A praseodymium ion doped phosphate crystal material, a preparation method and application thereof

Abstract

The application belongs to the technical field of inorganic functional crystals, and particularly relates to a praseodymium ion doped phosphate crystal material and a preparation method and application thereof. The application provides a praseodymium ion doped phosphate crystal material, a chemical formula of the praseodymium ion doped phosphate crystal material is shown as formula 1: Ba3Y 1‑x (PO4)3:xPr formula 1; in formula 1, 0

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of inorganic functional crystals, and particularly relates to a praseodymium ion doped phosphate crystal material and a preparation method and application thereof. BACKGROUND

[0002] Laser in the visible band of 400-760 nm is a basic light source in the fields of storage, display, processing and communication. As a typical representative of rare earth ions, praseodymium ion doped laser crystals can realize absorption in the blue light region and multi-wavelength emission from green light to red light band, and are important blue pump all-solid-state visible band laser materials. At present, praseodymium ion doped laser crystals mainly focus on halide crystals represented by fluorides, but the crystals have the shortcomings of difficult growth and poor thermal mechanical properties of the crystals themselves, which restrict the application development thereof.

[0003] With the substantial improvement of the output power of blue InGaN semiconductor lasers (LDs), a way of directly outputting visible band laser by pumping praseodymium ion doped oxide laser crystals with blue LD has attracted the attention of researchers. At present, laser output has been realized in Pr:YAlO3, Pr:Y3Al5O 12 , Pr:SrAl 12 O 19 and other oxide crystals pumped by blue LD, but the output power still stays at the milliwatt level and needs to be further improved.

[0004] In addition, scintillation crystals are luminescent materials that can produce efficient fluorescent emission under high-energy ray particle excitation, and have very wide applications in nuclear medical imaging, industrial nondestructive testing, port safety inspection, environmental monitoring, geological exploration, oil well drilling, high-energy physics and astronomical space physics.

[0005] Therefore, it is urgent to develop a dual-functional crystal material with visible light laser output and high output power and scintillation performance to meet the market demand. SUMMARY

[0006] The praseodymium ion doped phosphate crystal material provided by the application can realize efficient visible laser output with high output power when directly pumped by a blue LD, and has scintillation performance, can realize strong ultraviolet and visible light emission under irradiation or excitation of high-energy rays or particles, and can be applied as a dual-functional crystal in the fields of visible laser and radiation detection.

[0007] In order to achieve the above-mentioned purpose, the application provides the following technical scheme.

[0008] The application provides a praseodymium ion doped phosphate crystal material, and a chemical formula of the praseodymium ion doped phosphate crystal material is shown in formula 1.

[0009] Ba3Y 1-x (PO4)3:xPr formula 1.

[0010] In formula 1, 0 < x ≤ 0.3.

[0011] Preferably, the praseodymium ion doped phosphate crystal material belongs to a cubic system, and a space group is

[0012] Preferably, in formula 1, 0.01 ≤ x ≤ 0.3.

[0013] Preferably, x in formula 1 is 0.01, 0.03, 0.04, 0.08, 0.12, 0.16, 0.2 or 0.3.

[0014] The application provides a preparation method of the praseodymium ion doped phosphate crystal material.

[0015] According to the chemical composition of the praseodymium ion doped phosphate crystal material, preparation raw materials are sintered twice to obtain Ba3Y 1-x (PO4)3:xPr polycrystalline raw materials; the preparation raw materials include praseodymium oxide, yttrium oxide, inorganic barium salt and inorganic phosphate; the twice sintering includes first sintering and second sintering;

[0016] In a protective gas atmosphere, the Ba3Y 1-x (PO4)3:xPr polycrystalline raw materials are pulled and grown to obtain the praseodymium ion doped phosphate crystal material.

[0017] Preferably, the first sintering includes sequentially performing first grinding, first tabletting and first roasting;

[0018] The temperature of the first roasting is 1000-1500 DEG C, the time is 15-25 h, and the temperature rising rate from room temperature to the temperature of the first roasting is 150-250 DEG C / h.

[0019] Preferably, the second sintering includes sequentially performing second grinding, second tabletting and second roasting;

[0020] The temperature of the second roasting is 1100-1600 DEG C, the time is 20-40 h, and the temperature rising rate from room temperature to the temperature of the second roasting is 150-250 DEG C / h.

[0021] Preferably, the temperature for the pulling growth is 1750-1950 DEG C, the pulling speed is 0.5-3 mm / h, and the rotating speed is 5-15 r / min.

[0022] Preferably, after the pulling growth, an initial crystal is obtained, and the initial crystal is cooled from the temperature for the pulling growth to room temperature at a rate of 5-20 DEG C / h to obtain the praseodymium ion doped phosphate crystal material.

[0023] The praseodymium ion doped phosphate crystal material provided in the technical scheme or the praseodymium ion doped phosphate crystal material prepared by the preparation method is applied to visible laser output and radiation detection.

[0024] The praseodymium ion doped phosphate crystal material provided in the technical scheme or the praseodymium ion doped phosphate crystal material prepared by the preparation method is applied to visible laser output and radiation detection. 1-x The praseodymium ion doped phosphate crystal material (Pr:BYP) provided in the technical scheme is characterized in that yttrium and barium are mixedly occupied in the same crystallographic site in the crystal, the mixing and disordered occupation of barium and yttrium cause the crystal lattice to be distorted to a certain extent, thereby enhancing and broadening the absorption and emission peaks of praseodymium ions, so that the crystal can realize high-efficiency visible laser output when being directly pumped by a blue light LD. 1 5d 1 →4f 2 allowed transition, so that the crystal can generate 5d 1 →4f 2 transition and f-f emission in the blue to red light band, so that the crystal can realize strong ultraviolet and visible light emission under the irradiation or excitation of high-energy rays or particles, and exhibits excellent scintillation properties.

[0025] The praseodymium ion doped phosphate crystal material provided in the technical scheme or the praseodymium ion doped phosphate crystal material prepared by the preparation method is applied to visible laser output and radiation detection. 1-x (PO4)3:xPr polycrystalline raw material; the preparation raw material comprises praseodymium oxide, yttrium oxide, inorganic barium salt and inorganic phosphate salt; the Ba3Y1-x The Pr ion doped phosphate crystal material is obtained by pulling growth of the polycrystalline raw material of (PO4)3:xPr. The present application grows large size and high quality single crystal by using the pulling method, the crystal growth method is stable, the crystal has stable physical and chemical properties and good optical properties, the raw material is easy to obtain and can be directly used for blue light LD pumping, and can be excited by high-energy rays and particles to realize scintillation light output and many other advantages, and can be used as a multifunctional crystal material of visible light band laser crystal and scintillation crystal. BRIEF DESCRIPTION OF DRAWINGS

[0026] Figure 1 The fluorescence spectrum of the polycrystalline powder prepared in Example 1 of the present application;

[0027] Figure 2 The X-ray powder diffraction pattern of the crystal prepared in Example 2 of the present application, and the built-in figure is a crystal photo;

[0028] Figure 3 The fluorescence excitation emission spectrum of the crystal prepared in Example 2 of the present application;

[0029] Figure 4 The fluorescence decay curve of the crystal prepared in Example 2 of the present application;

[0030] Figure 5 The X-ray excitation emission spectrum of the crystal prepared in Example 2 of the present application. DETAILED DESCRIPTION

[0031] The present application provides a Pr ion doped phosphate crystal material, the chemical formula of which is shown in Formula 1:

[0032] Ba3Y 1-x (PO4)3:xPr Formula 1;

[0033] In Formula 1, 0 < x ≤ 0.3.

[0034] In the present application, all the preparation raw materials / components are commercially available products well known to those skilled in the art, unless otherwise specified.

[0035] In the present application, x in Formula 1 is preferably 0.01 ≤ x ≤ 0.3, more preferably 0.03 ≤ x ≤ 0.3. In the specific embodiments of the present application, x in Formula 1 is particularly preferably 0.01, 0.03, 0.04, 0.08, 0.12, 0.16, 0.2 or 0.3, and most preferably 0.12.

[0036] In the present application, the Pr ion doped phosphate crystal material is a single crystal material, which belongs to cubic system, and the space group is

[0037] In the present application, the praseodymium ion doped phosphate crystal material can realize multiple laser outputs from cyan light to deep red light under blue light excitation at 450 nm, and can realize scintillation light output under excitation of high-energy rays (such as x-rays, γ-rays and high-energy particles).

[0038] The present application provides a preparation method of the praseodymium ion doped phosphate crystal material as described in the above technical solution, which comprises the following steps:

[0039] According to the chemical composition of the praseodymium ion doped phosphate crystal material, the preparation raw materials are sintered twice to obtain Ba3Y 1-x (PO4)3:xPr polycrystalline raw materials; the preparation raw materials comprise praseodymium oxide, yttrium oxide, inorganic barium salt and inorganic phosphate salt.

[0040] In a protective gas atmosphere, the Ba3Y 1-x (PO4)3:xPr polycrystalline raw materials are pulled to grow to obtain the praseodymium ion doped phosphate crystal material.

[0041] According to the chemical composition of the praseodymium ion doped phosphate crystal material, the preparation raw materials are sintered twice to obtain Ba3Y 1-x (PO4)3:xPr polycrystalline raw materials; the preparation raw materials comprise praseodymium oxide, yttrium oxide, inorganic barium salt and inorganic phosphate salt. In the present application, the praseodymium oxide is specifically preferably Pr6O 11 . The yttrium oxide is specifically preferably Y2O3. The inorganic barium salt is specifically preferably barium carbonate (BaCO3). The inorganic phosphate salt is preferably dihydrogen phosphate salt, and is specifically preferably ammonium dihydrogen phosphate (NH4H2PO4). In specific embodiments of the present application, the above preparation raw materials are preferably dosed according to the molar ratio of each element in the chemical formula of the praseodymium ion doped phosphate crystal material.

[0042] In the present application, the first sintering preferably comprises sequentially performing first grinding, first tabletting and first roasting. The present application does not have special requirements for the specific implementation modes of the first grinding and the first tabletting. The first roasting is preferably performed in a muffle furnace, the temperature of the first roasting is preferably 1000-1500℃, more preferably 1100-1300℃, and most preferably 1200℃; the time of the first roasting is preferably 15-25h, more preferably 18-22h, and most preferably 20h; the temperature rising rate from room temperature to the temperature of the first roasting is preferably 150-250℃ / h, and more preferably 200℃ / h.

[0043] In the present application, after the first roasting is completed, the present application preferably cools the product obtained by the first roasting to room temperature, and then performs the second sintering.

[0044] In the present application, the second sintering preferably comprises sequentially performing second grinding, second tabletting and second calcination. The present application does not have special requirements for the specific embodiments of the second grinding and the second tabletting. The second calcination is preferably performed in a muffle furnace, the temperature of the second calcination is preferably 1100-1600℃, more preferably 1200-1500℃; the time of the second calcination is preferably 20-40h, more preferably 25-35h; the heating rate from room temperature to the temperature of the second calcination is preferably 150-250℃ / h, more preferably 200℃ / h.

[0045] In the present application, after the second calcination, the present application preferably cools the product obtained by the second calcination to room temperature to obtain Ba3Y 1-x (PO4)3:xPr polycrystalline raw material. The Ba3Y1(PO4)3 crystal is used as a seed crystal for subsequent pull-up growth.

[0046] After obtaining the Ba3Y 1-x (PO4)3:xPr polycrystalline raw material, the present application performs pull-up growth of the Ba3Y 1-x (PO4)3:xPr polycrystalline raw material in a protective gas atmosphere to obtain the praseodymium ion doped phosphate crystal material. The present application preferably places the Ba3Y 1-x (PO4)3:xPr polycrystalline raw material in an iridium gold crucible and places it in a pull-up furnace to perform the pull-up growth. The specific size of the iridium gold crucible is Φ55×50mm 3 . The protective gas is preferably a non-reactive gas, and is specifically preferably nitrogen or an inert gas, and the inert gas is specifically preferably argon. The temperature of the pull-up growth is preferably 1750-1950℃, more preferably 1800-1900℃, and most preferably 1850℃; the pull-up speed is preferably 0.5-3mm / h, more preferably 0.8-1.5mm / h, and specifically preferably 1mm / h; the rotation speed is preferably 5-15r / min, more preferably 8-12r / min, and most preferably 10r / min. The rotation speed is the rotation speed of the crystal sample in the pull-up growth. In the present application, the heating body is an iridium gold crucible, and zirconia is used as a heat preservation cover and a heat preservation material.

[0047] In the present application, after the pull-up growth, an initial crystal is obtained, and the present application preferably further comprises: cooling the initial crystal from the temperature of the pull-up growth to room temperature after pulling the initial crystal away from the liquid surface to obtain the praseodymium ion doped phosphate crystal material; and the cooling rate is preferably 5-20℃ / h.

[0048] The application provides application of the praseodymium ion doped phosphate crystal material in visible laser output and radiation detection.

[0049] In the application, the praseodymium ion doped phosphate crystal material can realize multiple wavelength emission from cyan light to deep red light under the excitation of 450 nm blue light, and can realize scintillation light output under the excitation of high-energy rays (such as x-rays, gamma rays and high-energy particles).

[0050] In the application, the praseodymium ion doped phosphate crystal material is preferably applied to the output of 470-500 nm cyan light laser, 590-620 nm orange light laser and 630-660 nm red light laser.

[0051] In the application, the praseodymium ion doped phosphate crystal material is preferably applied to scintillation light under the irradiation or excitation of high-energy rays. The irradiation or excitation of high-energy rays preferably includes the excitation of x-rays, gamma rays and high-energy particles.

[0052] The application has the following beneficial effects:

[0053] The praseodymium ion doped phosphate crystal provided by the application has a disordered structure caused by the mixed occupation of barium and yttrium, so that the absorption peak and the emission peak of praseodymium ions are largely broadened, and the crystal is very suitable for blue light LD pumping to realize laser output.

[0054] The praseodymium ion doped phosphate crystal provided by the application has a crystal field which does not affect the 4f 1 5d 1 →4f 2 transition of praseodymium ions, so that the crystal can generate 5d 1 →4f 2 transition and f-f emission from cyan to red light under the excitation of high-energy rays and particles.

[0055] The praseodymium ion doped phosphate laser crystal provided by the application can be grown into a single crystal with large size and good quality by a pulling method, the growth process of the crystal is stable, the crystal has stable physical and chemical properties and good optical properties, raw materials are easy to obtain and can be directly pumped by blue light LD, and the crystal can be excited by high-energy rays and particles to realize scintillation light output and has many other advantages, and can be used as a potential multifunctional crystal material of visible light band laser crystal and scintillation crystal.

[0056] In order to further illustrate the application, the technical solutions provided by the application are described in detail below with reference to the examples, but they should not be understood as limiting the protection scope of the application.

[0057] Example 1

[0058] In this example, Ba3Y 1-x (PO4)3:xPr polycrystalline powder is synthesized by solid phase sintering method. The specific method comprises the following steps:

[0059] The Ba2CO3, Y2O3, Pr6O 1-x , and NH4H2PO4 in the molar ratio of each substance in the chemical formula Ba3Y 11 (PO4)3:xPr (x = 0.01, 0.04, 0.08, 0.12, 0.16, 0.20) are accurately weighed and mixed and ground uniformly. After tabletting, they are loaded into a corundum crucible and heated at a rate of 200°C / h to 1200°C in a muffle furnace. They are calcined at 1200°C for 20h. After taking out, they are re-ground and mixed uniformly, tabletted, heated at a rate of 200°C / h to 1300°C, and calcined at 1300°C for 20h to obtain Ba3Y 1-x (PO4)3:xPr polycrystalline powder. The fluorescence spectrum of the polycrystalline powder is tested, as shown in Figure 1 It can be seen that with the increase of the doping concentration of praseodymium ions, the emission intensity first increases and then decreases, and the emission intensity is the strongest when the praseodymium ion concentration is 12at.% (x = 0.12).

[0060] Example 2

[0061] In this example, Ba3Y 0.88 (PO4)3:0.12Pr crystal is grown by the Czochralski method. The preparation process comprises the following steps:

[0062] The Pr6O 0.88 , Y2O3, BaCO3, and NH4H2PO4 in the molar ratio of each substance in the chemical formula Ba3Y 11 (PO4)3:0.12Pr (12% Pr:BYP) are accurately weighed and mixed and ground uniformly. After tabletting, they are heated at a rate of 200°C / h to 1200°C in a muffle furnace, calcined at 1200°C for 20h, taken out, re-ground and mixed uniformly, tabletted, heated at a rate of 200°C / h to 1300°C, and calcined at 1300°C for 20h. The synthesized sample is loaded into an iridium crucible with a size of Φ55x50mm 3 , placed into a pulling furnace, the heating body is an iridium crucible, zirconia is used as a heat preservation cover and heat preservation material, and the crystal is grown by the Czochralski method in a N2 atmosphere, with a growth temperature of 1850°C, a pulling speed of 1mm / h, and a crystal rotation speed of 10rpm / min. After the growth is completed, the crystal is slowly pulled away from the liquid surface, and is cooled to room temperature at a rate of 10°C / h. A crystal with a size of Φ15x25mm 3The high-quality 12% Pr:BYP crystal is monocrystalline. After grinding and sieving, a part of the crystal sample is tested by X-ray diffraction spectrum, and the result shows that the doping of praseodymium ions does not affect the crystal structure.

[0063] A 12% Pr:BYP crystal sample is taken, and is processed into a 3*3*2mm 3 thin slice for spectral performance test. The result is shown in Figure 2 , Figure 3 and Figure 4 . The 12% Pr:BYP crystal exhibits strong emission peaks at 482nm, 610nm and 642nm, and the half-peak widths are 12.6nm, 15.5nm and 7.7nm respectively. The three strong and wide emission peaks indicate that the Pr:BYP crystal has the potential to realize cyan, orange and red laser outputs.

[0064] The emission spectrum of the processed crystal material under X-ray excitation at different powers is tested, and the test result is shown in Figure 5 . The three main emission peaks increase in intensity with the increase of X-ray power, and the result indicates that the Pr:BYP crystal has great application prospects in radiation detection.

[0065] In summary, the praseodymium ion doped barium yttrium phosphate crystal is grown by the Czochralski method. In the crystal, the praseodymium ions act as active ions, and not only realize 470-500nm cyan light, 590-620nm orange light and 630-660nm red light emission, but also realize strong visible light reflection under the irradiation or excitation of high-energy rays or particles. The crystal can realize visible light band laser output and scintillation light output, and has wide application prospects in the fields of scientific research, industrial manufacturing and military.

[0066] Although the above embodiment describes the present application in detail, it is only a part of the embodiments of the present application, but not all the embodiments, and other embodiments can be obtained according to the present embodiment without creativity, and these embodiments all belong to the protection scope of the present application.

Claims

1. A praseodymium ion-doped phosphate crystalline material, characterized in that, The chemical formula of the praseodymium ion doped phosphate crystal material is shown as formula 1: Ba3Y 1-x (PO4)3:xPr Formula 1; In formula 1, 0.01≤x≤0.3; The praseodymium ion-doped phosphate crystal material belongs to a cubic system, and the space group is 2. The praseodymium ion-doped phosphate crystalline material of claim 1, wherein, x in formula 1 is 0.01, 0.03, 0.04, 0.08, 0.12, 0.16, 0.2 or 0.

3.

3. The method of producing a praseodymium ion-doped phosphate crystal material according to claim 1 or 2, characterized by, The method comprises the following steps: According to the chemical composition of the praseodymium ion-doped phosphate crystal material, the preparation raw material is sintered twice to obtain Ba3Y 1-x (PO4)3:xPr polycrystalline raw material; the preparation raw material comprises praseodymium oxide, yttrium oxide, an inorganic barium salt, and an inorganic phosphate; the twice sintering comprises a first sintering and a second sintering; The Ba3Y 1-x (PO4)3:xPr polycrystalline starting material is pulled to grow the praseodymium ion doped phosphate crystal material.

4. The preparation method according to claim 3, characterized in that, The first sintering comprises sequentially performing first grinding, first tabletting and first calcination; The temperature of the first calcination is 1000-1500℃, the time is 15-25h, and the temperature rising rate from room temperature to the temperature of the first calcination is 150-250℃ / h.

5. The production method according to claim 3 or 4, characterized by, The second sintering comprises sequentially performing second grinding, second tabletting and second calcination; The temperature of the second calcination is 1100-1600℃, the time is 20-40h, and the temperature rising rate from room temperature to the temperature of the second calcination is 150-250℃ / h.

6. The preparation method according to claim 3, characterized in that, The temperature of the pulling growth is 1750-1950℃, the pulling speed is 0.5-3mm / h, and the rotating speed is 5-15r / min.

7. The production method according to claim 3 or 6, characterized by, After the pulling growth is completed, an initial crystal is obtained, and the method further comprises: cooling the initial crystal from the temperature of the pulling growth to room temperature to obtain the praseodymium ion doped phosphate crystal material; and the cooling rate is 5-20℃ / h.

8. The praseodymium ion doped phosphate crystal material of claim 1 or 2 or the praseodymium ion doped phosphate crystal material prepared by the method of any one of claims 3-7 is applied in visible laser output and radiation detection.

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