CN110642515A - Preparation method and application of all-inorganic perovskite quantum dot glass - Google Patents
Preparation method and application of all-inorganic perovskite quantum dot glass Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
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- C03C3/00—Glass compositions
- C03C3/32—Non-oxide glass compositions, e.g. binary or ternary halides, sulfides or nitrides of germanium, selenium or tellurium
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
- C03C4/08—Compositions for glass with special properties for glass selectively absorbing radiation of specified wave lengths
- C03C4/085—Compositions for glass with special properties for glass selectively absorbing radiation of specified wave lengths for ultraviolet absorbing glass
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- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
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- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
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- G02B5/22—Absorbing filters
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Abstract
The invention discloses a preparation method and application of all-inorganic perovskite quantum dot glass, and belongs to the technical field of optical glass preparation. The invention mixes high-purity B2O3、SiO2、ZnO、SrCO3、Cs2CO3、PbBr2NaBr and Eu2O3Grinding to obtain mixed raw material, melting at 1150 ~ 1250 deg.C and air atmosphere at high temperature for 8 ~ 20min, pouring onto a preheated copper plate, cooling, shaping to obtain precursor glass, and sequentially performing high-temperature stress relief treatment and stress relief treatmentHigh-temperature heat treatment is carried out to obtain the fully inorganic perovskite CsPbBr3:Eu3+Quantum dot glass. The invention CsPbBr3:Eu3+The quantum dot glass has strong ultraviolet and blue light shielding capability, can completely block blue light between 400 and 475nm, has the ultraviolet light transmittance between 200 and 400nm of not more than 5 percent, and is CsPbBr3The homogeneous distribution of the quantum dots on the glass matrix allows a transmittance of more than 90% in the visible wavelength range, which is useful for uv and blue light shielding.
Description
Technical Field
The invention relates to a preparation method and application of all-inorganic perovskite quantum dot glass, and belongs to the technical field of optical glass preparation.
Background
Ultraviolet light has a major impact on human skin, eyes, the immune system and the biological genome. In addition, the ultraviolet irradiation can also significantly reduce the performance of the organic material, and when the material is placed in the UVB (280-320 nm) and UVA (320-400nm) areas under sunlight, the photoaging of the polymer material can be accelerated. Recently, researchers have found that prolonged exposure to blue light can cause serious damage to human skin and eyes. For example, blue light (440 nm) has been shown to have a significant effect on photoreceptor and retinal pigment epithelial cell function, leading to photochemical damage and photoreceptor cell death, leading to age-related macular degeneration. On the other hand, the cornea blocks UV below 300nm from reaching the retina, while the lens blocks most UV between 300nm and 400nm, so that blue light (400-475 nm) is more photochemically damaging to the eye than UV. Furthermore, blue light also inhibits melatonin secretion in humans, and the effect is most pronounced in the short wavelength range between 446 and 477nm, melatonin being an important hormone affecting sleep. Similar to uv, blue light also causes photoaging of the polymer material. In addition, blue light sources are more widespread in our daily lives than ultraviolet light sources. The most popular household LED product is one that employs a blue light chip that excites a yellow phosphor, and although the light produced thereby appears white to the naked eye, it exhibits a spike in the blue wavelength band 460-470nm of the spectrum, which can damage the retina of the human eye upon prolonged contact with a high power LED. Solar and artificial light sources, including LED lamps and fluorescent tubes, are the main sources of blue light, and the luminous flux of the emitted blue light has rapidly approached the internationally prescribed limit. With the increasing popularity of blue LED backlight display devices, such as mobile smartphones, ultra-portable tablets, and computer screens, our eyes are more exposed to blue light than in the past. Therefore, there is a need to develop a material that can effectively shield ultraviolet and blue light.
However, there are few reports on materials on the market that can shield both uv and blue light and can perform an effective shielding function for high pump power blue laser.
Disclosure of Invention
Aiming at the problems that the shielding materials in the prior art mostly show high photocatalytic or oxidative catalytic activity, which causes the generation of active oxygen and the degradation of various organic matters, and simultaneously aiming at CsPbBr3The invention provides a preparation method and application of all-inorganic perovskite quantum dot glass, and CsPbBr is used3:Eu3+The quantum dot glass has strong ultraviolet and blue light shielding capability, can completely block blue light between 400 and 475nm, has the ultraviolet light transmittance between 200 and 400nm of not more than 5 percent, and is CsPbBr3The homogeneous distribution of the quantum dots on the glass matrix enables a transmission rate of more than 90% in the visible wavelength range, and can be used for shielding ultraviolet and/or blue light.
A preparation method of all-inorganic perovskite quantum dot glass comprises the following specific steps:
(1) mixing high-purity B2O3、SiO2、ZnO、SrCO3、Cs2CO3、PbBr2NaBr and Eu2O3Grinding to obtain mixed powder;
(2) placing the mixed powder in the step (1) at 1150-1150 ~ 1250 ℃ and 1250 ℃ in an air atmosphere, melting at high temperature for 8 ~ 20min, pouring the molten powder onto a preheated copper plate, and cooling and forming to obtain precursor glass;
(3) sequentially carrying out high-temperature stress relief treatment and high-temperature heat treatment on the precursor glass in the step (2) to obtain the fully inorganic perovskite CsPbBr3:Eu3+Quantum dot glass.
The step (1) B2O3、SiO2ZnO and SrCO3Is a glass matrix, Cs2CO3、PbBr2NaBr and Eu2O3Is a microcrystalline material, and B in the mixed powder is calculated by mole fraction2O3 30~40%、SiO2 35~45%、ZnO 10~20%、SrCO 3 5~10%、Eu2O3 0.1~4.0%、Cs2CO3 8~12%、PbBr23 ~ 5% and NaBr 6 ~ 9%.
The temperature of the high-temperature stress relief treatment in the step (3) is 400 ~ 450 ℃, and the stress relief time is 3 ~ 5 h.
The temperature of the high-temperature heat treatment in the step (3) is 480 ~ 510 ℃, and the heat treatment time is 10 ~ 28 h.
The all-inorganic perovskite quantum dot glass is applied to shielding ultraviolet light and blue light.
The basic principle that the all-inorganic perovskite quantum dot glass can shield ultraviolet light and blue light is as follows: from CsPbBr3The absorption spectrum of the quantum dot can be seen, CsPbBr3Quantum dots have little absorption outside the ultraviolet and blue regions. In addition, the blue-green LED can effectively absorb harmful ultraviolet rays and blue light and convert the harmful ultraviolet rays and the blue light into green light, and due to the narrow full width at half maximum of the spectrum, the color purity of the emission spectrum can be ensured, so that the emission spectrum can be far away from the harmful wavelength of the blue light. In addition, the high luminous quantum yield, the high absorption efficiency and the high stability make the blue laser shielding capability.
The invention has the beneficial effects that:
(1) the invention CsPbBr3:Eu3+The quantum dot glass has strong ultraviolet and blue light shielding capability, can completely block blue light between 400 and 475nm, has the ultraviolet light transmittance between 200 and 400nm of not more than 5 percent, and is CsPbBr3The quantum dots are uniformly distributed on the glass matrix, so that the transmittance of the quantum dots in a visible wavelength range is over 90 percent, and CsPbBr3:Eu3+The quantum dot glass has the characteristics of high shielding efficiency, ultrahigh stability, high visible light transmittance, simple preparation process, low cost and the like;
(2) CsPbBr of the invention3:Eu3+The quantum dot glass can be used for high-hardness blue light-resistant films, blue light-resistant lens materials, outdoor ultraviolet shielding materials, multifunctional optical glass and the like.
Drawings
FIG. 1 shows that Eu is not doped in example 13+Precursor glass of (1), no Eu doping3+The precursor glass of (2) has X-ray diffraction (XRD) patterns of different heat treatment time and temperature;
FIG. 2 shows that Eu is not doped in example 13+The photoluminescence spectra of the precursor glass with different heat treatment time and temperature;
FIG. 3 shows that Eu is not doped in example 13+The absorption spectra of the precursor glass at different heat treatment times and temperatures;
FIG. 4 shows that Eu is not doped in example 23+Precursor glass of (1), CsPbBr without doping Eu3+ annealing treatment3Quantum dot glass, doped Eu3 +(3%) annealed CsPbBr3The X-ray diffraction (XRD) spectrum of the quantum dot glass sample is shown in figure 1 (a), Eu-doped3+(3%) annealed CsPbBr3The TEM image corresponding to the quantum dot glass is shown in FIG. 1 (b), Eu-doped3+(3%) the corresponding size distribution histogram of the annealed CsPbBr3 quantum dot glass is shown in fig. 1 (c), HRTEM image is shown in fig. 1 (d) and Fast Fourier Transform (FFT) mode image is shown in fig. 1 (e);
FIG. 5 shows that example 2 does not include Eu3+Precursor glass and doped Eu3+(3%) CsPbBr3Photos of quantum dot glass, and photos under the irradiation of a 460nm blue light chip;
FIG. 6 shows that Eu is not doped in example 23+Precursor glass and doped Eu3+(3%) CsPbBr3A transmission spectrogram of the quantum dot glass;
FIG. 7 shows the doping of Eu in different concentrations in example 23+CsPbBr of3XRD pattern of quantum dot glass;
FIG. 8 shows the doping of Eu in different concentrations in example 23+CsPbBr of3Emission spectrogram of quantum dot glass;
FIG. 9 shows an embodiment2 doping Eu in different concentrations3+CsPbBr of3A transmission spectrogram of the quantum dot glass;
FIG. 10 shows the doping of Eu in different concentrations in example 23+CsPbBr of3An absorption spectrogram of the quantum dot glass;
FIG. 11 shows Eu doping in example 33+(3%) blue laser mask schematic;
FIG. 12 shows Eu doping in example 33+(3%) CsPbBr3Emission spectra of quantum dot glass under different pumping powers;
FIG. 13 shows Eu doping in example 33+(3%) CsPbBr3Irradiating emission spectrograms of quantum dot glass at different times under the pumping power of 800 mW;
FIG. 14 shows Eu doping in example 33+(3%) CsPbBr3The surface temperature of the quantum dot glass changes along with the irradiation time under the pumping power of 800 mW;
FIG. 15 shows Eu doping in example 33+(3%) CsPbBr3The quantum dot glass has transmission spectrum under different environments.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but the scope of the present invention is not limited to the description.
Example 1: a preparation method of all-inorganic perovskite quantum dot glass comprises the following specific steps:
(1) mixing high-purity B2O3、SiO2、ZnO、SrCO3、Cs2CO3、PbBr2NaBr and Eu2O3Grinding to obtain mixed powder; wherein B is2O3、SiO2ZnO and SrCO3Is a glass matrix, Cs2CO3、PbBr2NaBr as microcrystalline material, in mole fraction, B in mixed powder2O3 32%、SiO2 35%、ZnO 10%、SrCO 3 5%、Cs2CO3 9%、PbBr2 3% and NaBr 6%;
(2) melting the mixed powder in the step (1) at 1200 ℃ in an air atmosphere for 15min at a high temperature, pouring the molten powder onto a copper plate preheated to 400 ℃, and cooling and forming to obtain precursor glass;
(3) sequentially carrying out high-temperature stress relief treatment and high-temperature heat treatment on the precursor glass in the step (2) to obtain the fully inorganic perovskite CsPbBr3The high-temperature stress relief treatment temperature is not 420 ℃, the stress relief time is 3 h, the high-temperature heat treatment temperature is 490 or 500 ℃, and the heat treatment time is 10, 15 or 22 h;
without doping Eu3+Precursor glass of (1), no Eu doping3+The X-ray diffraction (XRD) patterns of the precursor glasses of (1) at different heat treatment times and temperatures are shown in FIG. 1, from which it can be seen that CsPbBr appears in the precursor glasses at temperatures above 480 deg.C3A microcrystalline phase; without doping Eu3+The photoluminescence spectra of the precursor glass at different heat treatment times and temperatures are shown in fig. 2, and it can be seen that the PL relative intensity is enhanced with the extension of the proper heat treatment time; without doping Eu3+The absorption spectra of the precursor glass at different heat treatment times and temperatures are shown in fig. 3, and the optimal heat treatment temperature and time are further determined.
Example 2: a preparation method of all-inorganic perovskite quantum dot glass comprises the following specific steps:
(1) mixing high-purity B2O3、SiO2、ZnO、SrCO3、Cs2CO3、PbBr2NaBr and Eu2O3Grinding to obtain mixed powder; wherein B is2O3、SiO2ZnO and SrCO3Is a glass matrix, Cs2CO3、PbBr2NaBr and Eu2O3Is microcrystalline material, and B in the mixed powder is calculated by mole fraction2O3 32%、SiO2 35%、ZnO 10%、SrCO 3 5%、Cs2CO3 9%、PbBr2 3% and NaBr 6%, Eu2O3(0.1%, 0.3%, 0.5%, 1.0%, 1.5%, 2.0%, 2.5%, 3.0%, or 3.5%);
(2) melting the mixed powder in the step (1) at 1200 ℃ in an air atmosphere for 15min at a high temperature, pouring the molten powder onto a copper plate preheated to 400 ℃, and cooling and forming to obtain precursor glass;
(3) sequentially carrying out high-temperature stress relief treatment and high-temperature heat treatment on the precursor glass in the step (2) to obtain the fully inorganic perovskite CsPbBr3The high-temperature stress relief treatment temperature is not 420 ℃, the stress relief time is 3 h, the high-temperature heat treatment temperature is 500 ℃, and the heat treatment time is 22 h;
the sample of this embodiment is not doped with Eu3+Precursor glass of (1), no Eu doping3+Annealed CsPbBr3Quantum dot glass, doped Eu3+(3%) annealed CsPbBr3The X-ray diffraction (XRD) spectrum of the quantum dot glass is shown in figure 4 (a), Eu-doped3+(3%) annealed CsPbBr3The TEM image corresponding to the quantum dot glass is shown in FIG. 4 (b), Eu-doped3+(3%) annealed CsPbBr3The corresponding size distribution histogram of the quantum dot glass is shown in fig. 4 (c), the HRTEM image is shown in fig. 4 (d), and the Fast Fourier Transform (FFT) mode image is shown in fig. 4 (e), and it can be seen from fig. 1 that CsPbBr is precipitated in the borosilicate glass3Quantum dots, and CsPbBr due to confinement of the glass matrix3The quantum dots are uniformly distributed, the average size is 2.83nm, and the Eu doping can be proved3+The phase structure of the target sample is still CsPbBr3；
This example does not dope Eu3+Precursor glass and doped Eu3+(3%) annealed CsPbBr3The picture of the quantum dot glass and the picture excited by a 460nm blue light chip are shown in figure 5, the blocking effect of the material of the invention on blue light can be visually seen, and the embodiment does not mix Eu3+Precursor glass and doped Eu3+(3%) CsPbBr3The transmission spectrum of the quantum dot glass is shown in figure 6,
the important effect of the introduction of rare earth ions on the blue light shielding can be seen; eu doped with the same rare earth3+The XRD pattern, emission spectrum and absorption spectrum of the samples are shown in FIGS. 7, 8, 10 and 9 respectively, and Eu 7 ~ 10 is shown in FIG. 7 and 73+The introduction of (b) causes a significant blue shift of the PL spectrum and the dominance of XRD can be deduced from FIG. 7The broadening of diffraction peak further shows that the quantum size effect reduces the particles, and the transmittance of the glass to visible light is obviously improved, thereby meeting the requirements of shielding materials, so that Eu is3+The doping of (2) has two main functions, the band gap is adjusted firstly, and the emission spectrum is ensured to be far away from a blue light harm area as far as possible; secondly, it achieves the high visible light transmission we require while maintaining a high shielding effect.
Example 3: a preparation method of all-inorganic perovskite quantum dot glass comprises the following specific steps:
(1) mixing high-purity B2O3、SiO2、ZnO、SrCO3、Cs2CO3、PbBr2NaBr and Eu2O3Grinding to obtain mixed powder; wherein B is2O3、SiO2ZnO and SrCO3Is a glass matrix, Cs2CO3、PbBr2NaBr and Eu2O3Is microcrystalline material, and B in the mixed powder is calculated by mole fraction2O3 32%、SiO2 35%、ZnO 10%、SrCO 3 5%、 Cs2CO3 9%、PbBr2 3% and NaBr 6%, Eu2O3 3.0%；
(2) Melting the mixed powder in the step (1) at 1200 ℃ in an air atmosphere for 15min at a high temperature, pouring the molten powder onto a copper plate preheated to 400 ℃, and cooling and forming to obtain precursor glass;
(3) sequentially carrying out high-temperature stress relief treatment and high-temperature heat treatment on the precursor glass in the step (2) to obtain the fully inorganic perovskite CsPbBr3The high-temperature stress relief treatment temperature is not 420 ℃, the stress relief time is 3 h, the high-temperature heat treatment temperature is 500 ℃, and the heat treatment time is 22 h;
the sample is doped with rare earth Eu3+（3mol%）CsPbBr3Quantum dot glass, FIG. 11 is a schematic view of a blue laser shielding device, and FIG. 12 is Eu-doped glass with different pumping powers3+（3mol%）CsPbBr3Emission spectrum of quantum dot glass, it can be seen that as the pump power increasesThe emission intensity at 506nm of the emission spectrum was increased and then decreased, and it was noted that the emission intensity at 473nm was not changed as compared with the detection intensity before no laser irradiation, thereby confirming that Eu was doped3+（3mol%）CsPbBr3The quantum dot glass has a good shielding effect on 473nm blue laser, and considering the influence of a high-power irradiation thermal effect, the blue laser with 800mW pumping power is continuously irradiated for 6h as shown in FIG. 13, the emission intensity in the initial half hour is remarkably reduced, the temperature at a laser focusing point is detected as shown in FIG. 14, the temperature is remarkably increased in the initial half hour, the reduction of the emission intensity can be attributed to the change of the temperature, and it is worth noting that the emission intensity change at 473nm is not detected by a fiber spectrometer, and further proving that the Eu is further doped3+（3mol%）CsPbBr3The quantum dot glass has a good shielding effect on 473nm blue laser; meanwhile, we have explored the changes of the transmission spectrum of the Eu3+ (3 mol) doped CsPbBr3 quantum dot glass after annealing treatment in 480H placed in aqueous solution and organic solvent acetone under the conditions of high temperature of 300 ℃ and blue light chip irradiation of 460nm, and see FIG. 15, which shows that before the comparison treatment, the Eu doped glass after 480H treatment under different conditions is treated3+（3mol%）CsPbBr3The transmittance of the quantum dot glass in the visible light region with the wavelength of 500-800nm is still maintained, and the transmittance in the ultraviolet blue light region with the wavelength of 400-475nm is still lower than 5%, so that the material has excellent shielding effect, can be stably used for a long time, and CsPbBr3:Eu3+The quantum dot glass has the characteristics of high shielding efficiency, ultrahigh stability, high visible light transmittance, simple preparation process, low cost and the like, and has good market prospect.
The foregoing is a preferred embodiment of the present invention, and certain modifications and optimizations may be made for subsequent applications and manufacturing without departing from the principles of the present invention and are considered to be within the scope of the present invention.
Claims (5)
1. A preparation method of all-inorganic perovskite quantum dot glass is characterized by comprising the following specific steps:
(1) mixing high-purity B2O3、SiO2、ZnO、SrCO3、Cs2CO3、PbBr2NaBr and Eu2O3Grinding to obtain mixed powder;
(2) placing the mixed powder in the step (1) at 1150-1150 ~ 1250 ℃ and 1250 ℃ in an air atmosphere, melting at high temperature for 8 ~ 20min, pouring the molten powder onto a preheated copper plate, and cooling and forming to obtain precursor glass;
(3) sequentially carrying out high-temperature stress relief treatment and high-temperature heat treatment on the precursor glass in the step (2) to obtain the fully inorganic perovskite CsPbBr3:Eu3+Quantum dot glass.
2. The method for preparing the all-inorganic perovskite quantum dot glass according to claim 1, characterized in that: step (1) B2O3、SiO2ZnO and SrCO3Is a glass matrix, Cs2CO3、PbBr2NaBr and Eu2O3Is a microcrystalline material, and B in the mixed powder is calculated by mole fraction2O3 30~40%、SiO2 35~45%、ZnO 10~20%、SrCO3 5~10%、Eu2O3 0.1~4.0%、Cs2CO3 8~12%、PbBr23 ~ 5% and NaBr 6 ~ 9%.
3. The preparation method of the all-inorganic perovskite quantum dot glass according to claim 1, wherein the temperature of the high-temperature stress relief treatment in the step (3) is 400 ~ 450 ℃, and the stress relief time is 3 ~ 5 h.
4. The preparation method of the all-inorganic perovskite quantum dot glass according to claim 1, wherein the temperature of the high-temperature heat treatment in the step (3) is 480 ~ 510 ℃, and the heat treatment time is 10 ~ 28 h.
5. Use of an all inorganic perovskite quantum dot glass prepared by the method of any one of claims 1 ~ 4 for shielding ultraviolet and blue light.
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