CN110541198A - Europium ion doped fluoride crystal with display color gamut capable of being regulated and controlled in large range and preparation method thereof - Google Patents
Europium ion doped fluoride crystal with display color gamut capable of being regulated and controlled in large range and preparation method thereof Download PDFInfo
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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
Technical Field
The invention relates to an 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, in particular to a fluoride laser crystal doped with divalent europium ion Eu2+ and trivalent europium ion Eu3+ and a preparation method thereof, and belongs to the field of artificial crystals and luminescent and display materials.
Background
Since the first ruby laser in the world of the last 60 years, laser has been widely used in military and national lives due to its excellent characteristics. More closely related to us is the application of visible light lasers in the field of displays. Laser displays have unique advantages over conventional CRT, LCD, and even LED technologies. It has the advantages of large color gamut, dual high definition (geometric, color) video image display and true three-dimensional display, and is considered as a revolution in the human visual history by the international industry. As a novel display technology, the display device has wide application in the fields of large-screen laser home theaters, digital movies, military commands, exhibition and display, portable display terminals, space science and the like.
The mainstream projector schemes at present are DLP and 3LCD technologies, wherein 3LCD is a liquid crystal panel with three colors of red, green and blue, which is amplified by a lens and transmitted by a reflector. In the DLP working mode, light rays are subjected to color mixing after being rotated at a high speed by the color wheel and finally transmitted out through the prism. The two schemes both need red, green and blue tricolor laser as light sources, namely three visible laser crystals are needed to be pumped respectively to generate visible laser, and the system has certain complexity.
Disclosure of Invention
In one aspect, the present invention provides an europium ion-doped fluoride crystal having a chemical formula of Eu: MF2, wherein Eu comprises divalent Eu2+ and trivalent Eu3+, M is Ca or Sr, and Eu has a doping concentration of 0.1at% to 20.0 at%, preferably 0.2 at% to 8 at%.
The calcium fluoride crystal or strontium fluoride crystal doped with divalent europium ion Eu2+ and trivalent europium ion Eu3+ has a wide emission spectrum, and absorption bands of the divalent europium ion Eu2+ and the trivalent europium ion Eu3+ coincide in a certain range. The color gamut from blue light to red orange light is regulated and controlled by regulating the concentration of europium ions (Eu2+ and Eu3+) or regulating the excitation wavelength (300-400 nm).
preferably, the doping concentration of the europium ion Eu is 0.1at% to 10.0 at%, preferably 0.1at% to 8 at%.
preferably, the molar concentration ratio of the divalent europium ion Eu2+ to the trivalent europium ion Eu3+ is (1-10): 1, preferably (2-7): 1. According to the invention, under different Eu overall concentrations, the same excitation wavelength is adopted, and different Eu2+ and Eu3+ ion concentration ratios are utilized, so that a large range can be obtained, namely color gamut regulation from blue light to red light is realized, the proportion range is expanded, and the regulation range can be larger. Increasing the Eu concentration can gradually increase the proportion of Eu3+ concentration due to the special structure of CaF2 or SrF2 crystals. When a small amount of Eu3+ ions are doped in CaF2 or SrF2, the Eu3+ is reduced to Eu2+ by Vca degrees in the crystal, so that the Eu2+ concentration is higher at the moment. As the Eu doping amount is increased, the number of defects in CaF2 or SrF2 is smaller, and Eu3+ is more stable than Eu2+, so that the process of Eu3+ → Eu2+ is weakened, resulting in Eu3+ ions dominating, and further shifting the spectral color gamut from the blue region to the red region.
Preferably, the fluoride laser crystal has fluorescence peaks of Eu2+ ion 400 nm-450 nm and Eu3+ ion 550 nm-700 nm under the excitation of near ultraviolet wave band 300-400 nm. After rare earth ion Eu is doped into CaF2 or SrF2 crystal, a plurality of luminescence centers can be formed (for example, Eu2+ ion can provide blue luminescence, and Eu3+ ion can provide red and orange luminescence), namely, the luminescence centers are represented by wider absorption and emission spectrums, and the wide color gamut range can be obtained by adopting 300-400nm wavelength range excitation.
In another aspect, the present invention further provides a method for preparing the europium ion doped fluoride crystal, wherein raw material powders EuF3 and MF2 are weighed according to the chemical formula Eu: MF2, and the europium ion doped fluoride crystal is grown in an air atmosphere by a melt method.
In the invention, the europium ion doped fluoride crystal is grown in the air atmosphere by a melt method, so that the europium ion doped fluoride crystal is subjected to valence change under the influence of the growth atmosphere (air atmosphere), and divalent europium ion Eu2+ and trivalent europium ion Eu3+ coexist in the matrix crystal. By taking CaF2 as an example to illustrate the reaction mechanism, Eu3+ ions in raw materials enter CaF2 crystals to replace Ca2+ ions. In order to maintain the electrovalence balance, two Eu3+ ions should be substituted for three Ca2+ ions, producing Vca "and Euca" simultaneously and acting as donor and acceptor, respectively, as described in formulas (1) to (3):
Preferably, PbF2 is added as an oxygen scavenger in the raw powder, and the addition amount of PbF2 is 0.1-2.0 wt% of MF 2.
Preferably, the crystal is grown by a Bridgman method, and the crucible material is high-purity graphite or platinum. Preferably, the parameters of the Bridgman method include: 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.
Preferably, no seed crystal is added to the bottom of the crucible, or a Eu: MF2 single crystal rod with the normal direction of the end face being [111] oriented by an X-ray diffractometer is used as the seed crystal.
According to the invention, by utilizing the characteristic that divalent europium ion Eu2+ and trivalent europium ion Eu3+ coexist in a CaF2(SrF2) crystal matrix and absorption bands of the divalent europium ion Eu2+ and the trivalent europium ion Eu3+ have large-range overlapping, a laser crystal which realizes color gamut regulation from blue light to red orange light under the same excitation wavelength is obtained (1) by adjusting the concentration of europium ions (Eu2+ and Eu3 +); (2) by adjusting the excitation wavelength, the laser crystal which realizes the color gamut regulation from blue light to red orange light is obtained in the same europium ion concentration (Eu2+ and Eu3+) crystal. In the invention, the Eu: CaF2(SrF2) crystal belongs to an alkaline earth metal matrix, and when rare earth ions are doped into CaF2(SrF2), trivalent rare earth ions replace the lattice sites of calcium ions, and interstitial fluorine ions are generated to balance charges. Due to uncertain positions of interstitial fluoride ions, the rare earth doped CaF2(SrF2) crystal shows coexistence of multiple sites, so that the crystal has wider absorption and emission spectra.
Drawings
Fig. 1a is a room temperature emission spectrum of x at.% Eu: CaF2(x ═ 0.6,1.2,3.0,6.0) crystals at 398nm excitation;
FIG. 1b is an enlarged view of a portion of FIG. 1 a;
Fig. 2 is a color gamut display plot corresponding to room temperature emission spectra of x at.% Eu: CaF2(x ═ 0.6,1.2,3.0,6.0) crystals at 398nm excitation;
FIG. 3 is a room temperature emission spectrum of x at.% Eu: CaF2(x ═ 0.6,1.2,3.0,6.0) crystals under excitation in the 300-400nm band;
FIG. 4 is a color gamut display diagram corresponding to room temperature emission spectrum of x at.% Eu: CaF2(x ═ 0.6,1.2,3.0,6.0) crystal under excitation of 300-400nm band;
FIG. 5 is a color gamut display graph (b) corresponding to the room temperature emission spectrum (a) of the Eu: CaF2(x ═ 0.2) crystal prepared in example 6 under 398nm excitation and under 300-400nm band excitation;
FIG. 6 is a color gamut display graph (b) corresponding to the room temperature emission spectrum (a) of the Eu: CaF2(x ═ 10.0) crystal prepared in example 7 under 398nm excitation and the room temperature emission spectrum under 300-400nm band excitation.
Detailed Description
the present invention is further illustrated by the following examples, which are to be understood as merely illustrative and not restrictive.
In the invention, the chemical formula of the europium ion doped fluoride crystal (mainly calcium fluoride and strontium fluoride) with controllable color gamut is Eu: CaF2(SrF2), wherein the doping concentration of europium ion is 0.1 a.t-20.0 at.%, and two valence states of Eu2+ and Eu3+ exist in the calcium fluoride (strontium fluoride) crystal. When M is Ca, the doping concentration of the europium ion Eu is 0.1at% to 10.0 at%, preferably 0.1at% to 8 at%. When M is Sr, the doping concentration of the europium ion Eu is 0.1at% to 10.0 at%, and preferably 0.1at% to 8 at%. Wherein, the molar concentration ratio of the divalent europium ion Eu2+ to the trivalent europium ion Eu3+ can be (1-10): 1, and is preferably (2-7): 1. In the invention, the fluoride laser crystal has Eu2+ ion 400-450 nm and Eu3+ ion 550-700 nm fluorescence peaks under near ultraviolet wave band excitation, and the intensity, peak position and half-height width of each fluorescence peak are changed along with the change of Eu ion concentration. By adjusting the concentration of Eu ions and changing the excitation wavelength range (300-400nm), the display color gamut range regulation from blue light to red orange light can be obtained. The following exemplarily illustrates a method for preparing the europium ion-doped fluoride crystal.
Mixing raw materials EuF3 and CaF2(SrF2) according to a molar ratio of 0.001-0.2: 0.76-1.3, and mixing to obtain the raw material powder. In an alternative embodiment, 0.1-2 wt% (preferably in the range of 0.5-1 wt%) of the mass of CaF2(SrF2) of PbF2 is added as an oxygen scavenger. The raw material powder is fully ground, uniformly mixed and then put into a crucible, and a Eu: CaF2(SrF2) monocrystal coexisting with divalent europium ion Eu2+ and trivalent europium ion Eu3+ is grown in the crucible by a melt method. As an example for preparing the raw material powder, initial raw materials of EuF3, CaF2 (or SrF2) and PbF2 are selected, wherein EuF3 and CaF2 (or SrF2) are mixed according to a molar ratio of m: n, wherein m is 0.001-0.2, and n is 0.76-1.3. The mass of the PbF2 is 0.5-1 wt% of that of CaF2(SrF 2).
The method for growing the Eu: CaF2(SrF2) single crystal can be a Bridgman method. The material of the crucible can be platinum or high-purity graphite. No seed crystal is added at the bottom of the crucible or a Eu: CaF2(SrF2) single crystal rod with the normal direction of the oriented end face of the X-ray diffractometer being [111] is used as the seed crystal. Wherein, the crystal growth is carried out in the air without introducing special atmosphere. Wherein 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. After the growth is finished, the cooling rate can be 10-25 ℃/h after the growth is cooled to room temperature.
In the invention, europium ions exist at two valence states of Eu2+ and Eu3+ in calcium fluoride (strontium fluoride) crystals at the same time, and the control of the display color gamut from blue light to red orange light of the crystals with the same concentration under different excitation wavelengths and the control of the display color gamut from blue light to red orange light of the crystals with different europium ion doping concentrations under the same excitation wavelength (398nm) are realized by adjusting the concentration of the europium ions in the calcium fluoride (strontium fluoride) crystals and changing the wavelength of an excitation light source. Compared with the traditional fluorescent powder material, the preparation method is simple, the preparation period is short, the used raw materials are cheap and easy to obtain, and the method for realizing color gamut regulation is simple and has application value.
The Eu: CaF2(SrF2) crystal is cut into pieces, room temperature emission spectrum is tested on a FLs980 fluorescence spectrometer after optical-level polishing, and a scintillation xenon lamp with the wavelength range of 300-400nm is adopted as a pumping source.
the present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
Example 1: bridgman method for growing 0.6 at.% Eu: CaF2 crystal
The materials are weighed according to the respective mixture ratio, fully mixed in a vacuum glove box and placed in a platinum crucible. Growing the crystal by adopting a Bridgman method, growing in an air atmosphere, melting raw materials at 1400 ℃, starting to grow, wherein the Bridgman method has a Bridgman falling rate of 1.5mm/h, finishing the crystal growth after 120h, and then cooling to room temperature at a rate of 20 ℃/h. Example 1 0.6% Eu: CaF2 Crystal in proportions 1.59g of EuF3(5N), 98.41g of CaF2(5N), and 1 wt% of CaF2 were added as PbF 2. The molar concentration ratio of divalent europium ion Eu2+ and trivalent europium ion Eu3+ in the obtained 0.6 at.% Eu: CaF2 crystal is 5: 1.
Example 2: bridgman method for growing 1.2 at.% Eu: CaF2 crystal
The materials are weighed according to the respective mixture ratio, fully mixed in a vacuum glove box and placed in a platinum crucible. Growing the crystal by adopting a Bridgman method, growing in an air atmosphere, melting raw materials at 1400 ℃, starting to grow, wherein the Bridgman method has a Bridgman falling rate of 1.5mm/h, finishing the crystal growth after 120h, and then cooling to room temperature at a rate of 20 ℃/h. Example 2 1.2% Eu: CaF2 Crystal 3.15g of EuF3(5N), 96.85g of CaF2(5N), and 1 wt% of CaF2 were added to PbF 2. The molar concentration ratio of divalent europium ion Eu2+ and trivalent europium ion Eu3+ in the obtained 1.2 at.% Eu: CaF2 crystal is 4: 1.
Example 3: bridgman method for growing (3.0 at.% to 5.0 at.%) Eu: SrF2 crystal
The materials are weighed according to the respective mixture ratio, fully mixed in a vacuum glove box and placed in a platinum crucible. Growing the crystal by adopting a Bridgman method, growing in an air atmosphere, melting raw materials at 1400 ℃, starting to grow, wherein the Bridgman method has a Bridgman falling rate of 1.5mm/h, finishing the crystal growth after 120h, and then cooling to room temperature at a rate of 20 ℃/h. Example 3.0% Eu: CaF2 Crystal in proportion EuF3(5N)7.64g, CaF2(5N)92.36g, PbF2 was added in an amount of 1 wt% of CaF 2. The molar concentration ratio of divalent europium ion Eu2+ and trivalent europium ion Eu3+ in the obtained 3.0 at.% Eu: CaF2 crystal is 3: 1.
Example 4: bridgman method for growing 6.0 at.% Eu: CaF2 crystal
The materials are weighed according to the respective mixture ratio, fully mixed in a vacuum glove box and placed in a platinum crucible. Growing the crystal by adopting a Bridgman method, growing in an air atmosphere, melting raw materials at 1400 ℃, starting to grow, wherein the Bridgman method has a Bridgman falling rate of 1.5mm/h, finishing the crystal growth after 120h, and then cooling to room temperature at a rate of 20 ℃/h. Example 4 Eu: CaF2 Crystal 6.0% in proportion 14.60g of EuF3(5N), 85.40g of CaF2(5N), and 1 wt% of CaF2 were added to PbF 2. The molar concentration ratio of divalent europium ion Eu2+ and trivalent europium ion Eu3+ in the obtained 6.0 at.% Eu: CaF2 crystal is 2: 1.
Example 5: bridgman method for growing 6.0 at.% Eu SrF2 crystal
The materials are weighed according to the respective mixture ratio, fully mixed in a vacuum glove box and placed in a platinum crucible. Growing the crystal by adopting a Bridgman method, growing in an air atmosphere, melting raw materials at 1400 ℃, starting to grow, wherein the Bridgman method has a Bridgman falling rate of 1.5mm/h, finishing the crystal growth after 120h, and then cooling to room temperature at a rate of 20 ℃/h. Example 5 crystal of SrF2 with 6.0% Eu 9.60g of EuF3(5N), SrF2(5N)90.40g and PbF2 were weighed in a proportion of 1 wt% of SrF 2. The molar concentration ratio of divalent europium ion Eu2+ and trivalent europium ion Eu3+ in the obtained 6.0 at.% Eu: SrF2 crystal is 2: 1.
Fig. 1 is a room temperature emission spectrum of x at.% Eu: CaF2(x ═ 0.6,1.2,3.0,6.0) crystals grown in examples 1-4. Under 398nm excitation, a characteristic luminescence peak of divalent europium ion Eu2+424nm and a characteristic luminescence peak of trivalent europium ion Eu3+5D0 → 7FJ (J ═ 0,1,2,3,4) can be observed. With the increase of the europium ion concentration, the fluorescence intensity of the luminescence peak of trivalent europium ion Eu3+ is increased and then decreased, and when the Eu concentration is 6%, the maximum luminescence intensity is obtained. The divalent light emission peak intensity gradually decreases due to occurrence of Eu2+ → Eu3+ energy transfer.
Fig. 2 is a color gamut plot of room temperature emission spectra at 398nm excitation for the x at.% Eu CaF2(x 0.6,1.2,3.0,6.0) crystals grown in examples 1-4. Under the same 398nm wavelength excitation, the crystal display color gamut can be changed from blue light to orange-red light.
In FIG. 3, (a) - (d) are the room temperature fluorescence spectra of x at.% Eu: CaF2(x ═ 0.6,1.2,3.0,6.0) crystals grown in examples 1-4 at different excitation wavelengths (300-400 nm). By changing the excitation wavelength position, spectrograms with different characteristic peak fluorescence intensities of divalent europium ion Eu2+ and trivalent europium ion Eu3+ can be obtained in x at.% Eu: CaF2(x ═ 0.6,1.2,3.0,6.0) crystals.
FIG. 4 is a color gamut diagram of room temperature fluorescence spectra of x at.% Eu: CaF2(x is 0.6,1.2,3.0,6.0) crystals grown in examples 1-4 at different excitation wavelengths (300-400 nm). A display color gamut distribution varying from blue to red-orange color can be obtained in x at.% Eu: CaF2(x ═ 0.6,1.2,3.0,6.0) crystals at different excitation wavelengths.
example 6: bridgman method for growing 0.2 at.% Eu: CaF2 crystal
the materials are weighed according to the respective mixture ratio, fully mixed in a vacuum glove box and placed in a platinum crucible. Growing the crystal by adopting a Bridgman method, growing in an air atmosphere, melting raw materials at 1400 ℃, starting to grow, wherein the Bridgman method has a Bridgman falling rate of 1.5mm/h, finishing the crystal growth after 120h, and then cooling to room temperature at a rate of 20 ℃/h. Example 6 0.2% Eu: CaF2 Crystal in proportion EuF3(5N)0.53g, CaF2(5N)99.47g, PbF2 was added in an amount of 1 wt% of CaF 2. The molar concentration ratio of divalent europium ion Eu2+ and trivalent europium ion Eu3+ in the obtained 0.6 at.% Eu: CaF2 crystal is 7: 1.
Fig. 5 is a color gamut display graph (b) corresponding to the room temperature emission spectrum (a) of the Eu: CaF2(x ═ 0.2) crystal prepared in example 6 under 398nm excitation and under 300-400nm band excitation, and it can be seen that when the Eu doping amount is 0.2 at.%, the Eu2+ emission intensity is much higher than the Eu3+ emission intensity, and the crystal color gamut display falls in the blue region.
Example 7: bridgman method for growing 10.0at.% Eu: CaF2 crystal
The materials are weighed according to the respective mixture ratio, fully mixed in a vacuum glove box and placed in a platinum crucible. Growing the crystal by adopting a Bridgman method, growing in an air atmosphere, melting raw materials at 1400 ℃, starting to grow, wherein the Bridgman method has a Bridgman falling rate of 1.5mm/h, finishing the crystal growth after 120h, and then cooling to room temperature at a rate of 20 ℃/h. 10.0% Eu to CaF2 Crystal 23g of EuF3(5N), 77g of CaF2(5N) and 1 wt% of CaF2 were weighed in proportion. The molar concentration ratio of divalent europium ion Eu2+ and trivalent europium ion Eu3+ in the obtained 10.0at.% Eu: CaF2 crystal is 1: 1.
fig. 6 is a color gamut display graph (b) corresponding to the room temperature emission spectrum (a) of the Eu: CaF2(x ═ 10.0) crystal prepared in example 7 under 398nm excitation and under 300-400nm band excitation, and it can be seen that when the Eu doping amount is 10.0at.%, the Eu3+ emission intensity is much higher than the Eu2+ emission intensity, and the crystal color gamut display falls in the red-orange region.
Industrial applicability: the calcium fluoride crystal doped with the divalent europium ion Eu2+ and the trivalent europium ion Eu3+ provided by the invention has a wider emission spectrum, and absorption wave bands of the divalent europium ion Eu2+ and the trivalent europium ion Eu3+ are overlapped in a certain range. By adjusting the concentration of europium ions (Eu2+ and Eu3+), or by adjusting the excitation wavelength (300-400nm), the crystal material which can realize the color domain regulation from blue light to red orange light is obtained. Compared with the traditional fluorescent powder applied to the display field, the crystal material has simple encapsulation and better heat-conducting property, and is beneficial to prolonging the service life of the product.
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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| CN111559862A (en) * | 2020-05-19 | 2020-08-21 | 中国建材国际工程集团有限公司 | Europium ion doped light conversion glass and preparation method thereof |
| RU2747503C1 (en) * | 2020-07-09 | 2021-05-05 | Федеральное государственное бюджетное учреждение "Национальный исследовательский центр "Курчатовский институт" | Method for preparing a charge for growing fluoride single crystals |
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| CN111559862A (en) * | 2020-05-19 | 2020-08-21 | 中国建材国际工程集团有限公司 | Europium ion doped light conversion glass and preparation method thereof |
| RU2747503C1 (en) * | 2020-07-09 | 2021-05-05 | Федеральное государственное бюджетное учреждение "Национальный исследовательский центр "Курчатовский институт" | Method for preparing a charge for growing fluoride single crystals |
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Application publication date: 20191206 |