CN100427649C - Growth method of vanadium-doped yttrium aluminum garnet crystal - Google Patents
Growth method of vanadium-doped yttrium aluminum garnet crystal Download PDFInfo
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- CN100427649C CN100427649C CNB2006100295022A CN200610029502A CN100427649C CN 100427649 C CN100427649 C CN 100427649C CN B2006100295022 A CNB2006100295022 A CN B2006100295022A CN 200610029502 A CN200610029502 A CN 200610029502A CN 100427649 C CN100427649 C CN 100427649C
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- 239000013078 crystal Substances 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 27
- 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 title 1
- 229910019901 yttrium aluminum garnet Inorganic materials 0.000 title 1
- 238000010438 heat treatment Methods 0.000 claims abstract description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 10
- 239000010439 graphite Substances 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 7
- 239000002223 garnet Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 229910052720 vanadium Inorganic materials 0.000 claims description 8
- 230000006698 induction Effects 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 abstract description 13
- 150000002500 ions Chemical class 0.000 abstract 3
- 239000007789 gas Substances 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- 239000011733 molybdenum Substances 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
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Abstract
A process for growing V-YAG crystal by heating graphite heater or filling CO or H in furnace cavity2Reducing gas, or adding Si with high valence state to raw material4+Or Zr4+Ions. The method of the invention improves the tetrahedral lattice position V generating a saturable absorption band of 1.0-1.5 mu m in the crystal3+The ions account for the proportion of all V ions.
Description
Technical field
The invention belongs to optics and photoelectron material field, relate to crystal growth, particularly a kind of doped-vanadium yttrium garnet (V.YAG) crystalline growth method.
Background technology
Q-switch solid laser has output laser pulse weak point, peak power advantages of higher, is widely used in fields such as medical science, optical-fibre communications, measuring technology and nonlinear opticses.Than active Q-switching, that passive Q-switch has is simple in structure, volume is little, low cost and other advantages and being widely used.Early stage passive Q-adjusted material generally adopts organic dye and colour centre crystal, yet these materials have short shortcoming of poor chemical stability, work-ing life, are unfavorable for work steady in a long-term.Recently it is found that Cr
4+: the YAG crystal has wide absorption band and good saturated absorption characteristic at 0.9~1.2 mu m waveband, is mainly used in the passive Q-adjusted of Nd laser apparatus 1.06 μ m places.Doped-vanadium yttrium-iron-garnet crystal (V:YAG) is a kind of novel saturable absorption material, the saturable absorption band covers 1.0~1.5 μ m, broad application background is more arranged: can be used as Nd laser apparatus 1.06 μ m and 1.34 μ m (referring to Applied PhysicsB 1998,67:555~558.SPIE 2004.5460:292~302), and the passive Q-switch of Er laser apparatus 1.54 μ m (referring to AppliedOptics 2005,441704~1708).The human eye safe waveband 1.54 μ m laser apparatus that have special important application by the acquisition of frequency displacement 134 μ m laser (referring to Instruments and Experimental Techniques2005,48:239-240), have higher efficient than 1.06 μ m.Therefore, V:YAG has become one of most important passive Q-switch material.
10~1.5 μ m saturable absorption bands of V.YAG belong to the V of tetrahedron case
3+Ion.And V can present in the YAG crystal+3 ,+4 ,+multiple valence states, particularly tetrahedron case such as 5 are very beneficial for high valence state (>+3) V ionic and exist.Therefore, the tetrahedron case V that adopts the V:YAG crystal of general melt method for growing to contain
3+Concentration is very low, almost detects the existence less than above-mentioned saturable absorption band, must improve its concentration (referring to SPIE 1999,3724:329-333 through complicated reducing atmosphere The high temperature anneal; Optical Engineering 2002,41:1976-1982).Must take aftertreatment technology, this has not only increased V:YAG crystalline cost, has also increased the production cycle.
In sum, V.YAG has been widely used in producing the high-peak power laser pulse of several typical laser wavelength 1.06 μ m, 1.34 μ m and 1.54 μ m as a kind of saturable absorber with absorption band of non-constant width (about 500nm).But,, how to improve tetrahedron case V in the V.YAG crystal in order to improve the passive Q-adjusted performance of V:YAG crystalline
3+Ratio be the important techniques problem that needs solve.
Summary of the invention
Main purpose of the present invention is will overcome above-mentioned technology formerly to be difficult to obtain high density tetrahedron case V
3+The ionic shortcoming provides a kind of growth method of doped-vanadium yttrium-iron-garnet crystal, to improve the tetrahedron case V that produces 10~15 μ m saturable absorption bands in the crystal
3+Ion accounts for all V ionic ratios.
The technology of the present invention solution is as follows:
A kind of growth method of doped-vanadium yttrium-iron-garnet crystal adopts traditional crystal pulling method, falling crucible method or temperature gradient method growth V:YAG crystal, it is characterized in that the type of heating of V.YAG crystal growing process adopts graphite heater, or charges into CO or H in the burner hearth
2Reducing gas, or add the Si of high valence state in the proportioning raw materials
4+Or Zr
4+Ion.
In the time of the heating of described employing graphite resistance heating element, in the burner hearth for vacuum state or charge into inert protective gas or charge into CO or H
2Reducing gas
When described type of heating is induction heating or resistive heating, charge into CO or H in the burner hearth
2Reducing gas.
The S that adds high valence state in the described proportioning raw materials
1 4+Or Zr
4+Ion is by 0.1%~10% adding S that adds V ion atoms percentage composition in the raw material
1O
2Or ZrO
2Mode add.
We adopt inductively coupled plasma atomic emission spectrum to test V ionic overall weight percentage concentration in the V:YAG crystal of growing according to growth method of the present invention.Record thus that V.YAG crystalline V concentration is 0.25wt% in the specific embodiment 2, calculate atomicity volumetric concentration (N
0) be 1.3 * 10
20/ cm
3After cutting of crystal blank process and the polished finish, adopt Jasco V-570UV/VIS/NIR spectrophotometer test V:YAG crystalline room temperature absorption spectrum.According to the absorption cross (σ) of V.YAG crystal at 1342nm wavelength place in the uptake factor (α) at the 1342nm place of practical measurement and the document is 72 * 10
-18Cm
2, can calculate tetrahedron V in the crystal
3+Ionic atomicity volumetric concentration (N
1): N
1=α/σ.In the specific embodiment of the invention 2 V:YAG crystalline absorption spectrum as shown in Figure 2, the uptake factor of 1342nm is 082cm
-1, calculate tetrahedron V thus
3+Ionic atomicity volumetric concentration is 2.2 * 10
17/ cm
3N
1Divided by N
0Be tetrahedron V
3+Ion accounts for all V ionic ratios in the crystal.This ratio is 0.17% in the embodiment of the invention 2.This numerical value is big more, shows that promptly employed growing method helps tetrahedron V more
3+Ionic forms.
According to the present invention, the worker in this field makes improvements on the basis of existing growth apparatus, perhaps adopts composition of raw materials of the present invention, can obtain to have at 1.0~1.5 mu m wavebands the V:YAG crystal of saturable absorption characteristic low-cost, expeditiously.
Description of drawings
Fig. 1 be the inventive method at the induction heating crystal pulling method at H
2The V:YAG crystal of growing under the atmosphere (thickness is 2.2mm) see through spectrum.
Fig. 2 adopts the absorption spectrum of the V:YAG crystal (thickness is 55mm) that graphite resistance Heating temperature gradient method grows under high-purity (>99.995%) Ar atmosphere for the present invention.
Embodiment
The invention will be further described below in conjunction with embodiment.
Embodiment 1:
Employ V
2O
5, Al
2O
3, Y
2O
3Make initial feed, V
2O
5Doping content be 0.20at%, mix the back on hydropress briquetting, be put in the iridium crucible.Use the induction heating Czochralski grown crystal, make seed crystal through X-ray diffractometer accurate pointing normal line of butt end direction for the YAG single crystal rod of [111], growth atmosphere is mobile H
2The crystal blank of growth is deep green, and from blank cutting fritter sample, grinding the content that adopts ICP-AES to measure V in the crystal in the back is 014at%, is converted into the atomicity volumetric concentration and equals 3.2 * 10
19/ cm
3Cutting thickness is the wafer of 26mm from the crystal blank, and optical polish to thickness is 2.2mm, adopts the test of Jasco V-570UV/VIS/NIR spectrophotometer to see through spectrum as shown in Figure 1.The uptake factor that converses the 1342nm place is 0.24cm
-1, divided by its absorption cross 7.2 * 10
-18Cm
2, calculate tetrahedron V in the crystal
3+Ionic atomicity volumetric concentration is 3.36 * 10
16/ cm
3, accounting for all V ionic ratios is 011%.
Embodiment 2:
Adopt V
2O
3, Al
2O
3, Y
2O
3Make initial feed, V
2O
3Doping content be 0.78at%, mix back briquetting on hydropress, be put in the molybdenum crucible, crucible bottom is placed with through X-ray diffractometer accurate pointing normal line of butt end direction and is the YAG single crystal rod seed crystal of [111].Use the gradient furnace growing crystal of graphite heater heating, growth atmosphere is that purity is higher than 99995% argon gas.The crystal blank of growth is deep green, and from blank cutting fritter sample, grinding the content that adopts ICP-AES to measure V in the crystal in the back is 0.58at%, is converted into the atomicity volumetric concentration and equals 1.3 * 10
20/ cm
3Cutting thickness is the wafer of 6.0mm from the crystal blank, and optical polish to thickness is 5.5mm (behind the plated film as shown in Figure 2), adopts Jasco V-570UV/VIS/NIR spectrophotometer test absorption spectrum as shown in Figure 3, and the uptake factor at 1342nm place is 1.56cm
-1, divided by its absorption cross 7.2 * 10
-18Cm
2, calculate tetrahedron V in the crystal
3+Ionic atomicity volumetric concentration is 2.2 * 10
17/ cm
3, accounting for all V ionic ratios is 0.17%.
Embodiment 3:
Adopt V
2O
5, Al
2O
3, Y
2O
3, SiO
2Make initial feed, wherein V
2O
3Doping content be 0.80at%, SiO
2Doping content be 0.008at%, mix back briquetting on hydropress, be put in the molybdenum crucible, crucible bottom is placed with through X-ray diffractometer accurate pointing normal line of butt end direction and is the YAG single crystal rod seed crystal of [111].Use the gradient furnace growing crystal of graphite heater heating, growth atmosphere is that purity is higher than 99.995% argon gas.The crystal blank of growth is deep green.
Embodiment 4:
Adopt V
2O
5, Al
2O
3, Y
2O
3Make initial feed, wherein V
2O
5Doping content be 0.50at%, mix back briquetting on hydropress, be put in the molybdenum crucible, crucible bottom is placed with through X-ray diffractometer accurate pointing normal line of butt end direction and is the YAG single crystal rod seed crystal of [111].Use the crucible decline stove growing crystal of graphite heater heating, growth atmosphere is CO.It is green that the crystal blank of growth is.
Embodiment 5:
Adopt V
2O
3, Al
2O
3, Y
2O
3Make initial feed, wherein V
2O
3Doping content be 0.50at%, mix back briquetting on hydropress, be put in the molybdenum crucible, crucible bottom is placed with through X-ray diffractometer accurate pointing normal line of butt end direction and is the YAG single crystal rod seed crystal of [111].Use the crucible decline stove growing crystal of graphite heater heating, growth atmosphere is H
2The crystal blank of growth is deep green.
Embodiment 6:
Adopt V
2O
5, Al
2O
3, Y
2O
3, ZrO
2Make initial feed, wherein V
2O
3Doping content be 0.60at%, ZrO
2Doping content be 0.012at%, mix back briquetting on hydropress, be put in and use the induction heating Czochralski grown crystal in the iridium crucible, make seed crystal through X-ray diffractometer accurate pointing normal line of butt end direction for the YAG single crystal rod of [111], growth atmosphere is higher than 99.995% argon gas for mobile purity.The crystal blank of growth is deep green.
Claims (4)
1, a kind of growth method of doped-vanadium yttrium-iron-garnet crystal adopts traditional crystal pulling method, falling crucible method or temperature gradient method growth V:YAG crystal, it is characterized in that adopting in the V:YAG crystal growing process graphite heater to heat, or charges into CO or H in the burner hearth
2Reducing gas, or add the Si of high valence state in the proportioning raw materials
4+Or Zr
4+Ion.
2, the growth method of doped-vanadium yttrium-iron-garnet crystal according to claim 1, when it is characterized in that the heating of described employing graphite resistance heating element, in the burner hearth for vacuum state or charge into inert protective gas or charge into CO or H
2Reducing gas.
3, the growth method of doped-vanadium yttrium-iron-garnet crystal according to claim 1 when it is characterized in that described type of heating is induction heating or resistive heating, charges into CO or H in the burner hearth
2Reducing gas.
4, the growth method of doped-vanadium yttrium-iron-garnet crystal according to claim 1 is characterized in that in the described proportioning raw materials adding the Si of high valence state
4+Or Zr
4+Ion is by 0.1%~10% adding SiO that adds V ion atoms percentage composition in the raw material
2Or ZrO
2Mode add.
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CN101481821B (en) * | 2008-12-31 | 2012-09-05 | 吴晟 | Novel technology for growth of yttrium-aluminum garnet crystal and equipment thereof |
CN105696073A (en) * | 2016-02-16 | 2016-06-22 | 中科九曜科技有限公司 | Self-saturated absorption type Q-switching yttrium aluminum garnet laser crystal and growth method thereof |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS55109299A (en) * | 1979-02-14 | 1980-08-22 | Hitachi Metals Ltd | Garnet single crystal for ornament |
JPS55113697A (en) * | 1979-02-22 | 1980-09-02 | Hitachi Metals Ltd | Garnet single crystal body for decoration |
-
2006
- 2006-07-28 CN CNB2006100295022A patent/CN100427649C/en not_active Expired - Fee Related
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS55109299A (en) * | 1979-02-14 | 1980-08-22 | Hitachi Metals Ltd | Garnet single crystal for ornament |
JPS55113697A (en) * | 1979-02-22 | 1980-09-02 | Hitachi Metals Ltd | Garnet single crystal body for decoration |
Non-Patent Citations (3)
Title |
---|
Spectroscopic investigation of YAG crystal doped withtetrahedrally coordinated V3+ ions. Jian Ma et al.Phys.Stat.Sol.,Vol.(b) 243 No.8. 2006 * |
V:YAG-new passive Q-switch for diode-pumped solid statelasers. A.M.Malyarevich et al.Appl. Phys.B,Vol.67 . 1998 * |
YAG:V3+ single crystal growth and their selected properties. Z.Frukacz et. al.SPIE,Vol.3727 . 1999 * |
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