CN103160910A - Method for growing Ba8Ga16Ge30 thermoelectric monocrystal - Google Patents

Method for growing Ba8Ga16Ge30 thermoelectric monocrystal Download PDF

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CN103160910A
CN103160910A CN201110415867XA CN201110415867A CN103160910A CN 103160910 A CN103160910 A CN 103160910A CN 201110415867X A CN201110415867X A CN 201110415867XA CN 201110415867 A CN201110415867 A CN 201110415867A CN 103160910 A CN103160910 A CN 103160910A
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thermoelectric
crucible
monocrystal
growth method
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CN103160910B (en
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周燕飞
陈立东
吴汀
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Jiangsu Institute Of Advanced Inorganic Materials
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Shanghai Institute of Ceramics of CAS
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Abstract

The invention relates to a method for growing a Ba8Ga16Ge30 thermoelectric monocrystal. The method comprises the steps of: 1) preparing Ba, Ga and Ge elementary substances according to a molar ratio of 8.24-8.4:16:30, placing in a graphite crucible, packaging and vacuuming in a vacuum furnace, keeping warm at 1100-1200 DEG C for 9-12 h, slowly cooling to room temperature to give pure Ba8Ga16Ge30 polycrystalline, grinding the pure Ba8Ga16Ge30 polycrystalline to a fine powder, placing in a graphite crucible, sealing, placing in a crucible Bridgman furnace, pumping vacuum, slowly warming to 1100-1200 DEG C, keeping for 2-3 h to allow fully melting, and adjusting the position of the graphite crucible by a crucible descend rate of 0.1-6.0 mm/h so that the temperature gradient of solid-liquid interface of the crystal growth is controlled at 20-60 DEG C/cm for monocrystal growth. By using the Bridgman method, the crystal of multiple sizes and shapes can be obtained according to shape and size of the crucible.

Description

Ba 8Ga 16Ge 30The growth method of thermoelectric monocrystal
Technical field
The present invention relates to thermoelectric material field and field of crystal growth, be specifically related to a kind of I type cage shape germanium based thermoelectric compounds, Ba 8Ga 16Ge 30The growth method of thermoelectric monocrystal especially adopts the method for monocrystal growth of falling crucible method.
Background technology
Thermoelectric generation technology is to utilize the Sai Beike of semiconductor material (Seebeck) effect and Pa Er note (Peltier) effect directly to carry out the technology that heat energy and electric energy are changed mutually, comprises thermoelectric power generation and thermoelectric refrigeration.Thermoelectric material is a kind ofly heat energy and electric energy can be carried out directly the material of conversion mutually, thermo-electric device prepared therefrom has that volume is little, reliability is high, pollution-free, noiselessness, the Applicable temperature scope is wide and the characteristics such as long service life, has broad application prospects in thermoelectric power generation and thermoelectric refrigeration field.In recent years, due to day by day serious energy shortage and problem of environmental pollution, the research of thermoelectric material more and more comes into one's own.
The performance of thermoelectric material represents with zero dimension thermoelectricity capability figure of merit ZT usually, ZT=α 2σ T/ κ, wherein α is the Seebeck coefficient, and σ is specific conductivity, and κ is thermal conductivity, and T is absolute temperature.The ZT value of material is larger, and thermoelectric conversion efficiency is higher.The emphasis of thermoelectric material research both at home and abroad is how to realize increasing substantially of conversion efficiency of thermoelectric at present.And can find out from the expression formula of ZT, obtain higher conversion efficiency of thermoelectric, material must have larger Seebeck coefficient, higher specific conductivity and lower thermal conductivity.
I type germanium base cage compound, for example M 8Ga 16Ge 30, M is basic metal or alkaline-earth metal, has extremely low thermal conductivity, and is considered to have higher conversion efficiency of thermoelectric.Ba wherein 8Ga 16Ge 30Thermoelectric material is a more typical class in I type germanium base cage compound, and the thermoelectricity transport property that it has phonon glass-electron crystal (PGEC) is a kind of thermoelectric material that has potential application foreground in middle high-temperature temperature section.This compound belongs to isometric system, and spacer is Pm
Figure 201110415867X100002DEST_PATH_IMAGE001
N, comprise in structure by 24 framework atomic buildings by two regular hexagons, 12 tetrakaidecahedrons (Ge, Ga) that regular pentagon forms 24, and being formed by 12 pentagons by 20 framework atomic buildings.Comprise six tetrakaidecahedrons and two dodecahedrons by Ga and Ge atomic building in the unit cellular, between polyhedron by coplanar connection, alkaline-earth metal or alkali metal atom can be filled in inside, these atoms in polyhedron " cage " as new lattice scattering center, phonon is produced strong scattering, be expected the decrease lattice thermal conductivity.On the other hand, the sp by B III in skeleton construction～B IV atom 3Hydridization makes it have electrical property preferably, thereby is expected to obtain higher ZT value.
Present stage, the ZT value of I type germanium base cage compound thermoelectric material is about 1 left and right, belongs to the higher class material of middle high temperature section ZT value.Yet the I type germanium base cage compound thermoelectric material of preparation mostly is greatly polycrystalline material at present, and due to the fluctuation of component, the material for preparing under different situations has different performances, and the ZT value of the material of preparation actual measurement is often well below theoretical value.
At present, usually adopt scorification to prepare Ba 8Ga 16Ge 30Thermoelectricity polycrystalline material, the problem of its existence are in the raw material for preparing, unnecessary Ge impurity often to be arranged.Adopt zone melting method (J. Daniel Bryan, Nick P. Blake, Horia Metiu and Galen D. Stucky, " Nonstoichiometry and chemical purity effects in thermoelectric Ba such as people such as Bryan 8Ga 16Ge 30Clathrate ", J. Appl.Phys., 92,8281, (2002)) preparation the clathrate crystal in contain impurity Ge or Ga.
About Ba 8Ga 16Ge 30The preparation of thermoelectric monocrystal openly mainly contains flux method and crystal pulling method at present.Yet flux method is often easily brought impurity into, and the standby crystal of this legal system often mostly is diameter and is about 1～4 irregular Ba of mm 8Ga 16Ge 30Small-crystalline carries out thermoelectricity capability test sign and exists some difficulties.CN100445431C discloses a kind of Ga of employing and prepares the Ba of 5～8 mm as fusing assistant 8Ga 16Ge 30Monocrystalline, its size is still smaller, and due to Ga as fusing assistant, the consumption of Ga is 4～7 times of its stoichiometric ratio, not only consumption is many, causes cost to increase, and the crystal that easily makes preparation is with impurity Ga.
The people such as Saramat (A. Saramat, G. Svensson, and A. E. C. Palmqvist, Et al., " Large thermoelectric figure of merit at high temperature in Czochralski grown clathrate Ba 8Ga 16Ge 30" J. Appl.Phys., 99,023708,2006)) to have prepared length with crystal pulling method be that 46mm, diameter are the large-size crystals of 13mm, its ZT value is 1.35 when 900K.Again, the applicant before application CN101519800A disclose a kind of with the melt crystal pulling method Ba that grows 8Ga 16Ge 30The method of monocrystalline, the crystal mass of this method preparation is good, and technological process is also easily controlled, however its raw material that needs is still many.That is to say with crystal pulling method and prepare Ba 8Ga 16Ge 30Crystal, the raw material ratio that needs is more, and that high-purity Ba, Ga and Ge cost of material are relatively faced upward is expensive, therefore needs the new Ba of exploitation 8Ga 16Ge 30Method for monocrystal growth.
Falling crucible method, claim that again bridgeman crystal growth method (Bridgman-Stockbarge method) is a kind of growing method: by heating region the time, material in crucible is melted, when the crucible continuous decrease, the temperature of crucible bottom first drops to below the fusing point of material, and the beginning crystallization, crystal descends with crucible and continues to grow up.CN1213176C discloses a kind of Bridgman-Stockbarger method of germanic acid gallium strontium piezoquartz, yet, yet there are no the report falling crucible method for the preparation of I type germanium base cage compound thermoelectric monocrystal.
Summary of the invention
In the face of the problems referred to above that prior art exists, the inventor recognizes the growth that falling crucible method can be applied to I type germanium base cage compound thermoelectric monocrystal.At this, the invention provides a kind of Ba 8Ga 16Ge 30The growth method of thermoelectric monocrystal, comprise: steps A: the mol ratio by 8.24～8.4:16:30 is prepared Ba, Ga and Ge simple substance, is placed in plumbago crucible and vacuumizes to be packaged in vacuum oven, is incubated 9～12 hours under 1100～1200 ℃, then slowly cool to room temperature, get pure phase Ba 8Ga 16Ge 30Polycrystal; And step B: with gained pure phase Ba 8Ga 16Ge 30The polycrystal grind into powder, be placed in plumbago crucible, sealed graphite crucible, put into crucible decline stove, vacuumize, slowly be warming up to 1100～1200 ℃ of insulations and made the whole meltings of described powder in 2～3 hours, adjust the position of described plumbago crucible with the crucible fall off rate of 0.1～6.0 mm/ hour and carry out single crystal growing so that the thermograde of the solid-liquid interface of crystal growth is controlled in the scope of 20～60 ℃/cm.
The invention provides a kind of Ba of novelty 8Ga 16Ge 30The growth method of thermoelectric monocrystal, adopt falling crucible method, can obtain according to the shape and size of crucible the crystal of sizes and shape, can obtain easily the monocrystalline of desired size and regular shape thus, the monocrystalline purity that makes is high, quality is high, and the speed of growth is adjustable, technique is simple and easy to control, growth rate is high, the raw material of consumption is few, and cost is low.
Method of the present invention also can comprise step C: treat that crystal grows to desired size, slowly cool to and be incubated 9～12 hours under 700～800 ℃ and carry out anneal, then be cooled to room temperature.In step C: rate of temperature fall that can 20～60 ℃/hour slowly cools to 700～800 ℃.
In the present invention, the suitable vacuum tightness that vacuumizes in steps A and/or step B can be 10 -3～10 -4Pa.
In the present invention, a preferred example is, in step B, can carry out twice temperature-rise period, for example first slowly is warming up to 600～700 ℃, is filled with inert protective gas, and then slowly is warming up to 1100～1200 ℃.At this, the inert protective gas of employing can be argon gas or helium.
In the present invention, the plumbago crucible that adopts in steps A and/or step B preferably adopts inwall to scribble the plumbago crucible with stopper of boron nitride.More preferably, the plumbago crucible that adopts in step B be inwall scribble boron nitride with tapered bottom and plumbago crucible threaded plug.
In the present invention, in step B, described crucible decline stove can graphite as heating element, take with the stainless steel of water-cooled as seed crystal support.
In the present invention, the purity of the Ba of employing, Ga and Ge simple substance is at least 99.9%.For example adopt Ba(99.92%), Ga(99.999%) and Ge(99.999%).Adopt highly purified raw material, can further improve the quality that makes crystal.
In the present invention, in steps A and/or step B, the speed that slowly heats up can be 1 ℃/minute.
Preparation method of the present invention is simple, raw material that consume is few, the low and Ba that makes of cost 8Ga 16Ge 30The monocrystalline size and dimension is controlled, and quality is high.Method of the present invention is the applicable Ba that produces not only 8Ga 16Ge 30Monocrystalline also can be used for other known or unknown I type germanium base cage compound thermoelectric monocrystals, is conducive to the research and development of I type germanium base cage compound thermoelectric monocrystal.
Embodiment
Further illustrate the present invention with reference to following embodiment, should be understood that following embodiment only is used for explanation the present invention, and unrestricted the present invention.
Ba provided by the invention 8Ga 16Ge 30The preparation method of thermoelectric monocrystal can comprise the following steps.
At first adopting Ba, Ga, Ge is that raw material prepares pure phase Ba 8Ga 16Ge 30Polycrystal:
The raw material that the present invention adopts preferably adopts high pure raw material, and for example purity is at least 99.9% simple substance raw material, in one embodiment, can adopt Ba(99.92%), Ga(99.999%) and Ge(99.999%).Press Ba 8Ga 16Ge 30Stoichiometric ratio batching, should be understood that because the fusing point of Ba is relatively low, in order to make up the volatilization of Ba in melting process, Ba can increase by 3～5wt% weight on the original base amount, namely, can be by mol ratio preparation Ba, Ga and the Ge simple substance of 8.24～8.4:16:30.Load weighted metal simple-substance is packed in plumbago crucible, and preferred inwall evenly scribbles in the plumbago crucible with stopper of boron nitride (coat-thickness of boron nitride can be 0.1mm), then crucible is put into vacuum oven, vacuumizes, and preferred vacuum tightness is 10 -3～10 -4Pa, slowly heat up (for example 1 ℃/minute) is incubated 9～12 hours (for example 10 hours) to 1100～1200 ℃ (for example 1150 ℃), then slowly is down to room temperature, can obtain pure phase Ba 8Ga 16Ge 30Polycrystal.
The above-mentioned powder phase that makes that adopted the powder x-ray diffraction experiment test is found the Ba of itself and standard 8Ga 16Ge 30The powdery diffractometry card is consistent, proves that the product that makes is the Ba of pure phase 8Ga 16Ge 30
Then adopt Bridgman-Stockbarge method for growing Ba 8Ga 16Ge 30Monocrystalline.
1) with the polycrystal powder abrasive lapping powdered of above-mentioned preparation, be poured into plumbago crucible, preferred inwall evenly scribbles in the plumbago crucible of tapered bottom of boron nitride, sealed crucible (for example screwing screwed graphite cap), the crucible of sealing is moved to crucible decline stove with vacuum system (can graphite as heating element, take with the stainless steel of water-cooled as seed crystal support) in, system is vacuumized, preferred vacuum tightness is 10 -3～10 -4Pa, slowly heat up (for example 1 ℃/minute) is to 1100～1200 ℃ of design temperatures.At this, the strategy that preferably heats up can be: when first slowly being warming up to 600～700 ℃, first be filled with inert protective gas, then continue slowly to be warming up to 1100～1200 ℃ of design temperatures., highly purified inert protective gas be can adopt here, 99.99% argon gas or helium for example adopted.The plumbago crucible that adopts can be round shape or the square high purity graphite crucible of tapered bottom, but should understand the plumbago crucible that also can adopt on demand other shapes.The crucible inwall can evenly be coated with the boron nitride of the 0.1mm that has an appointment.Adopt in one embodiment circular plumbago crucible, preferably adopt threaded cap.In addition, the heating element of the crucible decline stove of employing can be graphite, and seed crystal support can be the stainless steel with water-cooled.
2) above-mentioned design temperature insulation 2～3 hours, melt is all melted, adjust the thermograde of solid-liquid interface that bushing position makes the crystal growth in the scope of 20～60 ℃/cm, the crucible fall off rate can be controlled between 0.1～6.0mm/h.
3) after the crystal growth finishes, slowly the rate of temperature fall of 20～60 ℃/hour (for example with) is down to 700～800 ℃ (for example 750 ℃) insulation 9～12 hours (for example 10 hours), the crystal of growing is carried out anneal, then be down to room temperature, can obtain high-quality Ba 8Ga 16Ge 30Monocrystalline.
The present invention further for example following examples so that the present invention to be described better.
Embodiment 1:
Embodiment 1: pure phase Ba 8Ga 16Ge 30The preparation of powder
According to the preparation of 8:16:30 mol ratio, Ba is excessive 4wt% on original stoichiometry basis with raw metal Ba, Ga, Ge.The load weighted raw material inwall of packing into is scribbled in the plumbago crucible of boron nitride, cover the graphite plug, plumbago crucible is moved to vacuum furnace, be evacuated to 10 -3～10 -4Begin after Pa slowly to be warming up to approximately 1150 ℃ by 1 ℃/min speed, then insulation approximately 10 hours slowly is down to room temperature and is namely obtained Ba 8Ga 16Ge 30Then polycrystalline bulk is ground to powder with polycrystalline bulk.
Embodiment 2
Pure Ba with embodiment 1 preparation 8Ga 16Ge 30Powder stock is placed in the plumbago crucible that scribbles boron nitride with tapered bottom, inwall, screws screwed graphite cap, and crucible is moved in crucible decline stove, and system is evacuated to 10 -3～10 -4After Pa, slowly heat up with 1 ℃/min, when temperature reaches 600～700 ℃, be filled with high-purity argon gas, then continue slowly to be warming up to 1130 ℃ of design temperatures; Design temperature insulation 3 hours, melt is all melted, adjusting bushing position makes the thermograde of solid-liquid interface of crystal growth in the scope of 25 ℃/cm, the crucible fall off rate is 0.3 mm/h, after the crystal growth finishes, then speed slow cooling to 750 a ℃ insulation with 25 ℃/h was down to room temperature in 10 hours, can obtain the cylindrical Ba of size Φ 10mm * 30mm 8Ga 16Ge 30Crystal.
Embodiment 3
Pure Ba with embodiment 1 preparation 8Ga 16Ge 30Powder stock is placed in the square graphite crucible that scribbles boron nitride with tapered bottom, inwall, square graphite crucible is put into internal diameter more bigger than square plumbago crucible, wall thickness is in the circular plumbago crucible of 1mm, screw screwed graphite cap, crucible is moved in crucible decline stove, system is evacuated to 10 -3～10 -4After Pa, slowly heat up with 1 ℃/min, when temperature reaches 600～700 ℃, be filled with high-purity argon gas, then continue slowly to be warming up to 1150 ℃ of design temperatures; Design temperature insulation 2 hours, melt is all melted, adjusting bushing position makes the thermograde of solid-liquid interface of crystal growth in the scope of 35 ℃/cm, the crucible fall off rate is 1 mm/h, after the crystal growth finishes, then speed slow cooling to 750 a ℃ insulation with 30 ℃/h was down to room temperature in 10 hours, can obtain the square Ba of sectional area 12mm * 12mm, length 25mm 8Ga 16Ge 30Crystal.
Embodiment 4
Pure Ba with embodiment 1 preparation 8Ga 16Ge 30Powder stock is placed in the plumbago crucible that scribbles boron nitride with tapered bottom, inwall, screws screwed graphite cap, and crucible is moved in crucible decline stove, and system is evacuated to 10 -3～10 -4After Pa, slowly heat up with 1 ℃/min, when temperature reaches 600～700 ℃, be filled with high-purity argon gas, then continue slowly to be warming up to 1100 ℃ of design temperatures; Design temperature insulation 3 hours, melt is all melted, adjusting bushing position makes the thermograde of solid-liquid interface of crystal growth in the scope of 20 ℃/cm, the crucible fall off rate is 0.1 mm/h, after the crystal growth finishes, then speed slow cooling to 700 a ℃ insulation with 20 ℃/h was down to room temperature in 10 hours, can obtain the cylindrical Ba of Φ 25mm * 35mm 8Ga 16Ge 30Crystal.
Embodiment 5
Pure Ba with embodiment 1 preparation 8Ga 16Ge 30Powder stock is placed in the square graphite crucible that scribbles boron nitride with tapered bottom, inwall, square graphite crucible is put into internal diameter more bigger than square plumbago crucible, wall thickness is in the circular plumbago crucible of 1mm, screw screwed graphite cap, crucible is moved in crucible decline stove, system is evacuated to 10 -3～10 -4After Pa, slowly heat up with 1 ℃/min, when temperature reaches 600～700 ℃, be filled with high-purity argon gas, then continue slowly to be warming up to 1200 ℃ of design temperatures; Design temperature insulation 2 hours, melt is all melted, adjusting bushing position makes the thermograde of solid-liquid interface of crystal growth in the scope of 60 ℃/cm, the crucible fall off rate is 6 mm/h, after the crystal growth finishes, then speed slow cooling to 800 a ℃ insulation with 60 ℃/h was down to room temperature in 10 hours, can obtain the square Ba of 20mm * 20mm, length 40mm 8Ga 16Ge 30Crystal.
Industrial applicability: method of the present invention. growth velocity is adjustable, and is simple for process, materials are few, the low and Ba that makes of cost 8Ga 16Ge 30The monocrystalline size and dimension is controlled, and quality is high.In addition, method of the present invention not only is suitable for and produces Ba 8Ga 16Ge 30Monocrystalline also can be used for other known or unknown I type germanium base cage compound thermoelectric monocrystals, is conducive to the research and development of I type germanium base cage compound thermoelectric monocrystal.

Claims (11)

1. Ba 8Ga 16Ge 30The growth method of thermoelectric monocrystal is characterized in that, comprising:
Steps A: the mol ratio by 8.24～8.4:16:30 is prepared Ba, Ga and Ge simple substance, is placed in plumbago crucible and vacuumizes to be packaged in vacuum oven, is incubated 9～12 hours under 1100～1200 ℃, then slowly cools to room temperature, gets pure phase Ba 8Ga 16Ge 30Polycrystal; And
Step B: with gained pure phase Ba 8Ga 16Ge 30The polycrystal grind into powder, be placed in plumbago crucible, sealed graphite crucible, put into crucible decline stove, vacuumize, slowly be warming up to 1100～1200 ℃ of insulations and made the whole meltings of described powder in 2～3 hours, adjust the position of described plumbago crucible with the crucible fall off rate of 0.1～6.0mm/ hour and carry out single crystal growing so that the thermograde of the solid-liquid interface of crystal growth is controlled in the scope of 20～60 ℃/cm.
2. Ba according to claim 1 8Ga 16Ge 30The growth method of thermoelectric monocrystal is characterized in that, also comprises step C: treat that crystal grows to desired size, slowly cool to and be incubated 9～12 hours under 700～800 ℃ and carry out anneal, then be cooled to room temperature.
3. Ba according to claim 2 8Ga 16Ge 30The growth method of thermoelectric monocrystal is characterized in that, in step C: slowly cool to 700～800 ℃ with the rate of temperature fall of 20～60 ℃/hour.
4. Ba according to claim 1 8Ga 16Ge 30The growth method of thermoelectric monocrystal is characterized in that, the vacuum tightness that vacuumizes in steps A and/or step B is 10 -3～10 -4Pa.
5. Ba according to claim 1 8Ga 16Ge 30The growth method of thermoelectric monocrystal is characterized in that, in step B, first slowly is warming up to 600～700 ℃, is filled with inert protective gas, and then slowly is warming up to 1100～1200 ℃.
6. Ba according to claim 4 8Ga 16Ge 30The growth method of thermoelectric monocrystal is characterized in that, described inert protective gas is argon gas or helium.
7. Ba according to claim 1 8Ga 16Ge 30The growth method of thermoelectric monocrystal is characterized in that, the plumbago crucible that adopts in steps A and/or step B is the plumbago crucible with stopper that inwall scribbles boron nitride.
8. Ba according to claim 7 8Ga 16Ge 30The growth method of thermoelectric monocrystal is characterized in that, the plumbago crucible that adopts in step B is the plumbago crucible with tapered bottom and threaded cap that inwall scribbles boron nitride.
9. Ba according to claim 1 8Ga 16Ge 30The growth method of thermoelectric monocrystal is characterized in that, in step B, described crucible decline stove with graphite as heating element, take with the stainless steel of water-cooled as seed crystal support.
10. Ba according to claim 1 8Ga 16Ge 30The growth method of thermoelectric monocrystal is characterized in that, the purity of described Ba, Ga and Ge simple substance is at least 99.9%.
11. the described Ba of any one according to claim 1～10 8Ga 16Ge 30The growth method of thermoelectric monocrystal is characterized in that, in steps A and/or step B, the speed that slowly heats up is 1 ℃/minute.
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CN105047809A (en) * 2015-06-30 2015-11-11 中国科学院宁波材料技术与工程研究所 SnSe-based thermoelectric material and preparation method thereof

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CN100445431C (en) * 2006-03-13 2008-12-24 同济大学 Preparation method of I-type germanium-radical clathrate single-crystal and new single-crystal filled with barium and strontium
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Cited By (3)

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Publication number Priority date Publication date Assignee Title
CN104451326A (en) * 2014-10-27 2015-03-25 华东理工大学 Novel clathrate thermoelectric material and preparation method thereof
CN105047809A (en) * 2015-06-30 2015-11-11 中国科学院宁波材料技术与工程研究所 SnSe-based thermoelectric material and preparation method thereof
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