Material capable of activating yellow long afterglow by sunlight and preparation method thereof

Abstract

The invention discloses a material capable of activating yellow long afterglow by sunlight and a preparation method thereof, and belongs to the field of photoelectric functional materials. The chemical expression of the material is Sr1-xGa2-ySi2-zO8: xEu < 2 + >, yMn < 2 + > and zTM, x is the amount of substance doped with Eu < 2 + >, x is greater than 0 and less than or equal to 0.1, y is the amount of substance doped with Mn < 2 + >, y is greater than 0 and less than or equal to 0.2, z is the amount of substance doped with TM, z is greater than 0 and less than or equal to 0.1, and TM is transition metal ions and comprises one or more of V, Nb, Ta, Mo and W ions. The material disclosed by the invention can emit yellow light in a range of 400-700nm under the excitation of sunlight, can maintain afterglow with relatively high strength for a relatively long time, is good in structural stability, and can fully meet the actual application requirements of the yellow long-afterglow luminescent material.

Description

Technical Field

[0001] The invention belongs to the technical field of photoelectric functional materials, and relates to a material capable of being activated by sunlight for a long yellow afterglow, and a preparation method thereof. Background Art

[0002] Long afterglow luminescent material, also known as long afterglow material, is a photoluminescent material that emits visible light when excited by a light source and stores part of the light energy. After the excitation stops, the energy is slowly released in the form of light. This unique luminescent property gives long afterglow materials great application potential in safety and emergency route signs, night vision monitoring and medical diagnosis. The light emitted by long afterglow materials includes many categories, such as SrAl2O4:Eu 2+ ,Dy 3+ The material emits green light, CaAl2O4:Eu 2+ , Nd 3+ 、Sr2MgSi2O7:Eu 2+ ,Dy 3+ The material emits blue light, ZnGa2O4:Cr 3+ The material emits near-infrared light.

[0003] Different application scenarios require different types of light. Although some progress has been made in the research of long afterglow materials in the blue, green and near-infrared bands, there is still a lack of long afterglow materials in the warm color range (550-660nm). Only a few warm-color long afterglow materials can be fully activated by sunlight. Even the more famous red long afterglow material Y2O2S:Eu 3+ , Ti 4+ ,Mg 2+ However, it also has problems such as high cost and low sensitivity to indoor light, which makes it unable to meet the demand for long afterglow materials in the warm color range in practical applications.

[0004] Yellow light (yellow light) has important applications in many fields because its wavelength (about 570-590nm) has unique biocompatibility, visibility, and effects on certain materials, making it widely used in biomedicine and healthcare, agriculture and plant growth, industrial inspection and production, communications and laser applications, aesthetics and artistic lighting, etc. For example, in the field of biomedicine and healthcare, yellow light is used in photodynamic therapy (PDT). Yellow light can penetrate shallow skin tissue and is used to treat certain skin diseases and cancers.

[0005] Therefore, it is necessary to provide a material that can be activated by sunlight to emit a long yellow afterglow and a preparation method thereof, so as to obtain a long afterglow material with good luminescence performance in the warm color region to meet the needs of practical applications. Summary of the invention

[0006] In order to overcome the problems in the background technology, the present invention prepares Sr 1-x Ga 2-y Si 2-z O8:xEu 2+ ,yMn 2+ , zTM material, Sr 1-x Ga 2-y Si 2-z O8:xEu 2+ ,yMn 2+ The zTM material can emit yellow light in the range of 400 to 700 nm under 365 nm light excitation, and after the excitation source is removed, the material can maintain luminescence for at least 12 hours.

[0007] In order to achieve the above object, the present invention is implemented by the following technical solutions:

[0008] In one aspect, the present invention provides a sunlight-activated yellow long afterglow material, the chemical expression of which is: Sr 1-x Ga 2-y Si 2-z O8:xEu 2+ ,yMn 2+ , zTM, where x is Eu 2+ The amount of doped substance, 0<x≤0.1, y is Mn 2+ The amount of the doped substance is 0<y≤0.2, z is the amount of the TM doped substance, 0<z≤0.1, and the TM is a transition metal ion, and TM includes one or more of V, Nb, Ta, Mo, and W ions.

[0009] Another aspect of the present invention provides a method for preparing the above-mentioned material, the preparation method comprising the following steps:

[0010] (1) SrCO3, Ga2O3, SiO2, Eu2O3, a manganese source, and a transition metal oxide are uniformly mixed according to a stoichiometric ratio, a reducing agent is added to the mixture, the mixture after the reducing agent is added is heated and melted, and then cooled to obtain a solid sample;

[0011] (2) The solid sample obtained in step (1) is crushed and then calcined to obtain a sunlight-activatable yellow long afterglow material.

[0012] Preferably, the manganese source includes one or more of MnO2, MnCO3, and MnO.

[0013] Preferably, the reducing agent comprises one of N4Si3, SnO and Al, and the amount of the reducing agent added is the sum of the amounts of europium oxide and manganese source substances.

[0014] Preferably, in step (1), the melting temperature is 1400-1700° C. and the holding time is 0.5-3 h.

[0015] Preferably, in step (2), the calcination temperature is 500-1400° C. and the holding time is 1-5 hours.

[0016] Beneficial effects of the present invention:

[0017] 1. The material of the present invention can emit yellow light in the range of 400 to 700 nm under the excitation of sunlight, and the afterglow duration can reach at least 12 hours, which has a relatively long afterglow time.

[0018] 2. In the present invention, high-valent transition metal ions are more likely to replace the 4-valent Si position, Eu 2+ Replace Sr, Mn 2+ Replacing Ga positions, the substitution positions are more dispersed, avoiding concentrated substitution positions, which are prone to high-dose doping substitution and cause structural collapse, making the material structure more stable.

[0019] 3. The present invention can achieve the purpose of increasing the trap density and ultimately improving the afterglow intensity by doping transition metal ions at a relatively low dose, which is beneficial to reducing material costs.

[0020] 4. The raw materials used in the preparation of the sunlight-activated yellow long afterglow material of the present invention are relatively easy to obtain, the preparation method is relatively simple, the preparation cost is low, and it is suitable for large-scale industrial production and application. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 This is the afterglow spectrum of the long afterglow material prepared in Example 1 of the present invention.

[0022] Figure 2 This is the XRD diagram of the long afterglow material prepared in Example 1 of the present invention.

[0023] Figure 3 This is the afterglow decay curve of the long afterglow material prepared in Example 1 of the present invention. DETAILED DESCRIPTION

[0024] The present invention is further described in detail below in conjunction with specific embodiments.

[0025] In the examples and comparative examples of the present invention, chemical reagents not otherwise specified were all commercially available analytically pure reagents for the experiments.

[0026] Example 1

[0027] This embodiment prepares the long afterglow material by the following method:

[0028] (1) Weigh 19.985 mmol of SrCO3, 19.985 mmol of Ga2O3, 19.999 mmol of SiO2, 0.015 mmol of Eu2O3, 0.03 mmol of MnO2, and 0.001 mmol of V2O5, mix the above raw materials evenly, transfer them to a corundum crucible, add 0.045 mmol of SnO to the corundum crucible, and then put the corundum crucible into a high-temperature muffle furnace at 1600°C to melt the raw materials. After 0.5 h, take out the corundum crucible and cool the molten material to obtain a solid sample.

[0029] (2) The solid sample is crushed and placed in a box furnace. The box furnace is set to heat up to 1000°C at a heating rate of 5°C / min. After keeping the temperature for 3 hours, the solid sample is taken out to obtain a long afterglow material. In this embodiment, the chemical expression of the long afterglow material is Sr 0.993 Ga 1.96 Si 1.999 O8: 0.007Eu 2+ , 0.04Mn 2+ , 0.001V 5+ . Denoted as SGSO:Eu,Mn,V.

[0030] Use a xenon lamp with a wavelength of 365nm (365nm xenon lamp excitation is the closest simulation of normal sunlight excitation. Usually, 365nm xenon lamp can excite, which means that sunlight can also excite) to excite the long afterglow material. After 1 minute of excitation, the afterglow spectrum of the long afterglow material is obtained as shown below: Figure 1 shown.

[0031] The XRD pattern of the long afterglow material is obtained by X-ray diffraction experiment. Figure 2 shown.

[0032] Example 2

[0033] This embodiment prepares the long afterglow material by the following method:

[0034] (1) Weigh 19.985 mmol of SrCO3, 19.985 mmol of Ga2O3, 19.999 mmol of SiO2, 0.015 mmol of Eu2O3, 0.03 mmol of MnO2, and 0.001 mmol of Ta2O5, mix the above raw materials evenly, transfer them to a corundum crucible, add 0.045 mmol of SnO to the corundum crucible, and then put the corundum crucible into a high-temperature muffle furnace at 1400°C to melt the raw materials. After 3 hours, take out the corundum crucible and cool the molten material to obtain a solid sample.

[0035] (2) The solid sample was crushed and placed in a box furnace. The box furnace was set to heat up to 1400°C at a heating rate of 5°C / min. After keeping the temperature for 1 hour, the solid sample was taken out to obtain a long afterglow material. The chemical expression of the long afterglow material is Sr 0.993 Ga 1.96 Si 1.999 O8: 0.007Eu 2+ , 0.04Mn 2+ , 0.001Ta 5+ .

[0036] The long afterglow material prepared in this embodiment has similar performance to that of embodiment 1.

[0037] Example 3

[0038] This embodiment prepares the long afterglow material by the following method:

[0039] (1) 19.985 mmol of SrCO3, 19.985 mmol of Ga2O3, 19.999 mmol of SiO2, 0.015 mmol of Eu2O3, 0.03 mmol of MnO2, and 0.001 mmol of Nb2O5 were mixed evenly and transferred to a corundum crucible. 0.045 mmol of SnO was added to the corundum crucible. The corundum crucible was then placed in a high-temperature muffle furnace at 1700°C to melt the raw materials. After 1 hour, the corundum crucible was taken out and the molten material was cooled to obtain a solid sample.

[0040] (2) The solid sample is crushed and placed in a box furnace. The box furnace is set to heat up to 500°C at a heating rate of 5°C / min. After keeping the temperature for 5 hours, the solid sample is taken out to obtain a long afterglow material. In this embodiment, the chemical expression of the long afterglow material is Sr 0.993 Ga 1.96 Si 1.999 O8: 0.007Eu 2+ , 0.04Mn 2+ , 0.001Nb 5+ .

[0041] The long afterglow material prepared in this embodiment has similar performance to that of embodiment 1.

[0042] pass Figure 1 It can be seen that in Example 1, Eu 2+ , Mn 2+ , TM was successfully doped with Sr 1-x Ga 2-y Si 2-z O8 structure, and Sr 1-x Ga 2-y Si 2-zThe O8 structure basically maintains the original structure, and the material structure stability is good.

[0043] pass Figure 2 It can be seen that the long afterglow material prepared in Example 1 of the present invention has a yellow afterglow in the range of 400-700nm under the excitation of a 365nm xenon lamp.

[0044] pass Figure 3 It can be seen that the long afterglow material prepared in Example 1 can still keep luminescence after 40000s, and has a relatively long afterglow time.

[0045] In summary, the material of the present invention can be excited by sunlight to emit yellow light of 400 to 700 nm, and at the same time, can maintain a longer and higher intensity afterglow. In addition, the present invention avoids the structural collapse caused by concentrated substitution by dispersing different ion substitution sites, thereby making the material structure more stable.

[0046] Finally, it should be noted that the above preferred embodiments are only used to illustrate the technical solutions of the present invention rather than to limit it. Although the present invention has been described in detail through the above preferred embodiments, those skilled in the art should understand that various changes can be made in form and details without departing from the scope defined by the claims of the present invention.

Claims

1. A sunlight-activated yellow long afterglow material, characterized in that: The chemical expression of the material is: Sr 1- x Ga 2-y Si 2-z O8:xEu 2+ ,yMn 2+ , zTM, where x is Eu 2+ The amount of doped substance, 0<x≤0.1, y is Mn 2+ The amount of the doped substance is 0<y≤0.2, z is the amount of the TM doped substance, 0<z≤0.1, and the TM is a transition metal ion, and TM includes one or more of V, Nb, Ta, Mo, and W ions.

2. The method for preparing a sunlight-activated yellow long afterglow material according to claim 1, characterized in that: The preparation method comprises the following steps: (1) SrCO3, Ga2O3, SiO2, Eu2O3, a manganese source, and a transition metal oxide are uniformly mixed according to a stoichiometric ratio, a reducing agent is added to the mixture, the mixture after the reducing agent is added is heated and melted, and then cooled to obtain a solid sample; (2) The solid sample obtained in step (1) is crushed and then calcined to obtain a sunlight-activatable yellow long afterglow material.

3. The preparation method according to claim 2, characterized in that: The manganese source includes one or more of MnO2, MnCO3, and MnO.

4. The preparation method according to claim 2, characterized in that: The reducing agent includes one of N4Si3, SnO and Al, and the amount of the reducing agent added is the sum of the amounts of europium oxide and manganese source substances.

5. The preparation method according to claim 2, characterized in that: In the step (1), the melting temperature is 1400-1700° C. and the holding time is 0.5-3 h.

6. The preparation method according to claim 2, characterized in that: In the step (2), the calcination temperature is 500 to 1400° C., and the insulation time is 1 to 5 hours.

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