CN101135060A - Re3+,Cr5+:LnVO4 automodulation laser crystal and preparation method and application thereof - Google Patents
Re3+,Cr5+:LnVO4 automodulation laser crystal and preparation method and application thereof Download PDFInfo
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- CN101135060A CN101135060A CNA2007101138428A CN200710113842A CN101135060A CN 101135060 A CN101135060 A CN 101135060A CN A2007101138428 A CNA2007101138428 A CN A2007101138428A CN 200710113842 A CN200710113842 A CN 200710113842A CN 101135060 A CN101135060 A CN 101135060A
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- 239000013078 crystal Substances 0.000 title claims abstract description 161
- 238000002360 preparation method Methods 0.000 title claims description 29
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 32
- 229910052769 Ytterbium Inorganic materials 0.000 claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 14
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 13
- 229910052765 Lutetium Inorganic materials 0.000 claims abstract description 13
- 238000005086 pumping Methods 0.000 claims abstract description 13
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical group [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000001105 regulatory effect Effects 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 23
- 229910052741 iridium Inorganic materials 0.000 claims description 8
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 230000003287 optical effect Effects 0.000 claims description 3
- -1 Nd 3+ Substances 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 125000006850 spacer group Chemical group 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 abstract description 27
- 238000010521 absorption reaction Methods 0.000 abstract description 20
- 229920006395 saturated elastomer Polymers 0.000 abstract description 9
- 229910052727 yttrium Inorganic materials 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 238000011982 device technology Methods 0.000 abstract 1
- 239000011651 chromium Substances 0.000 description 102
- 229910052804 chromium Inorganic materials 0.000 description 19
- 238000000137 annealing Methods 0.000 description 16
- 239000000126 substance Substances 0.000 description 12
- 238000005498 polishing Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 229910019655 synthetic inorganic crystalline material Inorganic materials 0.000 description 7
- 230000008646 thermal stress Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052702 rhenium Inorganic materials 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- JNDMLEXHDPKVFC-UHFFFAOYSA-N aluminum;oxygen(2-);yttrium(3+) Chemical compound [O-2].[O-2].[O-2].[Al+3].[Y+3] JNDMLEXHDPKVFC-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002223 garnet Substances 0.000 description 1
- 239000010437 gem Substances 0.000 description 1
- 229910001751 gemstone Inorganic materials 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 229910019901 yttrium aluminum garnet Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
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Abstract
The present invention relates to Re3+, Cr5+:LnVO4 crystal and self-modulating pulse laser pumping the said crystal, and belongs to the field of laser crystal and device technology. The Re3+, Cr5+:LnVO4 crystal has zirconite structure and general expression of Ln1-xRexV1-yCryO4, where, Re is Nd or Yb; Ln is Gd, Lu or Y; each of x and y is equal to 0.0001-0.1. The Re3+, Cr5+:LnVO4 crystal may be used as self Q-switching material, and by means of the combination of the emission peal of Re3+ ion near to 1 micron and the absorption peak of Cr5+ ion in 900-1300 nm and the saturated absorption characteristic of Cr5+ ion, self-modulating pulse laser beam in 1.01-1.08 micron is generated. The self-modulating pulse laser device with the said crystal has the features of simple structure, small size, low loss, high stability, high conversion efficiency, high laser beam quality, low cost, etc.
Description
Technical field
The present invention relates to have the Re of zircon structure
3+, Cr
5+: LnVO
4(Re=Nd or Yb; Ln=Gd, Lu, or Y) crystal, the self-regulated Q device made from this crystal and use this crystalloid opposite end face or profile pump produces the method for the pulse laser of self-modulation.Belong to crystal growth and Laser Devices technical field.
Background technology
Along with the increase of people to the demand of high power laser light, as a kind of effective ways that obtain high power pulses laser, Q-regulating technique has obtained using widely at present.Transfer the Q mode to have initiatively and passive two kinds.Initiatively transfer Q that acousto-optic, electric-optically Q-switched etc. is arranged, the Laser Devices of this dual mode are bulky, and price is also than higher, the requirement of the miniaturization of incompatibility laser apparatus.It is more convenient to adopt passive Q-adjusted mode to obtain pulse laser, is the wider a kind of method of using at present.Passive Q-adjusted accent Q mode and set laser crystal and the saturated absorption sheet self-regulated Q mode that comprises again with laser crystals pumping saturation absorbing sheet.Because self-regulated Q mode has advantages such as little, the simple in structure and low-loss of volume, become the focus of people's research gradually.The more self-regulated Q material of research mainly is Re at present
3+, Cr
4+: YAG (Re=Nd or Yb) crystal.Because the most stable valence state of Cr ion is+3 valencys, Cr
3+The ionic form replaces the case of the Al in the crystal, form Cr
4+Ion will mix other ions in the crystal, as Ca
2+, Mg
2+Deng compensating; And because Re
3+: YAG (Re=Nd or Yb) crystalline absorption band is narrower, and absorption cross is less, needs the emission wavelength in strict controlling pumping source and with the crystal of large-size or higher-doped concentration, so just can obtain Re when pumping
3+, Cr
4+: YAG (Re=Nd or Yb) pulse laser.In view of Re
3+: LnVO
4(Ln=Gd, Lu, or Y) is with respect to Re
3+: absorption band that YAG is wide and big absorption cross, and Cr
5+Ion and V
5+Valence state and similar ionic radius that ion is identical are with Re
3+, Cr
5+: LnVO
4(Re=Nd or Yb; Ln=Gd, Lu, or Y) can overcome above-mentioned Re as novel self-regulated Q crystal
3+, Cr
4+: YAG (Re=Nd or Yb) is in preparation and use the difficulty that runs into.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, a kind of self-regulated Q material Re is provided
3+, Cr
5+: LnVO
4(Re=Nd or Yb; Ln=Gd, Lu, or Y) crystal.
The present invention also provides Re
3+, Cr
5+: LnVO
4Crystal laser self-regulated Q device.
Another task of the present invention also provides Re
3+, Cr
5+: LnVO
4Crystal is as the method for self-regulated Q material production pulse laser.
Summary of the invention
Gordian technique of the present invention is at LnVO
4There is Re simultaneously in (Ln=Gd, Lu, or Y) crystal
3+(Re=Nd or Yb) ion and Cr
5+Ion, and utilize Cr
5+The ionic saturated absorption and in the absorption of 900-1300nm wave band to Re
3+Emitted laser is modulated near 1 μ m, realizes self-regulated Q pulse laser.
Terminological interpretation
Re
3+, Cr
4+: YAG is the abbreviation of neodymium (or ytterbium) and the two doped yttrium aluminium garnet crystals of tetravalence chromium;
Re
3+: YAG (Re=Nd or Yb) is that neodymium (or ytterbium) doped yttrium aluminum garnet crystalline is called for short;
Re
3+: LnVO
4Be that (Re=Nd or Yb) is the abbreviation of neodymium (or ytterbium) adulterated vanadate;
Re
3+, Cr
5+: LnVO
4Be the two abbreviations of mixing vanadate crystal of neodymium (or ytterbium) and tetravalence chromium.
By this area convention, use above-mentioned abbreviation in the present specification.
Detailed Description Of The Invention
One, Re
3+, Cr
5+: LnVO
4Crystal
Re of the present invention
3+, Cr
5+: LnVO
4(Re=Nd or Yb; Ln=Gd, Lu, or Y) crystal has following general formula:
Ln
1-xRe
xV
1-yCr
yO
4, wherein, Re=Nd or Yb; Ln=Gd, Lu or Y, x, y=0.0001～0.1 is abbreviated as Re
3+, Cr
5+: LnVO
4All Re that mention in the following description
3+, Cr
5+: LnVO
4Crystal all is to have above general formula.
Re
3+, Cr
5+: LnVO
4Crystal is the crystal that a class has the zircon structure, and spacer is I4
1/ amd, when R=Gd, unit cell parameters: a=b=7.212 , c=6.346 ; When R=Lu, unit cell parameters: a=b=7.025 , c=6.234 ; When R=Y, unit cell parameters: a=b=7.118 , c=6.289 .
At Re
3+, Cr
5+: LnVO
4In the crystal, Re
3+Ionic replacement Ln
3+Ion, Cr
5+Ionic replacement V
5+Ion is because Re
3+And Cr
5+Ion respectively with Ln
3+And V
5+Valence state is identical, and atomic radius is approaching, can not make LnVO
4Considerable change appears in crystalline crystalline network and unit cell parameters.Re
3+, Cr
5+: LnVO
4Crystal utilization Re wherein
3+Ion is as active ions, Cr
5+Ion is as the saturated absorption ion, and set laser crystal and saturated absorption crystal are all over the body.
Above-mentioned Re
3+, Cr
5+: LnVO
4R in the crystal
5+Ion has absorption peak in the scope of 0.9～1.3 μ m, this and Re
3+Near the emission peak of ion 1 μ m coincides, and makes crystal have the characteristic of self-modulation.
The preferred Re of the present invention
3+, Cr
5+: LnVO
4Crystal is one of following:
Nd
3+, Cr
5+: GdVO
4Crystal, Nd
3+, Cr
5+: YVO
4Crystal, Yb
3+, Cr
5+: YVO
4Crystal.
Because Yb
3+Ionic concn can be up to 1～25mol%, then corresponding used Cr
5+Ionic can be regulated in the very wide scope.That shown in Figure 1 is Nd, Cr:GdVO
4The crystalline absorption spectrum, wherein Nd and Cr doping content all are 1mol%, Nd
3+, Cr
5+: GdVO
4Crystal utilization Nd wherein
3+Ion is as active ions, Cr
5+Ion is as the saturated absorption ion, and set laser crystal and saturated absorption crystal are all over the body.The π polarization is that the polarization of incident light direction is parallel with a (or b) axle with crystalline c axle respectively with the σ polarization among Fig. 1.
Two, Re
3+, Cr
5+: LnVO
4The crystalline preparation method
Re of the present invention
3+, Cr
5+: LnVO
4The crystalline preparation method adopts Czochralski grown, and used growing apparatus is an induction heating pull-type single crystal growing furnace, and crystal growth step comprises:
According to Ln
1-xRe
xV
1-yCr
yO
4(Re=Nd or Yb; Ln=Gd, Lu, or Y, x, y=0.0001～0.1) in the formula each component the molar ratio weighing raw material and mix, place Iridium Crucible, shove charge; Single crystal growing furnace vacuumizes, and inflation is warmed up to 1750-1850 ℃ and makes the polycrystal fusing; Following seeded growth crystal, crystal growth temperature is between 1750-1850 ℃.Crystal growth finishes and is cooled to room temperature, comes out of the stove.
In the aforesaid method, the pull rate of preferred crystal growth is 0.5～2 millimeter/hour, 10～30 rev/mins of rotating speeds.
In the aforesaid method, preferred crystal growth atmosphere is the oxygen of volume ratio 1-2% and the nitrogen of surplus.
The crystal of coming out of the stove is annealed under 1100-1300 ℃ temperature, then the crystal that grows up to is processed, is polished, perhaps plated film again.
More than said crystal processed, polished, perhaps plated film more all adopts state of the art to get final product.Wherein, the crystal plated film is at Re
3+, Cr
5+: LnVO
4The crystalline both ends of the surface plate deielectric-coating.
Advantage with crystal pulling method is to obtain large size, high-quality Re within a short period of time
3+, Cr
5+: LnVO
4Crystalline material.The present invention does not do special qualification to growing method, all gets final product by the method for crystal growth by crystal pulling prior art.
Re
3+, Cr
5+: LnVO
4Crystal is used to make laser self-regulated Q device, need not to add modulator element.
Three, laser self-regulated Q device
Laser self-regulated Q device of the present invention is with Re
3+, Cr
5+: LnVO
4Crystal is as self-regulated Q material, and deielectric-coating, Re are polished or be coated with to the crystal both ends of the surface
3+, Cr
5+: LnVO
4The logical light face of crystalline is circular or square, and optical direction thickness is 0.1-10mm.
Above-mentioned laser self-regulated Q device can be with laser diode or ti sapphire laser as pumping source pump-coupling Ln
1-xRe
xV
1-yCr
yO
4Crystal need not to add modulator element, obtains the pulsed laser of self-modulation.Can produce 1.01-1.08 μ m self-modulation pulse laser.
Four, Re
3+, Cr
5+: LnVO
4Crystal is as the method for self-regulated Q material production pulse laser
A kind of method that produces self-regulated Q pulse laser is characterized in that, with Re
3+, Cr
5+: LnVO
4Crystal is simultaneously as laserable material and self-regulated Q material, and these crystal both ends of the surface are polished or are coated with deielectric-coating again, with this crystal of pumping source pumping, need not to add modulator element, produces the pulse laser of self-modulation.Using and Re
3+The matched end face of absorption or during the pumping of profile pump source, Re
3+(Re=Yb or Nd) ion produces 1.01-1.08 μ m laser, passes through LnVO
4(Ln=Gd, Lu, Y) Cr in the crystal
5+The ionic saturated absorption realizes self-regulated Q effect, forms 1.01-1.08 μ m pulse laser.
Described self-regulated Q material Re
3+, Cr
5+: LnVO
4The logical light face of crystalline is circular or square, and optical direction thickness can design as required, is generally 0.1-10mm.
Described pumping source will with the Re fit, can be end face or profile pump source, specifically be selected from and Yb
3+, Nd
3+Matched laser diode of ionic absorption band or titanium precious stone laser.Can select according to practical situation.
Re of the present invention
3+, Cr
5+: LnVO
4Crystal is preferably selected the laser mirror that adapts for use as the method for self-regulated Q material production pulse laser, perhaps directly the deielectric-coating that is plated on the laser mirror is plated in crystal end-face formation suitable cavity without laser mirror.
Self-regulated Q pulse laser take-off equipment as shown in Figure 2, wherein, laser diode (LD), focalizer, the average mirror that is coated with the suitable media film or plano-concave mirror M1 and laser crystals, the average mirror that is coated with the suitable media film or plano-concave mirror M2 order light successively are communicated with.
Excellent results of the present invention is as follows:
The present invention adopts the host crystal of the zircon structure crystal of easy preparation as self-regulated Q, with Re
3+Near emission and the Cr of ion 1 micron
5+Near the absorption characteristic of ion 1 micron combines, and produces self-regulated Q pulse laser.Re
3+Ion doping zircon structure crystal has that absorption cross is big, absorption spectrum live width, preparation are relatively easy to characteristics, therefore can obtain the output of high-level efficiency laser easily.Self-regulated Q crystal Re of the present invention
3+, Cr
5+: LnVO
4(Re=Yb or Nd; Ln=Gd, Lu, or Y) be crystal with zircon structure, gain medium is combined with the saturated absorption medium, produce pulse laser device simple in structure, easy to use, miniaturization.The pulse laser output that produces, laser has the characteristics of good stability, efficiency of conversion height, good beam quality.
Description of drawings
Fig. 1 is that Nd and Cr doping content all are the Nd of 1mol%, Cr:GdVO4 crystalline absorption spectrum.Wherein, X-coordinate is wavelength (nm), and ordinate zou is a uptake factor, and π is that the polarization of incident light direction is parallel with a (or b) axle with crystalline c axle respectively with σ.
Fig. 2 is a self-regulated Q pulse laser take-off equipment synoptic diagram, and wherein, 1 is laser diode LD, and 2 is focalizer, and 3 for being coated with the average mirror or the plano-concave mirror M1 of suitable media film, and 4 is Nd, Cr:GdVO
4Crystal, 5 for being coated with the average mirror or the plano-concave mirror M2 of suitable media film.
Embodiment
The present invention will be further described below in conjunction with embodiment.Wherein, embodiment 1-6 is about Re
3+, Cr
5+: LnVO
4Crystalline preparation and processing, embodiment 7-10 is about Re
3+, Cr
5+: LnVO
4The example of crystalline Laser Devices design, but the present invention is not limited to this.
Embodiment 1:Nd, Cr:GdVO
4The crystalline preparation.
Use GdVO
4, NdVO
4And GdCrO
4Be initial feed, press chemical equation: (1-x-y) GdVO
4+ xNdVO
4+ yGdCrO
4=Nd
1-xGd
xV
1-yCr
yO
4The polycrystal of preparation growing crystal; Perhaps,
Use Gd
2O
3, Nd
2O
3, V
2O
5, Cr
2O
3Be raw material, press chemical equation: (1-x) Gd
2O
3+ xNd
2O
3+ (1-y) V
2O
5+ yCr
2O
3+ yO
2=Nd
1-xGd
xV
1-yCr
yO
4In the polycrystal of mol ratio preparation growing crystal.
X=0.012 in the following formula, y=0.01.
The polycrystal that configures is placed in the Iridium Crucible.Single crystal growing furnace vacuumizes, inflation: 2%O
2+ N
2, the mode of employing heating in medium frequency is warmed up to 1800 ℃ and makes the polycrystal fusing; Following seeded growth crystal, the GdVO of use a direction
4Seed crystal, the pull rate of crystal growth are 0.5～2 millimeter/hour, 10～30 rev/mins of rotating speeds, and crystal growth temperature is between 1790-1850 ℃.Crystal growth finishes and is cooled to room temperature, and crystal is come out of the stove; The crystal of coming out of the stove is placed in the resistance furnace anneals, and annealing temperature is 1200 ℃, and annealing time is 8 hours, can partly discharge growth of Nd like this
1-xGd
xV
1-yCr
yO
4The thermal stresses that produces in the crystal process.
Then as required to the crystal of growth process, polishing and plated film.
Embodiment 2:Nd, Cr:LuVO
4The crystalline preparation.
Use LuVO
4, NdVO
4And LuCrO
4Be initial feed, press chemical equation: (1-x-y) LuVO
4+ xNdVO
4+ yLuCrO
4=Nd
1-xGd
xV
1-yCryO
4The polycrystal of preparation growing crystal; Perhaps,
Use Lu
2O
3, Nd
2O
3, V
2O
5, Cr
2O
3Be raw material, press chemical equation: (1-x) Lu
2O
3+ xNd
2O
3+ (1-y) V
2O
5+ yCr
2O
3+ yO
2=Nd
1-xLu
xV
1-yCr
yO
4In the polycrystal of mol ratio preparation growing crystal.
X=0.011 in the following formula, y=0.01.
The polycrystal that configures is placed in the Iridium Crucible.Single crystal growing furnace vacuumizes, inflation: 2%O
2+ N
2, the mode of employing heating in medium frequency is warmed up to 1800 ℃ and makes the polycrystal fusing; Following seeded growth crystal, the LuVO of use a direction
4Seed crystal, the pull rate of crystal growth are 0.5～2 millimeter/hour, 10～30 rev/mins of rotating speeds, and crystal growth temperature is between 1790-1850 ℃.Crystal growth finishes and is cooled to room temperature, and crystal is come out of the stove; The crystal of coming out of the stove is placed in the resistance furnace anneals, and annealing temperature is 1200 ℃, and annealing time is 8 hours, can partly discharge growth of Nd like this
1-xLu
xV
1-yCr
yO
4The thermal stresses that produces in the crystal process.
Nd, Cr:LuVO
4The same Nd of crystalline annealing, processing, polishing and plated film, Cr:GdVO
4Crystal.
Embodiment 3:Nd, Cr:YVO
4The crystalline preparation.
Use YVO
4, NdVO
4And YCrO
4Be initial feed, press chemical equation: (1-x-y) YVO
4+ xNdVO
4+ yYCrO
4=Nd
1-xY
xV
1-yCr
yO
4The polycrystal of preparation growing crystal; Perhaps,
Use Y
2O
3, Nd
2O
3, V
2O
5, Cr
2O
3Be raw material, press chemical equation: (1-x) Y
2O
3+ xNd
2O
3+ (1-y) V
2O
5+ yCr
2O
3+ yO
2=Nd
1-xY
xV
1-yCr
yO
4In the polycrystal of mol ratio preparation growing crystal.
X=0.015 in the following formula, y=0.01.
The polycrystal that configures is placed in the Iridium Crucible.Single crystal growing furnace vacuumizes, inflation: 2%O
2+ N
2, the mode of employing heating in medium frequency is warmed up to 1800 ℃ and makes the polycrystal fusing; Following seeded growth crystal, the YVO of use a direction
4Seed crystal, the pull rate of crystal growth are 0.5～2 millimeter/hour, 10～30 rev/mins of rotating speeds, and crystal growth temperature is between 1790-1850 ℃.Crystal growth finishes and is cooled to room temperature, and crystal is come out of the stove; The crystal of coming out of the stove is placed in the resistance furnace anneals, and annealing temperature is 1200 ℃, and annealing time is 8 hours, can partly discharge growth of Nd like this
1-xLu
xV
1-yCr
yO
4The thermal stresses that produces in the crystal process.
Nd, Cr:YVO
4The same Nd of crystalline annealing, processing, polishing and plated film, Cr:GdVO
4Crystal.
Embodiment 4:Yb, Cr:GdVO
4The crystalline preparation.
Use GdVO
4, YbVO
4And GdCrO
4Be initial feed, press chemical equation: (1-x-y) GdVO
4+ xYbVO
4+ yGdCrO
4=Yb
1-xGd
xV
1-yCryO
4The polycrystal of preparation growing crystal; Perhaps,
Use Gd
2O
3, Yb
2O
3, V
2O
5, Cr
2O
3Be raw material, press chemical equation: (1-x) Gd
2O
3+ xYb
2O
3+ (1-y) V
2O
5+ yCr
2O
3+ yO
2=Yb
1-xGd
xV
1-yCryO
4In the polycrystal of mol ratio preparation growing crystal.
X=0.01 in the following formula, y=0.01.
The polycrystal that configures is placed in the Iridium Crucible.Single crystal growing furnace vacuumizes, inflation: 2%O
2+ N
2, the mode of employing heating in medium frequency is warmed up to 1800 ℃ and makes the polycrystal fusing; Following seeded growth crystal, the GdVO of use a direction
4Seed crystal, the pull rate of crystal growth are 0.5～2 millimeter/hour, 10～30 rev/mins of rotating speeds, and crystal growth temperature is between 1790-1850 ℃.Crystal growth finishes and is cooled to room temperature, and crystal is come out of the stove; The crystal of coming out of the stove is placed in the resistance furnace anneals, and annealing temperature is 1200 ℃, and annealing time is 8 hours, can partly discharge growth Yb like this
1-xGd
xV
1-yCr
yO
4The thermal stresses that produces in the crystal process.
Then as required to the crystal of growth process, polishing and plated film.
Embodiment 5:Yb, Cr:LuVO
4The crystalline preparation.
Use LuVO
4, YbVO
4And LuCrO
4Be initial feed, press chemical equation: (1-x-y) LuVO
4+ xYbVO
4+ yLuCrO
4=Yb
1-xGd
xV
1-yCr
yO
4The polycrystal of preparation growing crystal; Perhaps,
Use Lu
2O
3, Nd
2O
3, V
2O
5, Cr
2O
3Be raw material, press chemical equation: (1-x) Lu
2O
3+ xYb
2O
3+ (1-y) V
2O
5+ yCr
2O
3+ yO
2=Yb
1-xLu
xV
1-yCr
yO
4In the polycrystal of mol ratio preparation growing crystal.
X=0.012 in the following formula, y=0.01.
The polycrystal that configures is placed in the Iridium Crucible.Single crystal growing furnace vacuumizes, inflation: 2%O
2+ N
2, the mode of employing heating in medium frequency is warmed up to 1800 ℃ and makes the polycrystal fusing; Following seeded growth crystal, the LuVO of use a direction
4Seed crystal, the pull rate of crystal growth are 0.5～2 millimeter/hour, 10～30 rev/mins of rotating speeds, and crystal growth temperature is between 1790-1850 ℃.Crystal growth finishes and is cooled to room temperature, and crystal is come out of the stove; The crystal of coming out of the stove is placed in the resistance furnace anneals, and annealing temperature is 1200 ℃, and annealing time is 8 hours, can partly discharge growth Yb like this
1-xLu
xV
1-yCr
yO
4The thermal stresses that produces in the crystal process.
Yb, Cr:LuVO
4The same Yb of crystalline annealing, processing, polishing and plated film, Cr:GdVO
4Crystal.
Embodiment 6:Yb, Cr:YVO
4The crystalline preparation.
Use YVO
4, YbVO
4And YCrO
4Be initial feed, press chemical equation: (1-x-y) YVO
4+ xYbVO
4+ yYCrO
4=Yb
1-xY
xV
1-yCr
yO
4The polycrystal of preparation growing crystal; Perhaps,
Use Y
2O
3, Yb
2O
3, V
2O
5, Cr
2O
3Be raw material, press chemical equation: (1-x) Y
2O
3+ xYb
2O
3+ (1-y) V
2O
5+ yCr
2O
3+ yO
2=Yb
1-xY
xV
1-yCr
yO
4In the polycrystal of mol ratio preparation growing crystal.
X=0.01 in the following formula, y=0.01.
The polycrystal that configures is placed in the Iridium Crucible.Single crystal growing furnace vacuumizes, inflation: 2%O
2+ N
2, the mode of employing heating in medium frequency is warmed up to 1800 ℃ and makes the polycrystal fusing; Following seeded growth crystal, the YVO of use a direction
4Seed crystal, the pull rate of crystal growth are 0.5～2 millimeter/hour, 10～30 rev/mins of rotating speeds, and crystal growth temperature is between 1790-1850 ℃.Crystal growth finishes and is cooled to room temperature, and crystal is come out of the stove; The crystal of coming out of the stove is placed in the resistance furnace anneals, and annealing temperature is 1200 ℃, and annealing time is 8 hours, can partly discharge growth Yb like this
1-xLu
xV
1-yCr
yO
4The thermal stresses that produces in the crystal process.
Yb, Cr:YVO
4The same Yb of crystalline annealing, processing, polishing and plated film, Cr:GdVO
4Crystal.
Embodiment 7: with emission wavelength is the laser diode end-face pump end face polishing of 808 nanometers or the plating Nd to the high transmittance film of 1.06 μ m laser, Cr:GdVO
4The crystal intracavity mirror is realized the self-regulated Q pulse laser output of 1.06 μ m.Its experimental installation as shown in Figure 2, wherein, laser diode 1, focalizer 2, the average mirror that is coated with the suitable media film or plano-concave mirror 3 and laser crystals 4, the average mirror that is coated with the suitable media film or plano-concave mirror 5 order light successively are communicated with.
Embodiment 8: be the laser diode end-face pump end face polishing of 980 nanometers or plate the high Yb that sees through film of 1.02 μ m, Cr:GdVO with emission wavelength
4Crystal is realized the output of 1.02 μ m self-regulated Q pulse lasers.
Embodiment 9: as described in embodiment 7 or 8, different is to use Re, Cr:LuVO
4(Lu
1-xRe
xV
1-yCr
yO
4) crystal is as self-modulation material production adjusting Q pulse laser.
Embodiment 10: as described in embodiment 7 or 8, different is to use Re, Cr:YVO
4(Y
1-xRe
xV
1-yCr
yO
4) crystal is as self-modulation material production adjusting Q pulse laser.
Claims (8)
1.Re
3+, Cr
5+: LnVO
4Crystal has following general formula:
Ln
1-xRe
xV
1-yCr
yO
4, wherein Re=Nd or Yb; Ln=Gd, Lu, or Y; X, y=0.0001～0.1 has the zircon structure, and spacer is I4
1/ amd, when R=Gd, unit cell parameters: a=b=7.212 , c=6.346 ; When R=Lu, unit cell parameters: a=b=7.025 , c=6.234 ; When R=Y, unit cell parameters: a=b=7.118 , c=6.289 can realize self-regulated Q1.01～1.08 μ m pulse lasers output.
2. Re as claimed in claim 1
3+, Cr
5+: LnVO
4Crystal is characterized in that preferred one of following:
Nd
3+, Cr
5+: GdVO
4Crystal, Nd
3+, Cr
5+: YVO
4Crystal, Yb
3+, Cr
5+: YVO
4Crystal.
3. the described Re of claim 1
3+, Cr
5+: LnVO
4The crystalline preparation method adopts Czochralski grown, and step is as follows:
According to Ln
1-xRe
xV
1-yCr
yO
4(Re=Nd or Yb; Ln=Gd, Lu, or Y, x, y=0.0001～0.1) in the formula each component the molar ratio weighing raw material and mix, place Iridium Crucible, shove charge; Single crystal growing furnace vacuumizes, and inflation is warmed up to 1750-1850 ℃ and makes the polycrystal fusing; Following seeded growth crystal, crystal growth temperature is between 1750-1850 ℃; Crystal growth finishes and is cooled to room temperature, comes out of the stove; The crystal of coming out of the stove is annealed under 1100-1300 ℃ temperature.
4. Re as claimed in claim 3
3+, Cr
5+: LnVO
4The crystalline preparation method, the pull rate that it is characterized in that crystal growth is 0.5～2 millimeter/hour, 10～30 rev/mins of rotating speeds.
5. Re as claimed in claim 3
3+, Cr
5+: LnVO
4The crystalline preparation method is characterized in that crystal growth atmosphere is the oxygen of volume ratio 1-2% and the nitrogen of surplus.
6. the described Re of claim 1
3+, Cr
5+: LnVO
4Crystal is used to make laser self-regulated Q device, Re
3+, Cr
5+: LnVO
4Deielectric-coating, Re are polished or be coated with to the crystal both ends of the surface
3+, Cr
5+: LnVO
4The logical light face of crystalline is circular or square, and optical direction thickness is 0.1-10mm.
7. method that produces self-regulated Q pulse laser is with the Re of claim 1
3+, Cr
5+: LnVO
4Crystal is simultaneously as laserable material and self-regulated Q material, and these crystal both ends of the surface are polished or are coated with deielectric-coating again, with this crystal of pumping source pumping, need not to add modulator element, produces the pulse laser of 1.01-1.08 μ m self-modulation.
8. a kind of method that produces self-regulated Q pulse laser as claimed in claim 7 is characterized in that with laser diode or ti sapphire laser adopting the mode pumping Re of end face or profile pump as pumping source
3+, Cr
5+: LnVO
4Crystal.
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|---|---|---|---|
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| CNB2007101138428A CN100494517C (en) | 2007-09-26 | 2007-09-26 | Re3+, cr5+: lnVO4self-regulating laser crystal, its preparation method and application |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101603206B (en) * | 2009-07-07 | 2012-05-23 | 福州高意通讯有限公司 | Method for preparing Cr<3+>, Nd<3+>:YVO4 crystal and Cr<4+>, Nd<3+>:YVO4 crystal |
| CN104051959A (en) * | 2014-07-04 | 2014-09-17 | 青岛镭视光电科技有限公司 | Self-Q-switched laser |
| CN108923236A (en) * | 2018-08-01 | 2018-11-30 | 山东大学 | It is a kind of based on neodymium ion doped vanadate crystal laser |
| CN109950784A (en) * | 2019-04-10 | 2019-06-28 | 上海禾赛光电科技有限公司 | Laser and laser radar |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100500953C (en) * | 2004-11-25 | 2009-06-17 | 福建福晶科技股份有限公司 | Cerium vanadate crystal material of scintillating crystal |
-
2007
- 2007-09-26 CN CNB2007101138428A patent/CN100494517C/en active Active
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101603206B (en) * | 2009-07-07 | 2012-05-23 | 福州高意通讯有限公司 | Method for preparing Cr<3+>, Nd<3+>:YVO4 crystal and Cr<4+>, Nd<3+>:YVO4 crystal |
| CN104051959A (en) * | 2014-07-04 | 2014-09-17 | 青岛镭视光电科技有限公司 | Self-Q-switched laser |
| CN108923236A (en) * | 2018-08-01 | 2018-11-30 | 山东大学 | It is a kind of based on neodymium ion doped vanadate crystal laser |
| CN109950784A (en) * | 2019-04-10 | 2019-06-28 | 上海禾赛光电科技有限公司 | Laser and laser radar |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100494517C (en) | 2009-06-03 |
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