CN110541198A - A europium ion-doped fluoride crystal whose display color gamut can be adjusted in a large range and its preparation method - Google Patents

A europium ion-doped fluoride crystal whose display color gamut can be adjusted in a large range and its preparation method Download PDF

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CN110541198A
CN110541198A CN201810534216.4A CN201810534216A CN110541198A CN 110541198 A CN110541198 A CN 110541198A CN 201810534216 A CN201810534216 A CN 201810534216A CN 110541198 A CN110541198 A CN 110541198A
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crystal
europium ion
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苏良碧
于浩
钱晓波
王静雅
姜大朋
张博
吴庆辉
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Shanghai Institute of Ceramics of CAS
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    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
    • C09K11/7732—Halogenides
    • C09K11/7733—Halogenides with alkali or alkaline earth metals
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    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
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Abstract

The invention provides a europium ion doped fluoride crystal with a display color gamut capable of being regulated and controlled in a large range and a preparation method thereof, wherein the chemical formula of the europium ion doped fluoride crystal is Eu: MF2, wherein the europium ion Eu comprises divalent europium ion Eu2+ and trivalent europium ion Eu3+, M is Ca or Sr, and the doping concentration of the europium ion Eu is 0.1at% to 20.0 at%.

Description

一种显示色域可大范围调控的铕离子掺杂氟化物晶体及其制 备方法A europium ion-doped fluoride crystal whose display color gamut can be adjusted in a large range and its preparation preparation method

技术领域technical field

本发明涉及一种显示色域可大范围调控的铕离子掺杂氟化物晶体及其制备方法，具体涉及到一种包含二价铕离子Eu2+和三价铕离子Eu3+掺杂的氟化物激光晶体及其制备方法，属于人工晶体和发光与显示材料领域。The invention relates to a europium ion-doped fluoride crystal whose display color gamut can be adjusted in a large range and a preparation method thereof, in particular to a fluorine doped with divalent europium ions Eu 2+ and trivalent europium ions Eu 3+ The invention discloses a compound laser crystal and a preparation method thereof, which belong to the field of artificial crystals and light-emitting and display materials.

背景技术Background technique

自上世纪60年代世界上第一台红宝石激光器诞生以来，激光以其优异的特性，广泛的应用于军事和国民生活当中。与我们更加息息相关的是可见光激光在显示领域的应用。相对于传统的CRT、LCD乃至LED技术而言，激光显示具有其独特的优势。其具有大色域、双高清(几何、颜色)视频图像显示和真三维显示的优点，被国际业界视为人类视觉史上的革命。作为一种新型显示技术，其在大屏幕激光家庭影院、数字电影、军事指挥、展览展示、便携显示终端以及空间科学等领域有着广泛的应用。Since the birth of the world's first ruby laser in the 1960s, lasers have been widely used in military and national life due to their excellent characteristics. What is more closely related to us is the application of visible light lasers in the display field. Compared with traditional CRT, LCD and even LED technologies, laser display has its unique advantages. It has the advantages of large color gamut, double high-definition (geometry, color) video image display and true three-dimensional display, and is regarded by the international industry as a revolution in the history of human vision. As a new type of display technology, it is widely used in large-screen laser home theaters, digital movies, military command, exhibitions, portable display terminals, and space science.

目前主流的投影机的方案是DLP和3LCD技术，其中3LCD是将红、绿、蓝三色液晶板上，通过透镜放大和反光镜透射出。而DLP工作方式则将光线通过色轮高速旋转后颜色混合，最后经过棱镜透射出。两种方案都需要红绿蓝三基色激光作为光源，即需要三种可见激光晶体分别泵浦产生可见光激光，系统具有一定的复杂性。The current mainstream projector solutions are DLP and 3LCD technologies, in which 3LCD uses red, green, and blue three-color liquid crystal panels, which are magnified by lenses and transmitted by mirrors. The DLP working method is to mix the light through the high-speed rotation of the color wheel, and finally transmit it through the prism. Both schemes require red, green, and blue primary color lasers as light sources, that is, three visible laser crystals are required to be pumped separately to generate visible light lasers, and the system has certain complexity.

发明内容Contents of the invention

一方面，本发明提供了一种铕离子掺杂氟化物晶体，所述铕离子掺杂氟化物晶体的化学式为Eu:MF2，其中铕离子Eu包含二价铕离子Eu2+和三价铕离子Eu3+，M为Ca或Sr，所述铕离子Eu的掺杂浓度为0.1at％～20.0at.％，优选为0.2at％～8at％。In one aspect, the present invention provides a europium ion-doped fluoride crystal, the chemical formula of the europium ion-doped fluoride crystal is Eu:MF 2 , wherein the europium ion Eu comprises divalent europium ion Eu 2+ and trivalent europium ion The ion Eu 3+ , M is Ca or Sr, and the doping concentration of the europium ion Eu is 0.1 at% to 20.0 at.%, preferably 0.2 at% to 8 at%.

二价铕离子Eu2+和三价铕离子Eu3+掺杂的氟化钙晶体或氟化锶晶体具有较宽的发射光谱，且二价铕离子Eu2+和三价铕离子Eu3+吸收波段在一定范围内重合。通过调节铕离子(Eu2+和Eu3+)浓度，或通过调节激发波长(300～400nm)，获得实现从蓝光到红橙光的色域调控。Divalent europium ions Eu 2+ and trivalent europium ions Eu 3+ doped calcium fluoride crystals or strontium fluoride crystals have a broad emission spectrum, and divalent europium ions Eu 2+ and trivalent europium ions Eu 3+ The absorption bands overlap within a certain range. By adjusting the concentration of europium ions (Eu 2+ and Eu 3+ ), or by adjusting the excitation wavelength (300-400nm), the color gamut control from blue light to red-orange light can be achieved.

较佳地，所述铕离子Eu的掺杂浓度为0.1at％～10.0at.％，优选为0.1at％～8at.％。Preferably, the doping concentration of the europium ions Eu is 0.1 at% to 10.0 at.%, preferably 0.1 at% to 8 at.%.

较佳地，所述二价铕离子Eu2+和三价铕离子Eu3+的摩尔浓度比为(1～10)：1，优选为(2～7):1。本发明在不同Eu整体浓度下时，采用同一激发波长，利用不同Eu2+和Eu3+离子浓度比例，可以获得大范围，即从蓝光到红光的色域调控，扩大比例范围，可以使得调控范围更大。提高Eu浓度可以使得Eu3+所占浓度比例逐渐升高，这是因为CaF2或 SrF2晶体的特殊结构。在CaF2或SrF2中掺入少量Eu3+离子时，晶体中Vca°会将Eu3+还原为 Eu2+，使得此时Eu2+浓度较高。随着Eu掺杂量提高，CaF2或SrF2中缺陷数量较少，且Eu3+相比Eu2+更加稳定，故而Eu3+→Eu2+这一过程被削弱，导致Eu3+离子占主导，进而使得光谱色域从蓝光区向红光区移动。Preferably, the molar concentration ratio of divalent europium ions Eu 2+ to trivalent europium ions Eu 3+ is (1-10):1, preferably (2-7):1. The present invention adopts the same excitation wavelength and different Eu 2+ and Eu 3+ ion concentration ratios under different Eu overall concentrations to obtain a large range, that is, the color gamut control from blue light to red light, and expand the ratio range, which can make The control range is larger. Increasing the concentration of Eu can make the concentration ratio of Eu3+ gradually increase, which is because of the special structure of CaF 2 or SrF 2 crystals. When a small amount of Eu3+ ions are doped into CaF 2 or SrF 2 , V ca° in the crystal will reduce Eu 3+ to Eu 2+ , making the concentration of Eu 2+ higher at this time. With the increase of Eu doping amount, the number of defects in CaF 2 or SrF 2 is less, and Eu 3+ is more stable than Eu 2+ , so the process of Eu 3+ →Eu 2+ is weakened, resulting in Eu 3+ ions Dominant, which in turn shifts the spectral color gamut from blue to red.

较佳地，所述氟化物激光晶体在近紫外波段300～400nm激发下，具有Eu2+离子400nm～450nm，Eu3+离子550nm～700nm荧光峰。CaF2或SrF2晶体中在掺入稀土离子Eu 后，会形成多种发光中心(例如，Eu2+离子可以提供提供蓝光发光，与此同时，Eu3+离子可以提供红橙光发光)，即表现为较宽的吸收和发射光谱，采用300-400nm波长范围激发，可以获得大范围的色域范围调控。Preferably, the fluoride laser crystal has fluorescence peaks at 400nm-450nm for Eu 2+ ions and 550nm-700nm for Eu 3+ ions under near-ultraviolet excitation at 300-400nm. After doping rare earth ion Eu in CaF 2 or SrF 2 crystal, a variety of luminescent centers will be formed (for example, Eu 2+ ions can provide blue light emission, and at the same time, Eu 3+ ions can provide red-orange light emission), That is to say, it is characterized by a wide absorption and emission spectrum, and the excitation in the wavelength range of 300-400nm can obtain a wide range of color gamut regulation.

另一方面，本发明还提供了一种如上所述的铕离子掺杂氟化物晶体的制备方法，根据化学式Eu:MF2称取原料粉体EuF3和MF2，采用熔体法在空气气氛中生长所述铕离子掺杂氟化物晶体。On the other hand, the present invention also provides a method for preparing europium ion-doped fluoride crystals as described above. According to the chemical formula Eu:MF 2 , the raw material powders EuF 3 and MF 2 are weighed, and the melt method is used in an air atmosphere. The europium ion-doped fluoride crystals were grown in .

本发明中，采用熔体法在空气气氛中生长所述铕离子掺杂氟化物晶体，使得铕离子掺杂氟化物晶体受生长气氛(空气气氛)的影响发生变价，导致二价铕离子Eu2+和三价铕离子Eu3+共存于基质晶体当中。以CaF2作为示例说明反应机理，原料中Eu3+离子进入CaF2晶体中，取代Ca2+离子。为了保持电价平衡，两个Eu3+离子应取代三个Ca2+离子，同时产生 Vca”及Euca·并分别作为施主和受主，具体过程如公式(1)-(3)中描述：In the present invention, the europium ion-doped fluoride crystal is grown in an air atmosphere by a melt method, so that the valence of the europium ion-doped fluoride crystal is affected by the growth atmosphere (air atmosphere), resulting in divalent europium ion Eu 2 + and trivalent europium ions Eu 3+ coexist in the host crystal. Taking CaF 2 as an example to illustrate the reaction mechanism, Eu 3+ ions in the raw material enter into the CaF 2 crystal and replace Ca 2+ ions. In order to maintain the price balance, two Eu 3+ ions should replace three Ca 2+ ions, and at the same time Vca” and Euca should be generated as donors and acceptors respectively. The specific process is described in formulas (1)-(3):

较佳地，在原料粉体中加入PbF2作为除氧剂，所述PbF2的加入量是MF2的0.1～2.0wt％。Preferably, PbF 2 is added to the raw material powder as an oxygen scavenger, and the amount of PbF 2 added is 0.1-2.0 wt% of MF 2 .

较佳地，采用坩埚下降法生长晶体，坩埚材料采用高纯石墨或铂金。较佳地，所述坩埚下降法的参数包括：生长温度1300～1400℃；生长时间100～300小时；坩埚下降速率0.02～1.5mm/小时。Preferably, the crucible drop method is used to grow the crystal, and the material of the crucible is high-purity graphite or platinum. Preferably, the parameters of the crucible lowering method include: a growth temperature of 1300-1400° C.; a growth time of 100-300 hours; and a crucible lowering rate of 0.02-1.5 mm/hour.

较佳地，坩埚底部不加入籽晶、或放入采用经X射线衍射仪定向端面法线方向为[111] 的Eu:MF2单晶棒作为籽晶。Preferably, no seed crystal is added to the bottom of the crucible, or a Eu:MF 2 single crystal rod oriented with the end face normal direction [111] through the X-ray diffractometer is used as the seed crystal.

本发明中，利用二价铕离子Eu2+和三价铕离子Eu3+共存于CaF2(SrF2)晶体基质之中且二者吸收波段具有较大范围重叠的特性，(1)通过调节铕离子(Eu2+和Eu3+)浓度，获得在同一激发波长下实现从蓝光到红橙光的色域调控的激光晶体；(2)通过调节激发波长，在同一铕离子浓度(Eu2+和Eu3+)晶体中，获得实现从蓝光到红橙光的色域调控的激光晶体。本发明中，Eu:CaF2(SrF2)晶体属于碱土金属基质，当稀土离子掺入CaF2(SrF2) 时，三价稀土离子取代钙离子格位，会产生间隙氟离子以平衡电荷。由于间隙氟离子位置不确定，故而稀土掺杂CaF2(SrF2)晶体表现出多格位共存，进而使得其具有较宽的吸收及发射光谱。In the present invention, divalent europium ions Eu 2+ and trivalent europium ions Eu 3+ coexist in the CaF 2 (SrF 2 ) crystal matrix, and the absorption bands of the two have a large overlapping characteristic, (1) by adjusting Europium ion (Eu 2+ and Eu 3+ ) concentration, to obtain a laser crystal that realizes color gamut control from blue light to red-orange light at the same excitation wavelength; (2) By adjusting the excitation wavelength, the same europium ion concentration (Eu 2 + and Eu 3+ ) crystals, a laser crystal that realizes color gamut regulation from blue light to red-orange light is obtained. In the present invention, the Eu:CaF 2 (SrF 2 ) crystal belongs to alkaline earth metal matrix. When rare earth ions are doped into CaF 2 (SrF 2 ), trivalent rare earth ions replace calcium ion sites, and interstitial fluorine ions are generated to balance charges. Since the position of interstitial fluorine ions is uncertain, the rare earth doped CaF 2 (SrF 2 ) crystal exhibits multi-site coexistence, which makes it have a broad absorption and emission spectrum.

附图说明Description of drawings

图1a为x at.％Eu:CaF2(x＝0.6,1.2,3.0,6.0)晶体在398nm激发下的室温发射光谱；Figure 1a is the room temperature emission spectrum of x at.%Eu:CaF 2 (x=0.6, 1.2, 3.0, 6.0) crystal excited at 398nm;

图1b为图1a中的局部放大图；Figure 1b is a partially enlarged view in Figure 1a;

图2为x at.％Eu:CaF2(x＝0.6,1.2,3.0,6.0)晶体在398nm激发下的室温发射光谱所对应的色域显示图；Fig. 2 is a color gamut display diagram corresponding to the emission spectrum at room temperature of x at.%Eu:CaF 2 (x=0.6, 1.2, 3.0, 6.0) crystal excited at 398nm;

图3为x at.％Eu:CaF2(x＝0.6,1.2,3.0,6.0)晶体在300-400nm波段激发下的室温发射光谱；Fig. 3 is the room temperature emission spectrum of x at.%Eu:CaF 2 (x=0.6, 1.2, 3.0, 6.0) crystal excited in the 300-400nm band;

图4为x at.％Eu:CaF2(x＝0.6,1.2,3.0,6.0)晶体在300-400nm波段激发下室温发射光谱所对应的色域显示图；Fig. 4 is a display diagram of the color gamut corresponding to the room temperature emission spectrum of x at.%Eu:CaF 2 (x=0.6, 1.2, 3.0, 6.0) crystal excited in the 300-400nm band;

图5为实施例6制备的Eu:CaF2(x＝0.2)晶体在398nm激发下的室温发射光谱(a)和在300-400nm波段激发下室温发射光谱所对应的色域显示图(b)；Figure 5 is the room temperature emission spectrum (a) of the Eu:CaF 2 (x=0.2) crystal prepared in Example 6 under excitation at 398nm and the corresponding color gamut display diagram (b) of the emission spectrum at room temperature under excitation at 300-400nm band ;

图6为实施例7制备的Eu:CaF2(x＝10.0)晶体在398nm激发下的室温发射光谱(a)和在300-400nm波段激发下室温发射光谱所对应的色域显示图(b)。Fig. 6 is the room temperature emission spectrum (a) of the Eu:CaF 2 (x=10.0) crystal prepared in Example 7 under the excitation of 398nm and the corresponding color gamut display diagram (b) of the room temperature emission spectrum under the excitation of 300-400nm band .

具体实施方式Detailed ways

以下通过下述实施方式进一步说明本发明，应理解，下述实施方式仅用于说明本发明，而非限制本发明。The present invention will be further described below through the following embodiments. It should be understood that the following embodiments are only used to illustrate the present invention, not to limit the present invention.

本发明中，显示色域可调控的铕离子掺杂氟化物晶体(主要是指氟化钙和氟化锶)的化学式为Eu:CaF2(SrF2)，其中铕离子的掺杂浓度为0.1a.t％-20.0at.％，且铕离子在氟化钙(氟化锶)晶体中同时存在Eu2+和Eu3+两种价态。当M为Ca时，所述铕离子Eu的掺杂浓度为0.1at％～10.0at.％，优选为0.1at％～8at.％。当M为Sr时，所述铕离子Eu的掺杂浓度为0.1at％～10.0at.％，优选为0.1at％～8at.％。其中，二价铕离子Eu2+和三价铕离子Eu3+的摩尔浓度比可为(1～10):1，优选为(2～7):1。在本发明中，氟化物激光晶体在近紫外波段激发下，具有Eu2+离子400nm～450nm，Eu3+离子550nm～700nm荧光峰，各荧光峰强度、峰位及半高宽大小随Eu离子浓度变化而发生变化。通过调节Eu离子浓度及改变激发波长范围(300-400nm)，可以获得从蓝光到红橙光的显示色域范围调控。以下示例性地说明铕离子掺杂氟化物晶体的制备方法。In the present invention, the chemical formula of europium ion-doped fluoride crystals (mainly referring to calcium fluoride and strontium fluoride) with adjustable color gamut is Eu:CaF 2 (SrF 2 ), wherein the doping concentration of europium ions is 0.1 at%-20.0at.%, and europium ions exist in both Eu 2+ and Eu 3+ valence states in calcium fluoride (strontium fluoride) crystals. When M is Ca, the doping concentration of the europium ion Eu is 0.1 at% to 10.0 at.%, preferably 0.1 at% to 8 at.%. When M is Sr, the doping concentration of the europium ion Eu is 0.1 at% to 10.0 at.%, preferably 0.1 at% to 8 at.%. Wherein, the molar concentration ratio of divalent europium ions Eu 2+ to trivalent europium ions Eu 3+ may be (1-10):1, preferably (2-7):1. In the present invention, the fluoride laser crystal has fluorescence peaks of 400nm to 450nm for Eu 2+ ions and 550nm to 700nm for Eu 3+ ions under near-ultraviolet excitation. changes with concentration changes. By adjusting the Eu ion concentration and changing the excitation wavelength range (300-400nm), the display color gamut range from blue light to red orange light can be adjusted. The preparation method of europium ion-doped fluoride crystal is exemplarily described below.

将原料EuF3和CaF2(SrF2)按照摩尔比0.001～0.2：0.76～1.3进行配料，得到原料粉体。在可选的实施方式中，加入质量为CaF2(SrF2)的0.1～2wt％(优选范围为0.5～1wt％)的PbF2作为除氧剂。将原料粉体经过充分研磨混合均匀后装入坩埚内，采用熔体法于坩埚内生长二价铕离子Eu2+和三价铕离子Eu3+共存的Eu:CaF2(SrF2)单晶体。作为一个制备原料粉体的示例，选择初始原料EuF3，CaF2(或SrF2)及PbF2，其中EuF3与CaF2(或 SrF2)按摩尔比m:n进行配料，其中m为0.001～0.2，n为0.76～1.3。PbF2加入的质量为 CaF2(SrF2)质量的0.5～1wt％。The raw material EuF 3 and CaF 2 (SrF 2 ) are mixed according to the molar ratio of 0.001-0.2:0.76-1.3 to obtain the raw material powder. In an optional embodiment, 0.1-2 wt% (preferably 0.5-1 wt%) of PbF 2 is added as an oxygen scavenger with a mass of CaF 2 (SrF 2 ). The raw material powder is fully ground and mixed evenly, and then loaded into a crucible, and a single crystal of Eu:CaF 2 (SrF 2 ) coexisting with divalent europium ions Eu 2+ and trivalent europium ions Eu 3+ is grown in the crucible by the melt method. As an example of preparing raw material powder, select the initial raw materials EuF 3 , CaF 2 (or SrF 2 ) and PbF 2 , where EuF 3 and CaF 2 (or SrF 2 ) are mixed in a molar ratio m:n, where m is 0.001 ~0.2, n is 0.76~1.3. The mass of PbF 2 added is 0.5-1 wt% of the mass of CaF 2 (SrF 2 ).

Eu:CaF2(SrF2)单晶体的生长方法可为坩埚下降法。所用坩埚的材料可为铂金或高纯石墨。坩埚底部不加入籽晶或放入采用经X射线衍射仪定向端面法线方向为[111]的Eu:CaF2 (SrF2)单晶棒作为籽晶。其中，晶体生长在空气中进行，不需要通入特殊气氛。其中坩埚下降法的参数包括：生长温度1300～1400℃；生长时间100～300小时；坩埚下降速率0.02～1.5mm/小时。生长结束后冷却至室温冷却速率可为10～25℃/小时。The method for growing the Eu:CaF 2 (SrF 2 ) single crystal may be the crucible drop method. The material of the crucible used can be platinum or high-purity graphite. No seed crystal was added to the bottom of the crucible, or a Eu:CaF 2 (SrF 2 ) single crystal rod oriented by an X-ray diffractometer with the normal direction of the end face [111] was used as the seed crystal. Among them, the crystal growth is carried out in the air, and no special atmosphere is needed. The parameters of the crucible descent method include: a growth temperature of 1300-1400° C.; a growth time of 100-300 hours; and a crucible descent rate of 0.02-1.5 mm/hour. Cool to room temperature after the growth is over, and the cooling rate can be 10-25° C./hour.

在本发明中，利用铕离子在氟化钙(氟化锶)晶体中同时存在Eu2+和Eu3+两种价态，通过调节氟化钙(氟化锶)晶体中铕离子的浓度以及改变激发光源波长，实现同一浓度晶体在不同激发波长下获得从蓝光到红橙光的显示色域调控，以及不同铕离子掺杂浓度晶体在同一激发波长下(398nm)获得从蓝光到红橙光的显示色域调控。相比传统荧光粉材料，本发明的制备方法简单，制备周期短，使用的原料廉价易得，且实现色域调控方法简单，具有应用价值。In the present invention, two valence states of Eu 2+ and Eu 3+ exist simultaneously in the calcium fluoride (strontium fluoride) crystal by using europium ion, by adjusting the concentration of europium ion in the calcium fluoride (strontium fluoride) crystal and Change the wavelength of the excitation light source to realize the control of the display color gamut from blue light to red-orange light under different excitation wavelengths for crystals with the same concentration, and from blue light to red-orange light under the same excitation wavelength (398nm) for crystals with different europium ion doping concentrations Display color gamut control. Compared with traditional fluorescent powder materials, the preparation method of the present invention is simple, the preparation cycle is short, the raw materials used are cheap and easy to obtain, and the method for realizing color gamut regulation is simple, which has application value.

将Eu:CaF2(SrF2)晶体切割成片，经过光学级抛光后在FLs980荧光光谱仪上测试室温发射光谱，泵浦源采用的波长范围为300-400nm的闪烁氙灯。The Eu:CaF 2 (SrF 2 ) crystal was cut into slices, and after optical grade polishing, the emission spectrum at room temperature was tested on a FLs980 fluorescence spectrometer. The pump source used a flashing xenon lamp with a wavelength range of 300-400nm.

下面进一步例举实施例以详细说明本发明。同样应理解，以下实施例只用于对本发明进行进一步说明，不能理解为对本发明保护范围的限制，本领域的技术人员根据本发明的上述内容作出的一些非本质的改进和调整均属于本发明的保护范围。下述示例具体的工艺参数等也仅是合适范围中的一个示例，即本领域技术人员可以通过本文的说明做合适的范围内选择，而并非要限定于下文示例的具体数值。Examples are given below to describe the present invention in detail. It should also be understood that the following examples are only used to further illustrate the present invention, and should not be construed as limiting the protection scope of the present invention. Some non-essential improvements and adjustments made by those skilled in the art according to the above contents of the present invention all belong to the present invention scope of protection. The specific process parameters and the like in the following examples are only examples of suitable ranges, that is, those skilled in the art can make a selection within a suitable range through the description herein, and are not limited to the specific values exemplified below.

实施例1：坩埚下降法生长0.6at.％Eu:CaF2晶体Embodiment 1: Growth of 0.6at.% Eu:CaF 2 crystals by crucible descending method

按各自配料比例称料，在真空手套箱内充分混合，置于铂金坩埚内。采用坩埚下降法生长晶体，空气气氛中生长，1400℃熔融原料并开始生长，坩埚下降速率为1.5mm/h，120h后晶体生长完毕，然后按20℃/h降温至室温。实施例1中0.6％Eu:CaF2晶体:按比例称量 EuF3(5N)1.59g，CaF2(5N)98.41g，PbF2的加入量是CaF2的1wt％。所得0.6at.％Eu:CaF2晶体中二价铕离子Eu2+和三价铕离子Eu3+的摩尔浓度比为5：1。Weigh the ingredients according to their respective proportions, mix them thoroughly in a vacuum glove box, and place them in a platinum crucible. The crucible descending method is used to grow crystals in an air atmosphere. The raw material is melted at 1400°C and the growth begins. The crucible descending rate is 1.5mm/h. After 120h, the crystal growth is completed, and then the temperature is cooled to room temperature at 20°C/h. 0.6% Eu:CaF 2 crystals in Example 1: EuF 3 (5N) 1.59g, CaF 2 (5N) 98.41g were weighed in proportion, and the amount of PbF 2 added was 1wt% of CaF 2 . The molar concentration ratio of divalent europium ion Eu 2+ and trivalent europium ion Eu 3+ in the obtained 0.6at.% Eu:CaF 2 crystal is 5:1.

实施例2：坩埚下降法生长1.2at.％Eu:CaF2晶体Embodiment 2: Growth of 1.2at.% Eu:CaF 2 crystals by crucible descending method

按各自配料比例称料，在真空手套箱内充分混合，置于铂金坩埚内。采用坩埚下降法生长晶体，空气气氛中生长，1400℃熔融原料并开始生长，坩埚下降速率为1.5mm/h，120h后晶体生长完毕，然后按20℃/h降温至室温。实施例2中1.2％Eu:CaF2晶体:按比例称量 EuF3(5N)3.15g，CaF2(5N)96.85g，PbF2的加入量是CaF2的1wt％。所得1.2at.％Eu:CaF2晶体中二价铕离子Eu2+和三价铕离子Eu3+的摩尔浓度比为4：1。Weigh the ingredients according to their respective proportions, mix them thoroughly in a vacuum glove box, and place them in a platinum crucible. The crucible descending method is used to grow crystals in an air atmosphere. The raw material is melted at 1400°C and the growth begins. The crucible descending rate is 1.5mm/h. After 120h, the crystal growth is completed, and then the temperature is cooled to room temperature at 20°C/h. 1.2% Eu:CaF 2 crystal in Example 2: EuF 3 (5N) 3.15g, CaF 2 (5N) 96.85g were weighed in proportion, and the amount of PbF 2 added was 1wt% of CaF 2 . The molar concentration ratio of divalent europium ion Eu 2+ and trivalent europium ion Eu 3+ in the obtained 1.2at.% Eu:CaF 2 crystal is 4:1.

实施例3：坩埚下降法生长(3.0at.％-5.0at.％)Eu:SrF2晶体Embodiment 3: growing (3.0at.%-5.0at.%) Eu:SrF 2 crystals by crucible descending method

按各自配料比例称料，在真空手套箱内充分混合，置于铂金坩埚内。采用坩埚下降法生长晶体，空气气氛中生长，1400℃熔融原料并开始生长，坩埚下降速率为1.5mm/h，120h后晶体生长完毕，然后按20℃/h降温至室温。实施例3中3.0％Eu:CaF2晶体:按比例称量 EuF3(5N)7.64g，CaF2(5N)92.36g，PbF2的加入量是CaF2的1wt％。所得3.0at.％Eu:CaF2晶体中二价铕离子Eu2+和三价铕离子Eu3+的摩尔浓度比为3：1。Weigh the ingredients according to their respective proportions, mix them thoroughly in a vacuum glove box, and place them in a platinum crucible. The crucible descending method is used to grow crystals in an air atmosphere. The raw material is melted at 1400°C and the growth begins. The crucible descending rate is 1.5mm/h. After 120h, the crystal growth is completed, and then the temperature is cooled to room temperature at 20°C/h. 3.0% Eu:CaF 2 crystals in Example 3: EuF 3 (5N) 7.64g, CaF 2 (5N) 92.36g were weighed in proportion, and the amount of PbF 2 added was 1wt% of CaF 2 . The molar concentration ratio of divalent europium ion Eu 2+ and trivalent europium ion Eu 3+ in the obtained 3.0at.% Eu:CaF 2 crystal is 3:1.

实施例4：坩埚下降法生长6.0at.％Eu:CaF2晶体Embodiment 4: Growth of 6.0at.% Eu:CaF 2 crystals by crucible descending method

按各自配料比例称料，在真空手套箱内充分混合，置于铂金坩埚内。采用坩埚下降法生长晶体，空气气氛中生长，1400℃熔融原料并开始生长，坩埚下降速率为1.5mm/h，120h后晶体生长完毕，然后按20℃/h降温至室温。实施例4中6.0％Eu:CaF2晶体:按比例称量 EuF3(5N)14.60g，CaF2(5N)85.40g，PbF2的加入量是CaF2的1wt％。所得6.0at.％Eu:CaF2晶体晶体中二价铕离子Eu2+和三价铕离子Eu3+的摩尔浓度比为2：1。Weigh the ingredients according to their respective proportions, mix them thoroughly in a vacuum glove box, and place them in a platinum crucible. The crucible descending method is used to grow crystals in an air atmosphere. The raw material is melted at 1400°C and the growth begins. The crucible descending rate is 1.5mm/h. After 120h, the crystal growth is completed, and then the temperature is cooled to room temperature at 20°C/h. 6.0% Eu:CaF 2 crystals in Example 4: EuF 3 (5N) 14.60g, CaF 2 (5N) 85.40g were weighed in proportion, and the amount of PbF 2 added was 1wt% of CaF 2 . The molar concentration ratio of divalent europium ion Eu 2+ and trivalent europium ion Eu 3+ in the obtained 6.0at.% Eu:CaF 2 crystal is 2:1.

实施例5：坩埚下降法生长6.0at.％Eu:SrF2晶体Embodiment 5: Growth of 6.0at.% Eu:SrF 2 crystals by crucible descending method

按各自配料比例称料，在真空手套箱内充分混合，置于铂金坩埚内。采用坩埚下降法生长晶体，空气气氛中生长，1400℃熔融原料并开始生长，坩埚下降速率为1.5mm/h，120h后晶体生长完毕，然后按20℃/h降温至室温。实施例5中6.0％Eu:SrF2晶体:按比例称量 EuF3(5N)9.60g，SrF2(5N)90.40g，PbF2的加入量是SrF2的1wt％。所得6.0at.％Eu:SrF2晶体晶体中二价铕离子Eu2+和三价铕离子Eu3+的摩尔浓度比为2：1。Weigh the ingredients according to their respective proportions, mix them thoroughly in a vacuum glove box, and place them in a platinum crucible. The crucible descending method is used to grow crystals in an air atmosphere. The raw material is melted at 1400°C and the growth begins. The crucible descending rate is 1.5mm/h. After 120h, the crystal growth is completed, and then the temperature is cooled to room temperature at 20°C/h. 6.0% Eu:SrF 2 crystals in Example 5: 9.60 g of EuF 3 (5N) and 90.40 g of SrF 2 (5N) were weighed in proportion, and the amount of PbF 2 added was 1 wt% of SrF 2 . The molar concentration ratio of divalent europium ion Eu 2+ and trivalent europium ion Eu 3+ in the obtained 6.0at.% Eu:SrF 2 crystal is 2:1.

图1为实施例1-4中生长的x at.％Eu:CaF2(x＝0.6,1.2,3.0,6.0)晶体的室温发射光谱。在398nm激发下，可以观察到二价铕离子Eu2+424nm特征发光峰以及三价铕离子Eu3+ 5D0→7FJ(J＝0,1,2,3,4)特征发光峰。随着铕离子浓度升高，三价铕离子Eu3+发光峰荧光强度先增大后减小，当Eu浓度为6％时，获得最大发光强度。二价发光峰强度逐渐下降，这是由于发生了Eu2+→Eu3+能量传递。Fig. 1 is the room temperature emission spectrum of x at.%Eu:CaF 2 (x=0.6, 1.2, 3.0, 6.0) crystals grown in Examples 1-4. Under 398nm excitation, the characteristic luminescence peak of divalent europium ion Eu 2+ at 424nm and the characteristic luminescence peak of trivalent europium ion Eu 3+ 5 D 0 → 7 F J (J=0,1,2,3,4) can be observed . As the concentration of europium ions increases, the fluorescence intensity of the luminescence peak of trivalent europium ions Eu 3+ first increases and then decreases. When the Eu concentration is 6%, the maximum luminescence intensity is obtained. The intensity of the divalent luminescence peak decreases gradually, which is due to the Eu 2+ →Eu 3+ energy transfer.

图2为实施例1-4中生长的x at.％Eu:CaF2(x＝0.6,1.2,3.0,6.0)晶体的398nm激发下室温发射光谱对应的显示色域图。在同一398nm波长激发下，可以使得晶体显示色域从蓝光变化到橙红光。Fig. 2 is a display color gamut corresponding to the emission spectrum at room temperature under 398nm excitation of x at.%Eu:CaF 2 (x=0.6, 1.2, 3.0, 6.0) crystals grown in Examples 1-4. Under the excitation of the same 398nm wavelength, the crystal display color gamut can be changed from blue light to orange-red light.

图3中(a)-(d)为实施例1-4中生长的x at.％Eu:CaF2(x＝0.6,1.2,3.0,6.0)晶体在不同激发波长下(300-400nm)的室温荧光光谱。通过改变激发波长位置，可以在x at.％Eu:CaF2(x＝0.6,1.2,3.0,6.0)晶体中获得具有不同二价铕离子Eu2+和三价铕离子Eu3+特征峰荧光强度的光谱图。(a)-(d) in Fig. 3 are x at.%Eu:CaF 2 (x=0.6,1.2,3.0,6.0) crystals grown in Examples 1-4 under different excitation wavelengths (300-400nm) Room temperature fluorescence spectroscopy. By changing the position of the excitation wavelength, fluorescence with different divalent europium ions Eu 2+ and trivalent europium ions Eu 3+ characteristic peaks can be obtained in x at.%Eu:CaF 2 (x=0.6,1.2,3.0,6.0) crystals Intensity spectrogram.

图4为实施例1-4中生长的x at.％Eu:CaF2(x＝0.6,1.2,3.0,6.0)晶体在不同激发波长下(300-400nm)的室温荧光光谱所对应的显示色域图。在不同的激发波长下，可以在x at.％Eu:CaF2(x＝0.6,1.2,3.0,6.0)晶体中获得从蓝光到红橙光颜色变化的显示色域分布。Figure 4 shows the display colors corresponding to the room temperature fluorescence spectra of x at.%Eu:CaF 2 (x=0.6, 1.2, 3.0, 6.0) crystals grown in Examples 1-4 under different excitation wavelengths (300-400nm) domain map. Under different excitation wavelengths, the display color gamut distribution of the color change from blue light to red orange light can be obtained in x at.%Eu:CaF 2 (x=0.6, 1.2, 3.0, 6.0) crystal.

实施例6：坩埚下降法生长0.2at.％Eu:CaF2晶体Embodiment 6: Growth of 0.2at.% Eu:CaF 2 crystals by crucible descending method

按各自配料比例称料，在真空手套箱内充分混合，置于铂金坩埚内。采用坩埚下降法生长晶体，空气气氛中生长，1400℃熔融原料并开始生长，坩埚下降速率为1.5mm/h，120h后晶体生长完毕，然后按20℃/h降温至室温。实施例6中0.2％Eu:CaF2晶体:按比例称量 EuF3(5N)0.53g，CaF2(5N)99.47g，PbF2的加入量是CaF2的1wt％。所得0.6at.％Eu:CaF2晶体中二价铕离子Eu2+和三价铕离子Eu3+的摩尔浓度比为7：1。Weigh the ingredients according to their respective proportions, mix them thoroughly in a vacuum glove box, and place them in a platinum crucible. The crucible descending method is used to grow crystals in an air atmosphere. The raw material is melted at 1400°C and the growth begins. The crucible descending rate is 1.5mm/h. After 120h, the crystal growth is completed, and then the temperature is cooled to room temperature at 20°C/h. 0.2% Eu:CaF 2 crystal in Example 6: EuF 3 (5N) 0.53g, CaF 2 (5N) 99.47g were weighed in proportion, and the amount of PbF 2 added was 1wt% of CaF 2 . The molar concentration ratio of divalent europium ion Eu 2+ and trivalent europium ion Eu 3+ in the obtained 0.6at.% Eu:CaF 2 crystal is 7:1.

图5为实施例6制备的Eu:CaF2(x＝0.2)晶体在398nm激发下的室温发射光谱(a)和在300-400nm波段激发下室温发射光谱所对应的色域显示图(b)，从图中可知当Eu掺杂量为0.2at.％时，Eu2+发光强度远高于Eu3+发光强度，晶体色域显示落在蓝光区。Figure 5 is the room temperature emission spectrum (a) of the Eu:CaF 2 (x=0.2) crystal prepared in Example 6 under excitation at 398nm and the corresponding color gamut display diagram (b) of the emission spectrum at room temperature under excitation at 300-400nm band , it can be seen from the figure that when the Eu doping amount is 0.2 at.%, the Eu 2+ luminous intensity is much higher than the Eu 3+ luminous intensity, and the crystal color gamut shows that it falls in the blue region.

实施例7：坩埚下降法生长10.0at.％Eu:CaF2晶体Embodiment 7: Growth of 10.0at.% Eu:CaF 2 crystals by crucible descending method

按各自配料比例称料，在真空手套箱内充分混合，置于铂金坩埚内。采用坩埚下降法生长晶体，空气气氛中生长，1400℃熔融原料并开始生长，坩埚下降速率为1.5mm/h，120h后晶体生长完毕，然后按20℃/h降温至室温。10.0％Eu:CaF2晶体:按比例称量EuF3(5N)23g，CaF2(5N)77g，PbF2的加入量是CaF2的1wt％。所得10.0at.％Eu:CaF2晶体中二价铕离子 Eu2+和三价铕离子Eu3+的摩尔浓度比为1：1。Weigh the ingredients according to their respective proportions, mix them thoroughly in a vacuum glove box, and place them in a platinum crucible. The crucible descending method is used to grow crystals in an air atmosphere. The raw material is melted at 1400°C and the growth begins. The crucible descending rate is 1.5mm/h. After 120h, the crystal growth is completed, and then the temperature is cooled to room temperature at 20°C/h. 10.0% Eu:CaF 2 crystal: weigh EuF 3 (5N) 23g, CaF 2 (5N) 77g in proportion, and the addition amount of PbF 2 is 1wt% of CaF 2 . The molar concentration ratio of divalent europium ion Eu 2+ and trivalent europium ion Eu 3+ in the obtained 10.0at.% Eu:CaF 2 crystal is 1:1.

图6为实施例7制备的Eu:CaF2(x＝10.0)晶体在398nm激发下的室温发射光谱(a)和在300-400nm波段激发下室温发射光谱所对应的色域显示图(b)，从图中可知当Eu掺杂量为10.0at.％时，Eu3+发光强度远高于Eu2+发光强度，晶体色域显示落在红橙光区。Fig. 6 is the room temperature emission spectrum (a) of the Eu:CaF 2 (x=10.0) crystal prepared in Example 7 under the excitation of 398nm and the corresponding color gamut display diagram (b) of the room temperature emission spectrum under the excitation of 300-400nm band , It can be seen from the figure that when the Eu doping amount is 10.0 at.%, the Eu 3+ luminous intensity is much higher than the Eu 2+ luminous intensity, and the crystal color gamut shows that it falls in the red-orange light region.

产业应用性：本发明提供的二价铕离子Eu2+和三价铕离子Eu3+掺杂的氟化钙晶体具有较宽的发射光谱，且二价铕离子Eu2+和三价铕离子Eu3+吸收波段在一定范围内重合。通过调节铕离子(Eu2+和Eu3+)浓度，或通过调节激发波长(300-400nm)，获得可以实现从蓝光到红橙光色域调控的晶体材料。相比传统荧光粉应用于显示领域，晶体材料封装简单，且导热性能更优，有利于产品使用寿命的增长。Industrial applicability: the calcium fluoride crystal doped with divalent europium ions Eu 2+ and trivalent europium ions Eu 3+ provided by the present invention has a wider emission spectrum, and divalent europium ions Eu 2+ and trivalent europium ions The Eu 3+ absorption bands overlap within a certain range. By adjusting the concentration of europium ions (Eu 2+ and Eu 3+ ), or by adjusting the excitation wavelength (300-400nm), a crystal material capable of adjusting the color gamut from blue light to red-orange light is obtained. Compared with traditional phosphors used in the display field, the packaging of crystal materials is simple, and the thermal conductivity is better, which is conducive to the increase of product service life.

Claims (9)

1. The europium ion-doped fluoride crystal is characterized by having a chemical formula of Eu: MF2, wherein europium ion Eu comprises divalent europium ion Eu2+ and trivalent europium ion Eu3+, M is Ca or Sr, and the doping concentration of europium ion Eu is 0.1at% to 20.0 at%.
2. the europium ion-doped fluoride crystal of claim 1, wherein the europium ion Eu is doped at a concentration of 0.1 to 10.0at.%, preferably 0.1 to 8 at.%.
3. the europium ion-doped fluoride crystal of claim 1 or 2, wherein the molar concentration ratio of divalent europium ion Eu2+ to trivalent europium ion Eu3+ is (1-10): 1, preferably (2-7): 1.
4. The europium ion-doped fluoride crystal of any one of claims 1 to 3, wherein the fluoride laser crystal has fluorescence peaks of Eu2+ ion 400nm to 450nm and Eu3+ ion 550nm to 700nm when excited in the near ultraviolet band of 300 to 400 nm.
5. A method for the preparation of crystal of europium ion-doped fluoride as claimed in any one of claims 1 to 4, wherein raw material powders EuF3 and MF2 are weighed according to the formula Eu: MF2, and the crystal of europium ion-doped fluoride is grown in an air atmosphere by a melt method.
6. The preparation method according to claim 5, wherein PbF2 is added as an oxygen scavenger to the raw powder, and the amount of PbF2 added is 0.1-2.0 wt% of MF 2.
7. the method according to claim 5 or 6, wherein the crystal is grown by a Bridgman method, and the crucible material is high purity graphite or platinum.
8. The preparation method according to claim 7, characterized in that no seed crystal is added to the bottom of the crucible, or a Eu: MF2 single crystal rod oriented with the normal direction of the end face of [111] by an X-ray diffractometer is used as the seed crystal.
9. a method as claimed in claim 7 or 8, characterized in that the parameters of the Bridgman method comprise: the growth temperature is 1300-1400 ℃; the growth time is 100-300 hours; the descending speed of the crucible is 0.02-1.5 mm/h.
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