CN101210346B - Horizontal zone melting method for growing tellurium zinc cadmium single-crystal - Google Patents
Horizontal zone melting method for growing tellurium zinc cadmium single-crystal Download PDFInfo
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Abstract
The invention relates to a device and a method for horizontal zone-melting growth of CdZnTe single crystal. The device comprises a furnace body, a quartz long crystal tube, a long zone-melting boat and a Cd source boat, wherein the furnace body comprises a Cd source furnace and a horizontal zone-melting long crystal furnace consisting of a plurality of sequentially arranged small furnaces; the quartz long crystal tube with the Cd source boat and the zone-melting long boat arranged therein is arranged in the furnace body; and the zone-melting long boat is provided with a head neck and a tail neck. The method for horizontal zone-melting growth of CdZnTe single crystal comprises the following steps of: disposing Cd, Zn and a seed crystal in the zone-melting long boat, disposing Cd in the Cd source boat, arranging the zone-melting long boat and the Cd source boat in the quartz long crystal tube, sealing the quartz long crystal tube, placing in the horizontal zone-melting furnace body, heating to synthesize a CdZnTe ingot, refining the CdZnTe ingot by zone-melting purification to improve the purity of the CdZnTe ingot, and growing CdZnTe single crystal under induction of the seed crystal. The CdZnTe single crystal produced by the device and the method of the invention has high yield and high purity, and fully meets the application requirement.
Description
Technical field
The present invention relates to the preparation of monocrystalline, particularly the zone-refine of tellurium zinc cadmium and the growth method of Te-Zn-Cd monocrystal in the II-VI family broadband semiconductor compound.
Background technology
Rockwell international scientific center utilized molecular beam epitaxy to produce P-on-N heterojunction flush type HgCdTe LONG WAVE INFRARED focus plane detector array (LWIR FPA) in 1992, and its performance has been represented the highest level of LONG WAVE INFRARED focus planardetector.Under 77K, the average R of HgCdTe.A is up to 310 Ω cm
2(λ
C=10 μ, A=50 μ x50 μ), (seeing Journal of ElectronicMaterials, Vol.22, No.8,1993 pp1049～1053).Cd
0.96Zn
0.04Te (211) B substrate and HgCdTe lattice parameter just in time are complementary, and can grow the HgCdTe epitaxial film of low-dislocation-density, if there is not qualified CdZnTe substrate just can not obtain good HgCdTe LONG WAVE INFRARED focus plane detector array.Medium wave and short-wave infrared focus plane detector array (MWIR and SWIR FPA) also are in the world at present sensitive infrared eyes, and their substrate also must be the CdZnTe monocrystal material.Therefore the CdZnTe substrate becomes the requisite critical material of manufacturing HgCdTe infrared focal plane detector.
The Cd of X=0.1～0.2
1-XZn
XTe is an excellent material of making X ray, gamma-rays and αShe Xiantanceqi, its advantage is the energy resolution height, response speed is fast, power consumption is little, be suitable for working under the room temperature, can have portable function after making the miniaturization of focal plane array detector, this just causes field personnel's such as medical instrument, nuclear radiation detection technology and astrophysics extensive interest very soon.
No matter do the epitaxial substrate of HgCdTe, still make high energy detector, all need highly purified Te-Zn-Cd monocrystal body.The growing tellurium zinc cadmium single-crystal material is to adopt Bridgman (Bridgman) method in the prior art, though this method adopts the high pure raw materials of 7N (99.99999%), but the purity of the Te-Zn-Cd monocrystal that obtains tends to descend to some extent, causes Te-Zn-Cd monocrystal body purity main reasons for decrease to have two: the one, and when batching, have and introduce some impurity contaminations artificially; The 2nd, the brilliant container of various length is as the low pollution that causes of purity of quartz, graphite, boron nitride etc.Impurity concentration was wayward when this just made the Te-Zn-Cd monocrystal body of Bridgman (Bridgman) method growth of vertical or level, and the purity of Te-Zn-Cd monocrystal body is difficult to guarantee, and then has a strong impact on the product qualified rate of this monocrystal material.In addition, application number is to propose with the vapor transportation method CdZnTe to be purified in 200510023575.6 the Chinese invention patent " detector with the method for purification and the device thereof of CdTe, ZnTe and CdZnTe raw material ", its shortcoming is, product is the polycrystal of accurate chemical ratio, can't be used for substrate material, the speed that is exactly vapor transportation in addition is slower, and then making tellurium zinc cadmium polycrystalline efficient is low, is not suitable for using in industry.
Summary of the invention
The objective of the invention is to overcome deficiency of the prior art, a kind of horizontal zone melting growing tellurium zinc cadmium Cd is provided
1-xZn
xThe apparatus and method of Te monocrystalline, the zone-refine and the single crystal growing of tellurium zinc cadmium are combined, before growing single-crystal, carry out zone-refine repeatedly earlier, remove the impurity on artificial pollution impurity and the long brilliant container, utilize the seed crystal guiding to grow Te-Zn-Cd monocrystal then, the purity of the Te-Zn-Cd monocrystal that grows is all higher than the purity of the Te-Zn-Cd monocrystal of any Bridgman method growth, and stable.
Technical scheme of the present invention:
A kind of horizontal zone melting growing tellurium zinc cadmium Cd
1-xZn
xThe device of Te monocrystalline, this device comprise body of heater, quartzy long brilliant pipe, the molten long brilliant boat in district and cadmium source boat:
Described body of heater comprises end to end cadmium source stove and the long brilliant stove of horizontal zone melting that temperature is controlled respectively, and the long brilliant stove of level is made up of a plurality of bogeys that are arranged in order; Be placed with quartzy long brilliant pipe in the body of heater, be provided with the molten long brilliant boat in cadmium Yuan Zhouhe district in the long brilliant pipe of this quartz, cadmium source boat is positioned at the temperature controlled region of cadmium source stove, and the molten long brilliant boat in district is positioned at the temperature controlled region of the molten long brilliant stove in district; The molten long brilliant boat in described district is provided with head necking down and afterbody necking down.
The molten long brilliant boat in described district is the molten long brilliant boat of molten long brilliant boat in graphite district or quartzy district.
A kind of horizontal zone melting growing tellurium zinc cadmium Cd
1-xZn
xThe method of Te monocrystalline, elder generation puts into tellurium, zinc and seed crystal and distinguishes molten long brilliant boat, cadmium is put into cadmium source boat, after will distinguishing again that molten long brilliant boat and cadmium source boat are disposable and putting into quartzy long brilliant pipe tube sealing, place the horizontal zone melting body of heater to heat, synthetic tellurium zinc cadmium ingot bar, through zone-refine tellurium zinc cadmium ingot bar repeatedly, the seed crystal guiding by the head necking down that is positioned at the molten long brilliant boat in district grows Te-Zn-Cd monocrystal on tellurium zinc cadmium ingot bar again.
The method of described horizontal zone melting growing tellurium zinc cadmium single-crystal comprises the steps:
1. the high purity zinc of 99.99999% high purity tellurium and 99.99999% or 99.99999% zinc telluridse synthetic material are placed the molten long brilliant boat in district, the high purity cadmium with 99.99999% is positioned in the boat of cadmium source, and places a seed crystal in the head necking down of the molten long brilliant boat in district;
2. successively the molten long brilliant boat in cadmium Yuan Zhouhe district is put into quartzy long brilliant pipe, the long brilliant pipe of quartz is vacuumized the back tube sealing;
3. the long brilliant pipe of quartz is placed on the body of heater, make the molten long brilliant boat in district in quartzy long brilliant the pipe be in the temperature controlled region that long brilliant stove is melted in the district, cadmium source boat is in the temperature controlled region of cadmium source stove;
4. the molten long brilliant stove in district in the body of heater and the temperature of cadmium source stove simultaneously raise, after treating that temperature rises to 600 ℃, slowing down temperature rise rate is 45～80 ℃/h, no longer raise in advance synthetic tellurium zinc cadmium ingot bar when the temperature of the temperature controlled region of the molten long brilliant stove in district rises to 900 ℃ of left and right sides after temperature rises to 780 ℃～850 ℃ in the temperature controlled region of the residing cadmium of boat source, cadmium source stove;
5. select two bogeys that spacing distance is 150～250mm in the molten long brilliant stove in district, its temperature to 1150 that raises ℃～1200 ℃, the temperature maintenance of residue bogey is in 1000 ℃～1050 ℃, first melting zone and second melting zone appear on the molten long brilliant boat in district, the molten long brilliant stove of turnover zone, make the molten head in district begin to move to caudal directions from the molten long brilliant boat in district, translational speed is 10～20mm/h, treat that first melting zone is to the afterbody of the molten long brilliant boat in district, to distinguish molten long brilliant stove rapidly is retracted into zero position and paused 5～15 minutes, the zone-refine of beginning next round obtains highly purified tellurium zinc cadmium ingot bar through the zone-refine of many wheels;
6. keep first melting zone, and this melting zone is moved to the position that seed crystal in the long brilliant boat head necking down is melted in the district, behind melt back seed crystal 3mm～5mm, carry out the growth of Te-Zn-Cd monocrystal again with the speed of 1～3mm/h.
After vacuumizing, described quartzy long brilliant pipe charges into a certain amount of hydrogen or argon gas.
Described 99.99999% high purity tellurium and 99.99999% high purity zinc place the molten long brilliant boat in district according to following method: Sheng Chang Cd as required
1-xZn
xThe Te single crystal is selected the X value: during the growth substrates material, and X=0.04; During growth high energy detector material, X=0.1～0.2, then high purity tellurium is divided into head, middle part and afterbody that three equal parts evenly are laid on the molten long brilliant boat in district, 99.99999% high purity zinc at the long brilliant boat of Qu Rong middle part is according to selected X value and the proportional placement of 99.99999% high purity tellurium, the placement amount that the placement amount of long brilliant boat head 99.99999% high purity zinc of Qu Rong is distinguished the brilliant boat of molten length middle part 99.99999% high purity zinc is few, and the placement amount that long brilliant boat afterbody 99.99999% high purity zinc is melted in the district is many than the placement amount of the brilliant boat of molten length middle part, district 99.99999% high purity zinc.
The preparation process of described zinc telluridse synthetic material is:
1. 99.99999% high purity tellurium is positioned in the molten long brilliant boat in district, 99.99999% high purity zinc is positioned in the boat of cadmium source, and the molten long brilliant boat in cadmium Yuan Zhouhe district placed quartzy long brilliant pipe respectively, the long brilliant pipe of this quartz is put into body of heater, make the molten long brilliant boat in district be positioned at the temperature controlled region of the long brilliant stove of horizontal zone melting, make cadmium source boat be positioned at the temperature controlled region of cadmium source stove;
2. the stove body temperature that raises, and the temperature controlled region temperature maintenance that makes cadmium source stove is in 800～900 ℃;
3. select many adjacent bogeys in the molten long brilliant stove in district, be heated to 1200～1300 ℃ simultaneously, all the other bogey temperature maintenance form single big melting zone in 1000～1100 ℃ on the molten long brilliant boat in district, with the molten long brilliant stove of the slow turnover zone of speed of 3～5mm/h, generate the zinc telluridse synthetic material.
Technique effect of the present invention:
Tube sealing after the disposable charging of employing in the apparatus and method of horizontal zone melting growing tellurium zinc cadmium single-crystal 1. of the present invention, later on through repeatedly zone-refine and long monocrystalline process obtain Te-Zn-Cd monocrystal, the impurity that has significantly reduced artificial contaminating impurity and instrument surface is stained, the Te-Zn-Cd monocrystal purity height of production.
The apparatus and method of horizontal zone melting growing tellurium zinc cadmium single-crystal 2. of the present invention adopt the two-region to melt and purify, and have improved the efficient of zone-refine, and the purity of the tellurium zinc cadmium ingot bar after purifying improves greatly.
The apparatus and method of horizontal zone melting growing tellurium zinc cadmium single-crystal 3. of the present invention adopt different ratios to prepare burden in the molten long brilliant boat in district, Te-Zn-Cd monocrystal ingot composition genital areas after synthetic is molten to be reached after purifying and is evenly distributed, and has guaranteed the yield rate of synthetic back Te-Zn-Cd monocrystal.
Description of drawings
Fig. 1 is the apparatus structure synoptic diagram of horizontal zone melting growing tellurium zinc cadmium single-crystal of the present invention.
Embodiment
Elaborate the process that the apparatus and method of utilizing horizontal zone melting growing tellurium zinc cadmium single-crystal of the present invention are made Te-Zn-Cd monocrystal below in conjunction with accompanying drawing and specific embodiment.But should therefore not limit protection scope of the present invention.
Please see Figure 1, Fig. 1 is the apparatus structure synoptic diagram of horizontal zone melting growing tellurium zinc cadmium single-crystal of the present invention.As seen from the figure, the device of horizontal zone melting growing tellurium zinc cadmium single-crystal of the present invention comprises body of heater 1, quartzy long brilliant pipe 2, the molten long brilliant boat 3 in district and cadmium source boat 4: described body of heater 1 comprises end to end cadmium source stove 12 and the long brilliant stove 11 of horizontal zone melting that temperature is controlled respectively, and the molten long brilliant stove 11 in district is made up of eight bogeys that are arranged in order; Be placed with quartzy long brilliant pipe 2 in the body of heater 1, be provided with cadmium source boat 4 and the long brilliant boat 3 of Qu Rong in the long brilliant pipe 2 of this quartz, cadmium source boat 4 is positioned at the temperature controlled region of cadmium source stove 12, and the molten long brilliant boat 3 in district is positioned at the temperature controlled region of the molten long brilliant stove 11 in district; The molten long brilliant boat 3 in described district is provided with head necking down 31 and afterbody necking down 32.
Present embodiment is to utilize the needed substrate Cd of apparatus and method growth HgCdTe extension of the present invention
0.96Zn
0.04Te (211) B monocrystalline specifically comprises the steps:
1. 99.99999% high purity tellurium equably lay in the molten long brilliant boat 3 in the district of graphite matter, 99.99999% high purity zinc then is divided into head, middle part and afterbody three equal parts, wherein, head is by the molar ratio batching of 1% zinc and 99% cadmium, and synthetic back bath composition is Cd
0.99Zn
0.01Te; Afterbody is the molar ratio batching of 7% zinc and 93% cadmium, and the composition of synthetic back melt is Cd
0.93Zn
0.07Te, and the middle part is the molar ratio of 4% zinc and 96% cadmium, synthetic back melt is Cd
0.96Zn
0.04Te, and in the head necking down 31 of the molten long brilliant boat 3 in district, place the seed crystal 7 that length is 30mm, the high purity cadmium with 99.99999% is positioned in the cadmium source boat 4;
2. successively cadmium source boat 4 and the long brilliant boat 3 of Qu Rong are put into quartzy long brilliant pipe 2,, after long brilliant pipe 2 vacuumizes to quartz, charge into a certain amount of argon gas and do shielding gas in order to reduce the evaporation of tellurium zinc cadmium, and then tube sealing;
3. the long brilliant pipe 2 of quartz is placed in the body of heater 1, make the district in the long brilliant pipe 1 of quartz melt the temperature controlled region that long brilliant boat 3 is in the molten long brilliant stove 11 in district, cadmium source boat 4 is in the temperature controlled region of cadmium source stove 12;
4. the molten long brilliant stove 11 in district in the body of heater 1 and the temperature of cadmium source stove 12 simultaneously raise, under same temperature, the cadmium vapour pressure is than the high order of magnitude of tellurium vapour pressure, cadmium steam after the evaporation is transported to the molten long brilliant boat 3 in district continuously, and with tellurium generation chemical reaction, generate cadmium telluride, when temperature is increased to 419 ℃, zinc begin the fusing and with tellurium generation chemical reaction, form the solid zinc telluridse, comparatively small amt because of zinc, can not cause fierce chemical reaction, treat that temperature rises to 600 ℃ after, what cadmium transported speeds up, also accelerate with the reaction of tellurium, slow down temperature rise rate to 50～80 ℃/h, keep no longer raising after temperature rises to 780 ℃ in the temperature controlled region of the residing cadmium of boat source, cadmium source stove 12, carry out the pre-synthetic of tellurium-zincium-cadmium crystal when the temperature of the temperature controlled region of the molten long brilliant stove 11 in district rises to 900 ℃, make whole tellurium zinc cadmium polycrystalline ingot keep solid-state, the distribution of zinc when originally preparing burden is because there be pre-synthesizing big variation can not occur;
5. select two bogeys that spacing distance is 150mm in the molten long brilliant stove 11 in district, its temperature to 1150 that raises ℃, the temperature maintenance of six bogeys of residue is in 1000 ℃ ℃, first melting zone 5 and second melting zone 6 appear on the tellurium zinc cadmium ingot bar in the molten long brilliant boat 3 in district, the molten long brilliant stove of turnover zone, make the melting zone begin to move to caudal directions from the head of the molten long brilliant boat 3 in district, translational speed is 10mm/h, because the segregation coefficient of zinc in tellurium zinc cadmium melt is greater than 1, therefore zone-refine makes the content of zinc move to head from afterbody, therefore will make the distribution of zinc in the molten long brilliant boat 3 in district when batching is that head is few, afterbody is many, after treating that the afterbody necking down 32 of the molten long brilliant boat 3 in district is walked out in first melting zone 5, to distinguish molten long brilliant stove 11 rapidly is retracted into zero position and paused 5 minutes, the zone-refine of beginning next round, through repeatedly zone-refine, move in the afterbody necking down 32 of the molten long brilliant boat 3 in district polluting impurity, be included in impurity that when batching stain and quartzy long brilliant pipe 2 inwall impurity be dissolved in the tellurium zinc cadmium melt after through repeatedly zone-refine, these impurity significantly reduce, obtain highly purified tellurium zinc cadmium ingot bar at last, the zinc content of quite a few approaches 4% in this tellurium zinc cadmium ingot bar;
6. keep first melting zone 5, and this first melting zone 5 is moved to the position of seed crystals 7 in the head necking down 31 of distinguishing molten long brilliant boat 3, after melt back seed crystal 7 reaches 3mm, carry out the growth of Te-Zn-Cd monocrystal with the speed of 1mm/h to afterbody from the head of distinguishing molten long brilliant boat 3 again.
Measure the ir transmissivity of 16 μ m, check out the shallow level impurity content of substrate slice,, obtain 40% Te-Zn-Cd monocrystal substrate, surpass 60%, illustrate that shallow level impurity content is extremely low at 16 μ m place ir transmissivities through 10 zone-refines.The structural integrity of Te-Zn-Cd monocrystal is better, and XRD twin crystal peak width at half height is less than 40 second of arcs, and dislocation desity is low 105/cm
2, reach the requirement of HgCdTe epitaxial substrate fully.
Present embodiment is to utilize the needed Cd of apparatus and method growth high energy detector of the present invention
0.9Zn
0.1The Te monocrystalline.Specifically comprise as follows in the operating process:
Because Cd
0.9Zn
0.1The content of zinc is higher in the Te monocrystalline, before zone-refine, the zinc content of this tellurium zinc cadmium ingot bar afterbody reaches 20%, contact with tellurium if before the Te-Zn-Cd monocrystal body is synthetic, zinc directly is positioned in the brilliant boat 3 of the molten length in district, chemical reaction when zinc and tellurium fusing is very fierce, and melt may be ejected into outside the molten long brilliant boat 3 in district, for synthetic reposefully, keep the content distribution of initial zinc in the molten long brilliant boat 3 in whole district constant, the zinc telluridse synthetic material that must employing have synthesized is as starting material.
Zinc telluridse synthetic material synthetic is similar to the synthetic of tellurium zinc cadmium, operates in device of the present invention, and the synthetic step is as follows:
1. 99.99999% high purity tellurium is positioned in the molten long brilliant boat 3 in district, 99.99999% high purity zinc is positioned in the cadmium source boat 4, and the long brilliant boat 3 of cadmium source boat 4 and Qu Rong is positioned over respectively in the quartzy long brilliant pipe 2, the long brilliant pipe 2 of quartz is placed in the body of heater 1, cadmium source boat 4 is in the temperature controlled region of cadmium source stove 12, and the molten long brilliant boat 3 in district is in the temperature controlled region of the molten long brilliant stove in district;
2. the temperature of body of heater 1 that raises, and the temperature maintenance that makes the cadmium source boat 4 in stove 12 temperature controlled region of cadmium source is in 900 ℃;
3. five adjacent ports are heated to 1290 ℃ simultaneously in molten long brilliant stove 3 temperature controlled region in selection district, remain the port temperature maintenance in 1150 ℃, form single melting zone on the molten long brilliant boat 11 in district, and are slowly mobile with the speed of 5mm/h, synthesize the zinc telluridse synthetic material.
Utilize the needed Cd of apparatus and method growth high energy detector of the present invention
0.9Zn
0.1The concrete operations step of Te single crystal is as follows:
1. 99.99999% high purity tellurium is laid in equably molten the length in the brilliant boat 3 in district of graphite matter, the zinc telluridse synthetic material then is divided into head, middle part and afterbody three equal parts, wherein prepare burden by the molar ratio of 2.5% zinc at the head of the molten long brilliant boat 3 in district, afterbody is the molar ratio batching of 17.5% zinc, and the middle part is the molar ratio batching of 10% zinc, and placement one length is the seed crystal 7 of 30mm in the head necking down 31 of the molten long brilliant boat 3 in district, and the cadmium with 99.99999% is positioned in the cadmium source boat 4;
2. successively cadmium source boat 4 and the long brilliant boat 3 of Qu Rong are put into quartzy long brilliant pipe 2, the long brilliant pipe 2 of quartz is vacuumized the back tube sealing,, after vacuumizing, charge into a certain amount of argon gas as shielding gas in order to reduce the evaporation of tellurium zinc cadmium, and then tube sealing;
3. the long brilliant pipe 2 of quartz is placed in the body of heater 1, make the district in the long brilliant pipe 1 of quartz melt the temperature controlled region that long brilliant boat 3 is in the molten long brilliant stove 11 in district, cadmium source boat 4 is in the temperature controlled region of cadmium source stove 12;
4. the molten long brilliant stove 11 in district in the body of heater 1 and the temperature of cadmium source stove 12 simultaneously raise, under same temperature, the cadmium vapour pressure is than the high order of magnitude of tellurium vapour pressure, cadmium steam after the evaporation is transported to the molten long brilliant boat 3 in district continuously, and with tellurium generation chemical reaction, generate cadmium telluride, owing to replace metallic zinc with zinc telluridse, when therefore temperature is increased to 419 ℃, not can with tellurium generation intensive chemical reaction, after treating that temperature rises to 600 ℃, what cadmium transported speeds up, also accelerate with the reaction of tellurium, slow down temperature rise rate to 50 ℃/h, keep no longer raising after temperature rises to 780 ℃ in the temperature controlled region of the residing cadmium of boat source, cadmium source stove 12, carry out the pre-synthetic of tellurium-zincium-cadmium crystal when the temperature of the temperature controlled region of the molten long brilliant stove 11 in district rises to 900 ℃, make whole tellurium zinc cadmium polycrystalline ingot keep solid-state, the distribution of zinc when originally preparing burden is because there be pre-synthesizing big variation can not occur;
5. select two bogeys that spacing distance is 150mm in the molten long brilliant stove 11 in district, its temperature to 1200 that raises ℃, the temperature maintenance of six bogeys of residue is in 1050 ℃, first melting zone 5 and second melting zone 6 appear on the molten long brilliant boat 3 in district, the molten long brilliant stove 11 of turnover zone, make the molten head in district begin to move to caudal directions from the molten long brilliant boat 3 in district, translational speed is 10mm/h, because the segregation coefficient of zinc in tellurium zinc cadmium melt is greater than 1, therefore zone-refine makes the content of zinc move to head from afterbody, therefore will make the distribution of zinc in the molten long brilliant boat 3 in district when batching is that head is few, afterbody is many, after treating that the afterbody necking down 32 of the molten long brilliant boat 3 in district is walked out in second melting zone 6, to distinguish molten long brilliant stove 11 rapidly is retracted into zero position and paused 5 minutes, the zone-refine of beginning next round, through repeatedly zone-refine, the impurity that pollutes is moved in the afterbody necking down 32 of the molten long brilliant boat 3 in district, comprise after the quartzy inwall impurity of growing brilliant pipe 2 is dissolved in the tellurium zinc cadmium melt and also significantly reducing through zone-refine, obtain highly purified tellurium zinc cadmium ingot bar at last, this makes, and the zinc content of quite a few approaches 10% in the tellurium zinc cadmium ingot bar;
6. keep first melting zone 5, and this melting zone is moved to the position of seed crystals 7 in the head necking down 31 of distinguishing molten long brilliant boat 3, after melt back seed crystal 7 reaches 3mm, carry out the growth of Te-Zn-Cd monocrystal with the speed of 1mm/h to afterbody from the head of distinguishing molten long brilliant boat 3 again.
It is Cd that said process finishes back acquisition component
0.9Zn
0.1The high energy detector material of Te.
In the blending process before tellurium-zincium-cadmium crystal is synthetic, if the molar ratio that head, middle part and afterbody be respectively 5%, 20% and 35% zinc that is distributed in of zinc telluridse crystalline component is prepared burden, can obtain component at last is Cd
0.8Zn
0.2The high energy detector material of Te.
The above-mentioned two kinds of high energy detector materials that obtain, 16 μ m ir transmissivities through checking 40% Te-Zn-Cd monocrystal all surpass 60%, the content that its shallow level impurity is described seldom, the resistivity of material is higher than 5 * 10
10Ω cm meets the requirement of high energy detector.
Adopt the apparatus and method of horizontal zone melting growing tellurium zinc cadmium single-crystal of the present invention, simple and quick, the growth efficiency height has significantly reduced the impurity that pollutes simultaneously, obtain highly purified Te-Zn-Cd monocrystal, meet fully as the substrate of tellurium cadmium mercury epitaxial growth and the requirement of high energy detector material.
Undoubtedly; the apparatus and method of horizontal zone melting growing tellurium zinc cadmium single-crystal of the present invention are enumerated the mode of connection and the numerical parameter that also have other numerical value and the conversion and are changed in embodiment; in a word, the protection domain of the apparatus and method of horizontal zone melting growing tellurium zinc cadmium single-crystal of the present invention comprises that also other conspicuous to those skilled in the art conversion substitutes.
Claims (7)
1. the device of a horizontal zone melting growing tellurium zinc cadmium single-crystal is characterized in that this device comprises body of heater (1), quartzy long brilliant pipe (2), the molten long brilliant boat (3) in district and cadmium source boat (4):
Described body of heater (1) comprises end to end cadmium source stove (12) and the long brilliant stove (11) of horizontal zone melting that temperature is controlled respectively, and the molten long brilliant stove in district (11) is made up of a plurality of bogeys that are arranged in order; Be placed with quartzy long brilliant pipe (2) in the body of heater (1), be provided with the molten long brilliant boat (3) in cadmium source boat (4) and district in the long brilliant pipe of this quartz (2), cadmium source boat (4) is positioned at the temperature controlled region of cadmium source stove (12), and the molten long brilliant boat in district (3) is positioned at the temperature controlled region of the molten long brilliant stove in district (11); The molten long brilliant boat in described district (3) is provided with head necking down (31) and afterbody necking down (32).
2. the device of horizontal zone melting growing tellurium zinc cadmium single-crystal according to claim 1 is characterized in that the molten long brilliant boat in described district is the molten long brilliant boat of molten long brilliant boat in graphite district or quartzy district.
3. the method for a horizontal zone melting growing tellurium zinc cadmium single-crystal, it is characterized in that earlier tellurium, zinc and seed crystal being put into the molten long brilliant boat (3) in district, cadmium is put into cadmium source boat (4), to distinguish again molten long brilliant boat (3) and cadmium source boat (4) disposable put into quartzy long brilliant manage (2) tube sealing after, place horizontal zone melting body of heater (1) heating, synthetic tellurium zinc cadmium ingot bar, through zone-refine tellurium zinc cadmium ingot bar repeatedly, guide by the seed crystal (7) of the head necking down (31) that is positioned at the molten long brilliant boat in district (3) again and on tellurium zinc cadmium ingot bar, grow Te-Zn-Cd monocrystal.
4. the method for horizontal zone melting growing tellurium zinc cadmium single-crystal according to claim 3 is characterized in that comprising the steps:
1. 99.99999% high purity tellurium and 99.99999% high purity zinc or 99.99999% zinc telluridse synthetic material are placed the molten long brilliant boat (3) in district, 99.99999% high purity cadmium is positioned in the cadmium source boat (4), and in the head necking down (31) of the molten long brilliant boat in district (3), places a seed crystal (7);
2. successively cadmium source boat (4) and the molten long brilliant boat in district (3) are put into quartzy long brilliant pipe (2), the long brilliant pipe of quartz (2) is vacuumized the back tube sealing;
3. the long brilliant pipe of quartz (2) is placed on the body of heater (1), make the district in the long brilliant pipe of quartz (1) melt the temperature controlled region that long brilliant boat (3) is in the molten long brilliant stove in district (11), cadmium source boat (4) is in the temperature controlled region of cadmium source stove (12);
4. the molten long brilliant stove (11) in district in the body of heater (1) and the temperature of cadmium source stove (12) simultaneously raise, after treating that temperature rises to 600 ℃, slowing down temperature rise rate is 45～80 ℃/h, no longer raise after temperature rises to 780～850 ℃ in the temperature controlled region of cadmium source boat (4) residing cadmium source stove (12), the temperature of the temperature controlled region of the molten long brilliant stove in district (11) is pre-synthetic tellurium zinc cadmium ingot bar in the time of 850～950 ℃;
5. select two bogeys that spacing distance is 150～250mm in the molten long brilliant stove in district (11), its temperature to 1150～1200 ℃ raise, the temperature maintenance of residue bogey is in 1000～1050 ℃, go up appearance first melting zone (5) and second melting zone (6) at the molten long brilliant boat in district (3), the molten long brilliant stove (11) of turnover zone, make the melting zone begin to move to caudal directions from the head of the molten long brilliant boat in district (3), translational speed is 10～20mm/h, treat that first melting zone (5) is to the afterbody of the molten long brilliant boat in district (3), to distinguish molten long brilliant stove (11) rapidly is retracted into zero position and paused 5～15 minutes, the zone-refine of beginning next round obtains highly purified tellurium zinc cadmium ingot bar through the zone-refine of many wheels;
6. keep first melting zone (5), and this melting zone is moved to the position that the long interior seed crystal of brilliant boat (3) head necking down (31) (7) is melted in the district, behind melt back seed crystal (7) 3～5mm, carry out the growth of Te-Zn-Cd monocrystal again with the speed of 1～3mm/h.
5. the method for horizontal zone melting growing tellurium zinc cadmium single-crystal according to claim 4 is characterized in that charging into hydrogen or argon gas after described quartzy long brilliant pipe vacuumizes.
6. the method for horizontal zone melting growing tellurium zinc cadmium single-crystal according to claim 4 is characterized in that described 99.99999% high purity tellurium and 99.99999% high purity zinc place the molten long brilliant boat (3) in district according to following method:
Sheng Chang Cd as required
1-xZn
xThe Te single crystal is selected the X value: during the growth substrates material, and X=0.04; During growth high energy detector material, X=0.1～0.2, then 99.99999% high purity tellurium is divided into the head that three equal parts evenly are laid on the molten long brilliant boat in district (3), middle part and afterbody, 99.99999% high purity zinc at the long brilliant boat of Qu Rong (3) middle part is according to selected X value and the proportional placement of 99.99999% high purity tellurium, the placement amount that the placement amount of long brilliant boat (3) head of Qu Rong 99.99999% high purity zinc is distinguished the molten brilliant boat of length (3) middle part 99.99999% high purity zinc is few, and the placement amount that long brilliant boat (3) afterbody 99.99999% high purity zinc is melted in the district is many than the placement amount of the molten brilliant boat of length in district (3) middle part 99.99999% high purity zinc.
7. the method for horizontal zone melting growing tellurium zinc cadmium single-crystal according to claim 4 is characterized in that the preparation process of described zinc telluridse synthetic material is:
1. 99.99999% high purity tellurium is positioned in the molten long brilliant boat in district (3), 99.99999% high purity zinc is positioned in the cadmium source boat (4), and cadmium source boat (4) and the molten long brilliant boat in district (3) placed quartzy long brilliant pipe (2) respectively, the long brilliant pipe of this quartz (2) is put into body of heater (1), make the molten long brilliant boat in district (3) be positioned at the temperature controlled region of the molten long brilliant stove in district (11), make cadmium source boat (4) be positioned at the temperature controlled region of cadmium source stove (12);
2. the temperature of body of heater (1) that raises, and the temperature controlled region temperature maintenance that makes cadmium source stove (12) is in 800～900 ℃;
3. select many adjacent bogeys in the molten long brilliant stove in district (11), be heated to 1200～1300 ℃ simultaneously, all the other bogey temperature maintenance are in 1000～1100 ℃, go up the single big melting zone of formation at the molten long brilliant boat in district (3), with the molten long brilliant stove (11) of the slow turnover zone of speed of 3～5mm/h, generate the zinc telluridse synthetic material.
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| CN101871123B (en) * | 2010-06-12 | 2012-11-07 | 上海大学 | Method and device for growing cadmium zinc telluride crystals in mobile tellurium solvent melting zone |
| CN102392294B (en) * | 2011-11-15 | 2014-04-09 | 中国科学院上海技术物理研究所 | Horizontal vacuum zone-melting preparation method of high-purity semiconductor material |
| CN103184347B (en) * | 2011-12-28 | 2014-09-17 | 广东先导稀材股份有限公司 | Preparation method of high purity cadmium |
| CN103183322B (en) * | 2011-12-28 | 2014-12-10 | 广东先导稀材股份有限公司 | Preparation method of high purity tellurium |
| CN102864496A (en) * | 2012-09-20 | 2013-01-09 | 上海大学 | Device for growing tellurium-zinc-cadmium crystals by traveling heater method |
| CN105154978B (en) * | 2015-10-14 | 2017-12-15 | 云南鑫耀半导体材料有限公司 | Gallium arsenide polycrystal magnetic field growth furnace and growing method |
| CN108660512A (en) * | 2018-04-18 | 2018-10-16 | 苏州西奇狄材料科技有限公司 | A kind of method of THM stoves and its production cadmium telluride or Te-Zn-Cd monocrystal body |
| CN108546986B (en) * | 2018-04-19 | 2020-09-15 | 中国科学院半导体研究所 | Seed crystal protection device and single crystal growth method |
| CN109402730A (en) * | 2018-11-12 | 2019-03-01 | 昆明理工大学 | A kind of equipment of real-time observation directional solidification process |
| CN111809240B (en) * | 2020-06-12 | 2022-01-18 | 先导薄膜材料（广东）有限公司 | Preparation method of high-purity cadmium telluride |
| CN111809243B (en) * | 2020-09-08 | 2020-12-15 | 宁波碲晶光电科技有限公司 | Method for preparing cadmium telluride or cadmium zinc telluride polycrystal material |
| CN111809235B (en) * | 2020-09-08 | 2020-12-22 | 宁波碲晶光电科技有限公司 | Method for preparing cadmium telluride or cadmium zinc telluride polycrystal material |
| CN114059170A (en) * | 2021-11-09 | 2022-02-18 | 安徽光智科技有限公司 | Growth method of cadmium telluride crystal |
| CN115726031B (en) * | 2022-09-26 | 2023-06-09 | 湖南大合新材料有限公司 | Method and equipment for synthesizing tellurium-zinc-cadmium polycrystal |
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| CN1657403A (en) * | 2005-01-26 | 2005-08-24 | 上海大学 | Purification method of CdTe, ZnTe and CdZnTe as raw material for detector and its device |
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