CN103993355A - Preparation method of CuInS2 monocrystals and preparation device of CuInS2 monocrystals - Google Patents
Preparation method of CuInS2 monocrystals and preparation device of CuInS2 monocrystals Download PDFInfo
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- CN103993355A CN103993355A CN201410193673.3A CN201410193673A CN103993355A CN 103993355 A CN103993355 A CN 103993355A CN 201410193673 A CN201410193673 A CN 201410193673A CN 103993355 A CN103993355 A CN 103993355A
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Abstract
The invention discloses a preparation method of CuInS2 monocrystals, comprising the following steps: uniformly mixing high-purity raw material powders Cu, In and S; vacuum packaging the mixed high-purity raw material powders into a reactor, and preparing a CuInS2 polycrystalline ingot by a single-temperature rocking-furnace mixed crystal method to be used as a raw material for growth of follow-up seeds and monocrystals, preparing a small CuInS2 monocrystalline ingot by a Bridgman method to be used as seeds; and finally growing large CuInS2 monocrystalline ingot by a magnetic field and a seed-assisted travelling heat method. The invention also discloses a preparation device of CuInS2 monocrystals. The preparation device is composed of a reaction vessel, a vertical furnace and an applied magnetic field system. According to the invention, the problem that growth rate is slow when CuInS2 crystals are prepared by a conventional travelling heat method is improved; growth rate of crystals and utilization rate of crystals are raised; preparation technological problems of large-diameter monocrystals CuInS2 are solved effectively; and theoretical and practical foundations are provided for preparation of CuInS2 thin film solar cells with excellent performance.
Description
Technical field
The present invention relates to a kind of crystal material growth technique and device, particularly relate to a kind of CuInS
2crystal growth technique and device, be applied to the technical field of function materials of thin film solar cell.
Background technology
Along with the fast development of human society modernization construction, the fossil fuel resources such as coal, oil, Sweet natural gas are exhausted nearly, and can produce a large amount of obnoxious flavoures in the time using these fossil resources, cause environment for human survival to worsen.Current photovoltaic solar is as new and renewable sources of energy, is one of sustainable, free of contamination energy few in number.The solar energy resources of China is abundant, develops sun power, to saving conventional energy resources and conservation of nature environment, has very important meaning.
Compared with crystal silicon solar energy battery, thin-film solar cells has obvious technical superiority and cost advantage, is popular development trend.Wherein CuInS
2the energy gap of crystal is 1.5eV left and right, approaches the best energy gap of solar cell.Unijunction CuInS
2the theoretical transformation of homojunction solar cell is most effective reaches 32%, in all solar cells, is the highest.And CuInS
2not containing any toxic ingredient, environmental sound.
In order to prepare efficient CuInS
2base thin film solar battery, need to obtain high-quality absorption layer, best component and grain-size, and be appreciated that inherence/external defect and the impact of doping on its photoelectric properties, it is also understood that simultaneously and control self compensation effect, these researchs all need to prepare high-quality monocrystalline CuInS
2material.Preparation CuInS
2the method of single crystal is a lot, has pressure sintering, In solvent auxiliary moving heating method, the gaseous-phase transmission method that iodine is transfer agent, vertical bridgman method and gradient freeze method etc.Wherein, pressure sintering and gradient freeze method can only be prepared CuInS
2polycrystalline ingot, and with it study the phase transformation law of CuInS and as raw material make thin-film solar cells.The speed of vertical bridgman method growing crystal, but the crystal forming rate of the method is lower, and gained crystal ingot is often multiple crystal grain compositions.In solvent auxiliary moving heating method and I
2vapor Transport can be dodged the disturbance that in process of growth, phase transformation causes, more easily obtains the CuInS of monocrystalline
2crystal ingot, but their speed of growth is slower, makes it in industrial production, be difficult to application, therefore needs to find a kind of CuInS of high-effect high-quality
2method for preparing single crystal.
Summary of the invention
In order to solve prior art problem, the object of the invention is to overcome the deficiency that prior art exists, a kind of CuInS is provided
2the preparation method of single crystal and CuInS
2single crystal preparation facilities, so that speed and higher efficiency obtain high-quality large scale CuI nS faster
2single crystal, and be the CuInS that processability is superior
2thin-film solar cells provides theory and practice basis.
Create object for reaching foregoing invention, the present invention adopts following technical proposals:
A kind of CuInS
2the preparation method of single crystal, comprises the following steps:
A. adopt pure reaction vessel dry for standby; As the preferred technical scheme of the present invention, the quartz crucible that employing purity reaches 5N is as reaction vessel, quartz crucible is placed in to acetone soln immersion and approaches 12 hours, and repeatedly clean and remove remaining acetone with deionized water, again quartz crucible is placed in to wang aqueous solution immersion and approaches 24 hours, and repeatedly clean and remove remaining chloroazotic acid with deionized water, and then soak and approach 15 minutes in the HF solution that is 5% in mass concentration, and repeatedly rinse with deionized water, be finally placed in baking oven dry for standby;
B. the reaction vessel inwall in above-mentioned steps a is plated to carbon, on reaction vessel inwall, plate one deck carbon film, then by the reaction vessel dry for standby of processing through plating carbon; As the preferred technical scheme of the present invention, the reaction vessel in above-mentioned steps a is packed in plating carbon boiler tube, make to plate reaction vessel in carbon boiler tube at least to 10
-1~ 10
-3vacuum environment under, make to plate carbon stove and be at least warming up to 950 ~ 1100 DEG C of baking reaction vessels, pass into subsequently alcohol carbon is plated in the surface of reaction vessel, after plating carbon, burn the carbon-coating at the uncovered edge of reaction vessel afterbody with oxyhydrogen flame, and with deionized water wash reaction vessels surface repeatedly, finally the reaction vessel of processing is placed in to vacuum drying oven dry for standby;
C. press CuInS
2the stoichiometry of crystal is compared to feed composition proportioning, keep the S powder in raw material excessive, after the raw material powder of Cu, In and tri-kinds of components of S is fully mixed, pack in first reaction vessel through the processing of above-mentioned steps b plating carbon, again reaction vessel is sealed and vacuumized, again reaction vessel is put in people's constant temperature vertical furnace, and control constant temperature vertical furnace with setting speed be slowly warmed up to target temperature and insulation, raw material is fully melted, and then be cooled to target temperature insulation with setting speed, finally constant temperature vertical furnace is as cold as to room temperature, obtains CuInS
2polycrystalline ingot; As the preferred technical scheme of the present invention, after Cu, In and tri-kinds of raw material powders of S are fully mixed, pack in reaction vessel, then by reaction vessel sealing, and vacuumize at least to 10
-3pa, again reaction vessel is put in people's constant temperature vertical furnace, and control constant temperature vertical furnace and be slowly warmed up to and approach 200 DEG C to approach the speed of 10 DEG C/h, controlling subsequently constant temperature vertical furnace is warmed up to and approaches after 1150 DEG C and be incubated 2h to approach the speed of 40 DEG C/h again, raw material is fully melted, and then be cooled to and approach after 700 DEG C and be incubated 10h by the speed that approaches 30 DEG C/h, finally constant temperature vertical furnace is as cold as to room temperature, obtain CuInS
2polycrystalline ingot;
D. the CuInS preparing in above-mentioned steps c that surface has been ground to corrosion and cleaned
2polycrystalline ingot is pulverized, and packs in second reaction vessel through the processing of above-mentioned steps b plating carbon, again to the CuInS in reaction vessel
2polycrystal powder continues to add extra S powder, then reaction vessel is sealed and taken out very, then reaction vessel is put into the high-temperature constant warm area on the top of the sectional vertical stove with two flat-temperature zones, controls subsequently sectional vertical stove and is raised to target temperature insulation, makes CuInS
2polycrystal powder fully melts, then make reaction vessel decline in sectional vertical furnace chamber with setting speed, reaction vessel is declined and middle transition warm area through high-temperature constant warm area and cryogenic thermostat district after, enter cryogenic thermostat district completely, again so that cryogenic thermostat district cools to target temperature insulation, finally the temperature of sectional vertical stove is down to room temperature, thereby in reaction vessel, obtains the CuInS in (112) crystal orientation
2seed crystal, as the preferred technical scheme of the present invention, CuInS will be housed
2the reaction vessel sealing of polycrystal powder, and vacuumize at least to 10
-3pa, again reaction vessel is put into the high-temperature constant warm area of sectional vertical stove, set high-temperature constant warm area temperature and approach 1150 DEG C, and set cryogenic thermostat district temperature and approach 1060 DEG C, the thermograde of simultaneously controlling middle transition warm area approaches 9 DEG C/cm, after sectional vertical stove being raised to approach the speed of 40 DEG C/h subsequently to the temperature of setting, insulation approaches 2h, then make reaction vessel to approach speed uniform descent in sectional vertical furnace chamber of 1mm/h, reaction vessel is declined through also entering cryogenic thermostat district after middle transition warm area completely, be incubated 10h to approach after the speed of 4 DEG C/h cools to cryogenic thermostat district to approach 960 DEG C again, and then by the speed that approaches 10 DEG C/h by the greenhouse cooling in cryogenic thermostat district to approaching 700 DEG C, finally the temperature of sectional vertical stove is down to room temperature, thereby obtain the CuInS in (112) crystal orientation
2seed crystal,
E. by the CuInS preparing in above-mentioned steps c
2polycrystalline ingot and the CuInS preparing in above-mentioned steps d
2seed crystal cuts respectively, the corrosion of polishing and bromine methyl alcohol, then cleans, dry, completes CuInS
2polycrystalline ingot and CuInS
2the pre-treatment of seed crystal, then by the CuInS in pretreated (112) crystal orientation
2seed crystal is put into the 3rd reaction container bottom through the processing of above-mentioned steps b plating carbon, and and seed crystal bag close contact, at CuInS
2above seed crystal, put into In powder and make solvent, then put into pretreated CuInS on In powder
2polycrystalline ingot, again reaction vessel is sealed and vacuumized, then reaction vessel is put into sectional vertical stove, sectional vertical stove and accessory has two flat-temperature zones, be respectively the high-temperature constant warm area that is positioned at sectional vertical stove top and the cryogenic thermostat district that is positioned at sectional vertical stove bottom, between high-temperature constant warm area and cryogenic thermostat district, be middle transition warm area, at initial growth CuInS
2when single crystal, make the CuInS in reaction vessel
2polycrystalline ingot in high-temperature constant warm area, makes the CuInS in reaction vessel completely
2lower part of seed crystal in high-temperature constant warm area in, make upper part of solvent of the In powder in reaction vessel in high-temperature constant warm area simultaneously, then heat up and make the temperature of high-temperature constant warm area reach target temperature insulation, also apply rotatingfield at middle transition warm area simultaneously, then make reaction vessel increase, enough seed crystals are melted, then change the travel direction of reaction vessel, reaction vessel is declined, and make the whole CuInS in reaction vessel
2polycrystalline ingot moves past middle transition warm area downwards, finally the temperature of sectional vertical stove is down to room temperature, thereby obtains CuInS in reaction vessel
2single crystal; As the preferred technical scheme of the present invention, by the CuInS in pretreated (112) crystal orientation
2seed crystal is put into reaction container bottom, and and seed crystal bag close contact, at CuInS
2above seed crystal, put into successively In powder and CuInS
2polycrystalline ingot, then by reaction vessel sealing, and vacuumize at least to 10
-5pa, then reaction vessel is put into sectional vertical stove, at initial growth CuInS
2when single crystal, the thermograde of controlling the middle transition warm area of sectional vertical stove approaches 40 DEG C/cm, then heat up with the speed that approaches 20 DEG C/h, after making the temperature of high-temperature constant warm area reach 920 DEG C and be incubated 1h, apply rotatingfield to middle transition warm area, then make reaction vessel increase simultaneously, enough seed crystals are melted, change again the travel direction of reaction vessel, reaction vessel is declined with the speed of 1cm/d, then make the whole CuInS in reaction vessel
2polycrystalline ingot moves past middle transition warm area downwards, finally the temperature of sectional vertical stove is down to room temperature, thereby obtains CuInS
2single crystal.
Implement CuInS of the present invention
2the preparation method's of single crystal CuInS
2single crystal preparation facilities, formed by reaction vessel and vertical furnace, reaction vessel is arranged at the inside of vertical furnace, reaction vessel can carry out the lifting moving of above-below direction in vertical furnace along the internal chamber of body of heater, vertical furnace is the sectional type vertical furnace with two flat-temperature zones, be positioned at sectional vertical stove upper chamber and form high-temperature constant warm area, be positioned at sectional vertical stove bottom furnace chamber and form cryogenic thermostat district, between high-temperature constant warm area and cryogenic thermostat district, it is middle transition warm area, middle transition warm area is formed the thermograde heating up from bottom to top by heating member, outside at heating member is also provided with magnetic field generator, apply rotatingfield to middle transition warm area, reaction vessel is from top to bottom successively by seeding section, necking segment and three sections of one of crystal initial growth section are formed by connecting, wherein the cross-sectional dimension of seeding section is greater than the cross-sectional dimension of crystal initial growth section, in crystal initial growth section, pack CuInS into
2seed crystal, packs solvent indium powder in necking segment, in seeding section, pack CuInS into
2polycrystalline.
Above-mentioned reaction vessel preferably adopts quartz crucible.
The present invention compared with prior art, has following apparent outstanding substantive distinguishing features and remarkable advantage:
1. the present invention uses magnetic field and the auxiliary mobile heating method of seed crystal to prepare large scale CuI nS
2method, improved conventional mobile heating method and prepared CuInS
2when crystal, the problem that the speed of growth is slower has improved the speed of growth of crystal and the utilization ratio of crystal simultaneously;
2. the present invention evenly mixes high pure raw material powder Cu, In, S, and vacuum seal packs reactor into, and has prepared CuInS by the method for single warm area rocking furnace mixed crystal
2polycrystalline ingot, makes the raw material of follow-up seed crystal and single crystal growing, then prepares little CuInS by Bridgman method
2single crystal ingot is made seed crystal, finally with the auxiliary mobile heating method of magnetic field and the seed crystal large CuInS that grows
2monocrystalline, effectively solves major diameter single crystal CuInS
2preparation technology's problem, and be the CuInS that processability is superior
2thin film solar cell provides the basis of theory and practice.
Brief description of the drawings
Fig. 1 is preferred embodiment of the present invention CuInS
2the structural representation of single crystal preparation facilities.
Embodiment
Details are as follows for the preferred embodiments of the present invention:
In the present embodiment, referring to Fig. 1, a kind of CuInS
2single crystal preparation facilities, formed by reaction vessel 5 and vertical furnace, reaction vessel 5 is arranged at the inside of vertical furnace, reaction vessel 5 for maximum outside diameter be the quartz crucible of Ф 30mm, reaction vessel 5 can carry out the lifting moving of above-below direction in vertical furnace along the internal chamber of body of heater 1, the direction of quartz crucible motion is the direction of arrow of v in Fig. 1, vertical furnace is the sectional type vertical furnace with two flat-temperature zones, be positioned at sectional vertical stove upper chamber and form high-temperature constant warm area, be positioned at sectional vertical stove bottom furnace chamber and form cryogenic thermostat district, between high-temperature constant warm area and cryogenic thermostat district, it is middle transition warm area 2, middle transition warm area 2 is formed the thermograde heating up from bottom to top by heating member 3, outside at heating member 3 is also provided with magnetic field generator 4, apply rotatingfield to middle transition warm area 2, reaction vessel 5 is from top to bottom successively by seeding section 6, necking segment 7 and 8 three sections of one of crystal initial growth section are formed by connecting, wherein the cross-sectional dimension of seeding section 6 is greater than the cross-sectional dimension of crystal initial growth section 8, in crystal initial growth section 8, pack CuInS into
2seed crystal, packs solvent indium powder in necking segment 7, in seeding section 6, pack CuInS into
2polycrystalline.This device is the auxiliary mobile heat growth stove in magnetic field, adopts seed crystal and add the auxiliary of magnetic field in single crystal growth process, to obtain desirable growth interface, prepares the large-sized CuInS2 single crystal of high quality.
In the present embodiment, referring to Fig. 1, a kind of CuInS
2the preparation method of single crystal, comprises the following steps:
A. adopt quartz crucible that purity reaches 5N as reaction vessel 5, quartz crucible is placed in to acetone soln to be soaked 12 hours, and repeatedly clean and remove remaining acetone with deionized water, quartz crucible being placed in to wang aqueous solution soaks 24 hours again, and repeatedly clean and remove remaining chloroazotic acid with deionized water, and then soak 15 minutes in the HF solution that is 5% in mass concentration, and repeatedly rinse with deionized water, be finally placed in baking oven dry for standby;
B. the inner wall of quartz crucible in above-mentioned steps a is plated to carbon, that is, the quartz crucible in above-mentioned steps a is packed in plating carbon boiler tube, make to plate quartz crucible in carbon boiler tube at least to 10
-3vacuum environment under, make to plate carbon stove and be at least warming up to 1100 DEG C of baking quartz crucibles, pass into subsequently alcohol carbon is plated in the surface of quartz crucible, on inner wall of quartz crucible, plate one deck carbon film, after plating carbon, burn the carbon-coating at the uncovered edge of quartz crucible afterbody with oxyhydrogen flame, and with deionized water cleaning quartz crucible surface repeatedly, finally the quartz crucible of processing is placed in to vacuum drying oven dry for standby;
C. press CuInS
2the stoichiometry of crystal is compared to feed composition proportioning, keep the S powder in raw material excessive, as extra sulphur compensation, by the raw material powder of Cu, In and tri-kinds of components of S after ball milling fully mixes, pack in first quartz crucible through the processing of above-mentioned steps b plating carbon, again quartz crucible is sealed, and be evacuated to 10
-3pa, again quartz crucible is put in people's constant temperature vertical furnace, and control constant temperature vertical furnace and be slowly warmed up to 200 DEG C with the speed of 10 DEG C/h, controlling subsequently constant temperature vertical furnace is warmed up to after 1150 DEG C with the speed of 40 DEG C/h and is incubated 2h again, raw material is fully melted, and then be cooled to after 700 DEG C and be incubated 10h by the speed of 30 DEG C/h, finally constant temperature vertical furnace is as cold as to room temperature, obtain CuInS
2polycrystalline ingot;
D. the CuInS preparing in above-mentioned steps c that surface has been ground to corrosion and cleaned
2polycrystalline ingot is pulverized, and packs in second quartz crucible through the processing of above-mentioned steps b plating carbon, to the CuInS in quartz crucible
2in polycrystal powder, continue to add extra S powder, as extra sulphur compensation, CuInS will be housed
2the quartz crucible sealing of polycrystal powder, and be evacuated to 10
-4pa, then quartz crucible is put into the high-temperature constant warm area on the top of the sectional vertical stove with two flat-temperature zones, set 1150 DEG C of high-temperature constant warm area temperature, and set 1060 DEG C of cryogenic thermostat district temperature, control the 9 DEG C/cm of thermograde of middle transition warm area 2 simultaneously, after sectional vertical stove being raised to the temperature of setting with the speed of 40 DEG C/h subsequently, be incubated 2h, make CuInS
2polycrystal powder fully melts, then make speed uniform descent in sectional vertical furnace chamber of quartz crucible with 1mm/h, quartz crucible is declined and middle transition warm area 2 through high-temperature constant warm area and cryogenic thermostat district after, enter cryogenic thermostat district completely, after making cryogenic thermostat district cool to 960 DEG C with the speed of 4 DEG C/h again, be incubated 10h, and then by the speed of 10 DEG C/h by the greenhouse cooling to 700 DEG C in cryogenic thermostat district, finally the temperature of sectional vertical stove is down to room temperature, thereby obtains the CuInS in (112) crystal orientation
2seed crystal;
E. by the CuInS preparing in above-mentioned steps c
2polycrystalline ingot and the CuInS preparing in above-mentioned steps d
2the bromine methyl alcohol corrosion that seed crystal cuts respectively, polishing and concentration are 5%, then cleans, dry, completes CuInS
2polycrystalline ingot and CuInS
2the pre-treatment of seed crystal, then by the CuInS in pretreated (112) crystal orientation
2seed crystal is put into the 3rd the quartz crucible bottom through the processing of above-mentioned steps b plating carbon, and and seed crystal bag close contact, at CuInS
2above seed crystal, put into In powder and make solvent, then put into pretreated CuInS on In powder
2polycrystalline ingot, then by quartz crucible sealing, and be evacuated to 10
-5pa, then quartz crucible is put into sectional vertical stove, sectional vertical stove and accessory has two flat-temperature zones, be respectively the high-temperature constant warm area that is positioned at sectional vertical stove top and the cryogenic thermostat district that is positioned at sectional vertical stove bottom, between high-temperature constant warm area and cryogenic thermostat district, be middle transition warm area 2, at initial growth CuInS
2when single crystal, make the CuInS in quartz crucible
2polycrystalline ingot in high-temperature constant warm area, makes the CuInS in quartz crucible completely
2lower part of seed crystal in high-temperature constant warm area in, make upper part of solvent of the In powder in quartz crucible in high-temperature constant warm area simultaneously, and control the 40 DEG C/cm of thermograde of the middle transition warm area 2 of sectional vertical stove, then heat up with the speed of 20 DEG C/h, the temperature that makes high-temperature constant warm area is after 920 DEG C and is incubated 1h, also apply rotatingfield at middle transition warm area 2 simultaneously, then make quartz crucible increase, enough seed crystals are melted, change again the travel direction of quartz crucible, quartz crucible is declined with the speed of 1cm/d, make the whole CuInS in quartz crucible
2polycrystalline ingot moves past magnetic field environment downwards, finally the temperature of sectional vertical stove is down to room temperature, thereby obtains CuInS in quartz crucible
2single crystal.The present embodiment is put quartz crucible in the auxiliary mobile heating furnace of people's vertical magnetic field, and while starting to grow, indium solvent is positioned at stove highest temperature centerline, start after rotatingfield, by the quartz crucible suitable distance that rises, melt enough seed crystals, decline again, move past whole polycrystalline ingot, thereby make CuInS
2single crystal.
The present embodiment adopts finite element method for simulating different physical, to the CuInS with Bridgman method growth
2the CuInS of mobile heating method growth for seed crystal and polycrystalline ingot
2single crystal.Considered the heat exchanging process such as thermal conduction, convection current, radiation, the processing parameters such as thermograde, quartz crucible shape and translational speed, lifting/lowering temperature speed are to crystal thermal stress distribution, the impact of component fractional condensation and growth interface pattern.
By reference to the accompanying drawings the embodiment of the present invention is illustrated above, but the invention is not restricted to above-described embodiment, can also make multiple variation according to the object of innovation and creation of the present invention, the change made under all spirit according to technical solution of the present invention and principle, modification, substitute, combination, simplify, all should be equivalent substitute mode, as long as goal of the invention according to the invention, only otherwise deviate from CuInS of the present invention
2the preparation method of single crystal and CuInS
2the know-why of single crystal preparation facilities and inventive concept, all belong to protection scope of the present invention.
Claims (8)
1. a CuInS
2the preparation method of single crystal, is characterized in that, comprises the following steps:
A. adopt pure reaction vessel dry for standby;
B. the reaction vessel inwall in above-mentioned steps a is plated to carbon, on reaction vessel inwall, plate one deck carbon film, then by the reaction vessel dry for standby of processing through plating carbon;
C. press CuInS
2the stoichiometry of crystal is compared to feed composition proportioning, keep the S powder in raw material excessive, after the raw material powder of Cu, In and tri-kinds of components of S is fully mixed, pack in first reaction vessel through the processing of above-mentioned steps b plating carbon, again reaction vessel is sealed and vacuumized, again reaction vessel is put in people's constant temperature vertical furnace, and control constant temperature vertical furnace with setting speed be slowly warmed up to target temperature and insulation, raw material is fully melted, and then be cooled to target temperature insulation with setting speed, finally constant temperature vertical furnace is as cold as to room temperature, obtains CuInS
2polycrystalline ingot;
D. the CuInS preparing in above-mentioned steps c that surface has been ground to corrosion and cleaned
2polycrystalline ingot is pulverized, and packs in second reaction vessel through the processing of above-mentioned steps b plating carbon, again to the CuInS in reaction vessel
2polycrystal powder continues to add extra S powder, then reaction vessel is sealed and taken out very, then reaction vessel is put into the high-temperature constant warm area on the top of the sectional vertical stove with two flat-temperature zones, controls subsequently sectional vertical stove and is raised to target temperature insulation, makes CuInS
2polycrystal powder fully melts, then make reaction vessel decline in sectional vertical furnace chamber with setting speed, reaction vessel is declined and middle transition warm area through high-temperature constant warm area and cryogenic thermostat district after, enter cryogenic thermostat district completely, again so that cryogenic thermostat district cools to target temperature insulation, finally the temperature of sectional vertical stove is down to room temperature, thereby in reaction vessel, obtains the CuInS in (112) crystal orientation
2seed crystal;
E. by the CuInS preparing in above-mentioned steps c
2polycrystalline ingot and the CuInS preparing in above-mentioned steps d
2seed crystal cuts respectively, the corrosion of polishing and bromine methyl alcohol, then cleans, dry, completes CuInS
2polycrystalline ingot and CuInS
2the pre-treatment of seed crystal, then by the CuInS in pretreated (112) crystal orientation
2seed crystal is put into the 3rd reaction container bottom through the processing of above-mentioned steps b plating carbon, and and seed crystal bag close contact, at CuInS
2above seed crystal, put into In powder and make solvent, then put into pretreated CuInS on In powder
2polycrystalline ingot, again reaction vessel is sealed and vacuumized, then reaction vessel is put into sectional vertical stove, sectional vertical stove and accessory has two flat-temperature zones, be respectively the high-temperature constant warm area that is positioned at sectional vertical stove top and the cryogenic thermostat district that is positioned at sectional vertical stove bottom, between high-temperature constant warm area and cryogenic thermostat district, be middle transition warm area, at initial growth CuInS
2when single crystal, make the CuInS in reaction vessel
2polycrystalline ingot in high-temperature constant warm area, makes the CuInS in reaction vessel completely
2lower part of seed crystal in high-temperature constant warm area in, make upper part of solvent of the In powder in reaction vessel in high-temperature constant warm area simultaneously, then heat up and make the temperature of high-temperature constant warm area reach target temperature insulation, also apply rotatingfield at middle transition warm area simultaneously, then make reaction vessel increase, enough seed crystals are melted, then change the travel direction of reaction vessel, reaction vessel is declined, and make the whole CuInS in reaction vessel
2polycrystalline ingot moves past middle transition warm area downwards, finally the temperature of sectional vertical stove is down to room temperature, thereby obtains CuInS in reaction vessel
2single crystal.
2. CuInS according to claim 1
2the preparation method of single crystal, is characterized in that: in above-mentioned steps d, CuInS will be housed
2the reaction vessel sealing of polycrystal powder, and vacuumize at least to 10
-3pa, again reaction vessel is put into the high-temperature constant warm area of sectional vertical stove, set high-temperature constant warm area temperature and approach 1150 DEG C, and set cryogenic thermostat district temperature and approach 1060 DEG C, the thermograde of simultaneously controlling middle transition warm area approaches 9 DEG C/cm, after sectional vertical stove being raised to approach the speed of 40 DEG C/h subsequently to the temperature of setting, insulation approaches 2h, then make reaction vessel to approach speed uniform descent in sectional vertical furnace chamber of 1mm/h, reaction vessel is declined through also entering cryogenic thermostat district after middle transition warm area completely, be incubated 10h to approach after the speed of 4 DEG C/h cools to cryogenic thermostat district to approach 960 DEG C again, and then by the speed that approaches 10 DEG C/h by the greenhouse cooling in cryogenic thermostat district to approaching 700 DEG C, finally the temperature of sectional vertical stove is down to room temperature, thereby obtain the CuInS in (112) crystal orientation
2seed crystal.
3. according to CuInS described in claim 1 or 2
2the preparation method of single crystal, is characterized in that: in above-mentioned steps e, by the CuInS in pretreated (112) crystal orientation
2seed crystal is put into reaction container bottom, and and seed crystal bag close contact, at CuInS
2above seed crystal, put into successively In powder and CuInS
2polycrystalline ingot, then by reaction vessel sealing, and vacuumize at least to 10
-5pa, then reaction vessel is put into sectional vertical stove, at initial growth CuInS
2when single crystal, the thermograde of controlling the middle transition warm area of sectional vertical stove approaches 40 DEG C/cm, then heat up with the speed that approaches 20 DEG C/h, after making the temperature of high-temperature constant warm area reach 920 DEG C and be incubated 1h, apply rotatingfield to middle transition warm area, then make reaction vessel increase simultaneously, enough seed crystals are melted, change again the travel direction of reaction vessel, reaction vessel is declined with the speed of 1cm/d, then make the whole CuInS in reaction vessel
2polycrystalline ingot moves past middle transition warm area downwards, finally the temperature of sectional vertical stove is down to room temperature, thereby obtains CuInS
2single crystal.
4. according to CuInS described in claim 1 or 2
2the preparation method of single crystal, is characterized in that: in above-mentioned steps c, after Cu, In and tri-kinds of raw material powders of S are fully mixed, packs in reaction vessel, then by reaction vessel sealing, and vacuumize at least to 10
-3pa, again reaction vessel is put in people's constant temperature vertical furnace, and control constant temperature vertical furnace and be slowly warmed up to and approach 200 DEG C to approach the speed of 10 DEG C/h, controlling subsequently constant temperature vertical furnace is warmed up to and approaches after 1150 DEG C and be incubated 2h to approach the speed of 40 DEG C/h again, raw material is fully melted, and then be cooled to and approach after 700 DEG C and be incubated 10h by the speed that approaches 30 DEG C/h, finally constant temperature vertical furnace is as cold as to room temperature, obtain CuInS
2polycrystalline ingot.
5. according to CuInS described in claim 1 or 2
2the preparation method of single crystal, is characterized in that: in above-mentioned steps a, the quartz crucible that employing purity reaches 5N, as reaction vessel, is placed in acetone soln immersion by quartz crucible and approaches 12 hours, and repeatedly clean and remove remaining acetone with deionized water; Again quartz crucible is placed in to wang aqueous solution immersion and approaches 24 hours, and repeatedly clean and remove remaining chloroazotic acid with deionized water; And then soak and approach 15 minutes in the HF solution that is 5% in mass concentration, and repeatedly rinse with deionized water; Finally be placed in baking oven dry for standby.
6. according to CuInS described in claim 1 or 2
2the preparation method of single crystal, is characterized in that: in above-mentioned steps b, the reaction vessel in above-mentioned steps a is packed in plating carbon boiler tube, make to plate reaction vessel in carbon boiler tube at least to 10
-1~ 10
-3vacuum environment under, make to plate carbon stove and be at least warming up to 950 ~ 1100 DEG C of baking reaction vessels, pass into subsequently alcohol carbon is plated in the surface of reaction vessel, after plating carbon, burn the carbon-coating at the uncovered edge of reaction vessel afterbody with oxyhydrogen flame, and with deionized water wash reaction vessels surface repeatedly, finally the reaction vessel of processing is placed in to vacuum drying oven dry for standby.
One kind implement the claims 1 described in CuInS
2the preparation method's of single crystal CuInS
2single crystal preparation facilities, formed by reaction vessel (5) and vertical furnace, described reaction vessel (5) is arranged at the inside of described vertical furnace, described reaction vessel (5) can carry out the lifting moving of above-below direction in described vertical furnace along the internal chamber of body of heater (1), it is characterized in that: described vertical furnace is the sectional type vertical furnace with two flat-temperature zones, be positioned at sectional vertical stove upper chamber and form high-temperature constant warm area, be positioned at sectional vertical stove bottom furnace chamber and form cryogenic thermostat district, between high-temperature constant warm area and cryogenic thermostat district, be middle transition warm area (2), described middle transition warm area (2) is formed the thermograde heating up from bottom to top by heating member (3), also be provided with magnetic field generator (4) in the outside of described heating member (3), apply rotatingfield to described middle transition warm area (2), described reaction vessel (5) is from top to bottom successively by seeding section (6), (8) three sections of one of necking segment (7) and crystal initial growth section are formed by connecting, the cross-sectional dimension of wherein said seeding section (6) is greater than the cross-sectional dimension of described crystal initial growth section (8), in described crystal initial growth section (8), pack CuInS into
2seed crystal, packs solvent indium powder in described necking segment (7), in described seeding section (6), pack CuInS into
2polycrystalline.
8. CuInS according to claim 7
2single crystal preparation facilities, is characterized in that: described reaction vessel (5) is quartz crucible.
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| CN105648520A (en) * | 2016-03-18 | 2016-06-08 | 江苏中电振华晶体技术有限公司 | Seed crystal capable of reinforcing seeding temperature signals and seeding method thereof |
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| CN103993355B (en) | 2016-11-02 |
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