CN101831703A - Borate compound gadolinium-lanthanum-scandium borate and mono-crystal, preparation method and application thereof - Google Patents
Borate compound gadolinium-lanthanum-scandium borate and mono-crystal, preparation method and application thereof Download PDFInfo
- Publication number
- CN101831703A CN101831703A CN200910111241A CN200910111241A CN101831703A CN 101831703 A CN101831703 A CN 101831703A CN 200910111241 A CN200910111241 A CN 200910111241A CN 200910111241 A CN200910111241 A CN 200910111241A CN 101831703 A CN101831703 A CN 101831703A
- Authority
- CN
- China
- Prior art keywords
- crystal
- borate
- glsb
- boric acid
- mono
- 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.)
- Pending
Links
Images
Landscapes
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The invention relates to a borate compound gadolinium-lanthanum-scandium borate and a mono-crystal, a preparation method and application thereof. The compound has a chemical formula of GdxLa1-xSc3(BO3)4, and a crystal structure space group is R32. The mono-crystal of the compound has the following unit cell parameters: a=9.7933 angstroms, c=7.9540 angstroms, gamma=120 degrees, Z=3; the unit cell volume V is equal to 660.65 angstrom<3>; and the borate compound is prepared by adopting a molten salt method. The mono-crystal is used for nonlinear optical frequency conversion and is also used for harmonic generators of visible and ultraviolet regions.
Description
Technical field
The present invention relates to a kind of novel non-linear optic crystal.
Background technology
Ultra-Violet Laser has a wide range of applications at aspects such as Laser Micro-Machining, semiconductor lithography, optical information storage, laser medicines as a kind of important light source.At present the Excimer UV laser apparatus that uses has the defective that can't overcome, as bulky, and apparatus expensive, the maintenance cost height, beam quality is poor, needs to be equipped with expensive optical system and focuses on etc.Therefore replacing excimer laser has become trend of the times.The core component of full solid state ultraviolet laser system is the non-linear optic crystal that can produce the ultraviolet harmonic wave.So need develop ultraviolet non-linear optic crystal, for the full solid state ultraviolet laser system provides reliability and durability frequency doubling device with outstanding over-all properties and application prospect.
Non-linear optic crystal YAl
3(BO
3)
4(YAB) at visible and ultraviolet region bigger nonlinear optical coefficients and moderate degree of birefringence are arranged, but owing to difficulty grows high-quality monocrystalline, thereby limited its practical application.Replace the position of Al to be LnSc with Sc
3(BO
3)
4(Ln=lanthanon) (referring to USA Magazine " Optical Materials " Vol.18,243,2001).CeSc wherein
3(BO
3)
4(referring to USA Magazine " International Journal of Inorganic Materials " Vol.2,101,2000) have non-centrosymmetrical tripartite phase (huntite) structure, and LaSc
3(BO
3)
4(LSB) (referring to USA Magazine " Materials ResearchSocity " Vol.16,38,2001) then are the monocline phase.When mixing the less lanthanon of radius among the LSB of monocline phase, can be transformed into tripartite phase, for example: self-frequency-doubling crystal La
1-xNd
xSc
3(BO
3)
4(referring to USA Magazine " Materials Research Socity " Vol.16,38,2001) must adopt the trivalent ion of filled shell in order to guarantee the transmitance of ultraviolet region.Y is mixed among the LSB, successfully grow large-sized non-linear optic crystal Y
xLa
ySc
z(BO
3)
4(x+y+z=4) (referring to USA Magazine " Chemistry Material " Vol.17,2687,2005).The present invention mixes Gd among the LSB, grows novel large-sized non-linear optic crystal Gd
xLa
1-xSc
3(BO
3)
4(GLSB).The GLSB monocrystalline has the higher non-linearity optical coefficient, wide transmission region, and moderate degree of birefringence, bigger hardness, the fusing point height, chemical property, thermal property are stablized.Non-linear optic crystal GLSB can be used as frequency doubling device and is used for the full solid state ultraviolet laser system.
Summary of the invention
The object of the present invention is to provide a kind of non-linear optic crystal Gd
xLa
1-xSc
3(BO
3)
4, be called for short GLSB.This crystal belongs to trigonal system, and spacer is: R32.
Technical essential of the present invention provides a kind of method of the GLSB of preparation monocrystalline, it is characterized in that: use molten-salt growth method, as fusing assistant, grow tripartite phase monocrystal by the pyrosol top-seeded solution growth with borate.
Realize that technical scheme of the present invention is:
By the synthetic GLSB of solid state reaction, chemical equation is:
xGd
2O
3+(1-x)La
2O
3+3Sc
2O
3+4B
2O
3＝2Gd
xLa
1-xSc
3(BO
3)
4
Raw material is mixed according to a certain percentage, and sintering under 1100 ℃ of high temperature is measured solid state reaction synthetic GLSB polycrystalline sample with X-ray powder diffraction.Fig. 1, the X-ray diffraction spectrogram of GLSB, wherein Fig. 1 a is the diffractogram of solid phase synthesis GLSB powdered sample, Fig. 1 b is the GLSB monocrystalline last diffractogram of pulverizing.
With the little monocrystalline of molten-salt growth GLSB, with Li
6B
4O
9As fusing assistant, proportioning raw materials is Gd
2O
3/ La
2O
3/ Sc
2O
3/ B
2O
3/ Li
2CO
3=0.4: 0.6: 3: 14: 15.With the Pt crucible of packing into after the former abrasive lapping (diameter 30mm), put into 1100 ℃ muffle furnace, behind the constant temperature 24h, slowly reduce to 800 ℃ from 1100 ℃.Fusing assistant rare nitric acid flush away of heat.
By single crystal structure determination, compound Gd
0.22La
0.78Sc
3(BO
3)
4Spacer be: R32, cell parameter is:
γ=120 °, Z=3.Unit-cell volume is:
Its structure iron is provided by Fig. 2.This structure has following characteristics:
Tripartite phase GLSB belongs to typical C aMg
3(BO
3)
4(huntite) structure (Fig. 2).Near planar BO
3Group extends along the ab face, and Gd and La atom are positioned at distored rhizoma sparganic and live the center, and the Sc atom is positioned at distored octahedra center.Triangular prism is isolated each other, two ScO
6The octahedra limit of sharing.Triangular prism links to each other by the summit with octahedra.
Large size single crystal is grown with molten-salt growth method, adopts Li
6B
4O
9As fusing assistant, melt is prepared in following mol ratio: Gd
0.4La
0.6Sc
3(BO
3)
4: Li
6B
4O
9=1: (1-3).With platinum crucible as container, resistance furnace heating, 808AP unit temperature control is changed material earlier in muffle furnace, raw material is added in batches, all melts to raw material, is transferred to after the cooling in the flux growth stove.Be warming up to 1100 ℃, constant temperature 48 hours fully melts raw material and mixes.Use the spontaneous crystallization method and obtain seed crystal.Be warming up to 1100 ℃ again, constant temperature 48 hours, raw material fully melted and mix, be cooled to 980 ℃ then, and with seed crystal in melt, seed crystal breaks away from liquid level behind the several hrs, reduce to 970 ℃ again, when following seed crystal, constant temperature several days to seed crystal are no longer grown up also no longer melt-off, speed with 0.5～4 ℃/d begins slow cooling, reduces to 900 ℃.Crystal is lifted from liquid level, reduce to room temperature with the speed of 15 ℃/h then, promptly obtain GLSB monocrystalline (Fig. 3).
The crystal optics working method is as follows: the crystal blank is carried out orientation, and cutting, various wafers or device for non-linear optical are made in polishing.
The GLSB crystal is processed into the wafer of 1 mm thick, and polishing records the printing opacity curve (Fig. 4) of GLSB, and its ultraviolet sees through the limit less than 200 nanometers.Adopt minimum deflection angle method to measure the crystalline specific refractory power, drawing its degree of birefringence is 0.078, helps realizing the ultraviolet region phase matched.
The GLSB crystal belongs to D
3Point group according to the Kleiman Symmetry Condition, has an independently Clock Multiplier Factor d
11, its effective Clock Multiplier Factor d
EffAs follows:
d
Eff=d
11Cos θ cos3 Φ (class)
d
Eff=d
11Cos
2θ sin3 Φ (two classes)
θ is the angle between the optical axis of crystal (being the Z axle, also is triad axis) and the incident light in the formula, Φ be incident light on crystal x-y plane (promptly with the vertical plane of Z axle) projection and the angle of x axle.
We have measured GLSB crystalline phase matched ability with powder frequency multiplication testing method, confirm that GLSB can realize Nd:YAG laser (2 frequencys multiplication of λ=1.064um), and the powder frequency-doubled effect is 5 times of KDP.
The GLSB crystal has the higher non-linearity optical coefficient, wide transmission region, and moderate degree of birefringence, bigger hardness, the fusing point height, chemical property, thermal property are stablized, and good mechanical property is easy to processing.
The GLSB crystal can be realized Nd:YAG laser (2 frequencys multiplication of λ=1.064um), and, can predict that GLSB can be used in the harmonic generators of 2 frequencys multiplication of Nd:YAG laser, 3 frequencys multiplication, 4 frequencys multiplication, 5 frequencys multiplication, even be used to produce short wavelength's harmonic generators more than 200nm.So can predict, GLSB will be at various non-linear optical fields, as the harmonic generators of electric-optical appliance, pyroelectric electric device, ultraviolet region, optical parameter from the near infrared to the ultraviolet region and optical amplifier, obtain widespread use, and will open up the nonlinear optics application of vacuum ultraviolet from the aspects such as fiber waveguide device that can see the ultraviolet region.
Description of drawings
Fig. 1, the X-ray diffraction spectrogram of GLSB, wherein 1a is the diffractogram of solid phase synthesis GLSB powdered sample, Fig. 1 b is the GLSB monocrystalline last diffractogram of pulverizing.Fig. 2, the crystal unit cell structure intention of GLSB.Fig. 3 is with the GLSB crystal of molten-salt growth.Fig. 4, GLSB crystal printing opacity curve.
Embodiment
Embodiment 1:GLSB's is synthetic.
Adopt solid-phase synthesis sintering under high temperature (1100 ℃) to form, its chemical equation is as follows:
xGd
2O
3+(1-x)La
2O
3+3Sc
2O
3+4B
2O
3＝2Gd
xLa
1-xSc
3(BO
3)
4
And adding 3wt%LiBO
2Carry out to promote reaction.The concrete operations step is, raw material is mixed in agate mortar and careful the grinding, the alumina crucible of packing into then (among the Φ 30 * 30mm), is put into muffle furnace, behind 800 ℃ of sintering 2h, take out crucible and be cooled to room temperature, this moment, sample was more loose, took out sample and ground again evenly, placed crucible again, in 1100 ℃ of knot 12h that reburn, at this moment sample is formed together in muffle furnace.Put into its taking-up mortar and smash grinding to pieces and promptly get product this moment.Measure solid state reaction synthetic GLSB polycrystalline sample with X-ray powder diffraction.The GLSB powdered sample is carried out X-ray diffraction analysis, and (Fig. 1 is consistent with the GLSB monocrystalline last X ray picture (Fig. 1 b) of pulverizing a) to the gained spectrogram.
Embodiment 2: the little monocrystalline of growth GLSB.
The little monocrystalline of spontaneous nucleation growth GLSB is with Li
6B
4O
9As fusing assistant, proportioning raw materials is Gd
2O
3/ La
2O
3/ Sc
2O
3/ B
2O
3/ Li
2CO
3=0.4: 0.6: 3: 14: 15 is Gd
0.4La
0.6Sc
3(BO
3)
4: Li
6B
4O
9=1: 2.5.Raw material mixed in mortar and careful the grinding after, the Pt crucible of packing into (among the Φ 30 * 30mm), is put into 1100 ℃ muffle furnace, behind the constant temperature 24h, is reduced to 800 ℃ with the speed of 10 ℃/h from 1100 ℃.Fusing assistant promptly obtains the GLSB monocrystalline of granularity for the millimeter magnitude with rare nitric acid flush away of heat.
Embodiment 3: growing large-size GLSB monocrystalline.
Large size single crystal is grown with molten-salt growth method, adopts Li
6B
4O
9As fusing assistant, melt is prepared in following mol ratio: Gd
0.4La
0.6Sc
3(BO
3)
4: Li
6B
4O
9=1: 2.5.With platinum crucible as container, resistance furnace heating, 808AP unit temperature control is changed material earlier in muffle furnace, raw material is added in batches, all melts to raw material, is transferred to after the cooling in the homemade growth furnace.Be warming up to 1100 ℃, constant temperature 48 hours fully melts raw material and mixes.Fall liquation then and reduce to 980 ℃, and with seed crystal in melt, seed crystal breaks away from liquid level behind the several hrs, reduces to 970 ℃ again, following seed crystal, constant temperature several days begin slow cooling with the speed of 0.5～2 ℃/d when seed crystal is no longer grown up, and reduce to 900 ℃.Crystal is lifted from liquid level, reduce to room temperature with the speed of 15 ℃/h then, obtain 35 * 30 * 8mm
3GLSB monocrystalline (Fig. 3).
Embodiment 4:GLSB crystal double frequency is used.
Get GLSB monocrystalline blank, cut into 3 * 3 * 3 millimeters cubes, a cubes wherein limit is parallel to optical direction.Optical direction becomes about 35 ° of angles with crystalline crystallography C axle.Two faces perpendicular to optical direction are logical light face.To lead to the light mirror polish.Promptly make varactor doubler spare.With a branch of wavelength is that the laser of 1064 nanometers prolongs this GLSB frequency doubling device of optical direction incident, and promptly producing wavelength is the laser output of 532nm.
Claims (5)
1. borate compound boric acid gadolinium lanthanum scandium, it is characterized in that: chemical formula is Gd
xLa
1-xSc
3(BO
3)
4, the crystalline structure spacer is R32.
2. the single crystal of the described borate compound boric acid of claim 1 gadolinium lanthanum scandium, it is characterized in that: its chemical formula is Lu
0.22La
0.78Sc
3(BO
3)
4, spacer is R32, cell parameter is
γ=120 °, Z=3, unit-cell volume is
3. the preparation method of the boric acid gadolinium lanthanum scandium single crystal of a claim 2 is characterized in that: use molten-salt growth method, as fusing assistant, grow monocrystalline by the pyrosol top-seeded solution growth with borate.Concrete grammar is: pyrosol is prepared Gd in following mol ratio
0.4La
0.6Sc
3(BO
3)
4: Li
6B
4O
9=1: (1-3); The temperature range of crystal growth is 1000 → 850 ℃, 0.5～4 ℃/day of cooling rate, 5～40 rev/mins of crystal rotating speeds.
4. the purposes of the described boric acid gadolinium of claim 2 a lanthanum scandium single crystal, it is characterized in that: this crystal is used to prepare the nonlinear optical frequency conversion device.
5. the purposes of the boric acid gadolinium lanthanum scandium single crystal of a claim 4 is characterized in that: the nonlinear optical frequency conversion device is the harmonic generators of visible and ultraviolet region.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910111241A CN101831703A (en) | 2009-03-13 | 2009-03-13 | Borate compound gadolinium-lanthanum-scandium borate and mono-crystal, preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910111241A CN101831703A (en) | 2009-03-13 | 2009-03-13 | Borate compound gadolinium-lanthanum-scandium borate and mono-crystal, preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101831703A true CN101831703A (en) | 2010-09-15 |
Family
ID=42715913
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910111241A Pending CN101831703A (en) | 2009-03-13 | 2009-03-13 | Borate compound gadolinium-lanthanum-scandium borate and mono-crystal, preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101831703A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103882523A (en) * | 2014-04-01 | 2014-06-25 | 中国科学院福建物质结构研究所 | Chromium-doped aluminium borate scandium-lanthanum tunable laser crystal |
| CN105836755A (en) * | 2016-03-23 | 2016-08-10 | 厦门大学 | Gadolinium borate and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101295119A (en) * | 2007-04-26 | 2008-10-29 | 中国科学院福建物质结构研究所 | Novel nonlinear optical crystal boric acid aluminum gallium bismuth |
| CN101295118A (en) * | 2007-04-26 | 2008-10-29 | 中国科学院福建物质结构研究所 | Nonlinear optical crystal boric acid lutetium lanthanum scandium |
-
2009
- 2009-03-13 CN CN200910111241A patent/CN101831703A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101295119A (en) * | 2007-04-26 | 2008-10-29 | 中国科学院福建物质结构研究所 | Novel nonlinear optical crystal boric acid aluminum gallium bismuth |
| CN101295118A (en) * | 2007-04-26 | 2008-10-29 | 中国科学院福建物质结构研究所 | Nonlinear optical crystal boric acid lutetium lanthanum scandium |
Non-Patent Citations (1)
| Title |
|---|
| YUNKUI LI ET AL.: ""Phase transition,growth,and optical properties of NdxLa1-xSc3(BO3)4 crystals"", 《JOURNAL OF MATERIALS RESEARCH》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103882523A (en) * | 2014-04-01 | 2014-06-25 | 中国科学院福建物质结构研究所 | Chromium-doped aluminium borate scandium-lanthanum tunable laser crystal |
| CN105836755A (en) * | 2016-03-23 | 2016-08-10 | 厦门大学 | Gadolinium borate and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101545138B (en) | Non-linear optical crystal-sodium beryllate borate, growth method and application thereof | |
| WO2017121024A1 (en) | K3ba3li2al4b6o20f compound, nonlinear optical crystal thereof, and preparation method therefor and use thereof | |
| CN101295118A (en) | Nonlinear optical crystal boric acid lutetium lanthanum scandium | |
| WO2019174105A1 (en) | Calcium metaborate birefringent crystal, preparation method therefor and use thereof | |
| CN102021640B (en) | Aluminum-barium fluoborate (BaAlBo3F2) non-linear optical crystal, and growth method and application thereof | |
| CN102094245A (en) | Selenium-gallium-aluminum-barium compound, selenium-gallium-aluminum-barium nonlinear optical crystal and preparation methods and applications of compound and nonlinear optical crystal | |
| CN110029397A (en) | Compound lithium germanium oxide caesium and lithium germanium oxide caesium nonlinear optical crystal and preparation method and purposes | |
| CN103741217A (en) | Sodium yttrium borate, sodium yttrium borate nonlinear optical crystal as well as preparation method and application of sodium yttrium borate nonlinear optical crystal | |
| CN1110335A (en) | Non-linear optical crystal strontium boroberyllate | |
| CN102352533A (en) | Novel nonlinear optical crystal beryllium-sodium-cesium borate | |
| CN105502329B (en) | RbNaMgP2O7Compound, RbNaMgP2O7Nonlinear optical crystal and its preparation method and purposes | |
| CN102828245A (en) | NaCaBe2B2O6 nonlinear optical crystal, its growth method and application thereof | |
| CN101831703A (en) | Borate compound gadolinium-lanthanum-scandium borate and mono-crystal, preparation method and application thereof | |
| CN106868588A (en) | Rb3Ba3Li2Al4B6O20F compounds, nonlinear optical crystal and its preparation method and purposes | |
| CN101974783B (en) | Compound cesium lithium borate (CLBO) nonlinear optical crystal, preparation method and application thereof | |
| CN115504480B (en) | Compound zinc barium borate and zinc barium borate birefringent crystal, and preparation method and application thereof | |
| CN1321228C (en) | Boron aluminate, non-linear optic crystal of boron aluminate, growth method and usage | |
| CN105839185A (en) | Cs2LiPO4 compound and Cs2LiPO4 nonlinear optical crystal as well as preparation method and application thereof | |
| US10005675B2 (en) | Li4Sr(BO3)2 compound, Li4Sr(BO3)2 nonlinear optical crystal, preparation method and use thereof | |
| CN102260912A (en) | Novel nonlinear optical crystal low-temperature phase kalium beryllium borate | |
| CN102260911A (en) | Novel nonlinear optical crystal medium temperature-phase potassium beryllium borate | |
| CN111005069B (en) | Magneto-optical crystal CaxMyCe(1-x-y)X3Process for their preparation and their use | |
| CN100572615C (en) | A kind of alkali metal borate compounds and monocrystalline thereof and preparation method | |
| CN1122732C (en) | Non-linear optical crystal of magnesium zinc bromophosphate and its preparing process and application | |
| CN106868589A (en) | K3Sr3Li2Al4B6O20F compounds, nonlinear optical crystal and its preparation method and purposes |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20100915 |