CN105780117A - Er<3+>/Pr<3+> co-doped Na5Lu9F32 monocrystal and growth method thereof - Google Patents

Abstract

The invention discloses an Er<3+>/Pr<3+> co-doped Na5Lu9F32 monocrystal and a growth method thereof. Ions Er<3+> and Pr<3+> are doped in a Na5Lu9F32 monocrystal and Pr<3+> is used as a sensitizing ion. The content of OH- ions in the monocrystal is low, no absorption occurs at a wave band 2.7mu m, and the maximum phonon energy is low (440cm<-1>). Under the excitation of a 98nm laser diode, a greatly enhanced 2.7mu m luminous effect is obtained. By adopting a heating temperature field up-shifting method to perform crystal growth, the growth method has the characteristics of simple equipment, strong practicability and the like. The technique can overcome the defects of colored tapes, growth stripes and the like caused by mechanical transmission to the crystal, and facilitate obtaining a high-quality monocrystal.

Description

A kind of Er3+/Pr3+Codope Na5Lu9F32Monocrystal and growing method thereof

Technical field

The present invention relates to Na₅Lu₉F₃₂Monocrystal, be specifically related to a kind of have strengthen 2.7 μm middle-infrared band emission characteristics Er³⁺/Pr³⁺Codope Na₅Lu₉F₃₂Monocrystal and growing method thereof.

Background technology

In recent years, due to the important application at aspects such as laser medicine operation, remote sensing, laser radar, chemical sensitisation and military affairs, The solid state laser of mid-infrared 2.7 μm center wave band is paid much attention to by domestic and international research institution.

Rare earth ion doped inorganic material is one of effective way obtaining near-infrared and mid-infrared laser.Most of group of the lanthanides races are dilute Soil ion has abundant level structure.Wherein Er³⁺Rare earth ion⁴I_11/2→⁴I_13/2Energy level is jumped up and can be produced the fluorescence of 2.7 μm Launch, with Er³⁺For the research that 2.7 μm mid-infrared laser materials of the centre of luminescence are the most certain, mainly Er³⁺Single doping LiYF₄、 CaF₂、YAlO₃、SrLaGa₃O₇、BaY₂F₈Crystal and Er³⁺Fluoride glass matrix with rare earth sensitized ions codope.

Er³⁺Energy level on it in ion⁴I_11/2Fluorescence lifetime than lower energy level⁴I_13/2Short, therefore Er³⁺Ion list doped crystal is in 2.7 μm The luminous efficiency of wave band is relatively low, and luminous intensity is more weak, and this will seriously restrict such material at 2.7 mu m waveband mid-infrared lasers Application in device.Due to Er³⁺:⁴I_13/2With Pr³⁺:³F₄Energy level closely, is co-doped with in the material into Pr³⁺Ion, it is right Er³⁺Ion plays sensibilization, it is possible to effectively Er³⁺:⁴I_13/2Energy on energy level transfers to Pr³⁺:³F₄On ion, subtract Few Er³⁺In ion⁴I_13/2Population on energy level, it is achieved to Er³⁺Energy level under ion⁴I_13/2Effectively go population effect, from And improve Er³⁺Ion is in the luminous efficiency of 2.7 μm middle-infrared bands.

Fluoride is owing to its matrix phonon energy is low, rare earth luminescence efficiency high, middle-infrared band transmitance is high and materialization Can stably wait feature, be the preferred material launched as 2.7 μm mid-infrareds.As laser material fluoride mainly by glass with Two kinds of forms of monocrystal.Although passing through Pr in fluoride glass³⁺The sensibilization of rare earth ion achieves Er³⁺2.7 μm of ion Mid-infrared strengthens illumination effect, but for the nonoxide glass materials such as fluoride, high-quality chunk sizes glass preparation, Particularly the insoluble own defect of aspect such as glass material mechanical performance, thermal property, physical and chemical performance and bad mechanical strength and Technological difficulties restrict its development, also become the biggest obstacle that the nonoxide glass optical fiber such as extraordinary fluoride move towards practical.With glass Glass state material is compared, and the rigidity Cycle-symmetry structure of monocrystal is conducive to obtaining high luminous efficiency and realizing the output of laser； Compared with corresponding fluoride glass matrix, fluoride single crystal body material has the calorifics of excellence, machinery, chemical stability, more Add and be easily worked, the application being more suitable in Laser Devices；Select suitable material as rare earth ion doped matrix, use The rare earth ion doped monocrystal of semiconductor LD pump-coupling is not only the effective way obtaining 2.7 μm mid-infrared light sources, and There is the advantages such as all solid state, good stability, miniaturization and device.

Research for fluoride single crystal body up to now is concentrated mainly on LiYF₄In monocrystal, at Er³⁺/Pr³⁺Codope LiYF₄ Monocrystal achieves luminous (see J.Hu, et al., " Enhanced 2.7mm emission from of enhancing of 2.7 μm middle-infrared bands diode-pumped Er³⁺/Pr³⁺co-doped LiYF₄Single crystal grown by Bridgman method ", Materials Research Bulletin 48, (2013): 2604-2608).But at the LiYF obtained₄In monocrystal, due to LiF and YF₃Prepare former The easy hygroscopicity of material, LiYF₄Monocrystal exists the OH of certain content^-Radical ion, because OH^-Radical ion to～2.7 mu m waveband light Exist and absorb, this absorption bands and Er³⁺2.7 μm mid-infrared fluorescent emission bands of ion coincide, therefore to 2.7 μm mid-infrareds Laser delivery efficiency produces serious influence, and the constant absorption to 2.7 μm emission band can cause the heating of operation material simultaneously.For Can efficiently realize the laser output of 2.7 mu m wavebands, need to reduce in material the concentration of OH-radical ion and reduce laser host material Absorption at 2.7 mu m wavebands.

Na₅Lu₉F₃₂Being the fluoride of a kind of stable performance, the maximum phonon energy of this fluoride is 440cm^-1, therefore rare earth from Son luminous efficiency in this matrix is high.Na₅Lu₉F₃₂Generally existed by two kinds of forms of powder and monocrystal body.The document in past was once Through reporting rare earth ion doped Na₅Lu₉F₃₂The preparation of nano crystalline substance material and optical property (see R.E.Thoma, et al., " The sodium fluoride-lanthnide trifluoride syetem ", Inorganic Chemistry, 5 (7), (1966): 1222-1229；I.M.Shmytko, et al., " Fine structure of Na₅Lu₉F₃₂Nanocrystallites formed at the initial Stage of crystallization ", Physics of the Solid State, 51 (9), (2009): 1907-1911；Shili Gai, et al., " Facile Synthesis and up-conversion properties of monodisperse rare earth fluoride nanocrystals ", Dalton Trans., 41, (2012): 11716-11724.), owing to nano-powder material exists serious scattering to light, limit powder material The application of material；Nano-powder material is due to higher surface-active simultaneously, easily reunites and reaction, and performance is the most unstable；Furthermore, Owing to the preparation of most nano-powder is below the melt temperature of crystal, therefore rare earth ion is typically easy to absorption at nano-powder Surface, hardly enters in the case of crystal.These characteristics of nano-powder so that its range of application is significantly affected. The Integral luminous effect of monocrystal and heigh clarity, the application advantage in the specific areas such as flicker is polycrystal powder material institute Incomparable, but to be always a class the most difficult and be difficult to the technology that breaks through for single crystal growth.For Na₅Lu₉F₃₂, also The rare earth ion doped Na of relatively large body size can not produced₅Lu₉F₃₂Monocrystal.In the present invention with Na₅Lu₉F₃₂For base Matter, is co-doped with wherein into Er³⁺/Pr³⁺, be surprised to find, it is thus achieved that Er³⁺/Pr³⁺: Na₅Lu₉F₃₂Its OH of monocrystal^-Containing of ion Measure extremely low, to 2.7 mu m wavebands almost without absorption.

The growing technology of monocrystal is mainly by czochralski method and Bridgman-Stockbarger method.Czochralski method is to put into raw material in Iridium Crucible to be fused into Melt, allows seed crystal contact bath surface, then slow the most upwards lifting crystal growth at moderate temperatures.Its equipment costly, Technology requires height.Owing to crucible is opening, when having high corrosion with rodent fluoride single crystal body for growth, it is stainless Steel equipment was greatly lowered by serious infringement, service life, also needed to the gas shield device of complexity in burner hearth simultaneously, Therefore be not suitable for growing fluoride single crystal body.Bridgman-Stockbarger method is in the case of temperature field keeps stablizing, and passes through mechanical transmission Slowly decline crucible so that the melt of growth steps into the low-temperature region of below crystallization temperature and carries out crystal growth from high-temperature region, The Bridgman-Stockbarger method improved can fully seal platinum crucible, thus can completely cut off air and steam, prevents the fluorination of volatilization under high temperature The corrosion to equipment of the thing gas.But owing to crucible and growth raw material are in machine driving state, crystal growth is brought by machine driving In crystal, such as produce substantial amounts of colour band, growth striation, the undesirable element such as quality having a strong impact on crystal, be unfavorable for high-quality The large-scale production of fluoride single crystal body.

Summary of the invention

The technical problem to be solved is to provide a kind of OH^-Radical content is few, wave band does not absorb near 2.7 μm mid-infrareds Er³⁺/Pr³⁺Doped fluoride monocrystal and growing method thereof, and this monocrystal have excellence mechanical performance, thermal property, Physical and chemical performance, 2.7 μm mid-infrareds of enhancing are launched and high optical transmittance.

The present invention solves the technical scheme that above-mentioned technical problem used: a kind of Er³⁺/Pr³⁺Codope Na₅Lu₉F₃₂Monocrystal, This Na₅Lu₉F₃₂Monocrystal is a kind of rare earth ion Er³⁺/Pr³⁺The monocrystal of codope, its molecular formula is Na₅Lu_(9-x-y)Er_xPr_yF₃₂, wherein 0.09≤x≤0.45,0.0009≤y≤0.009.

Er³⁺/Pr³⁺It is co-doped with Na₅Lu₉F₃₂Under 980nm laser diode excites, Er³⁺With Pr³⁺The mol ratio of ion exists When 1: 0.01～0.02, the illumination effect of 2.7 μm middle-infrared bands is optimal.

A kind of Er³⁺/Pr³⁺Codope Na₅Lu₉F₃₂The growing method of monocrystal, comprises the following steps:

The dispensing of raw material:

(1), by 40mol%NaF, 56.48～59.316mol%LuF₃, 0.66～3.3mol%ErF₃, 0.024～0.22mol%PrF₃ Mole percent specific concentration component composition, weigh NaF, LuF of corresponding weight respectively₃、ErF₃And PrF₃, mixing is placed on In device for grinding, mixing 5～6 hours of milling, obtain uniform powder；

The hydrogen fluoride high-temperature process of raw material:

(2), above-mentioned compound is placed in boat-shaped Platinum crucible, then is installed in the platinum pipeline of tube type resistance furnace, the most first use N₂Gas gets rid of the air in platinum pipeline, then at temperature 770～800 DEG C, under logical HF gas, reaction treatment 1～5 hours, removes Remove the H that may contain₂O and oxyfluoride, absorb the HF gas in tail gas, reaction knot by NaOH solution in course of reaction Shu Hou, stops logical HF gas, closes tube type resistance furnace, finally use high-purity N₂Gas gets rid of the HF gas of residual in platinum pipeline Body, obtains mixed with Er³⁺And Pr³⁺Polycrystalline powder；

Crystal growth:

(3), above-mentioned polycrystalline powder is placed in device for grinding clays into power, be subsequently placed in Pt crucible and be compacted, seal Pt crucible；

(4), the Pt crucible of sealing is placed in Si-Mo rod stove, carries out crystal growth with adding shifting method on thermal temperature field, growth crystal Parameter is: furnace body temperature is 990～1020 DEG C, and inoculation temperature is 860～880 DEG C, the thermograde of solid liquid interface be 50～ 80 DEG C/cm, drive mechanism moving and adds thermal temperature field and carry out crystal growth, it is 0.4～2mm/h that thermal field moves speed；

The in-situ annealing of crystal

(5), after crystal growth terminates, stop mechanical mobile device, warm to room temperature with per hour 20～50 DEG C of decline stoves, carry out crystalline substance The in-situ annealing of body, finally obtains Er³⁺/Pr³⁺The Na of codope₅Lu₉F₃₂Monocrystal.

NaF, LuF described in step (1)₃、ErF₃And PrF₃Purity be all higher than 99.99%.

The structural representation of the device used by the present invention is as shown in Figure 1.Its burner hearth includes being placed in surrounding heat-insulation layer 9 (mainly by Al₂O₃ Foamed brick and asbestos form), upper heat-preserving cover plate 10 is (by Al₂O₃Foamed brick form) and lower baffle plate 4 (by Al₂O₃Foamed brick Composition) in, Si-Mo rod heater 5 is as heater element, by collet 2 supporting al₂O₃Ceramic cylinder 3, fills up in cylinder 3 Al₂O₃Powder 8 is to play fixing platinum crucible 7 and insulation effect.With fire box temperature respectively with single platinum rhodium thermoelectricity bottom platinum crucible Even 1 detects with single platinum rhodium thermocouple 6, completes seeded process according to the temperature that thermocouple 1 measures, and thermocouple 6 is as temperature control Thermocouple, the thermograde of the solid liquid interface between high-temperature region and low-temperature space can be come with size by the thickness of lower baffle plate 4 Regulation, the temperature of burner hearth can be regulated by watt level.Whole stove is fixed on fixed mount and mechanical driving device 11.

Owing to crystal growth is mainly completed with the regulation of temperature gradient of solid-liquid interface by the control of precision mechanical transmission 11, Keeping static due to crucible and growth raw material in growth course, heater moves up, because referred to herein as " adding shifting method on thermal temperature field ".

Advantages of the present invention:

1, Pr is mixed in the material³⁺Rare earth sensitized ions, passes through Er³⁺:⁴I_13/2To Pr³⁺:³F₄Effective energy transfer, subtract Lack Er³⁺In ion⁴I_13/2Population on energy level, it is achieved to Er³⁺Energy level under ion⁴I_13/2Effectively go population effect, Thus improve Er³⁺Ion is in the luminous efficiency of 2.7 μm middle-infrared bands.

2, due to growth Na₅Lu₉F₃₂The raw material of monocrystal is NaF and LuF₃, the dispensing through step (1), step (2) high temperature HF process, the Pt sealed crucible of step (3), growth and the crystal in-situ annealing of step (5) of step (4), so can obtain bigger The crystal higher with quality, Na₅Lu₉F₃₂OH in monocrystal^-The content of ion is low, the embodiment measured from Fig. 4 Er³⁺/Pr³⁺: Na₅Lu₉F₃₂With comparative example Er³⁺/Pr³⁺: LiYF₄Finding out through spectrogram of monocrystal, Er³⁺/Pr³⁺: Na₅Lu₉F₃₂Single Crystal has beyond thought low OH^-Ion concentration, in 2.7 μm middle-infrared bands almost without absorption, transmitance is high, so And LiYF₄Monocrystal exists a certain amount of OH^-Ion, the absorption coefficient in 2.7 μm is 0.144cm^-1.This due to NaF, LuF₃And Na₅Lu₉F₃₂It is difficult to moisture absorption comparatively speaking formed.Therefore 2.7 μm mid-infrared laser delivery efficiencies will not be produced shadow Ring.The heating of crystal will not be caused simultaneously, can efficiently realize the laser output of 2.7 mu m wavebands and stable operation.Can from Fig. 4 To obtain, Na₅Lu₉F₃₂(reach 7150cm^-1) compare LiYF₄(reach 6417cm^-1) monocrystal has wide through model in middle-infrared band Enclose, simultaneously according to the Raman spectrum Fig. 2, Na measured₅Lu₉F₃₂Fluoride single crystal body maximum phonon energy is only 440cm^-1, because of This it be a kind of to possess the crystalline material that luminous efficiency is high, rare earth ion doping content in this crystal is high.

3, the shifting method on thermal temperature field that adds of this method is mainly passed through: 1. descend thickness and the size of heat shield 4；2. the thickness of heat shield 10 is gone up Degree and size；3. the means such as the thickness of heat-insulation layer 9 and material realize comparatively ideal longitudinal direction and transverse temperature distribution, the speed of growth Realized by precision drive mechanical control equipment.The crucible sealed can completely cut off air and steam, can grow under air ambient, Severe contamination equipment caused without expensive high-vacuum apparatus and fluoride volatilization and corrosion function, therefore this Fa Keming The aobvious production cost reduced and the mass output rate of raising crystal, and equipment is relatively easy, practical.Simultaneously because crucible is former with growth Material remains static, the colour band in therefore this technology overcomes in growth course the crystal caused by machine driving, growth The defects such as striped, are conducive to obtaining high-quality monocrystal and carrying out large-scale production.

Accompanying drawing explanation

Fig. 1 is the structural representation of equipment therefor of the present invention；

The Raman spectrogram of Fig. 2 is embodiment one acquisition monocrystal；

X-ray powder diffraction (XRD) figure (a) and standard cube phase Na of the monocrystal that Fig. 3 is obtained by embodiment one₅Lu₉F₃₂ X-ray powder diffraction figure (b)；

Fig. 4 is embodiment one Er³⁺/Pr³⁺Codope Na₅Lu₉F₃₂Monocrystal through spectrogram (a) and reference examples one Er³⁺/Pr³⁺ Codope LiYF₄Monocrystal through spectrogram (b).

Detailed description of the invention

Below in conjunction with accompanying drawing embodiment, the present invention is described in further detail.

Embodiment one

A kind of rare earth ion doped Na₅Lu₉F₃₂The growing method of monocrystal, including following concrete steps:

(1), form according to following ratio: 40mol%NaF, 59.31mol%LuF₃, 0.66mol%ErF₃, 0.03mol%PrF₃, Weigh total amount be 150 grams, purity respectively prepare raw material more than 99.99%, mixing is placed in device for grinding, mixing 5 hours of milling, Obtain uniform powder；

(2), above-mentioned compound is placed in boat-shaped Platinum crucible, then is installed in the platinum pipeline of tube type resistance furnace, then first Use N₂Gas gets rid of the air in platinum pipeline, then temperature 770 DEG C, under logical HF gas, reaction treatment 5 hours, reaction treatment Terminate, close HF gas and tube type resistance furnace, use N₂Gas cleans the HF gas of residual in pipeline, obtains polycrystalline powder；

(3), above-mentioned polycrystalline powder is placed in device for grinding clays into power, be subsequently placed in Pt crucible and be compacted, seal Pt crucible；

(4), the Pt crucible of sealing is placed in Si-Mo rod stove, carries out crystal growth with adding shifting method on thermal temperature field, growth crystal Parameter is: furnace body temperature is 990 DEG C, and inoculation temperature is 860 DEG C, and the thermograde of solid liquid interface is 50 DEG C/cm, drives machinery Device starts upper shifting and adds thermal temperature field and carry out crystal growth, and it is 0.4mm/h that thermal field moves speed；

(5), after crystal growth terminates, stop mechanical mobile device, warm to room temperature with per hour 20 DEG C of decline stoves, carry out crystal In-situ annealing, finally take out sample, peel platinum thin slice off, obtain Er³⁺/Pr³⁺The Na of codope₅Lu₉F₃₂Monocrystal.

Reference examples one

Essentially identical with embodiment one, in different simply steps (1), raw material forms according to following ratio: 51.5mol%LiF, 48.01mol%YF₃, 0.47mol%ErF₃, 0.02mol%PrF₃.Furnace body temperature is 950 DEG C, and inoculation temperature is 850 DEG C.? To Er³⁺/Nd³⁺Codope LiYF₄Monocrystal

Reference examples two

Essentially identical with embodiment one, in different simply steps (1), raw material forms according to following ratio: 40mol%NaF, 59.34mol%LuF₃, 0.66mol%ErF₃.Obtain Er³⁺The Na of single doping₅Lu₉F₃₂Monocrystal.

Cutting the embodiment one obtained, reference examples one, reference examples two monocrystal, polishing obtains sample, and is analyzed With test.The Raman spectrum of the monocrystal that embodiment one measures is shown in Fig. 2, only draws this monocrystal matrix maximum phonon energy For 440cm^-1, it is seen that it radiates probability height of jumping up to be doped in the rare earth ion in this host material, has high luminous efficiency. Fig. 3 is X-ray powder diffraction figure (a) and standard Na of embodiment one₅Lu₉F₃₂The main diffraction peak of XRD (b) be all consistent, Therefore the sample that embodiment one growth is obtained is Na₅Lu₉F₃₂Phase material.The XRD of reference examples one monocrystal and standard LiYF₄Unanimously, therefore reference examples one obtain for LiYF₄Phase material.Fig. 4 is embodiment one Er³⁺/Pr³⁺Codope Na₅Lu₉F₃₂ Monocrystal through spectrogram (a) and reference examples one Er³⁺/Pr³⁺Codope LiYF₄Monocrystal through spectrogram (b).Embodiment one In, Er³⁺/Pr³⁺Codope Na₅Lu₉F₃₂In 2.7 μm middle-infrared bands almost without absorption, there is beyond thought low OH^-From Sub-concentration, but LiYF₄Monocrystal exists a certain amount of OH^-Ion, the absorption coefficient in 2.7 μm is 0.144cm^-1。 Meanwhile, at middle-infrared band, Na₅Lu₉F₃₂(reach 7150cm^-1) compare LiYF₄(reach 6417cm^-1) monocrystal has and more widen Through scope.Sample small pieces therein, record Er with inductively coupled plasma atomic emission spectrometer (ICP)³⁺With Nd³⁺ Molar content in crystal, Er in embodiment one³⁺/Pr³⁺Ion doping Na₅Lu₉F₃₂The molecular formula of monocrystal is Na₅Lu_8.9091Er_0.09Pr_0.0009F₃₂, x: y=1: 0.01, the molecular formula of reference examples two monocrystal is Na₅Lu_8.91Er_0.09F₃₂.980nm swashs Optical diode excites down, measures embodiment one and reference examples two emissive porwer at 2.7 mu m wavebands, embodiment one Er³⁺/Pr³⁺Double Doping Na₅Lu₉F₃₂2.7 μm fluorescence intensities of monocrystal are 5.2 (arbitrary units), and reference examples two Er³⁺Single doping Na₅Lu₉F₃₂ 2.7 μm fluorescence intensities of monocrystal are only 1.3 (arbitrary units), and the ratio of fluorescence intensity is 4, it is seen that at essentially identical Er³⁺Dense Under degree, Pr³⁺Incorporation 2.7 μm fluorescence intensities have been greatly enhanced.The Na obtained by " adding shifting method on thermal temperature field " growth₅Lu₉F₃₂ The defect of monocrystal is few, physical and chemical performance good, mechanical strength is high, and it can be cut into device, has stronger light to float simultaneously In vain, flash and the resistivity of photochemical degradating, become the collection luminescent properties of great competitiveness and the novel of physical and chemical performance one Mid-infrared function monocrystal.

Embodiment two

Essentially identical with embodiment one, in different simply steps (1), raw material forms according to following ratio: 40mol%NaF, 56.42mol%LuF₃, 3.3mol%ErF₃, 0.28mol%PrF₃, mixing is placed in device for grinding, mixing 6 hours of milling；Step Suddenly temperature 800 DEG C in (2), under logical HF gas, reaction treatment 1 hour；In step (4), the parameter of growth crystal is: body of heater Temperature is 1020 DEG C, and inoculation temperature is 880 DEG C, and the thermograde of solid liquid interface is 80 DEG C/cm, thermal field moves speed and is 2mm/h；Step (5) warms to room temperature with per hour 50 DEG C of decline stoves, finally obtains Er³⁺/Pr³⁺The Na of codope₅Lu₉F₃₂Single Crystal.

Reference examples three

Essentially identical with embodiment two, in different simply steps (1), raw material forms according to following ratio: 40mol%NaF, 56.8mol%LuF₃, 3.3mol%ErF₃.Obtain Er³⁺The Na of single doping₅Lu₉F₃₂Monocrystal.

The monocrystal of embodiment two with reference examples three growth is carried out performance test, the monocrystal that embodiment two obtains with reference examples three XRD essentially identical with Fig. 3, therefore the sample that obtained of growth is Na₅Lu₉F₃₂Phase material.Sample small pieces therein, Er is recorded with inductively coupled plasma atomic emission spectrometer (ICP)³⁺With Pr³⁺Molar content in crystal, embodiment two Middle Er³⁺/Pr³⁺Ion doping Na₅Lu₉F₃₂The molecular formula of monocrystal is Na₅Lu_8.541Er_0.45Pr_0.009F₃₂, x: y=1: 0.02, reference examples The molecular formula of three monocrystal is Na₅Lu_8.55Er_0.45F₃₂.980nm laser diode excites down, measures embodiment two and reference examples three At the emissive porwer of 2.7 mu m wavebands, embodiment two Er³⁺/Pr³⁺Codope Na₅Lu₉F₃₂2.7 μm fluorescence intensities of monocrystal are 13.6 (arbitrary units), and reference examples three Er³⁺Single doping Na₅Lu₉F₃₂It is (the most single that 2.7 μm fluorescence intensities of monocrystal are only 4.2 Position), the ratio of fluorescence intensity is 3.2, it is seen that at essentially identical Er³⁺Under concentration, Pr³⁺Incorporation that 2.7 μm have been greatly enhanced is glimmering Luminous intensity.The Na obtained by " adding shifting method on thermal temperature field " growth₅Lu₉F₃₂The defect of monocrystal is few, physical and chemical performance good, Mechanical strength is high, can be cut into device.

Embodiment three

Essentially identical with embodiment one, in different simply steps (1), raw material forms according to following ratio: 40mol%NaF, 57.77mol%LuF₃, 2.1mol%ErF₃, 0.13mol%PrF₃, mixing is placed in device for grinding, mixing 5.5 hours of milling； Temperature 780 DEG C in step (2), under logical HF gas, reaction treatment 3 hours；In step (4), the parameter of growth crystal is: stove Temperature is 1010 DEG C, and inoculation temperature is 870 DEG C, and the thermograde of solid liquid interface is 60 DEG C/cm, thermal field moves speed and is 1.2mm/h；Step (5) warms to room temperature with per hour 30 DEG C of decline stoves, finally obtains Er³⁺/Nd³⁺The Na of codope₅Lu₉F₃₂ Monocrystal.

Reference examples four

Essentially identical with embodiment two, in different simply steps (1), raw material forms according to following ratio: 40mol%NaF, 57.9mol%LuF₃, 2.1mol%ErF₃.Obtain Er³⁺The Na of single doping₅Lu₉F₃₂Monocrystal.

To embodiment three and reference examples four growth containing Er³⁺/Pr³⁺Codope and Er³⁺Single doping Na₅Lu₉F₃₂Monocrystal carries out performance Test, embodiment three is essentially identical with Fig. 3 with the XRD of the monocrystal that reference examples four obtains, and therefore grows the sample obtained For Na₅Lu₉F₃₂Phase material.Sample small pieces therein, record with inductively coupled plasma atomic emission spectrometer (ICP) Er³⁺With Pr³⁺Molar content in crystal, Er in embodiment three³⁺/Pr³⁺Ion doping Na₅Lu₉F₃₂The molecular formula of monocrystal is Na₅Lu_8.609Er_0.27Pr_0.0043F₃₂, x: y=1: 0.016, the molecular formula of reference examples four monocrystal is Na₅Lu_8.73Er_0.27F₃₂。980nm Laser diode excites down, measures embodiment three and reference examples four emissive porwer at 2.7 mu m wavebands, embodiment three Er³⁺/Pr³⁺ Codope Na₅Lu₉F₃₂2.7 μm fluorescence intensities of monocrystal are 34.3 (arbitrary units), and reference examples four Er³⁺Single doping Na₅Lu₉F₃₂2.7 μm fluorescence intensities of monocrystal are only 3.8 (arbitrary units), and the ratio of fluorescence intensity is 9, it is seen that essentially identical Er³⁺Under concentration, Pr³⁺Incorporation 2.7 μm fluorescence intensities have been greatly enhanced.Obtained by " adding shifting method on thermal temperature field " growth Na₅Lu₉F₃₂The defect of monocrystal is few, physical and chemical performance good, mechanical strength is high, can be cut into device.

Claims (3)

1. an Er³⁺/Pr³⁺Codope Na₅Lu₉F₃₂Monocrystal, it is characterised in that this Na₅Lu₉F₃₂Monocrystal be a kind of rare earth from Sub-Er³⁺/Pr³⁺The monocrystal of codope, the chemical molecular formula of monocrystal is Na₅Lu_(9-x-y)Er_xPr_yF₃₂, wherein 0.09≤x≤0.45, 0.0009≤y≤0.009, and x: y=1: 0.01～0.02.

2. a kind of Er as claimed in claim 1³⁺/Pr³⁺Codope Na₅Lu₉F₃₂The growing method of monocrystal, it is characterised in that bag Include following steps:

(1), by 40mol%NaF, 56.42～59.31mol%LuF₃, 0.66～3.3mol%ErF₃, 0.03～0.28mol%PrF₃ Mole percent specific concentration component composition, weigh NaF, LuF of corresponding weight respectively₃、ErF₃And PrF₃, mixing is placed on In device for grinding, mixing 5～6 hours of milling, obtain uniform powder；

(2), above-mentioned compound is placed in boat-shaped Platinum crucible, then is installed in the platinum pipeline of tube type resistance furnace, the most first use N₂Gas gets rid of the air in platinum pipeline, then at temperature 770～800 DEG C, under logical HF gas, reaction treatment 1～5 hours, removes Remove the H that may contain₂O and oxyfluoride, absorb the HF gas in tail gas, reaction knot by NaOH solution in course of reaction Shu Hou, stops logical HF gas, closes tube type resistance furnace, finally use high-purity N₂Gas gets rid of the HF gas of residual in platinum pipeline Body, obtains mixed with Er³⁺And Nd³⁺Polycrystalline powder；

(3), above-mentioned polycrystalline powder is placed in device for grinding clays into power, be subsequently placed in Pt crucible and be compacted, seal Pt crucible；

(4), the Pt crucible of sealing is placed in Si-Mo rod stove, carries out crystal growth with adding shifting method on thermal temperature field, growth crystal Parameter is: furnace body temperature is 990～1020 DEG C, and inoculation temperature is 860～880 DEG C, the thermograde of solid liquid interface be 50～ 80 DEG C/cm, drive mechanism moving and adds thermal temperature field and carry out crystal growth, it is 0.4～2mm/h that thermal field moves speed；

(5), after crystal growth terminates, stop mechanical mobile device, warm to room temperature with per hour 20～50 DEG C of decline stoves, carry out crystalline substance The in-situ annealing of body, finally obtains Er³⁺/Pr³⁺The Na of codope₅Lu₉F₃₂Monocrystal.

Growing method the most according to claim 2, it is characterised in that NaF, the LuF described in step (1)₃、ErF₃With PrF₃Purity be all higher than 99.99%.