CN102108553A - Laser crystal, growth device and method thereof and laser working element prepared from crystal - Google Patents
Laser crystal, growth device and method thereof and laser working element prepared from crystal Download PDFInfo
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Abstract
The invention discloses a thulium/holmium-doped yttrium aluminum garnet crystal, a growth device and method for preparing the crystal and a laser working element prepared from the crystal. The chemical formula of the crystal is Tm, Ho: Y3Al5O12, and the crystal is a cubic one of which the space group is Ia3d, wherein the thulium doping concentration is 1.99-2.01*10<21>/cm<3>, and the holmium doping concentration is 5.00-5.05*10<19>/cm<3>. The crystal provided by the invention solves the problems of short service life of the existing crystal, and small diameter, short service life, uneven optical quality and high cracking possibility of the blank. The laser working element prepared from the crystal solves the defects of small dimension and instable performance of the existing working element.
Description
Technical field
The present invention relates to the laser crystals field, in particular to a kind of yag crystal laser of thulium doped, holmium, the laser work element for preparing growing apparatus, the method for this laser crystals and utilize this crystal to be prepared from.
Background technology
Laser crystals is that the energy that the external world can be provided is converted into the crystalline material with height collimation and monochromaticity laser relevant on room and time by optical resonator, is the operation material of crystal laser.Laser crystals is made up of luminescence center and host crystal two portions.The luminescence center of most of laser crystals is made of active ions, and the positively charged ion that active ions partly replace in the host crystal forms the doping type laser crystals.When active ions become host crystal component a part of, then constitute self-activated laser crystal.
The used active ions of laser crystals are mainly transition-metal ion and trivalent rare earth ions.The 4f electronics of trivalent rare earth ions is subjected to the shielding effect of 5s and 5p out-shell electron, and crystal field is weakened its effect, but the perturbation of crystal field makes the 4f transition of electron of original abstinence become possibility, produces the absorption and the fluorescent line of arrowband.So the spectrum of trivalent rare earth ions in different crystal changes so greatly unlike transition-metal ion.Trivalent rare earth ions at present commonly used is thulium or holmium, and (Ho Tm:YAG) can launch the output of 2.09～2.12 mu m range continuously adjustable laser as the laser apparatus of laser crystals, at home and abroad has been subjected to paying attention to widely with the yag crystal of mixing thulium, holmium.Its main application is mainly used in the new infrared countermeasure system (ATIRCM) of antagonism infrared guidance at military aspect.In addition, because the laser of its output and the absorption peak of water are close, human body is very high to this holmium laser absorption rate, cell tissue outside the target spot then is subjected to thermal damage hardly, therefore, this type of laser apparatus also becomes ideal surgical laser light source, and has been successfully used to various fields such as ophthalmology, surgery, internal medicine, gynaecology, Otorhinolaryngologic Department, cardiology department, Dermatology Department, Urology Surgery, protrusion of intervertebral disc, urinary stone disease.
But regrettably, the crystal blank diameter of the yag crystal of mixing thulium, holmium for preparing at present is smaller, life-span is short, optical quality is inhomogeneous, and ftracture easily, crystalline material be difficult to obtain that size is big, the laser apparatus working element of stable performance according to this, thereby causes the power of laser apparatus lower, can not realize that high power CW exports.
Summary of the invention
Less in order to solve the crystal diameter that exists in the prior art, problems such as life-span weak point the invention provides a kind of laser crystals, and provide a kind of preparation this crystalline equipment, method and the laser works element that utilizes this crystal preparation.
Crystal-chemical formula provided by the invention is Tm, Ho:Y
3Al
5O
12, spacer is Ia3d, the isometric system crystal, and wherein, the doping content of Tm is 1.99～2.01 * 10
21Individual/cm
3, the doping content of Ho is Ho:5.00～5.05 * 10
19Individual/cm
3Preferably, the doping content of Tm is 2.00 * 10
21Individual/cm
3, the doping content of Ho is 5.00 * 10
19Individual/cm
3
The present invention also provides preparation above-mentioned crystalline growing apparatus, comprises seed rod, seed crystal, melt, crucible and resistance heater, different with existing installation is, alumina bubble brick also is set on this device, and on the corresponding height of alumina bubble brick vision slit, has increased louvre.Preferably, the aperture of louvre is 10mm, and quantity is 4.
The invention provides this crystalline method of preparation, this method comprises: with purity greater than 99.999% Tm
2O
3And Ho
2O
3, with Y
2O
3And Al
2O
3After making the molding mass piece, put into single-crystal growing apparatus, vacuumize then, fill shielding gas, heating is the dissolving melt fully; Treat to carry out pulling growth after melt fully dissolves, in whole pulling growth process temperature fluctuation be controlled at ± 1 ℃ in.
In embodiment provided by the invention, the high purity Tm of employing
2O
3And Ho
2O
3Pressurization preparation technology prepares through heating.
In embodiment provided by the invention, the crystal pulling rate is 1.0～1.5mm/hr in the pulling growth step, and the crystal rotating speed is 10～30rpm, and the stove internal gas pressure is controlled at 0.025～0.050Mpa, and crystal diameter is controlled at 55～76mm.Preferably, the provider of seed crystal is to being (111).
The present invention also provides a kind of laser works element, and this laser works element is formed through diffusion interlinked prepared by crystal provided by the invention, is of a size of 6-8mm * 100-140mm.Preferably, diffusion interlinked technology is carried out in single crystal growing furnace or Si-Mo rod stove, and bonding temperature is 1400～1600, constant temperature time 48～72 hours.
By crystal provided by the invention, solved existing crystal life-span weak point, blank diameter is smaller, and the life-span is short, and optical quality is inhomogeneous, easily the rimose problem.The laser works element that is made by this crystal has solved that the work on hand component size is less, the defective of unstable properties.
Description of drawings
Fig. 1 a kind of crystal preparation method's provided by the invention schematic flow sheet;
Fig. 2 " pressurization of heating " provided by the invention ion-exchange preparation technology;
Fig. 3 shows the single-crystal growing apparatus that prior art adopts;
Fig. 4 shows single-crystal growing apparatus provided by the invention;
Fig. 5 a shows the longitudinal temperature changes in distribution graphic representation of existing growing apparatus and growing apparatus provided by the invention;
Fig. 5 b shows the radial temperature profile change curve of existing growing apparatus and growing apparatus provided by the invention.
Embodiment
To be described in further detail goal of the invention of the present invention, technical scheme and beneficial effect below.
Be noted that following detailed description all is exemplary, is intended for the requested to provide further explanation of the invention.Unless otherwise, all technology used herein and scientific terminology have the identical meanings with general technical staff of the technical field of the invention's common sense.
Little in order to solve the crystal diameter that exists in the prior art, the life-span is short, and optical quality is inhomogeneous, problems of crack easily, and (this crystalline chemical formula is Tm, Ho:Y for Tm, Ho:YAG) crystal to the invention provides a kind of yttrium aluminum garnet of mixing thulium, holmium
3Al
5O
12(abbreviate Tm as, Ho:YAG), the composition of raw materials chemical formula is Y
3 (1-x-y)Tm
3xHo
3yAl
5O
12This crystal is an isometric system, its spacer is Ia3d, thulium holmium yttrium aluminum garnet (Tm, Ho:YAG) crystal mixed provided by the present invention, the doping content of Tm can be controlled at 1.99～2.01 * 1021/cm3 scope, and the doping content of Ho can be controlled at 5.00～5.05 * 1019/cm3.Preferably, the doping content of Tm is 2.00 * 10 in the crystal
21Individual/cm
3, the doping content of Ho is 5.00 * 10
19Individual/cm
3
The present invention also provides a kind of preparation above-mentioned crystalline method, the idiographic flow of this method as shown in Figure 1:
1. prepare highly purified Tm with " pressurization of heating " ion exchange technique
2O
3And Ho
2O
3Raw material, the material purity that makes remains on 99.999%.
Fig. 2 shows the preparation process of " pressurization of heating " ion exchange technique: rare earth element that at first will be to be purified is adsorbed on the Zeo-karb with ionic condition, the avidity of tervalent rare earth ion and resin is greater than the Ca2+ of divalence in adsorption process, non-rare earth ion such as Mg2+, therefore can remove the most Ca2+ in the feed liquid after absorption-water washing process is finished, the Mg2+ plasma, thoroughly remove in order to guarantee non-rare earth impurity, can allow the overfeeding of rare earth ion appropriateness, be adsorbed on separating of main body rare earth ion that resin goes up mutually and other rare earth impurities to be removed;
Then, adopting ethylenediamine tetraacetic acid (EDTA) (EDTA) to make eluent gets off rare earth ion desorb from the resin cation (R.C.), adding suitable nitric acid adjustment acidity in the earth solution under the desorb all separates out EDTA, simultaneously can remove impurity such as non-rare earth impurity Fe, Ti, Zr with the oxalic acid precipitation rare earth then, calcination under 850 degree at last, rare earth oxalate becomes the rare earth oxide product.
The plant and instrument that adopts in this preparation process has:
Separator column,
Separator column,
Stainless steel ion exchange column, pressurization adopt automatically and report to the police, the metering force (forcing) pump of automatic shutdown.Operating pressure 6MPa; The employing electrically heated of heating.Sepn process is finished under 60 ℃ of set temperature, and molten material is finished in enamel reactor.Finishing apparatus is made up of stainless steel reaction jar and synthetic glass filtering system.Total system is finished in a closed system substantially, reduces the secondary pollution of non-rare earth to product to greatest extent.
2. the calculating of proportioning raw materials and preparation
In crystal formation process, the reaction equation between each raw material is:
3(1-x-y)Y
2O
3+3xTm
2O
3+3yAl
2O
3+5Tm
2O
3＝2Y
3(1-x-y)Tm
3xHo
3yAl
5O
12
As everyone knows, at Tm, in the Ho:YAG single crystal lattice, Y
3+It is 8 regular dodecahedron center that ion is in the oxonium ion ligancy.Rare earth ion Tm
3+And Ho
3+Ion partly replaces Y
3+The ionic seat.Therefore, calculating Y
2O
3During consumption, should deduct the Tm that adds corresponding to substituting, the Y of the number of ions of Ho
2O
3Quality.
The contriver is according to the feed ratio of each raw material of crystalline thermal defect equilibrium concentration Theoretical Calculation, and the doping proportioning in the above-mentioned reaction equation is arranged on x=0.03～0.12, carried out a large amount of experiments in the scope of y=0.001～0.06.According to thermal defect equilibrium concentration theory, case concentration (what active ions are every cubic centimetre have) can be expressed as: and n=(d% * mh * Nv * p)/Mh.In crystal provided by the invention, for host crystal, the doping content of Tm can be controlled at 1.99～2.01 * 10
21Individual/cm
3Scope, the doping content of Ho can be controlled at Ho:5.00～5.05 * 10
19Individual/cm
3In the specific embodiment provided by the invention, for making that final doping content is Tm:2 * 10
21Individual/cm
3, Ho:5 * 10
19Individual/cm
3, can calculate each raw material feed ratio by case concentration.Wherein, YAG, mh=3, Nv are constant 6.02 * 1023g/mol, p=4.56g/cm
3, Mh is matrix molar mass 593.7g/mol, thus Tm:d%=14.42% (at), Ho:d%=0.36% (at), ratio of components is: Y
2O
3: Tm
2O
3: Ho
2O
3: Al
2O
3=235: 40: 1: 460 (at%)=343.8: 100: 2.448: 303.9 (wt%).By aforementioned calculation as can be known, in this specific embodiment, the total mole number of rare earths material and Al
2O
3The ratio of mole number be 3: 5.
In order to guarantee stoichiometric ratio accurately, must be before weighing with the calcination respectively of various raw materials, to drive away moisture and other volatile substances.With the calcination that various raw materials carry out in silicon carbide rod furnace, the calcination condition can be a normal pressure, and temperature is under 800 ℃, constant temperature time 10 hours.With the various raw materials of precision balance weighing, precision is in the milligram level, raw material ground and mixed in agate glass alms bowl that will take by weighing according to predetermined proportion, pack into then in the Plastic Bottle, be that rotation mixed 20 hours on 5 rev/mins the mixer at rotating speed, again raw material is packed in the latex rubber bag of multilayer (being preferably 3～5 layers), tie up when being strictly on guard against pressurization oil plant incoming stock in.The shape of latex rubber bag is similar to crucible but size is bigger, makes the raw material geomery after the pressurization can guarantee to put into easily crucible; Add pre-compaction forming in the oil press, put into isostatic pressing machine at last and pressurize, applying pressure is 800～1000kg/cm2, makes the molding mass piece.
3. the formation of monocrystalline
3.1 single-crystal growing apparatus: the importance that the present invention is different from prior art is that the single-crystal growing apparatus that the present invention adopts is different from the single-crystal growing apparatus that prior art adopts.Fig. 3 shows the single-crystal growing apparatus that prior art adopts, and 1 is seed rod among Fig. 3, and the 2nd, seed crystal, the 3rd, crystal, the 4th, melt, 5-7 are heat protection screens on the molybdenum, the 8th, crucible, the 9th, crucible tray, 10-12 are molybdenum side heat protection screens, the 13rd, interior screen tube, the 14th, resistance heater, the 15th, pallet, the 16th, battery lead plate, the 17th, molybdenum platform cover, the 18th, connection piece, the 19th, aluminum oxide pad.The single-crystal growing apparatus that the present invention adopts as shown in Figure 4, it is with the different of existing growing apparatus, also is provided with radio-frequency induction circle 20, ZrO on the device
2Lid 21, ZrO
2Powder 22, silica tube 23, alumina bubble brick 24 more particularly, have increased louvre on the corresponding height of alumina bubble brick 24 vision slits of the present invention, and the aperture of louvre is 10mm, and quantity is 4.Crystal bar 1 can refer to lift and rotate according to the top arrow.
Because adopted this single-crystal growing apparatus, on the corresponding height of alumina bubble brick vision slit, increase louvre, increased near interface crystalline heat radiation insulation, form secondary or three symmetrical distributions, set up rational temperature field thus, realized the comprehensive matching design of crystal growth parameter.This device has not only kept the high stability of machine driven system, and guarantees that temperature controlling system has high precision (fluctuation is less than ± 1 ℃).
Fig. 5 a, Fig. 5 b show the temperature distributing curve diagram of the device that existing apparatus shown in Figure 3 and the present invention shown in Figure 4 adopt respectively, and Fig. 5 a represents the longitudinal temperature changes in distribution, and Fig. 5 b represents the symmetry of radial temperature profile.
The variation of its longitudinal temperature of growing apparatus of adopting of the present invention is less as can be seen from Fig. 5 a, does not have temperature jump; From Fig. 5 b as can be seen the growing apparatus that adopts of the present invention formed comparatively ideal temperature field, radial temperature profile changes level and smooth, being distributed symmetrically property of longitudinal temperature is greatly improved, and the temperature variation of existing growing apparatus is bigger, and growing apparatus provided by the invention has been realized the high precision control to temperature in whole single crystal growth process.
3.2 single crystal growth process
The material piece that is shaped is put into the Iridium Crucible of single-crystal growing apparatus, carry out single crystal growing.With the raw material of the pre-compaction forming crucible of packing into, place above-mentioned growing apparatus then, close fire door and vacuumize according to the general requirement and the method for drawing growth, fill shielding gas.Then gradually the heating, treat that melt fully dissolves after, seed crystal gradually descends.After seed crystal contact melt is also stable, the beginning pulling growth.In the process of beginning pulling growth, need suitably adjust temperature at following seed crystal.Can be with the seed crystal of any direction crystal provided by the invention of growing, preferred (111) direction of the present invention.In process of growth, the crystal pulling rate is controlled at 1.0～1.5mm/hr, and the crystal rotating speed is controlled at 10～30rpm, and the stove internal gas pressure is controlled at 0.025～0.050Mpa (1.5kg/cm
2), crystal diameter is controlled at 55～76mm.Temperature control precision is in ± 1 ℃, in this single crystal growth process, also needs to pay close attention to the following aspects:
Influence the step of crystal cleavage: early stage what grow, the crystal shouldering is suitably slow, allows change to take on and goes the fruit degree slowly level and smooth, avoids taking out shoulder formation, thereby eliminates the stress concentration at this position; After isodiametric growth finishes, evenly slowly heat up, and crystal diameter received gradually narrow down to about ∮ 10mm; Do not allowing crystal break away from slowly cooling blowing out under the situation of melt.
The growth interface mode control: a temperature design is the key factor of solid-liquid interface shape control.The temperature field is to guarantee the normal utmost point key condition of pulling method single crystal growing.The solid-liquid interface macroshape is exactly the important embodiment of its temperature distribution.Radial symmetry gradient helps forming the interface of more protruding (to melt) on the increase liquid level.For this reason, must increase the heat radiation of near interface crystalline.In order to address this problem, the measure that the present invention takes is: increase louvre on the corresponding height of insulating brick vision slit, make into secondary or three symmetrical distributions.
The control of crystalline size: receive neck and expand shoulder, isodiametric growth.In the pulling method process of growth, the size of crystal diameter realizes by adjusting heating power (being temperature).After beginning to lift, evenly slow elevated temperature is slowly received the seed crystal diameter carefully, minimum locating generally than about the little 1mm of seed crystal.Neck length is generally in 10mm.After, reduce temperature gradually, allow crystal diameter enlarge gradually, to form " shoulder " portion.The purpose of receiving thin neck is: effectively get rid of the dislocation that is present in the seed crystal, with the crystal of necks such as assurance higher quality is arranged.In shouldering, crystal diameter changes heating schedule successively and changes the isodiametric growth stage over to by crystal before reaching predetermined size.
The crystal maximum length that makes by aforesaid method can reach 241mm, and isometrical maximum length can reach 141mm, and maximum diameter can reach 76mm.
4. the preparation of laser works element
The crystal that above-mentioned preparation technology is obtained passes through the preparation technology that steps such as sample form slection design, crystal aftertreatment, crystal mass initial survey, crystal processing, the detection of laser work element quality, crystal plated film, working element performance test are finished the laser works element.
Sample form slection design: according to the shape and size of customer requirements, select the crystal blank, the parallel crystal initial and tail sections that cuts grinds, polishes two cut surfaces, observes the stress distribution situation in the crystal then on stressometer; The crystal that both ends of the surface have been polished cuts into piece by the shape and size of customer requirements again.
Crystal aftertreatment: Tm, the Ho:YAG crystal is in the whole process of growth, and encephalic all is an inert atmosphere.Under hot conditions, regular meeting's anoxic in the crystal, and then form colour center (point) defective; Simultaneously, crystal is grown under big thermal gradient condition, also has thermal stresses in the protocrystal.Both of these case is all to Tm, and the application of Ho:YAG crystal in Laser Devices causes disadvantageous effect.Therefore, must carry out high-temperature heat treatment to crystal.The crystal of well cutting is put into silicon carbide rod furnace, carry out high-temperature heat treatment in atmosphere, the highest thermostat temperature is 1200～1250 ℃, and constant temperature time is 48～72 hours.
Crystal mass initial survey: 1. outward appearance: whether regular, whether crystal has cracking if observing crystalline color and profile; 2. scattering particles: by detection means a detecting instrument: wavelength 6328AHe-Ne laser apparatus is observed, testing conditions: He-Ne laser power 21mW, and He-Ne light from first to last laterally moved inject Tm, the Ho:YAG crystal bar is observed in the crystal and is had or not a scattering point.23 ℃ of ambient temperature, humidity 65%.B optically focused forceful electric power tube; 3. core and striation: the crystal that grows is with polarisation inspection " core " and striation; 4. stress detects: model is a WYL-2 type stressometer, testing conditions: with Tm, the Ho:YAG crystal lies on the sheet glass of stressometer, and rotation is observed in whole crystal and had or not area of high stress.23 ℃ of ambient temperature, humidity 65%.
Crystal processing: non-uniformly " core " district cuts laser bar in that no scattered particle striation is light.Crystal element diffusion interlinked is required crystal element can't directly cutting processing prepares from the crystal blank time and a kind of alternate ways that adopts also is the technology that recent development is in the world got up, and gone together and extensively payes attention to, and difficulty is very big.Mainly show the precision sizing (making it to reach the optical cement degree) of big bonding face and the special processing of crystal binding surface.The present invention adopts the diffusion interlinked technology of laser bar to prepare big element.Bonding is to carry out in single crystal growing furnace or Si-Mo rod stove, and the diffusion interlinked device and the single-crystal growing apparatus of employing are close, just in crucible, pack into be not the clean optical cement of raw material but surface cleaning good treat the bonding assembly, last stay-warm case adopts dull and stereotyped ZrO
2Get final product.Bonding temperature is between 1400～1600 ℃.Connect bad if temperature is crossed low meeting; The too high crystal assembly that then may cause melts, or takes place bonding with crucible.During bonding, constant temperature time 48～72 hours.
By above-mentioned working method, the rod-shaped laser working element size that makes can reach the mm of (6-8) mm * (100-140), the mm of the mm of tabular being of a size of (3-5) mm of processing * (50-71) * (60-105).
5. the laser work element quality detects: the crystal that makes is carried out energy level fluorescence lifetime on the crystal laser, and laser damage in crystal, Tm, Tm in the Ho:YAG crystal, Ho ionic concn etc. is tested.
5.1 energy level fluorescence lifetime (2.0974um) on the crystal laser
Detect principle and method: use impulse semiconductor laser, wavelength 785nm, line width 2.7nm, pulse width 200us, pulse energy～10mJ, beam shaping is focused on, about 200 * the 200um of waist spot size, pump light is directly beaten at the crystalline center, and specimen directly is attached on the input slit of monochromator, and the wavelength of monochromator is transferred at 2.0974um, the InAs photodetector is installed behind the monochromator input slit, detectable signal has the digital oscilloscope storage of 100MHz, with edge behind the cursor read pulse drop to peak value the time 1/e time Δ t, multiple averaging just obtains this crystalline upper laser level fluorescence lifetime.Proofing unit is by forming with the lower section: impulse semiconductor laser, shaping focusing system, sample table, monochromator, InAs detector, digital oscilloscope.
5.2 laser damage in crystal
Detect principle and method: use Q impulse Nd:YAG laser apparatus, wavelength 1064nm, pulse width 10nS, beam spread is arrived Φ 25mm, light hurdle card with 10 * 10mm goes out a square hot spot, spatial filter through 10: 4, on the back image planes of spatial filter, obtain the even unmodulated hot spot of 4 * 4mm, sample is placed on this position, adjust laser apparatus output pulse energy, reach detection power density 1GW/ ‰ cm2, and surpass 20%, 100 pulses of each sample Continuous irradiation are observed plane of crystal at last under 400 power microscopes and whether inside has damage.Proofing unit is made up of following components: laser apparatus, beam expanding lens, spatial filter, vacuum system, sample, energy meter, microscope.
5.3Tm, Tm in the Ho:YAG crystal, Ho ionic concn
Test sample is Φ 22 * 5mm crystal, and laboratory temperature is 22 ℃, and humidity 60% adopts X-line fluorescence analyser (XRF), detects the letter order of the crystal middle-weight rare earths element that obtains
6. crystal plated film: to crystal plating anti-reflection film (antireflection loss), total reflection film, partial reflection film and half reflection film, the method for plated film is conventional means, does not repeat them here.
7. working element performance test: to Tm, the Ho:YAG crystal has carried out the 2 μ m room temperature laser reality of LD pumping.The data that the principle experiment is used are as follows: 1. the optical maser wavelength of LD pumping source is: 785nm; 2. the power of LD pumping source is: 30W; 3. Tm, Ho:YAG crystalline doping content is respectively: Tm:2 * 10
21, Ho:5 * 10
194. laser cavity design data: the total reflective mirror reflectivity is 99.95%, and the outgoing mirror reflectivity is 30%; 5. working temperature: 25 ℃.In application, Tm, Ho:YAG crystal be in the 1000HZ repetition rate, and the pumping time reaches the 2um laser output of 12W during for 1ms.Light-phototransformation rate reaches 30%.
Through above-mentioned technological process, finish the course of processing of whole working element.
The present invention also provides the laser apparatus that adopts above-mentioned working element, and this laser apparatus can realize exporting continuously under the room temperature 12W.Technical scheme provided by the invention has solved the batch process problem of 785nm laser diode, Tm, and the Ho:YAG crystal will (particularly military field) obtain to widely apply in all solid state laser.
Prepare high purity Tm with " pressurization of heating " ion exchange technique
2O
3, Ho
2O
3Raw material, the resin of employing are Zeo-karb, and polynary post is two adsorption columns, four separator columns, and eluent is EDTA, and the high pure rare earth product that operating pressure 6MPa makes is 99.9992% through its purity of ICP-MS instrument detecting.。
With highly purified raw material according to mass ratio Y
2O
3: Tm
2O
3: Ho
2O
3: Al
2O
3=2406: take by weighing at 700: 17: 2127, make rare earths material and Al
2O
3The mol ratio strictness be controlled to be 3: 5, and make that final doping content is Tm:2 * 10
21, Ho:5 * 10
19Individual/cm
3, the raw material that takes by weighing was put into grinding machine for grinding 24 hours, in the latex rubber bag of packing into then, add pre-compaction forming in the oil press.
With the raw material of the pre-compaction forming crucible of packing into, place growing apparatus as shown in Figure 4 then, close fire door and vacuumize, fill shielding gas.Heating is gradually then closed and is started vacuum pump behind the fire door to extract original air in the stove out.Treating that vacuum tightness reaches starts medium-frequency generator after the requirement of experiment and heats, and continues to vacuumize.Keeping higher vacuum (10
-3MmHg) below, when heating power reach raw material when fusing power 60% the time, stop to vacuumize, and charge into rare gas element rapidly (Ar), pressure generally is controlled at 0.04～0.06Mpa..After charging into rare gas element, continuing to heat up allows raw material melt, and its process is first quick and back slow.Generally need to continue insulation about 1 hour after the raw material running down.
After treating that raw material fully melts, seed crystal gradually descends.Seed crystal contact melt, need suitably be adjusted temperature (also being power) and make the seed end size to fit in the process of beginning pulling growth at following seed crystal, and the fluctuation of temperature is less than ± 1 ℃.Continue to keep this power number and can begin pulling growth after 0.5 hour.The provider of seed crystal is to being (111), and in process of growth, the crystal pulling rate is controlled at 1.0mm/hr, and the crystal rotating speed is controlled at 10～30rpm scope,
Early stage what grow, the crystal shouldering is suitably slow, allows change to take on go the fruit degree slowly level and smooth, avoids taking out shoulder formation; After isodiametric growth finishes, evenly slowly heat up, and crystal diameter received gradually narrow down to about ∮ 10mm; Do not allowing crystal break away from slowly cooling blowing out under the situation of melt.
On the corresponding height of insulating brick vision slit, increase louvre, make into secondary or three symmetrical distributions, increased radial symmetry gradient on the liquid level, help forming more protruding interface.
In the pulling method process of growth, begin to lift the evenly slow elevated temperature in back, the speed control of intensification is in 400 ℃/h scope, and slowly receipts are thin with the seed crystal diameter, minimum locating generally than about the little 1mm of seed crystal.Neck length is generally in 10mm.After, reducing temperature gradually, the speed control of cooling allows crystal diameter enlarge gradually in 250 ℃/h scope, to form " shoulder " portion.In shouldering, before crystal diameter reaches the reservation size, change heating schedule successively and change the isodiametric growth stage over to by crystal, after isodiametric growth finishes, heating up gradually, it is little of a certain size (about 10mm, this process is ending) to allow crystal diameter receive, and crystal stops the rotation and lifts, but do not break away from liquid level, the blowing out of lowering the temperature again.After the blow-on, rap crystal from side, crystal will easily disconnect in the junction with solidified melt.Make crystal prototype 1.
To finish the preparation technology of laser works element by the crystal prototype 1 that above-mentioned preparation technology obtains through steps such as sample form slection design, crystal aftertreatment, crystal mass initial survey, crystal processing, the detection of laser work element quality, crystal plated film, working element performance tests.
Wherein in the crystal complete processing, adopt diffusion interlinked device provided by the invention.Bonding temperature is at 1400 ℃, constant temperature time 52 hours.By above-mentioned working method, the rod-shaped laser working element size that makes can reach 6mm * 100mm.
Working element performance test: can pull by visual inspection and with hand and judge whether on the bonding; Under 5～10mW He-Ne laser, observe bonding face not scatter point hole and bubble etc. are arranged; Under stressometer, observe its stress distribution; In interferometer, observe interferogram.
The working element of above-mentioned test passes is applied in the laser apparatus, has realized exporting continuously under the room temperature 12W.
Its preparation method and embodiment 1 is approximate, the ratio difference of raw material just, and crystal pulling rate, crystal rotating speed, stove internal gas pressure are different, make crystal prototype 2 and 3, and concrete ratio and growth parameter(s) are as shown in table 1:
Table 1
Can draw from the above description, laser crystals provided by the invention, it is bigger to have a crystal volume, the advantage that the life-span is long; The preparation crystalline equipment that provides has been set up rational temperature field, has realized the comprehensive matching design of crystal growth parameter, has promptly not only kept the high stability of machine driven system, and guarantees that temperature controlling system has high precision (fluctuation is less than ± 1 ℃); Method provided by the invention, it has easy operation, is suitable for the advantage of suitability for industrialized production; The working element that utilizes laser crystals provided by the invention to make, its big I reaches 6-8mm * 100-140mm, can realize the high power CW output of laser apparatus.
More than explanation is a preferred implementation of the present invention only, is not limited to the present invention, and for a person skilled in the art, the present invention can have various changes and variation.Within the spirit and principles in the present invention all, any modification of being done, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. a laser crystals is characterized in that, described crystalline chemical formula is Tm, Ho:Y
3Al
5O
12, be that spacer is the isometric system crystal of Ia3d, wherein, the doping content of described Tm is 1.99～2.01 * 10
21Individual/cm
3, the doping content of Ho is Ho:5.00～5.05 * 10
19Individual/cm
3
2. crystal according to claim 1 is characterized in that, the doping content of Tm is 2.00 * 10 in the described crystal
21Individual/cm
3, the doping content of Ho is 5.00 * 10
19Individual/cm
3
3. one kind prepares claim 1 or 2 described crystalline growing apparatuss, comprise seed rod (1), seed crystal (2), melt (4), crucible (8), resistance heater (14) is characterized in that, alumina bubble brick (24) also is set on the described device, and on the corresponding height of described alumina bubble brick (24) vision slit, has increased louvre.
4. 3 described growing apparatuss as requested is characterized in that described louvre aperture is 10mm, and quantity is 4.
5. claim 1 or 2 described crystalline preparation methods is characterized in that described method comprises:
With purity greater than 99.999% Tm
2O
3And Ho
2O
3, with Y
2O
3And Al
2O
3After making the molding mass piece, put into single-crystal growing apparatus;
Vacuumize, fill shielding gas, heating is the dissolving melt fully;
Carry out pulling growth, temperature fluctuation is controlled at ± 1 ℃ in.
6. 5 described preparation methods as requested is characterized in that described Tm
2O
3And Ho
2O
3Pressurization preparation technology is prepared from through heating.
7. 5 described preparation methods as requested is characterized in that in the described pulling growth step, the crystal pulling rate is 1.0～1.5mm/hr, and the crystal rotating speed is 10～30rpm, and the stove internal gas pressure is controlled at 0.025～0.050Mpa, and crystal diameter is controlled at 55～76mm.
8. 5 described preparation methods as requested is characterized in that in the described pulling growth step, the provider of seed crystal is to being (111).
9. a laser works element is characterized in that, described laser works element is formed through diffusion interlinked prepared by claim 1 or 2 described crystal, and described working element is of a size of 6-8mm * 100-140mm.
10. 9 described working elements as requested is characterized in that described diffusion interlinked technology is carried out in single crystal growing furnace or Si-Mo rod stove, and bonding temperature is 1400～1600, constant temperature time 48～72 hours.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105887200A (en) * | 2016-05-31 | 2016-08-24 | 山东省科学院新材料研究所 | Thulium-holmium-codoped strontium lanthanum gallate laser crystal, preparation method and application of crystal |
| CN106252206A (en) * | 2016-08-30 | 2016-12-21 | 成都晶九科技有限公司 | Nd:YAG laser crystal large area bonding technology |
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| CN201194309Y (en) * | 2008-04-17 | 2009-02-11 | 成都东骏激光有限责任公司 | Laser crystal of high comprehensive performance |
| CN101560696A (en) * | 2009-06-03 | 2009-10-21 | 北京雷生强式科技有限责任公司 | Laser crystals doped with holmium, chromium, erbium, thulium and yttrium aluminum garnet, and preparation method thereof |
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Patent Citations (3)
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| US5103457A (en) * | 1990-02-07 | 1992-04-07 | Lightwave Electronics Corporation | Elliptical mode cavities for solid-state lasers pumped by laser diodes |
| CN201194309Y (en) * | 2008-04-17 | 2009-02-11 | 成都东骏激光有限责任公司 | Laser crystal of high comprehensive performance |
| CN101560696A (en) * | 2009-06-03 | 2009-10-21 | 北京雷生强式科技有限责任公司 | Laser crystals doped with holmium, chromium, erbium, thulium and yttrium aluminum garnet, and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105887200A (en) * | 2016-05-31 | 2016-08-24 | 山东省科学院新材料研究所 | Thulium-holmium-codoped strontium lanthanum gallate laser crystal, preparation method and application of crystal |
| CN106252206A (en) * | 2016-08-30 | 2016-12-21 | 成都晶九科技有限公司 | Nd:YAG laser crystal large area bonding technology |
| CN106252206B (en) * | 2016-08-30 | 2018-10-19 | 成都晶九科技有限公司 | Nd：YAG laser crystal large area bonding technology |
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