WO2020209973A2 - Procédé de fabrication de nanocristaux semi-conducteurs colloïdaux - Google Patents

Procédé de fabrication de nanocristaux semi-conducteurs colloïdaux Download PDF

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WO2020209973A2
WO2020209973A2 PCT/US2020/022278 US2020022278W WO2020209973A2 WO 2020209973 A2 WO2020209973 A2 WO 2020209973A2 US 2020022278 W US2020022278 W US 2020022278W WO 2020209973 A2 WO2020209973 A2 WO 2020209973A2
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WO2020209973A3 (fr
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Keith KAHEN
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Lumisyn LLC
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent materials, e.g. electroluminescent or chemiluminescent
    • C09K11/08—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials
    • C09K11/70—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent materials, e.g. electroluminescent or chemiluminescent
    • C09K11/08—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials
    • C09K11/62—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing gallium, indium or thallium
    • 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
    • C30B29/40—AIIIBV compounds wherein A is B, Al, Ga, In or Tl and B is N, P, As, Sb or Bi
    • C30B29/44—Gallium phosphide
    • 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
    • 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
    • C30B7/14—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions the crystallising materials being formed by chemical reactions in 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
    • B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/30—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
    • H10K30/35—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains comprising inorganic nanostructures, e.g. CdSe nanoparticles
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/20—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials
    • H10P14/26—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials using liquid deposition
    • H10P14/265—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials using liquid deposition using solutions
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/20—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials
    • H10P14/34—Deposited materials, e.g. layers
    • H10P14/3402—Deposited materials, e.g. layers characterised by the chemical composition
    • H10P14/3414—Deposited materials, e.g. layers characterised by the chemical composition being group IIIA-VIA materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/20—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials
    • H10P14/34—Deposited materials, e.g. layers
    • H10P14/3402—Deposited materials, e.g. layers characterised by the chemical composition
    • H10P14/3424—Deposited materials, e.g. layers characterised by the chemical composition being Group IIB-VIA materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/20—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials
    • H10P14/34—Deposited materials, e.g. layers
    • H10P14/3451—Structure
    • H10P14/3452—Microstructure
    • H10P14/3461—Nanoparticles

Definitions

  • the present disclosure relates to methods of making colloidal semiconductor nanocrystals having improved emissive properties.
  • colloidal semiconductor nanocrystals have many potential uses, for example, as gain material for optically-pumped cw (continuous wave) lasers and as phosphors for solid-state lighting and displays.
  • cw continuous wave
  • phosphors for solid-state lighting and displays.
  • the present disclosure provides methods for preparing colloidal semiconductor nanocrystals that may have one or more of the following advantages: tighter nanocrystal particle size distribution; improved nanocrystal yield; improved emission color purity; high photoluminescence quantum efficiency; improved photoluminescence efficiency at elevated temperatures; and improved photoluminescence efficiency under high excitation optical flux densities.
  • FIG. 1 is a cross-sectional view of a colloidal semiconductor nanocrystal according to certain embodiments of the present disclosure.
  • FIG. 2 is a schematic diagram of a mechanical injection device according to certain embodiments of the present disclosure that may be used for making colloidal semiconductor nanocrystals.
  • Group I herein refers specifically to IA (Group Number 1 of the modern IUPAC system)
  • Group II herein refers to both IIA and IIB (Group Numbers 2 and 12 of the modern IUPAC system)
  • Group III refers specifically to IIIA (Group Number 13 of the modern IUPAC system)
  • Group IV refers specifically to IVA (Group Number 14 of the modern IUPAC system)
  • Group V refers specifically to VA (Group Number 15 of the modern IUPAC system)
  • Group VI refers specifically to VIA (Group Number 16 of the modern IUPAC system)
  • Group VII refers specifically to VIIA (Group Number 17 of the modern IUPAC system).
  • the nanocrystals may be referred to as“colloidal”.
  • the term“colloidal” means that they form a colloidal solution, in which the nanocrystals do not settle at the bottom of the solution, but remain in a generally suspended state. Since the nanocrystals are suspended, the nanocrystals are at least partially dispersed in the solution.
  • conventional self-assembled quantum dots are formed by classical semiconductor growth processes, such as molecular beam epitaxy (MBE) or metal-organic chemical vapor deposition (MOCVD).
  • nano such as nanocrystal
  • prefix“nano” generally refers to a component having an average size, such as an average length, width, or diameter, of from about 0.1 to about 100 nm.
  • non-homogeneous refers to a composition of parts or elements that are not substantially identical throughout.
  • methods for making colloidal semiconductor nanocrystals of the present disclosure may be used to form III-V class semiconductors, II-VI class semiconductors, IV class semiconductors, IV-VI class semiconductors, I-III-VI class semiconductors, or I-IV-VII class semiconductors.
  • the semiconductor materials may be binary, ternary, quaternary or higher order.
  • 3 semiconductor materials that may be formed by methods of the present disclosure, alone or in combination, include InP, InGaP, InN, InPN, InPSb, InAlP, GaN, GaP, InAs, InSb, GaAs, GaSb, AlAs, AlSb, InAsSb, GaAsSb, AlAsSb, InAlP, InAlSb, InAlAs, CdSe, CdZnSe, ZnSe, CdTe, CdZnSTe, Ge, Si, GeSi, CuInS, and CsPbBr.
  • InGaP generally refers to any composition represented by InxGa(l-x)P, where subscript X is greater than zero and less than 1 (0 ⁇ X ⁇ 1).
  • colloidal semiconductor nanocrystals of the present disclosure may be referred to a“core” nanocrystals. Additional layers of semiconductor material may optionally be provided over the core nanocrystal to form a“shell” around the core (a“shelled semiconductor nanocrystal”).
  • FIG. 1 is a cross-sectional view of a shelled semiconductor nanocrystal 100 having a semiconductor core 102 and semiconductor shell 104. Although the methods of the present disclosure may be applied to the shell formation, in some embodiments, methods of the present disclosure are used to form the core semiconductor nanocrystals and the shell is formed by conventional methods.
  • the shell may comprise a semiconductor having a wider bandgap than the core nanocrystals. Some non-limiting examples of shell semiconductor materials include class IV, II- VI, III-V, or IV- VI semiconductors, or combinations thereof. In some embodiments, the shell may include up to about 100 monolayers of the wider bandgap semiconductor.
  • the colloidal semiconductor nanocrystals formed by methods of the present disclosure remain unshelled. Unless context indicates otherwise, any discussion herein referring to a semiconductor core may also apply to an unshelled semiconductor nanocrystal.
  • the elemental composition of the core may be homogeneous.
  • the elemental composition of the core is non-homogeneous and varies along at least a portion of the core radius.
  • the core may include inner and outer regions having different elemental compositions or distributions of components, wherein one or both of the regions may have a non-homogeneous distribution of components.
  • Methods of making colloidal semiconductor nanocrystals generally involve combining cation and anion semiconductor precursors in appropriate solvents in a reaction vessel.
  • the nanocrystal composition may be controlled by adjusting the ratios of precursors, the sequence of 4 addition, concentration and type of ligands, reaction time, reaction temperature and other factors. It has been unexpectedly found that colloidal semiconductor nanocrystals having superior properties may be prepared by using one or more mechanical injection devices capable of injecting substantially all of a precursor solution into a reaction vessel within about 250 milliseconds (ms), alternatively within 200 ms, alternatively within 100 ms, alternatively within 50 ms or alternatively within 10 milliseconds.
  • ms milliseconds
  • substantially all it is meant that at least 90% of the predetermined volume for injection is provided into the reaction vessel within such time. Alternatively, at least 95% of the predetermined volume for injection is provided. Alternatively, at least 98% of the predetermined volume for injection is provided. It is difficult and sometimes impossible for such injections to be made manually in such a short time.
  • the mechanical injection device 200 includes an injection vessel 202 for holding the volume of semiconductor precursor solution 204 to be injected and a mechanical injector 206 in physical communication with the injection vessel via some appropriate connector 208.
  • the mechanical injector applies a force to cause transfer of the precursor solution into the reaction vessel through an opening 210 in the injection vessel.
  • the injection vessel is a syringe having a plunger 212 and a needle 214 with an opening at the end, and the mechanical injector is connected to the plunger to force the precursor solution out of the syringe needle and into the reaction vessel (not shown).
  • the syringe or other injection vessel includes a cylindrical tube 216 capable of withstanding pressures of at least 0.5 MPa, alternatively at least 1 MPa, alternatively at least 5 MPa.
  • the tube may be made of plastic, glass, metal, ceramic or a combination thereof.
  • the tube may optionally be internally coated with a polymer or other suitable material.
  • a mechanical injector is dedicated to a particular injection vessel. In some embodiments, a mechanical injector shared among more than one injection vessel, for example, by moving it or the injection vessel into appropriate position.
  • the mechanical injector includes a pneumatic cylinder, a hydraulic cylinder, an electric motor, a magnet or a spring.
  • the mechanical injector may be further coupled to electronic control devices such as a computer or a manual switch to trigger injection.
  • a semiconductor precursor solution may include a cation precursor, for example, a group II, III, or IV precursor.
  • group II cation precursors are Cd(Me)2, CdO, CdCCb, Cd(Ac)2, CdCh, Cd(NC> 3 )2, CdS04, Cd oleate, Cd stearate, ZnO, ZnC03, Zn(Ac)2, Zn(Et)2, Zn stearate, Zn oleate, MgO, Mg stearate, Mg oleate, Hg 2 0, 5
  • group III cation precursors are In(Ac)3, InCb, In(acac)3, In(Me)3, Ih2q3, Ga(acac)3, GaCl3, Ga(Et)3, and Ga(Me)3.
  • group IV cation precursors are alkylsilane and alkylgermane compounds. Other appropriate cation precursors well known in the art may also be used.
  • a semiconductor precursor solution may include an anion precursor, for example, a group Y or VI precursor.
  • anion precursors are bis(trimethylsilyl)sulfide, tri-n-alkylphosphine sulfide, aminosulfide, hydrogen sulfide, tri-n-alkylphosphine selenide, aminoselenide, tri-n-alkylphosphine telluride, aminotelluride, bis(trimethylsilyl)telluride, tris(trimethylsilyl)phosphine, triethylphosphite, sodium phosphide, potassium phosphide, trimethylphosphine, tris(dimethylamino)phosphine, tricyclopentylphosphine, tricyclohexylphosphine, triallylphosphine, di-2-norbornylphosphine, dicyclopentylphosphine
  • a semiconductor precursor solution may include both a cation precursor and an anion precursor.
  • a semiconductor precursor may be added to the reaction vessel prior to subsequent injections of other precursor solutions.
  • coordination ligands include alkyl phosphine, alkyl phosphine oxide, alkyl phosphate, alkyl amine, alkyl phosphonic acid, and fatty acids.
  • the alkyl chain of the coordination ligand is typically a hydrocarbon chain of length greater than 4 carbon atoms and less than 30 carbon atoms, which can be saturated, unsaturated, or oligomeric in nature. It may also have aromatic groups in its structure.
  • Non-limiting examples of suitable coordination (growth) ligands and ligand mixtures include, but are not limited to, trioctylphosphine, tributylphosphine, tri(dodecyl)phosphine, trioctylphosphine oxide, tributylphosphate, trioctyldecyl phosphate, trilauryl phosphate, tris(tridecyl)phosphate, triisodecyl phosphate, bis(2-ethylhexyl)phosphate, hexadecylamine, oleylamine, octadecylamine, bis(2-ethylhexyl)amine, octylamine, dioctylamine, cyclododecylamine, N,N-dimethyltetradecylamine, N,N-dimethyldodecylamine, 6 phenylphosphonic acid, hexylamine,
  • the coordinating ligand can be used by diluting the coordinating ligand with at least one solvent selected from a group consisting of, for example, 1-nonadecene, 1-octadecene, cis-2-methyl-7-octadecene, 1 -heptadecene, 1- pentadecene, 1 -tetradecenedioctylether, dodecyl ether, and hexadecyl ether, or the like.
  • solvent selected from a group consisting of, for example, 1-nonadecene, 1-octadecene, cis-2-methyl-7-octadecene, 1 -heptadecene, 1- pentadecene, 1 -tetradecenedioctylether, dodecyl ether, and hexadecyl ether, or the like.
  • the growth ligands may include column II metals, such as Zn, Cd or Mg.
  • the zinc compound is zinc carboxylate having the formula:
  • R is a saturated, unsaturated, linear, and/or branched Ci to C 30 hydrocarbyl.
  • the term“hydrocarbyl” refers to a hydrocarbon radical.
  • R is a Ci to C 30 hydrocarbyl and may be an aryl or may be substituted with an aryl.
  • the term“aryl” mean an aromatic radical.
  • suitable zinc compounds include, but are not limited to, zinc acetate, zinc undecylenate, zinc stearate, zinc myristate, zinc laurate, zinc oleate, zinc palmitate, or combinations thereof.
  • non-coordinating or weakly coordinating solvents include higher homologues of both saturated and unsaturated hydrocarbons. Mixture of two or more solvents may also be used.
  • the solvents used in accordance with the present disclosure may be coordinating or non-coordinating, a list of possible candidates being given above.
  • the solvent may have a boiling point above that of the growth temperature; as such, prototypical coordinating and non coordinating solvents are trioctylphosphine and octadecene, respectively.
  • lower boiling solvents are used as carriers for the precursors; for example, tris(trimethylsilyl)phosphine can be mixed with hexane in order to enable accurate injections of small amounts of the precursor. 7
  • the methods for making colloidal semiconductor nanocrystals may be performed under airless conditions, for example, involving conventional gloveboxes and/or Schlenk lines
  • a reaction vessel may be charged with a reaction solution including a solvent, either coordinating (solvent reacts or forms bonds with the precursors or with the nanocrystal surface) or non-coordinating (solvent does not react or form bonds with precursors or with the nanocrystal surface), or both.
  • Some growth ligands or a semiconductor precursor material may also be added.
  • the reaction solution may be degassed, optionally with mechanically stirring.
  • the volume of the reaction solution depends on the desired quantity of product, but in some embodiments may be up to about 1 L, alternatively up to about 500 mL, alternatively up to about 100 mL, alternatively up to about 20 mL.
  • a first injection device is loaded with an appropriate volume of a first semiconductor precursor solution.
  • the first semiconductor precursor solution may include a solvent, an In precursor, a P precursor and optionally some growth ligands.
  • the volume of first semiconductor precursor solution to be injected may be at least 5 % of the volume of the reaction solution.
  • a second injection device is loaded with an appropriate volume of a second semiconductor precursor solution.
  • the second semiconductor precursor solution may include a solvent, a Ga precursor, a P precursor and optionally some growth ligands.
  • the volume of second semiconductor precursor solution to be injected may be at least 5 % of the volume of the reaction solution.
  • a third injection device is loaded with an appropriate volume of a third semiconductor precursor solution.
  • the third semiconductor precursor solution may include a solvent, a Ga precursor, optionally a P precursor and optionally some growth ligands.
  • the volume of third semiconductor precursor solution to be injected may be at least 5 % of the volume of the reaction solution. 8
  • the reaction solution is heated in the reaction vessel to temperature in a range of about 225 °C to about 325 °C, with vigorously stirring.
  • the above semiconductor precursor solutions may be kept at a temperature well below that of the reaction flask in order to avoid unwanted reactions of the precursor solutions while in their respective injection device.
  • a first volume of the first semiconductor precursor solution is injected into the reaction vessel concurrently with a second volume of the second semiconductor precursor solution.
  • Each injection is complete within 250 ms or less as described earlier.
  • the term“concurrently” means that the injection times for the first and second solutions overlap for a period of time, although the start and/or end times of each injection may not be simultaneous.
  • the first and second semiconductor precursor solutions are injected at substantially the same time and within substantially the same time period.
  • substantially the same time it is meant that any time between the start of the first and second injections is less than about 10% of the first or second injection time period (whichever is longer).
  • “substantially the same time period” generally means that the difference between the first and second time periods is less than about 10%.
  • the concurrent injection may form a non-homogeneous intermediate semiconductor nanocrystal.
  • a third volume of the third semiconductor precursor is injected into the reaction vessel.
  • the injection is complete within 250 ms or less.
  • the third injection starts at substantially the same time as the time the first and/or second injection ends (whichever ends later if the first and second injections do not end at the same time).
  • substantially the same time it is meant that any time between the start of the third injection and the end of the first and/or second injections is less than about 10% of the third injection time period.
  • the temperature may optionally be lowered to allow the colloidal semiconductor nanocrystals to grow and further develop for a period of time, e.g., 1 to 400 minutes. During this“growth period” additional precursors may be added to further modify the nanocrystal composition.
  • the third injection may form a non- homogeneous colloidal semiconductor nanocrystal.
  • the solvents used in the first, second or third syringe can be coordinating or non coordinating, a list of possible candidates having been given above.
  • the solvent may have a boiling point above that of the growth temperature; however, in some cases, lower boiling solvents may be used as carriers for the semiconductor precursors, such as, hexane 9 or heptane.
  • the list of possible growth ligands and candidate anion and cation precursors have also been discussed above.
  • the colloidal semiconductor nanocrystals may optionally be shelled.
  • the shelling temperatures may be in a range of about 150 °C to about 300 °C.
  • the shell precursors may be slowly dripped together from separately prepared solutions or the shell precursors may be added one-half monolayer at a time (again typically at a slow rate).
  • the surfaces of the nanocrystals may be etched in weak acids and then annealed at elevated temperatures (e.g., from 180 °C to 260 °C) prior to shelling.
  • a weak acid is acetic acid.
  • ligands may be added to a growth solution prior to the initiation of the shelling procedure.
  • useful ligands may include primary amines, such as, hexadecylamine, or acid-based amines, such as, oleylamine.

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  • Chemical & Material Sciences (AREA)
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  • Inorganic Chemistry (AREA)
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Abstract

Un procédé de fabrication de nanocristaux semi-conducteurs colloïdaux consiste à charger un récipient de réaction avec une solution de réaction. Un premier volume d'une première solution de précurseur de semi-conducteur est fourni dans un premier dispositif d'injection et injecté mécaniquement dans la solution de réaction, sensiblement tout le premier volume étant injecté dans une première période de temps d'environ 250 millisecondes ou moins.
PCT/US2020/022278 2019-03-12 2020-03-12 Procédé de fabrication de nanocristaux semi-conducteurs colloïdaux Ceased WO2020209973A2 (fr)

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