CN116948638B - Multicolor high-quantum-yield solution-processable heat-activated delayed fluorescence onion-like carbon quantum dot and preparation and application thereof - Google Patents
Multicolor high-quantum-yield solution-processable heat-activated delayed fluorescence onion-like carbon quantum dot and preparation and application thereof Download PDFInfo
- Publication number
- CN116948638B CN116948638B CN202310551239.7A CN202310551239A CN116948638B CN 116948638 B CN116948638 B CN 116948638B CN 202310551239 A CN202310551239 A CN 202310551239A CN 116948638 B CN116948638 B CN 116948638B
- Authority
- CN
- China
- Prior art keywords
- onion
- solution
- delayed fluorescence
- activated delayed
- carbon quantum
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 230000003111 delayed effect Effects 0.000 title claims abstract description 70
- 238000006862 quantum yield reaction Methods 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 20
- 239000002243 precursor Substances 0.000 claims abstract description 20
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 12
- CLYVDMAATCIVBF-UHFFFAOYSA-N pigment red 224 Chemical compound C=12C3=CC=C(C(OC4=O)=O)C2=C4C=CC=1C1=CC=C2C(=O)OC(=O)C4=CC=C3C1=C42 CLYVDMAATCIVBF-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000004729 solvothermal method Methods 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 48
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 17
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 16
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 8
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 241000234282 Allium Species 0.000 claims description 6
- 235000002732 Allium cepa var. cepa Nutrition 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- 239000012046 mixed solvent Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 3
- 230000003472 neutralizing effect Effects 0.000 claims description 3
- 238000004440 column chromatography Methods 0.000 claims 2
- 239000007788 liquid Substances 0.000 claims 2
- 239000011259 mixed solution Substances 0.000 claims 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 abstract description 14
- 238000007725 thermal activation Methods 0.000 abstract description 6
- 230000003993 interaction Effects 0.000 abstract description 2
- 239000000178 monomer Substances 0.000 abstract description 2
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 238000001228 spectrum Methods 0.000 description 12
- 238000000502 dialysis Methods 0.000 description 10
- 238000001704 evaporation Methods 0.000 description 10
- 239000000758 substrate Substances 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000010408 film Substances 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 7
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 7
- 230000005284 excitation Effects 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 5
- 238000004528 spin coating Methods 0.000 description 5
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical group ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 238000000137 annealing Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 230000004075 alteration Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 230000006911 nucleation Effects 0.000 description 3
- 238000010899 nucleation Methods 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 229920000144 PEDOT:PSS Polymers 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000004770 highest occupied molecular orbital Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000007738 vacuum evaporation Methods 0.000 description 2
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 description 1
- GEQBRULPNIVQPP-UHFFFAOYSA-N 2-[3,5-bis(1-phenylbenzimidazol-2-yl)phenyl]-1-phenylbenzimidazole Chemical compound C1=CC=CC=C1N1C2=CC=CC=C2N=C1C1=CC(C=2N(C3=CC=CC=C3N=2)C=2C=CC=CC=2)=CC(C=2N(C3=CC=CC=C3N=2)C=2C=CC=CC=2)=C1 GEQBRULPNIVQPP-UHFFFAOYSA-N 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000000089 atomic force micrograph Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000001748 luminescence spectrum Methods 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000011970 polystyrene sulfonate Substances 0.000 description 1
- 229960002796 polystyrene sulfonate Drugs 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000010129 solution processing Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- 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
- C09K11/65—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
- H10K50/115—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising active inorganic nanostructures, e.g. luminescent quantum dots
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Optics & Photonics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biophysics (AREA)
- Composite Materials (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Luminescent Compositions (AREA)
Abstract
The invention relates to the field of carbon nano materials, in particular to a multicolor high-quantum-yield solution-processable thermally-activated delayed fluorescence onion-like carbon quantum dot, and preparation and application thereof. According to the invention, pyromellitic acid and 3,4,9, 10-perylene tetracarboxylic dianhydride are used as carbon source precursors, and the thermal activation delayed fluorescence onion-like carbon quantum dot which can be processed in a solution can be obtained through a solvothermal method under the condition of concentrated sulfuric acid. The multicolor high-quantum-yield heat-activated delayed fluorescence onion-like carbon quantum dot prepared by the invention is a onion-like three-dimensional structure formed by connecting monomer carbon quantum dots through intermolecular weak interaction force, and has wide application prospect.
Description
Technical Field
The invention relates to the field of carbon nano materials, in particular to a multicolor high-quantum-yield solution-processable thermally-activated delayed fluorescence onion-like carbon quantum dot, and preparation and application thereof.
Background
The carbon quantum dot (CarbonQuantumDots, CQDs) has the advantages of adjustable band gap emission, high light/heat stability, good solution processability, low toxicity and the like, and has wide application prospect in the field of photoelectric devices. Under the drive of the forward voltage, electrons and holes of the cathode and the anode can be respectively injected into the organic light-emitting layer between the electrodes to be recombined to form excitons, and then radiation transition occurs. In recent years, the breakthrough progress of the electro-active LEDs based on CQDs, especially the successful realization of the electroluminescence of intrinsically narrow-emitting CQDs, has greatly driven the broad application of the next generation high performance display field.
However, under electrical excitation, limited by electron spin exclusion, fluorescent-Emitting organic materials can only capture 25% of singlet excitons (s=0), and fluorescent CQDs-based electroluminescent Diodes (LEDs) have limited external quantum efficiencies (ExternalQuantumEfficiency, EQE) with theoretical EQEs of only 5%. Therefore, the remaining 75% of triplet excitons (s=1) are efficiently utilized, and it is expected to significantly improve the device performance, both in the phosphorescent form and in the delayed fluorescent form, thereby achieving an EQE close to 25% and high device luminance.
Electroluminescent LEDs based on phosphorescent CQDs are realized with EQEs exceeding 5% by linking the zero-dimensional CQDs with pi channel chains to form a two-dimensional organic framework structure. By designing unique structures, lowering triplet energy levels, enhancing spin-orbit coupling, and balancing electron-holes makes it possible to achieve high device efficiency in CQDs using triplet excitons. However, due to the large energy level difference (Δe ST) between the singlet and triplet states, phosphorescent emission typically exhibits one broad emission peak or even two emission peaks, and is affected by spin-forbidden transitions, with lifetimes typically in the millisecond/second range.
Thermally activated delayed fluorescence (THERMALLY ActivatedDelayedFluorescence, TADF) with radiative transitions from the triplet back to the singlet state (T 1→S1→S0) is a promising approach to overcome this situation. Small Δe ST (0.1-0.3 eV) is critical to produce strong reverse intersystem crossing and by enhancing charge transfer efficiency between energy levels, lifetime can be shortened to nanosecond/microsecond range while achieving polychromatic emission. Notably, strategies for achieving TADF emission have been widely reported, including heavy atom doping, matrix assist, and the like. For example, blue TADF emission has been achieved by confining carbon dots in zeolite with a Quantum Yield (QY) of 52.14%, but exhibiting a longer lifetime (up to 350 ms). It follows that simple structural modification or doping of CQDs still presents significant non-radiative recombination losses, and that samples generally have poor solution processability, which severely hampers further practical use of TADF of CQDs in electroluminescent LEDs.
For triplet emissive materials with metal coordination structures and donor-acceptor structures in organic LEDs, Δe ST is proportional to the overlap of the Highest Occupied Molecular Orbital (HOMO) and the Lowest Unoccupied Molecular Orbital (LUMO). Thus, designing the building blocks of a molecule for specific assembly is an efficient way to regulate the S 1 and T 1 energy levels. CQDs exhibit monomer molecular geometry with steric hindrance aberrations through pi-pi conjugated interactions of the carbon core with surrounding organic molecules and steric hindrance synergism. And it is desirable to form a specific three-dimensional spatial configuration by structural assembly of the monomeric CQDs, adjust the track overlap, and make Δe ST smaller, thereby achieving TADF emission. Thus, the preparation of the thermally activated delayed fluorescence CQDs with adjustable emission wavelength, which can be processed by solution, has high quantum yield and short service life, is a necessary path for developing high-efficiency electro-LEDs, and still has great challenges.
Disclosure of Invention
The invention provides a thermal-activation delayed fluorescence onion-like carbon quantum dot which can be processed by a solution with multicolor high quantum yield, and a preparation method and application thereof, and aims to solve the problems that the carbon quantum dot solid reported at present is insoluble and can not be processed by the solution, fluorescence emission often shows excitation-dependent defect state characteristics, excitation-independent eigenstate emission quantum yield is low, emission wavelength is short and fluorescence service life is long.
The invention aims to provide a multicolor high-quantum-yield solution-processable thermally-activated delayed fluorescence onion-like carbon quantum dot.
Still another object of the present invention is to provide a method for preparing the onion-like carbon quantum dots.
It is a further object of the present invention to provide the use of onion-like carbon quantum dots as described above.
The multicolor high quantum yield solution processable thermally activated delayed fluorescence onion-like carbon quantum dots according to the present invention can be prepared by a method comprising the steps of:
taking trimesic acid and 3,4,9, 10-perylene tetracarboxylic dianhydride with the mass ratio of 2:1 as carbon source precursors, dissolving the precursors in concentrated sulfuric acid by ultrasonic, adding 1-2 mL of methanol and formamide into a reaction system for auxiliary nucleation and assembly,
The reaction solution is reacted for about 15 minutes to 4 hours at the temperature of 110 ℃ to 200 ℃ and then naturally cooled to room temperature, thereby obtaining the multicolor heat-activated delayed fluorescence onion-like carbon quantum dot solution.
The multicolor high-quantum-yield solution-processable heat-activated delayed fluorescence onion-like carbon quantum dot provided by the invention, wherein the volume-mass ratio mL/mg of concentrated sulfuric acid to carbon source precursor is 5:1-10:1.
The multicolor high quantum yield solution-processable heat-activated delayed fluorescence type onion-like carbon quantum dot is prepared by neutralizing multicolor heat-activated delayed fluorescence type onion-like carbon quantum dot solution with 0.01mol/L aqueous solution such as sodium hydroxide or potassium hydroxide or sodium carbonate aqueous solution until pH=7, filtering, placing the filtrate in a dialysis bag (1000-3500 Da) for dialysis for two days in deionized water, and changing deionized water every three hours. After dialysis, collecting the solution in the dialysis bag, and purifying by a silica gel column to obtain onion-like carbon quantum dot solid powder.
According to the technical scheme of the invention, pyromellitic acid and 3,4,9, 10-perylene tetracarboxylic dianhydride are selected as carbon source precursors, and the thermal activation delayed fluorescence onion-like carbon quantum dots which can be processed in solution with multicolor high quantum yield are synthesized by controlling the reaction sites of the precursors of 3,4,9, 10-perylene tetracarboxylic dianhydride and the chemical connection of the pyromellitic acid, controlling the solvothermal reaction conditions such as reaction time and reaction temperature, adding catalysts and the like.
According to the technical scheme of the invention, the reaction solvent concentrated sulfuric acid/methanol/formamide is very important to prepare the multicolor high-quantum-yield solution-processable heat-activated delayed fluorescence onion-like carbon quantum dots. If the reaction solvent is changed into other solvents such as acetone, ethyl acetate, methylene dichloride and the like, other reaction conditions are kept consistent, and the multicolor high-quantum-yield heat-activated delayed fluorescence onion-like carbon quantum dots which can be processed by the solution cannot be obtained.
According to the technical scheme of the invention, the alkali plays a very important role in regulating the formation of onion-like carbon quantum dots and the emission wavelength of the eigen-state multicolor heat activated delayed fluorescence in a reaction system. If 0.01mol/L sodium hydroxide or potassium hydroxide or sodium carbonate aqueous solution and the like are not added for neutralization, multicolor high-quantum-yield solution-processable heat-activated delayed fluorescence onion-like carbon quantum dots can not be synthesized by changing other reaction conditions such as temperature, time and the like.
According to the technical scheme, the multi-color high-quantum-yield solution-processable heat-activated delayed fluorescence onion-like carbon quantum dot solution can be obtained by a one-step solvothermal method, and the multi-color high-quantum-yield solution-processable heat-activated delayed fluorescence onion-like carbon quantum dot solid is further optimized.
The thermal activation delay fluorescence emission peak of the onion-like carbon quantum dot prepared by the invention is not changed along with the change of the excitation wavelength, and the total quantum yield is up to 42.3-61.0% under the optimal condition.
The onion-like carbon quantum dot prepared by the invention has the characteristics of solution processing, high quantum yield, high charge transmission, matching and the like.
The method disclosed by the invention is simple, novel in structure, excellent in performance and suitable for preparing the thermally activated delayed fluorescent carbon quantum dots.
The multicolor high-quantum-yield solution-processable thermally-activated delayed fluorescence onion-like carbon quantum dot prepared by the invention has wide application prospect in the fields of photoelectric devices, biomedicine, sensors and the like. Compared with an electroluminescent diode device prepared by taking fluorescent emitted carbon quantum dots as a light-emitting layer, the electroluminescent diode device has the advantages of low starting voltage, high brightness, high external quantum efficiency and the like, and is expected to be used as a novel thermal activation delayed fluorescence light-emitting material with low cost and environmental friendliness in the field of electroluminescent diodes.
Drawings
FIG. 1 is an ultraviolet absorption spectrum of solid multicolor heat-activated delayed fluorescence onion-like carbon quantum dots prepared in example 1;
FIG. 2 is a spectrum diagram of the solid multicolor heat-activated delayed fluorescence onion-like carbon quantum dots prepared in example 1 under excitation of different wavelengths;
FIG. 3 is a time-resolved spectrum of the solid multicolor heat-activated delayed fluorescence onion-like carbon quantum dots prepared in example 1;
FIG. 4 is a spherical aberration electron microscope image of multicolor heat-activated delayed fluorescence onion-like carbon quantum dots prepared in example 1;
FIG. 5 is a three-dimensional reconstruction of red thermally activated delayed fluorescence onion-like carbon quantum dots prepared in example 1;
FIG. 6 is a Raman spectrum of the multicolor heat-activated delayed fluorescence onion-like carbon quantum dots prepared in example 1;
FIG. 7 is an X-ray photoelectron spectrum of the multicolor heat-activated delayed fluorescence type onion-like carbon quantum dot prepared in example 1;
FIG. 8 is an X-ray diffraction spectrum of the multicolor heat-activated delayed fluorescence type onion-like carbon quantum dots prepared in example 1;
FIG. 9 is an infrared spectrum of the multicolor heat-activated delayed fluorescence type onion-like carbon quantum dots prepared in example 1;
FIG. 10 is an atomic force microscope image of the thin film multicolor heat-activated delayed fluorescence type onion-like carbon quantum dots prepared in example 1;
FIG. 11 is a scanning electron microscope image of the thin film multicolor heat-activated delayed fluorescence type onion-like carbon quantum dots prepared in example 1;
FIG. 12 is a graph showing the intensity change of the thin film red thermally-activated delayed fluorescence onion-like carbon quantum dots prepared in example 1 under vacuum-oxygen and high temperature cycles;
fig. 13 is a structure of a single color electroluminescent diode device prepared in example 2;
FIG. 14 is a graph showing the luminescence spectrum of the electroluminescent diode based on multicolor heat-activated delayed fluorescence onion-like carbon quantum dots prepared in example 2 according to the change of voltage;
FIG. 15 is a graph of current density vs. voltage vs. luminance characteristics of an electroluminescent diode based on multicolor thermally activated delayed fluorescence type onion-like carbon quantum dots prepared in example 2;
FIG. 16 is a graph of external quantum efficiency vs. voltage characteristics of an electroluminescent diode based on multicolor thermally activated delayed fluorescence type onion-like carbon quantum dots prepared in example 2;
FIG. 17 is a graph of color coordinates of an electroluminescent diode based on multicolor heat-activated delayed fluorescence type onion-like carbon quantum dots prepared in example 2;
fig. 18 is a structure of a flexible electroluminescent diode device prepared in example 2;
FIG. 19 is a photograph of the electroluminescent diode based on red thermally activated delayed fluorescence onion-like carbon quantum dots prepared in example 2 at different bends;
FIG. 20 is a graph showing luminescence spectra of the electroluminescent diode based on red thermally activated delayed fluorescence onion-like carbon quantum dots prepared in example 2 under different bending conditions;
Fig. 21 is a graph showing current density-voltage-luminance characteristics of the electroluminescent diode based on red thermally activated delayed fluorescence-like onion-like carbon quantum dots prepared in example 2 at different bends.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to the accompanying drawings.
According to the technical scheme, the pyromellitic acid and 3,4,9, 10-perylene tetracarboxylic dianhydride with the mass ratio of 2:1 are used as carbon source precursors, ultrasonic stirring is carried out to enable the pyromellitic acid and the 3,4,9, 10-perylene tetracarboxylic dianhydride to be fully dissolved in concentrated sulfuric acid, for example, 0.01-1 g of the pyromellitic acid and 0.01-1 g of the 3,4,9, 10-perylene tetracarboxylic dianhydride are used as carbon source precursors, and ultrasonic stirring is carried out to enable the pyromellitic acid and the 3,4,9, 10-perylene tetracarboxylic dianhydride to be fully dissolved in 5-20 mL of concentrated sulfuric acid. And then adding a small amount of mixed solvent of methanol and formamide into the carbon source precursor solution to promote reaction nucleation and assembly. The volume mass ratio of the concentrated sulfuric acid to the carbon source precursor is 5:1-10:1. The solution was then transferred to a beaker and a polytetrafluoroethylene-lined stainless steel autoclave. And carrying out solvothermal reaction at 110 ℃ and 200 ℃ for 15 minutes to 4 hours respectively, and naturally cooling the reaction kettle to room temperature to obtain onion-like carbon quantum dot solution with light blue, light green, light yellow, light brown and light pink appearance.
The solution after the above reaction was collected and neutralized to ph=7 with 20 to 100mL of an alkaline aqueous solution (0.01 mol/L aqueous sodium hydroxide or potassium hydroxide or sodium carbonate, etc.). Then filtering, placing the filtrate in a dialysis bag (1000-3500 Da) and dialyzing in deionized water for two days, and changing deionized water every three hours. After dialysis, collecting the solution in the dialysis bag, and purifying by a silica gel column to obtain solid powder similar to onion-shaped carbon quantum dots.
Example 1 preparation of multicolor high Quantum yield solution processable thermally activated delayed fluorescence-like onion-like carbon Quantum dots
And weighing trimesic acid and 3,4,9, 10-perylene tetracarboxylic dianhydride solid with the mass ratio of 2:1 as carbon source precursors, and dissolving the carbon source precursors in concentrated sulfuric acid by ultrasonic stirring. 1-2 mL of methanol and formamide are added into the reaction system to assist nucleation and assembly. The solution was transferred to a 10mL beaker and a 25mL capacity stainless steel autoclave lined with polytetrafluoroethylene, and the lid was screwed down. The solvent thermal reaction is carried out for 15 minutes and 4 hours at 110 ℃ and 200 ℃ respectively, then a beaker and a reaction kettle are naturally cooled to room temperature, thus obtaining onion-like carbon quantum dot solution with light blue, light green, light brown and light pink appearance, then 0.01mol/L aqueous solution such as aqueous solution of sodium hydroxide or potassium hydroxide or sodium carbonate is used for neutralization until pH=7, then the solution is filtered, and the filtrate is taken and placed in a dialysis bag (1000-3500 Da) to be dialyzed for two days in deionized water, and deionized water is changed every three hours. After dialysis, collecting the solution in the dialysis bag, and purifying by a silica gel column to obtain onion-like carbon quantum dot solid powder.
The onion-like carbon quantum dot powder fluoresces blue, green, yellow, orange and red under a hand held ultraviolet lamp (365 nm), corresponding to ultraviolet visible absorption peaks at 415,466,494,543 and 586nm (figure 1). Unlike the reported carbon dots that excite dependent defect state emission characteristics, they exhibit excitation independent eigenstate emission characteristics. At a delay of 10 μs, the emission peaks of the polychromatic delayed fluorescence onion-like carbon quantum dot solutions were located at 450,500,525,566 and 611nm, respectively (fig. 2). Time resolved spectroscopy showed that polychromatic delayed fluorescence had lifetimes of 31.2,28.6,25.1,21.9 and 18.0 μs, respectively (fig. 3), exhibiting significant short-lifetime delayed fluorescence properties. The absolute total quantum yield was measured to be as high as 42.3-61.0%.
The high resolution spherical aberration electron microscope observed a 10-15nm sized onion like structure (fig. 4) with a multi-layered structure inside and an average distance between each layer of about 0.4nm. By scanning the structure at different angles (-70 deg. to 70 deg.), a three-dimensional spherical structure can be observed after three-dimensional reconstruction (fig. 5). The ratio of I G/ID in the Raman spectrum of the onion-like carbon quantum dot is as high as 1.7-2.1 (figure 6), which shows that the graphitization degree of the carbon quantum dot is higher and corresponds to the characteristic peak of the X-ray diffraction spectrum (002) (figure 7). The X-ray photoelectron spectroscopy results indicated that the carbon spot consisted mainly of two elements, carbon and oxygen (fig. 8). Solid infrared spectra demonstrated the presence of hydroxyl, carbonyl, etc. functional groups in the onion-like structure (fig. 9). The edge functional groups of the carbon dots have very important regulatory effects on the formation of onion-like structures and the delay of fluorescence emission.
After the onion-like carbon quantum dots are prepared into the film, an atomic force microscope (figure 10) and a scanning tunnel microscope (figure 11) show that the film formed by the onion-like carbon quantum dots has smooth and flat surface, and is beneficial to being applied to electroluminescent diodes. And the film can still maintain higher emission intensity after being exposed to oxygen and being prevented from being cycled at high temperature for many times (figure 12), which shows that the active luminescent layer prepared by the film has higher oxygen/temperature tolerance and plays a key role in preparing an efficient and stable electroluminescent device.
Example 2 preparation of electroluminescent diode based on multicolor thermal activation delayed fluorescence onion-like carbon Quantum dots
The multicolor high quantum yield solution processable thermally activated delayed fluorescence type onion-like carbon quantum dots prepared in example 1 were applied as an active light emitting layer to a monochromatic electroluminescent diode. As shown in fig. 13, the light emitting diode device structure comprises, in order from bottom to top, a transparent glass substrate (glass), an anode layer (ITO), a hole injection layer poly 3, 4-ethylenedioxythiophene, polystyrene sulfonate (PEDOT: PSS), an active light emitting layer poly (9-vinylcarbazole) (PVK) and a multicolor high quantum yield solution processable thermally activated delayed fluorescence type onion-like carbon quantum dot, an electron transport layer 1,3, 5-tris (1-phenyl-1H-benzimidazol-2-yl) benzene (TPBi), and a cathode layer (Ca/Al). The electroluminescent diode device structure is described as ITO/PEDOT PSS/PVK CQDs/TPBi/Ca/Al.
The preparation method of the monochromatic electroluminescent diode device comprises the following steps:
(1) And ultrasonically cleaning the ITO glass of the transparent conductive substrate by using an acetone solution, an isopropanol solution and deionized water, and drying by using dry nitrogen after cleaning. And then baked in an oven at 150 ℃ for 10min. Wherein the ITO on the glass substrate is used as an anode layer of the device;
(2) Transferring the dried substrate into a vacuum chamber, and carrying out ultraviolet ozone pretreatment on ITO glass for 15min under an oxygen pressure environment;
(3) PEDOT PSS was spin-coated on the treated ITO at 2000 revolutions per minute (rpm), spin-coating time 35s, and thickness 40nm. Then annealing for 15min in a baking box at 150 ℃;
(4) PVK prepared by spin coating on the PEDOT PSS layer is o-dichlorobenzene solution of heat activated delayed fluorescence onion-like carbon quantum dots, the rotating speed is 4500rpm, the spin coating time is 45s, and the thickness is 10nm. Then annealing for 30min in a baking box at 80 ℃;
(5) The ITO was then transferred into a nitrogen glove box. Vacuum evaporation 40nmTPBi, air pressure 3×10 -4 Pa, evaporation rate 0.lnm/s, evaporation rate and thickness monitored by film thickness instrument;
(6) Then vacuum evaporating 10nmCa,100nmAL, the air pressure is 3X 10 -4 Pa, the evaporating speed is 0.l and 0.3nm/s, the evaporating speed and thickness are monitored by a film thickness instrument;
(7) Directly testing the current-voltage-brightness characteristics of the device without packaging the device, and simultaneously testing the luminous spectrum parameters of the device;
The electroluminescent spectrum can obviously observe that the emission peaks are respectively positioned at 444,494,523,574 nm and 620nm (figure 14), which are matched with the photoluminescent spectrum, and the position of the emission peak is not changed along with the change of voltage, so that the electroluminescent spectrum is very stable. The current density-voltage-luminance characteristic of the device is shown in fig. 15. The single diode can achieve low turn-on voltages of 4.5-3.2V, maximum brightness of 7546cd/m 2, maximum current efficiency of 26.2cd/a, maximum external quantum efficiency of 8.7% (fig. 16), and emission spectrum chromaticity coordinates of (0.1745,0.1940), (0.2653,0.4276), (0.2976,4959), (0.4865,0.4994), and (0.6220,0.3747), respectively (fig. 17).
The red high quantum yield solution processable thermally activated delayed fluorescence type onion-like carbon quantum dots prepared in example 1 were applied as an active light emitting layer to monochromatic electroluminescent LEDs. As shown in fig. 18, the light emitting diode device structure includes, in order from bottom to top, a transparent polyethylene terephthalate (PET) substrate, an anode layer (ITO), a hole injection layer PEDOT: PSS, an active light emitting layer PVK, and a red high quantum yield solution processable thermally activated delayed fluorescence type onion-like carbon quantum dot, an electron transport layer TPBi, and a cathode layer (Ca/Al). The electroluminescent diode device structure is described as ITO/PEDOT PSS/PVK CQDs/TPBi/Ca/Al.
The preparation method of the flexible electroluminescent diode device comprises the following steps:
(1) And ultrasonically cleaning the flexible conductive PET substrate by using an acetone solution, an isopropanol solution and deionized water, and drying by using dry nitrogen after cleaning. And then baked in an oven at 90 ℃ for 10min. Wherein the ITO on the flexible substrate is used as an anode layer of the device;
(2) Transferring the dried substrate into a vacuum chamber, and carrying out ultraviolet ozone pretreatment on ITO on the flexible substrate for 15min under an oxygen pressure environment;
(3) PEDOT is spin-coated on the treated ITO at 2000rpm for 35s and 40nm in thickness. Then annealing for 15min in a drying oven at 90 ℃;
(4) PVK prepared by spin coating on the PEDOT PSS layer is o-dichlorobenzene solution of red heat-activated delayed fluorescence onion-like carbon quantum dots, the rotating speed is 4500rpm, the spin coating time is 45s, and the thickness is 10nm. Then annealing for 30min in an 80 ℃ baking box;
(5) The ITO was then transferred into a nitrogen glove box. Vacuum evaporation 40nmTPBi, air pressure 3×10 -4 Pa, evaporation rate 0.lnm/s, evaporation rate and thickness monitored by film thickness instrument;
(6) Then vacuum evaporating 10nmCa,100nmAL, the air pressure is 3X 10 -4 Pa, the evaporating speed is 0.l and 0.3nm/s, the evaporating speed and thickness are monitored by a film thickness instrument;
(7) Directly testing the current-voltage-brightness characteristics of the device without packaging the device, and simultaneously testing the luminous spectrum parameters of the device;
the flexible electro-active device can be repeatedly bent for a plurality of times, and good device performance can be maintained after bending (fig. 19). The electroluminescent spectrum was found to be significantly at 620nm (fig. 20), which is substantially consistent with its electroluminescent spectrum on a glass substrate, and the emission peak position was unchanged by voltage changes, and was very stable. The current density-voltage-luminance characteristic of the device is shown in fig. 21. The single diode can achieve a low turn-on voltage of 4.5V with a maximum luminance of 2554cd/m 2 and a maximum current efficiency of 1.05cd/a (fig. 21).
The embodiment is implemented on the premise of the technical scheme of the invention, and detailed implementation modes and processes are given, but the protection scope of the invention is not limited to the embodiment.
Claims (7)
1. The multicolor high-quantum-yield solution-processable heat-activated delayed fluorescence onion-like carbon quantum dot is characterized in that the multicolor high-quantum-yield solution-processable heat-activated delayed fluorescence onion-like carbon quantum dot is prepared by the following steps:
taking trimesic acid and 3,4,9, 10-perylene tetracarboxylic dianhydride with the mass ratio of 2:1 as carbon source precursors, dissolving the precursors in concentrated sulfuric acid by ultrasonic waves, and adding 1-2mL of mixed solvent of methanol and formamide to obtain reaction mixed liquid, wherein the volume mass ratio mL/mg of the mixed solvent of methanol and formamide to the carbon source precursors is 1:1-1:2;
Carrying out solvothermal reaction on the reaction mixed solution for 15 minutes to 4 hours at the temperature of 110 ℃ to 200 ℃, and then naturally cooling to room temperature, so as to obtain a solution of the multicolor high quantum yield solution-processable heat-activated delayed fluorescence onion-like carbon quantum dots;
and neutralizing the solution of the multicolor high-quantum-yield solution-processable heat-activated delayed fluorescence onion-like carbon quantum dots to pH=7 by using an alkali solution, dialyzing by deionized water, and purifying by column chromatography to obtain the multicolor high-quantum-yield solution-processable heat-activated delayed fluorescence onion-like carbon quantum dot solid powder.
2. The multicolor high quantum yield solution processable thermally activated delayed fluorescence-like onion-like carbon quantum dot of claim 1, wherein said alkali solution is 0.01mol/L sodium hydroxide or potassium hydroxide or sodium carbonate aqueous solution.
3. The multicolor high quantum yield solution processable thermally activated delayed fluorescence like onion shaped carbon quantum dot of claim 1, wherein the volume mass ratio mL/mg of concentrated sulfuric acid to carbon source precursor is 5:1-10:1.
4. A method of preparing multicolor high quantum yield solution processable thermally activated delayed fluorescence like onion shaped carbon quantum dots, said method comprising the steps of:
taking trimesic acid and 3,4,9, 10-perylene tetracarboxylic dianhydride with the mass ratio of 2:1 as carbon source precursors, dissolving the precursors in concentrated sulfuric acid by ultrasonic waves, and adding 1-2mL of mixed solvent of methanol and formamide to obtain reaction mixed liquid, wherein the volume mass ratio mL/mg of the mixed solvent of methanol and formamide to the carbon source precursors is 1:1-1:2;
Carrying out solvothermal reaction on the reaction mixed solution for 15 minutes to 4 hours at the temperature of 110 ℃ to 200 ℃, and then naturally cooling to room temperature, so as to obtain a solution of the multicolor high quantum yield solution-processable heat-activated delayed fluorescence onion-like carbon quantum dots;
and neutralizing the solution of the multicolor high-quantum-yield solution-processable heat-activated delayed fluorescence onion-like carbon quantum dots to pH=7 by using an alkali solution, dialyzing by deionized water, and purifying by column chromatography to obtain the multicolor high-quantum-yield solution-processable heat-activated delayed fluorescence onion-like carbon quantum dot solid powder.
5. The method for preparing multicolor high quantum yield solution processable thermally activated delayed fluorescence like onion shaped carbon quantum dots according to claim 4, wherein the volume mass ratio mL/mg of concentrated sulfuric acid to carbon source precursor is 5:1-10:1.
6. The method for preparing multicolor high quantum yield solution processable thermally activated delayed fluorescence like onion shaped carbon quantum dots of claim 5, wherein said alkali solution is 0.01mol/L sodium hydroxide or potassium hydroxide or sodium carbonate aqueous solution.
7. Use of the multicolor high quantum yield solution processable thermally activated delayed fluorescence like onion shaped carbon quantum dots of claim 1 for electroluminescent diodes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310551239.7A CN116948638B (en) | 2023-05-17 | 2023-05-17 | Multicolor high-quantum-yield solution-processable heat-activated delayed fluorescence onion-like carbon quantum dot and preparation and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310551239.7A CN116948638B (en) | 2023-05-17 | 2023-05-17 | Multicolor high-quantum-yield solution-processable heat-activated delayed fluorescence onion-like carbon quantum dot and preparation and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116948638A CN116948638A (en) | 2023-10-27 |
| CN116948638B true CN116948638B (en) | 2024-05-07 |
Family
ID=88450120
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310551239.7A Active CN116948638B (en) | 2023-05-17 | 2023-05-17 | Multicolor high-quantum-yield solution-processable heat-activated delayed fluorescence onion-like carbon quantum dot and preparation and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116948638B (en) |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106566538A (en) * | 2016-10-08 | 2017-04-19 | 北京师范大学 | High-quantum-yield eigenstate-fluorescence-adjustable carbon dot and preparing method and application thereof |
| WO2020073527A1 (en) * | 2018-10-11 | 2020-04-16 | 武汉华星光电半导体显示技术有限公司 | Macromolecular thermally activated delayed fluorescence material and preparation method therefor |
| CN111040759A (en) * | 2019-12-12 | 2020-04-21 | 青岛农业大学 | Carbon quantum dot-based visible light excited thermal-activation delayed fluorescent material and preparation method and application thereof |
| WO2020082601A1 (en) * | 2018-10-22 | 2020-04-30 | 武汉华星光电半导体显示技术有限公司 | Dark red photothermally activated delayed fluorescence material, synthesis method therefor and electroluminescent device |
| WO2020113789A1 (en) * | 2018-12-05 | 2020-06-11 | 武汉华星光电半导体显示技术有限公司 | Green light thermally activated delayed fluorescent material, synthesis method thereof, and electroluminescent device |
| WO2021171984A1 (en) * | 2020-02-25 | 2021-09-02 | 東レ株式会社 | Organic el display device, production method for cured product, and production method for organic el display device |
| CN113416539A (en) * | 2021-05-06 | 2021-09-21 | 北京师范大学 | High-quantum-yield solution-processable solid blue fluorescent-red phosphorescent carbon quantum organic framework and preparation and application thereof |
| CN113444257A (en) * | 2021-06-21 | 2021-09-28 | 安徽理工大学环境友好材料与职业健康研究院(芜湖) | Preparation method and application of unsaturated coordination manganese-based metal organic framework composite material |
| WO2021189528A1 (en) * | 2020-03-23 | 2021-09-30 | 武汉华星光电半导体显示技术有限公司 | Thermally activated delayed fluorescent material and synthesis method therefor, and electroluminescent device |
| JP2022027562A (en) * | 2020-07-29 | 2022-02-10 | 東ソー・ファインケム株式会社 | Porous zinc complex and its manufacturing method |
| CN115321519A (en) * | 2022-08-03 | 2022-11-11 | 北京师范大学 | High-quantum-yield intrinsic-state fluorescence-adjustable carbon dot and preparation method and application thereof |
| CN115627000A (en) * | 2022-11-02 | 2023-01-20 | 天能新能源(湖州)有限公司 | High-temperature-resistant polyimide diaphragm, preparation method thereof and application thereof in preparation of lithium ion battery |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11205756B2 (en) * | 2018-12-05 | 2021-12-21 | Wuhan China Star Optoelectronics Semiconductor Display Technology Co., Ltd. | Green light thermally activated delayed fluorescence (TADF) material and application thereof |
| US11613530B2 (en) * | 2019-04-29 | 2023-03-28 | Wuhan China Star Optoelectronics Semiconductor Display Technology Co., Ltd. | Thermally activated delayed fluorescent molecular material, method for synthesizing the same, and organic electroluminescent device |
-
2023
- 2023-05-17 CN CN202310551239.7A patent/CN116948638B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106566538A (en) * | 2016-10-08 | 2017-04-19 | 北京师范大学 | High-quantum-yield eigenstate-fluorescence-adjustable carbon dot and preparing method and application thereof |
| WO2020073527A1 (en) * | 2018-10-11 | 2020-04-16 | 武汉华星光电半导体显示技术有限公司 | Macromolecular thermally activated delayed fluorescence material and preparation method therefor |
| WO2020082601A1 (en) * | 2018-10-22 | 2020-04-30 | 武汉华星光电半导体显示技术有限公司 | Dark red photothermally activated delayed fluorescence material, synthesis method therefor and electroluminescent device |
| WO2020113789A1 (en) * | 2018-12-05 | 2020-06-11 | 武汉华星光电半导体显示技术有限公司 | Green light thermally activated delayed fluorescent material, synthesis method thereof, and electroluminescent device |
| CN111040759A (en) * | 2019-12-12 | 2020-04-21 | 青岛农业大学 | Carbon quantum dot-based visible light excited thermal-activation delayed fluorescent material and preparation method and application thereof |
| WO2021171984A1 (en) * | 2020-02-25 | 2021-09-02 | 東レ株式会社 | Organic el display device, production method for cured product, and production method for organic el display device |
| WO2021189528A1 (en) * | 2020-03-23 | 2021-09-30 | 武汉华星光电半导体显示技术有限公司 | Thermally activated delayed fluorescent material and synthesis method therefor, and electroluminescent device |
| JP2022027562A (en) * | 2020-07-29 | 2022-02-10 | 東ソー・ファインケム株式会社 | Porous zinc complex and its manufacturing method |
| CN113416539A (en) * | 2021-05-06 | 2021-09-21 | 北京师范大学 | High-quantum-yield solution-processable solid blue fluorescent-red phosphorescent carbon quantum organic framework and preparation and application thereof |
| CN113444257A (en) * | 2021-06-21 | 2021-09-28 | 安徽理工大学环境友好材料与职业健康研究院(芜湖) | Preparation method and application of unsaturated coordination manganese-based metal organic framework composite material |
| CN115321519A (en) * | 2022-08-03 | 2022-11-11 | 北京师范大学 | High-quantum-yield intrinsic-state fluorescence-adjustable carbon dot and preparation method and application thereof |
| CN115627000A (en) * | 2022-11-02 | 2023-01-20 | 天能新能源(湖州)有限公司 | High-temperature-resistant polyimide diaphragm, preparation method thereof and application thereof in preparation of lithium ion battery |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116948638A (en) | 2023-10-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Fresta et al. | Beyond traditional light-emitting electrochemical cells–a review of new device designs and emitters | |
| CN108389982B (en) | Light emitting diode device and display device | |
| Zhu et al. | Solution-processable single-material molecular emitters for organic light-emitting devices | |
| Kalyani et al. | Novel materials for fabrication and encapsulation of OLEDs | |
| Rehmann et al. | Advanced device architecture for highly efficient organic light‐emitting diodes with an orange‐emitting crosslinkable iridium (III) complex | |
| CN113416539B (en) | High-quantum-yield solution-processable solid blue fluorescent-red phosphorescent carbon quantum organic framework and preparation and application thereof | |
| CN101203538B (en) | New luminescent compositions and their uses | |
| EP1974399B1 (en) | Improved carbon nanotube based semiconducting devices and methods for their production | |
| JP6240598B2 (en) | Photoelectric device and its application | |
| Sun et al. | Toward Eco‐friendly Green Organic Semiconductors: Recent Advances in Spiro [fluorene‐9, 9′‐xanthene](SFX)‐Based Optoelectronic Materials and Devices | |
| JP2013518373A (en) | Organic electroluminescent devices with integrated layers for color conversion | |
| JP6898930B2 (en) | Charge transfer salts, electronic devices and methods of their formation | |
| Zhao et al. | Optimizing the central steric hindrance of cross-linkable hole transport materials for achieving highly efficient RGB QLEDs | |
| He et al. | Highly efficient polymer light-emitting devices using a phosphorescent sensitizer | |
| CN101323781A (en) | Nanometer fluorescent microspheres and uses thereof | |
| Huang et al. | Construction of deep-blue AIE luminogens with TPE and oxadiazole units | |
| Gao et al. | A method towards 100% internal quantum efficiency for all-inorganic cesium halide perovskite light-emitting diodes | |
| KR20070004641A (en) | Organic materials with tunable electric and electroluminescent properties | |
| CN116948638B (en) | Multicolor high-quantum-yield solution-processable heat-activated delayed fluorescence onion-like carbon quantum dot and preparation and application thereof | |
| JPH08100052A (en) | Conjugate polymer in which fluorescent core is incorporated and its production | |
| CN115028626B (en) | Thermally-induced delayed fluorescent material and preparation method and application thereof | |
| CN115321519B (en) | High-quantum-yield eigenstate fluorescence-adjustable carbon dot and preparation method and application thereof | |
| CN115528197A (en) | All-carbon-dot organic electroluminescent device and preparation method thereof | |
| CN102807556B (en) | Organic semiconductor material containing naphthalene, anthracene, dibenzothiophene sulfone units and preparation method and application thereof | |
| Yuan et al. | The emergence and prospects of carbon dots with solid-state photoluminescence for light-emitting diodes |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |