CN1320723A - Technique for growing Nd-doped gadolinium calcium borate crystal by crucible lowering-down method - Google Patents

Technique for growing Nd-doped gadolinium calcium borate crystal by crucible lowering-down method Download PDF

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CN1320723A
CN1320723A CN 01105414 CN01105414A CN1320723A CN 1320723 A CN1320723 A CN 1320723A CN 01105414 CN01105414 CN 01105414 CN 01105414 A CN01105414 A CN 01105414A CN 1320723 A CN1320723 A CN 1320723A
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crucible
crystal
bridgman
growing
calcium borate
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CN1123650C (en
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钟真武
范世
徐家跃
罗军
孙仁英
钱国兴
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Shanghai Institute of Ceramics of CAS
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Shanghai Institute of Ceramics of CAS
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Abstract

A technique for growing Nd-doped gadolinium calcium borate by crucible lowering-down method includes uniformly mixing initial raw materials in proportion as NdxGd1-xCa1O(BO3)3 (where X=4-10 mole%), pre-calcining at 950-1100 deg.C, mixing again, loading in Pt crucible with 0.1-0.3 mm of wall thickness, melting raw material and top of seed crystal at 1480-1600 deg.C and lowering down the crucible at less than or equal to 3 mm/hr. Its advantages are stable temp field, and simultaneous growth of different monocrystals with more crucibles.

Description

The Bridgman-Stockbarge method for growing technology of Nd-doped gadolinium calcium borate crystal
The present invention relates to a kind of Bridgman-Stockbarge method for growing technology of Nd-doped gadolinium calcium borate crystal, promptly use the Bridgman-Stockbarge method for growing Nd-doped gadolinium calcium borate crystal.Belong to the single crystal growing field.
The compound of function is an important trend of functional materials development.Along with the development of photoelectron technology, people wish some can be produced the active ions such as the Nd of laser transition 3+, Yb 3+Deng mixing in the non-linear optic crystal, thereby the function that realizes laser and nonlinear optics is compound, forms laser self-frequency-doubling's multifunctional crystal, i.e. the self-frequency-doubling crystal.It can utilize the non-linear effect of matrix that the fundamental frequency light that the active ions stimulated radiation produces is carried out frequency inverted, obtains frequency doubled light.Compare with the laser apparatus that uses laser crystals and frequency-doubling crystal simultaneously, the characteristics of self-frequency-doubling laser are that volume is little, and simple in structure, light path is adjusted easily.Therefore, the self-frequency-doubling crystal is the class functional composite material with bright application prospect.
Nd-doped gadolinium calcium borate [Nd xGd 1-xCa 4O (BO 3) 3Nd 3+: GdCa 4O (BO 3) 3Nd:GdCOB] monocrystalline is rare earth activation ion Nd 3+Part replaces the Gd among the frequency-doubling crystal GdCOB 3+(x=4-10%) new pattern laser of Xing Chenging has excellent comprehensive performances from the frequency multiplication matrix material.Its physical and chemical stability is good, deliquescence not, and from the frequency-doubling conversion efficiency height, threshold value is low.Ti sapphire laser pumping with the 1560mW power input has obtained 14.4% efficiency of conversion.Compare with current widely used self-frequency-doubling crystal NYAB (non-congruent melting), the Nd:GdCOB crystal is excellent property not only, and because its congruent melting, can be from melt direct growth, large size, high-quality monocrystalline have more easily been obtained, so it is since 1996 come out, just cause people's extensive concern, become a new focus of exploring from double-frequency material.
Regrettably, crystal pulling method (Czochralski) is all adopted in the growth of Nd:GdCOB monocrystalline up to now both at home and abroad.The essential characteristic of this growth method is in the crystal pulling method single crystal growing furnace, by high frequency or resistive heating, be melted in the Nd:GdCOB raw material in the platinum crucible, again through sowing, operations such as necking down, rotary pulling, grow the Nd:GdCOB monocrystalline of certain orientation and certain size.
During with Czochralski grown Nd:GdCOB monocrystalline, there is following problem: because thermograde is bigger near the solid-liquid interface, add the anisotropy of the thermal expansion of crystal own, be easy to generate cracking, thereby the seed crystal direction need be limited (generally using the b direction of principal axis).In addition, crucible is opened wide in the crystal pulling method, and boron oxide volatilizees easily, and bath component departs from seriously, causes crystal yield low and be prone to parcel.And this method unit per unit area yield, efficient is lower, is difficult to realize the suitability for industrialized production of Nd:GdCOB monocrystalline.
The purpose of this invention is to provide a kind of reliable and stable Nd-doped gadolinium calcium borate Nd xGd 1-xCa 4O (BO 3) 3Crystal Bridgman-Stockbarge method for growing technology is to realize this novel self-frequency-doubling crystal's suitability for industrialized production.
The objective of the invention is to realize by following technological approaches.At first with high-purity (99.9%, as follows) after initial calcic, boron, gadolinium and the pre-treatment of niobium chemical feedstocks, inserting the bottom lays in the crucible of certain orientation crystal seed, crucible is placed the Bridgman single crystal growing furnace, melt raw material and crystal seed top, under certain furnace temperature, the growth interface thermograde maintains in the proper range, the control dropping speed of the crucible can grow complete transparent high quality Nd:GdCOB single crystal.
Detailed content of the present invention is as follows:
1. the pre-treatment of raw material: ingredient requirement is not particularly limited, as long as the purity of crystal growth, can obtain the proportion raw material that requires can both use.As carbonate, oxalate, nitrate, oxide compound, oxyhydroxide and organic acid salt, as acetate, what preferentially recommend is oxide compound and carbonate.For example with CaCO 3(or CaO), Gd 2O 3, H 3BO 3(or B 2O 3) and Nd 2O 3Press Nd xGd 1-xCa 4O (BO 3) 3The molecular formula mixing, wherein neodymium volume (mole) is between 4-10%.Pre-burning is no less than 12 hours under 950～1100 ℃ of furnace temperature, mixes once more.
2. above-mentioned powder that mixes and crystal seed are put into the crucible that thickness is 0.1～0.3mm, crucible is airtight through gas welding sealing, component volatilization when preventing powder fusion at high temperature.Crucible material is not had strict restriction, and only otherwise at high temperature do not react with the crystal of growth, as the crucible of precious metal material systems such as platinum crucible, iridium crucible, even alloy material that can heatproof makes, but preferentially recommends platinum crucible.
3. seed orientation is＜010 〉,＜201 〉,＜100〉and,＜001 〉, or along any direction.Can not add crystal seed, but variant on the crystal mass that grows.
4. crucible melt raw material and crystal seed top in the Bridgman single crystal growing furnace, in furnace temperature is 1480～1600 ℃ of scopes, growth interface temperature ladder maintains 30-40 ℃/cm, with≤3 millimeters/hour speed decline crucible, can obtain the complete Nd:GdCOB monocrystalline identical with the platinum crucible shape.
5. look and grow crystalline shape and size difference, can in the Bridgman single crystal growing furnace, lay one or more at least crucibles, grow the simultaneously Nd:GdCOB monocrystalline of different shapes, different size, that is crucible shape, controllable number, can be selected by shape, the size of growing crystal, as cylindrical, rectangular cylindricality, other Polygons etc.
The present invention compares with crystal pulling method, and its advantage is: the temperature field is stable, and component is not volatile, and the Nd:GdCOB perfection of crystal of growth is good, no macroscopic view and microdefect; The yield rate height; Crystalline size and profile are controlled easily, and little thermograde makes crystal not easy to crack.In addition, this method processing unit is simple, easy to operate, and energy consumption obviously reduces, and helps realizing suitability for industrialized production (seeing Table 1).
The comparison of table 1 the present invention and Czochralski grown Nd:GdCOB monocrystalline
Method Processing condition Crystal mass Production level
Crystal pulling method The growth parameter(s) complexity, crystalline form is single, apparatus expensive Easily produce cracking, melt composition easily departs from, and is prone to striation The unit per unit area yield, efficient is low, energy consumption height, not industrialization
The present invention The temperature field is stable, and crystalline form is variable, and equipment is simple, and is easy to operate No macroscopic view and microdefect; Integrity is good, and is not easy to crack The unit fecund, the yield rate height, energy consumption and cost are low, can realize industrialized mass production
Substantive distinguishing features that the present invention gives prominence to and obvious improvement are fully showed by following embodiment, but are limited the present invention by no means.
Embodiment 1: with high pure raw material (99.9%) CaCO 3, Gd 2O 3, H 3BO 3, Nd 2O 3Press the molar fraction of x=4%, be mixed with Nd 0.04Gd 0.96Ca 4O (BO 3) 3, uniform mixing, 950 ℃ of following pre-burnings 20 hours, mixing once more, inserting wall thickness is in the cylindrical platinum crucible of 0.1mm, adopts＜010〉bearing circle cylindricality crystal seed.Crucible is airtight.In the Bridgman single crystal growing furnace, in 1480 ℃ of following melt raw materials and crystal seed top, growth interface temperature ladder maintains about 30 ℃/cm, with 1 millimeter/hour decline crucible, and the cylindrical transparent Nd:GdCOB perfect crystal of growing.
Embodiment 2: get x=0.07, the oxalate preparation of raw material is become Nd 0.07Gd 0.93Ca 4O (BO 3) 3Behind the uniform mixing 1050 ℃ of following pre-burnings 16 hours, mixing once more, together with＜201〉to put into wall thickness be 0.2 millimeter rectangular cylindricality platinum crucible for the rectangular cylindricality crystal seed of direction, at 1550 ℃ of following melt raw materials and crystal seed top, the growth interface temperature is terraced at 35 ℃/cm, with 2 millimeters/hour speed decline crucible, and the rectangular cylindricality Nd:GdCOB perfect crystal of growing.All the other are with embodiment 1.
Embodiment 3: press Nd 0.10Gd 0.90Ca 4O (BO 3) 3Chemical formula is with raw materials of Ca O, Gd 2O 3, H 3BO 3, Nd 2O 3Behind the mixing 1100 ℃ of following pre-burnings 12 hours, together with＜001〉the hexagon crystal seed of direction puts into the platinum crucible of 0.3 millimeter of wall thickness, at 1600 ℃ of following melt raw materials and welding crystal seed, growth interface temperature ladder is 40 ℃/cm, with 3 millimeters/hour speed decline crucible, growth of Nd: GdCOB perfect crystal.All the other are with embodiment 1.
Embodiment 4: press example 1,2,3 described processing condition, with＜010 〉,＜201 〉,＜100 〉,＜001〉etc. different orientation, difform crystal seed are put into 10 difform platinum crucibles, the 10 difform Nd:GdCOB crystal of can growing simultaneously.

Claims (9)

1. the Bridgman-Stockbarge method for growing technology of the Nd-doped gadolinium calcium borate monocrystalline of growing, comprising: powder pre-burning, mixing is characterized in that:
(1) initial feed carbonate, oxalate, nitrate, organic acid salt, oxide compound, oxyhydroxide are pressed Nd xGd 1-xCa 4O (BO 3) 3The chemical formula batch mixes; X=4-10% mole wherein;
(2) mixed powder pre-burning under 950～1100 ℃ of furnace temperature is no less than 12 hours, mixes once more;
(3) put into the crucible of precious metal material or alloy material making with mixing powder and crystal seed after the pre-burning; Crucible makes it airtight through the gas welding sealing;
(4) crucible fused raw material and crystal seed top in the Bridgman single crystal growing furnace, temperature is 1480～1600 ℃, and the growth interface thermograde is 30-40 ℃/cm, and dropping speed of the crucible is less than≤3 millimeters/hour.
2. by the Bridgman-Stockbarge method for growing technology of the described Nd-doped gadolinium calcium borate monocrystalline of claim 1, it is characterized in that described seed orientation is＜010 〉,＜201 〉,＜100〉and,＜001 〉, or along any direction;
3. by the Bridgman-Stockbarge method for growing technology of the described Nd-doped gadolinium calcium borate monocrystalline of claim 1, it is characterized in that in single crystal growing furnace, to lay one or more crucibles the neodymium-doped GdCOB crystal of the different shapes of growing simultaneously and size.
4. by the Bridgman-Stockbarge method for growing technology of the described Nd-doped gadolinium calcium borate monocrystalline of claim 3, it is characterized in that describedly being shaped as cylindrical or being rectangular cylindricality, or be other Polygonss.
5. by the Bridgman-Stockbarge method for growing technology of the described Nd-doped gadolinium calcium borate monocrystalline of claim 1, it is characterized in that preferentially recommending initial feed is oxide compound or carbonate; What crucible material was preferentially recommended is platinum crucible.
6. by the Bridgman-Stockbarge method for growing technology of the described Nd-doped gadolinium calcium borate monocrystalline of claim 1, it is characterized in that also can not add crystal seed grows.
7. by the Bridgman-Stockbarge method for growing technology of the described Nd-doped gadolinium calcium borate monocrystalline of claim 1, it is characterized in that:
(1) raw material is pressed Nd 0.04Gd 0.96Ca 4O (BO 3) 3Chemical formula proportioning, batch mixes evenly back mix once more in 950 ℃ of pre-burnings 20 hours;
(2) mixed powder and＜010〉bearing circle cylindricality crystal seed, put into the cylindrical platinum crucible of wall thickness 0.1mm, airtight;
(3) in 1480 ℃ with fused raw material and crystal seed top, growth interface temperature ladder is 30 ℃/cm, the speed decline crucible with 1 millimeter/hour grows cylindrical crystal.
8. by the Bridgman-Stockbarge method for growing technology of the described Nd-doped gadolinium calcium borate monocrystalline of claim 1, it is characterized in that:
(1) raw material is pressed Nd 0.07Gd 0.93Ca 4O (BO 3) 3Chemical formula proportioning, batch mixes evenly back mix once more in 1050 ℃ of pre-burnings 16 hours;
(2) mixed powder and＜201〉the rectangular cylindricality crystal seed of direction, put into the rectangular cylindricality platinum crucible of wall thickness 0.2mm, make it airtight through gas welding;
(3) in 1550 ℃ with fused raw material and crystal seed top, growth interface temperature ladder is 35 ℃/cm, with 2 millimeters/speed at one hour rating decline crucible, grows rectangular pillar-shaped crystal.
9. by the Bridgman-Stockbarge method for growing technology of the described Nd-doped gadolinium calcium borate monocrystalline of claim 1, it is characterized in that:
(1) raw material is pressed Nd 0.10Gd 0.90Ca 4O (BO 3) 3Chemical formula proportioning, batch mixes evenly back mix once more in 1100 ℃ of pre-burnings 12 hours;
(2) mixed powder and＜001〉direction hexagon crystal seed, put into the platinum crucible that wall thickness is 0.3mm;
(3) in 1600 ℃ of fusions, 40 ℃/cm of growth interface temperature ladder is with 3 millimeters/hour speed decline crucible.
CN 01105414 2001-02-23 2001-02-23 Technique for growing Nd-doped gadolinium calcium borate crystal by crucible lowering-down method Expired - Fee Related CN1123650C (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1332070C (en) * 2004-12-24 2007-08-15 中国科学院金属研究所 Structure of initiating terminal in directional solidification in method of seed crystal, and application
CN102074887A (en) * 2010-01-13 2011-05-25 山东大学 Self frequency conversion solid state laser based on neodymium doped gadolinium calcium oxborate crystal
CN102660772A (en) * 2012-04-25 2012-09-12 中国科学院福建物质结构研究所 Nonlinear optics crystal boric acid of oxygen, cadmium and lutetium
US9257869B2 (en) 2010-04-08 2016-02-09 Robert Bosch Gmbh Method and device for charging a battery
CN108360062A (en) * 2018-02-02 2018-08-03 北京中材人工晶体研究院有限公司 A kind of method that multistep is synthetically prepared rear-earth-doped gadolinium gallium aluminium crystal raw material repeatedly
CN114875487A (en) * 2022-04-26 2022-08-09 宁波大学 Preparation method of calcium oxide holmium borate crystal

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1322174C (en) * 2004-04-02 2007-06-20 中国科学院上海硅酸盐研究所 Technique for developing crystal of bismuth boric acid through falling curcible method

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1332070C (en) * 2004-12-24 2007-08-15 中国科学院金属研究所 Structure of initiating terminal in directional solidification in method of seed crystal, and application
CN102074887A (en) * 2010-01-13 2011-05-25 山东大学 Self frequency conversion solid state laser based on neodymium doped gadolinium calcium oxborate crystal
US9257869B2 (en) 2010-04-08 2016-02-09 Robert Bosch Gmbh Method and device for charging a battery
CN102660772A (en) * 2012-04-25 2012-09-12 中国科学院福建物质结构研究所 Nonlinear optics crystal boric acid of oxygen, cadmium and lutetium
CN108360062A (en) * 2018-02-02 2018-08-03 北京中材人工晶体研究院有限公司 A kind of method that multistep is synthetically prepared rear-earth-doped gadolinium gallium aluminium crystal raw material repeatedly
CN108360062B (en) * 2018-02-02 2021-11-12 中材人工晶体研究院有限公司 Method for preparing rare earth doped gadolinium gallium aluminum single crystal raw material by multi-step repeated synthesis
CN114875487A (en) * 2022-04-26 2022-08-09 宁波大学 Preparation method of calcium oxide holmium borate crystal

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