CN115466614A - White luminescent soft material based on lanthanide series eutectic solvent and carbon dots and preparation method thereof - Google Patents
White luminescent soft material based on lanthanide series eutectic solvent and carbon dots and preparation method thereof Download PDFInfo
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
- C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
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Abstract
The invention discloses a white luminescent soft material based on a lanthanide eutectic solvent and carbon dots and a preparation method thereof, wherein the preparation method comprises the following steps: mixing and heating an amide substance and a europium salt to obtain a first eutectic solvent; mixing and heating an amide substance and terbium salt to obtain a second eutectic solvent; heating and drying the mixed solution of the carbon source and the surface passivator, and then stirring and pyrolyzing to prepare a blue light carbon dot; and mixing the first eutectic solvent, the second eutectic solvent, the blue light carbon dots and the diluent in proportion to prepare the white luminescent soft material.
Description
Technical Field
The invention belongs to the technical field of white light materials, and particularly relates to a white luminescent soft material based on a lanthanide eutectic solvent and carbon dots and a preparation method thereof.
Background
The statements herein merely provide background information related to the present disclosure and may not necessarily constitute prior art.
White light materials are receiving attention from researchers for their application in the fields of lighting, display, smart materials, and the like. White light materials are typically composed of a combination of three primary color emitters (i.e., red, green, and blue) or two complementary color emitters (e.g., blue and yellow). At present, the best solution for realizing artificial white light is a light emitting diode, namely a white light LED. The technology for realizing white light can be divided into two categories: one is a semiconductor chip combining a plurality of emission colors to realize white light, which is expensive and difficult to popularize. The second is to excite a monochromatic semiconductor chip to emit a monochromatic light, which can excite the phosphor powder to emit fluorescence, and the monochromatic light and the fluorescence are mixed to form white light. The method for realizing white light by combining the semiconductor chip and the fluorescent substance is the mainstream choice in the field of white light illumination at present, such as coating yellow fluorescent powder on a blue light LED chip and coating red, green and blue tricolor fluorescent powder on an ultraviolet light LED chip.
The white light LED obtained by the method has the problems that solid fluorescent powder is easy to settle and difficult to disperse, and the like, and the luminous effect is seriously influenced due to uneven distribution; in addition, the bonding strength between the phosphor and the substrate is insufficient, resulting in limited ductility of the substrate, making it difficult to apply to a flexible display device.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a white luminescent soft material based on a lanthanide series eutectic solvent and a carbon point and a preparation method thereof.
In order to realize the purpose, the invention is realized by the following technical scheme:
in a first aspect, the invention provides a preparation method of a white luminescent soft material based on a lanthanide eutectic solvent and a carbon dot, which comprises the following steps:
mixing and heating an amide substance and a europium salt to obtain a first eutectic solvent;
mixing and heating an amide substance and terbium salt to obtain a second eutectic solvent;
heating and drying a mixed solution of a carbon source and a surface passivator, and then stirring and pyrolyzing to prepare a blue-light carbon dot;
and mixing the first eutectic solvent, the second eutectic solvent, the blue light carbon dots and the diluent in proportion to prepare the white luminescent soft material.
In a second aspect, the invention provides a white luminescent soft material based on a lanthanide eutectic solvent and carbon dots, which is prepared by the preparation method.
In a third aspect, the present invention provides a white LED, including an LED chip and a white light emitting soft material layer loaded on the LED chip.
The beneficial effects achieved by one or more of the embodiments of the invention are as follows:
the lanthanide series luminescent fluid is obtained by directly utilizing lanthanide series metal ions with luminous capacity to synthesize the IV type eutectic solvent, can overcome the problems of uneven doping and concentration quenching of powder samples, does not need to introduce conventional solvents, avoids the dilemma that lanthanide series luminescent compounds are restricted by solvents, and obtains white luminescent soft materials more efficiently and simply.
The reason for selecting PDES as the diluent is that CD is directly dissolved in the luminescence DES which has too strong fluorescence to obtain white light, and the luminescence DES needs to be diluted to control the luminescence intensity in a range similar to CD; while PDES does not adversely affect the light-emitting ability of the three components and can impart the liquid polymerization ability to the mixed liquid.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 is a flow chart of a process for preparing a white light-emitting material according to the present invention;
FIG. 2 is a flow chart of a process for making red emitting EuDES according to an embodiment of the present invention (a) and a photograph of red emitting EuDES (b);
FIG. 3 is a process flow diagram (a) of the preparation of TbDES emitting green light and a photograph (b) of TbDES emitting green light in an embodiment of the invention;
FIG. 4 is a flow chart of a process for preparing carbon dots in an embodiment of the present invention;
in fig. 5, (a) is the emission spectrum of CETP-4, λ ex =365nm, and the inset shows the corresponding optical photograph of the white luminescent fluid, (b) is the CIE chromaticity coordinates of the respective luminescent components and the white luminescent fluid, (c) is a photograph of the LED device under natural light and ultraviolet light, and (d) is the luminescence diagram of the luminescent elastomer under excitation of a 365nm ultraviolet lamp.
In FIG. 6, a is the IR spectrum of EuDES and b is the IR spectrum of TbDES.
In FIG. 7, a is a DSC chart of EuDES, b is a DSC chart of TbDES, and c is a TGA chart of EuDES and TbDES.
In FIG. 8, a is a viscosity law diagram of EuDES and TbDES obtained under different raw material ratios, b is a viscosity change law diagram of EuDES-8 and TbDES-8 at different temperatures, c is a conductivity diagram of EuDES and TbDES obtained under different raw material ratios, and d is a cyclic voltammogram of EuDES-8 and TbDES-8.
In FIG. 9, a is the fluorescence excitation and emission spectra of EuDES-8, b is the fluorescence excitation and emission spectra of TbDES-8, and c is the quantum yield plot of EuDES and TbDES with different ligand content.
In FIG. 10, a is the infrared spectrum of CDs and the raw materials TEPA and EDTA, b is the ultraviolet-visible absorption and fluorescence spectrum of 0.2mg/mL CDs water solution, and c is the fluorescence emission spectrum of 0.2mg/mL CDs water solution under different excitation wavelengths.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
The inventors have found that lanthanide compounds are visible (e.g. Eu) 3+ 、Tb 3+ ) And near infrared region (e.g. Nd) 3+ 、Er 3+ 、Yb 3+ ) Has strong luminous capability, narrow emission, high color purity, long excited state life, excellent light stability and the likeHas the advantages of simple process and low cost. However, in order to solve the problem that lanthanide as a luminescence center is easily coordinated and causes fluorescence quenching when encountering a polar protic solvent, the inventors tried to reduce the contact between lanthanide metal ions and a solvent by using a solvophobic ligand, but the problem could not be solved fundamentally, and the selection of the ligand in the lanthanide luminescent complex is also affected, thereby restricting the development of the lanthanide luminescent material.
The inventors have found through experiments that the use of a novel solvent instead of a conventional solvent such as an ionic liquid and a eutectic solvent significantly increases the luminous intensity of a lanthanide salt in the eutectic solvent compared to water, methanol or ethanol, and is stable in light emission and not affected by the external temperature and water content.
In a first aspect, the invention provides a preparation method of a white luminescent soft material based on a lanthanide eutectic solvent and carbon dots, which comprises the following steps:
blending and heating an amide substance and a europium salt to obtain a first eutectic solvent EuDES;
mixing and heating an amide substance and terbium salt to obtain a second eutectic solvent TbDES;
heating and drying a mixed solution of a carbon source and a surface passivator, and then stirring and pyrolyzing to prepare a blue-light carbon dot;
and mixing the first eutectic solvent, the second eutectic solvent, the blue light carbon dots and the diluent in proportion to prepare the white luminescent soft material.
In some embodiments, the amide-based material is urea.
In some embodiments, the europium salt is europium nitrate.
In some embodiments, the terbium salt is terbium nitrate.
In some embodiments, the molar ratio of europium salt to amide is 1:2 to 1:8;
the molar ratio of the terbium salt to the amide substance is 1:2-1:8.
When the ratio of europium salt or terbium salt to amide is 1:1, both of them cannot form uniform and stable liquid, and when the ratio is 1.
The eutectic solvent obtained by europium nitrate is light pink under sunlight, the eutectic solvent obtained by terbium nitrate is colorless, and the eutectic solvent respectively show orange red fluorescence and green fluorescence under the irradiation of ultraviolet light.
In some embodiments, the temperature of the blending heating is 50 to 60 ℃ and the time of the blending heating is 0.5 to 1.5 hours.
In some embodiments, the carbon source is ethylenediaminetetraacetic acid disodium salt.
In some embodiments, the surface passivating agent is tetraethylenepentamine.
Preferably, the pyrolysis temperature is 200-250 ℃ and the pyrolysis time is 1-3h.
In some embodiments, the mass ratio of EuDES to TbDES in the white soft material is 2:1-3:1, and the mass of the blue light carbon dots is adjusted to achieve a concentration of 0.1-0.5mg/mL in the mixture.
In some embodiments, the diluent is PDES.
In a second aspect, the invention provides a white luminescent soft material based on a lanthanide eutectic solvent and carbon dots, which is prepared by the preparation method.
In a third aspect, the present invention provides a white LED, including an LED chip and a white light emitting soft material layer loaded on the LED chip.
The design of the white light LED is divided into two steps, wherein in the first step, amide substances such as urea and the like are mixed and heated with europium salt or terbium salt to obtain two eutectic solvents with red or green luminous capability, then a solvent-free thermal decomposition method is adopted to synthesize a hydrophilic blue light carbon dot in one step, and then the two lanthanide-based eutectic solvents and the carbon dot are mixed according to a proper proportion to obtain a white luminous fluid.
And the second step is to use the white luminous fluid to be solidified on the ultraviolet LED chip by a glue dripping mode so as to obtain the luminous device.
The present invention will be further described with reference to the following examples.
Example 1
(1) Preparation of lanthanide eutectic solvent (LnDES)
The synthetic method of the eutectic solvent is that europium nitrate and terbium nitrate are respectively blended with urea, and the mixture is heated for one hour at 55 ℃ to obtain clear and transparent liquid.
The mass ratio of europium nitrate and urea is adjusted to be 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1, when 1:1 and 1.
Adjusting mass ratios of terbium nitrate and urea, namely 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9 and 1, respectively, wherein stable target products cannot be formed when 1:1 and 1 are used, and the mass ratios of 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1 and 10 are respectively marked as TbDES-1, tbDES-2, tbDES-3, tbDES-4, tbDES-5, tbDES-6, tbDES-8 and TbDES-8, as shown in a table.
TABLE 1
As shown in fig. 2 and 3, the proportion of the lanthanide salt and urea capable of forming a eutectic solvent is 1:2-1:8, and when the proportion is 1:1, both of them cannot form a uniform and stable liquid, and when the proportion is 1.
In addition, the eutectic solvent obtained by europium nitrate is light pink under sunlight, the eutectic solvent obtained by terbium nitrate is colorless, and the eutectic solvent respectively show orange red fluorescence and green fluorescence under the irradiation of ultraviolet light.
(2) Preparation of blue light carbon dots
Synthesizing carbon points, wherein the selected carbon source is ethylene diamine tetraacetic acid disodium salt, the surface passivator is tetraethylenepentamine, and a solvent-free thermal decomposition method is adopted.
The experimental procedure was to dissolve 1.27g disodium ethylenediaminetetraacetate in 15ml water, place in a three-necked flask, and add 5ml tetraethylenepentamine. Heating at 150 deg.C, stirring strongly for 1 hr, and removing water; then heated at 220 ℃ and stirred strongly for reaction for 2h.
(3) White light tuning liquid and white light obtaining device
In experiments to tune white light liquids, the blue component was selected without dialyzed carbon dots, the green component was TbDES-8 (1:9), the red component was EuDES-8 (1:9), and Polymerizable DES (PDES) was used as the diluent.
The general idea and mode of adjusting white light are that after the relation of the optimal CD concentration, the proportion between the EuDES and the TbDES and the lighting condition is obtained through experiments, the CD concentration is fixed to be 0.2mg/mL, and the proportion between the EuDES and the TbDES is 2:1-3:1. The amounts of PDES, euDES and TbDES are then adjusted to control the fluorescence intensity of the luminescent DES to match that of the carbon dots, thereby obtaining a white liquid (CTEP).
The reason for selecting PDES as the diluent is that CD is directly dissolved in the luminescence DES which has too strong fluorescence to obtain white light, and the luminescence DES needs to be diluted to control the luminescence intensity in a range similar to CD; while PDES does not adversely affect the light-emitting ability of the three components and can impart the liquid polymerization ability to the mixed liquid.
As shown in fig. 5, the obtained white liquid was a pale yellow transparent liquid under sunlight, and the pale yellow was caused by the dispersion of carbon dots; exhibits white fluorescence under UV light with CIE coordinates (0.31,0.33).
After the white light liquid is obtained, the white light liquid is solidified on the ultraviolet light LED chip by adopting a glue dripping method, bright white light emitted by the LED can be seen after a circuit is switched on, and the short circuit phenomenon can not occur.
In addition to this, the white liquid is polymerized into an elastomer, and although the fluorescence intensity is reduced due to the crosslinked structure, a fluorescent elastomer having a plurality of fluorescent colors is obtained.
Results and discussion
First from the Infrared maps of EuDES and TbDESAs shown in FIG. 6, it can be seen that 3070-3590 cm in LnDES -1 The broad band of (a) corresponds to N-H or O-H stretching vibrations, which may come from urea and crystal water. And 1650 and 1580cm -1 The left and right peaks correspond to the C = O stretching vibration of 1470cm -1 The peak of (a) corresponds to the C-N stretching vibration, and the existence of Urea in the LnDES is proved. And the stretching vibration peak of the amino group is blue-shifted compared with the stretching vibration peak of the raw material Urea in DES, because the carbonyl group in Urea participates in forming a coordination bond to change the electron density, therefore, the Urea is supposed to coordinate with europium ion or terbium ion through the carbonyl oxygen, thereby forming the lanthanide eutectic solvent.
DSC tests show that the melting point of LnDES is reduced with the increase of the dosage of the ligand, the minimum of EuDES can reach-61 ℃, and the minimum of TbDES can reach-66 ℃. This is also an indirect evidence of the difference in coordination structure among LnDES of different ligand contents.
In addition, the thermal decomposition temperature of the europium-based DES is 265 ℃, the thermal decomposition temperature of the terbium-based DES is 259 ℃, and both have good thermal stability.
According to rheological tests, the viscosity of LnDES is lower, and can be reduced to below 100cP with the increase of ligand ratio, unlike the higher viscosity of the common type III DES.
The viscosity of the LnDES is changed, which in turn affects the conductivity, and the conductivity of the lower viscosity LnDES-8 is doubled compared to the higher viscosity LnDES-1. In addition, lnDES has a wide electrochemical window close to 2V.
Fluorescence spectrum tests show that the maximum emission peak of the europium-based eutectic solvent is 613nm under the excitation of 365nm ultraviolet light, the maximum emission peak of the terbium-based DES is 543nm under the excitation of 365nm ultraviolet light, and other secondary peaks are comprehensively analyzed to show that the emission accords with the characteristic emission of two elements of europium and terbium, no emission peak from a ligand is found, and the fact that the LnDES emission wavelength is not affected by different ligand dosages is proved, but according to quantum yield results, the quantum yield of the LnDES can be improved by about 30% to the maximum due to the larger ligand dosage.
The carbon dots should be synthesized by using disodium ethylenediamine tetraacetic acidDecomposition, and in situ surface grafting reaction of the amine groups of tetraethylenepentamine with the carboxyl groups from the pyrolysed mass, as can be confirmed from the IR results, which can be seen in the IR spectrum at 1669cm of carbon dots -1 ，1593cm -1 The two peaks correspond to the C = O bond stretching vibration of the amide group, and the peak is 3390cm -1 The broad peak at (a) corresponds to the N-H stretching vibration in the amide group.
According to the fluorescence spectrum, the emission peak of the carbon dots after dialysis shifts from 435nm before dialysis to about 455nm, and as can be seen from the CIE chromaticity diagram, the emission color also approaches to cyan, so that the carbon dots are not suitable for being used as blue light components, and therefore, in experiments for tuning white light, carbon dots which are not dialyzed are selected as the blue light components.
In summary, urea, europium nitrate and terbium nitrate are used for respectively obtaining red light-emitting EuDES and TbDES, carbon dots with blue light emission capability are synthesized, the three are dissolved in PDES according to a proper proportion to obtain liquid with white light emission capability, and the liquid is cured on an ultraviolet LED chip in a glue dripping mode to obtain a white light LED.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a white luminescent soft material based on a lanthanide eutectic solvent and carbon dots is characterized in that: the method comprises the following steps:
blending and heating an amide substance and a europium salt to obtain a first eutectic solvent EuDES;
mixing and heating an amide substance and terbium salt to obtain a second eutectic solvent TbDES;
heating and drying the mixed solution of the carbon source and the surface passivator, and then stirring and pyrolyzing to prepare a blue light carbon dot;
and mixing the first eutectic solvent, the second eutectic solvent, the blue light carbon dots and the diluent in proportion to prepare the white luminescent soft material.
2. The method for preparing white luminescent soft material based on lanthanide eutectic solvent and carbon dots as claimed in claim 1, characterized in that: the amide substance is urea;
or, the europium salt is europium nitrate;
or the terbium salt is terbium nitrate.
3. The method for preparing white luminescent soft material based on lanthanide eutectic solvent and carbon dots as claimed in claim 1, characterized in that: the molar ratio of europium salt to amide is 1:2-1:8;
the molar ratio of the terbium salt to the amide substance is 1:2-1:8.
4. The method for preparing white luminescent soft material based on lanthanide eutectic solvent and carbon dots as claimed in claim 1, characterized in that: the temperature of the blending heating is 50-60 ℃, and the time of the blending heating is 0.5-1.5h.
5. The method for preparing white luminescent soft material based on lanthanide eutectic solvent and carbon dots as claimed in claim 1, characterized in that: the carbon source is ethylene diamine tetraacetic acid disodium salt.
6. The method for preparing white luminescent soft material based on lanthanide eutectic solvent and carbon dots as claimed in claim 1, characterized in that: the surface passivator is tetraethylenepentamine;
preferably, the pyrolysis temperature is 200-250 ℃ and the pyrolysis time is 1-3h.
7. The method for preparing white luminescent soft material based on lanthanide eutectic solvent and carbon dots as claimed in claim 1, characterized in that: in the white luminescent soft material, the mass ratio of EuDES to TbDES is 2:1-3:1, and the mass of the blue light carbon dots is adjusted to make the concentration of the blue light carbon dots in the mixture reach 0.1-0.5mg/mL.
8. The method for preparing white luminescent soft material based on lanthanide eutectic solvent and carbon dots as claimed in claim 1, characterized in that: the diluent is PDES.
9. A white luminescent soft material based on a lanthanide eutectic solvent and carbon dots is characterized in that: prepared by the preparation method of any one of claims 1 to 8.
10. A white LED, characterized by: comprising an LED chip and the white light emitting soft material layer of claim 9 loaded on the LED chip.
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