CN113755166A - Hydrophobic white light carbon dot and preparation method thereof - Google Patents
Hydrophobic white light carbon dot and preparation method thereof Download PDFInfo
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- 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
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/50—Wavelength conversion elements
- H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
- H01L33/502—Wavelength conversion materials
- H01L33/504—Elements with two or more wavelength conversion materials
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
Abstract
The invention discloses a hydrophobic white light carbon dot and a preparation method thereof, and the hydrophobic white light carbon dot which has hydrophobic characteristics and can emit white fluorescence is prepared by taking o-phenylenediamine and 1,2, 4-benzenetricarboxylic acid as raw materials and carrying out solvothermal reaction in a solvent ethanol at 180-220 ℃. The preparation method of the hydrophobic white light carbon dot is simple, the hydrophobic characteristic of the hydrophobic white light carbon dot can be utilized to quickly obtain solid powder, and the acquisition process of the solid product is simplified. The hydrophobic white light carbon dots can be used as a fluorescent conversion layer material for preparing a white light LED device with excellent performance.
Description
Technical Field
The invention belongs to the technical field of nano carbon luminescent materials, and relates to a carbon dot capable of emitting white light, in particular to a white light carbon dot with a hydrophobic characteristic.
Background
Light Emitting Diodes (LEDs) are currently the most commonly used lighting sources due to their advantages of low power consumption, long service life, small size, and fast response. Fluorescent materials currently used as LED lighting devices mainly include rare earth, semiconductor and carbon-based nanomaterials (angelate chemie, 2015, 127(18): 5450-.
Among them, the synthesis process of rare earth and semiconductor fluorescent materials is mature, and stable and excellent fluorescence performance is shown in solid-state lighting devices (Modern Physics Letters B, 2020, 34(21): 2050222.). However, rare earth resources are not renewable, and heavy metal elements in semiconductor fluorescent Materials are toxic, which limits their application in lighting devices (Journal of Materials Science, 2012, 48(6): 2352-.
In contrast, carbon-based nanomaterials have the advantages of wide sources and low toxicity, and particularly, Carbon Dots (CDs), which are widely concerned, of fluorescent materials, show excellent optical performance and stability (Science Bulletin, 2020, doi: http:// doi.org/10.1016/j.scib. 2020.12.015), so that the carbon-based nanomaterials have a wide application prospect in the field of illumination as fluorescent conversion materials.
When carbon dots are applied to lighting devices such as LEDs, the excitation mode directly affects the lighting performance of the devices. White light emission can be achieved by exciting a yellow carbon dot with a blue chip, but as the device ages, there is a risk of blue light leakage, which may cause damage to the human eye (Journal of Alloys and Compounds, 2018, 764: 17-23.). In contrast, the mode of using the ultraviolet chip to excite the white carbon dot to realize white light emission can not only avoid blue light leakage, but also have higher color rendering index, and can meet the illumination requirements of different application scenes (RSC Advances, 2018, 8(8): 4006-.
The existing white light carbon dots are usually realized by a complementary color carbon dot blending mode, namely blue and yellow carbon dots or red, green and blue carbon dots are mixed according to a certain mass ratio (Advanced Materials, 2018, 30(1): 1704740), the process needs a large amount of experimental trials and related LED device tests, the optimal ratio of carbon dot mixing can be finally determined, and the process is complex and is not beneficial to industrialization.
In addition, researchers also directly synthesize white carbon dots by a one-step solvothermal reaction with ethanol as a carbon source and sulfuric acid as an oxidant (Nano Research, 2021: 1-8.). The white carbon dots can realize white fluorescence under the excitation of 365nm wavelength, and blue, cyan and orange fluorescent carbon dots can be separated through further purification. Due to the lack of red fluorescent component, the white carbon dot ultimately yields only an LED device with a color rendering index of 87.8.
In addition to synthesizing white light carbon dots with multiple fluorescence emission centers, Li et al (Nanoscale phosphors, 2020, 5(6): 928-; 933.) use 1, 4-diaminonaphthalene as carbon source, CHCl3As a Cl element dopant, a white carbon dot having a single fluorescence emission center was synthesized. But is limited by the narrow fluorescence emission wavelength range of the single luminescence center, and when the white carbon dot is applied to an LED device, only white light with the color rendering index of 70.6 is obtained.
Therefore, the uncontrollable synthesis of the white carbon point fluorescence emission center is the main reason for the low color rendering index of the current LED device, and a proper raw material and a proper method need to be found to realize the controllable preparation of the white carbon point and improve the luminous performance of the corresponding LED device.
In addition, the surface of the white carbon dot prepared at present contains a large amount of functional groups containing nitrogen and oxygen elements, so that the white carbon dot has good hydrophilicity, and the fluorescence performance of the white carbon dot is influenced by absorbing moisture in the air when the white carbon dot is exposed in the air. Therefore, the preparation of the hydrophobic white carbon dots is more beneficial to improving the storage capacity of the carbon dots and the light emitting life of the LED device.
Disclosure of Invention
The invention aims to provide a hydrophobic white carbon dot and a preparation method of the white carbon dot.
The hydrophobic white-light carbon dot is prepared by carrying out solvothermal reaction on o-phenylenediamine and 1,2, 4-benzenetricarboxylic acid serving as raw materials in solvent ethanol at 180-220 ℃, and has a hydrophobic characteristic and can emit white fluorescence.
The hydrophobic white light carbon dots can be dispersed in organic solvents such as ethanol, and the fluorescence emission peak of the solution can cover the wavelength range of 400-750 nm.
Further, the hydrophobic white carbon dots can be prepared by the following method: dissolving o-phenylenediamine and 1,2, 4-benzenetricarboxylic acid in a solvent ethanol according to a molar ratio of (1-3) to 1, heating to 180-220 ℃ in a closed environment to perform a solvothermal reaction, and pouring a reaction product into water to separate out hydrophobic white light carbon dots.
Furthermore, the solvent thermal reaction temperature is preferably 180-200 ℃, and the solvent thermal reaction time is preferably 6-14 h.
Furthermore, the solvent ethanol for the solvent thermal reaction is preferably used in an amount of 5 to 10mL per 1mmol of raw material.
Based on the hydrophobic property of the white carbon dots, the white carbon dot solid powder can be quickly purified. Specifically, the reaction product is filtered, poured into water with the volume 6-10 times that of the reaction product to separate out a precipitate, and the precipitate is filtered, washed and dried to obtain the purified hydrophobic white-light carbon dot solid powder.
The invention preferably adopts a vacuum freeze drying mode to dry the white carbon dot solid powder.
The fluorescence emission peak of the organic solution of the hydrophobic white carbon point can cover a visible light region of 400-750 nm, and corresponding CIE chromaticity coordinates are obtained by calculating the fluorescence (PL) spectrum of the white carbon point solution and are all in the white light region specified by the International Commission on illumination.
Therefore, the invention also provides application of the hydrophobic white carbon point in preparing an LED device.
Specifically, the invention provides application of the hydrophobic white carbon dots as a fluorescence conversion layer material in an LED device.
More specifically, the hydrophobic white light carbon dot solid powder is mixed with PVP, dissolved in absolute ethyl alcohol, dripped into a lamp cup cover of an LED device, dried to obtain a lamp cup, and then the lamp cup is arranged on the surface of a chip with the light-emitting wavelength of 380nm to prepare the white light LED device.
Wherein, the hydrophobic white light carbon dot solid powder and PVP are preferably mixed according to the mass ratio of (0.5-2) to 1.
The preparation method of the hydrophobic white light carbon dot is simple, the hydrophobic characteristic of the hydrophobic white light carbon dot can be utilized to quickly obtain solid powder, and the acquisition process of a solid product is simplified.
The hydrophobic white carbon dots can emit white light under the condition of solution, the light-emitting range covers a visible light region, and the hydrophobic white carbon dots are used as a fluorescent conversion layer material to be applied to preparation of a white LED device, so that a white light illumination light source with excellent performance can be obtained.
Drawings
FIG. 1 is a picture of a real object of white light carbon dot solution prepared in example 1 under natural light and irradiation of 365nm ultraviolet lamp.
FIG. 2 is a fluorescence emission (PL) spectrum of a white light carbon dot solution prepared in example 1.
FIG. 3 is a CIE chromaticity diagram of a white light carbon dot solution prepared in example 1.
FIG. 4 is a Transmission Electron Microscope (TEM) image of a white carbon dot solid powder prepared in example 1.
Fig. 5 is an X-ray diffraction (XRD) spectrum of a white carbon dot solid powder prepared in example 1.
Fig. 6 is a water contact angle test chart of a white carbon dot solid prepared in example 1.
FIG. 7 is an infrared (FTIR) spectrum of solid white carbon dot powder and starting material prepared in example 1.
FIG. 8 is a PL spectrum of a white light carbon dot solution prepared in example 2.
FIG. 9 is a PL spectrum of a white light carbon dot solution prepared in example 3.
FIG. 10 is a CIE chromaticity coordinate diagram and a luminescence entity diagram of an application example for preparing a white light LED.
Detailed Description
The following detailed description of embodiments of the present invention is provided in connection with the accompanying drawings and examples. The following examples are only for more clearly illustrating the technical solutions of the present invention so as to enable those skilled in the art to better understand and utilize the present invention, and do not limit the scope of the present invention.
The names and abbreviations of the experimental methods, production processes, instruments and equipment involved in the examples and comparative examples of the present invention are those commonly known in the art and are clearly and clearly understood in the relevant fields of use, and those skilled in the art can understand the conventional process steps and apply the corresponding equipment according to the names and perform the operations according to the conventional conditions or conditions suggested by the manufacturers.
The various starting materials or reagents used in the examples of the present invention and comparative examples are not particularly limited in their sources, and are all conventional products commercially available. They may also be prepared according to conventional methods well known to those skilled in the art.
Example 1.
Weighing 0.21g of o-phenylenediamine and 0.22g of 1,2, 4-benzenetricarboxylic acid, dissolving in 20mL of absolute ethyl alcohol, pouring the mixed solution into a 50mL high-pressure reaction kettle, sealing, placing in a forced air drying oven, heating to 200 ℃, carrying out thermal reaction on the mixed solution with a heat-preservation solvent for 10 hours, and naturally cooling to obtain a white light carbon dot solution.
Filtering out larger impurities in the white light carbon dot solution by using a 0.22 mu m filter membrane, directly pouring the filtered solution into 200mL of deionized water, and stirring to fully separate out a precipitate.
And (3) carrying out suction filtration on the precipitate by using a 0.22 mu m filter membrane, washing the precipitate for 2-3 times by using deionized water, freezing the collected precipitate in an ultralow-temperature refrigerator at the temperature of-80 ℃ for 30min, and freeze-drying the precipitate in a freeze dryer for 2h to obtain white-light carbon dot solid powder.
2.5mg of the white light carbon dot solid powder prepared above was redissolved in 4mL of anhydrous ethanol, and FIG. 1 shows that the solution was a pale red solution under natural light and was able to directly emit white fluorescence under the irradiation of 365nm UV lamp.
FIG. 2 is a PL spectrum of a white carbon dot solution tested at an excitation wavelength of 400nm, with the emission peak covering the range of 400-750 nm. By computational fitting of the PL spectra, the corresponding CIE chromaticity coordinates are (0.37, 0.35) as shown in fig. 3.
The above characterization results confirm that the product prepared in this example can realize white light emission under ultraviolet or near ultraviolet excitation.
Fig. 4 is a TEM image of white carbon dot solid powder. When observed at low magnification, fig. 4(a) shows that the white carbon dots have good monodispersity and uniform particle size. FIG. 4(b) is a magnified view of one of the carbon dots, showing that the carbon dots have different sizes insidesp 2The conjugated structure domain and the lattice fringes are clearly visible, the interplanar distances of 0.24 nm and 0.28nm respectively correspond to the crystal faces (1120) and (101) of the graphite, the white light carbon points can be preliminarily considered to be aggregates formed by carbon points with different particle sizes, the carbon points with different particle sizes emit different fluorescence, and finally the white light is obtained through compounding.
In the white light carbon dot solid powder XRD spectrum of FIG. 5, the diffraction angle at 26.48 degrees corresponds to the graphite (002) crystal face and conforms to the structural characteristics of the carbon dot. In addition, peaks at diffraction angles of 15.5 °, 16.6 ° and 23.2 ° represent other by-products such as amino cellulose generated during the reaction. The amino cellulose has certain hydrophobicity after crystallization, and during the crystallization process, the amino group on the surface of the cellulose and the functional group on the surface of the white-light carbon dot form a hydrogen bond effect, and the white-light carbon dot is embedded in the amino cellulose to form an aggregate of the white-light carbon dot.
Fig. 6 shows the water contact angle test results for white carbon dot solids. And pressing the white carbon dots into a film by using a tablet press, dripping water on the surface of the film, and testing the angle between the tangent line of the surface of the water drop and the horizontal plane of the film to obtain the contact angle between the white carbon dots and water. In the figure, the left contact angle is 98.5 degrees, the right contact angle is 99.5 degrees, and the contact angles are both more than 90 degrees, which shows that the white carbon point has better hydrophobicity.
FIG. 7 is an FTIR spectrum of starting materials 1,2, 4-benzenetricarboxylic acid and o-phenylenediamine with white carbon dots prepared. In the figure, the length is 3500-3300 cm-1、3200～2400cm-1And 1300cm-1The peaks appeared at the position are respectively derived from the stretching vibration of amino, hydroxyl and C-O/C-N,it is shown that the surfaces of 1,2, 4-benzene tricarboxylic acid, O-phenylenediamine and white light carbon dots have similar functional groups containing elements such as N, O and the like. However, since these functional groups tend to be hydrophilic, the strong hydrophobicity of the white carbon dot does not arise from itself. This also confirms the conclusion that its hydrophobicity is derived from the by-product, amino cellulose.
Example 2.
Weighing 0.11g of o-phenylenediamine and 0.22g of 1,2, 4-benzenetricarboxylic acid, dissolving in 20mL of absolute ethyl alcohol, pouring the mixed solution into a 50mL high-pressure reaction kettle, sealing, placing in a forced air drying oven, heating to 200 ℃, carrying out thermal reaction on the mixed solution with a heat-preservation solvent for 6 hours, and naturally cooling to obtain a white light carbon point solution.
The white carbon dot solution was filtered and dried under the conditions of example 1 to obtain a white carbon dot solid powder.
Taking 2.5mg of the white light carbon dot solid powder prepared above, redissolving in 4mL of absolute ethyl alcohol, testing the PL spectrogram of the white light carbon dot solid powder as shown in figure 8, and calculating to obtain CIE chromaticity coordinates (0.25 and 0.23) which belong to cold white light.
Example 3.
Weighing 0.34g of o-phenylenediamine and 0.22g of 1,2, 4-benzenetricarboxylic acid, dissolving in 20mL of absolute ethyl alcohol, pouring the mixed solution into a 50mL high-pressure reaction kettle, sealing, placing in a forced air drying oven, heating to 180 ℃, carrying out thermal reaction on the mixed solution with a heat-preservation solvent for 14h, and naturally cooling to obtain a white light carbon dot solution.
The white carbon dot solution was filtered and dried under the conditions of example 1 to obtain a white carbon dot solid powder.
Taking 2.5mg of the white light carbon dot solid powder prepared above, redissolving in 4mL of absolute ethyl alcohol, testing the PL spectrogram of the white light carbon dot solid powder as shown in figure 9, and calculating to obtain CIE chromaticity coordinates (0.29 and 0.35) which belong to warm white light.
Application example.
The white light carbon dot solid powder prepared in example 1 was used as a raw material to prepare a white light LED device.
0.5g of PVP is weighed into a 4mL centrifuge tube, and 2mL of absolute ethyl alcohol is added to prepare PVP ethanol solution.
To 200. mu.L of the above solution was added 3.5mg of the white carbon dot solid powder prepared in example 1, and the mixture was thoroughly and uniformly mixed.
And (3) dripping 30 mu L of the obtained mixture into an LED lamp cup, completely drying at room temperature, dripping 30 mu L of the mixture, repeating the operation, dripping 4 times in total, and completely curing to obtain the LED lamp cup.
And (3) mounting the prepared LED lamp cup on an ultraviolet LED chip with the wavelength of 380nm to obtain a white light LED device.
Fig. 10 shows the operating state and CIE chromaticity diagram of the above white LED device.
It can be seen that its CIE chromaticity coordinates are (0.34 ), very close to the chromaticity coordinates of pure white light (0.33 ).
As shown in the inset, after the constructed LED device is powered on, a picture is taken of its operating state, and bright white light is visible. Measuring the CIE chromaticity coordinates, Correlated Color Temperature (CCT) and Color Rendering Index (CRI) of the LED device by a Spectrascan PR655 type spectral scanning colorimeter, wherein the CIE chromaticity coordinates are (0.34 ) and are very close to the chromaticity coordinates (0.33 ) of pure white light; CCT =5088K, close to 4900K for daylight; CRI =91, which reaches the standard of LED devices for indoor illumination in China (CRI > 80).
The above embodiments of the present invention are not intended to be exhaustive or to limit the invention to the precise form disclosed. Various changes, modifications, substitutions and alterations to these embodiments will be apparent to those skilled in the art without departing from the principles and spirit of this invention.
Claims (10)
1. The hydrophobic white-light carbon dot is prepared by carrying out solvothermal reaction on o-phenylenediamine and 1,2, 4-benzenetricarboxylic acid serving as raw materials in solvent ethanol at 180-220 ℃, and has a hydrophobic characteristic and can emit white fluorescence.
2. The method for preparing the hydrophobic white-light carbon dot according to claim 1, wherein the method comprises the steps of dissolving o-phenylenediamine and 1,2, 4-benzenetricarboxylic acid in a solvent ethanol according to a molar ratio of (1-3) to 1, heating to 180-220 ℃ in a closed environment to perform solvothermal reaction, and pouring a reaction product into water to separate out the hydrophobic white-light carbon dot.
3. The method for preparing a hydrophobic white carbon dot according to claim 2, wherein the solvent thermal reaction temperature is 180-200 ℃ and the reaction time is 6-14 h.
4. The method for preparing a hydrophobic white carbon dot according to claim 2, wherein 5-10 mL of ethanol is used per 1mmol of raw material in the solvothermal reaction.
5. The preparation method of the hydrophobic white-light carbon dot according to claim 2, wherein the reaction product is filtered and poured into water with 6-10 times of volume to precipitate out, and the precipitate is filtered, washed and dried to obtain the purified hydrophobic white-light carbon dot solid powder.
6. The method of claim 5, wherein the white carbon solid powder is dried by vacuum freeze-drying.
7. Use of the hydrophobic white carbon dot of claim 1 in the preparation of an LED device.
8. Use of the hydrophobic white carbon dots according to claim 1 as a material for a phosphor conversion layer in an LED device.
9. The application of claim 8, wherein the hydrophobic white light carbon dot solid powder is mixed with PVP, dissolved in absolute ethyl alcohol, dripped into a lamp cup cover of an LED device to be cured to obtain a lamp cup, and the lamp cup is mounted on the surface of a chip with the light-emitting wavelength of 380nm to prepare the white light LED device.
10. The method as claimed in claim 9, wherein the hydrophobic white carbon dot solid powder is mixed with PVP in a mass ratio of 0.5-2: 1.
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