Novel yellow fluorescent powder with high temperature sensing sensitivity and preparation method thereof

Abstract

The invention relates to bismuth ion doped gallium germanate yellow fluorescent powder with high temperature sensing sensitivity and a preparation method thereof, the yellow fluorescent powder with high temperature sensing sensitivity has a chemical general formula of Ba3SbGa3Ge2O14: xBi < 3 + >, x is more than or equal to 0.0025 and less than or equal to 0.08; the material emits yellow light under excitation of 334 nm, the emission broadband is within the range of 400-700 nm, the peak value is 527 nm, the emission intensity changes rapidly along with temperature changes, and the material has high temperature sensing sensitivity of 4.155% K <-1 >. The preparation method has the advantages of simplicity, safety, greenness, low cost and the like.

Description

Technical Field

[0001] The present invention relates to the technical field of inorganic luminescent materials, in particular to a bismuth ion-doped gallium germanate-based yellow phosphor with high temperature sensing sensitivity and a preparation method thereof. Background Art

[0002] As a basic parameter, temperature plays an important role in various fields from industry to science. Temperature measurement accuracy is one of the most measured physical quantities in industrial production activities, so its accuracy is crucial. However, for many physical conditions and applications, it is difficult to obtain clear knowledge of temperature. 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 technology has been continuously developed. Among them, luminescence-based measurement methods have received widespread attention. In general, all temperature-related luminescence properties such as excitation spectrum, emission spectrum, decay lifetime, and emission rise time can be used to detect temperature by their changes with temperature. However, luminescence can penetrate the medium, realize real-time and remote operation, and make luminescence-based measurements more competitive, so the development of luminescent temperature measurement materials with higher temperature sensitivity is a very popular direction.

[0003] Compared with 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 composition and crystal structure of the local lattice and are easily affected by the environment, resulting in significant thermal quenching, which makes them suitable for temperature sensing. Their broadband emission has the advantages of better resistance to peak shift and lower requirements for measuring instruments, and their broadband absorption spectrum allows for a wider selection of excitation wavelengths, thereby reducing requirements for lasers and reducing costs.

[0004] Therefore, this patent prepares down-conversion luminescent materials through a high-temperature solid-phase method. The synthesized luminescent materials are stable and have 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 the present invention is that the large logarithm Bi 3+ The single peak relative sensitivity value of the doped luminescent material is generally less than 2.5% K -1 The present invention provides a yellow phosphor with high temperature sensing sensitivity to realize non-contact optical temperature measurement application.

[0006] The present invention adopts the following scheme to solve the above problems:

[0007] A new type of yellow phosphor with high temperature sensing sensitivity, wherein the 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 a P321 space group; the excitation spectrum of the phosphor is a broadband located at 250 to 400 nm, the emission spectrum is a broadband located at 400 to 700 nm, and the strongest emission peak is 527 nm.

[0009] The method for preparing the phosphor comprises the following steps:

[0010] (1) Weighing: Weigh the raw materials containing Ba, Sb, Ge, Ga, O, and Bi elements according to their chemical composition, and 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 and place in a reaction container;

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

[0013] The method for preparing the novel yellow phosphor with high temperature sensing sensitivity is that the novel yellow phosphor is formed by mixing a Ba compound, an Sb compound, a Ge compound, a Ga compound and a Bi compound and then sintering them.

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

[0015] In the method for preparing the novel yellow phosphor with high temperature sensing sensitivity, the Sb-containing compound is a mixture of one or more of Sb oxides, carbonates, oxalates, acetates, nitrates and hydroxides.

[0016] In the method for preparing the novel yellow phosphor with high temperature sensing sensitivity, the Ge-containing compound is a mixture of one or more of Ge oxides, carbonates, oxalates, acetates, nitrates and hydroxides.

[0017] In the method for producing the novel yellow phosphor with high temperature sensing sensitivity, the Ga-containing compound is a mixture of one or more of Ga oxides, carbonates, oxalates, acetates, nitrates and hydroxides.

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

[0019] In the method for preparing the novel yellow phosphor with high temperature sensing sensitivity, 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 method for producing the novel yellow phosphor with high temperature sensing sensitivity has a temperature of 1350 degrees and a sintering time of about 6 hours.

[0021] The advantages of this technology are:

[0022] 1. The novel yellow phosphor with high temperature sensing sensitivity of the present invention is prepared by a high-temperature solid-phase method, which has a simple preparation process, low equipment requirements, no specific pressure and atmosphere requirements during the synthesis process, a simple preparation process, and low energy consumption.

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

[0024] 3. The novel yellow phosphor with high temperature sensing sensitivity of the present invention uses low-priced bismuth ion compounds as the activator source, has no pollution to the environment, reduces the cost, and is used in the field of non-contact optical temperature measurement.

[0025] 4. The novel yellow phosphor with high temperature sensing sensitivity of the present invention realizes broadband emission in the wavelength range of 400-700nm after ultraviolet excitation, and the emission peak is about 527nm, showing yellow emission, with high relative sensitivity of 4.155%K -1 . BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 The new 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 standard card;

[0027] Figure 2 The new yellow phosphor Ba3SbGa3Ge2O with high temperature sensing sensitivity prepared in Example 1-5 14 :xBi 3+ , where 0.0025≤x≤0.08 is the emission spectrum;

[0028] Figure 3 Preparation of a new yellow phosphor Ba3SbGa3Ge2O with high temperature sensing sensitivity for Experimental Example 4 14 :0.04Bi 3+ Excitation and emission spectra;

[0029] Figure 4 Preparation of a new yellow phosphor Ba3SbGa3Ge2O with high temperature sensing sensitivity for Experimental Example 4 14 :0.04Bi 3+ The variable temperature emission spectrum of

[0030] Figure 5 Preparation of a new yellow phosphor Ba3SbGa3Ge2O with high temperature sensing sensitivity for Experimental Example 4 14 :0.04Bi 3+ Relative sensitivity diagram in the temperature range of 303 to 423 K;

[0031] Figure 6 Preparation of a new yellow phosphor Ba3SbGa3Ge2O with high temperature sensing sensitivity for Example 4 14 :0.04Bi 3+ Photographs excited by 365nm UV light; DETAILED DESCRIPTION

[0032] The following is a detailed description of an embodiment of the present invention. This embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation method and a specific operation process are given, but the protection scope of the present invention is not limited to the following embodiment.

[0033] Select BaCO3, Sb2O3, Ga2O3, GeO2, and Bi2O3 as starting compound raw materials, and weigh the four compound raw materials according to the molar ratio of each element to prepare the corresponding materials;

[0034] Example 1

[0035] A new type of yellow phosphor with high temperature sensing sensitivity in this embodiment 1 is composed of 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] High-purity BaCO3 (analytical grade), Sb2O3 (purity 99.99%), Ga2O3 (purity 99.99%), GeO2 (purity 99.99%), and Bi2O3 (purity 99.99%) are used as starting materials, with a molar ratio of Ba:Sb:Ga:Ge:Bi=3:1:3:2:0.0025; the mass of each oxide or carbonate is accurately weighed, and the weighed raw materials are mixed and ground in an agate mortar for 0.5 h to obtain a mixture; a crucible containing the mixture is placed in a high-temperature muffle furnace, sintered at 1350°C for 6 h, and after cooling to room temperature with the furnace, a bismuth ion-doped high-temperature sensitive yellow phosphor material is obtained by grinding.

[0037] Example 2

[0038] A new type of yellow phosphor with high temperature sensing sensitivity in this embodiment 2 is composed of Bi 3+ It is obtained by doping gallium germanate, with the chemical formula: Ba3SbGa3Ge2O 14 :0.0025Bi 3+ , the preparation method is as follows:

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

[0040] Example 3

[0041] A new type of yellow phosphor with high temperature sensing sensitivity in this embodiment 3 is composed of 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] High-purity BaCO3 (analytical grade), Sb2O3 (purity 99.99%), Ga2O3 (purity 99.99%), GeO2 (purity 99.99%), and Bi2O3 (purity 99.99%) are used as starting materials, with a molar ratio of Ba:Sb:Ga:Ge:Bi=3:1:3:2:0.01; the mass of each oxide or carbonate is accurately weighed, and the weighed raw materials are mixed and ground in an agate mortar for 0.5 h to obtain a mixture; a crucible containing the mixture is placed in a high-temperature muffle furnace, sintered at 1350°C for 6 h, and after cooling to room temperature with the furnace, a new type of yellow phosphor with high temperature sensing sensitivity is obtained by grinding.

[0043] Example 4

[0044] A new type of yellow phosphor with high temperature sensing sensitivity in this embodiment 4 is composed of 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] High-purity BaCO3 (analytical grade), Sb2O3 (purity 99.99%), Ga2O3 (purity 99.99%), GeO2 (purity 99.99%), and Bi2O3 (purity 99.99%) are used as starting materials, with a molar ratio of Ba:Sb:Ga:Ge:Bi=3:1:3:2:0.04; the mass of each oxide or carbonate is accurately weighed, and the weighed raw materials are mixed and ground in an agate mortar for 0.5 h to obtain a mixture; a crucible containing the mixture is placed in a high-temperature muffle furnace, sintered at 1350°C for 6 h, and after cooling to room temperature with the furnace, a new type of yellow phosphor with high temperature sensing sensitivity is obtained by grinding.

[0046] Example 5

[0047] A new type of yellow phosphor with high temperature sensing sensitivity in this embodiment 5 is composed of 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] High-purity BaCO3 (analytical grade), Sb2O3 (purity 99.99%), Ga2O3 (purity 99.99%), GeO2 (purity 99.99%), and Bi2O3 (purity 99.99%) are used as starting materials, with a molar ratio of Ba:Sb:Ga:Ge:Bi=3:1:3:2:0.06; the mass of each oxide or carbonate is accurately weighed, and the weighed raw materials are mixed and ground in an agate mortar for 0.5 h to obtain a mixture; a crucible containing the mixture is placed in a high-temperature muffle furnace, sintered at 1350°C for 6 h, and after cooling to room temperature with the furnace, a new type of yellow phosphor with high temperature sensing sensitivity is obtained by grinding.

[0049] Example 6

[0050] A new type of yellow phosphor with high temperature sensing sensitivity in this embodiment 6 is composed of 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] High-purity BaCO3 (analytical grade), Sb2O3 (purity 99.99%), Ga2O3 (purity 99.99%), GeO2 (purity 99.99%), and Bi2O3 (purity 99.99%) are used as starting materials, with a molar ratio of Ba:Sb:Ga:Ge:Bi=3:1:3:2:0.08; the mass of each oxide or carbonate is accurately weighed, and the weighed raw materials are mixed and ground in an agate mortar for 0.5 h to obtain a mixture; a crucible containing the mixture is placed in a high-temperature muffle furnace, sintered at 1350°C for 6 h, and after cooling to room temperature with the furnace, a bismuth ion-doped high-temperature sensitive yellow phosphor is obtained by grinding.

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

[0053] like Figure 2 The new yellow phosphor Ba3SbGa3Ge2O with high temperature sensing sensitivity in Experimental Example 1-6 is shown. 14 :xBi 3 + , the emission spectrum of 0.0025≤x≤0.08, with the change of x value, the emission intensity first increases and then decreases, and x=0.04 is the optimal doping concentration.

[0054] like Figure 3 The new yellow phosphor Ba3SbGa3Ge2O with high temperature sensing sensitivity in Experimental Example 4 is shown. 14 :0.04Bi 3+ Excitation and emission spectra: the excitation range of the luminescent material is 250-400nm, and the emission spectrum is a broadband yellow emission of 400-700nm, with a peak at 527nm.

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

[0056] like Figure 5 The new yellow phosphor Ba3SbGa3Ge2O with high temperature sensing sensitivity prepared in Example 4 is shown. 14 :0.04Bi 3+ The relative sensitivity diagram in the temperature range of 303 to 423 K is first calculated by the Arrhenius formula Calculate the activation energy and then use the sensitivity formula The sensitivity was calculated and its relative sensitivity was as high as 4.155%K -1 .

[0057] like Figure 6 As shown in the figure, after 365nm light excitation, the new yellow phosphor Ba3SbGa3Ge2O with high temperature sensing sensitivity is prepared in Example 4. 14 :0.04Bi 3+ A yellow luminescence was produced.

Claims

1. A novel yellow phosphor with high temperature sensing sensitivity and a preparation method thereof, characterized in that: The chemical composition 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 of 400 to 700 nm, and the strongest emission peak is 527 nm.

2. The bismuth ion-doped gallium germanate-based yellow phosphor with high temperature sensing sensitivity according to claim 1, characterized in that: The method for preparing the phosphor comprises the following steps: (1) Weighing: Weigh the raw materials containing Ba, Sb, Ge, Ga, O, and Bi elements according to their chemical composition, and the stoichiometric ratio is 3:1:3:2:x; (2) Grinding: Grind for 30 minutes to mix evenly and place in a reaction container; (3) Sintering: Sintering is carried out in an air atmosphere, then cooled to room temperature, and ground to obtain the target product, which is a yellow phosphor with high temperature sensing sensitivity.

3. The bismuth ion-doped gallium germanate-based yellow phosphor with high temperature sensing sensitivity according to claim 2, characterized in that: The bismuth ion-doped gallium germanate-based yellow phosphor with high temperature sensing sensitivity is prepared by mixing a Ba compound, an Sb compound, a Ga compound, a Ge compound and a Bi compound and then sintering the mixture; The Ba-containing compound is a mixture of one or more of Ba oxides, carbonates, oxalates, acetates, nitrates and hydroxides. The Sb-containing compound is a mixture of one or more of Sb oxides, carbonates, oxalates, acetates, nitrates and hydroxides. The Ga-containing compound is a mixture of one or more of Ga oxides, carbonates, oxalates, acetates, nitrates and hydroxides. The Ge-containing compound is a mixture of one or more of Ge oxides, carbonates, oxalates, acetates, nitrates and hydroxides. The Bi-containing compound is a mixture of one or more of Bi oxides, carbonates, oxalates, acetates, nitrates and hydroxides.

4. The bismuth ion-doped gallium germanate-based yellow phosphor with high temperature sensing sensitivity according to claim 2, characterized in that: During the sintering process, the temperature is 1350 degrees, and then the temperature is kept constant for 6 hours.

5. The bismuth ion-doped gallium germanate-based yellow phosphor with high temperature sensing sensitivity according to claim 2, characterized in that: The phosphor emits yellow light with a peak of 527nm under ultraviolet light, and the temperature sensitivity is as high as 4.155%K -1 .

6. The bismuth ion-doped gallium germanate-based yellow phosphor with high temperature sensing sensitivity according to claims 1-5 has great application prospects in the field of non-contact optical temperature measurement.

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