Gallate-based luminescent material as well as preparation method and application thereof
The preparation of the gallate-based luminescent material LiGa1-xO2:xMo6+ is solved by the high-temperature sintering method of the existing green long afterglow material, and the problems of harsh preparation conditions and limited afterglow duration are achieved, and the efficient band of 510-530nm required for neonatal jaundice treatment is achieved. The emission and ultra-long afterglow effects meet the light source needs of neonatal jaundice phototherapy instruments.
Patent Information
- Application Number
- CN202411343546.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-09-25
- Publication Date
- 2025-01-03
AI Technical Summary
The existing green long afterglow materials on the market are harsh in preparation conditions and limited afterglow duration, which cannot meet the requirements of efficient emission and ultra-long afterglow for 510-530nm band required for neonatal jaundice treatment.
The gallate-based luminescent material LiGa1-xO2:xMo6+ is used, with LiGaO2 as the matrix and Mo6+ as doped ions, and is prepared in an air atmosphere by high-temperature sintering method, so that the peak emission band is located at 528nm and has an ultra-long afterglow duration.
The material exhibits excellent afterglow brightness and duration under 372nm ultraviolet excitation, with the optimal afterglow duration up to 65 hours, meeting the wavelength index requirements of neonatal jaundice phototherapy instruments, reducing additional power requirements, and achieving portability and energy-saving effects.
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Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of luminescent materials, and in particular to a gallate-based luminescent material and a preparation method and application thereof. Background Art
[0002] Jaundice is a common symptom of newborns, also known as hyperbilirubinemia. Phototherapy can convert bilirubin into water-soluble isomers and dipyrrole compounds, thereby accelerating bilirubin excretion. It has low side effects and the treatment process is painless and non-invasive. It is a commonly used, safe and efficient treatment method and is currently widely used in clinical practice. Literature shows that green light is effective, safe and has few adverse reactions to the treatment of neonatal jaundice. Among them, the effective green light wavelength is 510-530nm [Shanghai Journal of Preventive Medicine, 2010, 22(04)]. At the same time, the therapeutic effect of combined blue-green light irradiation is better than continuous blue light irradiation alone, and can effectively avoid various adverse reactions such as diarrhea and rash in children [Hebei Medicine, 2013, 35(10)]. Therefore, exploring high-performance green light emitting luminescent materials has clinical effects and practical significance, and can provide help for clinical treatment.
[0003] At present, LED light sources are widely used in phototherapy for neonatal jaundice due to their high efficiency, energy saving and long life. However, confining newborns in the light box for a long time may cause inconvenience to family members and caregivers, especially when they need to move or take care of multiple babies. Therefore, the development of a portable and power-free phototherapy device has a certain market prospect, which requires the use of long-afterglow materials that can emit green light. Currently, most of the green long-afterglow materials on the market are lanthanide ion-activated luminescent materials, such as SrAl2O4:Eu 2+ ,Dy 3+ Since lanthanide ions are easy to change valence, they usually need to be synthesized in a reducing atmosphere, the preparation conditions are relatively harsh, and the afterglow duration is limited. Therefore, it is particularly important to find a luminescent material with ultra-long afterglow, simple preparation process, and efficient emission in the band around 510-530nm. Summary of the invention
[0004] The main purpose of the present invention is to provide a gallate-based luminescent material with a simple preparation process, an emission band that highly overlaps with the band required for treating neonatal jaundice, and an ultra-long afterglow effect, as well as a preparation method and application thereof.
[0005] To achieve the above object, the present invention provides a gallate-based luminescent material, the chemical formula of which is LiGa 1-x O2:xMo 6+ , where x = 0.005~0.045.
[0006] Furthermore, the material is based on LiGaO2 and Mo6+ The ions are doping ions.
[0007] The present invention also provides an application of the gallate-based luminescent material in preparing a neonatal jaundice phototherapy device. In this application, the gallate-based luminescent material is used to prepare a light source of the neonatal jaundice phototherapy device, such as an LED lamp.
[0008] The present invention also provides a method for preparing the above-mentioned gallate-based luminescent material, comprising the following steps:
[0009] (1) weighing a lithium source, a gallium source and a molybdenum source, mixing them and grinding them evenly to obtain a mixed powder;
[0010] (2) The mixed powder is subjected to high-temperature sintering treatment, cooled to room temperature, and then ground evenly to obtain the gallate-based luminescent material.
[0011] Furthermore, in step (1), the lithium source is any one of lithium-containing carbonates, oxides, oxalates, and acetates, or a mixture of two or more of them in any proportion.
[0012] Furthermore, in step (1), the gallium source is any one of gallium-containing carbonates, oxides, oxalates, acetates, or a mixture of two or more thereof in any proportion.
[0013] Furthermore, in step (1), the molybdenum source is any one of molybdenum-containing carbonates, oxides, oxalates, and acetates, or a mixture of two or more of them in any proportion.
[0014] Furthermore, in step (2), the high temperature sintering treatment is carried out in an air atmosphere at a temperature of 1200 to 1300° C. for a time of 4 to 6 hours.
[0015] The beneficial effects of the present invention are embodied in:
[0016] (1) The gallate-based green luminescent material of the present invention uses LiGaO2 as the matrix, Mo 6+ To dope ions, the material produces a broad-peak emission with a peak value at around 528nm under ultraviolet excitation at around 372nm. This emission band highly overlaps with the band required for the treatment of neonatal jaundice, and can meet the wavelength index requirements of the corresponding light source of the neonatal jaundice phototherapy device.
[0017] (2) After being fully excited by a 365nm ultraviolet lamp, the gallate-based luminescent material of the present invention exhibits excellent afterglow brightness and duration, with the best afterglow duration lasting up to 65 hours. The luminescent material can still emit bright green light after the excitation stops, reducing the need for additional power. A strong portable phototherapy light source can be achieved, with significant energy-saving effects.
[0018] (3) The gallate-based luminescent material of the present invention is composed of transition metal ions Mo6+ As sensitizing ions, efficient emission is achieved, and the cost is lower than that of rare earth elements as luminescent centers. The luminescent material of the present invention is prepared by a high-temperature solid phase method, can be synthesized in an air atmosphere, has a simple process, and has low requirements on production equipment. BRIEF DESCRIPTION OF THE DRAWINGS
[0019] Figure 1 XRD patterns of the gallate-based luminescent materials and LiGaO2 standard cards prepared in Examples 1 to 5 of the present invention;
[0020] Figure 2 The afterglow decay curve diagram of the gallate-based luminescent materials prepared in Examples 1 to 5 of the present invention;
[0021] Figure 3 Excitation and emission spectra of the gallate-based luminescent materials prepared in Examples 1 to 5;
[0022] Figure 4 XRD patterns of the luminescent materials and LiGaO2 standard cards prepared in Comparative Examples 1 to 5 of the present invention;
[0023] Figure 5 These are the excitation and emission spectra of the luminescent materials prepared in Comparative Examples 1 to 5 of the present invention. DETAILED DESCRIPTION
[0024] In order to make the technical scheme of the present invention more clearly understood by those skilled in the art, the following embodiments are listed for illustration. It should be pointed out that the following embodiments do not limit the protection scope of the present invention.
[0025] Unless otherwise specified, the raw materials, reagents or devices used in the following examples can be obtained from conventional commercial sources or by existing known methods.
[0026] Example 1
[0027] Preparation of Gallate-based Luminescent Materials
[0028] The chemical formula of the gallate-based luminescent material prepared in this embodiment is: LiGa 0995 O2:0.005Mo 6+ , the specific preparation process is as follows:
[0029] Li2CO3, Ga2O3, and MoO3 raw materials were weighed according to a molar ratio of 1.15:0.995:0.005 (Li2CO3 was weighed in excess of 15% to suppress the formation of impurity LiGa5O8, the same below), the above raw materials were placed in an agate mortar, and an appropriate amount of ethanol was added (the amount of ethanol added was sufficient to wet the raw materials, the same below), and ground for 30 minutes to obtain a mixed powder. The mixed powder was transferred to an alumina crucible, heated to 1250°C in a muffle furnace under air atmosphere, and sintered at high temperature for 5 hours. After the product was naturally cooled to room temperature, it was ground into powder to obtain LiGa 0.995 O2:0.005Mo 6+ Luminous materials.
[0030] Depend on Figure 1 The XRD patterns shown show that the LiGa prepared in this example 0.995 O2:0.005Mo 6+ The luminescent material has a good fit with the standard card, with almost no impurity peaks, and a small amount of low-intensity impurity peaks belonging to LiGa5O8.
[0031] Depend on Figure 2 The afterglow decay curve shows that the afterglow brightness of the luminescent material prepared in this embodiment is 1.67 mcd / m after one minute. 2 The lowest brightness that can be recognized by human eye perception cells is 0.32mcd / m 2 The afterglow intensity of the luminescent material is maintained at 0.32mcd / m 2 The duration of the above is 20 hours and 25 minutes.
[0032] Example 2
[0033] Preparation of Gallate-based Luminescent Materials
[0034] The chemical formula of the gallate-based luminescent material prepared in this embodiment is: LiGa 0.985 O2:0.015Mo 6+ , the specific preparation process is as follows:
[0035] Li2CO3, Ga2O3, and MoO3 raw materials were weighed in a molar ratio of 1.15:0.985:0.015, and the raw materials were placed in an agate mortar, and an appropriate amount of ethanol was added and ground for 30 minutes to obtain a mixed powder. The mixed powder was transferred to an alumina crucible, and heated to 1200°C at a heating rate of 5°C / min in a muffle furnace under air atmosphere, and sintered at high temperature for 6 hours. After the product was naturally cooled to room temperature, it was ground into powder to obtain LiGa 0.985 O2:0.015Mo 6+ Luminous materials.
[0036] Depend on Figure 1The XRD patterns shown show that the LiGa prepared in this example 0.985 O2:0.015Mo 6+ The luminescent material has a good fit with the standard card, with almost no impurity peaks, and a small amount of low-intensity impurity peaks belonging to LiGa5O8.
[0037] Depend on Figure 2 The afterglow decay curve shows that the afterglow brightness of the luminescent material prepared in this embodiment is 2.36 mcd / m after one minute. 2 The lowest brightness that can be recognized by human eye perception cells is 0.32mcd / m 2 The afterglow intensity of the luminescent material is maintained at 0.32mcd / m 2 The duration of the above is 20 hours and 50 minutes.
[0038] Example 3
[0039] Preparation of Gallate-based Luminescent Materials
[0040] The chemical formula of the gallate-based luminescent material prepared in this embodiment is: LiGa 0.975 O2:0.025Mo 6+ , the specific preparation process is as follows:
[0041] Li2CO3, Ga2O3, and MoO3 raw materials were weighed in a molar ratio of 1.15:0.975:0.025, and the raw materials were placed in an agate mortar, and an appropriate amount of ethanol was added and ground for 30 minutes to obtain a mixed powder. The mixed powder was transferred to an alumina crucible, and heated to 1240°C at a heating rate of 5°C / min in a muffle furnace under air atmosphere, and sintered at high temperature for 5.3h. After the product was naturally cooled to room temperature, it was ground into powder to obtain LiGa 0.975 O2:0.025Mo 6+ Luminous materials.
[0042] Depend on Figure 1 The XRD patterns shown show that the LiGa prepared in this example 0.975 O2:0.025Mo 6+ The luminescent material has a good fit with the standard card, with almost no impurity peaks, and a small amount of low-intensity impurity peaks belonging to LiGa5O8.
[0043] Depend on Figure 2 The afterglow decay curve shows that the afterglow brightness of the luminescent material prepared in this embodiment is 3.51 mcd / m after one minute. 2 The lowest brightness that can be recognized by human eye perception cells is 0.32mcd / m 2 The afterglow intensity of the luminescent material is maintained at 0.32mcd / m 2 The duration of the above is 45 hours and 50 minutes.
[0044] Example 4
[0045] Preparation of Gallate-based Luminescent Materials
[0046] The chemical formula of the gallate-based luminescent material prepared in this embodiment is: LiGa 0.965 O2:0.035Mo 6+ , the specific preparation process is as follows:
[0047] Li2CO3, Ga2O3, and MoO3 raw materials were weighed according to a molar ratio of 1.15:0.965:0.035, and the above raw materials were placed in an agate mortar, and an appropriate amount of ethanol was added and ground for 30 minutes to obtain a mixed powder. The mixed powder was transferred to an alumina crucible, and heated to 1280°C at a heating rate of 5°C / min in a muffle furnace under air atmosphere, and sintered at high temperature for 4.5h. After the product was naturally cooled to room temperature, it was ground into powder to obtain LiGa 0.965 O2:0.035Mo 6+ Luminous materials.
[0048] Depend on Figure 1 The XRD patterns shown show that the LiGa prepared in this example 0.965 O2:0.035Mo 6+ The luminescent material has a good fit with the standard card, with almost no impurity peaks, and a small amount of low-intensity impurity peaks belonging to LiGa5O8.
[0049] Depend on Figure 2 The afterglow decay curve shows that the afterglow brightness of the luminescent material prepared in this embodiment is 2.13 mcd / m after 10 seconds. 2 The lowest brightness that can be recognized by human eye perception cells is 0.32mcd / m 2 The afterglow intensity of the luminescent material is maintained at 0.32mcd / m 2 The above duration is 64 hours and 45 minutes.
[0050] Example 5
[0051] Preparation of Gallate-based Luminescent Materials
[0052] The chemical formula of the gallate-based luminescent material prepared in this embodiment is: LiGa 0.955 O2:0.045Mo 6+ , the specific preparation process is as follows:
[0053] Li2CO3, Ga2O3, and MoO3 raw materials were weighed in a molar ratio of 1.15:0.955:0.045, placed in an agate mortar, added with an appropriate amount of ethanol, and ground for thirty minutes to obtain a mixed powder. The mixed powder was transferred to an alumina crucible, heated to 1300°C in a muffle furnace at a heating rate of 5°C / min under air atmosphere, and sintered at high temperature for 4 hours. After the product was naturally cooled to room temperature, it was ground into powder to obtain LiGa 0.955 O2:0.045Mo 6+ Luminous materials.
[0054] Depend on Figure 1 The XRD patterns shown show that the LiGa prepared in this example 0.955 O2:0.045Mo 6+ The luminescent material has a good fit with the standard card, with almost no impurity peaks, and a small amount of low-intensity impurity peaks belonging to LiGa5O8.
[0055] Depend on Figure 2 The afterglow decay curve shows that the afterglow brightness of the luminescent material prepared in this embodiment is 2.27 mcd / m after 10 seconds. 2 The lowest brightness that can be recognized by human eye perception cells is 0.32mcd / m 2 The afterglow intensity of the luminescent material is maintained at 0.32mcd / m 2 The duration of the above is 19 hours.
[0056] Material performance analysis of Examples 1 to 5:
[0057] Figure 1 The XRD patterns of the gallate-based luminescent materials prepared in Examples 1 to 5 are shown. 1- x O2:xMo 6+ The series of luminescent materials correspond well to the LiGaO2 standard card, and a small amount of low-intensity impurity peaks are attributed to LiGa5O8, indicating that the above preparation method can obtain LiGaO2 as the main phase of the material LiGa 1-x O2:xMo 6+ .
[0058] Figure 2 The afterglow decay curves of the gallate-based luminescent materials prepared in Examples 1 to 5 are shown. The test was performed after pre-excitation with a 365nm UV lamp for 15 minutes. It can be seen that LiGa 1-x O2:xMo 6+ The afterglow duration of the series of luminescent materials first increases and then decreases with the increase of Mo doping amount. When x=0.035, the afterglow time is the longest, reaching 64 hours and 45 minutes.
[0059] Figure 3 The excitation and emission spectra of the gallate-based luminescent materials prepared in Examples 1 to 5 are shown. Under the excitation of a 372nm xenon lamp in a spectrometer, LiGa 1-x O2:xMo 6+ The luminescent material produces emission at around 528nm. 6+ When the doping amount is 0.025, the emission intensity of the luminescent material is the maximum.
[0060] Comparative Example 1
[0061] On the basis of Example 1, Li2CO3, Ga2O3 and MoO3 were weighed in a molar ratio of 1.05:0.975:0.025, and the other step conditions were the same to prepare a luminescent material.
[0062] Comparative Example 2
[0063] On the basis of Example 1, Li2CO3, Ga2O3 and MoO3 were weighed in a molar ratio of 1.1:0.975:0.025, and the other step conditions were the same to prepare a luminescent material.
[0064] Comparative Example 3
[0065] On the basis of Example 1, Li2CO3, Ga2O3 and MoO3 were weighed in a molar ratio of 1.15:0.975:0.025, and the other step conditions were the same to prepare a luminescent material.
[0066] Comparative Example 4
[0067] On the basis of Example 1, Li2CO3, Ga2O3 and MoO3 were weighed in a molar ratio of 1.2:0.975:0.025, and the other step conditions were the same to prepare a luminescent material.
[0068] Comparative Example 5
[0069] On the basis of Example 1, Li2CO3, Ga2O3 and MoO3 were weighed in a molar ratio of 1.25:0.975:0.025, and the other step conditions were the same to prepare a luminescent material.
[0070] Material performance analysis of Comparative Examples 1 to 5:
[0071] Depend on Figure 4 From the XRD spectrum shown, it can be seen that under lithium-rich conditions, the LiGaO2 luminescent material prepared in the comparative example has a good fit with the standard card, and the impurity peak is greatly reduced, indicating that the obtained luminescent material is easier to obtain a pure phase as the Li concentration increases.
[0072] Depend on Figure 5It can be seen from the displayed excitation and emission spectra that under the excitation of a 372nm spectrometer xenon lamp, the luminescence intensity of both Comparative Examples 3 and 4 is relatively strong. Based on the principle of saving raw materials, 15% excess Li2CO3 was finally selected to synthesize a luminescent material that can be used to treat neonatal jaundice.
[0073] Comparative Example 6
[0074] On the basis of Example 1, the doping of MoO3 was omitted, and Li2CO3 and Ga2O3 were weighed in a molar ratio of 1.15:1. The conditions of other steps were the same.
[0075] Analysis of the results of Comparative Example 6: In the absence of Mo doping, the LiGaO2 prepared in Comparative Example 6 does not emit light, and the excitation and emission spectra and afterglow curve cannot be obtained, indicating that the luminescence performance of the luminescent material is mainly affected by Mo ion doping.
[0076] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims
1. A gallate-based luminescent material, characterized in that: Its chemical formula is LiGa 1-x O2:xMo 6+ , where x = 0.005~0.
045.
2. The gallate-based light-emitting material according to claim 1, characterized in that: The material is based on LiGaO2 and Mo 6+ The ions are doping ions.
3. Use of the gallate-based luminescent material as described in claim 1 or 2 in the preparation of a neonatal jaundice phototherapy device.
4. The method for preparing a gallate-based luminescent material according to claim 1 or 2, characterized in that: The following steps are involved: (1) weighing a lithium source, a gallium source and a molybdenum source, mixing them and grinding them evenly to obtain a mixed powder; (2) The mixed powder is subjected to high-temperature sintering treatment, cooled to room temperature, and then ground evenly to obtain the gallate-based luminescent material.
5. The method for preparing a gallate-based luminescent material according to claim 4, characterized in that: In step (1), the lithium source is any one of lithium-containing carbonates, oxides, oxalates, and acetates, or a mixture of two or more of them in any proportion.
6. The method for preparing a gallate-based luminescent material according to claim 4, characterized in that: In step (1), the gallium source is any one of gallium-containing carbonates, oxides, oxalates, and acetates, or a mixture of two or more of them in any proportion.
7. The method for preparing a gallate-based luminescent material according to claim 4, characterized in that: In step (1), the molybdenum source is any one of molybdenum-containing carbonates, oxides, oxalates, and acetates, or a mixture of two or more of them in any proportion.
8. The method for preparing a gallate-based luminescent material according to claim 4, characterized in that: In step (2), the high temperature sintering treatment conditions are air atmosphere, temperature 1200-1300° C., and time 4-6 hours.