CN101864595B - Erbium-doped gadolinium lithium fluoride crystal and growth method thereof - Google Patents
Erbium-doped gadolinium lithium fluoride crystal and growth method thereof Download PDFInfo
- Publication number
- CN101864595B CN101864595B CN2010101923383A CN201010192338A CN101864595B CN 101864595 B CN101864595 B CN 101864595B CN 2010101923383 A CN2010101923383 A CN 2010101923383A CN 201010192338 A CN201010192338 A CN 201010192338A CN 101864595 B CN101864595 B CN 101864595B
- Authority
- CN
- China
- Prior art keywords
- crystal
- erbium
- lithium fluoride
- doped
- growth
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Landscapes
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The invention relates to an erbium-doped gadolinium lithium fluoride crystal and a growth method thereof, belonging to the technical field of optoelectronic materials. The conventional erbium-doped yttrium lithium fluoride crystal has low doping concentration for the reasons of ionic radius matching; and in the growth process of the conventional erbium-doped yttrium lithium fluoride crystal, the crystal with large size is difficult to grow as the yttrium lithium fluoride has high melting point and the raw material has high volatility. The erbium-doped gadolinium lithium fluoride crystal belongs to a tetragonal crystal system and takes rare earth erbium as an activated ion, wherein the erbium-doped gadolinium lithium fluoride crystal has a molecular formula of Er: LiGdF4, and the crystal matrix is gadolinium lithium fluoride. The growth method of the erbium-doped gadolinium lithium fluoride crystal is characterized in that LiF is excessively added according to LiF: GdF3=16.5 to 17:7.76 to 8, and the crystal growth process parameters are determined as: the pulling speed is 0.3 to 0.8mm/h, the rotation speed is 3 to 10rpm, and the growth temperature is 745 to 755 DEG C. The erbium-doped gadolinium lithium fluoride crystal is a laser crystal and is suitable for a high-power solid laser.
Description
Technical field
The present invention relates to a kind of erbium-doped gadolinium lithium fluoride crystal and growth method thereof, erbium-doped gadolinium lithium fluoride crystal is a kind of laser crystals, and skeleton symbol is Er:GLF, belongs to the photoelectron material technical field.
Background technology
Er-doped laser has characteristics such as characteristics of atmospheric transmission is good, the smog penetrativity strong, good confidentiality, is applied to fields such as laser ranging, lidar, photoelectric interference, remote sensing, environmental monitoring, optical communication.In addition, er-doped laser has absorption more by force in water, thus not only to eye-safe, and can accurately get involved biological tissue, therefore, using value is also arranged at medical field such as ophthalmologic operation.
The used laserable material of er-doped laser is the er-doped crystal, comprises crystal of fluoride, like Er:LiYF
4, belonging to tetragonal system, its thermal refractive index coefficient is less, and the specific refractory power that causes that heats up reduces and can increase because of the light path that thermal expansion causes by partial offset, thereby thermal lensing effect is very little.The laser generation threshold value greatly reduces, and gain obviously improves, characteristics such as have the peak width of absorption, fluorescence lifetime is long, heat effect is little.Although Er:LiYF
4The laser crystals excellent performance, still, because of the reason of erbium, ruthenium ion radius coupling aspect, doping content is low, has only 20at.%.
Existing Er:LiYF
4The crystalline growth method is following:
1, growth material preparation
LiF: YF in theory
3=1: 1, in fact LiF presses LiF: YF
3=13: 12 excessive addings cooperate the crystal growth technique parameter again, can grow the crystal of lattice perfection.Therefore, the proportioning of each component is following in the raw material, ErF
3Be x mole, YF
3Be (1-x) mole, LiF is 1.083 (1-x) moles, and wherein the span of x is: 0.005mol≤x≤0.2mol.With said component thorough mixing, handle through HF atmosphere, get block growth material with the hydropress briquetting.
2, crystal growth
Adopt Czochralski grown Er:LiYF
4Crystal.With the prepared growth material single crystal growing furnace of packing into, vacuumize, charge into argon gas, the significant parameter of crystal growth is confirmed as: pull rate 1mm/h, speed of rotation 5rpm, 810 ℃ of growth temperatures.
3, annealing
After crystal growth finishes, adopt the mode of in-situ annealing slowly furnace temperature to be reduced to room temperature, take out crystal.
Said growing method also has its deficiency, at growth Er:LiYF
4In the crystalline process, because LiYF
4Fusing point is high, and as 810 ℃, thereby volatility of raw material is serious, is difficult to grow large-sized Er:LiYF
4Crystal has only Φ 13mm * 20mm like crystalline size.
Summary of the invention
In order to improve the doping content of er-doped crystal of fluoride; And grow large-sized crystal; We propose the scheme of a kind of erbium-doped gadolinium lithium fluoride crystal and growth method thereof; Wherein fibrous root is confirmed suitable growth protocols according to the difference of gadolinium, yttrium, and the erbium-doped gadolinium lithium fluoride crystal of being grown not only has and Er:LiYF
4Similar spectrum, and doping content is high, size is big, can be used in great-power solid laser.
The present invention's erbium-doped gadolinium lithium fluoride crystal belongs to tetragonal system, is active ions with the rare earth erbium, it is characterized in that, said erbium-doped gadolinium lithium fluoride crystal molecular formula is Er:LiGdF
4, crystal substrate is a gadolinium lithium fluoride.
Its step of the present invention's growth method comprises growth material preparation, crystal growth and annealing, it is characterized in that LiF presses LiF: GdF
3=16.5～17: 7.76～8 excessive addings; The crystal growth technique parameter is confirmed as pull rate: 0.3～0.8mm/h, speed of rotation: 3～10rpm, growth temperature: 745～755 ℃.
Its effect of the present invention is Er:LiGdF
4Crystal belongs to tetragonal system and zero defect; Because erbium, gadolinium ion radius coupling; Doping content reaches as high as 100at.%; As required, the doping content that control is actual, best, this highly doped effect can be that peak value the present invention's the erbium-doped gadolinium lithium fluoride crystal fluorescence spectrum figure is found out from accompanying drawing.LiGdF
4Fusing point is 750 ℃, and the crystalline growth temperature adapts with it, and therefore, volatility of raw material alleviates, thereby can grow large-sized crystal easily, like Φ 30mm * 50mm.
Description of drawings
Accompanying drawing is the present invention's erbium-doped gadolinium lithium fluoride crystal fluorescence spectrum figure, and this figure double as is a Figure of abstract.
Embodiment
The present invention's erbium-doped gadolinium lithium fluoride crystal belongs to tetragonal system, is active ions with the rare earth erbium, and said erbium-doped gadolinium lithium fluoride crystal molecular formula is Er:LiGdF
4, crystal substrate is a gadolinium lithium fluoride, the concentration of mixing of erbium is 20～50at.%.
The present invention's growth method is specific as follows:
1, growth material preparation
LiF presses LiF: GdF
3=16.5～17: 7.76～8 excessive addings.The proportioning of each component is following in the raw material, ErF
3Be x mole, GdF
3Be (1-x) mole, LiF is 2.125 (1-x) moles, and wherein the span of x is: 0.005mol≤x≤1mol.With said component thorough mixing, handle through HF atmosphere, get block growth material with the hydropress briquetting.
2, crystal growth
Adopt Czochralski grown Er:LiGdF
4Crystal.With the prepared growth material single crystal growing furnace of packing into, vacuumize, charge into argon gas, the significant parameter of crystal growth is confirmed as: pull rate: 0.3～0.8mm/h; Speed of rotation: 3～10rpm, growth temperature: 745～755 ℃.
3, annealing
Crystal growth finishes, and adopts the mode of in-situ annealing slowly furnace temperature to be reduced to room temperature, takes out crystal.
Be an object lesson below, LiF presses LiF: GdF
3=17: 8 excessive addings.Get x=0.3, the proportioning of each component is following in the raw material, ErF
30.3 mole, GdF
30.7 mole, the LiF1.4875 mole.With said component thorough mixing, handle through HF atmosphere, get block growth material with the hydropress briquetting.Adopt Czochralski grown Er:LiGdF
4Crystal.With pack into iridium crucible and put into the Frequency Induction Heating single crystal growing furnace of prepared growth material, be evacuated to 10
-4Pa charges into argon gas.The significant parameter of crystal growth is confirmed as: pull rate: 0.5mm/h, speed of rotation: 7rpm, growth temperature: 750 ℃.Crystal growth finishes, and adopts the mode of in-situ annealing slowly furnace temperature to be reduced to room temperature, takes out crystal.This crystal is an erbium-doped gadolinium lithium fluoride crystal, belongs to cubic strain, and crystal mass is better, is of a size of Φ 30mm * 50mm.Through test, the concentration of mixing of erbium is 30at.%.Through spectrum test, the present invention's erbium-doped gadolinium lithium fluoride crystal is compared with existing erbium-doped yttrium lithium fluoride crystal, and the photoluminescence peak wavelength is close, and photoluminescence peak increases, and sees shown in the accompanying drawing.
Claims (2)
1. erbium-doped gadolinium lithium fluoride crystal growth method, its step comprises growth material preparation, crystal growth and annealing, it is characterized in that, LiF presses LiF: GdF
3=16.5～17: 7.76～8 excessive addings; The crystal growth technique parameter is confirmed as pull rate: 0.3～0.8mm/h, speed of rotation: 3～10rpm, growth temperature: 745～755 ℃.
2. erbium-doped gadolinium lithium fluoride crystal growth method according to claim 1 is characterized in that the proportioning of each component is following in the raw material, ErF
3Be x mole, GdF
3Be (1-x) mole, LiF is 2.125 (1-x) moles, and wherein the span of x is: 0.005mol≤x≤1mol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101923383A CN101864595B (en) | 2010-06-07 | 2010-06-07 | Erbium-doped gadolinium lithium fluoride crystal and growth method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101923383A CN101864595B (en) | 2010-06-07 | 2010-06-07 | Erbium-doped gadolinium lithium fluoride crystal and growth method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101864595A CN101864595A (en) | 2010-10-20 |
| CN101864595B true CN101864595B (en) | 2012-05-23 |
Family
ID=42956513
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010101923383A Expired - Fee Related CN101864595B (en) | 2010-06-07 | 2010-06-07 | Erbium-doped gadolinium lithium fluoride crystal and growth method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101864595B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102321482A (en) * | 2011-05-24 | 2012-01-18 | 南京航空航天大学 | Photoluminescence material with frequency synergistic light conversion and preparation method as well as use thereof |
| CN103820854A (en) * | 2014-02-20 | 2014-05-28 | 宁波大学 | Ce<3+> doped gadolinium lithium fluoride ultraviolet laser crystal and preparation method thereof |
| CN104099665B (en) * | 2014-07-09 | 2017-12-15 | 北京雷生强式科技有限责任公司 | A kind of lithium yttrium fluoride composite crystal and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1287680A (en) * | 1998-10-19 | 2001-03-14 | 皇家菲利浦电子有限公司 | Luminescent material |
| US6212215B1 (en) * | 1995-03-24 | 2001-04-03 | The Regents Of The University Of California | Hybrid solid state laser system using a neodymium-based master oscillator and an ytterbium-based power amplifier |
| CN101265028A (en) * | 2008-04-18 | 2008-09-17 | 中国计量学院 | Rare earth doping LiYF4 microcrystalline glass and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004198778A (en) * | 2002-12-19 | 2004-07-15 | Kogaku Giken:Kk | Two-wavelength reflection preventing film and forming method of the film |
| KR20110030425A (en) * | 2008-05-16 | 2011-03-23 | 가부시끼가이샤 도꾸야마 | Pretreated metal fluorides and process for production of fluoride crystals |
| CN101660205A (en) * | 2009-09-04 | 2010-03-03 | 长春理工大学 | Laser crystal of sodium tungstate with waveband of 2 microns |
-
2010
- 2010-06-07 CN CN2010101923383A patent/CN101864595B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6212215B1 (en) * | 1995-03-24 | 2001-04-03 | The Regents Of The University Of California | Hybrid solid state laser system using a neodymium-based master oscillator and an ytterbium-based power amplifier |
| CN1287680A (en) * | 1998-10-19 | 2001-03-14 | 皇家菲利浦电子有限公司 | Luminescent material |
| CN101265028A (en) * | 2008-04-18 | 2008-09-17 | 中国计量学院 | Rare earth doping LiYF4 microcrystalline glass and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| JP特开2004-198778A 2004.07.15 |
| Takeshi Hirai， et al."4f–5d absorption of gadolinium ions in sodium gadolinium tetrafluorides".《Chemical Physics Letters》.2007,第446卷138页右栏第1段至139页左栏第3段. |
| Takeshi Hirai, et al."4f–5d absorption of gadolinium ions in sodium gadolinium tetrafluorides".《Chemical Physics Letters》.2007,第446卷138页右栏第1段至139页左栏第3段. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101864595A (en) | 2010-10-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101619492A (en) | Chromium and praseodymium sensitized ions co-doped gadolinium gallium garnet novel laser crystal activated by erbium ions | |
| CN103194796A (en) | Infrared laser crystal in Ho-Pr codoping lutecium lithium fluoride, and preparation method thereof | |
| CN101864595B (en) | Erbium-doped gadolinium lithium fluoride crystal and growth method thereof | |
| CN102586870A (en) | Holmium-doped gadolinium-yttrium-barium fluoride crystal and growth method thereof | |
| CN102659319A (en) | Oxyfluoride glass ceramic and preparation method thereof | |
| CN102766905B (en) | Erbium ion activated 1.55 micron waveband gallate laser crystalss and preparation method thereof | |
| CN101378174A (en) | Gadolinium gallium garnet novel laser crystal activated by erbium ion co-doped with sensitized ion | |
| CN102766906B (en) | Erbium ion activated 3 micron waveband gallate laser crystals and preparation method thereof | |
| CN101054728A (en) | Molybdate crystal for laser and excited Raman frequency shift and preparing method and use thereof | |
| CN102618928A (en) | High-efficiency mid-infrared laser crystal and preparation method thereof | |
| CN103014854A (en) | Ho<3+>/Pr<3+> codoping lithium yttrium fluoride monocrystal and preparation method thereof | |
| CN102797038A (en) | Mg-Yb-Er doped lithium niobate laser crystals and preparation method thereof | |
| CN103103610A (en) | Neodymium-doped yttrium fluoride gadolinium lithium crystal and growing method of same | |
| CN101643935A (en) | 2mum-waveband K (Yb/Tm) W laser crystal | |
| CN101298695A (en) | Growth method of calcium niobate monocrystal | |
| CN103073191B (en) | SiO2-NaF-Eu:YAG system glass ceramic preparation method | |
| CN103757699B (en) | A kind of europium ion-doped gadolinium fluoride sodium optical crystal and preparation method thereof | |
| CN102691104A (en) | Ytterbium-doped gadolinium yttrium aluminum garnet crystal and growth method thereof | |
| CN101864597A (en) | Holmium and thulium-doped gadolinium gallate laser crystal | |
| CN102605425B (en) | Laser matrix crystal of lead chlorofluoride doped with rare earth ions and preparation method thereof | |
| CN101717997A (en) | Neodymium-doped silicic acid lutecium gadolinium laser crystal and preparation method thereof | |
| Kim et al. | Tm-doped Langasite (La3Ga5SiO14) crystals grown by the Czochralski method for optical applications | |
| CN101717998A (en) | Neodymium-doped silicic acid yttrium lutetium laser crystal and preparation method thereof | |
| CN101660205A (en) | Laser crystal of sodium tungstate with waveband of 2 microns | |
| CN101619493A (en) | Chromium and praseodymium sensitized ions co-doped gadolinium gallium garnet novel laser crystal activated by erbium ions |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120523 Termination date: 20130607 |