CN109437557B - Green-white fluorescent silver quantum cluster doped fluorophosphate glass based on non-bridging oxygen coordination and preparation method thereof - Google Patents
Green-white fluorescent silver quantum cluster doped fluorophosphate glass based on non-bridging oxygen coordination and preparation method thereof Download PDFInfo
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Abstract
The invention discloses green and white fluorescent silver quantum cluster doped fluorophosphate glass based on non-bridging oxygen coordination, which comprises the following components in percentage by mole: ZnF2(30－55％)、P2O5(25－55％)、SnO2(5－10％)、In2O3(5-10%) and Ag (0.1-3%), and is prepared by a two-step method of high-temperature melting. The glass prepared by the invention has the characteristics of wide visible light wave band spectrum and high-efficiency fluorescence and good physical and chemical stability, can be prepared into a sheet to be applied to modulating solar spectrum to improve the energy conversion efficiency of a solar cell, or can be matched with an ultraviolet LED chip to be used as a fluorescence conversion layer to be applied to white light LED illumination.
Description
Technical Field
The invention relates to noble metal-doped inorganic fluorescent glass and a preparation method thereof, in particular to green-white fluorescent silver quantum cluster-doped fluorophosphate glass based on non-bridging oxygen coordination and a preparation method thereof.
Background
Noble metal quantum clusters, in particular silver quantum clusters ([ Ag ]m]n+) The metal molecular luminescent material is a novel metal molecular luminescent material and has excellent optical, spectroscopic, catalytic and other properties. [ Ag ]m]n+The quantum cluster is composed of only a few to tens of atoms (Ag)0) Ion (Ag)+) Composition, continuous energy level of bulk metallic material divided thereinThe quantum fluorescence is split into discrete energy levels, strong quantum effect and molecular state fluorescence are generated, and the wide-spectrum adjustable fluorescence has the advantages of high fluorescence efficiency, so that the quantum fluorescence can be applied to the fields of biosensing, data storage, temperature detection, display, illumination and the like. Due to [ Ag ]m]n+The quantum cluster has high chemical activity, so the key point for obtaining the high-efficiency luminescent molecule lies in how to stabilize [ Agm]n+And (5) quantum clusters. Using organic polymers or proteins with [ Ag ]m]n+The formed complex structure can be effectively stabilized in inorganic glassm]n+Quantum clusters, but still suffer from poor thermal stability.
Disclosure of Invention
The invention aims to provide green-white fluorescent silver quantum cluster doped fluorophosphate glass based on non-bridging oxygen coordination and a preparation method thereof, aiming at the defects of the prior art.
The purpose of the invention is realized by the following technical scheme: a non-bridging oxygen coordination based green and white fluorescent silver quantum cluster doped fluorophosphate glass having the following composition (mole percent):
the invention also provides a preparation method of the green and white fluorescent silver quantum cluster doped fluorophosphate glass based on non-bridging oxygen coordination, which comprises the following steps:
(1) respectively adopting ZnF2、H3PO4、SnO2、In2O3And AgNO3ZnF is introduced into the powder raw material according to the mol percentage2、P2O5、SnO2、In2O3And Ag, calculating the mass percent of the Ag, and weighing the raw materials in proportion;
(2) ZnF is reacted with2、H3PO4And AgNO3Mixing the raw material powder in an agate mortar uniformly, placing the mixture in a corundum crucible, melting the mixture for 0.5 to 1 hour at the temperature of 1150-1250 ℃ in the air atmosphere, pouring the glass melt into a copper mold for moldingObtaining a glass block, and then crushing and grinding the glass block into powder by using an agate mortar;
(3) all the glass powder prepared in the step 2 and the SnO weighed in the step 12、In2O3Powder raw materials are evenly mixed in an agate mortar, placed in a corundum crucible, melted for 0.5 to 1 hour at the temperature of 1000-1100 ℃ in the air atmosphere, and poured into a copper mold for molding to obtain a glass block;
(4) and (4) carrying out plane grinding and polishing on the glass prepared in the step (3) to prepare a transparent glass sheet.
The fluorescent silver quantum cluster in the glass has a wide-spectrum excitation band in an ultraviolet band (240-370nm), and the central wavelength is 280 nm; the fluorescent silver quantum cluster in the glass has a central wavelength of wide-spectrum emission band emission in a visible wave band (350-800) and is positioned at 600 nm. This is primarily the luminescence of silver ions. The fluorescent silver quantum cluster in the glass has a wide-spectrum excitation band in an ultraviolet band (240-400nm), and the central wavelength is 320 nm; the fluorescent silver quantum cluster in the glass has a central wavelength of emission in a wide spectrum emission band of a visible wave band (380-800) and is positioned at 480 nm. This is based on a non-charge-balanced zinc-oxygen tetrahedron [ ZnO ]4]Or phosphorus-oxygen tetrahedrons [ PO ] with non-bridging oxygens4]And doped Ag concentration regulated [ Agm]n+Luminescence of the quantum clusters. All components of the glass are inorganic substances, so the glass has good physical and chemical stability and thermal stability, can be made into a sheet to be applied to modulating solar spectrum to improve the energy conversion efficiency of a solar cell, or can be matched with an ultraviolet LED chip to be used as a fluorescence conversion layer to be applied to white light LED illumination.
Drawings
Fig. 1 is a comparison of XRD spectra of fluorescent silver quantum cluster doped glass and non-doped glass of example 1;
FIG. 2 is a transmission electron micrograph of the fluorescent silver quantum cluster doped glass of example 1;
FIG. 3 is a graph comparing the absorption spectra of the fluorescent silver quantum cluster doped glass and the non-doped glass of example 1;
fig. 4 is a fluorescence spectrum of the fluorescent silver quantum cluster doped glass of example 1, wherein the left side of the graph is an excitation spectrum, the monitoring wavelength is 480nm, the right side is an emission spectrum, and the excitation wavelength is 320 nm.
Detailed Description
In inorganic glass, silver exists in three forms, namely silver ions (Ag) in the order of size from small to large+) Silver quantum cluster ([ Ag ]m]n+) And silver nanoparticles. [ Ag ]m]n+With a certain charge, from a few to tens of atoms (Ag)0) Ion (Ag)+) Composition, low degree of polymerization, small size (sub-nanometer scale). The silver nanoparticles are made of Ag0Atom constitution, nanometer level size, high polymerization degree and large size (nanometer level). The green and white fluorescent silver quantum cluster doped fluorophosphate glass based on non-bridging oxygen coordination needs to inhibit the formation of nano silver, mainly because the green and white fluorescent silver quantum cluster doped fluorophosphate glass has strong Surface Plasmon Resonance (SPR) absorption effect in a visible light band and does not generate any fluorescence emission. To produce [ Ag ] in large quantities in a glass matrixm]n+Requires Ag+Is partially reduced to Ag0At the same time, Ag should be inhibited+Is totally reduced to Ag0. Due to Ag+Ag is easy to be reduced in inorganic glass network0Therefore, in the present invention we introduce appropriate amount of Sn4+Partially stabilizing silver to Ag as an oxidizing agent+Simultaneous control of doped Ag concentration by solubility strategy [ Agm]n+M value of degree of polymerization of (1), using a non-charge-balanced zinc-oxygen tetrahedron [ ZnO ]4]Or phosphorus-oxygen tetrahedrons [ PO ] with non-bridging oxygens4]Through [ Ag ]m]n+Strategies to modulate [ Ag ] as Charge Compensation Agentsm]n+The number of charges n is the value.
The invention adopts non-bridge oxygen or non-charge balancing cation polyhedrons and [ Ag ] in inorganic glass networkm]n+The quantum clusters form similar complex structures, and can effectively stabilize [ Ag ]m]n+The quantum clusters can also improve the high-temperature stability and the size uniformity of the fluorescent material.
The glass has the high-efficiency fluorescence characteristic of wide visible light wave band spectrum and good physical and chemical stability, can be made into a sheet for modulating solar spectrum to improve the energy conversion efficiency of a solar cell, or is matched with an ultraviolet LED chip as a fluorescence conversion layer for white light LED illumination.
Example 1
According to composition 38.4ZnF2-40P2O5-10SnO2-10In2O3ZnF weighed at-1.6 Ag (mol%)2、H3PO4、SnO2、In2O3And AgNO3And (3) powder raw materials. ZnF is reacted with2、H3PO4And AgNO3The raw material powder is uniformly mixed in an agate mortar, placed in a corundum crucible, melted for 45 minutes at 1150 ℃ in the air atmosphere, and the glass melt is poured into a copper mold to be molded to obtain a glass block, and then crushed and ground into powder by the agate mortar. Mixing glass powder with SnO2、In2O3The powder raw materials are uniformly mixed in an agate mortar, placed in a corundum crucible, melted for 45 minutes at 1000 ℃ in the air atmosphere, and the glass melt is poured into a copper mold to be molded to obtain a glass block, and the glass block is subjected to plane grinding and polishing to prepare the transparent glass sheet.
As shown in fig. 1, XRD analysis showed that the glass sample was amorphous. The silver quantum clusters present in the glass can be detected by transmission electron microscopy, absorption spectroscopy and fluorescence spectroscopy tests. The transmission electron micrograph of the glass shown in FIG. 2 shows that: a large number of sub-nanometer silver quantum clusters are uniformly distributed in the glass. The absorption spectrum shown in fig. 3 shows that: the central absorption wavelength of the fluorescent silver quantum cluster in the glass is 320nm, and the glass has an absorption peak. As can be seen from the fluorescence spectrum shown in fig. 4: the fluorescent silver quantum cluster in the glass has a wide-spectrum excitation band in an ultraviolet band (240-400nm), and the central wavelength is 320 nm; the fluorescent silver quantum cluster in the glass has a central wavelength of emission in a wide spectrum emission band of a visible wave band (380-800) and is positioned at 480 nm. By utilizing an integrating sphere and a fluorescence spectrum test, the fluorescence quantum efficiency of the sample obtained by the test is 90.2%, so that the fluorescent silver quantum cluster doped glass provided by the embodiment of the invention has the characteristic of efficiently converting ultraviolet photons into visible photons within a wider waveband. All components of the glass are inorganic substances, so the glass has good physical and chemical stability and thermal stability, can be made into a sheet to be applied to modulating solar spectrum to improve the energy conversion efficiency of a solar cell, or can be matched with an ultraviolet LED chip to be used as a fluorescence conversion layer to be applied to white light LED illumination.
Example 2
According to composition 29.9ZnF2-55P2O5-10SnO2-5In2O3ZnF weighed at-0.1 Ag (mol%)2、H3PO4、SnO2、In2O3And AgNO3And (3) powder raw materials. ZnF is reacted with2、H3PO4And AgNO3The raw material powder is uniformly mixed in an agate mortar, placed in a corundum crucible, melted for 30 minutes at 1150 ℃ in the air atmosphere, and the glass melt is poured into a copper mold to be molded to obtain a glass block, and then crushed and ground into powder by the agate mortar. Mixing glass powder with SnO2、In2O3The powder raw materials are uniformly mixed in an agate mortar, placed in a corundum crucible, melted for 30 minutes at 1000 ℃ in the air atmosphere, and the glass melt is poured into a copper mold to be molded to obtain a glass block, and the glass block is subjected to plane grinding and polishing to prepare the transparent glass sheet.
XRD analysis showed that the glass sample was amorphous. The glass transmission electron micrograph shows that: a large number of sub-nanometer silver quantum clusters are uniformly distributed in the glass. The absorption spectrum is as follows: the central absorption wavelength of the fluorescent silver quantum cluster in the glass is 320nm, and the glass has an absorption peak. The fluorescence spectrum is visible: the fluorescent silver quantum cluster in the glass has a wide-spectrum excitation band in an ultraviolet band (240-400nm), and the central wavelength is 320 nm; the fluorescent silver quantum cluster in the glass has a central wavelength of emission in a wide spectrum emission band of a visible wave band (380-800) and is positioned at 480 nm. By utilizing an integrating sphere and a fluorescence spectrum test, the fluorescence quantum efficiency of the sample obtained by the test is 72.6%, so that the fluorescent silver quantum cluster doped glass provided by the embodiment of the invention has the characteristic of efficiently converting ultraviolet photons into visible photons within a wider waveband. All components of the glass are inorganic substances, so the glass has good physical and chemical stability and thermal stability, can be made into a sheet to be applied to modulating solar spectrum to improve the energy conversion efficiency of a solar cell, or can be matched with an ultraviolet LED chip to be used as a fluorescence conversion layer to be applied to white light LED illumination.
Example 3
According to composition 55ZnF2-32P2O5-5SnO2-5In2O3-3Ag (mol%), weighing ZnF2、H3PO4、SnO2、In2O3And AgNO3And (3) powder raw materials. ZnF is reacted with2、H3PO4And AgNO3The raw material powder is uniformly mixed in an agate mortar, placed in a corundum crucible, melted for 60 minutes at 1250 ℃ in the air atmosphere, and the glass melt is poured into a copper mold to be molded to obtain a glass block, and then crushed and ground into powder by the agate mortar. Mixing glass powder with SnO2、In2O3The powder raw materials are uniformly mixed in an agate mortar, placed in a corundum crucible, melted for 60 minutes at 1100 ℃ in the air atmosphere, and the glass melt is poured into a copper mold to be molded to obtain a glass block, and the glass block is subjected to plane grinding and polishing to prepare the transparent glass sheet.
XRD analysis showed that the glass sample was amorphous. The glass transmission electron micrograph shows that: a large number of sub-nanometer silver quantum clusters are uniformly distributed in the glass. The absorption spectrum is as follows: the central absorption wavelength of the fluorescent silver quantum cluster in the glass is 320nm, and the glass has an absorption peak. The fluorescence spectrum is visible: the fluorescent silver quantum cluster in the glass has a wide-spectrum excitation band in an ultraviolet band (240-400nm), and the central wavelength is 320 nm; the fluorescent silver quantum cluster in the glass has a central wavelength of emission in a wide spectrum emission band of a visible wave band (380-800) and is positioned at 480 nm. By utilizing an integrating sphere and a fluorescence spectrum test, the fluorescence quantum efficiency of the sample obtained by the test is 70.1%, so that the fluorescent silver quantum cluster doped glass provided by the embodiment of the invention has the characteristic of efficiently converting ultraviolet photons into visible photons within a wider waveband. All components of the glass are inorganic substances, so the glass has good physical and chemical stability and thermal stability, can be made into a sheet to be applied to modulating solar spectrum to improve the energy conversion efficiency of a solar cell, or can be matched with an ultraviolet LED chip to be used as a fluorescence conversion layer to be applied to white light LED illumination.
Example 4
According to composition 53.5ZnF2-25P2O5-10SnO2-10In2O3ZnF weighed at-1.5 Ag (mol%)2、H3PO4、SnO2、In2O3And AgNO3And (3) powder raw materials. ZnF is reacted with2、H3PO4And AgNO3The raw material powder is uniformly mixed in an agate mortar, placed in a corundum crucible, melted for 60 minutes at 1200 ℃ in the air atmosphere, and the glass melt is poured into a copper mold to be molded to obtain a glass block, and then crushed and ground into powder by the agate mortar. Mixing glass powder with SnO2、In2O3The powder raw materials are uniformly mixed in an agate mortar, placed in a corundum crucible, melted for 60 minutes at 1050 ℃ in air atmosphere, poured into a copper mold for molding to obtain a glass block, and subjected to plane grinding and polishing to prepare the transparent glass sheet.
XRD analysis showed that the glass sample was amorphous. The glass transmission electron micrograph shows that: a large number of sub-nanometer silver quantum clusters are uniformly distributed in the glass. The absorption spectrum is as follows: the central absorption wavelength of the fluorescent silver quantum cluster in the glass is 320nm, and the glass has an absorption peak. The fluorescence spectrum is visible: the fluorescent silver quantum cluster in the glass has a wide-spectrum excitation band in an ultraviolet band (240-400nm), and the central wavelength is 320 nm; the fluorescent silver quantum cluster in the glass has a central wavelength of emission in a wide spectrum emission band of a visible wave band (380-800) and is positioned at 480 nm. By utilizing an integrating sphere and a fluorescence spectrum test, the fluorescence quantum efficiency of the sample obtained by the test is 87.4%, so that the fluorescent silver quantum cluster doped glass provided by the embodiment of the invention has the characteristic of efficiently converting ultraviolet photons into visible photons within a wider waveband. All components of the glass are inorganic substances, so the glass has good physical and chemical stability and thermal stability, can be made into a sheet to be applied to modulating solar spectrum to improve the energy conversion efficiency of a solar cell, or can be matched with an ultraviolet LED chip to be used as a fluorescence conversion layer to be applied to white light LED illumination.
Example 5
According to composition 30ZnF2-50P2O5-10SnO2-9.6In2O3ZnF weighed at-0.4 Ag (mol%)2、H3PO4、SnO2、In2O3And AgNO3And (3) powder raw materials. ZnF is reacted with2、H3PO4And AgNO3The raw material powder is uniformly mixed in an agate mortar, placed in a corundum crucible, melted for 45 minutes at 1150 ℃ in the air atmosphere, and the glass melt is poured into a copper mold to be molded to obtain a glass block, and then crushed and ground into powder by the agate mortar. Mixing glass powder with SnO2、In2O3The powder raw materials are uniformly mixed in an agate mortar, placed in a corundum crucible, melted for 45 minutes at 1050 ℃ in the air atmosphere, and the glass melt is poured into a copper mold to be molded to obtain a glass block, and the glass block is subjected to plane grinding and polishing to prepare the transparent glass sheet.
XRD analysis showed that the glass sample was amorphous. The glass transmission electron micrograph shows that: a large number of sub-nanometer silver quantum clusters are uniformly distributed in the glass. The absorption spectrum is as follows: the central absorption wavelength of the fluorescent silver quantum cluster in the glass is 320nm, and the glass has an absorption peak. The fluorescence spectrum is visible: the fluorescent silver quantum cluster in the glass has a wide-spectrum excitation band in an ultraviolet band (240-400nm), and the central wavelength is 320 nm; the fluorescent silver quantum cluster in the glass has a central wavelength of emission in a wide spectrum emission band of a visible wave band (380-800) and is positioned at 480 nm. By utilizing an integrating sphere and a fluorescence spectrum test, the fluorescence quantum efficiency of the sample obtained by the test is 78.6%, so that the fluorescent silver quantum cluster doped glass provided by the embodiment of the invention has the characteristic of efficiently converting ultraviolet photons into visible photons within a wider waveband. All components of the glass are inorganic substances, so the glass has good physical and chemical stability and thermal stability, can be made into a sheet to be applied to modulating solar spectrum to improve the energy conversion efficiency of a solar cell, or can be matched with an ultraviolet LED chip to be used as a fluorescence conversion layer to be applied to white light LED illumination.
Example 6
According to composition 40ZnF2-40P2O5-8SnO2-10In2O3-2Ag (mol%) ZnF was weighed2、H3PO4、SnO2、In2O3And AgNO3And (3) powder raw materials. ZnF is reacted with2、H3PO4And AgNO3The raw material powder is uniformly mixed in an agate mortar, placed in a corundum crucible, melted for 60 minutes at 1200 ℃ in the air atmosphere, and the glass melt is poured into a copper mold to be molded to obtain a glass block, and then crushed and ground into powder by the agate mortar. Mixing glass powder with SnO2、In2O3The powder raw materials are uniformly mixed in an agate mortar, placed in a corundum crucible, melted for 45 minutes at 1100 ℃ in the air atmosphere, poured into a copper mold for molding to obtain a glass block, and subjected to plane grinding and polishing to prepare the transparent glass sheet.
XRD analysis showed that the glass sample was amorphous. The glass transmission electron micrograph shows that: a large number of sub-nanometer silver quantum clusters are uniformly distributed in the glass. The absorption spectrum is as follows: the central absorption wavelength of the fluorescent silver quantum cluster in the glass is 320nm, and the glass has an absorption peak. The fluorescence spectrum is visible: the fluorescent silver quantum cluster in the glass has a wide-spectrum excitation band in an ultraviolet band (240-400nm), and the central wavelength is 320 nm; the fluorescent silver quantum cluster in the glass has a central wavelength of emission in a wide spectrum emission band of a visible wave band (380-800) and is positioned at 480 nm. By utilizing an integrating sphere and a fluorescence spectrum test, the fluorescence quantum efficiency of the sample obtained by the test is 74.5%, so that the fluorescent silver quantum cluster doped glass provided by the embodiment of the invention has the characteristic of efficiently converting ultraviolet photons into visible photons within a wider waveband. All components of the glass are inorganic substances, so the glass has good physical and chemical stability and thermal stability, can be made into a sheet to be applied to modulating solar spectrum to improve the energy conversion efficiency of a solar cell, or can be matched with an ultraviolet LED chip to be used as a fluorescence conversion layer to be applied to white light LED illumination.
Example 7
According to composition 38.8ZnF2-45P2O5-10SnO2-5In2O3ZnF weighed at-1.2 Ag (mol%)2、H3PO4、SnO2、In2O3And AgNO3And (3) powder raw materials. ZnF is reacted with2、H3PO4And AgNO3The raw material powder was uniformly mixed in an agate mortar, placed in a corundum crucible, melted at 1200 ℃ for 45 minutes in an air atmosphere, and the glass melt was poured into a copper mold to be molded to obtain a glass block, which was then crushed and ground into powder with an agate mortar. Mixing glass powder with SnO2、In2O3The powder raw materials are uniformly mixed in an agate mortar, placed in a corundum crucible, melted for 45 minutes at 1100 ℃ in the air atmosphere, poured into a copper mold for molding to obtain a glass block, and subjected to plane grinding and polishing to prepare the transparent glass sheet.
XRD analysis showed that the glass sample was amorphous. The glass transmission electron micrograph shows that: a large number of sub-nanometer silver quantum clusters are uniformly distributed in the glass. The absorption spectrum is as follows: the central absorption wavelength of the fluorescent silver quantum cluster in the glass is 320nm, and the glass has an absorption peak. The fluorescence spectrum is visible: the fluorescent silver quantum cluster in the glass has a wide-spectrum excitation band in an ultraviolet band (240-400nm), and the central wavelength is 320 nm; the fluorescent silver quantum cluster in the glass has a central wavelength of emission in a wide spectrum emission band of a visible wave band (380-800) and is positioned at 480 nm. By utilizing an integrating sphere and a fluorescence spectrum test, the fluorescence quantum efficiency of the sample obtained by the test is 86.7%, so that the fluorescent silver quantum cluster doped glass provided by the embodiment of the invention has the characteristic of efficiently converting ultraviolet photons into visible photons within a wider waveband. All components of the glass are inorganic substances, so the glass has good physical and chemical stability and thermal stability, can be made into a sheet to be applied to modulating solar spectrum to improve the energy conversion efficiency of a solar cell, or can be matched with an ultraviolet LED chip to be used as a fluorescence conversion layer to be applied to white light LED illumination.
The above-described embodiments are intended to illustrate rather than to limit the invention, and any modifications and variations of the present invention are within the spirit of the invention and the scope of the appended claims.
Claims (2)
1. A green and white fluorescent silver quantum cluster doped fluorophosphate glass based on non-bridging oxygen coordination is characterized by comprising the following components in percentage by mole:
2. the preparation method of the non-bridging oxygen coordination based green and white fluorescent silver quantum cluster doped fluorophosphate glass according to claim 1, which is characterized by comprising the following steps:
(1) ZnF is reacted with2、H3PO4、SnO2、In2O3And AgNO3Taking the powder raw materials according to the mol percentage;
(2) ZnF is reacted with2、H3PO4And AgNO3Uniformly mixing powder raw materials, melting at 1150-1250 ℃ for 0.5-1 hour in air atmosphere, pouring into a mold for molding to obtain a glass block, and then crushing and grinding the glass block into powder;
(3) mixing the powder prepared in the step 2 and the SnO weighed in the step 12、In2O3Uniformly mixing the powder raw materials, melting the powder raw materials for 0.5 to 1 hour at the temperature of 1000 to 1100 ℃ in an air atmosphere, and pouring the melted powder into a mold to obtain a glass block;
(4) and (4) carrying out plane grinding and polishing on the glass block material prepared in the step (3) to prepare a transparent glass sheet.
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