antimony trihydride is introduced, as it is formed, into the reaction medium.
• a suitable installation as described in the following text and illustrated by the experimental setup of Figure 1.
• the reaction medium is maintained at a temperature T 2 ranging from 140 to 250 ° C., preferably from 150 ° C. to 220 ° C., throughout the duration of formation of the antimonide nanoparticles.
• the reaction medium is maintained under an inert atmosphere, for example under an argon atmosphere, for the entire duration of formation of the antimonide nanoparticles.
• the antimonide nanoparticles are more particularly obtained in the form of a colloidal solution of nanoparticles.
• the method may include one or more subsequent steps of washing and / or purifying the nanoparticles.
• the method of the invention may comprise a subsequent thermal annealing step of the nanoparticles. This annealing step makes it possible to increase the crystallinity of the nanoparticles formed.
• This annealing can be carried out at a temperature T 3 ranging from 200 to 300 ° C., in particular around 220 ° C., in particular under an inert atmosphere. It can be operated for a period ranging from 30 minutes to 4 hours, in particular for about 1 hour.
• the annealing is carried out in situ, so as to avoid bringing the solution into contact with the ambient air.
• the average diameter of the antimonide nanoparticles obtained may be between 2 and 150 nm, in particular between 5 and 85 nm.
• the average diameter can be evaluated by scanning electron scanning (STEM).
• the antimonide nanoparticles obtained according to the process of the invention have an average diameter less than or equal to 30 nm, preferably less than or equal to 20 nm.
• the nanoparticles obtained have a good dispersion in size, especially less than or equal to 30%, preferably less than or equal to 20%.
• the nanoparticles may have a dispersion in size ranging from 20 to 30%.
• the size dispersion can be evaluated by nanocrystal analysis by STEM.
• the antimonide nanoparticles obtained can be suspended in a solvent, in particular in an apolar solvent, such as, for example, hexane, toluene or chloroform, to form a stable colloidal solution.
• a solvent such as, for example, hexane, toluene or chloroform
• the method of the invention can be implemented using a suitable antimonide nanoparticle production facility, comprising at least:
• reaction medium comprising at least one precursor of the metal element whose antimonide is to be formed
• said first and second containers being connected by a fluid communication channel, adapted to ensure the passage of the antimony trihydride from the first vessel into the reaction medium of the second vessel.
• Figure 1 shows an experimental laboratory setup.
• This assembly is composed more particularly of a first flask (1) in which is formed the reaction medium including in particular said metal precursor, a second flask (2) in which is formed antimony trihydride, and a pipe (3) connecting the two balloons, and allowing the injection of the antimony trihydride generated from the balloon (2) to the balloon (1).
• the assembly assembly is maintained, during the implementation of the process of the invention, under an inert atmosphere, in particular under argon or nitrogen atmosphere.
• Figure 1 Diagram of an assembly used for the formation of antimonide nanoparticles.
• Figure 3 STEM image of InSb nanoparticles obtained according to the protocol described in Example 2.1. after purification and HRTEM cliché (box) of an isolated indium antimonide nanoparticle.
• FIG. 4 STEM image of the nanoparticles of InSb obtained according to the protocol described in example 2.2. after purification;
• Figure 5 Diagram of the assembly used for the formation of indium antimonide nanoparticles as an example 2.3. ;
• FIG. 6 STEM plate (FIG. 6.a) and histogram of the size dispersion (FIG. 6.b) of the InSb nanoparticles obtained according to the protocol described in example 2.3; HRTEM ( Figure 6.c) and Fourier transform (Figure 6.d) of an isolated nanoparticle.
• reaction medium 1st part of the assembly: reaction medium
• a first assembly is formed of the tricol (1) in which the reaction medium is previously prepared at the temperature Ti (80 ° C) under an inert atmosphere.
• the flask is connected to a water cooler, itself connected to a vacuum ramp arranged under a extractor hood. These operations are carried out in such a way that the reaction medium remains under an inert atmosphere during the entire process (Schlenk technique). Unused neck passes are sealed with septa.
• the upper end of the refrigerant is connected to a trap (4) containing an aqueous solution of silver nitrate (AgNO 3 ) (concentration 3 ⁇ 10 -2 mol / L) to neutralize the molecules of SbH 3 which does not have not reacted during the growth of nanocrystals.
• AgNO 3 silver nitrate
• inert gas argon
• T 2 140-250 ° C.
• the central neck of a second tricolor (2) in which the antimony trihydride will be produced, is connected to a desiccant column (6) containing a few grams of phosphorus pentoxide powder (P 2 0 5 ).
• Another neck of the balloon (2) is then connected to the vacuum ramp to establish a circulation of inert gas (argon) in the assembly, while the last mouth of the tricol has been closed by a septum.
• the top of the desiccant column is connected to the tricolor (1) via a pipe (3) terminated by a metal needle which we will take care to plunge into the reaction medium through one of the two free septa of the tricolor (1).
• the antimony trihydride thus produced, dried and then conveyed to the flask (1) will be dissociated in the reaction medium, resulting in the germination and then the growth of the antimonide nanocrystals of the element M.
• the excess of gas will be neutralized by reaction with silver nitrate in the trapping device (4) at the outlet of the refrigerant.
• the mixture is first agitated and inert, then heated to about 80 ° C under primary vacuum for about one hour to allow it to degass. After reestablishing the argon circulation, the solution is heated at 220 ° C for about fifteen minutes to form the indium precursor (indium myristate). The solution contained in the flask (1) is then brought to a temperature of 155 ° C.
• the tricolor (2) is in turn placed under an inert atmosphere and about 3 mL of sulfuric acid solution 1 mol / L previously degassed are introduced therein. 1.5 ml of solution (also degassed) of potassium hydroxide (KOH) at 0.8 mol / l are then added to the glass vial (a) already containing 0.15 mmol of potassium tartrate and antimony (APT) . After complete dissolution (an ultrasonic bath can advantageously accelerate the process), the mixture is transferred to the vial (b) in which 0.23 mmol of potassium borohydride (KBH 4 ) has been deposited. Everything is then injected as quickly as possible into the flask (2) in order to begin the production of SbH 3 .
• the pH of the mixture prepared in the bottle (b), initially basic, is in contact with the acid contained in the flask (2) brought to a value of less than 7. This has the effect of initiating the reaction between the powders APT and KBH 4 and start, with stirring, the production of antimony trihydride.
• the translucent solution contained in the flask (2) then rapidly turns black. During the first minutes of synthesis, the initially colorless reaction medium contained in the flask (1) quickly becomes pale yellow. The color then turns in a few minutes to dark yellow then to black-brown, a sign of the growth of nanocrystals. After a quarter of an hour after the start of production of antimony trihydride, the gas injection needle is removed from the tricolor (1) and immersed in a trap containing a silver nitrate solution .
• the nanocrystals thus obtained are annealed at 220 ° C. for forty-five minutes.
• the mixture is then rapidly cooled to 70-80 ° C and then injected into a vessel containing about 5 mL of toluene to prevent solidification of the dodecylamine (mp 27-29 ° C).
• EDX Energy dispersive analysis
• the diffractogram X (FIG. 2, curve a) is produced on a deposit of these purified nanocrystals and deposited on a disoriented silicon substrate. This diffractogram was recorded by a Philips X'Pert device with a cobalt source operating at 50 kV and 35 mA.
• the diffractogram X obtained has peaks corresponding to a structure "zinc zinc" identical to that of solid indium antimonide (JCPDS card No. 04-001-0014). Other peaks, less intense, would appear to come from a slightly richer cubic crystalline phase of antimony type Ino i4 Sbo, 6 (JCPDS map No. 01-074-5940), marked with asterisks (*) on Figure 2.
• the high-resolution transmission electron microscopy (HRTEM) (JEOL 4000EX, used at 400 kV) of an isolated nanocrystal (box, FIG. 3) confirms that the nanocrystals obtained are well crystallized.
• the atomic planes can indeed be distinguished there.
• the mixture is first stirred and inert, and then heated under vacuum at 80 ° C for about two hours to allow it to degass.
• the indium precursor indium myristate
• the solution contained in the flask (1) is then raised to a temperature of 215 ° C.
• the tricolor (2) is in turn put under an inert atmosphere and about 2 mL of sulfuric acid solution 1 mol / L degassed before are introduced therein. 1 ml of solution (also degassed) of potassium hydroxide (KOH) at 0.8 mol / l are then added to the glass vial (a) already containing 0.1 mmol of potassium tartrate and antimony (APT). After complete dissolution (an ultrasonic bath can advantageously accelerate the process), the mixture is transferred to the vial (b) in which 0.15 mmol of potassium borohydride (KBH 4 ) was deposited. Everything is then injected as quickly as possible into the flask (2) in order to begin the production of SbH 3 .
• KOH potassium hydroxide
• the coloration of the initially translucent reaction medium turns black in a few seconds.
• the gas injection needle is removed from the tricolor (1) and immersed in a trap containing a solution of silver nitrate. The mixture is then rapidly cooled to 70-80 ° C, and then injected into a vessel containing about 10 mL of toluene to prevent solidification of the dodecylamine (mp 27-29 ° C).
• the diffractogram X (FIG. 2, curve b) produced on a deposit of these same nanocrystals comprises peaks corresponding to a "zinc blende" structure identical to that of solid indium antimonide (JCPDS card No. 04 -001 to 0014). Other peaks, less intense, would seem to come from a cubic crystalline phase slightly richer in antimony type Ino i4 Sbo, 6 (JCPDS card No. 01-074-5940).
• the STEM shows that the particles have an average diameter of 85 nm, with a size dispersion of about 20%.
• the protocol implemented from the assembly described in FIG. 5, is as follows.
• the mixture is first agitated and inert, then heated to about 80 ° C under primary vacuum for about one hour to allow it to degass. After reestablishing the circulation of argon, the solution is heated to 220 ° C for about fifteen minutes to form the indium precursor (indium myristate). The solution contained in the flask (1) is then brought to a temperature of 165 ° C.
• the tricolor (2) is in turn placed under an inert atmosphere and about 6 mL of sulfuric acid solution 1 mol / L previously degassed are introduced therein. 3 ml of solution (also degassed) of potassium hydroxide (KOH) at 0.8 mol / l are then added to the glass vial (a) already containing 0.28 mmol of potassium tartrate and antimony (APT). After complete dissolution (an ultrasonic bath can advantageously accelerate the process), the mixture is transferred to the vial (b) in which 0.42 mmol of potassium borohydride (KBH 4 ) has been deposited. After closing valves RI and R2, the whole is then injected into the balloon (2) to begin the production of SbH 3 .
• KOH potassium hydroxide
• the pH of the mixture prepared in the bottle (b), initially basic, is in contact with the acid contained in the flask (2) brought to a value of less than 7. This has the effect of initiating the reaction between the powders APT and KBH 4 and start, with stirring, the production of antimony trihydride.
• the translucent solution contained in the flask (2) then rapidly turns black. After about a minute, the valves R1 and R2 are simultaneously open to allow the free flow of gas to the balloon (1).
• the initially colorless reaction medium contained in the flask (1) quickly becomes pale yellow. The color then turns in a few minutes to dark yellow then to black-brown, a sign of the growth of nanocrystals.
• the valves R1 and R2 are simultaneously closed. The gas injection needle is removed from the tricolor (1) and immersed in a trap containing a silver nitrate solution.
• the nanocrystals thus obtained are annealed at 220 ° C. for forty-five minutes.
• the mixture is then rapidly cooled to 70-80 ° C, and then injected into a vessel containing about 5 mL of toluene to prevent solidification of the dodecylamine.
• the scanning electron microscopy (STEM) image (Cari Zeiss Ultra 55+) (FIG. 6. a) shows that the particles have an average diameter of 9 nm, with a dispersion in size of less than 15% (FIG. .b).

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