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WO2012035109A1 - Cristaux mixtes contenant des matériaux semiconducteurs, leur procédé de production et leurs applications - Google Patents

Cristaux mixtes contenant des matériaux semiconducteurs, leur procédé de production et leurs applications Download PDF

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Publication number
WO2012035109A1
WO2012035109A1 PCT/EP2011/066027 EP2011066027W WO2012035109A1 WO 2012035109 A1 WO2012035109 A1 WO 2012035109A1 EP 2011066027 W EP2011066027 W EP 2011066027W WO 2012035109 A1 WO2012035109 A1 WO 2012035109A1
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Prior art keywords
nanoparticles
mixed crystal
mixed
semiconductor particles
protective matrix
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German (de)
English (en)
Inventor
Tobias Otto
Nikolai Gaponik
Alexander EYCHMÜLLER
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Technische Universitaet Dresden
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Technische Universitaet Dresden
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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, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/88—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing selenium, tellurium or unspecified chalcogen elements
    • C09K11/881—Chalcogenides
    • C09K11/883—Chalcogenides with zinc or cadmium
    • 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, e.g. electroluminescent, chemiluminescent materials
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
    • 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, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/56—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing sulfur
    • C09K11/562—Chalcogenides
    • C09K11/565—Chalcogenides with zinc cadmium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J61/00—Gas-discharge or vapour-discharge lamps
    • H01J61/02—Details
    • H01J61/38—Devices for influencing the colour or wavelength of the light
    • H01J61/42—Devices for influencing the colour or wavelength of the light by transforming the wavelength of the light by luminescence
    • H01J61/44—Devices characterised by the luminescent material

Definitions

  • the invention relates to novel mixed crystals of semiconductor materials in a protective matrix, a process for their preparation and their applications in various materials, eg. B. a l s phosphor in fluorescent lamps, in laser technology or as a packaging material for nanoparticles.
  • Nanoparticles or nanoparticles denote a composite of a few to a few thousand atoms or molecules.
  • the name refers to their size, which is usually 1 to 100 nanometers. They are distinguished by their particular chemical and physi cal properties, which differ significantly from those of solids or larger particles. For example, they have greater chemical reactivity due to their large specific surface area.
  • Some semiconductor nanoparticles have specific fluorescence properties. By optical or electrical excitation, the electrons can be temporarily put into an excited state and send spontaneously light of a certain wavelength on their return to the original state.
  • the energy of the emitted light depends not only on the material, but also on the particle size.
  • particles can be made from the same material solely by the choice of particle size, which fluoresce at different wavelengths. Small particles emit at smaller wavelengths, larger particles emit at longer wavelengths.
  • Typical materials of this type, which are used as semiconductors are z. B. compounds from Groups 3, 6, 1 1, 12, 13, 15, 16 of the Periodic Table of the Elements according to the current l UPAC Convention, z.
  • Nanoparticles are mainly produced by syntheses in solvents. However, technical applications are hardly conceivable with these colloidal solutions. The nanoparticles therefore have to be bound to substrates such as powders, glass surfaces or polymers by means of deposition methods in order to produce new materials. However, the nanoparticles on such materials without a shielding matrix, which protects them from chemical or physical influences, very sensitive and therefore not stable. The encapsulation prevents, for example, oxidation and light corrosion. Without a protective matrix, the nanoparticles would also aggregate into larger entities, thereby losing their unique properties. At first, only accumulations of nanoparticles are formed, which may later turn into large particles without fluorescence.
  • z For example, introducing nanoparticles into polymers and casting films out of them. From the application US 2007/034833 A1 is z.
  • z For example, it is known to embed semiconductor nanocrystals in an organic polymer matrix of polyurethane or polyurea, wherein the nanoparticles retain their luminescent properties.
  • these polymers have the disadvantage that they are thermally and mechanically unstable. At higher temperatures, for example, the polymer softens and the nanoparticles flow.
  • nanoparticles in polymers are randomly distributed and have no ordered structure as in a crystal. Due to their lack of crystallinity, they are therefore unable to align nanoparticles. An ordered structure, however, would be desirable, since it z. B. can generate polarized light.
  • German patent application DE 10 2008 062 283 A1 has shown that nanoparticles can also be embedded in inorganic gels which have sufficient stability. But here, too, the nanoparticles are randomly distributed and disordered, and even higher layer thicknesses, such as those of a crystal, can not be achieved.
  • US 2004/0219221 A1 describes a process for the production of inorganic crystals, which are coated with a layer of nanoparticles (eg gold).
  • nanoparticles eg gold
  • no stabilizers are used, resulting in that the nanoparticles do not are incorporated into the crystal, but are completely adsorbed by the surface of the salt crystals, so that it eventually comes to a termination of further crystal growth.
  • the salt in this sense is not a matrix and the nanoparticles are not protected.
  • US Pat. No. 7,794,600 B1 discloses a method for reducing impurities in nanoparticle crystals, wherein the nanoparticles are first prepared in a solution and subsequently removal of the impurity is carried out by means of chromatographic methods. US Pat. No. 7,794,600 B1 thus merely describes a method for producing nanoparticle crystals in as pure a form as possible, but does not disclose mixed crystals next to them.
  • US 2010/0148152 A1 discloses a method for producing semiconductor nanowires, wherein growth of the nanowires from a metal salt-containing reaction solution takes place in an electric field between two electrodes.
  • the nanowires can be formed from a semiconductor material on which deposit metal due to the electric field.
  • the object is achieved by mixed crystals containing semiconductor particles and a protective matrix, characterized in that the semiconductor particles and the protective matrix are different, the semiconductor particles of compounds of the elements of the groups 12 & 15, 12 & 16, 13 & 15 and / or 14 & 16 of the periodic table of the elements, the semiconductor particles have an average size of 1-100 nm, the mixed crystal has a predominantly crystalline structure, the mass content of the semiconductor particles in the mixed crystal of 10 "9 to 10% , preferably 10 "7 to 5%, the mass content of the protective matrix is at least 90%, preferably up to 99%, and the mixed crystal has a diameter of at least 100 nm.
  • semiconductor crystals of nanoparticles can be grown in a protective matrix with a crystalline structure that incorporates the nanoparticles into the crystal lattice.
  • the semiconductor nanoparticles consist of compounds of the elements of the groups 12 & 15, 12 & 16, 13 & 15 and / or 14 & 16 of the Periodic Table of the Elements, or of doped semiconductor nanoparticles such.
  • the semiconductor particles are selected from a group consisting of CdSe, CdS, CdTe, ZnSe, ZnSeTe, HgTe, HgCdTe, ZnO, ZnS, ZnTe, BeSe, BeTe, HgS, GaAs, InP, InSb, InAs, GaSb, GaN, AlN, InN, GaS, GaSe, GaTe, InS, InSe, InTe, SnS, CuS, Cu 2 S, CuInSe 2 , CuInGaSe 2 , CuInS 2 and CuInGaS 2 .
  • semiconductor nanoparticles are also core-shell particles from the above particles such.
  • CdSe / CdS core-shell particles i. Particles with a core of CdSe coated with CdS.
  • the nanoparticles have a diameter of 1-100 nm.
  • the particles may be spherical, tubular, hexagonal or needle-shaped.
  • nanoparticles of CdSe, CdTe or CdSe / CdS core-shell particles are easy to prepare and have high quantum yields.
  • all inorganic and organic crystallizable salts and organic compounds which have a sufficient solubility and which do not quench the fluorescence of the nanoparticles, such as, for example, are used for the protection matrix.
  • fluorescence-quenching iron, chromium or cobalt salts are used for the protection matrix.
  • the substances for the protective matrix ie the salts or organic compounds, preferably have a solubility of at least 10 g / l at 20 ° C. in the solvent used. Poorly soluble salts form only very slowly and very small crystals.
  • Suitable salts are, for. B. NaCl, KBr, KBr0 3 , LiCl, LiBr, Li 2 S0 4 , NaBr, Nal, Na 2 S0 4 , NaN0 3 , Na 3 P0 4 , KCl, K 2 S0 4 , MgCl 2 , MgBr 2 , CaCl 2 , CaBr 2 , BaCl 2 , Ba (NO 3 ) 2 , SrCl 2 , Sr (NO 3 ) 2 , AICI 3, Al (NO 3 ) 3 , ZnCl 2 , SnCl 2 , KH 2 PO 4 or CdCl 2 , where NaCl, KBr, KCl and KBr0 3 are particularly preferred.
  • a potassium salt tartrate and / or potassium dihydrogen phosphate As a protective matrix, a potassium salt tartrate and / or potassium dihydrogen phosphate.
  • organic compounds as a protective matrix in organic solvents are, for. As benzoic acid, anthracene, phenanthrene and / or benzil.
  • Suitable solvents for organic substances that serve as a protective matrix are, for. Toloul, hexane, dioxane or diethyl ether.
  • the colloidal solution is not stable and the rate of coagulation of the particles grows with increasing ionic strength, it is particularly recommended to use as protective matrix substances that have a medium solubility.
  • a particularly preferred salt is KBr0 3 .
  • This has the advantage of being less soluble than NaCl or KBr, which allows lower salt concentrations to be used and the ionic strength to be kept lower.
  • KBr0 3 has the advantage of being much more soluble at higher temperatures. Thus, the temperature of crystallization can also be better controlled.
  • the mass content of the nanoparticles in the mixed crystal is 10 "9 - 10%, preferably 10" 7-5%.
  • the mass content of the nanoparticles is in the mixed crystal is 10 "9-1%, preferably from 10" 9 - 10 "4% and ideally 10" 7-10 "4%.
  • the mixed crystal may also contain residues of stabilizers.
  • the stabilizers serve to increase the solubility of the semiconductor particles in the preparation of the mixed crystals and to facilitate the incorporation of the semiconductor particles in the protective matrix.
  • Typical stabilizers are for.
  • organic substances such as thiols, amines or phosphonic acids that have solubilizing properties, eg. As thioethanol, thioglycerol, thioglycolic acid.
  • the stabilizers do not have to be contained in the mixed crystal, since they decompose at higher temperatures and can escape from the crystal.
  • the invention also relates to a process for the preparation of the mixed crystals.
  • the mixed crystals are prepared by the following steps:
  • the nanoparticles can be synthesized directly in water. But it is also possible, they z.
  • Example, with the hot injection method (hot injection) represent, and then convert them into water or other suitable for crystallization solvent.
  • the nanoparticles prepared in aqueous solution can be prepared very quickly, simply and inexpensively.
  • the solution for the protective matrix should be saturated or at least approximately saturated, so that the mixed crystals crystallize faster.
  • concentration of nanoparticles in solution is ideally 10 "5 - 10 " 3 mol / l.
  • semiconductor nanoparticles selected from a group consisting of CdSe, CdS, CdTe, ZnSe, ZnSeTe, HgTe, HgCdTe, ZnO, ZnS, ZnTe, HgCdTe, BeSe, BeTe, HgS, GaAs, InP, are used.
  • the compound serving as a protective matrix is selected from a group consisting of NaCl, KBr, KBr0 3 , LiCl, LiBr, Li 2 SO 4 , NaBr, Nal, Na 2 SO 4 , NaNO 3 , Na 3 PO 4 , KCl, K 2 SO 4 , MgCl 2 , MgBr 2 , CaCl 2 , CaBr 2 , BaCl 2 , Ba (NO 3 ) 2 , SrCl 2 , Sr (NO 3 ) 2 , AICI 3 , Al ( N0 3 ) 3 , ZnCl 2 , SnCl 2 , CdCl 2 , potassium sodium tartrate, potassium hydrogen phosphate and / or benzoic acid.
  • Nanoparticles prepared in organic solvents are characterized by high photochemical stability and high fluorescence quantum yields.
  • the colloidal solutions of the nanoparticles blended with stabilizers are first concentrated and then mixed with concentrated solution of the protective matrix (eg NaCl).
  • the protective matrix eg NaCl
  • Solvent removal for example by evaporation of the solvent in a stream of air or leaving it in air, leads to supersaturation of the solution, which gives rise to first crystal nuclei. At this nanoparticles are then adsorbed. Further deprivation of solvent causes the crystal to grow.
  • the layered structure of the crystals includes the nanoparticles and in this way partial isomorphic mixed crystals are obtained in which lattice planes of the host crystals align with the lattice planes of the nanoparticles.
  • the crystallization can be influenced by the appropriate choice of temperature and pressure and the evaporation rate. This allows you to control the desired crystal size well. The slower the parameters are changed, the larger crystals are obtained and the greater the proportion of nanoparticles in the matrix. According to the invention, there is an ordered inclusion of non-aggregated nanoparticles during the crystallization of the crystal matrix. Contrary to the usual expectations, there is no aggregation or exclusion of the non-aggregated nanoparticles. The exclusion of impurities during crystallization is known to be used for the purification of salts (recrystallization).
  • a single crystal of a crystal matrix and nanoparticles is formed, wherein the nanoparticles are embedded in the structure of the matrix.
  • This single crystal is also referred to as mixed crystal in the sense of the invention, since it is characterized by a mixture of matrix and nanoparticles.
  • the size ratio of crystal matrix to nanoparticle is at least 10: 1.
  • a single crystal includes a host crystal of the semiconductor nanocrystals, the lattice planes of which may be aligned with one another, wherein at least one lattice plane of the crystal is aligned with the guest crystal.
  • nanoparticles are prepared in organic solvents, it is necessary to convert them into a water-soluble form. This is achieved, for example, with stabilizers that are adsorbed by the surface of the nanoparticles, thereby ensuring adequate colloidal stability and solubility in water.
  • suitable stabilizers are compounds which can be termed "soft acids” or “soft bases” according to the Pearson concept (or HSAB concept). These include z.
  • organic substances such as thiols, amines or phosphonic acids, which have solubilizing properties.
  • the substances T have proved to be ethanol, thioglycerol, thioglycolic acid and 3-mercaptopropionic acid.
  • an amount of stabilizer in 1, 2 to 3-fold molar excess of Cd used, for example in the ratio of Cd (CIO) 4 " 6H 2 0 to 3-mercaptopropionic 1: 1, 2 to max. 1: 3.
  • Nanoparticles having an electric dipole can be aligned in an electric field.
  • this dipole can be induced or amplified by irradiation with light corresponding to the absorption wavelength of the semiconductor nanocrystals (eg ⁇ 500 nm, 500 W xenon peak pressure lamp).
  • rod-shaped nanoparticles, such as CdSe / CdS in the aligned electric field of a plate capacitor under light irradiation and this state can be fixed by the incorporation of the aligned particles in the crystal matrix.
  • aligning is meant that the longitudinal axes of the rod-shaped particles are arranged in parallel and all pointing in the same direction, for example, by immersing the electrode plates of a plate capacitor in the heated solution of an organic solvent, preferably toluene
  • the solution is filled into a rectangular vessel with its opposing electrodes forming the plates of a plate capacitor, with a positive plate forming a transparent one
  • Electrode represents, for example, with indium tin oxide coated glass (ITO electrode), which is transparent, and the other, negative plate is designed to be cooled to 5 ° C.
  • ITO electrode indium tin oxide coated glass
  • the mixed crystals on the cooled electrode can crystallize out.
  • the nanocrystals are aligned in the crystal.
  • the mixed crystals obtained in this way can emit polarized light.
  • Aligned CdSe / CdS nanocrystals can also be prepared in aqueous solution, but then the electrodes must be isolated from the solvent attached, which z. B. with the help of a 1 mm thick borosilicate succeed.
  • substances for the protective matrix for example, KBr0 3 and benzoic acid are usable.
  • the produced mixed crystals are characterized by a high thermal stability, which predestines them compared to the usual embedding of nanoparticles in polymers.
  • the mixed crystals can be used in a temperature range of -273 ° C to 300 ° C.
  • the mixed crystals can also be easily stored in a dry environment after crystallization and require no solvent or dispersant.
  • the mixed crystals carry the optical properties of the colloidal solutions of the semiconductor nanoparticles. They emit light after excitation with short-wave light. They have an absorption edge and no maximum like organic dyes. By targeted incorporation of the nanoparticles in crystals can be produced with the crystals materials that achieve completely new properties compared to the known, incorporated in polymers nanoparticles.
  • rod-shaped emissive nanoparticles whose orientation in the crystal matrix is fixed as described above, for example, CdSe / CdS core-shell particles in a host lattice results in parallel structures that allow the emission of polarized light.
  • CdTe nanocrystals in NaCl or KCI single crystal showed thermal stability up to 300 ° C and also irradiation with a 1000 W xenon high pressure lamp did not reduce the optical properties. In this case, it is necessary to irradiate light having a wavelength within the absorption spectrum of the nanoparticles, for example at wavelengths of less than 600 nm (according to the absorption spectrum), in order to generate sufficiently excited charge carriers in the CdSe core.
  • the mixed crystals can z.
  • the "conversion layer” (luminescent layer) can be used to produce any wavelength difference due to the synthesis parameters (eg duration of crystal growth) narrow band and produce pure color light, which is important for white light applications.
  • the high thermal stability and stability under plasma discharges makes them ideal for use in fluorescent lamps.
  • Fig. 1 shows an emission spectrum of a gas discharge lamp with CdTe-KBr mixed crystals with mercury / nitrogen filling at 5 mbar. One can clearly see the emission band of CdTe at 657 nm.
  • the semiconductor particles in the protective matrix are thus sufficiently stable against thermal influences.
  • Rod-shaped nanoparticles such as CdSe / CdS core-shell particles can produce polarized light when aligned. This is done by aligning the rod-shaped nanoparticles in a DC field and then fixing the nanoparticles in the crystal matrix.
  • the mixed crystals can also serve. Since the nanoparticles are colloidally soluble in water, the mixed crystals can easily be dissolved in water again if necessary. By reprecipitation, the nanoparticles can easily be freed from the adhering protective matrix and can thus be easily separated from one another.
  • TeH 2 In a three-necked flask equipped with reflux condenser under argon within one hour 2.6 mmol of TeH 2 are poured into an aqueous solution containing 2.3 g (5.5 mmol) of Cd (CIO) 4 -6H 2 O and 0.756 g (7.1 mmol) 3-mercaptopropionic acid introduced.
  • the TeH 2 is produced electrochemically in an electrolysis cell provided with tellurium cathode and platinum anode, which contains 30% sulfuric acid as the electrolyte.
  • nanoparticles of size 1-5 nm can be produced under reflux with heating, which can have an emission maximum in the range of 520-780 nm.
  • the half-width of the emission signal is about 40 nm.
  • the heating time (1 00 ° C) determines the size of the nanoparticles.
  • the reaction is stopped by cooling the reaction mixture in a water bath. Since the nanoparticles have a broad size distribution, subsequent size fractionation is recommended by concentration of the colloidal solution, fractional precipitation with isopropanol and centrifuging. The precipitated nanoparticle fractions can then be redispersed in water.
  • the crystal growth is complete after about 2 months and the obtained 1 - 2 mm cubic mixed crystals are separated from the mother liquor by filtration, dried with filter paper and in a desiccator over silica gel.
  • the mixed crystals were irradiated for 8 hours with the light of a 1000 W xenon ultra-high pressure lamp at a distance of 10 cm. There was hardly any change in the emission wavelength maximum of the nanoparticles.
  • the synthesis known in the literature as the "hot injection” method, is divided into 2 steps:
  • the CdSe nuclei are formed by reaction of cadmium oxide with a selenium (O) complex in the high-boiling trioctylphosphine oxide (TOPO) at 365 ° C generated.
  • TOPO trioctylphosphine oxide
  • the CdS nuclei CdS are grown, which is produced by the reaction of cadmium oxide and sulfur in the high-boiling solvent TOPO.
  • TOPO high-boiling solvent
  • trioctylphosphonic acid TOPO
  • ODPA octadecylphosphonic acid
  • CdO CdO
  • TOPO trioctylphosphonic acid
  • ODPA octadecylphosphonic acid
  • CdO CdO
  • nanoparticles and metal salt are soluble in the same solvent, in this case water.
  • the nanocrystals prepared in the organic solvent which have adsorbed phosphonic acids as stabilizer molecules on their surface, must be mixed with water-soluble stabilizer molecules in order to pass into the aqueous phase.
  • this nanoparticle suspension 0.5 ml of this nanoparticle suspension are heated to 80 ° C and placed in 5 ml of saturated 80 ° C hot KBr0 3 solution and cooled their temperature in the air stream within 10 min to 20 ° C.
  • the resulting 0.1 to 1 mm needle-shaped crystals are filtered off, dried with filter paper and in a desiccator over silica gel.
  • Fig. 3 shows a CdSe / CdS-KBr0 3 mixed crystal under UV light. One can clearly see the fluorescence even at low concentrations of the semiconductor particles in the crystal.
  • the CdTe nanoparticles are prepared as described in Example 1.
  • nanoparticles of size 2.8 mm with the emission wavelength of 624 nm and nanoparticles of size 2.1 nm with the emission wavelength of 538 nm were used.
  • the crystal growth is complete after about 2 weeks and the resulting 2 mm mixed crystals are separated from the mother liquor by filtration, dried with filter paper and in a desiccator over silica gel.
  • Fig. 4 shows a CdSe / CdS-KBr0 3 mixed crystal under excitation with UV light. One clearly recognizes the fluorescence of the crystal.
  • CdSe / CdS nanoparticles are dissolved in toluene after synthesis.
  • a phase transfer in water is necessary.
  • Embodiment 5 Preparation of oriented, rod-shaped CdSe / CdS-benzoic acid mixed crystals
  • Rod-shaped CdSe / CdS-benzoic acid mixed crystals can be aligned in the electric field of a plate capacitor with a field strength of 200 kV / cm under irradiation with light and fix this state by incorporation into the crystal matrix.
  • CdSe / CdS nanoparticles are heated to 80 ° C and mixed with 10 ml of a 80 ° C and saturated solution of benzoic acid in toluene.
  • the electrode plates of the plate capacitor are dipped in the solution.
  • the solution is filled into a rectangular vessel with its opposing electrodes forming the plates of a plate capacitor, a positive plate containing a transparent electrode, e.g. B with indium tin oxide coated glass (ITO electrode), which is made translucent.
  • a positive plate containing a transparent electrode, e.g. B with indium tin oxide coated glass (ITO electrode), which is made translucent.
  • ITO electrode indium tin oxide coated glass
  • the other, negative plate is designed with the help of a Peltier element to 5 ° C coolable.
  • the negative plate (electrode) of the plate capacitor is gradually cooled by means of a Peltier element within 30 minutes to 10 ° C, so that the crystals of the protective matrix of benzoic acid crystallize together with the nanoparticles on the cooled electrode.
  • the resulting acicular crystals are then filtered off with filter paper and dried in a desiccator over silica gel.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Luminescent Compositions (AREA)

Abstract

L'invention concerne de nouveaux cristaux mixtes constitués de matériaux semiconducteurs provenant des éléments des groupes 12 & 15, 12 & 16, 13 & 15 et/ou 14 & 16 de la classification périodique des éléments, situés dans une matrice protectrice, un procédé pour leur production et leurs applications dans différents matériaux, par exemple dans des lampes fluorescentes, dans la technique laser ou comme matériau d'emballage pour nanoparticules. Les particules de semiconducteurs ont une taille moyenne comprise entre 1 et 100 nm et leur teneur dans les cristaux mixtes est de 10-9-10%.
PCT/EP2011/066027 2010-09-16 2011-09-15 Cristaux mixtes contenant des matériaux semiconducteurs, leur procédé de production et leurs applications Ceased WO2012035109A1 (fr)

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WO2013057702A1 (fr) * 2011-10-20 2013-04-25 Koninklijke Philips Electronics N.V. Source de lumière à boîtes quantiques
WO2015117876A1 (fr) * 2014-02-04 2015-08-13 Koninklijke Philips N.V. Points quantiques avec des ligands inorganiques dans une matrice inorganique
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JP6971972B2 (ja) * 2015-09-10 2021-11-24 リテック−ヴェルメーゲンズヴェルワルツングスゲゼルシャフト エムベーハーLITEC−Vermoegensverwaltungsgesellschaft mbH 光変換材料
CN116946999B (zh) * 2023-07-17 2025-06-27 中国机械总院集团武汉材料保护研究所有限公司 镉基磷酸盐纳米花、切削液及制备方法

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WO2013057702A1 (fr) * 2011-10-20 2013-04-25 Koninklijke Philips Electronics N.V. Source de lumière à boîtes quantiques
US9412916B2 (en) 2011-10-20 2016-08-09 Koninklijke Philips N.V. Light source with quantum dots
US9537059B2 (en) 2011-10-20 2017-01-03 Koninklijke Philips N.V. Light source with quantum dots
US10090443B2 (en) 2011-10-20 2018-10-02 Koninklijke Philips N.V. Light source with quantum dots
WO2015117876A1 (fr) * 2014-02-04 2015-08-13 Koninklijke Philips N.V. Points quantiques avec des ligands inorganiques dans une matrice inorganique
CN105940082A (zh) * 2014-02-04 2016-09-14 皇家飞利浦有限公司 在无机基质中具有无机配体的量子点
US10113109B2 (en) 2014-02-04 2018-10-30 Lumileds Llc Oxo- and hydroxo-based composite inorganic ligands for quantum dots
US10340427B2 (en) 2014-02-04 2019-07-02 Lumileds Llc Quantum dots with inorganic ligands in an inorganic matrix
CN105940082B (zh) * 2014-02-04 2019-07-05 亮锐控股有限公司 在无机基质中具有无机配体的量子点

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