CN1225951A - Low-temp.-phase barium metaborate large single crystal growing by air-cooled crystal growth method - Google Patents
Low-temp.-phase barium metaborate large single crystal growing by air-cooled crystal growth method Download PDFInfo
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Abstract
The air-cooled crystal method for growth of low-temp. phase beta-barium metaborate (beta-BBO) large monocrystal is mainly characterized by that when the molten-salt pulling method or molten-salt inoculating crystal method is used to grow BBO crystal, a compressed air is blown continuously through conduct to the upper surface of the growing crystal, so that the continuously cooling surface of the crystal surface can accelerate the dispersion of crystallization heat produced by crystallization at crystal growing interface and the impurity-discharging process to raise the BBO crystal growth speed by 3-5 times, up to 1.5-2.5 mm/day, and raise the crystal quality. The transmissivity of said crystal of UV 200-340 mm wave range is raised by 10%, and up to above 80%.
Description
The present invention relates to chemical field, relate in particular to field of crystal growth, particularly relate to a kind of air cooling Laue method of growing low temperature phase barium metaborate large single crystal.
(chemical molecular formula is β-BaB to low-temperature phase barium metaborate
2O
4, being called for short BBO) and crystal is a kind of important nonlinear optical material that has been widely used.Its greatest feature is to can be applicable to the uv-radiation that wavelength is as short as 200nm, is that present unique quadruple of the 1.06um laser of Nd: YAG that can realize arrives the frequency-doubling crystal of deep ultraviolet 0.265um.Except the important application on frequency multiplication, it is on OPO that BBO also has an important use.Above-mentioned two kinds of desired device sizes of application are all bigger, and the length of the former its optical direction is generally at 8～10mm, and the latter is then up to 15～20mm.Because the characteristic of bbo crystal laminate structure and some physical properties are as lower thermal conductivity, the viscosity of mother liquor of adding crystal growth is more high, this speed for growing crystal from the fusing assistant system becomes quite slow, and desire obtains large size, high-quality crystal is quite difficult.Therefore, how to improve the crystalline speed of growth and quality, shortening growth cycle is the major issue of pendulum in face of us to reduce production costs.The main method of growth BBO macrocrystal has three kinds at present.First kind is fused salt top-seeded solution growth (kyropoulos) [main reference document: " fused salt seed crystal method growing low temperature phase barium metaborate (BaB such as (1) Jiang Aidong
2O
4) monocrystalline ", " artificial lens " 15 volumes the 2nd phase 103-108 page or leaf, 1986.(2) W.R.Bosenberg etal., " Growthof large; high-quality beta-barium metaborate crystals. " J. crystal Growth 108 (1991) 394-398. (3) Yuriy.s.etal, " Growth of high-quality baritm metaborate crystals from Na
2O-NaFsolution. " J.Crystal Growth 131 (1993) 199-203.]: second kind is fused salt pulling method [main reference document: " fused salt pulling method for growing β-BaB such as (1) Tang Dingyuan
2O
4Crystal "; " artificial lens journal " 19 volumes the 1st phase 21-27 page or leaf; nineteen ninety. (2) R.S.Feigelson, " Solution growth of Barium metaborate crystal by top seeding. " J.crystalGrowth 97 (1989) 352-366.]: the third is pure melt czochralski method [main reference document: (1) K.Itoh etal. " β-Barium borate single crystal growth by a direct czochralski method " J. crystal Growth106 (1990) 728-731. (2) H.Kouta etal. " β 3-BaB2O4 single crystal growth by czochralski method II " J.crystal Growth 114 (1991) 676-682]. Above-mentioned first method is the topmost method of the practical macrocrystal of growth at present, and the problem that this method mainly exists is that crystalline growth velocity is slow, the cycle is long, and often occurs defective such as inclusion in the crystal, and yield rate is lower.The speed of growth and the crystal mass of second method all increase than first method, but the growth operation difficulty is bigger, and are difficult to continue perfectly to grow after crystal lifts certain thickness again.Compare with molten-salt growth method, the speed of growth of the third method increases substantially, and crystal mass is improved greatly owing to the growth system does not contain other impurity, but want its difficulty of crystal of growth of large size high quality bigger with this method, therefore the crystal not commercialization as yet of growth in this way so far.
The object of the present invention is to provide a kind of novel method of air cooling crystal growth BBO monocrystalline,, shorten growth cycle, reduce the growth cost, promote applying of bbo crystal to improve the speed of growth and the quality of bbo crystal.
Realize that technical scheme of the present invention is:, adopt NaF or Na with fused salt top-seeded solution growth or fused salt pulling method for growing BBO crystal
2O is as fusing assistant; The proportioning of growth raw material is: 67wt%BaB
2O
4: 33wt%NaF or 91.5wt%BaB
2O
4: 8.5wt%Na
2O, the temperature of saturation of the solution of above-mentioned two kinds of proportionings (growth temperature) is respectively 925 ℃ and 900 ℃: the direction of growth of seed crystal is the C direction of principal axis; The crystalline rotating speed is 5 rev/mins; Pulling rate changes from 0.5mm/ days to 3mm/ days at different growth phases.Reduce the temperature of solution gradually so that crystal is constantly grown, its rate of temperature fall is in the variation from 0.5 ℃/day to 3 ℃/day of different growth phases.After certain diameter (about 20mm) is arrived in crystal growth, with temperature be room temperature blow to the upper surface (seeing figure) of the bbo crystal of growing through purifying continuously by the platinum conduit of internal diameter 3mm with exsiccant pressurized gas (as air, nitrogen etc.), airshed at different growth phases from 3 liters/hour to 5 liters/hour change.Because plane of crystal constantly cooled off, the heat of crystallization that produces when making the crystallization of growth interface place distribute quickening, thereby improved the crystalline speed of growth.Also help simultaneously the impurities removal process at crystal growth interface place, improved the crystalline quality.
The present invention has been owing to adopted air cooling crystalline new technology, and the speed of growth that makes bbo crystal has improved 3～5 times than the speed of currently used molten-salt growth, reaches about 2mm/ days.And its crystal mass is significantly improved, and (200～340nm) transmitance has improved about 10% the crystalline ultraviolet band, reaches more than 80%.The size of growing crystal has reached Φ 65 * 20mm
3This method also is applicable to the crystal that other are grown with fused salt top-seeded solution growth or fused salt pulling method.
Accompanying drawing is the device synoptic diagram of air cooling Laue method growing low temperature phase barium metaborate large single crystal: 1 seed rod, 2 viewing windows, 3 platinum conduits, 4 seed crystals, the crystal of 5 growths, 6 platinum crucibles, 7 growth liquations, 8 interior boiler tubes, 9 heating units
Embodiment one, bbo crystal growth: 1. fusing assistant type: NaF; 2. proportioning raw materials: 67wt%BaB
2O
4: 33wt%NaF; 3. seeded growth direction: C axle; 4. growth temperature range: 925 → 880 ℃; 5. rate of temperature fall: different growth phases are variation from 0.5 ℃/day to 3 ℃/day; 6. crystal rotating speed: 5 rev/mins; 7. crystal pulling rate: different growth phases changed from 0.5mm/ days to 3mm/ days; 8. gaseous species: N
29. gas flow: different growth phases are from 3 liters/hour to 5 liters/hour change.Crystal growth result:, obtained Φ 65 * 20mm through growth in 15 days
3There are not cracking, high-quality bbo crystal.
Embodiment two: bbo crystal 1. fusing assistant type: the Na that grow
2O; 2. proportioning raw materials: 91.5wt%BaB
2O
4: 8.5wt%Na
2O; 3. seeded growth direction: C axle; 4. growth temperature range: 900 → 850 ℃; 5.6.7. with embodiment one; 8. gaseous species: air;
9. gas flow: different growth phases are from 3 liters/hour to 5 liters/hour change.Crystal growth result:, obtained Φ 65 * 18mm through growth in 18 days
3There are not cracking, high-quality bbo crystal.
Embodiment three: 1.2.3.4.5.6. is with embodiment one in the bbo crystal growth; 7. crystal pulling rate: O; 8. gaseous species: air; 9. gas flow: different growth phases can be from 3 liters/hour to 5 liters/hour change.The crystal growth result; Through growth in 15 days, obtained Φ 65 * 18mm
3There are not cracking, high-quality bbo crystal.
Claims (5)
1. air cooling Laue method growing low temperature phase barium metaborate large single crystal, be that the crystal with fused salt top-seeded solution growth or fused salt pulling method for growing is blown with through the method for purification with the exsiccant pressurized gas, it is characterized in that: adopt pressurized gas to blow to the upper surface of the bbo crystal of growing continuously by the corrosion resistant conduit of heatproof.
2. the air cooling Laue method of growing low temperature phase barium metaborate large single crystal as claimed in claim 1 is characterized in that: said pressurized gas can be an air.
3. the air cooling Laue method of growing low temperature phase barium metaborate large single crystal as claimed in claim 1 is characterized in that: said pressurized gas also can be a nitrogen.
4. the air cooling Laue method of growing low temperature phase barium metaborate large single crystal as claimed in claim 1 is characterized in that: said conduit is made with platinum.
5. the purposes of the air cooling Laue method of the growing low temperature phase barium metaborate large single crystal of a claim 1, it is characterized in that: this method also is applicable to the crystal that other are grown with fused salt top-seeded solution growth or fused salt pulling method.
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| CN 98104745 CN1078632C (en) | 1998-02-11 | 1998-02-11 | Low-temp.-phase barium metaborate large single crystal growing by air-cooled crystal growth method |
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| CN1225951A true CN1225951A (en) | 1999-08-18 |
| CN1078632C CN1078632C (en) | 2002-01-30 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1304648C (en) * | 2005-03-22 | 2007-03-14 | 山东大学 | Bismuth sodium potassium titanate series nonlead ferroelectric piezoelectric monocrystal and its growing method and equipment |
| CN102124150A (en) * | 2008-08-18 | 2011-07-13 | 长青太阳能股份有限公司 | Controlling transport of gas borne contaminants across a ribbon surface |
| CN103103604A (en) * | 2013-01-24 | 2013-05-15 | 天通控股股份有限公司 | Manufacturing method of large-size C-oriented sapphire crystals |
| CN103225107A (en) * | 2013-04-03 | 2013-07-31 | 福建福晶科技股份有限公司 | Method for rapid growth of high-quality BBO crystal |
| CN105002556A (en) * | 2014-04-21 | 2015-10-28 | 洛阳金诺机械工程有限公司 | Device for raising crystallization velocity of silicon core during drawing of silicone core |
| CN112779601A (en) * | 2020-12-23 | 2021-05-11 | 有研半导体材料有限公司 | Growth method of heavily arsenic-doped extremely-low-resistance silicon single crystal |
-
1998
- 1998-02-11 CN CN 98104745 patent/CN1078632C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1304648C (en) * | 2005-03-22 | 2007-03-14 | 山东大学 | Bismuth sodium potassium titanate series nonlead ferroelectric piezoelectric monocrystal and its growing method and equipment |
| CN102124150A (en) * | 2008-08-18 | 2011-07-13 | 长青太阳能股份有限公司 | Controlling transport of gas borne contaminants across a ribbon surface |
| CN102124150B (en) * | 2008-08-18 | 2013-07-31 | 长青太阳能股份有限公司 | Controlling transport of gas borne contaminants across a ribbon surface |
| CN103103604A (en) * | 2013-01-24 | 2013-05-15 | 天通控股股份有限公司 | Manufacturing method of large-size C-oriented sapphire crystals |
| CN103103604B (en) * | 2013-01-24 | 2016-04-20 | 天通控股股份有限公司 | Large size C is to sapphire crystal manufacture method |
| CN103225107A (en) * | 2013-04-03 | 2013-07-31 | 福建福晶科技股份有限公司 | Method for rapid growth of high-quality BBO crystal |
| CN105002556A (en) * | 2014-04-21 | 2015-10-28 | 洛阳金诺机械工程有限公司 | Device for raising crystallization velocity of silicon core during drawing of silicone core |
| CN112779601A (en) * | 2020-12-23 | 2021-05-11 | 有研半导体材料有限公司 | Growth method of heavily arsenic-doped extremely-low-resistance silicon single crystal |
| CN112779601B (en) * | 2020-12-23 | 2022-08-05 | 有研半导体硅材料股份公司 | Growth method of heavily arsenic-doped extremely-low-resistance silicon single crystal |
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|---|---|
| CN1078632C (en) | 2002-01-30 |
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