CN104630875B - Environment-friendly and energy-saving growth method of large-sized blocky information storage ferroelectric single crystals - Google Patents
Environment-friendly and energy-saving growth method of large-sized blocky information storage ferroelectric single crystals Download PDFInfo
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- CN104630875B CN104630875B CN201510041379.5A CN201510041379A CN104630875B CN 104630875 B CN104630875 B CN 104630875B CN 201510041379 A CN201510041379 A CN 201510041379A CN 104630875 B CN104630875 B CN 104630875B
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Abstract
The invention discloses a novel environment-friendly and energy-saving growth method of large-sized blocky information storage ferroelectric single crystals. The method comprises the following steps: heating an information storage ferroelectric single crystal raw material solution to realize the saturation equilibrium; seeding; transforming; carrying out programmed freezing growth; and performing post-treatment and heat crystal transferring. A single crystal mother liquid bottle does not need to be protected by protective gas and internal and external pressure balance can be controlled automatically in a liquid sealing way by using paraffin oil; air circulation between inside and outside is isolated by the paraffin oil and the temperature balance can be maintained precisely. According the method, the large-sized blocky information storage ferroelectric single crystals grow out indirectly; the manufacturing procedure is simple, the raw materials are simple and cheap, waste liquid is recyclable, no pollution or emission of the three wastes is caused; energy is saved since the crystals grow almost at room temperature; environmental friendliness is realized by virtue of growth in an aqueous solution; the manufacturing cost is low.
Description
Technical field
The present invention relates to novel molecular ferroelectric information stores the manufacturing technology of monocrystal, specifically a kind of new size block
The growing method of the environmental protection and energy saving of shape information Store ferroelectric single crystal.
Background technology
Ferroelectric material is that present information storage, microelectronics, remote sensing, laser etc. concern national economy and a class of national defence can not
Or the intelligent important materials lacking.And because its special dipole array structure and light harvesting, electricity, magnetic, heat, power etc. are in one
Characteristic makes it have the not replaceable special applications prospect of any material, can meet following highly integrated develop rapidly to material
The particular/special requirement of material.At present, the ferroelectric material quantity being used widely is very limited, and concentrates on inorganic oxide (such as
BaTiO3、PbTiO3, the ceramic ferroelectric body such as PTZ).But this kind of ceramic ferroelectric body material contains the heavy metal of hypertoxicity, garbage dirt
The heavier, density containing heavy metal of dye is big, need high, growth large single crystal difficulty of high temperature sintering energy consumption etc., producing, application and giving up
Gurry processes links and all there is many areas for improvement.
The ferroelectric of main application at present is all based on the ceramic Pb (Ti1- containing lead oxides and its derivant simultaneously
xZrx)O3, sintering temperature reached the high temperature between 600-1000 DEG C, also will maintain several days even some months in this high temperature,
And producing hypertoxic PbO garbage, scrap concrete is difficult, and high temperature sintering expends the huge energy.To for the survival of mankind
Natural environment causes serious expendable harm.The element resource of these heavy metals and some other doping has simultaneously
Limit, the development cost in later stage can be more high.
The large single crystal bulk-growth method of novel molecular ferroelectric material is also at the early-stage at present, the method not obtaining maturation,
For diisopropyl ammonium bromide high-performance iron electric material, the U.S.《Science》The crystalline size of the document report on magazine is smaller,
Only 1-2 millimeter；Through a series of DCOs characterize prove its properties all close to reached ceramic Barium metatitanate. water
Put down, saturated polarization and Curie temperature are all very high.But its large size single crystal bulk-growth is relatively difficult, and traditional：Flame method, carry
This materials all inapplicable such as traction therapy, heat-exchanging method and guiding temperature ladder method.Find sintering temperature and low and the ferroelectric material of environmental protection is state
The difficulty being difficult to for a long time capture of border materialogy research, the research of large size single crystal bulk-growth method is ground becoming following emphasis
Study carefully direction.
Content of the invention
Goal of the invention：In order to overcome the deficiencies in the prior art, the present invention provides a kind of new large scale block letter
The environmental protection and energy saving growing method of breath storage ferroelectric single crystal, only the temperate condition below 50 DEG C just need to can grow and obtain big crystalline substance
Body, solves the difficult technical barrier of large size single crystal bulk-growth in prior art.
Technical scheme：For achieving the above object, the present invention adopts the following technical scheme that：
A kind of environmental protection and energy saving growing method of new large scale bulk information Store ferroelectric single crystal, comprises the following steps：
1) material solution is utilized to prepare saturation mother solution；
2) seeding；
3) turn brilliant；
4) programmed cooling growth；
5) post processing；
6) hot crystal conversion, obtains new large scale bulk information Store ferroelectric single crystal；
Described step is all carried out in the mother liquid multi-cavity bottle in monocrystalline temperature chamber, the top setting fluid-tight of described mother liquid multi-cavity bottle.
Further, in the present invention, described step 1) in, the preparation process of described saturation mother solution is：
1-1) add raw material and deionized water in stock bottle, close the lid, described stock bottle is placed in described monocrystalline constant temperature
In groove；Described raw material is diisopropylamine bromide；
1-2) temperature is controlled to be 40 DEG C～50 DEG C in described monocrystalline temperature chamber；
1-3) stir, so that raw material is fully dissolved and reach saturation；
1-4) by step 1-3) resulting solution carries out heat filtering, obtains limpid saturation mother solution；
1-5) gained saturation mother solution is transferred in 50 DEG C of described mother liquid multi-cavity bottle, cover the lid with fluid-tight circle, put into
It is incubated in described monocrystalline temperature chamber；
After 1-6) being incubated 2～4 hours, the temperature in described mother liquid multi-cavity bottle has reached 40 DEG C～50 DEG C of saturation temperature.
Further, in the present invention, described step 2) in, the step of described seeding is：
2-1) described mother liquid multi-cavity bottle is connected with seed crystal, described seed crystal Height Adjustable；
2-2) described seed crystal is dropped at 5mm～20mm at the liquid level of described saturation mother solution, stand 5～10 points
Clock so that described seed crystal be warming up to consistent with the temperature of saturation mother solution；
2-2) described seed crystal is dropped to the centre position of the liquid level of described saturation mother solution, standing.
Further, in the present invention, described step 3) in, described turn of brilliant step is：Unlatching is stated in monocrystalline temperature chamber
Rotary apparatuss, rotating speed be 20～30 turns/min；Setting program is to be alternately rotated counterclockwise clockwise, stops between replacing along reciprocal cross
10 seconds～15 seconds.
Further, in the present invention, described step 4) in, seed crystal persistently rotates, and proceeds by programmed cooling growth,
Different phase according to growth controls different rate of temperature fall, including as follows：
At the 4-1) initial stage, rate of temperature fall is to lower the temperature 0.1 DEG C for every 3 days；
4-2) mid-term, rate of temperature fall is to lower the temperature 0.1 DEG C for every 2 days；
In the 4-3) later stage, rate of temperature fall is to lower the temperature 0.1 DEG C for every 1 day；
In 4-3) latter stage, rate of temperature fall is to lower the temperature 0.1 DEG C for every 0.5 day.
Cooling is too fast to be grown too fast, and mother liquid multi-cavity bottle bottom can separate out extra crystal, affects the growth of big crystal.
Further, in the present invention, described step 5) in, the method for described post processing is：Stop described step 4) in
Programmed cooling growth, in described mother liquid multi-cavity bottle add with described saturation mother solution mutually synthermal paraffin oil, simultaneously by bottom
Saturation mother solution constant speed is extracted out, maintains the total amount of liquid in described mother liquid multi-cavity bottle constant, all replaces with described to described saturation mother solution
Paraffin oil, is immersed in described paraffin oil through the big crystal that programmed cooling growth is formed.After preventing from pulling straight out crystal, crystal
Surface cooling is faster than inside, causes inside and outside unequal power distribution, produces stress cracking；Do standard for the hot crystal conversion of next step simultaneously
Standby.
Further, in the present invention, described step 6) in, the method for described hot crystal conversion is：Will be through step 5) after
The described mother liquid multi-cavity bottle processing takes out, and puts into and is heated to 155 DEG C in oil bath, cooling；Heating rate in described heating process
It is 10 DEG C with the rate of temperature fall in cooling procedure per hour.Guarantee that the temperature inside and outside crystal unanimously keeps stress equilibrium not open
Split.
Further, in the present invention, the top of described mother liquid multi-cavity bottle adopts paraffin oil fluid-tight.Mother liquid multi-cavity bottle does not need shielding gas
The protection of body, automatically controls internal and external pressure balance using paraffin oil isolation method；Put down in material solution heating, material solution saturation
Weighing apparatus, seeding, put crystalline substance, grow along despining seed crystal and programmed cooling during, air stream has been blocked by the isolation of paraffin oil
Logical, and then can preferably maintain hygral equilibrium.Inside and outside sealing coat uses inert non-water-soluble liquid paraffin oil.Exogenous QI in maintenance
Flatten weighing apparatus, intercept air current flow simultaneously, can preferably keep internal temperature, the particularly surface temperature of mother solution, because once having
Air current flow mother solution surface temperature will reduce, and can separate out little crystallite, thus having a strong impact on the stable growth of big crystal.
Further, in the present invention, described temperature chamber and mother liquid multi-cavity bottle are glass material, and the volume of described temperature chamber is
30 liters～100 liters, the size of described mother liquid multi-cavity bottle is 1 liter～10 liters.The smooth growth being beneficial to crystal of glass surface, glass simultaneously
Transparent convenient observation crystal growth condition, according to growing state timely adjustment growth conditionss, can be processed into not isometric glass
Container, low cost；Comparatively speaking, container used by traditional method is all noble metal or alloy etc., airtight opaque inconvenience
Observe crystal growth condition, cost is also high.
Further, in the present invention, it is provided with temperature-controlling system in described monocrystalline temperature chamber, described temperature-controlling system is that electricity adds
Gas ket water bath heating device, heating power is 0.5kw～5kw.
Beneficial effect：
Technical scheme in the present invention gradually forms during being the carrying out of scientific research task, and related scientific research task is subject to
Subsidy to following fund：The Department of Science and Technology 973 (2014CB848800), Jiangsu Province's Natural Science Fund In The Light (BK20130600,
BK20140056), state natural sciences fund (21422101,21301029) and the Ministry of Education new century talent and center for doctors's base
Gold.
Traditional ceramic ferroelectric materials are replaced by the present invention with molecular based diisopropyl ammonium bromide molecular based ferroelectric material, profit
With aqueous solution, large-sized ferroelectric single crystal material is synthesized by indirect phase in version method, preparation temperature falls below 50 DEG C,
Energy consumption is very low, production process does not produce noxious substance, three-waste free discharge, saves mass energy and reduces CO2With gray haze row
Put, waste liquid is capable of circulation to be continued to reuse, and greatly reduces environmental pollution, and reduces cost.The present invention utilizes molecular based ferroelectricity material
The research of material is prepared for a high performance molecule ferroelectric material, and grown large size single crystal by the method for environmental protection
Body, raw material is cheap and easily-available pollution-free, establishes material foundation for application.
1. this method adopts less than 50 DEG C of the temperature growth close to room temperature, relatively conventional 1000 DEG C about of high temperature molten
After melting, more very energy-conservation is compared in growth, greatlys save the electric energy consuming due to maintaining high temperature；Simplify high growth temperature simultaneously
Complicated procedures of forming, operation is simpler easily.
2. use water as solvent environmental protection；Rather than environmental toxicity is had using toluene, benzene, DMF, methanol, chloroform etc.
Organic solvent.Waste liquid after growth crystal can be recycled, and the raw material as next crystal growth directly feeds intake.Whole process does not have
Waste gas and waste liquid and waste residue is had to produce, very environmental protection.
3. adopt water bath with thermostatic control temperature programmed control, be that medium conducts heat to mother liquid multi-cavity bottle from the larger water of specific heat capacity, water energy is fine
Ground plays the big feature of specific heat capacity and maintains temperature stabilization, and temperature stability occurs without temperature fluctuation well, and program control Electrothermal ring work(
The response of rate moderate program occurs without over-heating and hysteresis soon.Because temperature stability is most important for growing, if
Occur fluctuation crystal occur dissolving and quick separate out, impact crystal mass or be changed into polycrystalline rather than monocrystalline.
4. do not need the crucible of the materials such as noble metal to be used it is only necessary to simple glass bottle is as mother liquid multi-cavity bottle, vial is transparent
Easily observe crystal growth condition, and cost is very low.Raw material is also the ammonium salt of small molecule very simple and easy to get simultaneously, and contains
The traditional ceramicses ferroelectric single crystal having heavy metal (lead, bismuth, barium etc.) is compared, and not only environmental protection is renewable, and cost of material is even more very
Low.
5., using the A crystal formation of the good crystallinity of growth first, recycle A crystal formation at 150 DEG C, brilliant through irreversible thermic
Type structural transformation becomes the feature of B crystal form, the B crystal form molecule ferroelectric single crystal required for indirectly having obtained, and for visible ray and
Infrared light transmittance height, the no low optical grade crystal of polycrystalline, defect concentration, have bypassed the difficult problem of direct growth B crystal form.
Specific embodiment
With reference to embodiment, the present invention is further described.
A kind of environmental protection and energy saving growing method of new large scale bulk information Store ferroelectric single crystal, comprises the following steps：
1) material solution is utilized to prepare saturation mother solution：
1-1) add raw material and deionized water in stock bottle, cover the latex lid of central aperture and put into a polytetrafluoro
Stirring rod, stock bottle is placed in described monocrystalline temperature chamber；Raw material is diisopropylamine bromide；
1-2) it is provided with temperature-controlling system in monocrystalline temperature chamber, temperature-controlling system is Electrothermal ring water bath heating device, heats work(
Rate is 0.5kw～5kw, opens and controls temperature to be 40 DEG C～50 DEG C in temperature-controlling system, monocrystalline temperature chamber；Monocrystalline temperature chamber and mother solution
Bottle is glass material, and the volume of temperature chamber is 30 liters～100 liters, and the size of mother liquid multi-cavity bottle is 1 liter～10 liters.
1-3) open polytetrafluoro stirring rod to stir 2 days, so that raw material is fully dissolved and reach saturation；
1-4) ready buchner funnel is also heated to 40 DEG C～50 DEG C, quickly by step 1-3) gained carry undissolved
The solution of raw material carries out heat filtering, obtains limpid saturation mother solution；
1-5) the rapid saturation mother solution by filtration gained is transferred in the mother liquid multi-cavity bottle of clean 50 DEG C, covers with fluid-tight circle
Lid, put in the middle of fluid-tight circle one carry suspension ring Glass rod, put in monocrystalline temperature chamber and be incubated；
1-6) after the insulation equilibrium process of 2～4 hours, the temperature in mother liquid multi-cavity bottle has reached 40 DEG C～50 DEG C of saturation temperature
Degree.
Whole operation process will be rapidly completed the solution it is necessary to ensure that obtained by the environment in the range of 45 DEG C～50 DEG C
It is saturation and any small crystal can not be separated out.
2) seeding：
2-1) described mother liquid multi-cavity bottle is connected with the intact seed crystal of 1 cubic millimeter of size, described seed crystal Height Adjustable；Seed crystal
Stick at thin silk thread one end, and silk thread is fixed on the Glass rod bottom with suspension ring；
2-2) described seed crystal is dropped at 5mm～20mm at the liquid level of described saturation mother solution, stand 5 minutes～10
Minute so that described seed crystal is warming up to consistent with the temperature of saturation mother solution, prevent that seed temperature is low to cause rapid crystallization；
2-2) described seed crystal is dropped to the centre position of the liquid level of described saturation mother solution, stand more than 2 hours；See
Examine dissolving and the crystallization situation of seed crystal, such as no substantially dissolve and rapid crystallization sign, then can carry out next step operation.
3) turn brilliant：
Open the rotary apparatuss stating in monocrystalline temperature chamber, rotating speed is 20～30 turns/min；Setting program is inverse time clockwise
Pin is alternately rotated, and switching per minute once, stops buffering for 10 seconds～15 seconds between replacing along reciprocal cross.
4) programmed cooling growth：
Seed crystal persistently rotates, and proceeds by programmed cooling growth, and the different phase according to growth controls different coolings
Speed, including as follows：
At the 4-1) initial stage, rate of temperature fall is to lower the temperature 0.1 DEG C for every 3 days；
4-2) mid-term, rate of temperature fall is to lower the temperature 0.1 DEG C for every 2 days；
In the 4-3) later stage, rate of temperature fall is to lower the temperature 0.1 DEG C for every 1 day；
In 4-3) latter stage, rate of temperature fall is to lower the temperature 0.1 DEG C for every 0.5 day；
Due to the little poor growth of initial stage seed crystal, the supersaturation precipitation raw material of needs is few, therefore rate of temperature fall is slow；Lower the temperature too fast meeting
Growth is too fast, and mother liquid multi-cavity bottle bottom can separate out extra crystal, affects the growth of big crystal；
5) post processing：
Treat crystal growth to the size of needs, stop step 4) in programmed cooling growth and rotate, to mother liquid multi-cavity bottle
The saturation mother solution constant speed of bottom is extracted out simultaneously, is maintained in mother liquid multi-cavity bottle by middle addition mutually synthermal paraffin oil with saturation mother solution
Total amount of liquid is constant, all replaces with paraffin oil to saturation mother solution, is immersed in paraffin through the big crystal that programmed cooling growth is formed
In oil.The mother solution extracted out can be continuing with next time, does not produce any garbage.
6) hot crystal conversion, obtains new large scale bulk information Store ferroelectric single crystal：
By through step 5) reprocessed mother liquid multi-cavity bottle takes out together with internal paraffin oil and crystal, puts in oil bath
It is heated to 155 DEG C, cooling, the rate of temperature fall in heating rate and cooling procedure in heating process is 10 DEG C per hour；Fall
To room temperature, crystal is taken out.
In step 6) before the A crystal formation that grown into, be completely transformed into required by thermic crystalline structure method of converting
Ferroelectric information stores the B crystal form large size single crystal body of material.It is the exclusive feature of this crystal that thermic crystalline structure changes, and bypasses
A difficult problem for direct growth B crystal form.
Above step is all carried out in the mother liquid multi-cavity bottle in monocrystalline temperature chamber, and the top of mother liquid multi-cavity bottle adopts paraffin oil fluid-tight.
Embodiment 1：
Take 400g raw material diisopropylamine bromide, put in the simple glass bottle of 1L, and add the deionized water of 600mL.Lid
Upper centre carries the latex lid of 0.5cm diameter perforate and puts into the long polytetrafluoro stirring rod of 40cm；Open constant temperature water bath
Constant temperature water circulation system, temperature is set in 45.0 DEG C, and heating power maintains 2kw；Open polytetrafluoro stirring rod to stir 2 days,
Rotating speed is 40 turns/min, so that raw material is fully dissolved and reaches saturation.By the buchner funnel of ready a diameter of 10cm and 1L sucking filtration
Bottle is heated to 45.0 DEG C, and heat filtering carries the solution of undissolved raw material, completes in quick 1 minute；And rapid will be filtrated to get
Limpid saturation hot solution is transferred in clean another vial being preheating to 50.0 DEG C, as mother liquid multi-cavity bottle, and covers band
There is the lid of paraffin oil fluid-tight, put into a long Glass rod of 40cm carrying suspension ring in the middle of fluid-tight circle, put into temperature chamber inside holding.
Through the equilibrium process of 4 hours, in mother liquid multi-cavity bottle, temperature reached 45.0 DEG C of saturation temperature.Whole operation process will be 45
Environment in the range of DEG C -50 DEG C is rapidly completed it is necessary to ensure that obtained solution is saturation and can not separate out any small
Crystal.
Intact bulk seed crystal close to 1 cubic millimeter of size is sticked at thin silk thread one end of 0.05mm diameter, and by silk thread
It is fixed on below the above-mentioned Glass rod bottom suspension ring with suspension ring.Seed crystal is dropped at saturation liquid level 1cm, stops 5 points
Clock, so that seed crystal is warmed up to the temperature the same with saturated solution, prevents that seed temperature is low to cause rapid crystallization.Again slowly by seed crystal
Drop to the centre position of mother solution liquid level, stand 2 hours.Observe dissolving and the crystallization situation of seed crystal.As no substantially dissolved
With rapid crystallization sign, then can carry out next step rotating crystal operation.
Open rotary apparatuss, setting program is to be alternately rotated counterclockwise clockwise, switching per minute once, in replacing along reciprocal cross
Between stop buffering for 10 seconds.Rotating speed is 20 turns/min.
Maintain seed crystal rotation, and start slow programmed cooling growth.Different phase according to growth controls different coolings
Speed.Due to seed crystal little poor growth, the supersaturation precipitation raw material of needs is few, and therefore rate of temperature fall maintains 0.1 DEG C often within first 5 days
The slower speed of 3 days；Be changed within subsequent 1 week 0.1 DEG C every 2 days, and 0.1 DEG C of the later stage daily and every 12 hours.Lower the temperature too fast meeting
Growth is too fast, and mother liquid multi-cavity bottle bottom can separate out extra crystal, affects the growth of big crystal.
Treat crystal growth to the size of needs, stop the rotation and keeping temperature is constant.Add in mother liquid multi-cavity bottle and mother
The solution constant speed of bottom is extracted out by the synthermal paraffin oil of liquid phase simultaneously, maintains total amount of liquid in bottle constant.To all replacing with
Paraffin oil, the mother solution of extraction is continuing with next time, does not produce any garbage.Whole process needs 10 minutes.Now big crystalline substance
Body invades bubble completely in paraffin oil.Purpose has two：One be prevent from pulling straight out crystal after, plane of crystal cooling is than internal
Hurry up, so cause inside and outside unequal power distribution, produce stress cracking；Another is the hot crystal conversion for next step.
Close constant temperature system.Above-mentioned mother liquid multi-cavity bottle is taken out together with internal paraffin oil and crystal, puts in oil bath
It is heated to 155 DEG C of maintenances can cool down for 1 minute, after being down to room temperature, crystal is taken out；Intensification rate of temperature fall all maintains 10 DEG C often
Hour is it is therefore an objective to guarantee that the temperature inside and outside crystal unanimously keeps stress equilibrium not ftracture.Whole process has the protection of paraffin oil
Therefore do not need body protection of ventilating, simple to operate.The A crystal formation of now early growth has passed through thermic crystalline structure method of converting
The ferroelectric information being completely transformed into needs stores the B crystal form large size single crystal body of material.It is this crystal that thermic crystalline structure changes
Exclusive feature, bypassed the difficult difficult problem of direct growth B crystal form.Gained crystal is block transparent monocrystal, and only middle have
Less minute bubbles are good through inspection crystal mass.
Embodiment 2：
Take 600g raw material diisopropylamine bromide, put in the simple glass bottle of 2L, and add the deionized water of 1L.In covering
Between with the latex lid of 0.7cm diameter perforate and put into the long polytetrafluoro stirring rod of 45cm.Constant temperature water bath adopts organic
The U-shaped bottle of the 30L of clear glass material, top adopts the aluminium alloy lid of central aperture, and central aperture is in order to put into mother liquid multi-cavity bottle.
Open the constant temperature water circulation system of constant temperature water bath, temperature is set in 50.0 DEG C, and heating power maintains 3kw；Open polytetrafluoro
Stirring rod stirs 3 days, and rotating speed is 50 turns/min, so that raw material is fully dissolved and reaches saturation.Cloth by ready a diameter of 10cm
Family name's funnel and 1L bottle,suction are heated to 50.0 DEG C, and heat filtering carries the solution of undissolved raw material, and rapid filtration under suction is it is desirable to 1 at twice
Complete in minute to prevent temperature from reducing；And rapid transfer to the limpid saturated solution of sucking filtration gained clean is preheating to 52.0
DEG C another isopyknic mother liquid multi-cavity bottle in, and cover the lid with paraffin oil fluid-tight, put into one in the middle of fluid-tight circle and carry
The Glass rod of the smooth surface of 50cm length of suspension ring, probes into rest in mother liquid multi-cavity bottle from perforate.Through the heat exchange of 3 hours
Journey, in mother liquid multi-cavity bottle, temperature has reached 50.0 DEG C of saturation temperature.
The intact bulk seed crystal of 1*1*1 size is sticked at thin silk thread one end of 0.05mm diameter, and silk thread is fixed on
Below the Glass rod bottom suspension ring with suspension ring stated.Seed crystal is dropped at saturation liquid level 2cm, stops 10 minutes.One is
Make seed crystal and saturated solution have temperature；Two is to make seed crystal face absorb water to form moisture film, prevents the crystallization of seed crystal face
Core causes rapid crystallization when contacting saturation mother solution.Turn down the interposition that seed crystal is dropped to mother solution liquid level by Glass rod height
Put standing.Observe dissolving and the crystallization situation of seed crystal, seed crystal has rapid crystallization sign after putting into seed crystal 20min, now pull-up
Seed crystal, temperature chamber is heightened 0.2 DEG C.Seed crystal was put into after as a child and was observed growth dissolving situation in mother solution by constant temperature 4 again, and 3 is little
Shi Houwu significant change, after 6 hours, seed crystal slightly grows.
Now open rotary switch rotation seed crystal, setting program is to be alternately rotated counterclockwise clockwise, switching one in every 90 seconds
Secondary, replace middle stopping to buffer for 15 seconds along reciprocal cross.Rotating speed is 30 turns/90 seconds.
Cooling process is opened, rate of temperature fall maintains 0.1 DEG C of every slower speed of 3 days within 1-6 days after 10 hours；Subsequent 2 weeks
Be changed to 0.1 DEG C every 2 days, the later stage be 0.1 DEG C daily.
Treat crystal growth to the size of needs, stop the rotation and keeping temperature is constant.Add and mother in growth bottle
The solution constant speed of bottom is extracted out by the synthermal paraffin oil of liquid phase simultaneously, and in bottle, total amount of liquid keeps constant, and in 20 minutes
All replace with paraffin oil.Mother solution is continuing with next time.Big crystal being invaded completely purpose in paraffin oil for the bubble has two：One
Be prevent from pulling straight out crystal after, plane of crystal cooling is fast, and internal cooling is slow, such internal-external temperature difference cause unequal power distribution and
Cracking；Another is the transformation of the A of the heating induction carrying out for final step to B crystal form.
Close temperature chamber water-bath system.It is placed with large-size crystals and the mother liquid multi-cavity bottle taking-up of paraffin oil by above-mentioned, put in advance
Be preheating in 50 DEG C of oil bath, and be heated to 155 DEG C with the heating rate of 10 DEG C/h, maintain 2 minutes after temperature programmed control with
Intensification phase same rate cools down.After being down to room temperature, crystal is taken out.Whole process crystal all invades bubble in paraffin oil, does not therefore need
Logical gas shield, simplifies operating process.It is complete that the A crystal formation of now early growth has passed through thermic crystalline structure method of converting
The ferroelectric information being changed into needs stores the B crystal form large size single crystal body of material.In addition to there are less amount of minute bubbles centre, through inspection
Test crystal mass good.
Embodiment 3：
Take 300g raw material, put in the simple glass bottle of 1L, and add the deionized water of 500mL.Put in temperature chamber, with
Open thermostatted water circulator bath system afterwards, temperature is set in 40.0 DEG C, and heating power maintains 1.5kw.Cover middle punching simultaneously
Latex lid with polytetrafluoro stirring rod；Open polytetrafluoro stirring rod to stir 1 day, rotating speed is 35 turns/min, makes solution reach full
With.With being preheating to 40℃The buchner funnel of a diameter of 10cm and quick 1 minute interior-heat of 1L bottle,suction filter and carry undissolved raw material
Solution；Subsequently quickly limpid saturation hot solution is transferred in the clean 1L vial being preheating to 40.0 DEG C, put rapidly
Enter temperature chamber inside holding and cover lid with paraffin oil fluid-tight, in the middle of fluid-tight circle, put into a long glass of 40cm carrying suspension ring
Glass rod.Through the equilibrium process of 2 hours, in mother liquid multi-cavity bottle, temperature stabilization was at 40.0 DEG C.Whole operation process must assure that gained
To solution be saturation and any small crystal can not be separated out.
Good for the quality of size about 0.5*0.5*0.5 millimeter and smooth surface block seed crystal is sticked at 0.05mm diameter
Thin silk thread one end, silk thread is integrally fixed at below the above-mentioned Glass rod bottom suspension ring with suspension ring.Seed crystal is dropped to close
Stop 8 minutes so that seed crystal reaches and solution identical temperature, crystal seed is inhaled when close to liquid level at saturation liquid level 0.5cm
Attached steam defines moisture film in seed crystal face, and moisture film has isolated the nuclei of crystallization of plane of crystal, can prevent seed crystal contact saturation
The moment rapid crystallization of solution.Afterwards seed crystal is dropped to the centre position of mother solution liquid level and stand.Period observes seed crystal
Dissolving and crystallization situation.3 as a child seed crystal slightly dissolve, illustrate that solution is dense because ambient temperature is low during heat filtering
Degree slightly reduces.After pull-out seed crystal, temperature chamber temperature is turned down 0.1 DEG C, constant temperature 3 as a child continues to draw in seed crystal in the middle of mother solution.
Through 4 as a child seed crystal no substantially dissolving and rapid crystallization sign, illustrate mother solution be fully saturated.
Open rotary apparatuss, setting program is to be alternately rotated counterclockwise clockwise, switching in every 100 seconds once, is replaced along reciprocal cross
Middle stopping buffers for 12 seconds.Rotating speed is 35 turns/100 seconds.
Start slow programmed cooling growth while maintaining the rotation of seed crystal program.It is within first week 0.1 DEG C of every relatively slower of 3 days
Degree；Be changed within subsequent 1 week 0.1 DEG C every 2 days, and 0.1 DEG C of the later stage daily.
Treat crystal growth to the size of needs, stop the rotation and keeping temperature is constant.Add and mother in growth bottle
The solution constant speed of bottom is extracted out by the synthermal paraffin oil of liquid phase simultaneously, maintains in bottle in bottle in constant 5 minutes of total amount of liquid
Solution all replaces with paraffin oil, and the mother solution of extraction is continuing with next time, does not produce any garbage.Now big crystal is complete
Invade bubble in paraffin oil.
Set constant temperature system rate of temperature fall as 10 DEG C/h until dropping to room temperature.Crystal is taken out vertical crystal pole axis axially,
Namely b axle is cut into a series of thin slices of 0.05-3mm thickness.Thin slice is put into the open glass of the 1L equipped with 500mL paraffin oil
In bottle, and put into be heated in oil bath 155 DEG C maintain 1 minute after cool down, intensification rate of temperature fall all maintains 20 DEG C per hour,
Ensure that the temperature inside and outside crystal is consistent.After being down to room temperature, crystal wafer is taken out.The A crystal formation of now early growth has passed through thermic
Crystalline structure method of converting is completely transformed into the B crystal form monocrystal of the ferroelectric information storage material of needs.Gained crystal is transparent
Monocrystal thin slice, only less minute bubbles, through inspection crystal mass good.
This material saturated polarization is more than 10 μ C/cm2, Curie temperature reaches 151 DEG C, properties all close to and reached height
Performance ceramic ferroelectric materials Barium metatitanate. level.
The above be only the preferred embodiment of the present invention it should be pointed out that：Ordinary skill people for the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (6)
1. a kind of large scale bulk information Store ferroelectric single crystal environmental protection and energy saving growing method it is characterised in that：Including following
Step：
1) material solution is utilized to prepare saturation mother solution；
2) seeding；
3) turn brilliant；
4) programmed cooling growth；
5) post processing；
6) hot crystal conversion, obtains new large scale bulk information Store ferroelectric single crystal；
Described step is all carried out in the mother liquid multi-cavity bottle in monocrystalline temperature chamber, the top setting fluid-tight of described mother liquid multi-cavity bottle；
Described step 1) in, the preparation process of described saturation mother solution is：
1-1) add raw material and deionized water in stock bottle, close the lid, described stock bottle is placed in described monocrystalline temperature chamber；
Described raw material is diisopropylamine bromide；
1-2) temperature is controlled to be 40 DEG C～50 DEG C in described monocrystalline temperature chamber；
1-3) stir, so that raw material is fully dissolved and reach saturation；
1-4) by step 1-3) resulting solution carries out heat filtering, obtains limpid saturation mother solution；
1-5) gained saturation mother solution is transferred in 50 DEG C of described mother liquid multi-cavity bottle, cover the lid with fluid-tight circle, put into described
It is incubated in monocrystalline temperature chamber；
After 1-6) being incubated 2～4 hours, the temperature in described mother liquid multi-cavity bottle has reached 40 DEG C～50 DEG C of saturation temperature；
Described step 4) in, described mother liquid multi-cavity bottle is connected with seed crystal, and the seed crystal after described seeding, turn brilliant process persistently rotates, and
Proceed by programmed cooling growth, the different phase according to growth controls different rate of temperature fall, including as follows：
At the 4-1) initial stage, rate of temperature fall is to lower the temperature 0.1 DEG C for every 3 days；
4-2) mid-term, rate of temperature fall is to lower the temperature 0.1 DEG C for every 2 days；
In the 4-3) later stage, rate of temperature fall is to lower the temperature 0.1 DEG C for every 1 day；
In 4-3) latter stage, rate of temperature fall is to lower the temperature 0.1 DEG C for every 0.5 day；
Described step 5) in, the method for described post processing is：Stop described step 4) in programmed cooling growth, to described mother solution
Add with described saturation mother solution mutually synthermal paraffin oil in bottle, the saturation mother solution constant speed of bottom is extracted out simultaneously, remain described
Total amount of liquid in mother liquid multi-cavity bottle is constant, all replaces with described paraffin oil to described saturation mother solution, grows through programmed cooling and is formed
Big crystal be immersed in described paraffin oil；
Described step 6) in, the method for described hot crystal conversion is：Will be through step 5) reprocessed described mother liquid multi-cavity bottle taking-up, put
Enter to be heated to 155 DEG C in oil bath, cooling；The rate of temperature fall in heating rate and cooling procedure in described heating process is
10 DEG C per hour.
2. the environmental protection and energy saving growing method of large scale bulk information Store ferroelectric single crystal according to claim 1, it is special
Levy and be：Described step 2) in, the step of described seeding is：
2-1) described mother liquid multi-cavity bottle is connected with seed crystal, described seed crystal Height Adjustable；
2-2) described seed crystal is dropped at 5mm～20mm at the liquid level of described saturation mother solution, stand 5～10 minutes, make
Described seed crystal be warming up to consistent with the temperature of saturation mother solution；
2-2) described seed crystal is dropped to the centre position of the liquid level of described saturation mother solution, standing.
3. the environmental protection and energy saving growing method of large scale bulk information Store ferroelectric single crystal according to claim 1, it is special
Levy and be：Described step 3) in, described turn of brilliant step is：Described mother liquid multi-cavity bottle is connected with seed crystal, after processing through described seeding, opens
Open the rotary apparatuss stated in monocrystalline temperature chamber, rotating speed is 20～30 turns/min；Setting program is to be alternately rotated counterclockwise clockwise,
Stop 10 seconds～15 seconds between replacing along reciprocal cross.
4. the environmental protection and energy saving growing method of large scale bulk information Store ferroelectric single crystal according to claim 1, it is special
Levy and be：The top of described mother liquid multi-cavity bottle adopts paraffin oil fluid-tight.
5. the environmental protection and energy saving growing method of large scale bulk information Store ferroelectric single crystal according to claim 1, it is special
Levy and be：Described temperature chamber and mother liquid multi-cavity bottle are glass material, and the volume of described temperature chamber is 30～100 liters, described mother liquid multi-cavity bottle
Size be 1～10 liter.
6. the environmental protection and energy saving growing method of large scale bulk information Store ferroelectric single crystal according to claim 1, it is special
Levy and be：It is provided with temperature-controlling system, described temperature-controlling system is Electrothermal ring water bath heating device, heating in described monocrystalline temperature chamber
Power is 0.5kw～5kw.
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| CN105862120B (en) * | 2016-03-29 | 2018-06-01 | 东南大学 | A kind of growing method of large scale information storage monocrystal |
| CN106192012B (en) * | 2016-09-07 | 2018-11-30 | 哈尔滨理工大学 | A kind of high dielectric constant diisopropylamine nitrate organic crystal and its growing method |
| CN109610005B (en) * | 2018-12-11 | 2020-11-17 | 武汉光谷信息光电子创新中心有限公司 | Proton exchange furnace and using method thereof |
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