WO2012163976A1 - Procédé continu de synthèse de nanoparticules semi-conductrices ternaires ou quaternaires à base des éléments ib, iiia, via de la classification périodique - Google Patents

Procédé continu de synthèse de nanoparticules semi-conductrices ternaires ou quaternaires à base des éléments ib, iiia, via de la classification périodique Download PDF

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WO2012163976A1
WO2012163976A1 PCT/EP2012/060167 EP2012060167W WO2012163976A1 WO 2012163976 A1 WO2012163976 A1 WO 2012163976A1 EP 2012060167 W EP2012060167 W EP 2012060167W WO 2012163976 A1 WO2012163976 A1 WO 2012163976A1
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micro
temperature
nanoparticles
synthesis mixture
synthesis
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Frank Rauscher
Min FU
Leslaw Mleczko
Werner Hoheisel
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Bayer Intellectual Property GmbH
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    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
    • C30B7/08—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by cooling of the solution
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G1/00—Methods of preparing compounds of metals not covered by subclasses C01B, C01C, C01D, or C01F, in general
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G15/00—Compounds of gallium, indium or thallium
    • C01G15/006—Compounds containing gallium, indium or thallium, with or without oxygen or hydrogen, and containing two or more other elements
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/46—Sulfur-, selenium- or tellurium-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • 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
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
    • 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

Definitions

  • the present invention is related to a process for continuous production of ternary or quaternary semiconducting nanoparticles based on IB, ill A, VIA elements of the periodic classification, in particular low-toxic AgInS2 and CuInSi in the liquid phase.
  • nano-material science has become an indispensable important field in the current material science development.
  • the progress of nano -material researches is bound to push physics, chemistry, biology and many other disciplines to a new level, and at the same time, also brings new opportunities in technological researches in 21st century.
  • solar cells With a growing urgency of the energy issues, solar cells as a renewable, clean energy has attracted worldwide attention.
  • Applying nano- material and technology to the solar cells might greatly increase the conversion efficiency of the current solar cells, lower the production cost of the solar ceils, and promote the development of new types of solar cells. Under such circumstances, the development of nano-material to be used in solar cells is becoming a new challenge.
  • Semiconducting nanoparticles are characterized by a quantum confinement of both the electron and hole in all three dimensions, which leads to an increase in the effective band gap of the material and shift both the optical absorption and emission of semiconducting nanoparticles depending on nanoparticle size: larger sized particles show smaller band gap and smaller particles show larger band gap wherein for a larger band gap a. nanoparticle size of 1 to 20 nm is usually preferred. These nanoparticles can be applied in the fields of printable electronics, functional polymer films, bio-diagnose, energy supply (e.g. solar ceils), energy storage, advanced displays applications.
  • energy supply e.g. solar ceils
  • the nanoscaie semiconductors have been synthesized both in gas phase and liquid phase processes.
  • the liquid phase synthesis is easier to realize in large scale production.
  • the liquid process can be either conducted as a batch or a continuous process. Discontinuous processes have been studied most extensively.
  • CN101054198A describes preparation of CuInS2 nanoparticles by solvothermal method in an autoclave.
  • copper salt, indium salt, sul fur source and an alkylamine were dispersed in the solvent to prepare the reaction precursor, which was heated for 12-24 hours to produce CuInS2 nanocrystal with 13-17nm in size.
  • This process is uneconomic and difficult to scale up because of long reaction time.
  • pressure is used in the system which means high requirement for used equipment.
  • the particle size is also comparably too large to exhibit the quantum confinement necessary for adequate luminescence which limits applications in solar cell or other photoeiectron devices.
  • Nairn et ai describes a single-source precursor ([(TOP)2CuIn(SR)4] (TOP ) (octyl)sP; R alky! ) decomposition method by UV light to synthesize CuInS2 NPs and yields organic soluble 2 nm nanoparticles with narrow size distribution [Nano Lett., 2006, 6, 1218-1223].
  • Lau et ai [Chem. Mater. 2003, 15, 3142-3147; J. Phys. Chem.
  • DEI 02006055218 describes a continuous process for the synthesis of binary system semiconducting nanoparticles in a microreaction system wherein temperature and volume flows are controlled and a separation of nucleation and growth process is achieved.
  • the system comprises components such as micro heat exchanger and residence reactor, which can optimize the chemical and engineering process parameters and thus allow production of nearly monodisperse and morphologically uniform nanoparticles.
  • Ligands such as trioctylphosphine, trioctylphosphine oxide and oleic acid are used to control the growth of nanoparticles.
  • DEI 02006055218 teaches that the separation between nucleation and growth process allows precise adjustment of ideal individual process parameters leading to optimal control of particle properties compared to batch processes.
  • capillary reactor has its limitation to extremely low volume flows and wide residence distribution because of the laminar flow profile usually resulting in a broad particle size distribution. Furthermore, the poor mixing situation in capillary reactor during reaction induces the formation of crystal with much surface defect and side-product, which significantly reduced photoiuminescence efficiency.
  • ternary or quaternary I-III-VI semiconducting nanoparticies are complex in comparison to the above mentioned binary systems. For example various cations have different reaction speed under different iigands, therefore nanoparticies with different composition and crystal structure will form depending on the selection of Iigands. Different composition or crystal structure will significantly affect the crystal optical properties and its applications in electronics. Objective of the invention
  • the objective of the present invention is to provide a continuous process for production of ternary or quaternary semiconducting nanoparticies based on IB, I II A. VIA elements of the periodic classification (I- III- VI semiconducting nanoparticies).
  • the process should provide reliable reproducible quality of nanoparticies, i.e. monodispersion, smaller particle size and narrow particle size distribution and also allow manufacture of these semiconducting nanoparticies in large quantities.
  • Another objective of the present invention is to synthesize ternary or quaternary I-III-VI semiconducting nanoparticies with defined crystal structures. Subject of invention
  • a new liquid synthesis process via microreaction technology based on simply solvothermal method was developed to overcome the obstacles in traditional batch process such as low reproducibility of particle properties, high production cost and scale -up problems and quality of nanoparticies (such as particles size distribution, emission range, crystal structure and quantum yield).
  • IB element is selected from copper and silver
  • IDA element is selected from gallium and indium
  • VI is selected from sulfur and seienide.
  • I semiconducting nanoparticies in the present invention are therefore CuInS2, AglnS:, CuInSe2, AgInSe2, CuGaS2, CuGaSe2, AgGaS2, AgGaSe2, CuJnGaS, CuAglnS, CuInGaSe, CuAglnSe, AgEiGaS, AglnGaSe, CuAgGaS, CuAgGaSe.
  • l-l ll-Vl semiconducting nanoparticies in present invention are CUE1S2, AgInS2, CuInSe2, AgInSe 2 , CuGaS3 ⁇ 4 CuInGaS, CuAglnS, AglnGaS.
  • i-III-VI semiconducting nanoparticies in present invention are CuInS2, AgInS2 because of lower toxicity.
  • nanoparticies comprises three consecutive steps: mixing of precursors, nucleation and growth. For the formation of uniform nanoparticies with a narrow size distribution the clean separation of these processes and their independent control is an indispensable prerequisite. Nucleation of nanoparticies initiates from a supersaturated solution at a nucleation temperature, and then growth of nanoparticies follows and is conducted at a growth temperature. The temperature of nucleation of nanoparticies is normally lower than that of growth.
  • the stable reaction conditions allow the production of high quality nanoparticies with lower surface crystal defect, monodispersion and narrow size distribution.
  • First object of the present invention is a method for continuous preparation of ternary or quaternary semiconducting nanoparticies based on IB, I IIA, VIA elements of the periodic classification (I-III-VI semiconducting nanoparticies) comprising the following steps:
  • step d) the synthesis mixture is cooled down, the cooling temperature being lower then the temperature of nucleation and particle growth.
  • synthesis mixture containing cation starting material, anion starting material, at least one ligand and at least one solvent is prepared.
  • Typical synthesis procedure is: cation starting material, anion starting material, and at least one ligand able to coordinate with the cations are mixed in at least one solvent and degassed in N? protection.
  • the mixture may be have to be heated or stirred to form clear or turbid flowable solution with a viscosity below 50 mPas preferably below 10 mPas.
  • Cation starting material in the sense of the present invention is a cation source, soluble in the synthesis solution by mixing or after heat treatment, normally metal salts selected from a group comprising copper salt, indium salt, silver salt and gallium salt.
  • Suitable copper salt is copper (I) acetate, copper (II) acetate, copper stearate, copper chloride, copper indine, copper nitrate, copper (I) sulfate, (PPli3)2CuIn(SEt)4 and (PPti3)2CuIn(SePh)4 or any mixture thereof.
  • Suitable Indium salt is indium acetate, indium chloride, indium stearate, indium nitrate, indium sulfate, (PPii3)2CuIn(SEt)4 and (PPli3)2CuIn(SePh)4 or any mixture thereof.
  • Suitable silver salt are silver nitrate, silver sulfate, silver acetate, or any mixture thereof.
  • Suitable gallium salt is gallium chloride, gallium acetate, gallium sulfate, gallium stearate or any mixture thereof.
  • Anion starting material in the sense of the present invention is an anion source soluble in the synthesis solution by mixing or after heat treatment, which is selected from the following group:
  • - Se starting material can be selected from the group comprising selenium, bis (trim ethylsilyl) selenide, or any mixture thereof.
  • - S starting material can be selected from the group comprising aikanethiois having one or more sulfhydryl functional groups, carbon disulfide, sulfur or any mixture thereof.
  • Aikanethiois having one or more sulfhydryl functional group are preferably octylthiol, isooctylthiol, dodecylthioi, hexadecanethioi, octadecanethiol, 1,8-dioctyl thiols, 1,6-dioctyl thiols.
  • Solvent is preferably a non or low polar solvent with high boiling point. The solvent should be stable and degrade as little as possible at reaction temperature.
  • the boiling point of solvent is above 200 °C, more preferably above 240 °C.
  • Solvent can be selected from the group comprising 1 -octadecene, diphenyl ether, dioctyl ether, diheptyl ether, octadecane, olefin, Diphyl THT (hydrogenated terphenyl), Diphyl DT (isomeric ditolyl ether), or any mixture thereof.
  • Ligand can be selected from the group comprising oleylamine, oleic acid, trioctyiphosphine, trioctyiphosphine oxide, myristic acid, aikanethiois having one or more than one sulfhydryl functional groups, or any mixture thereof.
  • Aikanethiois having one or more sulfhydryl functional group are preferably octylthiol, isooctylthiol, dodecylthioi, hexadecanethioi, octadecanethiol, 1 ,8-dioctyl thiols, 1,6-dioctyl thiols. It.
  • oieic acid induces wurzite-type CuInS2 nanoparticies
  • oieyiamine induce both chalcopyrite and wurzite-type CuInS2 nanoparticies depending on reaction time and temperature
  • myristic acid induce wurzite-type CuInS2 nanoparticies.
  • moiar ratio of two cations is (1 ⁇ 5):(5 ⁇ 1), preferred (1 ⁇ 2):(2 ⁇ 1).
  • molar ratio of any two cations is (1 ⁇ 5):(5 ⁇ 1) and preferred (1 ⁇ 2):(2 ⁇ 1), and the moiar ratio of the third cation to any one of above two cations is lower than 5 and preferred lower than 2.
  • a total amount of metal (i.e. copper, indium, silver and gallium) salts is in a concentration from 0.001 M to 1 M, preferably from 0.005 M to 0.5 M, and more preferably from 0.008 to 0.1 M in solvent.
  • the molar ratio of iigand to the total amount of metal salts is above 1, preferably from 1 to 80, and more preferably from 2 to 50.
  • the moiar ratio of anion starting material to metal salts normally higher production yield is obtained when anion starting material is in excess (more than stoichiometric amount).
  • the moiar ratio of the total amount of anion starting material to the total amount of metal salts is from 0.5 to 50 preferably from 1 to 25, and more preferably from 1 to 10.
  • the temperature for precursor solution preparation ranges from 25°C to 220°C, preferably from 40°C to 200°C, more preferably from 50°C to 180°C.
  • cation-containing precursor solution and anion- containing precursor solution are prepared separately. Synthesis mixture is then prepared by mixing cation-containing precursor solution and anion-containing precursor solution.
  • a total amount of metal (i.e. copper, indium, gallium and silver) salts is usually in a concentration from 0.001 M to 2 M, preferably from 0.005 M to 0.1 M, and more preferably from 0.008 to 0.2 M in solvent.
  • the molar ratio of ligand to the total amount of metal salts is above 1 , preferably from 1 to 80, and more preferably from 2 to 50.
  • the temperature for cation-containing precursor solution preparation ranges from 25°C to 220°C, preferably from 40°C to 200°C, more preferably from 50°C to 180°C.
  • Anion-containing precursor solution comprises anion starting material and at least one solvent.
  • Typical procedure for anion-containing precursor solution comprises mixing anion starting material with a solvent in flask and degassing to form an optical clear solution by simply stirring, heating or supersonicating.
  • the previously mentioned selected ligand may be added if the anion source is not readily soluble in the solvents used.
  • Solvent for anion-containing precursor solution can be selected from from the group comprising 1 - octadecene, diphenyl ether, dioctyl ether, diheptyl ether, octadecane, olefin, Diphy! THT (hydrogenated terphenyl), Diphyl DT (isomeric ditolyl ether), oleylamine, oleic acid, trioctylphosphine, trioctylphosphine oxide, myristic acid, alkanethiols having one or more than one sulfhydryl functional groups, or any mixture thereof.
  • Alkanethiols having one or more sulfhydryl functional group are preferably octylthiol, isooctylthiol, dodecyithioi, hexadecanethiol, octadecanethiol, 1 ,8 -dioctyl thiols, 1 ,6 -dioctyl thiols.
  • molar ratio of anion to cation normally higher production yield is obtained when anion starting material is in excess (more than stoichiometric amount).
  • molar ratio of anion starting material to the total amount of metal salts is from 1 to 50, and more preferably from 1 to 25.
  • Mixing of cation-containing precursor solution and anion-containing precursor solution can be achieved by traditional agitation or in a micro mixer.
  • Microreaction system usually refers to micro structured operation units with inner dimensions of from 10 nm to 1 mm, comprising elements such as micromixer, micro heat exchanger micro residence reactor, sensor (such as temperature sensor, pressure sensor, pH sensor), actuator (such as pressure controller, etc.) etc.
  • Used micromixer is typically based on the multilamination principle wherein the streams of fluids to be mixed are separately fanned out in a large number of thin lamellae.
  • the lamellae of the two fluids are alternately arranged so that an interdigital configuration is generated. Due to diffusion and secondary flows, the molecules of the fluids mix rapidly and efficiently.
  • a micromixer keeps them in good mixing condition.
  • used micro heat exchanger shows higher specific surface area, which increases the heat transfer efficiency therefore the synthesis mixture can be heated or cooled within several seconds, which permits separation of nucieation and growth progresses of iianoparticies by simply controlling the temperatures.
  • the heating/cooling procedure is conducted with a heating/cooling rate of > 1 K s, preferably with a heating/cooling rate of > 10 K s and most preferably with a heating/cooling rate of > 100 K/s.
  • Micro residence reactor is preferred to significantly improve heat transfer and for a faster and more efficient heating of synthesis mixture.
  • Most preferred micro residence reactor is a microstructured residence reactor with heat exchanging and static mixing features, which allows sustained cross-mixing during the reaction and reduce the formation of side-products.
  • Preferred micro residence reactor comprises a tube or capillary reactor, has a heat transfer surface area to volume ratio (A/V ratio) of at least 1000 1/m and also comprises static mixing features to enhance cross-mixing of the synthesis mixture and narrow the residence time distribution within the tube or capillary reactor.
  • the synthesis mixture can be heated or cooled by heating media to achieve the desired temperature.
  • Microwave can also be used to quickly heat the synthesis mixture.
  • the microreaction system for the continous preparation of ternary or quaternary l-l ll-VI semiconducting nanoparticles comprises at least one micro heat exchanger and at least one micro residence reactor, wherein step b) is conducted in the micro heat exchanger and step c) is conducted in the micro residence reactor.
  • step b) is conducted in the micro heat exchanger
  • step c) is conducted in the micro residence reactor.
  • detailed synthesis in micro reaction system comprises the following steps: synthesis mixture is pumped into at least one micro heat exchanger and heated to expected temperature for nucieation, and then the synthesis mixture is brought to expected temperature in at least one micro residence reactor for particle growth. It.
  • the synthesis mixture is cooled down, the cooling temperature being lower than the temperature of nucleation and the growth temperature. More preferably, the synthesis mixture is cooled in a further micro heat exchanger. it is preferred that the reaction process is monitored by online analytical measurement using online analytical measurement device.
  • Precursor soiutions or synthesis mixture can be stored in heatable containers.
  • the solutions or synthesis mixture are normally at room temperature. When precursor solutions or synthesis mixture is solid or sticky at room temperature, it has to be heated to keep the solution as one phase liquid.
  • Temperature of precursor solutions or synthesis mixture in heatable containers is normally from room temperature to 180 °C, preferably from 25 °C to 100 °C in all cases below temperature for nucleation.
  • the micro heat exchangers for heating or cooling usefully have heat transfer surface area to volume ratio (AN ratio) > 20,000 1/min, preferably > 25,000 1/m and in particular > 30,000 i/min and allows setting nucleation temperature > 200 °C, preferably from 220 °C to 300 °C and in particular from 230 °C to 290 °C.
  • a counter flow micro heat exchanger is preferred.
  • the residence time in micro heat exchangers for heating or cooling is usefully set out from 90 s to 0.18 s, preferably from 72 s to 0.36 s, and particu iariy from 36 s to 0.9 s at a flow rate of the synthesis mixture of 0.2 ml/min up to lOOmi/min, preferably from 0.25ml/min up to 50mi/min, and especially from 0.5ml/min to 20ml/min.
  • Micro residence reactor (4) usefully has heat transfer surface area to volume ratio (A/V ratio) > 800 1/m, preferably > 1000 1/m and in particular > 1200 1/m.
  • the set temperature is usually > 200 °C, preferably from 220 °C to 300 °C, and more preferably from 230 °C to 270 °C. Normally the set temperature in micro residence reactor for particle growth is less than or equal to that in micro heat exchanger for nucleation.
  • the micro residence reactor ensures the good radial mixing, high efficient heat transfer and narrow residence distribution.
  • the average residence time in micro residence reactor is usefully from 18 s to 150 min, preferably from 36 s to 120 min, and especially from 90 s to 60 min at a flow rate of the synthesis mixture from 100 ml / min to 0.2 ml / min, preferably from 50 mi / min to 0.25 mi / min and more preferably from 20 ml / min to 0.5 ml / min.
  • More than one micro residence reactors and/or micro heat exchangers can be connected sequentially for increasing the production capacity.
  • the micro residence reactor comprises static mixing internals and heat exchanging features.
  • Such a micro residence reactor is significantly narrower than that a tube or capillary and allows a narrow residence time distribution of synthesis mixture so nanoparticles with a narrow size distribution can be obtained.
  • anti-solvent is mixed with the cooled synthesis mixture for temporary precipitation of semiconducting nanoparticles. It is preferred, that the mixing procedure with is operated continuously in a micro mixer.
  • the mixing time in micro mixer (9) is usually ⁇ 10 s, preferably ⁇ 5 s, more preferably ⁇ 0.5 s.
  • semiconducting nanoparticles are separated from the cooled synthesis mixture.
  • Standard procedures such as ultrafiltration, membrane filtration, dialysis, centrifugation and evaporation can be used.
  • Anti-severation targeted for launch of the aggregation and precipitation of the nanoparticles, can be used to separate semiconducting nanoparticles from the cooled synthesis mixture.
  • Anti-solvent are typicaily selected from the group comprising acetone, methanol, ethanol, iso-propanol, propanol, or any mixture thereof.
  • the separated semiconducting nanoparticles are typically redispersed in an appropriate dispersion solvent and anti-solvent is added and mixed, and then semiconducting nanoparticles are separated by using the above standard procedures (ultrafiltration, membrane filtration, dialysis, centrifugation and evaporation).
  • the semiconducting nanoparticles are preferably washed 3 to 4 times through repeating the above washing procedure.
  • Dispersion solvent in present invention can be selected from toluene, chloroform, hexane, cyciohexane or any mixture thereof.
  • cleaned semiconducting nanoparticies can be dried in vacuum below 1 10 °C or redispersed in above mentioned appropriate dispersion solvent for analysis.
  • a uniform size of semiconducting nanoparticies, synthesized by the process in present invention, is obtained.
  • the size range of the nanoparticies is specifically from 1 nm to 20 nm, preferred 2 nm to 10 nm.
  • the synthesized ternary or quaternary I-III-VI semiconducting nanoparticies are of chalcopyrite and wurzite crystal structure depending on selected ligands and process parameters.
  • the process allows the uniform composition of semiconducting nanoparticies and reduces surface crystal defect which offers a higher photo lumine sc enc e quantum yield.
  • CuInS2 nanoparticies with high photoluminescence quantum yield of 13.9 % without any other post treatment were synthesized.
  • a further object of the present invention is therefore a semiconducting nanoparticle obtainable by the preparation process of the present invention.
  • the size and crystal structure of the semiconducting nanoparticl e can be controlled by adjusting reaction parameters in particular concentration, reaction condition (such as flow and temperature) and selected ligands.
  • a scale- up can be realized by just simply increasing the channel number, number of operation units, or parallel synthesis lines.
  • UV-VIS and Photoluminescence Spectra measurement UV-VIS absorption spectrum of the sample is measured by UV-VIS spectrophotometer (Specord 40, Analytik Jena). The sample is diluted by toluene until the absorption value of sample is lower than 0.1 at 366nm. The photoluminescence spectrum of the sample is measured by spectrofluorimeter (Fluorolog 3-22, HORIBA Jobin Yvon) at excitation wavelength of 366nm.
  • Quantum yield of sample is determined by comparing a standard dye with a. known quantum yield.
  • ATT0635 is used as standard dye.
  • Quantum yield of ATT0635 in water is 25% and its emission peak is 659nm.
  • the sample is diluted in toluene following the measurement rules of UV-V IS and photoluminescence spectra.
  • the quantum yield of sample is determined according to the following equation,
  • YQ refers quantum yield of sample
  • Ys refers quantum yield of standard dye
  • FQ FS refer integral intensity under photoluminescence spectrum of sample and standard dye, respectively.
  • AQ -fef As refer absorption at excitation wavelength of sample and standard dye, respectively.
  • DQ ⁇ 3 ⁇ 4 IX refer the refractive index of the corresponding solvent of sample and standard dye.
  • the crystal structure of samples was measured by X-ray diffraction devices (diffractometer D 5000, Siemens). The sample is dispersed on silicon wafer, dried and measured.
  • TEM Transmission Electron Microscopy
  • the semiconducting nanoparticies of the present invention can be used for the manufacture of electronic devices and in particular for printed eiectronic devices such as solar ceils.
  • Figure 1 Diagram of the continuous synthesis process of semiconducting nanoparticies according to the present invention.
  • Example 1 Example 1 , Example 2 and Example 3.
  • Figure 9 Diagram of the continuous synthesis process of semiconducting nanoparticies according to the present invention.
  • the synthesis mixture was heated in the first micro heat exchanger (counter flow micro heat exchanger, V « 0,3 mi, A « 0,0076 m 2 , Ehrfeld Mikrotechnik Bayer Technology Services GmbH) for nucleation and obtained nuclei were allowed to grow in the microstructured residence reactor with heat exchanging and static mixing features (Sandwichreactor, V « 30 ml, A « 0,03 m 2 Ehrfeld Mikrotechnik Bayer Technology Services GmbH), and then the synthesis mixture was quenched in second micro heat exchanger (counter flow heat exchanger, V « 0,3 ml, A « 0,0076 m 2 , Ehrfeld Mikrotechnik Bayer Technology Services GmbH) by cooling down.
  • first micro heat exchanger counter flow micro heat exchanger, V « 0,3 mi, A « 0,0076 m 2 , Ehrfeld Mikrotechnik Bayer Technology Services GmbH
  • second micro heat exchanger counter flow heat exchanger, V « 0,3 ml, A « 0,0076 m 2 , Ehrfeld Mikrotechnik Bayer Technology Services GmbH
  • the set temperatures in first micro heat exchanger and micro residence reactor were 260°C and 260°C respectively; the set temperature in the second micro heat exchanger was 25°C.
  • the residence time was 15 minutes. 4)
  • the cooled reacted solution was collected from the microreaction system and two equivalent volume of acetone was added to form suspension. The suspension was then centrifuged at 9000 rpm for 10 minutes and the supernatant was removed.
  • step 6) The step 5) was repeated for twice. Then the obtained CuInS2 nanoparticies were redispersed in toluene and stored under N; atmosphere.
  • UV-VIS absorption and photoiumiiiescence spectra of obtained CuInS2 nanoparticies are shown in Figure 8.
  • the emission peak of CuInS2 nanoparticies is at 614 nm.
  • XRD pattern ( Figure 6) shows that they are of chalcopyrite crystal structure. A quantum yield of 12% was measured.
  • the experiment recipe and procedure were the same as the one described in example I, but the set temperatures in micro heat exchanger and microstructured residence reactor with heat exchanging and static mixing features were 270°C and 250 °C respectively.
  • UV-VIS absorption and photoluminescence spectra of obtained CuInS2 nanoparticles are shown in Figure 8.
  • the emission peak of CuInS 2 nanoparticles is at 682 nm.
  • the precursor solution was heated in the first micro heat exchanger (counter flow heat exchanger, V « 0,3 ml, A « 0,0076 m 2 , Ehrfeld Mikrotechnik Bayer Technology Services GmbH) for nucleation and obtained nuclei were allowed to grow in the micro residence reactor with heat exchanging and static mixing features (Sandwichreactor, V « 30 ml, A « 0,03 m 2 Ehrfeld Mikrotechnik Bayer Technology Services GmbH). Then the solution was quenched in second micro heat exchanger (counter flow heat exchanger, V « 0,3 ml, A « 0,0076 m 2 , Ehrfeld Mikrotechnik Bayer Technology Services GmbH) by cooling down.
  • the set temperatures in first micro heat exchanger and micro residence reactor were 260°C and 240°C respectively; the set temperature in second micro heat exchanger was 25°C.
  • the residence time is 10 minutes.
  • 1 -octadecene 150 ml were added into 250 ml three bottle-neck flask in N2 protection. The mixture was degassed for 30 minutes in N2 (l OL/h) and then heated to 180°C until powders were completely dissolved to form cation-containing precursor solution. The above cation precursor solution was cooled down to 50°C.
  • first micro residence reactor with heat exchanging and static mixing features (Sandwichreactor, V * 30 mi, A « 0,03 m 2 Ehrfeld Mikrotechn ik Bayer Technology Services GmbH). Then the solution was quenched in second micro heat exchanger (counter flow micro heat exchanger, V « 0,3 ml, A « 0,0076 m 2 , Ehrfeld Mikrotechnik Bayer Technology Services GmbH) by cooling down.
  • the set temperatures in first micro heat exchanger and micro residence reactor were 260°C and 240°C respectively; the set temperature in the second micro heat exchanger was 25°C.
  • the residence time is 5 minutes.

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Abstract

L'invention concerne un procédé pour la préparation en continu, en phase liquide, de nanoparticules semi-conductrices ternaires ou quaternaires à base des éléments IB, IIIA, VIA de la classification périodique des éléments, en particulier l'AgInS2 et le CuInS2 peu toxiques. Une taille uniforme des nanoparticules semi-conductrices est obtenue dans une plage de taille de 1 nm à 20 nm, montrant une structure cristalline de type chalcopyrite ou wurzite. La taille et la structure cristalline des nanoparticules semi-conductrices peuvent être régulées en ajustant des paramètres de réaction, en particulier la concentration, la température, le flux et les ligands sélectionnés.
PCT/EP2012/060167 2011-06-03 2012-05-30 Procédé continu de synthèse de nanoparticules semi-conductrices ternaires ou quaternaires à base des éléments ib, iiia, via de la classification périodique Ceased WO2012163976A1 (fr)

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GB2588487A (en) * 2019-07-16 2021-04-28 Merck Patent Gmbh Continuous size separation of nanoparticles

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