Yellow fluorescent powder with high temperature sensing sensitivity and preparation method thereof

Abstract

The application relates to a bismuth ion doped gallium germanate yellow fluorescent powder with high temperature sensing sensitivity and a preparation method thereof. 14 xBi 3+ , 0.0025<=x<=0.08; the material has yellow light emission under 334nm excitation, the emission broadband is located in the range of 400-700nm, the peak value is located at 527nm, the emission intensity changes fast with the change of temperature, and the application has high temperature sensing sensitivity of 4.155%K ‑1 . The preparation method has the advantages of simplicity, safety, greenness and low cost.

Description

Technical Field

[0001] This invention relates to the field of inorganic luminescent materials technology, and in particular to a bismuth ion-doped gallium germanate-based yellow phosphor with high temperature sensing sensitivity and its preparation method. Background Technology

[0002] Temperature, as a fundamental parameter, plays a crucial role in various fields, from industry to science. Temperature measurement accuracy is one of the most frequently measured physical quantities in industrial production activities, making it paramount. However, for many physical conditions and applications, precise temperature knowledge is difficult to obtain. Temperature measurement relies on consistent physical phenomena at the molecular level to reflect changes in heat content on a larger scale. In recent years, non-contact temperature sensing technologies have been continuously developed. Among these, luminescence-based measurement methods have received widespread attention. Generally, all temperature-related luminescence properties, such as excitation spectra, emission spectra, decay lifetime, and emission rise time, can be used to detect temperature by utilizing their variations with temperature. However, luminescence can penetrate media, enabling real-time and remote operation, making luminescence-based measurements more competitive. Therefore, developing luminescent thermometric materials with higher temperature sensitivity is a very promising direction.

[0003] Compared to the sharp peaks of rare earth ions in optical thermometry, Bi 3+ It has the advantages of abundant reserves, low price, non-toxicity, and high stability. 3+ The outermost electrons of ions are highly sensitive to the local lattice composition and crystal structure, and are easily affected by the environment, resulting in significant thermal quenching, making them suitable for temperature sensing. Their broadband emission offers advantages such as better resistance to peak shifting and lower requirements for measuring instruments. Their broadband absorption spectrum allows for a wider selection of excitation wavelengths, thereby reducing the requirements for lasers and lowering costs.

[0004] Therefore, this patent prepares downconversion luminescent materials through a high-temperature solid-state method. The synthesized luminescent materials are stable and have a high single-peak relative temperature sensitivity, filling the research gap in the field of optical temperature sensing. Summary of the Invention

[0005] The technical problem to be solved by this invention is that large logarithm Bi 3+ The single-peak relative sensitivity of doped luminescent materials is generally below 2.5% K. -1 The present invention provides a yellow phosphor with high temperature sensing sensitivity to enable non-contact optical temperature measurement applications.

[0006] The present invention solves the above problems by adopting the following solution:

[0007] A novel yellow phosphor with high temperature sensing sensitivity, wherein the general chemical formula of the yellow phosphor is Ba3SbGa3Ge2O14 :xBi 3+ , 0.0025≤x≤0.08;

[0008] The main phase of the novel yellow phosphor with high temperature sensing sensitivity is a feldspar structure with space group P321; the excitation spectrum of the phosphor is a broadband spectrum in the range of 250-400 nm, the emission spectrum is a broadband spectrum in the range of 400-700 nm, and the strongest emission peak is at 527 nm.

[0009] The preparation method of the phosphor includes the following steps:

[0010] (1) Weighing: Weigh the raw materials containing Ba, Sb, Ge, Ga, O and Bi elements according to their chemical composition. The stoichiometric ratio is 3:1:3:2:x, where 0.0025≤x≤0.08;

[0011] (2) Grinding: Grind for 30 minutes to mix evenly, then put into a reaction vessel;

[0012] (3) Sintering: Sintering is carried out in an air atmosphere, then cooled to room temperature, and then ground to obtain the target product, a new type of yellow phosphor with high temperature sensing sensitivity.

[0013] The above-mentioned method for preparing a novel yellow phosphor with high temperature sensing sensitivity is described in which the novel yellow phosphor is prepared by sintering a mixture of Ba-containing compounds, Sb-containing compounds, Ge-containing compounds, Ga-containing compounds and Bi-containing compounds.

[0014] The method for preparing the novel yellow phosphor with high temperature sensing sensitivity described above, wherein the Ba-containing compound is one or more of Ba oxides, carbonates, oxalates, acetates, nitrates, and hydroxides.

[0015] The above-mentioned method for preparing a novel yellow phosphor with high temperature sensing sensitivity, wherein the Sb-containing compound is one or more of the following: Sb oxide, carbonate, oxalate, acetate, nitrate, and hydroxide.

[0016] The method for preparing the novel yellow phosphor with high temperature sensing sensitivity described above, wherein the Ge-containing compound is one or more of the following: Ge oxide, carbonate, oxalate, acetate, nitrate, and hydroxide.

[0017] The method for preparing the novel yellow phosphor with high temperature sensing sensitivity described above, wherein the Ga-containing compound is one or more of Ga oxides, carbonates, oxalates, acetates, nitrates, and hydroxides.

[0018] The above-mentioned method for preparing a novel yellow phosphor with high temperature sensing sensitivity, wherein the Bi-containing compound is one or more of Bi oxides, carbonates, oxalates, acetates, nitrates, and hydroxides.

[0019] The above-mentioned method for preparing a novel yellow phosphor with high temperature sensing sensitivity, wherein the Ba-containing compound is BaCO3, the Sb-containing compound is Sb2O3, the Ga-containing compound is Ga2O3, the Ge-containing compound is GeO2, and the Bi-containing compound is Bi2O3.

[0020] The above-mentioned method for producing a novel yellow phosphor with high temperature sensing sensitivity involves a temperature of 1350 degrees Celsius and a sintering time of approximately 6 hours.

[0021] The advantages of this technology are:

[0022] 1. The present invention relates to a novel yellow phosphor with high temperature sensing sensitivity, which is prepared by a high-temperature solid-state method. The preparation process is simple, has low equipment requirements, does not have specific pressure or atmosphere requirements during synthesis, and is easy to prepare with low energy consumption.

[0023] 2. The novel yellow phosphor of this invention with high temperature sensing sensitivity has high phase purity, and its phase structure does not change when placed in air, exhibiting good stability.

[0024] 3. The novel yellow phosphor with high temperature sensing sensitivity of the present invention uses a low-cost bismuth ion compound as the activator source, which is environmentally friendly and reduces costs, and can be used in the field of non-contact optical temperature measurement.

[0025] 4. The novel yellow phosphor of this invention, exhibiting high temperature sensing sensitivity, achieves broadband emission in the wavelength range of 400-700 nm after ultraviolet excitation, with an emission peak at approximately 527 nm, displaying yellow emission. It exhibits relatively high sensitivity, at 4.155% K. -1 . Attached Figure Description

[0026] Figure 1 The novel yellow phosphor Ba3SbGa3Ge2O with high temperature sensing sensitivity prepared in Example 4 14 0.04Bi 3+ and Ba3SbGa3Ge2O 14 X-ray diffraction (XRD) pattern of a standard card;

[0027] Figure 2 The novel yellow phosphor Ba3SbGa3Ge2O with high temperature sensing sensitivity prepared in Examples 1-5 14 :xBi 3+ The emission spectrum of which is 0.0025≤x≤0.08;

[0028] Figure 3 For Experiment 4, a novel yellow phosphor, Ba3SbGa3Ge2O, with high temperature sensing sensitivity was prepared. 14 0.04Bi 3+ Excitation and emission spectra;

[0029] Figure 4 For Experiment 4, a novel yellow phosphor, Ba3SbGa3Ge2O, with high temperature sensing sensitivity was prepared. 14 0.04Bi 3+ Variable temperature emission spectrum;

[0030] Figure 5 For Experiment 4, a novel yellow phosphor, Ba3SbGa3Ge2O, with high temperature sensing sensitivity was prepared. 14 0.04Bi 3+ Relative sensitivity plot in the temperature range of 303–423 K;

[0031] Figure 6 Example 4: Preparation of a novel yellow phosphor Ba3SbGa3Ge2O with high temperature sensing sensitivity 14 0.04Bi 3+ Photographs excited by 365nm ultraviolet light; Detailed Implementation

[0032] The embodiments of the present invention are described in detail below. These embodiments are implemented based on the technical solution of the present invention, and provide detailed implementation methods and specific operation processes. However, the scope of protection of the present invention is not limited to the following embodiments.

[0033] BaCO3, Sb2O3, Ga2O3, GeO2, and Bi2O3 were selected as starting compound raw materials. According to the molar ratio of each element, the four compound raw materials were weighed to prepare the corresponding materials.

[0034] Example 1

[0035] This embodiment 1 presents a novel yellow phosphor with high temperature sensing sensitivity, made from Bi... 3+ It is obtained by doping gallium germanate, with the chemical formula: Ba3SbGa3Ge2O 14 0.0025Bi 3+ The preparation method is as follows:

[0036] Using high-purity BaCO3 (analytical grade), Sb2O3 (99.99% purity), Ga2O3 (99.99% purity), GeO2 (99.99% purity), and Bi2O3 (99.99% purity) as starting materials, and in a molar ratio of Ba:Sb:Ga:Ge:Bi = 3:1:3:2:0.0025, the mass of each oxide or carbonate was accurately weighed. The weighed raw materials were mixed and ground in an agate mortar for 0.5 h to obtain a mixture. The crucible containing the mixture was placed in a high-temperature muffle furnace and sintered at 1350℃ for 6 h. After cooling to room temperature with the furnace, the mixture was ground to obtain a bismuth ion-doped high-temperature sensitive yellow phosphor material.

[0037] Example 2

[0038] This embodiment 2 presents a novel yellow phosphor with high temperature sensing sensitivity, made from Bi... 3+ It is obtained by doping gallium germanate, with the chemical formula: Ba3SbGa3Ge2O 14 0.0075Bi 3+ The preparation method is as follows:

[0039] Using high-purity BaCO3 (analytical grade), Sb2O3 (99.99% purity), Ga2O3 (99.99% purity), GeO2 (99.99% purity), and Bi2O3 (99.99% purity) as starting materials, and in a molar ratio of Ba:Sb:Ga:Ge:Bi = 3:1:3:2:0.0075, the mass of each oxide or carbonate was accurately weighed. The weighed raw materials were mixed and ground in an agate mortar for 0.5 hours to obtain a mixture. The crucible containing the mixture was placed in a high-temperature muffle furnace and sintered at 1350℃ for 6 hours. After cooling to room temperature with the furnace, the mixture was ground to obtain a bismuth ion-doped high-temperature sensitive yellow phosphor material.

[0040] Example 3

[0041] This embodiment 3 presents a novel yellow phosphor with high temperature sensing sensitivity, made from Bi... 3+ It is obtained by doping gallium germanate, with the chemical formula: Ba3SbGa3Ge2O 14 0.01Bi 3+ The preparation method is as follows:

[0042] Using high-purity BaCO3 (analytical grade), Sb2O3 (99.99% purity), Ga2O3 (99.99% purity), GeO2 (99.99% purity), and Bi2O3 (99.99% purity) as starting materials, and according to the molar ratio of Ba:Sb:Ga:Ge:Bi = 3:1:3:2:0.01, the mass of each oxide or carbonate was accurately weighed. The weighed raw materials were mixed and ground in an agate mortar for 0.5 hours to obtain a mixture. The crucible containing the mixture was placed in a high-temperature muffle furnace and sintered at 1350℃ for 6 hours. After cooling to room temperature with the furnace, it was ground to obtain a novel yellow phosphor with high temperature sensing sensitivity.

[0043] Example 4

[0044] This embodiment 4 presents a novel yellow phosphor with high temperature sensing sensitivity, made from Bi... 3+ It is obtained by doping gallium germanate, with the chemical formula: Ba3SbGa3Ge2O 14 0.04Bi 3+ The preparation method is as follows:

[0045] Using high-purity BaCO3 (analytical grade), Sb2O3 (99.99% purity), Ga2O3 (99.99% purity), GeO2 (99.99% purity), and Bi2O3 (99.99% purity) as starting materials, and in a molar ratio of Ba:Sb:Ga:Ge:Bi = 3:1:3:2:0.04, the mass of each oxide or carbonate was accurately weighed. The weighed raw materials were mixed and ground in an agate mortar for 0.5 hours to obtain a mixture. The crucible containing the mixture was placed in a high-temperature muffle furnace and sintered at 1350℃ for 6 hours. After cooling to room temperature with the furnace, it was ground to obtain a novel yellow phosphor with high temperature sensing sensitivity.

[0046] Example 5

[0047] This embodiment 5 presents a novel yellow phosphor with high temperature sensing sensitivity, made from Bi... 3+ It is obtained by doping gallium germanate, with the chemical formula: Ba3SbGa3Ge2O 14 0.06Bi 3+ The preparation method is as follows:

[0048] Using high-purity BaCO3 (analytical grade), Sb2O3 (99.99% purity), Ga2O3 (99.99% purity), GeO2 (99.99% purity), and Bi2O3 (99.99% purity) as starting materials, and in a molar ratio of Ba:Sb:Ga:Ge:Bi = 3:1:3:2:0.06, the mass of each oxide or carbonate was accurately weighed. The weighed raw materials were mixed and ground in an agate mortar for 0.5 hours to obtain a mixture. The crucible containing the mixture was placed in a high-temperature muffle furnace and sintered at 1350℃ for 6 hours. After cooling to room temperature with the furnace, it was ground to obtain a novel yellow phosphor with high temperature sensing sensitivity.

[0049] Example 6

[0050] This embodiment 6 presents a novel yellow phosphor with high temperature sensing sensitivity, made from Bi... 3+ It is obtained by doping gallium germanate, with the chemical formula: Ba3SbGa3Ge2O 14 0.08Bi 3+ The preparation method is as follows:

[0051] Using high-purity BaCO3 (analytical grade), Sb2O3 (99.99% purity), Ga2O3 (99.99% purity), GeO2 (99.99% purity), and Bi2O3 (99.99% purity) as starting materials, and in a molar ratio of Ba:Sb:Ga:Ge:Bi = 3:1:3:2:0.08, the mass of each oxide or carbonate was accurately weighed. The weighed raw materials were mixed and ground in an agate mortar for 0.5 hours to obtain a mixture. The crucible containing the mixture was placed in a high-temperature muffle furnace and sintered at 1350℃ for 6 hours. After cooling to room temperature with the furnace, it was ground to obtain a bismuth ion-doped high-temperature sensitive yellow phosphor.

[0052] like Figure 1 The image shows a novel yellow phosphor, Ba3SbGa3Ge2O, with high temperature sensing sensitivity, from Experiment Example 4. 14 0.04Bi 3+ and Ba3SbGa3Ge2O 14 The X-ray diffraction (XRD) pattern of the standard card (PDF#00-051-0141) indicates that the prepared phosphor is pure, free of impurities, and meets the requirements.

[0053] like Figure 2 The image shows a novel yellow phosphor, Ba3SbGa3Ge2O, with high temperature sensing sensitivity, as shown in Experiment Examples 1-6. 14 :xBi 3 + The emission spectrum of 0.0025≤x≤0.08 shows that the emission intensity first increases and then decreases as the value of x changes, with the optimal doping concentration being x=0.04.

[0054] like Figure 3 The image shows a novel yellow phosphor, Ba3SbGa3Ge2O, with high temperature sensing sensitivity, from Experiment Example 4. 14 0.04Bi 3+ The excitation and emission spectra of the luminescent material are as follows: the excitation range is 250–400 nm, and the emission spectrum is a broadband yellow emission of 400–700 nm with a peak at 527 nm.

[0055] like Figure 4 The image shows the novel yellow phosphor Ba3SbGa3Ge2O with high temperature sensing sensitivity at different temperatures in Experiment Example 4. 14 0.04Bi 3+ The emission spectrum of the [organism] shows that the emission intensity is almost zero at a temperature of 423 K.

[0056] like Figure 5 The image shows the novel yellow phosphor Ba3SbGa3Ge2O with high temperature sensing sensitivity prepared in Example 4 of this paper. 14 0.04Bi 3+ The relative sensitivity plot in the temperature range of 303–423 K was first obtained using the Arrhenius formula. Calculate the activation energy, and then use the sensitivity formula. The sensitivity was calculated, and its relative sensitivity is as high as 4.155% K. -1 .

[0057] like Figure 6 As shown, after excitation with 365nm light, a novel yellow phosphor Ba3SbGa3Ge2O with high temperature sensing sensitivity was prepared in Example 4. 14 0.04Bi 3+ It produced a yellow glow.

Claims

1. The application of a yellow phosphor with high temperature sensing sensitivity in the field of non-contact optical temperature measurement, characterized in that, The chemical composition formula of the phosphor is Ba3SbGa3Ge2O 14 :xBi 3+ , 0.0025≤x≤0.08; the phosphor can be effectively excited by light in the range of 250 to 400 nm, the emission spectrum is a broadband range of 400 to 700 nm, and the strongest emission peak is 527 nm.

2. The application according to claim 1, characterized in that, The phosphor preparation method includes the following steps: (1) Weighing: Weigh the raw materials containing Ba, Sb, Ga, Ge and Bi elements according to their chemical composition, with a stoichiometric ratio of 3:1:3:2:x; (2) Grinding: Grind for 30 minutes to mix evenly, then put into a reaction vessel; (3) Sintering: Sintering is carried out in an air atmosphere, then cooled to room temperature, and then ground to obtain the phosphor.

3. The application according to claim 2, characterized in that, The phosphor is formed by sintering a mixture of Ba-containing compounds, Sb-containing compounds, Ga-containing compounds, Ge-containing compounds, and Bi-containing compounds. The Ba-containing compound is one or more of the following: Ba oxides, carbonates, oxalates, acetates, nitrates, and hydroxides; The Sb-containing compound is one or more of the following: oxides, carbonates, oxalates, acetates, nitrates, and hydroxides of Sb. The Ga-containing compound is one or more of the following: Ga oxides, carbonates, oxalates, acetates, nitrates, and hydroxides; The Ge-containing compound is one or more of the following: oxides, carbonates, oxalates, acetates, nitrates, and hydroxides of Ge; The Bi-containing compound is one or more of the following: Bi oxides, carbonates, oxalates, acetates, nitrates, and hydroxides.

4. The application according to claim 2, characterized in that, Sinter at 1350℃ for 6 hours.

5. The application according to claim 1, characterized in that, The phosphor emits yellow light with a peak wavelength of 527 nm under ultraviolet light irradiation, and has a temperature sensitivity as high as 4.155% K. -1 .

Images