Inorganic crystal material and preparation method and application thereof

Abstract

The present application discloses an inorganic crystal material and its preparation method and application, which belongs to the field of inorganic optical functional crystal materials. The chemical formula of the inorganic crystal material is Nd x Dy y Lu 3‑x‑ y Al3ScGaO 12 ; Among them, 0.002≤x≤0.005, 0.005≤y≤0.05, 0.1≤x / y≤0.5; Nd 3+ 、Dy 3+ Replace Lu in crystals 3+ The lattice sites are distributed on the same lattice site. A preparation method for this inorganic crystal material is also provided, capable of growing single crystals measuring φ30 mm x (50-60) mm. This inorganic crystal material is used to achieve cyan laser output, capable of achieving 496 nm cyan laser output under 448 nm pumping. This inorganic crystal material has excellent optical quality and meets the requirements of high-power all-solid-state lasers.

Description

Technical Field

[0001] The present application relates to an inorganic crystal material and a preparation method and application thereof, belonging to the field of inorganic optical functional crystal materials. Background Art

[0002] Visible-band all-solid-state lasers have broad application prospects in laser processing, storage, display, lithography, biomedicine and other fields. Compared with long-wavelength lasers, short-wavelength laser processing has its unique advantages. It performs "cold" processing by directly destroying the chemical bonds within the material without generating a large amount of waste heat. Therefore, it becomes an ideal tool for processing fragile materials such as plastic products. It can also be used for metal punching, cutting and marking. In addition, the laser has good focusing performance and high resolution, making it the most ideal laser light source for laser processing such as optical engraving, 3D printing, high-precision circuit boards, solar cells, LED conductive film processing, wafer marking, and micro-drilling.

[0003] In recent years, with the continuous advancement of LED lighting research, the power of InGaN / GaN-based blue laser diodes has reached watts and above, while the cost has continued to decline. This has opened up the possibility of directly pumping laser crystals to generate visible-band laser light, ushering in a new era in the research and application of visible-band lasers. Directly pumping laser crystals with blue laser diodes can directly produce laser outputs in cyan, yellow, red, and orange wavelengths. This method offers advantages such as low signal-to-noise ratio, high stability, and high beam quality. Therefore, direct pumping to generate visible-band laser light is currently the most convenient method and has been a hot research topic in the laser field in recent years.

[0004] Doping Tb into laser gain medium 3+ 、Sm 3+ 、Dy 3+ 、Eu 3+ and Pr 3+ Rare earth ions such as Pr 3+ Laser crystals can emit fluorescence in multiple wavelengths (blue, green, red and orange), and there are many reported studies. Currently, the crystals that have achieved yellow laser light include Dy 3+ Activated YAG and LiLuF4 crystals, with their superior overall performance, have become the most widely studied yellow laser crystal materials. However, research into cyan lasers is currently lacking, with relatively few published reports. High-power cyan lasers are widely used in biomedicine, and further, cyan laser frequency doubling technology can produce ultraviolet lasers, a field in which research remains underdeveloped. Given the current weak research foundation for cyan laser materials, further research into novel cyan laser crystal materials has significant scientific and practical value. Summary of the Invention

[0005] The present application provides a co-doped Nd 3+ Dy sensitizing ion 3+ Activated inorganic crystalline material, namely crystalline Nd x Dy y Lu 3-x-y Al3ScGaO 12 , where 0.002≤x≤0.005, 0.005≤y≤0.05, 0.1≤x / y≤0.5; where Nd 3 + 、Dy 3+ 、Lu 3+ They are distributed on the same lattice site and connected with 8 O atoms to form a dodecahedron. 3+ Sc 3+ and Ga 3+ Distributed on the same lattice site, it is connected to the O atom in four-coordinate and eight-coordinate modes. Due to the disordered distribution of multiple ions on the same lattice site, the crystal field regulation effect and the Nd 3+ 、Dy 3+ The sensitization mechanism between ions, based on this crystal, using blue light LD pumping can achieve ~496nm cyan band laser.

[0006] According to the first aspect of the present application, there is provided an inorganic crystalline material, the chemical formula of the inorganic crystalline material is

[0007] Nd x Dy y Lu 3-x-y Al3ScGaO 12 ;

[0008] Among them, 0.002≤x≤0.005, 0.005≤y≤0.05, 0.1≤x / y≤0.5;

[0009] Nd 3+ 、Dy 3+ Replace Lu in crystals 3+ 's grids are distributed together on the same grid.

[0010] Optionally, the upper limit of x is selected from 0.0022, 0.0026, 0.0028, 0.0033, 0.0037, 0.0042, 0.0048 or 0.005; the lower limit is selected from 0.002, 0.0023, 0.0027, 0.0031, 0.0035, 0.0040, 0.0045 or 0.0048.

[0011] Optionally, the upper limit of y is selected from 0.0052, 0.0064, 0.0075, 0.0096, 0.018, 0.032, 0.044 or 0.05; the lower limit is selected from 0.005, 0.0062, 0.0074, 0.0095, 0.016, 0.030, 0.042 or 0.048.

[0012] The upper limit of x / y is selected from 0.12, 0.16, 0.25, 0.31, 0.38, 0.43, 0.46 or 0.5; the lower limit is selected from 0.1, 0.14, 0.22, 0.29, 0.36, 0.41, 0.44 or 0.48.

[0013] Optionally, Nd 3+ 、Dy 3+ 、Lu 3+ They are distributed on the same lattice site and connected with 8 O atoms to form a dodecahedron. 3+ Sc 3+ and Ga 3+ They are distributed on the same lattice site and connected to O atoms in four-coordinate and eight-coordinate modes.

[0014] Optionally, the absorption spectrum of the inorganic crystal material contains an absorption peak with a peak value of 448 nm.

[0015] Optionally, the absorption spectrum of the inorganic crystal material contains Nd 3+ and Dy 3+ The characteristic absorption peak of the ion is 0.596 cm at 448 nm. -1 .

[0016] Optionally, the inorganic crystal material contains four fluorescence peaks in the visible light band in the fluorescence spectrum under 448 nm pumping, and the peak values ​​of the four fluorescence peaks are respectively between 476 nm and 500 nm, between 562 and 598 nm, between 671 and 680 nm, and between 749 and 800 nm.

[0017] Preferably, the peak values ​​of the four fluorescence peaks are 496 nm, 582 nm, 677 nm and 763 nm, respectively, with the strongest peak wavelength being 496 nm.

[0018] Optionally, the resulting single crystal has at least one dimension exceeding 40 mm.

[0019] Preferably, the resulting single crystal has at least one dimension exceeding 50 mm.

[0020] Preferably, the resulting single crystal has at least one dimension exceeding 60 mm.

[0021] According to a second aspect of the present application, a method for preparing the above-mentioned inorganic crystal material is provided.

[0022] The method for preparing the above-mentioned inorganic crystal material comprises the following steps:

[0023] The polycrystalline powder of the inorganic crystal material is prepared by a high-temperature solid-phase sintering method of sesquioxide containing Nd, Dy, Lu, Al, Sc and Ga; and then the inorganic crystal material is grown by a melt pulling method.

[0024] Optionally, the following steps are included:

[0025] The raw materials Dy2O3, Nd2O3, Lu2O3, Sc2O3, Ga2O3 and Al2O3 are mixed uniformly, pre-sintered and sintered, and the pre-sintering and sintering are repeated to obtain a polycrystalline powder of the inorganic crystal material;

[0026] The polycrystalline powder is placed in a crucible, melted in an inert atmosphere, and grown using an intrinsic crystal polycrystalline raw material rod as a seed crystal to obtain a single crystal of the inorganic crystal material.

[0027] Optionally, the molar ratio of Nd, Dy, Lu, Al, Sc and Ga elements in the raw materials is

[0028] Nd:Dy:Lu:Al:Sc:Ga=x:y:3-xy:3:1:1

[0029] Among them, 0.002≤x≤0.005, 0.005≤y≤0.05, 0.1≤x / y≤0.5.

[0030] Optionally, the pre-sintering conditions are:

[0031] The pre-sintering temperature is 1100-1150° C., and the pre-sintering time is 24-30 hours.

[0032] Optionally, the upper limit of the pre-sintering temperature is selected from 1110°C, 1130°C, 1140°C or 1150°C; the lower limit is selected from 1100°C, 1110°C, 1120°C or 1140°C.

[0033] Optionally, the upper limit of the pre-sintering time is selected from 26 hours, 27 hours, 28 hours, 29 hours or 30 hours; the lower limit is selected from 24 hours, 25 hours, 26 hours, 27 hours or 28 hours.

[0034] Optionally, the sintering conditions are:

[0035] The sintering temperature is 1280-1350° C., and the pre-sintering time is 36-42 hours.

[0036] Optionally, the upper limit of the sintering temperature is selected from 1290°C, 1310°C, 1320°C, 1330°C, 1340°C or 1350°C; the lower limit is selected from 1280°C, 1295°C, 1310°C, 1325°C, 1335°C or 1340°C.

[0037] Optionally, the upper limit of the sintering time is selected from 37h, 38h, 39h, 40h or 42h; the lower limit is selected from 36h, 37h, 38h, 39h or 41h.

[0038] Optionally, the pre-sintering and sintering are repeated 0 to 3 times.

[0039] Specifically, the raw materials are Nd2O3, Dy2O3, Lu2O3, Al2O3, Sc2O3 and Ga2O3; the purity of each is 5N grade.

[0040] Specifically, the high-temperature solid-phase sintering method includes the following steps:

[0041] a) The raw materials are accurately weighed according to the chemical reaction ratio, ground evenly, pressed into sheets, placed in a platinum crucible, placed in a sintering furnace, and slowly heated to 1100-1150°C at a heating rate not exceeding 220°C / h. After maintaining the temperature for not less than 24-30 hours, the crucible is placed in a high-temperature sintering furnace and sintered at a constant temperature of 1280-1350°C for 36-42 hours, and the sample is taken out;

[0042] b) Repeat step a) until the X-ray powder diffraction pattern of the sample is completely consistent with that of the standard card.

[0043] Optionally, the growth conditions are:

[0044] The pulling rate of the seed crystal rod is 0.45-1.55 mm / h, the cooling rate is 1-24° C. / h, and the rotation rate of the seed crystal rod is 9-15 rpm.

[0045] Preferably, the pulling rate of the seed rod is 0.5-1.5 mm / h, the cooling rate is 1-10° C. / h, and the rotation rate of the seed rod is 10-15 rpm.

[0046] Optionally, the upper limit of the pulling rate is selected from 0.6 mm / h, 0.7 mm / h, 0.8 mm / h, 0.9 mm / h, 1.0 mm / h, 1.1 mm / h, 1.2 mm / h, 1.3 mm / h, 1.4 mm / h or 1.5 mm / h; the lower limit is selected from 0.5 mm / h, 0.6 mm / h, 0.7 mm / h, 0.8 mm / h, 0.9 mm / h, 1.0 mm / h, 1.1 mm / h, 1.2 mm / h, 1.3 mm / h or 1.4 mm / h.

[0047] Optionally, the upper limit of the cooling rate is selected from 2°C / h, 3°C / h, 4°C / h, 5°C / h, 6°C / h, 7°C / h, 8°C / h, 9°C / h or 10°C / h; the lower limit is selected from 1°C / h, 2°C / h, 3°C / h, 4°C / h, 5°C / h, 6°C / h, 7°C / h, 8°C / h or 9°C / h.

[0048] Optionally, the upper limit of the rotation rate of the seed rod is selected from 11 rpm, 12 rpm, 13 rpm, 14 rpm or 15 rpm; the lower limit is selected from 10 rpm, 11 rpm, 12 rpm, 13 rpm or 14 rpm.

[0049] Optionally, after the growth is completed, the crystal is lifted out of the liquid surface and cooled to room temperature at a rate of 5 to 65° C. / h to obtain a single crystal of the crystal material.

[0050] Preferably, the temperature is lowered to room temperature at a rate of 8-25°C / h.

[0051] Optionally, after the seed rod leaves the liquid surface, the upper limit of the cooling rate is selected from 10°C / h, 15°C / h, 20°C / h or 25°C / h; the lower limit is selected from 8°C / h, 10°C / h, 15°C / h or 20°C / h.

[0052] Optionally, the polycrystalline powder is loaded into a crucible, placed in a crystal pulling furnace, the crystal pulling furnace is evacuated and filled with high-purity argon, and then the temperature is raised to a temperature higher than the melting point and kept constant to completely melt the raw materials.

[0053] Optionally, an intrinsic crystal raw material rod obtained by hot isostatic pressing is used as a seed crystal.

[0054] Specifically, the melt pulling method includes the following steps:

[0055] The sintered polycrystalline material is placed in an iridium crucible and placed in a crystal pulling furnace. The crystal pulling furnace is evacuated and filled with high-purity argon gas, and then the temperature is raised to 50°C higher than the melting point and kept constant for half an hour to completely melt the raw material. Intrinsic crystal raw material rods are used as seed crystals. During the growth process, the pulling rate of the seed crystal rod is 0.45-1.55mm / h, the cooling rate is 1-24°C / h, and the rotation rate of the seed crystal rod is 9-15rpm. After the growth is completed, the crystal is lifted from the liquid surface and cooled to room temperature at a rate of 5-65°C / h to obtain a size of of transparent crystals.

[0056] According to a third aspect of the present application, an application of the above-mentioned inorganic crystal material is provided.

[0057] The inorganic crystal material described above is used as a cyan laser crystal material to realize the output of a cyan laser with a wavelength in the range of 496 nm under 448 nm pumping.

[0058] According to a fourth aspect of the present application, an all-solid-state laser is provided.

[0059] An all-solid-state laser comprising the inorganic crystal material described above;

[0060] The all-solid-state laser realizes laser output in the cyan wavelength range of 496 nm under 448 nm pumping.

[0061] Optionally, the all-solid-state laser further comprises a fiber-coupled semiconductor end-face pump module, a beam coupling system, an input mirror, a crystal material, and an output mirror;

[0062] The beam coupling system is located behind the fiber-coupled semiconductor end-face pump module;

[0063] The input mirror is located after the beam coupling system;

[0064] The output mirror is located behind the input mirror;

[0065] The inorganic crystalline material is located between the input mirror and the output mirror.

[0066] Optionally, the pump source of the fiber-coupled semiconductor end-pump module is a 448nm LD, adopting an end-pump mode;

[0067] The coupling mirror of the beam coupling system is a plane mirror;

[0068] The input mirror is a concave mirror.

[0069] The beneficial effects of this application include:

[0070] 1) The inorganic crystal material provided by this application is obtained by 3+ 、Nd 3+ Doped Lu3Al3ScGaO 12 Through polycrystalline material synthesis, crystal growth, concentration screening and spectral performance comparison, the optimal Dy and Nd doping concentration that can achieve 496nm cyan laser output can be obtained, which can be used in industrial fields such as mechanical cold processing and optical engraving. Only this formula can achieve ~496nm laser.

[0071] 2) The inorganic crystal material provided in this application has good optical quality and can meet the requirements of high-power all-solid-state lasers.

[0072] 3) The method for preparing the inorganic crystal material provided in this application can grow a single crystal with a size of ф30 mm×(50-60) mm.

[0073] 4) The inorganic crystal material provided in this application is used to achieve cyan band laser output, and can achieve 496 nm cyan band laser output under 448 nm pumping. BRIEF DESCRIPTION OF THE DRAWINGS

[0074] Figure 1 The sample S1 obtained by growth # Crystal photos.

[0075] Figure 2 Sample S1 # Absorption spectrum of .

[0076] Figure 3 Sample S1 # Fluorescence spectrum of .

[0077] Figure 4 It is Nd 3+ -Dy 3+ Schematic diagram of the energy transfer mechanism.

[0078] Figure 5 This is a schematic diagram of the laser experimental setup using the sample.

[0079] List of parts and reference numerals:

[0080] Figure 5 Among them, 1. Fiber-coupled semiconductor end-face pump module; 2. Beam coupling system prism; 3. Beam coupling system prism; 4. Input mirror; 5. Crystal sample; 6. Semiconductor saturable absorber (SA); 7. Output mirror. DETAILED DESCRIPTION

[0081] The present application is described in detail below with reference to embodiments, but the present application is not limited to these embodiments.

[0082] Unless otherwise specified, all raw materials and reagents used in this application were purchased from commercial sources and used directly without treatment. The instruments and equipment used adopted the protocols and parameters recommended by the manufacturers.

[0083] In the embodiment, the instrument used for crystal pulling method growth is a JGD-600 medium frequency pulling furnace produced by the 26th Institute of China Electronics Technology Group Corporation. The heating power, heating and cooling speed and pulling speed are controlled by a computer. The crucible used is an iridium crucible with a size of 80 mm × 60 mm.

[0084] In the embodiment, the raw materials used are Dy2O3, Nd2O3, Lu2O3, Sc2O3, Ga2O3 and Al2O3 with a purity of 99.999%.

[0085] In the examples, the absorption spectrum of the crystal samples was measured on a Lambda950 absorption spectrometer produced by Pekin-Elmer; the fluorescence spectrum under 448 nm pumping was measured on a FLS980 fluorescence spectrometer produced by Edinburgh, UK.

[0086] Example 1 Polycrystalline material preparation and crystal growth

[0087] 5N-grade Dy2O3, Nd2O3, Lu2O3, Sc2O3, Ga2O3, and Al2O3 are accurately weighed according to the ratio in the chemical formula (Nd:Dy:Lu:Al:Sc:Ga=x:y:3-xy:3:1:1), poured into a polytetrafluoroethylene canister, and zirconium balls of appropriate proportions and sizes and an appropriate amount of alcohol are added. The mixture is then mixed thoroughly in a mixer. The raw materials are pressed into sheets, placed in a corundum crucible, and placed in a conventional sintering furnace. The temperature is slowly raised to a pre-sintering temperature at a certain rate and maintained for a period of time. The crucible is then placed in a high-temperature sintering furnace and sintered at the sintering temperature for a period of time. The sample is then removed. The pre-sintering and sintering steps are repeated until the X-ray powder diffraction pattern fully matches the XRD standard JCPDS card of the crystal, thereby obtaining a polycrystalline sample of the crystalline material.

[0088] The sintered polycrystalline raw material is placed in an 80mm x 60mm iridium crucible. To prevent oxidation, the air in the crucible is first evacuated to a pressure of -0.25 Pa. High-purity argon is then introduced to a pressure of 0.14 MPa. The temperature is then raised to 50°C above the melting point and held constant for half an hour to completely melt the raw material. A polycrystalline rod of intrinsic crystal obtained by hot isostatic pressing is used as the seed crystal. During the growth process, the seed crystal rod's pull rate, cooling rate, and rotation rate are controlled. After growth is complete, the crystal is lifted from the liquid surface and cooled to room temperature at a predetermined rate to obtain a transparent single crystal sample of the crystalline material.

[0089] The preparation procedures were identical to those described above, with the differences being the values ​​of x, y, and x / y, as well as the polycrystalline synthesis and crystal growth conditions. Table 1 shows the relationship between the sample numbers, the pre-sintering and sintering conditions during high-temperature sintering, the seed rod pulling rate, cooling rate, and rotation rate during Czochralski crystal growth, the cooling rate from the liquid level to room temperature after growth, and the resulting sample dimensions.

[0090] Table 1

[0091]

[0092] Among them, single crystal sample S1 # The component ratio is x = 0.004, y = 0.01, x / y = 0.4, and the crystal photo obtained is as follows Figure 1 As shown, the single crystal sample S1# has a crystal size of 31 mm in diameter and 65 mm in length.

[0093] Single crystal sample S2 # The component ratio is x=0.008, y=0.01, x / y=0.8.

[0094] Single crystal sample S3 # The component ratio is x=0.0025, y=0.1, x / y=0.025.

[0095] Single crystal sample S4 # The component ratio is x=0.0045, y=0.05, x / y=0.09.

[0096] Single crystal sample S5 # The component ratio is x=0.001, y=0.05, x / y=0.02.

[0097] Determination of spectral properties of the samples obtained in Example 2

[0098] From the bulk crystal sample S1 # ~S5 # In the process, several sizes of 10.0×10.0×1.0mm are processed respectively. 3 The spectral performance of the crystal slices was tested and studied.

[0099] Taking crystal sample S1# as a typical example, its absorption spectrum is as follows Figure 2 As shown in the figure, the absorption spectrum of the sample shows that Dy 3+ and Nd 3+ Characteristic absorption peak of Dy 3+ There are 12 main characteristic absorption peaks, which are located at 327nm, 353nm, 367nm, 387nm, 448nm (absorption coefficient is 0.596cm -1 ), 479nm, 752nm, 804nm, 905nm, 1074nm, 1292nm, 1689nm, corresponding to Dy 3+ exist 6 H 15 / 2 Particles at the ground state energy level 6 P 3 / 2 + 4 I 9 / 2 、 6 P 7 / 2 + 6 I 11 / 2 、 6 P 5 / 2 + 4 M 19 / 2 、 4 F 7 / 2 + 4 I 13 / 2 、 4 I 15 / 2 、 4 F 9 / 2 、 6 F 3 / 2 、6 F 5 / 2 、 6 F 7 / 2 、 6 F 9 / 2 + 6 H 7 / 2 、 6 F 11 / 2 + 6 H 9 / 2 and 6 H 11 / 2 In addition, Nd appears in the 500-540nm, 560-600nm and 720-750nm bands. 3+ The characteristic absorption bands of Nd are located at 531nm, 589nm and 748nm, respectively. 3+ of 4 I 9 / 2 → 2 K 13 / 2 、 4 I 9 / 2 → 5 G 5 / 2 + 2 H 11 / 2 and 4 I 9 / 2 → 4 G 11 / 2 + 2 P 1 / 2 Energy level transition. Nd has a good sensitization effect on Dy, enhancing the crystal's absorption of pump light. Furthermore, because the former has relatively strong absorption intensity and a relatively wide absorption band, it matches commercial blue-light semiconductor pump sources, making several sample crystals very suitable for laser experiments using commercial 448nm blue-light diode pumping.

[0100] Taking crystal sample S1# as a typical example, the room temperature fluorescence spectrum under 448nm pumping is as follows Figure 3 As shown in the figure, the sample has four main fluorescence peaks in the visible light band, with peak values ​​at 496nm, 582nm, 677nm and 763nm, of which the strongest peak wavelength is 496nm. 3+ -Dy 3+ The energy transfer mechanism is shown in the following diagram: Figure 4 As shown. 3+ Ionic 4 F 9 / 2 Energy levels and Nd 3+ Ionic 2 G 9 / 2 The energy levels are close, and the energy will be transferred from Nd 3+ Ion to Dy 3+The ion transfer process is the quasi-resonance energy transfer ET1 process. 3+ ion 4 F 9 / 2 The fluorescence lifetime of the energy level indicates that the energy transfer efficiency of the ET1 process is 4.94%.

[0101] The obtained crystal sample S2 # ~S5 # The spectral performance was measured as described above and the results showed that:

[0102] S2 # Due to the high Nd doping concentration in the sample, the fluorescence emission of Nd dominates and masks the fluorescence emission of Dy.

[0103] S3 # Due to the high Dy doping concentration in the sample, the fluorescence intensity of the crystal in the cyan band is greatly reduced, while the fluorescence emission in other visible bands such as yellow light is very strong, which is not conducive to the realization of cyan band laser.

[0104] S4 # Due to the mismatch of Nd-Dy ion concentration ratio, the sample suffers from fluorescence quenching and cannot achieve effective cyan band fluorescence emission.

[0105] S5 # Since the concentration of Nd ions in the sample is too low, effective Nd-Dy sensitization cannot be achieved, and the absorption in the blue light band is very weak, which is not conducive to the realization of laser.

[0106] Application of the sample obtained in Example 3 in a laser device

[0107] Take sample S1 respectively # ~S5 # , processed into a size of 3mm×3mm×(5~10)mm, with the crystal ends 3mm×3mm polished and applied to the laser device. Figure 5 As shown, it includes a fiber-coupled semiconductor end-face pumping module 1, a beam coupling system, an input mirror 4, a crystal sample 5, a semiconductor saturable absorber (SA) 6, and an output mirror 7; the beam coupling system (including a beam coupling system prism 2 and a beam coupling system prism 3) is located after the fiber-coupled semiconductor end-face pumping module 1; the input mirror 4 is located after the beam coupling system; the output mirror 7 is located after the input mirror 4; the crystal sample 5 is located between the input mirror 4 and the output mirror 7, and the semiconductor saturable absorber (SA) 6 is located between the crystal sample 5 and the output mirror 7.

[0108] The crystal sample was placed in a water-sealed copper tube. The pump source used was a 448nm blue laser diode (LD) operating in end-pump mode. The input mirror was a 200mm diameter concave mirror with high transmittance at 448nm and high reflectance between 490 and 510nm. The coupling mirror was a plane mirror with transmittances of 0.5%, 1%, 2%, 3%, and 4% at a laser wavelength of 496nm. Laser spectra were measured using a Bristol 821B-IR laser wavelength meter, and laser power was measured using an LPE-1B power meter.

[0109] The results showed that the application of sample S1 # The laser device can achieve 496nm cyan laser output.

[0110] Replace the above samples with S2 # ~S5 # , applied to laser devices, the results showed that no effective ~496nm cyan laser output was achieved.

[0111] The above descriptions are merely a few embodiments of the present application and do not constitute any form of limitation to the present application. Although the present application discloses the preferred embodiments as above, they are not intended to limit the present application. Any technical personnel familiar with the present profession, without departing from the scope of the technical solution of the present application, using the technical content disclosed above to make slight changes or modifications are equivalent to equivalent implementation cases and fall within the scope of the technical solution.

Claims

1. An inorganic crystal material, characterized in that The chemical formula of the inorganic crystal material is Nd x Of y In 3-x-y Al3ScGaO 12 4 Among them, 0.002≤x≤0.005, 0.005≤y≤0.05, 0.1≤x / y≤0.5; Nd 3+ 、Dy 3+ Replace Lu in crystals 3+ 's grids are distributed together on the same grid.

2. The inorganic crystal material according to claim 1, characterized in that Nd 3+ 、Dy 3+ 、Lu 3+ They are distributed on the same lattice site and connected with 8 O atoms to form a dodecahedron. 3+ Sc 3+ and Ga 3+ They are distributed on the same lattice site and connected to O atoms in four-coordinate and eight-coordinate modes.

3. The inorganic crystal material according to claim 1, characterized in that The absorption spectrum of the inorganic crystal material contains an absorption peak with a peak value of 448 nm; The absorption spectrum of the inorganic crystal material contains Nd 3+ and Dy 3+ The characteristic absorption peak of the ion is 0.596 cm at 448 nm. -1 ; The inorganic crystal material contains four fluorescence peaks in the visible light band in the fluorescence spectrum under 448nm pumping, and the peak values ​​of the four fluorescence peaks are respectively between 476nm and 500nm, between 562nm and 598nm, between 671nm and 680nm, and between 749nm and 800nm.

4. The inorganic crystal material according to claim 3, characterized in that The peak values ​​of the four fluorescence peaks are 496 nm, 582 nm, 677 nm and 763 nm, respectively, with the strongest peak wavelength being 496 nm.

5. The inorganic crystal material according to claim 1, characterized in that The resulting single crystal has at least one dimension exceeding 40 mm.

6. The inorganic crystal material according to claim 1, characterized in that The resulting single crystal has at least one dimension exceeding 50 mm.

7. The method for preparing the inorganic crystal material according to any one of claims 1 to 6, characterized in that: The following steps are involved: The polycrystalline powder of the inorganic crystal material is prepared by a high-temperature solid-phase sintering method of sesquioxide containing Nd, Dy, Lu, Al, Sc and Ga; and then the inorganic crystal material is grown by a melt pulling method.

8. The preparation method according to claim 7, characterized in that The following steps are involved: The raw materials Dy2O3, Nd2O3, Lu2O3, Sc2O3, Ga2O3 and Al2O3 are mixed uniformly, pre-sintered and sintered, and the pre-sintering and sintering are repeated to obtain a polycrystalline powder of the inorganic crystal material; The polycrystalline powder is placed in a crucible, melted in an inert atmosphere, and grown using an intrinsic crystal polycrystalline raw material rod as a seed crystal to obtain a single crystal of the inorganic crystal material.

9. The preparation method according to claim 8, characterized in that In the raw materials, the molar ratio of Nd, Dy, Lu, Al, Sc and Ga elements is Nd:Dy:Lu:Al:Sc:Ga= x:y:3-xy:3:1:1 Among them, 0.002≤x≤0.005, 0.005≤y≤0.05, 0.1≤x / y≤0.

5.

10. The preparation method according to claim 8, characterized in that The conditions for the pre-sintering are: The pre-sintering temperature is 1100~1150℃, and the pre-sintering time is 24~30h.

11. The preparation method according to claim 8, characterized in that The sintering conditions are: The sintering temperature is 1280~1350℃, and the pre-sintering time is 36~42h.

12. The preparation method according to claim 8, characterized in that The pre-sintering and sintering are repeated 0 to 3 times.

13. The preparation method according to claim 8, characterized in that The growth conditions are: The pulling rate of the seed crystal rod is 0.45-1.55 mm / h, the cooling rate is 1-24° C. / h, and the rotation rate of the seed crystal rod is 9-15 rpm.

14. The preparation method according to claim 13, characterized in that After the growth is completed, the crystal is lifted out of the liquid surface and cooled to room temperature at a rate of 5 to 65° C. / h to obtain a single crystal of the crystal material.

15. The inorganic crystal material according to any one of claims 1 to 6 is used as a cyan laser crystal material to achieve output of a cyan laser with a wavelength in the 496nm band under 448nm pumping.

16. An all-solid-state laser, characterized in that: The inorganic crystal material according to any one of claims 1 to 6; The all-solid-state laser realizes 496nm cyan band laser output under 448nm pumping.

17. The all-solid-state laser according to claim 16, characterized in that: The all-solid-state laser also includes a fiber-coupled semiconductor end-face pump module, a beam coupling system, an input mirror, a crystal material, and an output mirror; The beam coupling system is located behind the fiber-coupled semiconductor end-face pump module; The input mirror is located after the beam coupling system; The output mirror is located behind the input mirror; The inorganic crystalline material is located between the input mirror and the output mirror.

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