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WO2012052041A1 - Polymère luminescent avec boîtes quantiques - Google Patents

Polymère luminescent avec boîtes quantiques Download PDF

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Publication number
WO2012052041A1
WO2012052041A1 PCT/EP2010/006395 EP2010006395W WO2012052041A1 WO 2012052041 A1 WO2012052041 A1 WO 2012052041A1 EP 2010006395 W EP2010006395 W EP 2010006395W WO 2012052041 A1 WO2012052041 A1 WO 2012052041A1
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luminescent
quantum dots
luminescent polymer
polymer according
polyamide
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PCT/EP2010/006395
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English (en)
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Ying Yuan
Frank Stefan Riehle
Michael Kruger
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Albert-Ludwigs-Universität Freiburg
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Priority to PCT/EP2010/006395 priority Critical patent/WO2012052041A1/fr
Publication of WO2012052041A1 publication Critical patent/WO2012052041A1/fr

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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
    • C09K11/02—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
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • 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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
    • 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
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/14—Macromolecular compounds

Definitions

  • the present invention relates to luminescent polymers which have luminescent quantum dots integrated therein.
  • Hybrid materials based on nanoparticles and polymeric systems show an increasing potential for the development of new functional composite materials. Examples are the incorporation of carbon nanostructures like carbon nanotubes into polymers to achieve superior mechanical strength, as well as the development of bulk-heterojunction devices out of semiconducting quantum dots (QDs) and semiconducting polymers as new hybrid-materials for LED and photovoltaic applications. Advantages of fluorescent semiconducting nanocrystals compared to conventional organic dyes are their higher photostability, their narrow light emission and their broad absorption characteristic enabling e.g. efficient energy down-conversion.
  • quantum dots have been incorporated in thin films out of ZnS and solvent based polymers with potential for flat panel displays as well as in polymerizable ionic liquid matrices.
  • One major challenge is to avoid aggregation processes and luminescence quenching while incorporating the QDs into a threedimensional matrix.
  • a quantum dot (QD) in the terminology of the present application signifies a semiconductor whose excitons are confined in all three spatial dimensions. As a result, they have properties that are between those of bulk semiconductors and those of discrete molecules.
  • Quantum dots are semiconductors whose conducting characteristics are closely related to the size and shape of the individual crystal. Generally, the smaller the size of the crystal, the larger the band gap, the greater the difference in energy between the highest valence band and the lowest conduction band l becomes. Therefore, more energy is needed to excite the dots and concurrently, more energy is released when the crystal returns to its resting state. For example, in fluorescent dye applications, this equates to higher frequencies of light emitted after excitation of the dot as the crystal size grows smaller, resulting in a colour shift from red to blue in the light emitted.
  • the main advantage in using quantum dots can be seen in a very precise control over the optical properties of the materials, due to the high level of control which can be achieved over the size of the crystals produced.
  • colloidal semiconductor nanocrystals are synthesized from precursive compounds dissolved in solution and there are colloidal methods to produce many different semiconductors.
  • Typical QDs are made from binary alloys such as cadmium selenide, cadmium sulphide, indium arsenide, and indium phosphide.
  • QDs may also be made from ternary alloys such as cadmium, selenide sulphide.
  • These quantum dots can contain as few hundred to a few thousands of atoms. This corresponds to about 2 to 10 nanometres. Large batches of quantum dots may be synthesized via colloidal synthesis. Due to the scalability and the convenience of bench-top conditions, colloidal synthetic methods are most promising for commercial applications and are furthermore acknowledged to represent the least toxic of the different forms of synthesis.
  • Such colour converting luminescent materials may, for instance, be used as coating material for white light emitting diodes (LED).
  • LED white light emitting diodes
  • quantum dots By converting blue portions of the radiation into red portions, the adaptation to the solar spectrum can be optimized and the so-called "cold" white light can be avoided for illumination.
  • quantum dots As a converting coating of UV and blue LEDs, all desired colours can be generated with a high accuracy and with minimized conversion losses.
  • illumination systems can be coated in order to generate radiation with a predetermined desired wavelength, for instance, by adapting the light emission to emit radiation which corresponds to the absorption characteristics, for instance, of chlorophyll.
  • Luminescent materials which emit light at well defined wavelengths can also be used as reference standards for three-dimensional microscopy.
  • Known luminescence conversion layers suffer from the disadvantage that their quantum efficiencies are mostly far below 50%.
  • conventional QD synthesis mostly implies a process comprising several steps because usually one or more protective layers have to be applied to a core material. This procedure is connected with higher material losses due to purification steps and side reactions.
  • the luminescent polymer is formed from a polyamide host structure with luminescent quantum dots integrated therein.
  • Polyamides or nylons are a versatile family of thermoplastics that have broad range properties ranging from relative flexibility to significant stiffness, strength and toughness.
  • Major properties such as resistance to chemicals, toughness, thermal stability and well established processability are key considerations that made polyamides suitable for a broad range of applications during the last few decades.
  • a hybrid material according to the present invention exhibits quantum yields of more than 65%, thus offering a high potential for applications in direct light and energy conversion.
  • a luminescent polymer according to the present invention suffers from bleaching effects much less than conventional luminescent polymers.
  • three-dimensional structures can be formed that are particularly suitable for being used as a standard in three-dimensional luminescent microscopy.
  • Polyamides comprise a wide range of materials, depending on the monomers employed. Commonly used products are designated as nylon 6; 6,6; 6,12; 1 1 and 12 with the nomenclature designing the number of carbon atoms that separate the repeating amide group. Nylon 6 and nylon 6,6 continue to be the most widespread types among polyamide commercial products.
  • polyamide engineering polymers Two basic reactions are used to synthesize polyamide engineering polymers: firstly the polymerization of a dibasic acid and a diamine or, secondly, the polymerization of an amino acid or lactam.
  • polyamides All commonly used polyamides can be employed according to the principles of the present invention, it could be shown that particularly advantageous characteristics can be achieved by fabricating the polyamide host as a 6 polyamide polymerized from 6 amino caproic acid.
  • the quantum dots comprise CdSe nanocrystals.
  • QD materials such as CdS, CdTe and ternary alloys out of e.g. CdZnSe and CdZnS can be used.
  • the quantum dot nanocrystal will be prepared by a colloidal synthesis method as mentioned above.
  • These core semiconductor materials allow for optimized size distribution, surface quality, and colour tuning in the visible spectrum.
  • CdZnS can be fine tuned across the entire blue region
  • CdZnSe nanocrystals can provide narrow band emission wavelengths from 500 to 550 nanometres and CdSe is used to make the most efficient and narrow band emission in the yellow red part of the visible spectrum (550 to 650 nanometres).
  • Each semiconductor material is chosen specifically to address the wavelength region of interest to optimize the physical size of the QD material, which is important to achieve good size distributions, high stability and efficiency as well as ease of processability.
  • quantum dots can include a ternary semiconductor alloy.
  • the use of a ternary semiconductor alloy can also permit use of the ratio of cadmium to zinc in addition to the physical size of the QD nanocrystal in order to tune the colour of the emission.
  • the quantum dots are provided with a protective ligand such as hexadecylamine (HDA), and Trioctylphosphineoxide (TOPO).
  • a protective ligand such as hexadecylamine (HDA), and Trioctylphosphineoxide (TOPO).
  • hexadecanol (HDO) can be used as the protective ligand.
  • HDA hexadecylamine
  • TOPO prevents a disintegration of the cadmium stearate in the presence of higher temperatures.
  • the advantageous characteristics of the luminescent polymer according to the present invention may most effectively be used when applying it to a lighting device as a wavelength transforming layer, using it for energy conversion in lighting systems for greenhouses or using it as a light absorbing layer in a solar concentrator cell.
  • a fluorescent standard for confocal imaging techniques can be provided in an advantageous way, said standard being fabricated from a three-dimensional hybrid material comprising a luminescent polymer according to the present invention.
  • the quantum dot polymer hybrid material can be cast into a desired three-dimensional form and polymerized in situ in a mold.
  • Figure 1 shows a schematic diagram of the fabrication of a luminescent polymer comprising a polyamide host and luminescent quantum dots integrated therein;
  • Figure 2 shows the absorption spectra of differently sized cadmium selenide quantum dots;
  • Figure 3 shows the photo-luminescence intensity of differently sized quantum dots
  • Figure 4 shows a laser scanning microscopical investigation of a thin film with a photo- luminescent wavelength of 566 nanometres
  • Figure 5 shows a laser scanning microscopical investigation of a thin film with a photo- luminescent wavelength of 589 nanometres
  • Figure 6 shows the laser scanning microscopical investigation of a thin film with a photo- luminescent wavelength of 630 nanometres
  • Figure 7 shows a schematic flow diagram of the fabrication process according to the present invention.
  • Figure 8 shows the bleaching characteristics of CdSe QD polymer films under different laser power exposure conditions.
  • Figure 1 shows the in situ polymerization of a CdSe quantum dot nylon hybrid material according to the present invention.
  • the material exhibits quantum yields of more than 65% with a high potential for applications in direct light and energy conversion.
  • the present invention provides an easy, reproducible one pot in situ polymerization to obtain a quantum dot polymer hybrid material out of prefabricated cadmium selenide quantum dots and nylon with photo-luminescent quantum yields exceeding 60%.
  • the CdSe quantum dots were synthesized at 300°C from Cd stearate and trioctylphosphine selenide (TOPSe) in an organic matrix consisting of trioctylphosphine oxide and hexadecylamine using a hot injection method as described in the article Y. Yuan et al., J. Nanosci. Nanotech., 2010, Vol.10, p.6014-6045.
  • TOPSe trioctylphosphine selenide
  • Cd and Se precursors a) 1 mmol of red brown cadmium oxide, CdO, and 4 mmol colourless stearic acid HSA , and a catalytic amount of succinic acid are heated for 5 to 60 minutes under inert gas to 200°C. The reaction that leads to the forming of cadmium stearate, Cd(SA) 2 is finished when a clear uncoloured solution is yielded. Cd(SA) 2 is solid at room temperature and can be used for fabricating cadmium selenide nanocrystals without further preparation steps. A slight excess of HSA is necessary for completely transforming CdO and for yielding the colourless solution.
  • Equation 1 shows the chemical reaction: CdO + 2 HSA Cd(SA) 2 + H 2 0 (200 °C) (1) b) 1 mmol black selenium, Se, is dissolved in 1 ml colourless trioctylphosphine, TOP, under inert gas at 200°C (6 to 24 hours). Trioctylphosphine selenide, TOPSe is generated as a reaction product. The reaction is finished if a clear colourless solution is yielded.
  • the 1 molar Se precursor solution can be stored at room temperature under air exclusion and can be used after a systematic aging process. This systematic aging of the Se precursor solution under air exposure is an essential step of the synthesis of strongly fluorescent CdSe nanocrystals.
  • the forming of trioctylphosphine selenide is described by the following reaction equation:
  • the reaction comprises hexadecylamine (HDA), and trioctylphosphine oxide( TOPO) ,in a molar ratio of 6 : 4.
  • the matrix at the same time serves as a solvent and as a ligand for forming the CdSe nanocrystals in a temperature region between 100°C and 300°C.
  • TOPO prevents the disintegration of cadmium stearate at high temperatures, such as 300°C.
  • the molar rate of Cd to Se is 1 : 1
  • the molar rate of Cd and Se, respectively, to the matrix is 1 : 100. All following synthesis steps are performed under inert gas atmosphere, for instance, nitrogen.
  • HDA is heated for 30 minutes to about 300°C.
  • HDA forms carbonate together with C0 2 from the air which is an inferior ligand for cadmium selenide nanocrystals.
  • C0 2 is removed again.
  • 0.1 mmol solid Cd(SA) 2 is dissolved in 4 mmol TOPO under an elevated temperature of about 100°C and is then added to 6 mmol HDA at 300°C.
  • the aged Se precursor solution is swiftly added to the uncoloured solution.
  • An instantaneous colour change to red indicates the forming of CdSe nanocrystals.
  • an annealing step for enhancing the fluorescence quantum efficiency is performed by heating the nanocrystals for about 2 hours to 300°C. During this step, defects are cured by annealing the crystal, while surface damaging processes such as, for instance, the Ostwald ripening, are suppressed due to the HDA ligands firmly bound to the surface of the nanocrystals.
  • the reaction mixture is slowly cooled until the solidification point is reached in order to promote performing of a protective HDA ligand sphere of up to 100 nanometres around the nanocrystals.
  • a protective HDA ligand sphere of up to 100 nanometres around the nanocrystals.
  • a protective ligand sphere for forming a protective ligand sphere, three conditions have to be fulfilled: a) presence of a sharp separation between nucleation and growth or forming of homogenous nanocrystals, which can be reached, for instance, by a well defined aging of the Se precursor under air atmosphere, b) the pre-treatment of the HDA ligand at 300°C in order to get rid of interfering C0 2 which allows annealing the HDA ligand at the crystal surface at high temperatures in order to promote healing of detrimental defects, and c) a slow cooling which allows the forming of a protective ligand sphere at the now highly organized crystal surface.
  • Another advantageous approach for synthesizing colloidal stable CdSe nanocrystals is the use of aliphatic alcohols such as hexadecanol (R-OH) as a novel ligand system.
  • This alcoholic ligand system leads to CdSe core quantum dots having medium quantum efficiency.
  • This ligand can be used for luminescent CdS, CdSe and CdTe quantum dots.
  • the alcoholic ligand system is very cost efficient and may be an advantageous ligand for all applications where not the optimization of the quantum efficiency but of the fluorescence stability under illumination is important.
  • nanocrystals with hexadecanol as a ligand have proved a higher light stable than cadmium selenide quantum dots with an HDA/TOP as ligands.
  • the TOPSe precursor (produced as described above) are filled with 1.21 g hexadecanol (HDO) and 40 mg cadmium laureate under inert gas atmosphere into a sealable microwave synthesis glass container.
  • HDO hexadecanol
  • cadmium laureate is solved within 3 minutes under fast stirring and then the reaction mixture is heated by means of 300 W microwave power to 200°C.
  • cadmium selenide core quantum dots can be synthesized with different sizes.
  • the CdSe quantum dots according to the present invention are fabricated without an additional anorganic protection layer such as ZnS or CdS (which is also called core shell materials).
  • the synthesis of the CdSe quantum dot polymer hybrid material according to the present invention is done as a simple "single pot reaction" without any pre-purification of the QD synthesis product.
  • the best results were achieved by performing the in situ polymerization under inert gas atmosphere, for instance, nitrogen. It could be shown that the in situ polymerization of a polyamide was able to maintain the superior fluorescence of the quantum dot also within the polymer material.
  • Other known polymers yielded hybrid materials with significantly deteriorated fluorescence efficiency.
  • a polyamide host material fabricated as described by the following reaction equation has been proved to be particularly efficient.
  • FIG. 3 shows that by stopping the reaction for fabricating the quantum dots, green 301 , yellow 302, orange 303 and red 304 emitting quantum dots were obtained by stopping the reaction after 3 seconds, 15 seconds, 60 seconds and 300 seconds, respectively. This led to differently sized quantum dots. In particular, it could be shown that green emitting QDs had a diameter of
  • reference numeral 201 represents the curve for the green quantum dots
  • reference numeral 202 the yellow
  • 203 the orange
  • 204 the red quantum dots.
  • the polymerization of 6 amino caproic acid monomers in the presence of as-prepared cadmium selenide quantum dots may advantageously be performed at 220 to 250°C in a straightforward process under ambient conditions or under nitrogen atmosphere. All four differently sized quantum dots can be incorporated into the nylon polymer and laser scanning microscopical, LSM imaging of the hybrid materials revealed the homogenous distribution of the yellow, orange and the red emitting quantum dots in the polymer while keeping their original emission colour as can be seen from Figures 4 to 6. The green emitting quantum dots, however, showed a red shift due to the further growth during the polymerization reaction (not shown in the Figure).
  • the flow diagram of Fig. 7 illustrates a method for fabricating the hybrid QD material according to the present invention.
  • Cd-stearate was prepared from 32.1 mg CdO (0.25 mmol) and 248.9 mg stearic acid (0.875 mmol) at 200 °C under nitrogen atmosphere. The reaction was stopped when a colourless solution appeared.
  • TOPO (99%) and stearic acid ( ⁇ 97%) were purchased from Sigma Aldrich, HDA (99%) was obtained from Fluka and CdO (99.998%) from Alfa Aesar.
  • Se powder (99.999%) and TOP (97%) were obtained from ABCR (Karlsruhe, Germany). 6-Aminocaproic acid ( ⁇ 99%) was purchased from Sigma Aldrich.
  • CdSe quantum dots with defined size typically a mixture of 277 mg Cd-stearat (0.25 mmol), and 3.866 g trioctylphosphine oxide (TOPO) (10 mmol) was added to preheated 3.622 g hexadecylamine (HDA) (15 mmol) was then degassed at 100 °C. 0.25 ml of a 1 M solution of Se in TOP was swiftly injected at 300 °C and the colourless solution became yellow within 1 s and turned to red after about 5 s.
  • TOPO trioctylphosphine oxide
  • HDA hexadecylamine
  • an in-situ synthesis of the quantum dot-nylon hybrid material was performed using the unpurified QDs.
  • Different amounts of as prepared CdSe QDs 40 mg, 80 mg and 200 mg, the concentration of the QDs in solution is estimated to be about 0.25 ⁇ 0.3 wt %) were obtained from their growth solution without applying any purification steps.
  • the QDs capped with a monolayer of TOPO/HDA ligands were re-dispersed in 2g of the nylon monomes 6-Aminocaproic acid (Company Sigma-Aldrich) Then, the mixture was heated to 220 ⁇ 250 °C with and without N 2 protection.
  • the quantum dots hybrid material can be processed while kept in liquid phase above 150°C and a multitude of different forms and shapes can be generated.
  • the transparency of the resulting product can be increased by fast cooling of the liquid phase.
  • Fig. 8 shows experimental details on the bleaching behaviour of the inventive hybrid material.
  • Fig. 8 is a graph showing bleaching experiments of CdSe QD polymer films (containing HDA capped QDs) under different laser power exposure conditions: After some time a constant intensity stays showing a stable fluorescent situation. After stopping the laser exposure the fluorescent intensity raises to the initial value (reversibility). The initial change in intensity after laser irradiation is depending on the laser power, the QD loading of the film and on the type of ligand shell around the QDs. The experiments have been performed at 2 Photon excitation conditions at an excitation wavelength of 780 nm. Commercially available QDs with the same emission wavelength of 630nm with an inorganic ZnS protective shell do not show a stable fluorescence under similar experimental conditions.
  • an easy and reproducible one pot in-situ polymerization process is presented, in order to obtain quantum dot polymer hybrid materials out of CdSe quantum dots and nylon with photoluminescent quantum yields exceeding 60%.
  • the CdSe quantum dots were synthesized at 300 °C from Cd-stearate and trioctylphosphine-selenide (TOPSe) in an organic matrix consisting out of trioctylphosphine-oxide and hexadecylamine using a hot injection method. Green, yellow, orange and red emitting quantum dots were obtained by stopping the reaction after 3s, 15s, 60s and 300s respectively leading to differently sized quantum dots
  • LSM Laser scanning microscopical Imaging of the hybrid materials revealed the homogenious distribution of the yellow, the orange and the red emitting quantum dots in the polymer while keeping their original emission color. In contrast the green emitting quantum dots showed a significant redshift due to further growth during the polymerization reaction. The best longterm stability and quantum yields of 65% were found for the red emitting quantum dot-polymer hybrid material, which exhibited only a little loss compared to the original red-emitting quantum dots (QE 72% ).
  • the quantum dot hybrid material can be processed under N 2 protection to prevent photooxidation while kept in liquid phase above 150°C and different forms and shapes are available.
  • the transparency of the resulting product can be increased by fast cooling of the liquid phase.
  • the red fluorescent quantum dot-polymer hybrid was further used as cover material for conventional low-cost blue LEDs to demonstrate the successful energy down conversion capability.
  • the so collected energy is converted to light emitting at longer wavelength with a narrow bandwith.
  • the polymer hybrid materials according to the present invention have high potential as light absorbing layers in solar concentrator cells, as phosphors for detectors or screens, or as energy converting layers for biofuel production. Since plants are using only 1 % of the energy of the sun spectrum for the photosnthesis their growth rate can be dramatically enhanced by focussing the energy towards the two absorption maxima of Chlorophyll a and b (400-500 nm and 600-700 nm, respectively).
  • the emission wavelength of our red emitting quantum dot polymer hybrid material matches exactly to the absorption maxima of chlorophyll b. This makes them ideal candidates for energy down conversion of UV, blue green, yellow or orange light into red light which then could be utilized for enhancing plant growth, and might have impact for future biofuel production application such as the improved growth of algaes as alternative biofuel material which is not in competition with the food production chain.

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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

La présente invention concerne des polymères luminescents qui ont des boîtes quantiques intégrées en leur sein. En particulier, un polymère luminescent selon la présente invention comprend un hôte de polyamide et des boîtes quantiques luminescentes intégrées en son sein. De plus, la présente invention concerne un procédé de fabrication d'un tel matériau hybride, un dispositif d'éclairage avec une couche transformant la longueur d'onde pour modifier la longueur d'onde de la radiation émise, ladite couche transformant la longueur d'onde comprenant un polymère luminescent, et un standard fluorescent pour des techniques d'imagerie confocale, ledit standard étant fabriqué à partir d'un matériau hybride tridimensionnel comprenant un tel polymère luminescent. Selon la présente invention, l'hôte de polyamide comprend du polyamide 6 qui est polymérisé à partir d'acide 6-aminocaproïque.
PCT/EP2010/006395 2010-10-19 2010-10-19 Polymère luminescent avec boîtes quantiques WO2012052041A1 (fr)

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