A doped blue long-afterglow Zn4B6O13 single crystal material, its preparation method and application
Patent Information
- Application Number
- CN202610968112.9
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-07-01
- Publication Date
- 2026-09-08
AI Technical Summary
现有未掺杂无机晶体材料的发光寿命通常较短，难以在停止激发后维持持续数十秒的可见余辉，其根本原因在于缺乏有效的本征陷阱能级或陷阱浓度不足，无法实现载流子的高效俘获和室温下的缓慢释放
本申请提供的无掺杂蓝光长余辉Zn4B6O13单晶材料，所述单晶材料的化学组成为Zn4B6O13，所述单晶材料中不含有作为发光中心或敏化中心的稀土离子和过渡金属离子；所述Zn4B6O13单晶材料在紫外光激发下产生蓝光发射，并在停止激发后具有可见蓝光长余辉，可作为一种新的无掺杂蓝光长余辉单晶材料，与依赖外源掺杂的长余辉材料相比，本发明材料组成简单、原料易得、晶体生长过程可控，可为防伪标识、夜间指示、紫外响应发光器件、光学信息存储和光电探测等应用提供新的材料选择。
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Abstract
Description
Technical Field
[0001] This invention relates to the field of inorganic luminescent materials technology, and more specifically, to a doped blue long-afterglow Zn4B6O 13 Single crystal materials, preparation methods and applications. Background Technology
[0002] Long-afterglow luminescent materials are materials that continue to emit light after the external excitation source is removed. Their unique energy storage and slow release characteristics make them valuable for applications in nighttime lighting, emergency indication, anti-counterfeiting, optical information storage, and photoelectric detection in special environments. The essence of the long-afterglow phenomenon lies in the existence of trap energy levels within the material that can capture excited charge carriers. The captured charge carriers are gradually released and recombine to emit light under thermal disturbance or external stimulation, thus achieving delayed emission after the excitation stops.
[0003] Currently, known long-afterglow materials generally rely on rare-earth ions or transition metal ions as luminescent or trapping centers. Typical doping systems include Eu²⁺. + Dy³ + Ce³ + Rare earth ions and Mn² + Cr³ + Transition metal ions, through the characteristic energy levels of exogenous ions, can capture, store, and delay the release of excitation energy. For example, aluminate systems (such as SrAl₂O₄:Eu²⁺) + ,Dy³ + ) and silicate systems (such as Sr2MgSi2O7:Eu² + ,Dy³ + These doped systems have been widely studied and applied. Although they have achieved good long afterglow performance, there are still several unavoidable problems in practical applications.
[0004] First, rare earth elements and some transition metal raw materials are expensive, especially heavy rare earth elements, which significantly increase material costs and limit their adoption in low-cost, large-scale applications. Second, the uniformity of dopant ion distribution in the crystal matrix is difficult to control; doping concentration gradients or local segregation can easily lead to batch-to-batch fluctuations in luminescence performance, posing a challenge to the reliability and consistency of the material. Third, the introduction of exogenous ions inevitably causes lattice distortion and stress field changes, increasing the difficulty of growing large-size single crystals with high optical quality. Especially for applications requiring centimeter-scale transparent single crystals, the doped system often struggles to balance afterglow performance and crystal quality. Furthermore, some rare earth doped systems also suffer from complex luminescence color control and difficulties in optimizing the balance between afterglow duration and brightness.
[0005] Borate systems are considered potential matrices for optoelectronic functional materials due to their rich composition, good chemical stability, low sintering temperature, and wide bandgap. Among them, Zn₄B₆O₅ 13 Belonging to the zinc borate system, it is characterized by its simple composition and well-defined structure. However, existing technologies regarding Zn4B6O... 13 Research on Zn4B6O has mainly focused on crystal structure analysis and basic optical property characterization; there are no reports on its use as a long-afterglow luminescent material. The question remains: can Zn4B6O be made luminescent without introducing external luminescent ions? 13 The ability of single crystals to exhibit blue light emission and long, visible afterglow at room temperature, while simultaneously achieving the controllable preparation of large-size transparent single crystals, remains an unsolved technical challenge in this field. Existing undoped inorganic crystal materials typically have short luminescence lifetimes, making it difficult to maintain a visible afterglow for tens of seconds after excitation ceases. The fundamental reason for this is the lack of effective intrinsic trap energy levels or insufficient trap concentration, which prevents efficient carrier trapping and slow release at room temperature.
[0006] In summary, how can we develop a Zn4B6O3 variety that combines long blue light afterglow performance with good crystal quality without relying on rare earth or transition metal doping? 13 The development of single-crystal materials and the establishment of a stable method for preparing large-size transparent single crystals are technical problems that urgently need to be solved in this field. Summary of the Invention
[0007] In view of this, the present invention addresses the technical deficiencies of the prior art by providing an undoped blue light long-persistence Zn4B6O that combines long blue light persistence performance with good crystal quality. 13 Single crystal materials and their preparation methods.
[0008] To solve the above problems, this application adopts the following technical solution: One of the objectives of this application is to provide a doped blue light long-persistence Zn4B6O 13 Single-crystal material, wherein the chemical composition of the single-crystal material is Zn4B6O 13 The single-crystal material does not contain rare earth ions or transition metal ions that serve as luminescent or sensitizing centers; the Zn4B6O 13 Single-crystal materials emit blue light when excited by ultraviolet light and have a long afterglow of visible blue light after excitation stops.
[0009] In some embodiments, the Zn4B6O 13 The single-crystal material exhibits blue light emission under 258 nm ultraviolet light excitation, with the main emission peak at room temperature located at 437 nm; after excitation is stopped at 255 nm ultraviolet light, afterglow emission can still be observed for tens of seconds.
[0010] One of the objectives of this application is to provide a doped blue light long-persistence Zn4B6O 13 The preparation method of single-crystal materials includes the following steps: Step S1, the zinc-containing compound and the boron-containing compound are mixed according to Zn4B6O 13 The stoichiometric ratios are mixed, the mixture is placed in a crucible, and then heated in a crystal growth furnace until it melts. The melt is stirred and homogenized to obtain a homogeneous melt. Step S2: Cool the homogeneous melt obtained in step S1 to the crystallization temperature, and then apply Zn4B6O... 13 Seed crystals are introduced to the surface of the melt; Step S3: Single crystal growth is performed under slow cooling conditions. After growth, the crystal is removed and cooled to room temperature to obtain Zn4B6O. 13 Single crystal.
[0011] In some embodiments, in step S1, the zinc-containing compound is ZnO and the boron-containing compound is H3BO3.
[0012] In some embodiments, in step S1, the purity of both ZnO and H3BO3 is above 99.99%; the melting temperature is 1000 ℃, and the heating rate is 1 ℃ / min.
[0013] In some embodiments, in step S1, the stirring and homogenization rate is 25 rpm and the stirring time is 3 days.
[0014] In some embodiments, in step S2, the seed crystal temperature is 917 °C; the seed crystal is a pre-grown Zn4B6O. 13 Single crystal.
[0015] In some embodiments, in step S3, the cooling rate during crystal growth is 1 °C / 200 h, and the growth time is 15 days.
[0016] In some embodiments, in step S3, the seed crystal is also rotated during the single crystal growth process, and the seed crystal rotation speed is maintained at 5-20 rpm.
[0017] In some embodiments, in step S3, after growth is completed, the temperature is cooled to room temperature at a rate of 10 °C / h.
[0018] In some embodiments, in step S1, the crucible is a platinum crucible; in step S3, the obtained Zn4B6O 13 The single crystal size reaches 60 mm × 60 mm × 38 mm.
[0019] The third objective of this application is to provide a doped blue light long-persistence Zn4B6O as described above.13 Undoped blue long-afterglow Zn4B6O prepared by the single crystal material or the preparation method described above 13 Applications of single-crystal materials in photoelectric detection, information storage, or display lighting.
[0020] The present application adopts the above technical solution, and its beneficial effects are as follows: The undoped blue light long afterglow Zn4B6O provided in this application 13 Single-crystal material, wherein the chemical composition of the single-crystal material is Zn4B6O 13 The single-crystal material does not contain rare earth ions or transition metal ions that serve as luminescent or sensitizing centers; the Zn4B6O 13 The single-crystal material emits blue light under ultraviolet light excitation and has a long visible blue light afterglow after excitation stops. It can be used as a new type of undoped blue light long afterglow single-crystal material. Compared with long afterglow materials that rely on external doping, the material composition of this invention is simple, the raw materials are readily available, and the crystal growth process is controllable. It can provide a new material option for applications such as anti-counterfeiting labels, night indicators, ultraviolet responsive light-emitting devices, optical information storage, and photoelectric detection.
[0021] This application also provides an undoped blue light long afterglow Zn4B6O 13 Preparation method of single crystal material, Zn4B6O obtained in this invention 13 The preparation of single crystals does not require the introduction of exogenous rare earth ions or transition metal ions, thus avoiding problems such as uneven distribution of doped ions, additional lattice distortion, and batch-to-batch luminescence performance fluctuations, which is beneficial for obtaining high-optical-quality single crystals. This invention uses a seed crystal-assisted melt growth method to prepare large-size transparent Zn4B6O. 13 Single crystals have a well-defined process route and can produce large-sized, transparent single crystal materials without obvious macroscopic inclusions. Attached Figure Description
[0022] To more clearly illustrate the technical solutions of the embodiments of this application, the drawings used in the description of the embodiments of this application or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.
[0023] Figure 1 The undoped blue light long-persistence Zn4B6O provided in the embodiments of the present invention 13 A flowchart illustrating the steps involved in preparing single-crystal materials.
[0024] Figure 2 The undoped blue light long-persistence Zn4B6O provided in the embodiments of the present invention 13 Single crystal photograph.
[0025] Figure 3 The undoped blue light long-persistence Zn4B6O provided in the embodiments of the present invention 13 X-ray diffraction peak pattern of single-crystal material ground into powder.
[0026] Figure 4 Zn4B6O provided for embodiments of the present invention 13 Room temperature fluorescence emission spectrum of a single crystal under 258 nm ultraviolet light excitation.
[0027] Figure 5 Zn4B6O provided for embodiments of the present invention 13 Long afterglow lifetime test curve of single crystal. Detailed Implementation
[0028] The embodiments of this application are described in detail below. Examples of these embodiments are shown in the accompanying drawings, wherein the same or similar reference numerals denote the same or similar elements or elements having the same or similar functions throughout. The embodiments described below with reference to the accompanying drawings are exemplary and intended to explain this application, and should not be construed as limiting this application. In the description of this application, it should be understood that the terms "upper", "lower", "horizontal", "inner", "outer", etc., indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings, and are only for the convenience of describing this application and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation, and therefore should not be construed as a limitation of this application. Furthermore, the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of this application, "multiple" means two or more, unless otherwise explicitly specified. To make the objectives, technical solutions, and advantages of this application clearer, the following detailed description is provided in conjunction with the accompanying drawings and embodiments.
[0029] The undoped blue light long-persistence Zn4B6O provided by this invention 13 Single-crystal material, wherein the chemical composition of the single-crystal material is Zn4B6O 13 The single-crystal material does not contain rare earth ions or transition metal ions that serve as luminescent or sensitizing centers; the Zn4B6O 13 Single-crystal materials emit blue light when excited by ultraviolet light and have a long afterglow of visible blue light after excitation stops.
[0030] This embodiment defines an undoped Zn4B6O13 The single-crystal material has a clearly defined chemical composition of Zn4B6O. 13 Furthermore, it excludes rare earth ions and transition metal ions as luminescent or sensitizing centers; it also defines the functional characteristics of the material, which emits blue light under ultraviolet light excitation and exhibits a long visible blue afterglow after excitation is stopped, thus eliminating the dependence on rare earth elements (such as Eu²⁺). + Dy³ + ) and transition metals (such as Mn²) + Cr³ + The dopant significantly reduces raw material costs and avoids the risk of price fluctuations in dopants; the absence of external ions avoids batch-to-batch fluctuations in luminescence performance caused by uneven doping; it eliminates lattice distortion and stress field caused by doping, reduces the density of internal crystal defects, and lays the foundation for obtaining high-optical-quality single crystals; and for the first time, it achieves long blue light persistence through intrinsic defects / traps in the material itself, expanding the technical path for achieving long persistence in doped systems.
[0031] In some embodiments, the Zn4B6O 13 The single-crystal material exhibits blue light emission under 258 nm ultraviolet light excitation, with the main emission peak at room temperature located at 437 nm; after excitation is stopped at 255 nm ultraviolet light, afterglow emission can still be observed for tens of seconds.
[0032] The undoped blue light long afterglow Zn4B6O provided in this application 13 Single-crystal material, wherein the chemical composition of the single-crystal material is Zn4B6O 13 The single-crystal material does not contain rare earth ions or transition metal ions that serve as luminescent or sensitizing centers; the Zn4B6O 13 The single-crystal material emits blue light under ultraviolet light excitation and has a long visible blue light afterglow after excitation stops. It can be used as a new type of undoped blue light long afterglow single-crystal material. Compared with long afterglow materials that rely on external doping, the material composition of this invention is simple, the raw materials are readily available, and the crystal growth process is controllable. It can provide a new material option for applications such as anti-counterfeiting labels, night indicators, ultraviolet responsive light-emitting devices, optical information storage, and photoelectric detection.
[0033] Please see Figure 1 This application also provides an undoped blue light long afterglow Zn4B6O 13 The method for preparing single-crystal materials includes the following steps S1 to S3, and the implementation of each step is described in detail below.
[0034] Step S1, the zinc-containing compound and the boron-containing compound are mixed according to Zn4B6O 13 The stoichiometric ratios are mixed, the mixture is placed in a crucible, and then heated in a crystal growth furnace until it melts. The melt is stirred and homogenized to obtain a homogeneous melt.
[0035] Specifically, in step S1, the zinc-containing compound is ZnO, and the boron-containing compound is H3BO3.
[0036] It is understandable that ZnO and H3BO3 are both common high-purity chemical raw materials, widely available and inexpensive; the decomposition reaction of the two at high temperatures is mild (H3BO3 gradually dehydrates to B2O3), making it easy to control the stoichiometric ratio and reduce component volatilization loss.
[0037] Furthermore, in step S1, the purity of both ZnO and H3BO3 is above 99.99%; the melting temperature is 1000℃, and the heating rate is 1℃ / min.
[0038] Understandably, high-purity raw materials (4N grade) minimize the quenching effect of impurity ions on long-afterglow luminescence, ensuring that the observed afterglow originates from intrinsic material defects rather than accidental impurities; a melting temperature of 1000℃ combined with a slow heating rate of 1℃ / min ensures complete melting without causing compositional deviation due to excessively rapid heating and violent decomposition and volatilization of H3BO3, thus guaranteeing the accuracy of the melt composition.
[0039] Furthermore, in step S1, the stirring and homogenization rate is 25 rpm, and the stirring time is 3 days.
[0040] It is understandable that long-term (3 days) low-speed (25 rpm) stirring makes the high-viscosity borate melt reach molecular-level uniformity and eliminate local concentration gradients. The uniform melt is a prerequisite for the subsequent growth of optically uniform single crystals without inclusions or streaks, which directly determines the crystal transparency and optical quality.
[0041] Further, in step S1, the crucible is a platinum crucible; in step S3, the obtained Zn4B6O 13 The single crystal size reaches 60 mm × 60 mm × 38 mm.
[0042] It is understandable that platinum crucibles are heat-resistant (>1000℃) and chemically inert, and do not react with Zn4B6O. 13 The melt reaction avoids contamination of the melt by crucible components; in addition, it clearly achieves large-size transparent single crystals at the centimeter level (60×60×38 mm), directly proving that the method has good scalability and repeatability, and meets the engineering requirements of practical device applications for crystal macroscopic size and processing.
[0043] Step S2: Cool the homogeneous melt obtained in step S1 to the crystallization temperature, and then apply Zn4B6O... 13 Seed crystals are introduced onto the surface of the melt.
[0044] Furthermore, in step S2, the seed crystal temperature is 917 ℃; the seed crystal is pre-grown Zn4B6O. 13 Single crystal.
[0045] Understandably, precisely controlling the temperature to 917℃ near the melting point ensures that the seed crystal neither completely melts back nor reaches thermal equilibrium with the melt, which is the key thermodynamic window for successful crystal introduction. The homogeneous seed crystal and the growing crystal lattice are perfectly matched, avoiding lattice mismatch and stress caused by the introduction of heterogeneous seed crystals, thus ensuring the continuity of growth and the integrity of the crystal.
[0046] Step S3: Single crystal growth is performed under slow cooling conditions. After growth, the crystal is removed and cooled to room temperature to obtain Zn4B6O. 13 Single crystal.
[0047] Furthermore, in step S3, the cooling rate during crystal growth is 1 ℃ / 200 h, and the growth time is 15 days.
[0048] It is understandable that the ultra-slow cooling rate (average 0.005℃ / h) provides a very weak thermodynamic driving force for crystal growth, keeping the solid-liquid interface in a near-equilibrium state, which greatly suppresses parasitic nucleation and dendrite growth, and is the core means to obtain centimeter-sized single crystals; the long growth time of 15 days ensures that the crystal has sufficient time for radial and axial expansion to reach the target size.
[0049] Specifically, in step S3, the seed crystal is rotated during the single crystal growth process, and the seed crystal rotation speed is maintained at 5-20 rpm.
[0050] It is understandable that rotation generates forced convection, stirring the melt to improve the radial symmetry of the temperature and concentration fields; under dynamic growth conditions, the solid-liquid interface tends to flatten, effectively reducing the thickness of the solute boundary layer, lowering the probability of macroscopic inclusions and microscopic stripes, and improving the optical uniformity of the crystal.
[0051] Specifically, in step S3, after growth is completed, the temperature is cooled to room temperature at a rate of 10 °C / h.
[0052] It is understandable that slow, controlled cooling allows for the gradual release of internal thermal stress in the crystal, avoiding cracking, dislocation multiplication, and thermal shock damage caused by rapid cooling. This cooling rate balances annealing efficiency and crystal integrity, ensuring that the final product is a transparent, crack-free single crystal. The undoped blue-light long-persistence Zn4B6O provided in the above embodiments of this application... 13 Preparation method of single crystal material, Zn4B6O obtained in this invention 13The preparation of single crystals does not require the introduction of exogenous rare earth ions or transition metal ions, thus avoiding problems such as uneven distribution of doped ions, additional lattice distortion, and batch-to-batch luminescence performance fluctuations, which is beneficial for obtaining high-optical-quality single crystals. This invention uses a seed crystal-assisted melt growth method to prepare large-size transparent Zn4B6O. 13 Single crystals have a well-defined process route and can produce large-sized, transparent single crystal materials without obvious macroscopic inclusions.
[0053] This application provides a doped blue light long afterglow Zn4B6O as described above. 13 Undoped blue long-afterglow Zn4B6O prepared by the single crystal material or the preparation method described above 13 Applications of single-crystal materials in photoelectric detection, information storage, or display lighting.
[0054] Specifically, in the field of photoelectric detection, its ultraviolet-excited blue afterglow can be used as a fluorescence conversion layer in deep ultraviolet / vacuum ultraviolet detectors; in the field of information storage, utilizing the optical behavior of "ultraviolet writing → afterglow reading," it can be used as an optical information storage medium to realize data writing and reading; in the field of display and lighting, its blue light emission can be used as an emergency indicator lighting or night-light display material without the need for continuous external power supply; by limiting its applications, the material's performance advantages are linked to specific industrial applications, clarifying the industrialization value and commercial prospects of the technical solution.
[0055] The technical solutions described above in this application will be explained in detail below with reference to specific embodiments.
[0056] Example 1: Zn4B6O 13 Preparation of single crystals.
[0057] Weigh out ZnO and H3BO3, both with a purity of 99.99%, and prepare Zn4B6O. 13 The stoichiometric mixture was placed in a 120 mm diameter platinum crucible and then placed in a temperature-controlled crystal growth furnace. The furnace temperature was increased to 1000 °C at a rate of 1 °C / min to completely melt the raw materials. The mixture was then stirred at 25 rpm for 3 days to ensure a homogeneous melt. After stirring, the melt was cooled to 917 °C at a rate of 5 °C / min, and a pre-grown Zn₄B₆O₃ crystal with dimensions of approximately 6 mm × 6 mm × 10 mm was formed. 13 A seed crystal was introduced onto the melt surface. During crystal growth, the temperature was slowly decreased at a rate of 1℃ / 200 h, and the seed crystal rotation speed was maintained at 5-20 rpm. After approximately 15 days of growth, the resulting crystal was removed and cooled to room temperature at a rate of 10℃ / h to obtain Zn4B6O. 13 Single crystal.
[0058] Please see Figure 2The undoped blue long-afterglow Zn4B6O prepared in Example 1 is shown. 13 Single-crystal photograph. (By...) Figure 2 It can be seen that the obtained Zn4B6O 13 The single crystals are transparent and massive in shape, with relatively large crystal sizes and no obvious macroscopic cracks or inclusions, indicating that the above-mentioned seed crystal-assisted melt growth method can obtain Zn4B6O with good transparency and integrity. 13 Single-crystal materials.
[0059] Example 2: Zn4B6O 13 Phase characterization of single crystals.
[0060] Take the Zn4B6O obtained in Example 1 13 Single-crystal samples were ground into powder and then subjected to powder X-ray diffraction analysis. (See also...) Figure 3 Zn4B6O prepared in Example 1 13 X-ray diffraction peak pattern of a single crystal after being ground into powder. Figure 3 It can be seen that the experimentally measured diffraction peak positions are related to Zn4B6O 13 Corresponding to the characteristic diffraction peaks, no obvious diffraction peaks of ZnO or other zinc borate impurities were observed, indicating that the prepared single crystal is Zn4B6O. 13 It is a crystalline phase with high phase purity.
[0061] Example 3: Zn4B6O 13 Fluorescence emission performance test of single crystal.
[0062] Take the Zn4B6O obtained in Example 1 13 Single-crystal samples were subjected to steady-state fluorescence testing at room temperature. Under 258 nm UV excitation, the samples exhibited blue light emission, with the main emission peak located at approximately 437 nm. This result indicates that Zn₄B₆O₃ without externally emitted ion doping... 13 Single crystals can emit blue light when excited by ultraviolet light.
[0063] Example 4: Zn4B6O 13 Long afterglow lifetime test of single crystal.
[0064] Take the Zn4B6O obtained in Example 1 13 The single-crystal sample was excited under 255 nm ultraviolet light for 10 s, and the blue afterglow decay curve was recorded. The results indicate that the undoped Zn4B6O... 13 Single crystals retain long afterglow of visible blue light even after ultraviolet light excitation is stopped.
[0065] Please see Figure 4 Zn4B6O prepared for the example 13The room-temperature fluorescence emission spectrum of the single crystal under 258 nm ultraviolet light excitation. The red curve in the figure represents Zn4B6O. 13 The emission intensity of a single crystal varies with the emission wavelength. (From...) Figure 4 It can be seen that Zn4B6O 13 The single crystal emits strong blue light when excited by ultraviolet light, with the main emission peak located at approximately 437 nm.
[0066] Please see Figure 5 Zn4B6O prepared for the example 13 The long afterglow lifetime test curve of single crystal Zn4B6O is shown in the figure. The pink dots in the figure represent the Zn4B6O after UV excitation is stopped. 13 The decay of single-crystal luminescence intensity over time. Figure 5 It can be seen that the luminescence intensity of the material continuously decreases after excitation is stopped, and afterglow signals can still be detected over a relatively long period of time, indicating that the Zn4B6O 13 Single crystals exhibit significant long afterglow luminescence properties.
[0067] The above are merely preferred embodiments of this application, and only specifically describe the technical principles of this application. These descriptions are only for explaining the principles of this application and should not be construed as limiting the scope of protection of this application in any way. Based on this explanation, any modifications, equivalent substitutions, and improvements made within the spirit and principles of this application, as well as other specific embodiments of this application that can be conceived by those skilled in the art without creative effort, should be included within the scope of protection of this application.
Claims
1. A doped blue light long afterglow Zn4B6O 13 Single crystal material, characterized in that, The chemical composition of the single crystal material is Zn4B6O. 13 The single-crystal material does not contain rare-earth ions or transition metal ions that serve as luminescent or sensitizing centers; the Zn4B6O 13 Single-crystal materials emit blue light when excited by ultraviolet light and have a long afterglow of visible blue light after excitation stops.
2. The undoped blue light long afterglow Zn4B6O according to claim 1 13 Single crystal material, characterized in that, The Zn4B6O 13 The single-crystal material exhibits blue light emission under 258 nm ultraviolet light excitation, with the main emission peak at room temperature located at 437 nm; after excitation is stopped at 255 nm ultraviolet light, afterglow emission can still be observed for tens of seconds.
3. A doped blue light long afterglow Zn4B6O as described in claim 1 or 2 13 The method for preparing single-crystal materials is characterized by, Includes the following steps: Step S1, the zinc-containing compound and the boron-containing compound are mixed according to Zn4B6O 13 The stoichiometric ratios are mixed, the mixture is placed in a crucible, and then heated to the point of melting in a crystal growth furnace. The melt is stirred and homogenized to obtain a homogeneous melt. Step S2: Cool the homogeneous melt obtained in step S1 to the crystallization temperature, and then apply Zn4B6O... 13 Seed crystals are introduced to the surface of the melt; Step S3: Single crystal growth is performed under slow cooling conditions. After growth, the crystal is removed and cooled to room temperature to obtain Zn4B6O. 13 Single crystal.
4. The preparation method according to claim 3, characterized in that, In step S1, the zinc-containing compound is ZnO, and the boron-containing compound is H3BO3.
5. The preparation method according to claim 4, characterized in that, In step S1, the purity of both ZnO and H3BO3 is above 99.99%; the melting temperature is 1000 ℃, and the heating rate is 1 ℃ / min.
6. The preparation method according to claim 3, characterized in that, In step S1, the stirring and homogenization rate is 25 rpm, and the stirring time is 3 days.
7. The preparation method according to claim 3, characterized in that, In step S2, the seed crystal temperature is 917℃; the seed crystal is a pre-grown Zn4B6O. 13 Single crystal.
8. The preparation method according to claim 3, characterized in that, In step S3, the cooling rate during crystal growth is 1 ℃ / 200 h, and the growth time is 15 days.
9. The preparation method according to claim 3, characterized in that, In step S3, the seed crystal is rotated during the single crystal growth process, and the seed crystal rotation speed is maintained at 5-20 rpm.
10. The preparation method according to claim 3, characterized in that, In step S3, after growth is completed, the temperature is cooled to room temperature at a rate of 10°C / h.
11. The preparation method according to claim 3, characterized in that, In step S1, the crucible is a platinum crucible; in step S3, the obtained Zn4B6O 13 The single crystal size reaches 60 mm × 60 mm × 38 mm.
12. The undoped blue light long afterglow Zn4B6O according to claim 1 or 2 13 Single crystal material or undoped blue long afterglow Zn4B6O prepared by any one of claims 3 to 11 13 Applications of single-crystal materials in photoelectric detection, information storage, or display lighting.