One-dimensional multicolor fluorescent fiber material and its application in LED

Abstract

The application discloses one-dimensional multicolor fluorescent fiber material and application thereof in LED, and belongs to the technical field of fluorescent material.The preparation of the application is as follows: (1) adding HCl solution into o-phenylenediamine solution, adding the obtained solution into NaCl solution, fully mixing, quickly adding H2O2 solution, fully mixing again, standing, centrifuging, washing and drying to obtain pure poly-o-phenylenediamine fiber; (2) adding poly-o-phenylenediamine fiber into NaOH solution or ethanol solution or mixed solution of the two, fully mixing and oscillating, washing to obtain one-dimensional multicolor fluorescent fiber material.Hydrogen peroxide is used as oxidant to oxidize and polymerize o-phenylenediamine into uniform poly-o-phenylenediamine fiber, and then OH ‑ / OH collaborative scheme is used to successfully realize controllable adjustment of fluorescent emission wavelength.After the material is applied to assemble into LED, different color light emission can be realized, which will be helpful for application of nano electronics and nano photonics and expand the research field of multicolor optical fiber.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of fluorescent materials, and particularly relates to one-dimensional multicolor fluorescent fiber materials and application thereof in LEDs. BACKGROUND

[0002] In the past few decades, fluorescent materials have attracted human attention due to their significant influence in the fields of biomedical imaging, anti-counterfeiting, photoelectric sensors, catalysts, etc. At present, fluorescent materials mainly include semiconductor quantum dots, carbon dots, rare earth fluorescent materials and organic fluorescent dyes, etc. However, how to realize multicolor fluorescence through a single material has been a great challenge in the field of fluorescent material research.

[0003] Generally, excellent fluorescent materials require low toxicity, simple preparation method, high fluorescent color purity and strong bleaching resistance. The rigid benzene ring structure of aromatic amines is conducive to conjugation, and the delocalization of π electrons is strong, so it is easy to be excited to produce fluorescence. In addition, the presence of amine groups also provides an effective active site for subsequent group modification and doping. Based on these two reasons, aromatic amines are the most promising candidate materials for realizing multicolor one-dimensional fluorescent materials. Among aromatic compounds, benzene diamine containing two amino groups is particularly special, in which, o-phenylenediamine is added with two adjacent amine groups on the benzene ring, which meets the structural basis of multicolor one-dimensional fluorescent materials. Patent publication No. CN 105254874 A discloses a method for preparing poly-o-phenylenediamine nanobeam by mixed solvent method, which uses o-phenylenediamine as raw material, and different sizes of poly-o-phenylenediamine nanobeam can be obtained by adjusting the proportion of ethanol and water, but it cannot realize the luminescence of poly-o-phenylenediamine material. SUMMARY

[0004] In view of the above problems, the present application provides one-dimensional multicolor fluorescent fiber materials and application thereof in LEDs, which first oxidize and polymerize o-phenylenediamine into poly-o-phenylenediamine by hydrogen peroxide, and then successfully realize the controllable adjustment of fluorescent emission wavelength by OH - -OH collaborative scheme. After the material of the present application is assembled into an LED, different color light emission can be realized.

[0005] The present application is realized by the following technical scheme:

[0006] A one-dimensional multicolor fluorescent fiber material, and a preparation method thereof, includes the following steps:

[0007] (1) Preparation of poly-o-phenylenediamine fiber: add HCl solution to o-phenylenediamine solution, add the obtained solution to NaCl solution, mix the solution on a shaker, then quickly add H2O2 solution, mix again on the shaker, and then let the obtained mixed solution stand for 22-24h, after centrifugation, washing and drying, pure poly-o-phenylenediamine fiber is obtained;

[0008] (2) Preparation of one-dimensional multi-color fluorescent fiber material: poly-o-phenylenediamine fiber is added into NaOH solution or ethanol solution or mixed solution of the two in a ratio of 7.5-8 g: 1 L, the obtained solution is mixed on a vibrator and oscillated for 0.5-2 h, and one-dimensional multi-color fluorescent fiber material is obtained after washing.

[0009] Further, in step (2), the volume ratio of NaOH to ethanol in the mixed solution is 2-2.5: 1.

[0010] Further, in step (2), the concentration of the NaOH solution is 0.1-0.2 mol / L.

[0011] Further, in step (1), the volume ratio of the o-phenylenediamine solution, HCl solution, NaCl solution and H2O2 solution is 1: 1-1.5: 0.5-1.5: 0.5-1.5.

[0012] Further, in step (1), the concentrations of the o-phenylenediamine solution, HCl solution and NaCl solution are 0.05-0.15 mol / L, 0.1-0.15 mol / L and 6.15-6.2 mol / L respectively, and the mass fraction of the H2O2 solution is 30-32%.

[0013] Further, in step (1), the drying temperature is 60-65℃, and the time is 22-24 h; the centrifugation speed is 8000-10000 r / min, and the time is 10-12 min.

[0014] Further, the color of the one-dimensional multi-color fluorescent fiber material is green, red or yellow.

[0015] Application of the one-dimensional multi-color fluorescent fiber material as described above, the one-dimensional multi-color fluorescent fiber material is applied in LED.

[0016] Further, the application specifically refers to adding one-dimensional multi-color fluorescent fiber material into silicone AB glue, stirring and mixing uniformly, pouring the obtained mixture on LED chip, and then curing and forming in an oven to obtain LED assembled by one-dimensional multi-color fluorescent fiber material.

[0017] Further, the mass ratio of the silicone AB glue to one-dimensional multi-color fluorescent fiber material is 30-100: 1.

[0018] Preparation principle of the one-dimensional multi-color fluorescent fiber material of the application:

[0019] In the application, NaOH is alkaline, and OH -After combining with the amino group in o-phenylenediamine, the H in the amino group is robbed, deprotonation occurs, the wavelength of fluorescence emission is blue-shifted, and the material produces green light; after the -OH in ethanol combines with the amino group in o-phenylenediamine, a hydrogen bond is generated, which causes the wavelength to be red-shifted, and the material produces red light; similarly, after NaOH is mixed with ethanol, under the joint action of OH - and -OH, the material produces yellow light.

[0020] Compared with the prior art, the application has the following advantages and beneficial effects:

[0021] 1. In the application, hydrogen peroxide is used as an oxidant to oxidize and polymerize o-phenylenediamine into uniform poly-o-phenylenediamine fibers, and then the OH - / -OH synergy scheme is used to successfully realize the controllable adjustment of the wavelength of fluorescence emission, and the preparation method is simple and easy to operate. After the one-dimensional multicolor fluorescent fiber material of the application is assembled into an LED, different colors of light can be realized, which will help the application of nano-electronics and nano-photonics and expand the research field of multicolor optical fibers.

[0022] 2. In the application, the wavelength of the poly-o-phenylenediamine fluorescent fiber is successfully shifted through deprotonation blue shift and hydrogen bond effect red shift, and micron / nanometer scale green, yellow and red fluorescent one-dimensional materials are obtained. The multicolor fluorescent behavior in the application is attributed to the different effects of OH - and -OH in ethanol on the amino group. The deprotonation process of the amino group caused by OH - causes the fluorescence emission wavelength to be blue-shifted, forming a green fluorescent fiber. The red fluorescent fiber is due to the formation of a hydrogen bond between -OH and -NH2. The synergistic effect of OH - / -OH realizes the intermediate wavelength emission of the yellow fluorescent fiber. BRIEF DESCRIPTION OF DRAWINGS

[0023] Figure 1 A fluorescence microscope morphology diagram of the green poly-o-phenylenediamine fluorescent fiber prepared in Example 1.

[0024] Figure 2 A fluorescence microscope morphology diagram of the yellow poly-o-phenylenediamine fluorescent fiber prepared in Example 2.

[0025] Figure 3 A fluorescence microscope morphology diagram of the red poly-o-phenylenediamine fluorescent fiber prepared in Example 3.

[0026] Figure 4 A fluorescence spectrum diagram of the green poly-o-phenylenediamine fluorescent fiber prepared in Example 1.

[0027] Figure 5Fluorescence spectrum of the yellow poly(o-phenylenediamine) fluorescent fiber prepared in Example 2.

[0028] Figure 6 Fluorescence spectrum of the red poly(o-phenylenediamine) fluorescent fiber prepared in Example 3.

[0029] Figure 7 Optical diagram of the LED assembled with the green poly(o-phenylenediamine) fluorescent fiber in Application Example 1.

[0030] Figure 8 Optical diagram of the LED assembled with the yellow poly(o-phenylenediamine) fluorescent fiber in Application Example 2.

[0031] Figure 9 Optical diagram of the LED assembled with the red poly(o-phenylenediamine) fluorescent fiber in Application Example 3.

[0032] Figure 10 Optical diagram of the LED capable of emitting white light in Application Example 4. DETAILED DESCRIPTION

[0033] The application will be further described in the following examples, which are only used to illustrate the application and do not limit the protection scope of the application.

[0034] Example 1

[0035] Preparation of the green poly(o-phenylenediamine) fluorescent fiber:

[0036] In 1.0 mL of 0.1 moL / L o-phenylenediamine aqueous solution, 1.0 mL of 0.12 moL / L HCl aqueous solution was added, then 0.5 mL of 6.18 moL / L NaCl aqueous solution was poured, the solution was mixed thoroughly on a shaker, then 0.5 mL of 30% H2O2 solution was quickly added, and the solution was mixed thoroughly again on the shaker for 60 s. After the above steps were completed, the solution was allowed to stand for 24 h, and the poly(o-phenylenediamine) fiber was allowed to grow fully without vibration. During this process, the solution changed from colorless and transparent to dark brown, accompanied by a large amount of brown-yellow precipitate. The precipitate was separated from the solution by high-speed centrifugation (10000 r / min, 10 min), then washed with deionized water three times, and the precipitate was dried in an oven at 60°C for 24 h to obtain pure poly(o-phenylenediamine) fiber. In 1 mL of 0.1 moL / L NaOH aqueous solution, 7.5 mg of poly(o-phenylenediamine) fiber was added, then the solution was mixed thoroughly on a shaker and gently shaken for 1 h, then the precipitate was washed once with deionized water to obtain green poly(o-phenylenediamine) fluorescent fiber.

[0037] Example 2

[0038] Preparation of the yellow poly(o-phenylenediamine) fluorescent fiber:

[0039] In 1.0 mL of 0.12 moL / L aqueous o-phenylenediamine solution, 1.2 mL of 0.15 moL / L aqueous HCl solution was added, then 1.0 mL of 6.15 moL / L aqueous NaCl solution was poured into the solution, the solution was mixed well on a shaker, then 1.0 mL of 30% H2O2 solution was quickly added, the solution was mixed well again on a shaker for 60 s, after the above steps were completed, the solution was allowed to stand for 22 h, allowing the poly-o-phenylenediamine fibers to grow fully without vibration, in the process, the solution changed from colorless and transparent to dark brown, accompanied by a large amount of brown-yellow precipitate. The precipitate was separated from the solution by high-speed centrifugation (8000 r / min, 12 min), then washed with deionized water three times, and the precipitate was dried in an oven at 60°C for 22 h to obtain pure poly-o-phenylenediamine fibers. In 1 mL of a mixed solution composed of 0.2 moL / L NaOH and ethanol in a volume ratio of 2:1, 7.8 mg of poly-o-phenylenediamine fibers were added, then the solution was mixed well on a vibrator and gently shaken for 1 h, then the precipitate was washed once with deionized water to obtain yellow poly-o-phenylenediamine fluorescent fibers.

[0040] Example 3

[0041] Preparation of red poly-o-phenylenediamine fluorescent fibers:

[0042] In 1.0 mL of 0.12 moL / L aqueous o-phenylenediamine solution, 1.2 mL of 0.15 moL / L aqueous HCl solution was added, then 1.0 mL of 6.15 moL / L aqueous NaCl solution was poured into the solution, the solution was mixed well on a shaker, then 1.0 mL of 30% H2O2 solution was quickly added, the solution was mixed well again on a shaker for 60 s, after the above steps were completed, the solution was allowed to stand for 22 h, allowing the poly-o-phenylenediamine fibers to grow fully without vibration, in the process, the solution changed from colorless and transparent to dark brown, accompanied by a large amount of brown-yellow precipitate. The precipitate was separated from the solution by high-speed centrifugation (8000 r / min, 12 min), then washed with deionized water three times, and the precipitate was dried in an oven at 60°C for 22 h to obtain pure poly-o-phenylenediamine fibers. In 1 mL of a mixed solution composed of 0.2 moL / L NaOH and ethanol in a volume ratio of 2:1, 7.8 mg of poly-o-phenylenediamine fibers were added, then the solution was mixed well on a vibrator and gently shaken for 1 h, then the precipitate was washed once with deionized water to obtain yellow poly-o-phenylenediamine fluorescent fibers.

[0043] Material characterization analysis

[0044] (I) Fluorescence microscopic analysis

[0045] The green, yellow and red poly-o-phenylenediamine fluorescent fibers prepared in Examples 1-4, respectively, were characterized by fluorescence microscopy, and the characterization results are shown in Figures 1-4 Figures 1-3 ​It can be seen that different samples emit green, yellow and red fluorescence of different colors, and all samples exhibit a very uniform fiber structure, as shown in Figure 4 After linking the green fiber with the blue chip, white light can be emitted, which proves the multicolor property of the fluorescent material.

[0046] (II) Fluorescence spectrum analysis

[0047] The green, yellow and red poly-o-phenylenediamine fluorescent fibers prepared in Examples 1-3 were characterized and analyzed by using a steady-state fluorescence spectrometer, and the characterization results are shown in Figures 4-6 Figures 4-6 It can be seen that the emission wavelengths of the green, yellow and red poly-o-phenylenediamine fluorescent fibers correspond to 540.8 nm, 577.2 nm and 637.3 nm respectively. This is because NaOH is alkaline, and the OH - in it will rob the H in the amino group after combining with the amino group in o-phenylenediamine, resulting in deprotonation and causing blue shift of the fluorescence emission wavelength, and the material produces green light (540.8 nm); the -OH in ethanol will form a hydrogen bond with the amino group in o-phenylenediamine after combining with the amino group, which causes red shift of the wavelength, and the material produces red light (637.3 nm); after mixing NaOH and ethanol, under the joint action of OH - and -OH, the material produces yellow light (577.2 nm).

[0048] Application Example 1

[0049] Silicone AB glue (the mass ratio of A glue and B glue is 1:1) was added into a centrifugal tube and stirred for 5 min, the green poly-o-phenylenediamine fluorescent fiber prepared in Example 1 was added into the AB glue and stirred uniformly, and the mass ratio of the AB glue to the green poly-o-phenylenediamine fluorescent fiber was 30:1, then the mixture was poured onto a UV LED chip, the LED was placed in an oven at 90°C for curing and molding, and an LED assembled by the green poly-o-phenylenediamine fluorescent fiber was obtained.

[0050] Application Example 2

[0051] Silicone AB glue (the mass ratio of A glue and B glue is 1:1) was added into a centrifugal tube and stirred for 5 min, the yellow poly-o-phenylenediamine fluorescent fiber prepared in Example 2 was added into the AB glue and stirred uniformly, and the mass ratio of the AB glue to the yellow poly-o-phenylenediamine fluorescent fiber was 60:1, then the mixture was poured onto a UV LED chip, the LED was placed in an oven at 90°C for curing and molding, and an LED assembled by the yellow poly-o-phenylenediamine fluorescent fiber was obtained.

[0052] Application Example 3

[0053] ​The silicone AB glue (the mass ratio of A glue and B glue is 1:1) was added into a centrifugal tube, stirred for 5 min, the green polyphenylene diamine fluorescent fiber prepared in Example 1 was added into the AB glue and stirred uniformly, wherein the mass ratio of the AB glue and the green polyphenylene diamine fluorescent fiber was 30:1, then the mixture was poured on the blue LED chip, the LED was placed in an oven at 90℃ to be cured and formed, and the LED capable of emitting white light was obtained.

[0054] Application Example 4

[0055] The silicone AB glue (the mass ratio of A glue and B glue is 1:1) was added into a centrifugal tube, stirred for 5 min, the green polyphenylene diamine fluorescent fiber prepared in Example 1 was added into the AB glue and stirred uniformly, wherein the mass ratio of the AB glue and the green polyphenylene diamine fluorescent fiber was 30:1, then the mixture was poured on the blue LED chip, the LED was placed in an oven at 90℃ to be cured and formed, and the LED capable of emitting white light was obtained.

[0056] Material application effect analysis

[0057] The optical diagrams of the LEDs obtained after the polyphenylene diamine fluorescent fibers of different colors were applied in the LEDs in Application Examples 1-4 were as shown in Figures 7-10 It can be known from Figure 7 that the green polyphenylene diamine fluorescent fiber assembled into the LED in Application Example 1 emitted green light in the dark field, and similarly, the yellow and red polyphenylene diamine fluorescent fibers in Application Examples 2 and 3 also emitted light of corresponding colors in the dark field, which were yellow Figure 8 and red Figure 9 respectively. It can be known from Figure 10 that the blue LED assembled with the green polyphenylene diamine fluorescent fiber in Application Example 4 could emit white light, which indicated that the material of the application could also realize the emission of white light through color mixing.

[0058] The above only describes the preferred embodiments of the application and is not used to limit the application, and any modification, equivalent replacement, etc. made within the spirit and principle of the application shall be included in the protection scope of the application.

Claims

1. Use of a one-dimensional green fluorescent fiber material in an LED, characterized in that, The application is particularly: in the silicone AB glue is added one-dimensional green fluorescent fiber material, stirring and mixing uniformly, the obtained mixture is poured on the blue LED chip, then curing in an oven, the LED which can emit white light is obtained; The preparation method of the one-dimensional green fluorescent fiber material comprises the following steps: (1) preparation of poly-o-phenylenediamine fiber: adding HCl solution into o-phenylenediamine solution, adding the obtained solution into NaCl solution, fully mixing the solution on a shaker, then quickly adding H2O2 solution, fully mixing again on the shaker, placing the obtained mixed solution for 22-24 h, after centrifugation, washing and drying, pure poly-o-phenylenediamine fiber is obtained; the volume ratio of the o-phenylenediamine solution, HCl solution, NaCl solution and H2O2 solution is 1:1-1.5:0.5-1.5:0.5-1.5; (2) preparation of one-dimensional green fluorescent fiber material: adding poly-o-phenylenediamine fiber into NaOH solution according to the ratio of 7.5-8 g:1 L, fully mixing and oscillating the obtained solution on a vibrator for 0.5-2 h, after washing, one-dimensional green fluorescent fiber material is obtained.

2. Use of the one-dimensional green luminescent fiber material according to claim 1 in LEDs, characterized in that, The mass ratio of the silicone AB glue and the one-dimensional green fluorescent fiber material is 30-100:

1.

3. Use of the one-dimensional green fluorescent fiber material according to claim 1 in LEDs, characterized in that, In step (2), the concentration of the NaOH solution is 0.1-0.2 mol / L.

4. Use of the one-dimensional green fluorescent fiber material according to claim 1 in LEDs, characterized in that, In step (1), the concentrations of the o-phenylenediamine solution, HCl solution and NaCl solution are respectively 0.05-0.15 mol / L, 0.1-0.15 mol / L and 6.15-6.2 mol / L, and the mass fraction of the H2O2 solution is 30-32%.

5. Use of the one-dimensional green fluorescent fiber material according to claim 1 in LEDs, characterized in that, In step (1), the drying temperature is 60-65℃, and the time is 22-24 h; the centrifugation speed is 8000-10000 r / min, and the time is 10-12 min.

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