CN101235542B - Single-crystal growth method for germanium zinc phosphide - Google Patents
Single-crystal growth method for germanium zinc phosphide Download PDFInfo
- Publication number
- CN101235542B CN101235542B CN2007101445996A CN200710144599A CN101235542B CN 101235542 B CN101235542 B CN 101235542B CN 2007101445996 A CN2007101445996 A CN 2007101445996A CN 200710144599 A CN200710144599 A CN 200710144599A CN 101235542 B CN101235542 B CN 101235542B
- Authority
- CN
- China
- Prior art keywords
- temperature
- crucible
- zinc phosphide
- cooled
- per hour
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Abstract
A method for synthesizing poly-crystal and growing single-crystal of zinc germanium phosphide relates to a method for synthesizing and the growing the zinc germanium phosphide. The method solves the problem of low synthesizing rate of the current method for synthesizing the zinc germanium phosphide poly-crystal, and the problem of uneasy to exclude foreign matter of the method for growing the zincgermanium phosphide single-crystal. The synthesis of the zinc germanium phosphide poly-crystal of the invention comprises the following steps: firstly, defining the quantity, secondly, increasing thetemperature, namely obtaining the zinc germanium phosphide poly-crystal material; the growth of the zinc germanium phosphide single-crystal protocaryon of the invention has the following steps: firstly, defining the quantity, secondly, increasing the temperature, thirdly, decreasing the copple and reducing the temperature, namely obtaining the zinc germanium phosphide single-crystal, the growth of the zinc germanium phosphide single-crystal with seed crystal of the invention has the following steps: firstly, defining the quantity, secondly, increasing the temperature, thirdly, decreasing thecopple and reducing the temperature, namely obtaining the zinc germanium phosphide single-crystal. The method of the invention has the advantages that the synthesizing rate of the poly-crystal synthesis is high, the growth of the single-crystal is easy to exclude the foreign matter, and the direction of the crystal is accordant.
Description
Technical field
The present invention relates to the method for germanium zinc phosphide crystal growth.
Background technology
Germanium zinc phosphide, chemical formula are ZnGeP
2, its monocrystalline is a kind of mid and far infrared wave band non-linear optic crystal of superior performance: nonlinear factor height, d
36Reach 75pm/V; Transmission region is wide: 0.7-13 μ m, can both realize phase matched, CO in very wide wavelength region
2Laser apparatus, Nd:YAG (Nd:Y
3Al
5O
12) laser apparatus, Ti jewel (Ti:Al
2O
3) laser apparatus, Ho:Tm:LYF (Ho:Tm:YLiF
4) laser apparatus etc. can be used as pumping source; The thermal conductivity height, thermal lensing effect is low, is difficult for causing the damage of crystal and optical element; The light injury threshold height.
Because the germanium zinc phosphide monocrystalline has excellent performance, utilize its nonlinear dielectric material as optical parametric oscillation, optical parameter amplification, second harmonic, four-time harmonic etc., can in, aspect the frequency inverted of far infrared band, especially the field that laser power is had relatively high expectations, obtain wide application prospect, as the monitoring of objectionable impurities in infrared spectra, Infrared Therapy apparatus, drug testing, infrared photoetching, the atmosphere, remote chemical sensitisation, infrared laser directional jamming, night vision equipment etc.
The germanium zinc phosphide monocrystalline is the crystal that is formed by germanium zinc phosphide polycrystalline oriented growth, the germanium zinc phosphide polycrystalline is synthetic can to adopt single warm area synthetic method, but low, the each resultant quantity of this method synthesis rate is little, and because phosphorous vapor is pressed height, easily blasts in the building-up process; The germanium zinc phosphide single crystal growing can be adopted the terraced method of level temperature, and this method growing crystal cross section is semicircle, and crystalline size is little, and during the processing device, has waste of material.Generally have thing phases such as zinc phosphide in the growth of germanium zinc phosphide monocrystalline, its density is lower than germanium zinc phosphide, so horizontal growth also is unfavorable for getting rid of these impurity.
Summary of the invention
There is the problem that is difficult for discharging impurity in the present invention for the growth method that solves the germanium zinc phosphide monocrystalline, and the method for the single crystal growing of germanium zinc phosphide is provided.
Germanium zinc phosphide monocrystalline of the present invention adopts the method for former nucleus growth, the method of former nucleus growth germanium zinc phosphide monocrystalline is carried out as follows: one, selecting purity for use is that zinc, germanium, phosphorus more than 99.999% is that 1: 1: 2～2.005 ratio is quantitative in molar ratio, reactant is put into synthetic boat, to synthesize boat places silica tube to vacuumize sealing, again silica tube is put into horizontal synthetic furnace, make the synthetic boat of placing phosphorus be positioned at the cold zone of horizontal synthetic furnace, the synthetic boat of placing zinc and germanium is positioned at the high-temperature zone of horizontal synthetic furnace; Two, heat up that to make the cold zone temperature be 400～600 ℃, the high-temperature zone temperature is 900～1080 ℃, and insulation is cooled to room temperature more than 3 hours again, promptly obtains the germanium zinc phosphide polycrystal; Three, the germanium zinc phosphide polycrystal that step 2 obtains is put into crucible, place silica tube to vacuumize sealing in crucible, the silica tube of sealing is put into crucible decline single crystal growing furnace, with crucible horizontal tangent bottom is reference line, the temperature of above base line is higher than 1026 ℃, the following temperature of reference line is lower than 1026 ℃, be incubated after material all melts to the crucible, again with per hour less than the speed decline crucible of 8mm, until the whole crystallizations of material, crucible stops to descend, again with after per hour 1～20 ℃ cooling rate is cooled to 900 ℃, be cooled to 600 ℃ with 10～50 ℃ cooling rate per hour, be cooled to 400 ℃ with 20～100 ℃ cooling rate per hour at last, room temperature is reduced in the single crystal growing furnace outage; Promptly obtain the germanium zinc phosphide monocrystalline.
The another kind of growth method of germanium zinc phosphide monocrystalline of the present invention adopts the method that seeded growth is arranged, have the method for seeded growth germanium zinc phosphide to carry out as follows: one, selecting purity for use is that zinc, germanium, phosphorus more than 99.999% is that 1: 1: 2～2.005 ratio is quantitative in molar ratio, reactant is put into synthetic boat, to synthesize boat places silica tube to vacuumize sealing, again silica tube is put into horizontal synthetic furnace, make the synthetic boat of placing phosphorus be positioned at the cold zone of horizontal synthetic furnace, the synthetic boat of placing zinc and germanium is positioned at the high-temperature zone of horizontal synthetic furnace; Two, heat up that to make the cold zone temperature be 400～600 ℃, the high-temperature zone temperature is 900～1080 ℃, and insulation is cooled to room temperature more than 3 hours again, promptly obtains the germanium zinc phosphide polycrystal; Three, choose directed germanium zinc phosphide monocrystalline as seed crystal, seed crystal is placed in the seed crystal trap of crucible inner bottom part, again the germanium zinc phosphide polycrystal is put into crucible, place silica tube to vacuumize sealing in crucible, the silica tube of sealing is put into crucible decline single crystal growing furnace, the contact position of seed crystal and polycrystal is a benchmark with this moment, make the temperature of the contact position of seed crystal and polycrystal be lower than 1026 ℃, perhaps guarantee to have at least the thick seed crystal of 5mm not molten, the temperature of polycrystal part is higher than 1027 ℃, after being incubated polycrystal to the crucible and all melting, less than the speed decline crucible of 8mm, until the whole crystallizations of material, crucible stops to descend with per hour, again with after per hour 1～20 ℃ cooling rate is cooled to 900 ℃, be cooled to 600 ℃ with 10～50 ℃ cooling rate per hour, be cooled to 400 ℃, the single crystal growing furnace outage with 20～100 ℃ cooling rate per hour at last, reduce to room temperature, promptly obtain the germanium zinc phosphide monocrystalline.
The germanium zinc phosphide monocrystalline that utilized seeded growth among the present invention, wherein seed crystal is the germanium zinc phosphide monocrystalline by conventional directed and the crystal with certain crystalline orientation that cutting method obtains.
The synthetic boat material of polycrystalline synthetic method and method for monocrystal growth is graphite, glass carbon, silica glass or boron nitride among the present invention.
The crucible material of method for monocrystal growth is graphite, glass carbon, silica glass or boron nitride among the present invention.
The present invention has the synthesis rate height, easily discharges the advantage of impurity.Germanium zinc phosphide polycrystalline synthesis rate has improved 50%～90% than method in the past, in the crystalline process of growth, because crucible is vertical the placement, the germanium zinc phosphide polycrystal all is discharged to impurity the top of crucible in the time of pyritous at boiling state, so impurity is removed easily, obtain high quality crystal, in the process of single crystal growing, the method that adopts crucible decline to lower the temperature is step by step carried out crystallisation by cooling, guaranteed the consistence of crystal growth, and add directed germanium zinc phosphide monocrystalline as seeding, can grow the germanium zinc phosphide monocrystalline of the required direction of growth, the germanium zinc phosphide monocrystalline that grows detects through the XRD diffractometer, and the crystalline direction of growth is consistent with the orientation of seed crystal.Synthetic germanium zinc phosphide polycrystalline of the present invention records the germanium zinc phosphide collection of illustrative plates as shown in Figure 1 through X-ray diffraction, the X-ray powder diffraction spectrogram of a line standard germanium zinc phosphide, the b line is a synthetic germanium zinc phosphide polycrystalline X-ray powder diffraction spectrogram of the present invention, and synthetic germanium zinc phosphide polycrystalline purity height of the present invention is described.
Description of drawings
Fig. 1 the present invention is a synthetic germanium zinc phosphide polycrystal XRD spectra, and Fig. 2 adopts the germanium zinc phosphide monocrystalline that the growth of seed crystal method is arranged for the present invention.
Embodiment
Embodiment one: the polycrystalline synthetic method of the germanium zinc phosphide of present embodiment is carried out as follows: one, selecting purity for use is that zinc, germanium, phosphorus more than 99.999% is that 1: 1: 2～2.005 ratio is quantitative in molar ratio, reactant is put into synthetic boat, to synthesize boat places silica tube to vacuumize sealing, again silica tube is put into horizontal synthetic furnace, make the synthetic boat of placing phosphorus be positioned at the cold zone of horizontal synthetic furnace, the synthetic boat of placing zinc and germanium is positioned at the high-temperature zone of horizontal synthetic furnace; Two, intensification makes the cold zone temperature at 400～600 ℃, and the high-temperature zone temperature is 900～1080 ℃, and insulation is cooled to room temperature more than 3 hours again; Promptly obtain the germanium zinc phosphide polycrystal.
Embodiment two: the difference of present embodiment and embodiment one is: heating up in the step 2 makes the cold zone temperature at 440～560 ℃, and the high-temperature zone temperature is 930～1050 ℃.Other step and parameter are identical with embodiment one.
Embodiment three: the difference of present embodiment and embodiment one is: heating up in the step 2 makes the cold zone temperature at 480～520 ℃, and the high-temperature zone temperature is 980～1000 ℃.Other step and parameter are identical with embodiment one.
Embodiment four: the difference of present embodiment and embodiment one is: heating up in the step 2 makes the cold zone temperature at 500 ℃, and the high-temperature zone temperature is 990 ℃.Other step and parameter are identical with embodiment one.
Embodiment five: the difference of present embodiment and embodiment one is: insulation is more than 4 hours in the step 2.Other step and parameter are identical with embodiment one.
Embodiment six: the difference of present embodiment and embodiment one is: the material of the synthetic boat in the step 1 is graphite, glass carbon, silica glass or boron nitride.
Embodiment seven: the difference of present embodiment and embodiment one is: zinc, germanium, phosphorus are that 1: 1: 2 ratio is quantitative in molar ratio in the step 1.Other step and parameter are identical with embodiment one.
Embodiment eight: the method for the former nucleus growth of germanium zinc phosphide monocrystalline of present embodiment is carried out as follows: one, selecting purity for use is that zinc, germanium, phosphorus more than 99.999% is that 1: 1: 2～2.005 ratio is quantitative in molar ratio, reactant is put into synthetic boat, to synthesize boat places silica tube to vacuumize sealing, again silica tube is put into horizontal synthetic furnace, make the synthetic boat of placing phosphorus be positioned at the cold zone of horizontal synthetic furnace, the synthetic boat of placing zinc and germanium is positioned at the high-temperature zone of horizontal synthetic furnace; Two, heat up that to make the cold zone temperature be 400～600 ℃, the high-temperature zone temperature is 900～1080 ℃, and insulation is cooled to room temperature more than 3 hours again, promptly obtains the germanium zinc phosphide polycrystal; Three, the germanium zinc phosphide polycrystal that step 2 obtains is put into crucible, place silica tube to vacuumize sealing in crucible, the silica tube of sealing is put into crucible decline single crystal growing furnace, with crucible horizontal tangent bottom is reference line, the temperature of above base line is higher than 1026 ℃, the following temperature of reference line is lower than 1026 ℃, be incubated after material all melts to the crucible, again with per hour less than the speed decline crucible of 8mm, until the whole crystallizations of material, crucible stops to descend, again with after per hour 1～20 ℃ cooling rate is cooled to 900 ℃, be cooled to 600 ℃ with 10～50 ℃ cooling rate per hour, be cooled to 400 ℃ with 20～100 ℃ cooling rate per hour at last, room temperature is reduced in the single crystal growing furnace outage; Promptly obtain the germanium zinc phosphide monocrystalline.
Embodiment nine: the difference of present embodiment and embodiment eight is: heating up in the step 2 and making the cold zone temperature is 440～560 ℃, and the high-temperature zone temperature is 930～1050 ℃.Other step and parameter are identical with embodiment eight.
Embodiment ten: the difference of present embodiment and embodiment eight is: heating up in the step 2 and making the cold zone temperature is 480～520 ℃, and the high-temperature zone temperature is 980～1000 ℃.Other step and parameter are identical with embodiment eight.
Embodiment 11: the difference of present embodiment and embodiment eight is: heating up in the step 2 and making the cold zone temperature is 500 ℃, and the high-temperature zone temperature is 990 ℃.Other step and parameter are identical with embodiment eight.
Embodiment 12: the difference of present embodiment and embodiment eight is: insulation is more than 4 hours in the step 2.Other step and parameter are identical with embodiment eight.
Embodiment 13: the difference of present embodiment and embodiment eight is: the material of the synthetic boat in the step 1 is graphite, glass carbon, silica glass or boron nitride.Other step and parameter are identical with embodiment eight.
Embodiment 14: the difference of present embodiment and embodiment eight is: the material of the crucible in the step 3 is graphite, glass carbon, silica glass or boron nitride.Other step and parameter are identical with embodiment eight.
Embodiment 15: the difference of present embodiment and embodiment eight is: the temperature of above base line is higher than 1080 ℃ in the step 3, and the following temperature of reference line is lower than 1000 ℃.Other step and parameter are identical with embodiment eight.
Embodiment 16: the difference of present embodiment and embodiment eight is: the temperature of above base line is higher than 1027 ℃ in the step 3, and the following temperature of reference line is lower than 1025 ℃.Other step and parameter are identical with embodiment eight.
Embodiment 17: the difference of present embodiment and embodiment eight is: in the step 3 with the speed decline crucible of 2～6mm per hour.Other step and parameter are identical with embodiment eight.
Embodiment 18: the difference of present embodiment and embodiment eight is: in the step 3 with the speed decline crucible of 4mm per hour.Other step and parameter are identical with embodiment eight.
Embodiment 19: the difference of present embodiment and embodiment eight is: in the step 3 at first with after per hour 4～16 ℃ cooling rate is cooled to 900 ℃, be cooled to 600 ℃ with 20～40 ℃ cooling rate per hour again, be cooled to 400 ℃ with 40～80 ℃ cooling rate per hour at last.Other step and parameter are identical with embodiment eight.
Embodiment 20: the difference of present embodiment and embodiment eight is: in the step 3 at first with after per hour 8～12 ℃ cooling rate is cooled to 900 ℃, be cooled to 600 ℃ with 25～35 ℃ cooling rate per hour again, be cooled to 400 ℃ with 50～70 ℃ cooling rate per hour at last.Other step and parameter are identical with embodiment eight.
Embodiment 21: the difference of present embodiment and embodiment eight is: in the step 3 at first with after per hour 10 ℃ cooling rate is cooled to 900 ℃, be cooled to 600 ℃ with 30 ℃ cooling rate per hour again, be cooled to 400 ℃ with 60 ℃ cooling rate per hour at last.Other step and parameter are identical with embodiment eight.
Embodiment 22: the difference of present embodiment and embodiment eight is: crucible is with per hour greater than 0 and descend less than the speed of 8mm in the step 3.Other step and parameter are identical with embodiment eight.
Embodiment 23: the germanium zinc phosphide monocrystalline of present embodiment has the method for seeded growth to carry out as follows: one, selecting purity for use is that zinc, germanium, phosphorus more than 99.999% is that 1: 1: 2～2.005 ratio is quantitative in molar ratio, reactant is put into synthetic boat, to synthesize boat places silica tube to vacuumize sealing, again silica tube is put into horizontal synthetic furnace, make the synthetic boat of placing phosphorus be positioned at the cold zone of horizontal synthetic furnace, the synthetic boat of placing zinc and germanium is positioned at the high-temperature zone of horizontal synthetic furnace; Two, heat up that to make the cold zone temperature be 400～600 ℃, the high-temperature zone temperature is 900～1080 ℃, and insulation is cooled to room temperature more than 3 hours again, promptly obtains the germanium zinc phosphide polycrystal; Three, choose directed germanium zinc phosphide monocrystalline as seed crystal, seed crystal is placed in the seed crystal trap of crucible inner bottom part, again the germanium zinc phosphide polycrystal is put into crucible, place silica tube to vacuumize sealing in crucible, the silica tube of sealing is put into crucible decline single crystal growing furnace, the contact position of seed crystal and polycrystal is a benchmark with this moment, make the temperature of the contact position of seed crystal and polycrystal be lower than 1026 ℃, perhaps guarantee to have at least the thick seed crystal of 5mm not molten, the temperature of polycrystal part is higher than 1027 ℃, after being incubated polycrystal to the crucible and all melting, less than the speed decline crucible of 8mm, until the whole crystallizations of material, crucible stops to descend with per hour, again with after per hour 1～20 ℃ cooling rate is cooled to 900 ℃, be cooled to 600 ℃ with 10～50 ℃ cooling rate per hour, be cooled to 400 ℃, the single crystal growing furnace outage with 20～100 ℃ cooling rate per hour at last, reduce to room temperature, promptly obtain the germanium zinc phosphide monocrystalline.
Embodiment 24: the difference of present embodiment and embodiment 23 is: heating up in the step 2 and making the cold zone temperature is 440～560 ℃, and the high-temperature zone temperature is 930～1050 ℃.Other step and parameter are identical with embodiment 23.
Embodiment 25: the difference of present embodiment and embodiment 23 is: heating up in the step 2 and making the cold zone temperature is 480～520 ℃, and the high-temperature zone temperature is 980～1000 ℃.Other step and parameter are identical with embodiment 23.
Embodiment 26: the difference of present embodiment and embodiment 23 is: heating up in the step 2 and making the cold zone temperature is 500 ℃, and the high-temperature zone temperature is 990 ℃.Other step and parameter are identical with embodiment 23.
Embodiment 27: the difference of present embodiment and embodiment 23 is: insulation is more than 4 hours in the step 2.Other step and parameter are identical with embodiment 23.
Embodiment 28: the difference of present embodiment and embodiment 23 is: the material of the synthetic boat in the step 1 is graphite, glass carbon, silica glass or boron nitride.Other step and parameter are identical with embodiment 23.
Embodiment 29: the difference of present embodiment and embodiment 23 is: the material of the crucible in the step 3 is graphite, glass carbon, silica glass or boron nitride.Other step and parameter are identical with embodiment 23.
Embodiment 30: the difference of present embodiment and embodiment 23 is: the temperature of seed crystal and polycrystalline contact position is lower than 1000 ℃ in the step 3, perhaps guarantees to have at least the thick seed crystal of 6mm not molten.Other step and parameter are identical with embodiment 23.
The embodiment hentriaconta-: the difference of present embodiment and embodiment 23 is: in the step 3 with the speed decline crucible of 1～7mm per hour.Other step and parameter are identical with embodiment 23.
Embodiment 32: 23 difference of present embodiment and embodiment is: in the step 3 with the speed decline crucible of 5mm per hour.Other step and parameter are identical with embodiment 23.
Embodiment 33: the difference of present embodiment and embodiment 23 is: in the step 3 at first with after per hour 4～16 ℃ cooling rate is cooled to 900 ℃, be cooled to 600 ℃ with 20～40 ℃ cooling rate per hour again, be cooled to 400 ℃ with 40～80 ℃ cooling rate per hour at last.Other step and parameter are identical with embodiment 23.
Embodiment 34: the difference of present embodiment and embodiment 23 is: in the step 3 at first with after per hour 8～12 ℃ cooling rate is cooled to 900 ℃, be cooled to 600 ℃ with 25～35 ℃ cooling rate per hour again, be cooled to 400 ℃ with 50～70 ℃ cooling rate per hour at last.Other step and parameter are identical with embodiment 23.
Embodiment 35: the difference of present embodiment and embodiment 23 is: in the step 3 at first with after per hour 10 ℃ cooling rate is cooled to 900 ℃, be cooled to 600 ℃ with 30 ℃ cooling rate per hour again, be cooled to 400 ℃ with 60 ℃ cooling rate per hour at last.Other step and parameter are identical with embodiment 23.
Embodiment 36: the difference of present embodiment and embodiment 23 is: the thickness of the seed crystal in the step 3 is greater than 5mm.Other step and parameter are identical with embodiment 23.
Embodiment 37: the difference of present embodiment and embodiment 23 is: crucible is with per hour greater than 0 and descend less than the speed of 8mm in the step 3.Other step and parameter are identical with embodiment 23.
Embodiment 38: the germanium zinc phosphide monocrystalline of present embodiment has the method for seeded growth to carry out as follows: one, selecting purity for use is that 99.999% zinc, germanium, phosphorus are that 1: 1: 2.005 ratio is quantitative in molar ratio, reactant is put into synthetic boat, to synthesize boat places silica tube to vacuumize sealing, again silica tube is put into horizontal synthetic furnace, make the synthetic boat of placing phosphorus be positioned at the cold zone of horizontal synthetic furnace, the synthetic boat of placing zinc and germanium is positioned at the high-temperature zone of horizontal synthetic furnace; Two, heat up that to make the cold zone temperature be 500 ℃, the high-temperature zone temperature is 1000 ℃, is incubated 4 hours, is cooled to room temperature again, promptly obtains the germanium zinc phosphide polycrystal; Three, choose directed germanium zinc phosphide monocrystalline as seed crystal, seed crystal is placed in the seed crystal trap of crucible inner bottom part, again the germanium zinc phosphide polycrystal is put into crucible, place silica tube to vacuumize sealing in crucible, the silica tube of sealing is put into crucible decline single crystal growing furnace, the contact position of seed crystal and polycrystal is a benchmark with this moment, the temperature that makes the contact position of seed crystal and polycrystal is 1000 ℃, the temperature of polycrystal part is 1050 ℃, after being incubated polycrystal to the crucible and all melting, with the speed decline crucible of 5mm per hour, until the whole crystallizations of material, crucible stops to descend, and again with after per hour 8 ℃ cooling rate is cooled to 900 ℃, is cooled to 600 ℃ with 15 ℃ cooling rate per hour, at last be cooled to 400 ℃ with 40 ℃ cooling rate per hour, room temperature is reduced in the single crystal growing furnace outage, promptly obtains the germanium zinc phosphide monocrystalline.
The germanium zinc phosphide monocrystalline of the growth that present embodiment makes detects through the XRD diffractometer, and the crystalline direction of growth is consistent with the orientation of seed crystal.
Claims (8)
1. the growth method of germanium zinc phosphide monocrystalline, the method that it is characterized in that the former nucleus growth of germanium zinc phosphide monocrystalline is carried out as follows: one, selecting purity for use is that zinc, germanium, phosphorus more than 99.999% is that 1: 1: 2～2.005 ratio is quantitative in molar ratio, reactant is put into synthetic boat, to synthesize boat places silica tube to vacuumize sealing, again silica tube is put into horizontal synthetic furnace, make the synthetic boat of placing phosphorus be positioned at the cold zone of horizontal synthetic furnace, the synthetic boat of placing zinc and germanium is positioned at the high-temperature zone of horizontal synthetic furnace; Two, heat up that to make the cold zone temperature be 400～600 ℃, the high-temperature zone temperature is 900～1080 ℃, and insulation is cooled to room temperature more than 3 hours again, promptly obtains the germanium zinc phosphide polycrystal; Three, the germanium zinc phosphide polycrystal that step 2 obtains is put into crucible, place silica tube to vacuumize sealing in crucible, the silica tube of sealing is put into crucible decline single crystal growing furnace, with crucible horizontal tangent bottom is reference line, the temperature of above base line is higher than 1026 ℃, the following temperature of reference line is lower than 1026 ℃, be incubated after material all melts to the crucible, again with per hour less than the speed decline crucible of 8mm, until the whole crystallizations of material, crucible stops to descend, again with after per hour 1～20 ℃ cooling rate is cooled to 900 ℃, be cooled to 600 ℃ with 10～50 ℃ cooling rate per hour, be cooled to 400 ℃ with 20～100 ℃ cooling rate per hour at last, room temperature is reduced in the single crystal growing furnace outage; Promptly obtain the germanium zinc phosphide monocrystalline.
2. the growth method of germanium zinc phosphide monocrystalline according to claim 1, it is characterized in that heating up in the step 2 makes the cold zone temperature at 500 ℃, and the high-temperature zone temperature is 990 ℃.
3. the growth method of germanium zinc phosphide monocrystalline according to claim 1 is characterized in that the temperature of above base line is higher than 1027 ℃ in the step 3, and the following temperature of reference line is lower than 1025 ℃.
4. the growth method of germanium zinc phosphide monocrystalline, it is characterized in that the germanium zinc phosphide monocrystalline has the method for seeded growth to carry out as follows: one, selecting purity for use is that zinc, germanium, phosphorus more than 99.999% is that 1: 1: 2～2.005 ratio is quantitative in molar ratio, reactant is put into synthetic boat, to synthesize boat places silica tube to vacuumize sealing, again silica tube is put into horizontal synthetic furnace, make the synthetic boat of placing phosphorus be positioned at the cold zone of horizontal synthetic furnace, the synthetic boat of placing zinc and germanium is positioned at the high-temperature zone of horizontal synthetic furnace; Two, heat up that to make the cold zone temperature be 400～600 ℃, the high-temperature zone temperature is 900～1080 ℃, and insulation is cooled to room temperature more than 3 hours again, promptly obtains the germanium zinc phosphide polycrystal; Three, choose directed germanium zinc phosphide monocrystalline as seed crystal, seed crystal is placed in the seed crystal trap of crucible inner bottom part, again the germanium zinc phosphide polycrystal is put into crucible, place silica tube to vacuumize sealing in crucible, the silica tube of sealing is put into crucible decline single crystal growing furnace, the contact position of seed crystal and polycrystal is a benchmark with this moment, make the temperature of the contact position of seed crystal and polycrystal be lower than 1026 ℃, perhaps guarantee to have at least the thick seed crystal of 5mm not molten, the temperature of polycrystal part is higher than 1027 ℃, after being incubated polycrystal to the crucible and all melting, less than the speed decline crucible of 8mm, until the whole crystallizations of material, crucible stops to descend with per hour, again with after per hour 1～20 ℃ cooling rate is cooled to 900 ℃, be cooled to 600 ℃ with 10～50 ℃ cooling rate per hour, be cooled to 400 ℃, the single crystal growing furnace outage with 20～100 ℃ cooling rate per hour at last, reduce to room temperature, promptly obtain the germanium zinc phosphide monocrystalline.
5. the growth method of germanium zinc phosphide monocrystalline according to claim 4 is characterized in that insulation is more than 4 hours in the step 2.
6. the growth method of germanium zinc phosphide monocrystalline according to claim 4, it is characterized in that in the step 3 at first with after per hour 4～16 ℃ cooling rate is cooled to 900 ℃, be cooled to 600 ℃ with 20～40 ℃ cooling rate per hour again, be cooled to 400 ℃ with 40～80 ℃ cooling rate per hour at last.
7. the growth method of germanium zinc phosphide monocrystalline according to claim 4, it is characterized in that in the step 3 at first with after per hour 10 ℃ cooling rate is cooled to 900 ℃, be cooled to 600 ℃ with 30 ℃ cooling rate per hour again, be cooled to 400 ℃ with 60 ℃ cooling rate per hour at last.
8. the growth method of germanium zinc phosphide monocrystalline according to claim 4, the material that it is characterized in that the synthetic boat in the step 1 are graphite, glass carbon, silica glass or boron nitride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101445996A CN101235542B (en) | 2007-11-14 | 2007-11-14 | Single-crystal growth method for germanium zinc phosphide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101445996A CN101235542B (en) | 2007-11-14 | 2007-11-14 | Single-crystal growth method for germanium zinc phosphide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101235542A CN101235542A (en) | 2008-08-06 |
| CN101235542B true CN101235542B (en) | 2010-06-02 |
Family
ID=39919434
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007101445996A Expired - Fee Related CN101235542B (en) | 2007-11-14 | 2007-11-14 | Single-crystal growth method for germanium zinc phosphide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101235542B (en) |
Families Citing this family (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101892514B (en) * | 2010-07-20 | 2012-05-30 | 中国科学院上海硅酸盐研究所 | Process for growing sodium nitrate monocrystal by Bridgman method |
| CN102060279B (en) * | 2010-11-29 | 2012-11-14 | 中山大学 | Device and method for synthesizing zinc germanium phosphide polycrystal |
| CN102540414A (en) * | 2010-12-15 | 2012-07-04 | 太仓南极风能源设备有限公司 | Bright-enhancement passive infrared night-vision glass |
| CN102191541B (en) * | 2011-04-02 | 2012-07-04 | 山东大学 | Dual-temperature-zone synthesis method and apparatus for phosphorus-silicon-cadmium polycrystal material |
| CN102168299B (en) * | 2011-04-02 | 2012-06-27 | 山东大学 | Method for growing phosphorus-silicon-cadmium single crystal |
| CN102168305B (en) * | 2011-04-02 | 2012-06-27 | 山东大学 | Synthesis method of phosphorus-silicon-cadmium polycrystal material |
| CN102437505B (en) * | 2011-11-25 | 2012-12-12 | 哈尔滨工业大学 | Manufacturing method of zinc germanium phosphide optical parametric oscillation element |
| CN102433590B (en) * | 2011-11-25 | 2014-04-09 | 哈尔滨工业大学 | Method for reducing absorption coefficient of zinc-germanium phosphide crystal |
| CN102618935B (en) * | 2012-01-19 | 2015-06-17 | 中国科学院安徽光学精密机械研究所 | Annealing method for infrared nonlinear single crystal of multi-component compound containing easily volatile components |
| CN104600299B (en) * | 2015-01-08 | 2017-07-07 | 华中科技大学 | A kind of lithium ion/sodium-ion battery negative active core-shell material, negative pole and battery |
| CN106400102B (en) * | 2016-10-26 | 2019-06-28 | 珠海鼎泰芯源晶体有限公司 | A kind of growth apparatus and its method of achievable monocrystalline online annealing |
| CN107268070A (en) * | 2017-06-10 | 2017-10-20 | 中国科学院合肥物质科学研究院 | A kind of method of low absorption phosphorus germanium zinc crystal growth |
| CN108277532B (en) * | 2018-01-26 | 2019-08-16 | 山东大学 | The heteroepitaxial growth method of phosphorus silicon-zinc crystal body for silicon lamination solar cell |
| CN110144624B (en) * | 2018-02-11 | 2020-09-08 | 中国科学院理化技术研究所 | Synthesis method of selenium-germanium-gallium-barium polycrystal and growth method of selenium-germanium-gallium-barium monocrystal |
| CN109137070B (en) * | 2018-04-04 | 2020-03-03 | 中国科学院理化技术研究所 | Zn3P2S8Preparation method and application of nonlinear optical crystal |
| CN110042461B (en) * | 2019-04-30 | 2021-06-08 | 哈尔滨工业大学 | Growth method of large-size zinc germanium phosphide crystal for increasing heat transfer |
| CN110424054B (en) * | 2019-09-03 | 2021-09-28 | 山东大学 | Preparation method and application of two-dimensional layered GeP single crystal nano film |
| CN113846258B (en) * | 2021-09-10 | 2022-09-16 | 海南大学 | Zn-Ge-Cu-Si-P high-entropy alloy material used as lithium ion battery cathode and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5611856A (en) * | 1994-05-19 | 1997-03-18 | Lockheed Sanders, Inc. | Method for growing crystals |
| CN1439604A (en) * | 2003-03-25 | 2003-09-03 | 四川大学 | Method and apparatus for preparing polycrystals of S-Ga-Ag |
| CN101050546A (en) * | 2007-05-09 | 2007-10-10 | 四川大学 | Method and equipment for synthesizing polycrystal of phosphor, germanium and zinc |
-
2007
- 2007-11-14 CN CN2007101445996A patent/CN101235542B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5611856A (en) * | 1994-05-19 | 1997-03-18 | Lockheed Sanders, Inc. | Method for growing crystals |
| CN1439604A (en) * | 2003-03-25 | 2003-09-03 | 四川大学 | Method and apparatus for preparing polycrystals of S-Ga-Ag |
| CN101050546A (en) * | 2007-05-09 | 2007-10-10 | 四川大学 | Method and equipment for synthesizing polycrystal of phosphor, germanium and zinc |
Non-Patent Citations (3)
| Title |
|---|
| G. A. Verozubova等.ZnGeP2 Synthesis and Growth from Melt.Materials Science and Engineering B48.1997,48191-197. * |
| 杨春晖, 张建.新型中、远红外波段非线性光学晶体磷化锗锌.人工晶体学报33 2.2004,33(2),141-143. |
| 杨春晖, 张建.新型中、远红外波段非线性光学晶体磷化锗锌.人工晶体学报33 2.2004,33(2),141-143. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101235542A (en) | 2008-08-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101235542B (en) | Single-crystal growth method for germanium zinc phosphide | |
| CN100564615C (en) | The preparation method of multi-element compounds semiconductor single-crystal and growing apparatus | |
| CN102758249B (en) | A kind of preparation method of colourless boule monocrystal | |
| CN101913636B (en) | Method for producing high-purity high-density alumina block material for sapphire single crystals | |
| CN101591808A (en) | Mix directionally solidified casting monocrystalline silicon of germanium and preparation method thereof | |
| CN101338453B (en) | Growth method of large size non-core YAG series laser crystal | |
| CN100425743C (en) | Process for growing gallium nitride single crystal utilizing new flux molten-salt growth method | |
| CN102934239A (en) | High-output apparatus for manufacturing a polycrystal silicon ingot for a solar cell | |
| CN101597790B (en) | Method for preparing cast polycrystalline silicon through melting silicon and doping nitrogen under nitrogen | |
| CN103789835A (en) | Improved gradient freeze GaAs single crystal growing method | |
| CN101348939B (en) | Growth method improving gallium arsenide single crystal utilization ratio | |
| CN101550586B (en) | Growing technique of ZnTe monocrystal | |
| CN101597787B (en) | Method for casting nitrogen-doped monocrystalline silicon with controllable nitrogen concentration under nitrogen | |
| CN101591807A (en) | Directionally solidified casting monocrystalline silicon of nitrating and preparation method thereof | |
| CN102965727B (en) | Polycrystalline silicon ingot and casting method thereof | |
| CN202090092U (en) | Single-crystal ingot casting furnace with temperature control seed crystal device | |
| CN105112990B (en) | A kind of method of the special-shaped nearly device frequency-doubling crystal of micro- drop-down oriented growth | |
| CN101597788B (en) | Method for preparing cast nitrogen-doped monocrystalline silicon through melting polycrystalline silicon under nitrogen | |
| CN102168305B (en) | Synthesis method of phosphorus-silicon-cadmium polycrystal material | |
| CN103205799A (en) | Method for growing C-oriented white stone crystals | |
| CN103397377A (en) | Uniform polycrystalline silicon crystal growing technology and ingot furnace thermal field heating device thereof | |
| WO2020248987A1 (en) | Photoelectric functional crystal m3re(po4)3, preparation method therefor, and application thereof | |
| CN113293429B (en) | Preparation method of monoclinic phase Ga2S3 single crystal | |
| CN203382850U (en) | Polycrystalline silicon ingot furnace thermal field heating device | |
| CN114561707B (en) | Infrared heating zone smelting furnace and method for preparing N-type bismuth telluride alloy by using same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C53 | Correction of patent of invention or patent application | ||
| CB03 | Change of inventor or designer information |
Inventor after: Yang Chunhui Inventor after: Xia Shixing Inventor after: Lei Zuotao Inventor after: Wang Meng Inventor before: Yang Chunhui Inventor before: Yang Chunhui Inventor before: Xia Shixing Inventor before: Wang Meng |
|
| COR | Change of bibliographic data |
Free format text: CORRECT: INVENTOR; FROM: YANG CHUNHUI G. A. VEROZUBOVA XIA SHIXING WANG MENG TO: YANG CHUNHUI XIA SHIXING LEI ZUOTAO WANG MENG |
|
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20100602 Termination date: 20211114 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |