A light-heat-electricity coupling controllable high-entropy perovskite oxide functional ceramic, a preparation method and application thereof

Abstract

This invention belongs to the field of multifunctional optical materials technology, and discloses a high-entropy perovskite oxide functional ceramic with tunable optical-thermal-electric coupling, its preparation method, and its application. The chemical formula of the functional ceramic is 0.6(Bi). 0.5 Na 0.4 K 0.1 ) 1‑1.5x Er x TiO3‑0.4[2 / 3(SrTiO3)‑1 / 3(Bi(Mg 2 / 3 Ni y Nb z [O3], 0≤x≤0.3, 0.1≤y≤0.5, 0.05≤z≤0.3, and 0.15≤2y+5z≤2.5; entropy value>1.61. Bi2O3, Na2CO3, TiO2, SrCO3, MgO, NiO, Nb2O5, Er2O3, and K2CO3 are uniformly mixed with a solvent, pre-fired, granulated, pressed into tablets, and then sintered. The functional ceramics of this invention possess photo-optical, photo-thermal, and photo-electric conversion functions, enabling applications in non-contact temperature sensing, display lighting, optical anti-counterfeiting, optoelectronic devices, and the medical field. Furthermore, the preparation method is low-cost and has a high yield.

Description

Technical Field

[0001] This invention belongs to the field of multifunctional optical materials technology, and in particular relates to a high-entropy perovskite oxide functional ceramic with tunable optical-thermal-electric coupling, its preparation method, and its application. Background Technology

[0002] Upconversion luminescent materials can convert infrared light into visible light, and have wide applications in important fields such as displays and lighting, super-resolution imaging, temperature sensing, optical therapy, solid-state lasers, optical anti-counterfeiting, and optoelectronic devices, thus attracting widespread attention from scientists worldwide. Upconversion luminescence has advantages such as high emission intensity, strong penetration, non-toxicity to biological tissues, and weak spontaneous background fluorescence, making it widely used in medical applications.

[0003] In recent years, the rapid development of temperature measurement relies on the non-invasive fluorescence intensity ratio (FIR) technology, which measures the difference in photoluminescence (PL) emission peaks of luminescent materials at different temperatures. This technology offers significant advantages such as rapid detection and high sensitivity. Photothermal therapy (PTT) is a physical therapy that converts absorbed light energy into heat through photothermal therapeutic agents (PTAs). The performance of PTT is closely related to the heat generation of PTAs, but insufficient heat at the treatment site or excessively high body temperature may lead to ineffective treatment or unpredictable damage to surrounding normal tissues. Developing novel materials with precise real-time intracellular temperature feedback and photothermal conversion capabilities is an effective method for controlling the temperature of the photothermal conversion process. Extensive research on novel photothermal materials has become a cutting-edge research area with broad and high-potential applications in physics, chemistry, and life sciences. 3+ With abundant stepped energy levels serving as luminescent centers, phosphors have become a key focus of FIR research. This technology has been widely applied as a non-invasive temperature detection technique to detect the temperature of PTA in biological systems. Functional ceramics, due to their long-term safety and stability, have been integrated into daily life, such as applications in high-temperature environments, scenarios requiring high mechanical strength and wear resistance, environments requiring high chemical stability, and the manufacture of large-size parts. Moreover, their low cost makes them suitable for large-scale industrial production, thus making the study of the photothermal properties of ceramics essential. Generally, photothermal ceramics with fluorescent properties are achieved through rare-earth ion doping.

[0004] Traditional contact temperature detection is widely used in many fields, but its slow response speed and poor adaptability to complex environments (such as those inside the body, in strong magnetic fields, and corrosive environments) are the main factors limiting its application. Therefore, non-contact temperature detection not only largely avoids these problems but also has advantages such as strong anti-interference and high signal resolution. Non-contact temperature sensors based on upconversion luminescence utilize the temperature-dependent radiative efficiency of specific energy levels of rare-earth ions. Temperature changes are used to change the upconversion emission intensity of rare-earth ions, thereby achieving temperature detection. Currently, fluorescence intensity ratio (FIR)-based testing techniques rarely consider the error caused by the heat generated by the material's own photothermal effect. This is because, under most application conditions, the laser power is constant, so the error is controllable. However, in biomedicine, especially in photothermal therapy, it is necessary to change the laser power to bring the material to the desired photothermal temperature. Therefore, a power-driven non-contact temperature measurement system needs to be developed for materials with photothermal effects.

[0005] Existing research has yielded few reports on the application of fluorescent photothermal ceramics in power-driven FIR detection. In 2022, researchers enhanced the non-radiative transition process of Er-containing KNN-based ceramic materials by introducing CCTO compounds, and investigated the effect of Yb doping content on the material's luminescent and photothermal properties. The experiments yielded a photothermal conversion temperature of 70℃ (at a driving power of 0.4W) and a power sensitivity of 0.61W. -1 This system only uses one photothermal conversion mechanism, resulting in relatively low photothermal conversion temperature and sensitivity. Summary of the Invention

[0006] To address the technical problem of relatively low photothermal conversion temperature and sensitivity in existing technologies, the present invention aims to provide a high-entropy perovskite oxide functional ceramic with tunable photothermal-electric coupling, its preparation method, and its application. This functional ceramic exhibits high photothermal conversion temperature and power sensitivity.

[0007] To achieve the above-mentioned objectives, the present invention provides the following technical solution:

[0008] A high-entropy perovskite oxide functional ceramic with tunable photo-thermal-electric coupling, wherein the chemical formula of the functional ceramic is 0.6(Bi) 0.5 Na 0.4 K 0.1 ) 1-1.5x Er x TiO3-0.4[2 / 3(SrTiO3)-1 / 3(Bi(Mg 2 / 3 Ni y Nb z)O3)], where 0≤x≤0.3, 0.1≤y≤0.5, 0.05≤z≤0.3, and 0.15≤2y+5z≤2.5; the entropy range of the functional ceramic is: S>1.61.

[0009] A further improvement of the present invention is that 0.01≤x≤0.2, 0.2≤y≤0.4, 0.1≤z≤0.25, and 0.3≤2y+5z≤2.

[0010] A further improvement of the present invention is that 0.01≤x≤0.05, 0.3≤y≤0.4, 0.15≤z≤0.2, and 1.5≤2y+5z≤2.

[0011] A method for preparing high-entropy perovskite oxide functional ceramics with tunable optical-thermal-electric coupling includes the following steps:

[0012] According to the chemical formula 0.6(Bi) 0.5 Na 0.4 k 0.1 ) 1-1.5x Er x TiO3-0.4[2 / 3(SrTiO3)-1 / 3(Bi(Mg 2 / 3Ni y Nb z Bi2O3, Na2CO3, TiO2, SrCO3, MgO, NiO, Nb2O5, Er2O3 and K2CO3 are mixed evenly with solvent, pre-fired, granulated, pressed into tablets and then sintered to obtain high-entropy perovskite oxide functional ceramics with tunable photo-thermal-electric coupling.

[0013] Wherein, 0≤x≤0.3, 0.1≤y≤0.5, 0.05≤z≤0.3, and 0.15≤2y+5z≤2.5; and the entropy range of functional ceramics is: S>1.61.

[0014] A further improvement of the present invention is that 0.01≤x≤0.2, 0.2≤y≤0.4, 0.1≤z≤0.25, and 0.3≤2y+5z≤2.

[0015] A further improvement of the present invention is that 0.01≤x≤0.05, 0.3≤y≤0.4, 0.15≤z≤0.2, and 1.5≤2y+5z≤2.

[0016] A further improvement of the present invention is that the solvent is ethanol, isopropanol or acetone; the pre-calcination temperature is 800℃-950℃ and the time is 2 hours to 3 hours; and a binder is added before granulation.

[0017] A further improvement of the present invention is that the binder is a PVA solution with a mass fraction of 5%-10%; after granulation, it is passed through an 80-120 mesh sieve.

[0018] A further improvement of the present invention is that the solvent is ethanol and the sintering process is as follows: first sintering at 550℃-650℃ for 2h-5h; then sintering at 1100℃-1200℃ for 1.5h-3h.

[0019] Applications of a high-entropy perovskite oxide functional ceramic with tunable photo-thermal-electric coupling in temperature sensing, display lighting, optical anti-counterfeiting, optoelectronic devices and medical fields.

[0020] Compared with the prior art, the present invention has the following beneficial effects:

[0021] This invention uses Bi₂O₃, Na₂CO₃, TiO₂, SrCO₃, MgO, NiO, Nb₂O₅, Er₂O₃, and K₂CO₃ as raw materials and a simple high-temperature solid-state reaction method to prepare 0.6 (Bi 0.5 Na 0.4 K 0.1 ) 1-1.5x Er x TiO3-0.4[2 / 3(SrTiO3)-1 / 3(Bi(Mg 2 / 3 Ni y Nb z Compared to existing processes that first prepare nano-precursors using solution-gel or hydrothermal methods before preparing ceramics, the functional ceramics of this invention utilize a solid-state method to prepare the precursors before ceramic preparation. This method is low-cost, high-yield, and simple, making it suitable for large-scale production.

[0022] This invention modulates the fluorescence intensity and photothermal conversion temperature characteristics of the material by focusing on the content of Er, Ni, and Nb ions. Because Er... 3+ Ions and Ni 2+ Ions excited by a 980nm laser undergo a dual effect of non-radiative transitions and infrared self-absorption, resulting in a material with a high photothermal conversion temperature, and based on Er... 3+ With its unique energy level structure, functional ceramics can acquire specific upconversion luminescence capabilities. At the same time, the NBT matrix material itself has good pyroelectric properties, ultimately realizing the synergistic coupling characteristics of photothermal conversion, photoelectric conversion and upconversion luminescence in the functional ceramic material system.

[0023] Functional ceramics, being fluorescent materials with photothermal properties, can be applied to non-contact temperature sensing. By irradiating the ceramic material with 980nm infrared light, a high photothermal conversion temperature and power sensitivity were achieved at relatively low power. The ceramic material prepared in this invention possesses tunable photo-thermal-electric coupling, enabling its application in non-contact temperature sensing, display lighting, optical anti-counterfeiting, optoelectronic devices, and the medical field. Attached Figure Description

[0024] Figure 1 The X-ray diffraction pattern of the ceramic sample provided in Example 1 of this invention;

[0025] Figure 2 The image shows the excitation spectrum of the ceramic sample provided in Example 1 of the present invention, wherein the wavelength of the emitted light is 980 nm.

[0026] Figure 3 The image shows the highest temperature at the center of the photothermal conversion of the ceramic sample provided in Example 1 of this invention, with an excitation wavelength of 980 nm and a power of 0.2 W.

[0027] Figure 4 The X-ray diffraction pattern of the ceramic sample provided in Example 2 of this invention;

[0028] Figure 5 The excitation spectrum of the sample provided in Embodiment 2 of the present invention is shown, wherein the wavelength of the emitted light is 980 nm;

[0029] Figure 6 The image shows the highest central temperature of the photothermal conversion of the sample provided in Example 3 of the present invention, with an excitation wavelength of 980 nm and a power of 1 W.

[0030] Figure 7 The X-ray diffraction pattern of the ceramic sample provided in Example 3 of this invention;

[0031] Figure 8 The image shows the highest temperature at the center of the photothermal conversion of the sample provided in Example 3 of this invention, with an excitation wavelength of 980 nm and a power of 0.4 W.

[0032] Figure 9 The image shows the highest temperature at the center of photothermal conversion of the sample provided in Example 3 of this invention, with an excitation wavelength of 980 nm and a power of 0.6 W.

[0033] Figure 10 The X-ray diffraction pattern of the ceramic sample provided in Example 4 of this invention;

[0034] Figure 11 The excitation spectrum of the sample provided in Example 4 of the present invention is shown, wherein the wavelength of the emitted light is 980 nm.

[0035] Figure 12 The image shows the highest temperature at the center of the photothermal conversion of the ceramic sample provided in Example 4 of this invention, with an excitation wavelength of 980 nm and a power of 0.8 W.

[0036] Figure 13 The dark current and photocurrent under 980nm excitation of the ceramic sample provided in Example 4 of the present invention are shown.

[0037] Figure 14 The X-ray diffraction pattern of the ceramic sample provided in Comparative Example 1 of this invention;

[0038] Figure 15 The image shows the excitation spectrum of the sample provided in Comparative Example 1 of this invention, wherein the wavelength of the emitted light is 980 nm.

[0039] Figure 16 The image shows the highest central temperature of the photothermal conversion of the ceramic sample provided in Comparative Example 1 of this invention, with an excitation wavelength of 980 nm and a power of 0.4 W.

[0040] Figure 17 The X-ray diffraction pattern of the ceramic sample provided in Comparative Example 2 of this invention;

[0041] Figure 18 The image shows the highest temperature at the center of the photothermal conversion of the ceramic sample provided in Comparative Example 2 of this invention. The excitation wavelength is 980 nm and the power is 0.4 W. Detailed Implementation

[0042] To facilitate understanding of the present invention, a more complete description will be given below with reference to the accompanying drawings. Preferred embodiments of the invention are shown in the drawings. However, the invention can be implemented in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided to provide a thorough and complete understanding of the disclosure of the invention.

[0043] Sodium bismuth titanate (Bi 0.5 Na 0.5 TiO3 (BNT) material, as a multifunctional A-site composite ion perovskite ferroelectric, has lower requirements for sintering atmosphere and temperature compared to other materials, good chemical stability, no strict requirements for humidity, long-term storage, and good reproducibility of the preparation process, thus it can be applied to large-scale industrial production. It has a high Curie temperature (320℃) and a relatively low permittivity (240~340℃), making it suitable for high-temperature applications. This invention, based on high-entropy theory, utilizes the introduction of multiple elements to prepare high-entropy perovskite oxide functional ceramics, achieving tunable opto-thermal-electric coupling through the synergistic effect of multiple mechanisms.

[0044] Because BNT-based ceramics have low phonon energies and contain defect states such as vacancies, they can effectively increase the radiative transitions and cross-relaxation between relevant energy levels within the material system, thereby increasing the number of effective luminescent energy level particles and enhancing the system's upconversion luminescence and photothermal conversion capabilities.

[0045] The chemical formula of the high-entropy perovskite oxide functional ceramic with tunable photo-thermal-electric coupling characteristics of the present invention is 0.6(Bi). 0.5 Na 0.4 K 0.1 ) 1-1.5x Er x TiO3-0.4[2 / 3(SrTiO3)-1 / 3(Bi(Mg 2 / 3Ni y Nb z )O3)], where x, y, z represent the mole fractions of the corresponding elements, and 0≤x≤0.3, 0.1≤y≤0.5, 0.05≤z≤0.3, and 0.15≤2y+5z≤2.5; meanwhile, the entropy value S of the functional ceramics is in the range of: S>1.61.

[0046] Preferably, the values ​​of x, y, and z are in the range of 0.01≤x≤0.2, 0.2≤y≤0.4, 0.1≤z≤0.25, and 0.3≤2y+5z≤2; simultaneously, the oxide entropy value range is S>1.61. Reason for preference: Within this range, the functional ceramics exhibit superior performance.

[0047] Further preferred values ​​are 0.01≤x≤0.05, 0.3≤y≤0.4, 0.15≤z≤0.2, and 1.5≤2y+5z≤2; meanwhile, the entropy range of the functional ceramic is S>1.61.

[0048] The present invention provides a method for preparing high-entropy perovskite oxide functional ceramics with tunable photo-thermal-electric coupling characteristics, comprising the following steps:

[0049] Using Bi₂O₃, Na₂CO₃, TiO₂, SrCO₃, MgO, NiO, Nb₂O₅, Er₂O₃, and K₂CO₃ as raw materials, the above raw materials are mixed in a certain proportion, and ethanol is used as a solvent. The mixture is then ground into a uniform powder in a ball mill. The powder is then dried and pre-fired. The pre-fired powder is then ground again, a binder is added, and the mixture is granulated. After pressing into tablets, it undergoes low-temperature debonding and high-temperature sintering, and is cooled to room temperature to obtain a high-entropy perovskite oxide functional ceramic with tunable photo-thermal-electric coupling characteristics, namely 0.6(Bi₂O₃, Na₂CO₃, TiO₂, SrCO₃, MgO, NiO, Nb₂O₅, Er₂O₃, and K₂CO₃. 0.5 Na 0.4 K 0.1 ) 1-1.5x Erx TiO3-0.4[2 / 3(SrTiO3)-1 / 3(Bi(Mg 2 / 3 Ni y Nb z )O3)] ceramics.

[0050] During mixing, the mass ratio of raw materials: ethanol: zirconium balls is 1:1:2.

[0051] The ball mill is a planetary ball mill, and the milling time is more than 6 hours.

[0052] The pre-firing is carried out at 800℃-950℃ for 2 to 3 hours;

[0053] The adhesive is a 5% PVA solution by mass.

[0054] During the granulation process, the powder is passed through an 80-120 mesh sieve.

[0055] During the tableting process, an SDY-20 manual and electric tablet press is used to compress the powder into shape under a pressure of 5-20 MPa.

[0056] The sintering process begins with low-temperature desizing followed by high-temperature sintering. The low-temperature desizing temperature is 550℃-650℃, and the time is 2h-5h; the high-temperature sintering temperature is 1100℃-1200℃, and the time is 1.5h-3h.

[0057] In this invention, unless otherwise specified, all raw materials used are commercially available products in the field. This invention does not impose any special limitations on the amount of the raw materials used, as long as they meet the general chemical formula.

[0058] Compared to existing processes that first prepare nano-precursors using solution-gel or hydrothermal methods and then prepare ceramics, the functional ceramics of this invention are prepared using a solid-state method to prepare the precursors before ceramic preparation. This method is low-cost, high-yield, and simple, making it suitable for large-scale production.

[0059] All raw materials used are commercially available, making them easy to obtain, the process simple, and the resulting products stable and reliable in quality, which is conducive to industrial production.

[0060] The high-entropy perovskite oxide functional ceramics exhibit a broad emission peak at 500nm-700nm when irradiated with a 960nm-990nm laser.

[0061] Furthermore, under irradiation with a 980nm laser at a power of 1mW or higher, the sample (i.e., high-entropy perovskite oxide functional ceramic) exhibits broad emission peaks at green light around 520nm and 550nm, and red light around 650nm, generating heat. As the laser power increases, the photothermal conversion temperature rises continuously, and the fluorescence intensity ratio (FIR) of the two emission peaks at 520nm and 550nm changes. Fitting analysis of the FIR data yields the material-related power sensitivity.

[0062] When the ceramic is irradiated by a laser in the 800nm-990nm range, the phenomenon of photothermal conversion occurs by adjusting the laser power, and the ratio of fluorescence intensity obtained by the ceramic at different powers changes.

[0063] The photo-thermal-electric coupled tunable high-entropy perovskite oxide functional ceramic prepared by the above-described method in this invention is a fluorescent material with photo-to-photo, photo-thermal, and photo-electric conversion functions, which can be applied in temperature sensing, display lighting, optical anti-counterfeiting, optoelectronic devices, and medical fields. Furthermore, the ceramic can be applied in the field of non-contact temperature sensing.

[0064] To further illustrate the present invention, the following detailed description, in conjunction with examples, of the optical-thermal-electric coupled tunable high-entropy perovskite oxide functional ceramics, their preparation methods, and applications provided by the present invention, should not be construed as limiting the scope of protection of the present invention.

[0065] The present invention will now be further described with reference to specific embodiments.

[0066] Example 1

[0067] x is 0.01, y is 1 / 3, z is 0, which is 0.6 (Bi) 0.5 Na 0.4 K 0.1 ) 0.985 Er 0.01 TiO3-0.4[2 / 3(SrTiO3)-1 / 3(Bi(Mg 2 / 3 Ni 1 / 3 [O3], with an entropy value of 1.70.

[0068] The preparation method of functional ceramic 1 is as follows:

[0069] Commercially available high-purity Bi₂O₃, Na₂CO₃, TiO₂, SrCO₃, NiO, MgO, Er₂O₃, and K₂CO₃ were used as raw materials. The mass of each oxide was accurately weighed according to the above formula. The weighed raw materials were placed in a clean agate jar, and anhydrous ethanol was used as the solvent. The mass ratio of raw materials:ethanol:zirconium balls was 1:1:2. The mixture was ground in a planetary ball mill to produce a uniformly mixed powder for 12 hours. The powder was then dried in an oven, placed in a corundum crucible, and pre-fired in a box furnace at 900℃ for 2 hours, followed by cooling to 600℃. The resulting product, after cooling in the furnace, was finely ground in an agate mortar and pestle. A 5% (w / w) PVA solution (binder) was added, and the mixture was thoroughly ground and mixed evenly. Granulation was then performed, and the granules were passed through an 80-120 mesh sieve. The powder was then pressed into 10mm diameter ceramic green sheets using an SDY-20 manual and electric press under a pressure of 5MPa. Ceramic green sheets were placed in a high-temperature furnace and continuously heated to 600℃ for 180 minutes to remove plastic buildup. The temperature was then continuously increased to 1190℃ for 2 hours, followed by sintering. The temperature was then reduced to 600℃ and allowed to cool naturally to obtain 0.6 (Bi) 0.5 Na 0.4 K 0.1 ) 0.985 Er 0.01 TiO3-0.4[2 / 3(SrTiO3)-1 / 3(Bi(Mg 2 / 3 Ni 1 / 3 )O3)] Ceramic materials.

[0070] See Figure 1 It can be seen that the ceramic sample has a single perovskite structure;

[0071] See Figure 2 It can be seen that the ceramic sample has peaks at 520nm, 550nm and 660nm when excited by a 980nm laser.

[0072] See Figure 3 The results show the relationship between the highest temperature at the center of the ceramic surface and time when irradiated with a 980nm laser at a power of 0.2W. The temperature reaches a stable stage after rising to 60.5℃.

[0073] Example 2

[0074] x is 0.02, y is 0, z is 1 / 3, which is 0.6 (Bi) 0.5 Na 0.4 K 0.1 ) 0.97 Er 0.02 TiO3-0.4[2 / 3(SrTiO3)-1 / 3(Bi(Mg 2 / 3 Ni 1 / 3 [O3], with an entropy value of 1.70.

[0075] The preparation method of functional ceramic 2 is as follows:

[0076] Commercially available high-purity Bi₂O₃, Na₂CO₃, TiO₂, SrCO₃, NiO, MgO, Er₂O₃, and K₂CO₃ were used as raw materials. The mass of each oxide was accurately weighed according to the above formula. The weighed raw materials were placed in a clean agate jar, and anhydrous ethanol was used as the solvent. The mass ratio of raw materials:ethanol:zirconium balls was 1:1:2. The mixture was ground in a planetary ball mill to produce a uniformly mixed powder for 18 hours. The powder was then dried in an oven, placed in a corundum crucible, and pre-fired in a box furnace at 900℃ for 2 hours, followed by cooling to 600℃. The resulting product, after furnace cooling, was finely ground in an agate mortar and pestle. A 5% (w / w) PVA solution (binder) was added, and the mixture was thoroughly ground and mixed evenly. Granulation was then performed, and the granules were passed through an 80-120 mesh sieve. The powder was then pressed into 10mm diameter ceramic green sheets using an SDY-20 manual and electric press under 20MPa pressure. Ceramic green sheets were placed in a high-temperature furnace and continuously heated to 600℃ for 180 minutes to remove plastic buildup. The temperature was then continuously increased to 1180℃ for 2 hours, followed by sintering. The temperature was then reduced to 600℃ and allowed to cool naturally to obtain 0.6 (Bi) 0.5 Na 0.4 K 0.1 ) 0.97 Er 0.02 TiO3-0.4[2 / 3(SrTiO3)-1 / 3(Bi(Mg 2 / 3Ni 1 / 3 )O3)] Ceramic materials.

[0077] See Figure 4 As can be seen, the ceramic sample has a perovskite main phase.

[0078] See Figure 5 It can be seen that the ceramic sample has emission peaks at 520nm, 550nm and 660nm under 980nm laser excitation, and the emission peak at the red light is relatively wide.

[0079] See Figure 6 The results show the relationship between the highest temperature at the center of the ceramic surface and time when irradiated with a 980nm laser at a power of 1W. The temperature reaches a stable stage after rising to 227℃.

[0080] Example 3

[0081] x is 0.03, y is 1 / 3, z is 0.1, which is 0.6 (Bi) 0.5 Na 0.4 K 0.1 ) 0.955 Er 0.03TiO3-0.4[2 / 3(SrTiO3)-1 / 3(Bi(Mg 2 / 3 Ni 1 / 3 Nb 0.1 [O3], with an entropy value of 1.75.

[0082] The preparation method of functional ceramic 3 is as follows:

[0083] Commercially available high-purity Bi₂O₃, Na₂CO₃, TiO₂, SrCO₃, NiO, MgO, Nb₂O₅, Er₂O₃, and K₂CO₃ were used as raw materials. The mass of each oxide was accurately weighed according to the above formula. The weighed raw materials were placed in a clean agate jar, and anhydrous ethanol was used as the solvent. The mass ratio of raw materials:ethanol:zirconium balls was 1:1:2. The mixture was ground in a planetary ball mill to produce a uniformly mixed powder for 24 hours. The powder was then dried in an oven, placed in a corundum crucible, and pre-fired in a box furnace at 850℃ for 2 hours, followed by cooling to 600℃. The resulting product, after furnace cooling, was finely ground in an agate mortar and pestle. A 5% (w / w) PVA solution (binder) was added, and the mixture was thoroughly ground and mixed evenly. Granulation was then performed, and the granules were passed through an 80-120 mesh sieve. The powder was then pressed into 10mm diameter ceramic green sheets using an SDY-20 manual and electric press under 20MPa pressure. Ceramic green sheets were placed in a high-temperature furnace and continuously heated to 600℃ for 180 minutes to remove plastic buildup. The temperature was then continuously increased to 1170℃ for 2.5 hours, followed by cooling to 600℃ and allowing to cool naturally to obtain 6(Bi). 0.5 Na 0.4 K 0.1 ) 0.955 Er 0.03 TiO3-0.4[2 / 3(SrTiO3)-1 / 3(Bi(Mg 2 / 3 Ni 1 / 3 Nb 0.1 )O3)] Ceramic materials.

[0084] See Figure 7 As can be seen, the ceramic sample has a single perovskite structure.

[0085] See Figure 8 As can be seen, when irradiated with a 980nm laser at a power of 0.4W, the highest temperature at the center of the ceramic surface changes over time. The temperature reaches a stable level after rising to 98℃.

[0086] See Figure 9 As can be seen, when irradiated with a 980nm laser at a power of 0.6W, the highest temperature at the center of the ceramic surface changes over time. The temperature reaches a stable level after rising to 131℃.

[0087] Example 4

[0088] x is 0.1, y is 1 / 3, z is 0, which is 0.6 (Bi) 0.5 Na 0.4 K 0.1 ) 0.85 Er 0.1 TiO3-0.4[2 / 3(SrTiO3)-1 / 3(Bi(Mg 2 / 3 Ni 1 / 3 [O3], with an entropy value of 1.75.

[0089] The preparation method of functional ceramic 4 is as follows:

[0090] Commercially available high-purity Bi₂O₃, Na₂CO₃, TiO₂, SrCO₃, NiO, MgO, Er₂O₃, and K₂CO₃ were used as raw materials. The mass of each oxide was accurately weighed according to the above formula. The weighed raw materials were placed in a clean agate jar, and anhydrous ethanol was used as the solvent. The mass ratio of raw materials:ethanol:zirconium balls was 1:1:2. The mixture was ground in a planetary ball mill to produce a uniformly mixed powder for 12 hours. The powder was then dried in an oven, placed in a corundum crucible, and pre-fired in a box furnace at 900℃ for 2 hours, followed by cooling to 600℃. The resulting product, after furnace cooling, was finely ground in an agate mortar and pestle. A 5% (w / w) PVA solution (binder) was added, and the mixture was thoroughly ground and mixed evenly. Granulation was then performed, and the granules were passed through an 80-120 mesh sieve. The powder was then pressed into 10mm diameter ceramic green sheets using an SDY-20 manual and electric press under 20MPa pressure. Ceramic green sheets were placed in a high-temperature furnace and continuously heated to 600℃ for 180 minutes to remove plastic buildup. The temperature was then continuously increased to 1190℃ for 2 hours, followed by sintering. The temperature was then reduced to 600℃ and allowed to cool naturally to obtain 0.6 (Bi) 0.5 Na 0.4 K 0.1 ) 0.85 Er 0.1 TiO3-0.4[2 / 3(SrTiO3)-1 / 3(Bi(Mg 2 / 3Ni 1 / 3 )O3)] Ceramic materials.

[0091] See Figure 10 As can be seen, the ceramic sample has a perovskite main phase.

[0092] See Figure 11 It can be seen that the ceramic sample has emission peaks at 520nm, 550nm and 660nm under 980nm laser excitation;

[0093] See Figure 12It can be seen that when irradiated with a 980nm laser at a power of 0.8W, the highest temperature at the center of the ceramic surface changes over time, and enters a stable stage after the temperature rises to 150℃.

[0094] See Figure 13 It can be seen that the dark current of the ceramic sample under the highest voltage of 10V and the photocurrent under 980nm excitation are different.

[0095] Example 5

[0096] x is 0.02, y is 1 / 3, z is 1 / 5, which is 0.6 (Bi) 0.5 Na 0.4 K 0.1 ) 0.985 Er 0.01 TiO3-0.4[2 / 3(SrTiO3)-1 / 3(Bi(Mg 2 / 3 Ni 1 / 3 Nb 1 / 5 [O3], with an entropy value of 1.80.

[0097] The preparation method of functional ceramic 5 is as follows:

[0098] Commercially available high-purity Bi₂O₃, Na₂CO₃, TiO₂, SrCO₃, NiO, MgO, Nb₂O₅, Er₂O₃, and K₂CO₃ were used as raw materials. The mass of each oxide was accurately weighed according to the above formula. The weighed raw materials were placed in a clean agate jar, and anhydrous ethanol was used as the solvent. The mass ratio of raw materials:ethanol:zirconium balls was 1:1:2. The mixture was ground in a planetary ball mill to produce a uniformly mixed powder for 12 hours. The powder was then dried in an oven, placed in a corundum crucible, and pre-fired in a box furnace at 850℃ for 2.5 hours, followed by cooling to 600℃. The resulting product, after cooling in the furnace, was finely ground in an agate mortar and pestle. A 5% (w / w) PVA solution was added as a binder, and the mixture was thoroughly ground and mixed evenly. Granulation was then performed, and the granules were passed through an 80-120 mesh sieve. The powder was then pressed into 10mm diameter ceramic green sheets using an SDY-20 manual and electric press under a pressure of 20MPa. Ceramic green sheets were placed in a high-temperature furnace and continuously heated to 600℃ for 180 minutes to remove plastic buildup. The temperature was then continuously increased to 1180℃ for 2 hours, followed by sintering. The temperature was then reduced to 600℃ and allowed to cool naturally to obtain 0.6 (Bi) 0.5 Na 0.4 K 0.1 ) 0.985 Er 0.01 TiO3-0.4[2 / 3(SrTiO3)-1 / 3(Bi(Mg 2 / 3 Ni 1 / 3 Nb 1 / 5 )O3)] Ceramic materials.

[0099] Example 6

[0100] x is 0.2, y is 1 / 2, z is 4 / 15, which is 0.6 (Bi) 0.5 Na 0.4 K 0.1 ) 0.7 Er 0.2 TiO3-0.4[2 / 3(SrTiO3)-1 / 3(Bi(Mg 2 / 3 Ni 1 / 2 Nb 4 / 15 [O3], with an entropy value of 1.79.

[0101] The preparation method of functional ceramic 6 is as follows:

[0102] Commercially available high-purity Bi₂O₃, Na₂CO₃, TiO₂, SrCO₃, NiO, MgO, Nb₂O₅, Er₂O₃, and K₂CO₃ were used as raw materials. The mass of each oxide was accurately weighed according to the above formula. The weighed raw materials were placed in a clean agate jar, and anhydrous ethanol was used as the solvent. The mass ratio of raw materials:ethanol:zirconium balls was 1:1:2. The mixture was ground in a planetary ball mill to produce a uniformly mixed powder for 18 hours. The powder was then dried in an oven, placed in a corundum crucible, and pre-fired in a box furnace at 900℃ for 2 hours, followed by cooling to 600℃. The resulting product, after furnace cooling, was finely ground in an agate mortar and pestle. A 5% (w / w) PVA solution (binder) was added, and the mixture was thoroughly ground and mixed evenly. Granulation was then performed, and the granules were passed through an 80-120 mesh sieve. The powder was then pressed into 10mm diameter ceramic green sheets using an SDY-20 manual and electric press under 20MPa pressure. Ceramic green sheets were placed in a high-temperature furnace and continuously heated to 600℃ for 180 minutes to remove plastic buildup. The temperature was then continuously increased to 1180℃ for 2 hours, followed by sintering. The temperature was then reduced to 600℃ and allowed to cool naturally to obtain 0.6 (Bi) 0.5 Na 0.4 K 0.1 ) 0.7 Er 0.2 TiO3-0.4[2 / 3(SrTiO3)-1 / 3(Bi(Mg 2 / 3Ni 1 / 2 Nb 4 / 15 )O3)] Ceramic materials.

[0103] Example 7

[0104] x is 0, y is 0.1, z is 0.05, which is 0.6 (Bi) 0.5 Na 0.4 K 0.1 )TiO3-0.4[2 / 3(SrTiO3)-1 / 3(Bi(Mg 2 / 3Ni0.1 Nb 0.05 [O3], with an entropy value of 1.65.

[0105] The preparation method of functional ceramic 7 is as follows:

[0106] Commercially available high-purity Bi₂O₃, Na₂CO₃, TiO₂, SrCO₃, NiO, MgO, Er₂O₃, and K₂CO₃ were used as raw materials. The mass of each oxide was accurately weighed according to the above formula. The weighed raw materials were placed in a clean agate jar, and anhydrous ethanol was used as the solvent. The mass ratio of raw materials:ethanol:zirconium balls was 1:1:2. The mixture was ground in a planetary ball mill to produce a uniformly mixed powder for 6 hours. The powder was then dried in an oven, placed in a corundum crucible, and pre-fired in a box furnace at 870℃ for 2.5 hours, followed by cooling to 600℃. The resulting product, after furnace cooling, was finely ground in an agate mortar and pestle. A 5% (w / w) PVA solution was added as a binder, and the mixture was thoroughly ground and mixed evenly. Granulation was then performed, and the granules were passed through an 80-120 mesh sieve. The powder was then pressed into 10mm diameter ceramic green sheets using an SDY-20 manual and electric press under a pressure of 5MPa. The ceramic green sheet is placed in a high-temperature furnace and continuously heated. It is held at 550℃ for 5 hours to remove the plastic. Then, the temperature is continuously increased and sintered at 1100℃ for 3 hours. After cooling to 600℃ and natural cooling, a high-entropy perovskite oxide functional ceramic with tunable photo-thermal-electric coupling is obtained.

[0107] Example 8

[0108] x is 0.3, y is 0.2, z is 0.15, which is 0.6 (Bi) 0.5 Na 0.4 K 0.1 ) 0.55 Er 0.3 TiO3-0.4[2 / 3(SrTiO3)-1 / 3(Bi(Mg 2 / 3 Ni 0.2 Nb 0.15 [O3], with an entropy value of 1.61.

[0109] The preparation method of functional ceramic 8 is as follows:

[0110] Commercially available high-purity Bi₂O₃, Na₂CO₃, TiO₂, SrCO₃, NiO, MgO, Er₂O₃, and K₂CO₃ were used as raw materials. The mass of each oxide was accurately weighed according to the above formula. The weighed raw materials were placed in a clean agate jar, and anhydrous ethanol was used as the solvent. The mass ratio of raw materials:ethanol:zirconium balls was 1:1:2. The mixture was ground in a planetary ball mill to produce a uniformly mixed powder for 10 hours. The powder was then dried in an oven, placed in a corundum crucible, and pre-fired in a box furnace at 900℃ for 2 hours, followed by cooling to 600℃. The resulting product, after cooling in the furnace, was finely ground in an agate mortar and pestle. A 5% (w / w) PVA solution was added as a binder, and the mixture was thoroughly ground and mixed evenly. Granulation was then performed, and the granules were passed through an 80-120 mesh sieve. The powder was then pressed into 10mm diameter ceramic green sheets using an SDY-20 manual and electric press under a pressure of 5MPa. The ceramic green sheet is placed in a high-temperature furnace and continuously heated. It is held at 650℃ for 2 hours to remove the plastic. Then, the temperature is continuously increased and sintered at 1200℃ for 1.5 hours. After cooling to 600℃ and natural cooling, a high-entropy perovskite oxide functional ceramic with tunable photo-thermal-electric coupling is obtained.

[0111] Example 9

[0112] x is 0.05, y is 0.4, z is 0.25, which is 0.6 (Bi) 0.5 Na 0.4 K 0.1 ) 0.925 Er 0.05 TiO3-0.4[2 / 3(SrTiO3)-1 / 3(Bi(Mg 2 / 3 Ni 0.4 Nb 0.25 [O3], with an entropy value of 1.82.

[0113] The preparation method of functional ceramic 9 is as follows:

[0114] Commercially available high-purity Bi₂O₃, Na₂CO₃, TiO₂, SrCO₃, NiO, MgO, Er₂O₃, and K₂CO₃ were used as raw materials. The mass of each oxide was accurately weighed according to the above formula. The weighed raw materials were placed in a clean agate jar, and anhydrous ethanol was used as the solvent. The mass ratio of raw materials:ethanol:zirconium balls was 1:1:2. The mixture was ground in a planetary ball mill to produce a uniformly mixed powder for 20 hours. The powder was then dried in an oven, placed in a corundum crucible, and pre-fired in a box furnace at 820℃ for 3 hours, followed by cooling to 600℃. The resulting product, after furnace cooling, was finely ground in an agate mortar and pestle. A 5% (w / w) PVA solution (binder) was added, and the mixture was thoroughly ground and mixed evenly. Granulation was then performed, and the granules were passed through an 80-120 mesh sieve. The powder was then pressed into 10mm diameter ceramic green sheets using an SDY-20 manual and electric press under a pressure of 5MPa. The ceramic green sheet is placed in a high-temperature furnace and continuously heated. It is held at 620℃ for 3 hours to remove the plastic. Then, the temperature is continuously increased and sintered at 1140℃ for 2 hours. After cooling to 600℃ and natural cooling, a high-entropy perovskite oxide functional ceramic with tunable photo-thermal-electric coupling is obtained.

[0115] Comparative Example 1

[0116] x is 0.01, y is 0, z is 1 / 3, which is 0.6 (Bi) 0.5 Na 0.4 K 0.1 ) 0.985 Er 0.01 TiO3-0.4[2 / 3(SrTiO3)-1 / 3(Bi(Mg 2 / 3 Nb 1 / 3 [O3], with an entropy value of 1.70.

[0117] The preparation method of functional ceramic 10 is as follows:

[0118] Using commercially available high-purity Bi2O3, Na2CO3, TiO2, SrCO3, and Nb2O 5、MgO, Er₂O₃, and K₂CO₃ were used as raw materials, and the mass of each oxide was accurately weighed according to the above formula. The weighed raw materials were placed in a clean agate jar, and anhydrous ethanol was used as a solvent. The mass ratio of raw materials:ethanol:zirconium balls was 1:1:2. The mixture was ground in a planetary ball mill to produce a uniformly mixed powder for 20 hours. The powder was then dried in an oven and placed in a corundum crucible. It was then placed in a box furnace and pre-fired at 820°C for 3 hours, followed by cooling to 600°C. The product obtained after furnace cooling was then ground finely in an agate mortar and pestle. A 5% (w / w) PVA solution was added as a binder, and the mixture was thoroughly ground and mixed evenly. The mixture was then granulated and passed through an 80-120 mesh sieve. The powder was pressed into 10mm diameter ceramic green sheets using an SDY-20 manual and electric press under a pressure of 5MPa. The ceramic green sheet is placed in a high-temperature furnace and continuously heated. It is held at 620℃ for 3 hours to remove the plastic. Then, the temperature is continuously increased and sintered at 1140℃ for 2 hours. After cooling to 600℃ and natural cooling, a high-entropy perovskite oxide functional ceramic with tunable photo-thermal-electric coupling is obtained.

[0119] See Figure 14 As can be seen, the ceramic sample has a perovskite main phase.

[0120] See Figure 15 It can be seen that the ceramic sample has emission peaks at 520nm, 550nm and 660nm under 980nm laser excitation;

[0121] See Figure 16 It can be seen that when irradiated with a 980nm laser at a power of 0.4W, the highest temperature at the center of the ceramic surface changes over time, and enters a stable stage after the temperature rises to 40℃.

[0122] The addition of rare earth ions Er enables the material system to exhibit upconversion luminescence characteristics under the action of 980nm laser, but the photothermal effect is not strong. Test results show that the relative photothermal conversion is only about 10℃.

[0123] Comparative Example 2

[0124] x is 0, y is 0, z is 1 / 3, which is 0.6Bi 0.5 Na 0.4 K 0.1 TiO3-0.4[2 / 3(SrTiO3)-1 / 3(Bi(Mg 2 / 3 Nb 1 / 3 [O3], with an entropy value of 1.70.

[0125] The preparation method of functional ceramic 11 is as follows:

[0126] Commercially available high-purity Bi₂O₃, Na₂CO₃, TiO₂, SrCO₃, Nb₂O₅, MgO, and K₂CO₃ were used as raw materials. The mass of each oxide was accurately weighed according to the above formula. The weighed raw materials were placed in a clean agate jar, and anhydrous ethanol was used as the solvent. The mass ratio of raw materials:ethanol:zirconium balls was 1:1:2. The mixture was ground in a planetary ball mill to produce a uniformly mixed powder for 20 hours. The powder was then dried in an oven, placed in a corundum crucible, and pre-fired in a box furnace at 820°C for 3 hours, followed by cooling to 600°C. The resulting product, after furnace cooling, was finely ground in an agate mortar and pestle. A 5% (w / w) PVA solution (binder) was added, and the mixture was thoroughly ground and mixed evenly. Granulation was then performed, and the granules were passed through an 80-120 mesh sieve. The powder was then pressed into 10mm diameter ceramic green sheets using an SDY-20 manual and electric press under a pressure of 5MPa. The ceramic green sheet is placed in a high-temperature furnace and continuously heated. It is held at 620℃ for 3 hours to remove the plastic. Then, the temperature is continuously increased and sintered at 1140℃ for 2 hours. After cooling to 600℃ and natural cooling, a high-entropy perovskite oxide functional ceramic with tunable photo-thermal-electric coupling is obtained.

[0127] See Figure 17 As can be seen, the ceramic sample has a perovskite main phase.

[0128] See Figure 18 As can be seen, when irradiated with a 980nm laser at a power of 0.4W, the temperature at the center of the ceramic surface changes very little over time.

[0129] When no rare earth element Er is added, the material system does not exhibit upconversion luminescence characteristics, but only a weak photothermal effect, with the sample temperature rising by about 10°C. When both Er and Ni are absent, the test results show only small temperature disturbances due to the influence of the laser's own radiation field and the ambient field, and the material system has almost no photothermal effect.

[0130] In this invention, the photothermal conversion temperature and luminescence intensity of the system are adjusted by regulating the content of Er, Nb, and Nb, utilizing the internal energy transfer mechanism of ceramics and the infrared self-absorption characteristics. The photo-thermal-electric coupling characteristics of the material system are also regulated by controlling the concentration of defects in the system and the combined effect of high-entropy oxide constituent elements on the perovskite ceramic crystal field.

[0131] The above description is only of the preferred embodiment of the present invention and should not be construed as limiting the scope of the claims. The present invention is not limited to the above embodiments, and variations in its specific structure are permitted. All variations made within the scope of the independent claims of the present invention are also within the scope of protection of the present invention.

[0132] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains.

Claims

1. A high-entropy perovskite oxide functional ceramic with tunable photo-thermal-electric coupling, characterized in that, The chemical formula of the functional ceramic is 0.6(Bi). 0.5 Na 0.4 K 0.1 ) 1-1.5x Er x TiO3-0.4[2 / 3(SrTiO3)-1 / 3(Bi(Mg 2 / 3 Ni y Nb z [O3], where 0.01≤x≤0.05, 0.3≤y≤0.4, 0.15≤z≤0.2, and 1.5≤2y+5z≤2; the entropy range of the functional ceramic is: S>1.61; Under irradiation with a 980nm laser with a power of 1mW or higher, high-entropy perovskite oxide functional ceramics exhibit broad emission peaks at green light near 520 nm and 550 nm and red light near 650 nm, and generate heat. High-entropy perovskite oxide functional ceramics exhibit photothermal conversion under 800nm-990nm laser irradiation by adjusting the laser power, resulting in changes in the fluorescence intensity ratio obtained by the ceramics at different powers.

2. A method for preparing high-entropy perovskite oxide functional ceramics with tunable photo-thermal-electric coupling, characterized in that, Includes the following steps: According to the chemical formula 0.6(Bi) 0.5 Na 0.4 K 0.1 ) 1-1.5x Er x TiO3-0.4[2 / 3(SrTiO3)-1 / 3(Bi(Mg 2 / 3 Ni y Nb z Bi2O3, Na2CO3, TiO2, SrCO3, MgO, NiO, Nb2O5, Er2O3 and K2CO3 are mixed evenly with solvent, pre-fired, granulated, pressed into tablets and then sintered to obtain high-entropy perovskite oxide functional ceramics with tunable photo-thermal-electric coupling. Wherein, 0.01≤x≤0.05, 0.3≤y≤0.4, 0.15≤z≤0.2, and 1.5≤2y+5z≤2; and the entropy range of functional ceramics is: S>1.61; Under irradiation with a 980nm laser with a power of 1mW or higher, high-entropy perovskite oxide functional ceramics exhibit broad emission peaks at green light near 520 nm and 550 nm and red light near 650 nm, and generate heat. High-entropy perovskite oxide functional ceramics exhibit photothermal conversion under 800nm-990nm laser irradiation by adjusting the laser power, resulting in changes in the fluorescence intensity ratio obtained by the ceramics at different powers.

3. The method for preparing photo-thermal-electrically coupled tunable high-entropy perovskite oxide functional ceramics according to claim 2, characterized in that, The solvent is ethanol, isopropanol or acetone; the pre-calcination temperature is 800℃-950℃ and the time is 2 hours to 3 hours; the binder is added before granulation.

4. The method for preparing photo-thermal-electrically coupled tunable high-entropy perovskite oxide functional ceramics according to claim 3, characterized in that, The binder is a PVA solution with a mass fraction of 5%-10%; after granulation, it is passed through an 80-120 mesh sieve.

5. The method for preparing photo-thermal-electrically coupled tunable high-entropy perovskite oxide functional ceramics according to claim 4, characterized in that, The solvent is ethanol, and the sintering process is as follows: first sinter at 550℃-650℃ for 2h-5h; then sinter at 1100℃-1200℃ for 1.5h-3h.

6. The application of a high-entropy perovskite oxide functional ceramic with tunable photo-thermal-electric coupling as described in claim 1 in temperature sensing, display lighting, optical anti-counterfeiting, and optoelectronic devices.

Images