CN105862129B - Compound caesium lead phosphorus oxygen and caesium lead phosphorus oxygen optical crystal and its production and use - Google Patents
Compound caesium lead phosphorus oxygen and caesium lead phosphorus oxygen optical crystal and its production and use Download PDFInfo
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- CN105862129B CN105862129B CN201510026658.4A CN201510026658A CN105862129B CN 105862129 B CN105862129 B CN 105862129B CN 201510026658 A CN201510026658 A CN 201510026658A CN 105862129 B CN105862129 B CN 105862129B
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Abstract
The present invention relates to a kind of compound caesium lead phosphorus oxygen and caesium lead phosphorus oxygen optical crystal and its production and use, the chemical formula of the optical crystal is CsPbPO4, molecular weight 435.07 belongs to rhombic system, and space group isPNma, cell parameter area=9.930 (9),b=5.655 (5),c=8.954 (8), V=502.8 (8)3,Z=4, caesium lead phosphoric-oxygenic compound is obtained using solid reaction process, then by the compound using high temperature solution method growth crystal, you can obtain caesium lead phosphorus oxygen optical crystal.Its transmission region is in 242nm between 2600nm, the crystal mechanical hardness is moderate, it is easy to cutting and polishing, suitable for making detector, aircraft, head-shield, the window material radome fairing, change the optics such as the prism of travel direction of light in the instrument such as lens or periscope, binocular, spectrometer in microscope and telescope.
Description
Technical field
The present invention relates to a kind of compound caesium lead phosphorus oxygen and the preparation method and purposes of caesium lead phosphorus oxygen optical crystal, the chemical combination
The chemical formula of thing is CsPbPO4。
Background technology
Inorganic phosphate due to abundant structural chemistry, simultaneously because its optics, catalysis, magnetics, fuel and
Potential application in terms of bone medical science so that the research to it turns into a focus.Phosphorus atoms pass through sp3Hydridization and oxygen atom key
Close, form rigid PO4Tetrahedron group.PO4Tetrahedron group is again by that with oxygen atom is enjoyed, can form the poly- of various configuration
Anionic group, so that phosphate compounds has abundant node configuration.Simultaneously as phosphate have it is rigid, anti-
Chemical corrosivity and heat endurance so that it has some excellent performances, so as to be widely used.For example, KDP,
DKDP, KTP and ADP etc., it is widely used due to its excellent nonlinear optical property.Although these materials
Crystal technique has reached its maturity, but there are still clearly disadvantageous part：Such as the easy deliquescence of crystal, growth cycle length, stratiform
Habit is serious and expensive etc..Therefore, it is still one extremely important and arduous to synthesize new optical crystal material
Work.
With the development of science and technology, proposing increasing demand to new function material, how boron is more effectively carried out
Hydrochlorate new material is designed to the topic of many scientific workers and business circles concern.In Development of Novel optical crystal, people
Still transparency range wide borate or phosphate crystal are selected.
The content of the invention
Present invention aims at provide a kind of compound caesium lead phosphorus oxygen, chemical formula CsPbPO4, molecular weight 435.07,
Synthesized using solid reaction process.
Another object of the present invention is to provide a kind of caesium lead phosphorus oxygen optical crystal, and the chemical formula of the crystal is CsPbPO4, molecule
Measure as 435.07, belong to rhombic system, space group Pnma, cell parameter is Z=4.
Still a further object of the present invention is to provide a kind of preparation method of caesium lead phosphorus oxygen optical crystal.
Another object of the present invention is to provide a kind of purposes of caesium lead phosphorus oxygen optical crystal, available for prepare detector, fly
Window material in row device, head-shield, radome fairing, lens or periscope, binocular, spectrometer in microscope and telescope
Deng the prism in instrument.
A kind of compound caesium lead phosphorus oxygen of the present invention, the chemical formula of the compound is CsPbPO4, molecular weight is
435.07, the compound is synthesized using solid reaction process.
A kind of caesium lead phosphorus oxygen optical crystal, the chemical formula of the crystal is CsPbPO4, molecular weight 435.07, belong to orthogonal
Crystallographic system, space group Pnma, cell parameter are Z=4.
The preparation method of described caesium lead phosphorus oxygen optical crystal, compound is synthesized using solid reaction process, it is molten using high temperature
Liquid method grows crystal, and concrete operations follow these steps to carry out：
A, using solid reaction process, Cs in molar ratio:Pb:P=1:1:1, which weighs raw material, is put into mortar, after grinding uniformly
Corundum crucible is put into, corundum crucible is placed in Muffle furnace, 400 DEG C is to slowly warm up to, constant temperature 12 hours, earthenware is taken out after cooling
Crucible, sample is ground uniformly, then be placed in crucible, Muffle furnace is warming up to 700 DEG C, constant temperature took out sample after 48 hours, put
Enter carefully to grind in mortar and obtain caesium lead phosphoric-oxygenic compound single-phase polycrystalline powder, then X-ray analysis, institute are carried out to the polycrystal powder
Obtain X-ray spectrogram and CsPbPO4Monocrystalline last X-ray spectrogram of pulverizing is consistent；
B, the caesium lead phosphoric-oxygenic compound single-phase polycrystalline powder for preparing step a and fluxing agent in molar ratio 1:1-8 is uniformly mixed
Close, be fitted into platinum crucible, 650-880 DEG C of temperature is heated to 1-80 DEG C/h of temperature heating rate, constant temperature 6-100 hours,
Obtain mixed molten liquid；
Or Cs in molar ratio:Pb:P=1:1:1 directly weighs raw material, is well mixed with fluxing agent, with 1-80 DEG C/h of temperature
Heating rate be heated to 650-880 DEG C of temperature, constant temperature 6-100 hours, obtain mixed molten liquid；
C, the obtained mixed molten liquids of step b are cooled to 595-830 DEG C, seed rod is stretched into below liquid level, with temperature
0.5-5 DEG C/h 5-100 DEG C of speed slow cooling, seed rod is proposed into liquid level, aggregation is had on seed rod, then with temperature 1-
80 DEG C/h speed is down to room temperature, obtains caesium lead phosphorus oxygen seed crystal；
D, step b mixed molten liquid is cooled to 590-820 DEG C, the obtained seed crystals of step c is fixed on seed rod, from
Lower seed crystal, first preheats 5-60 minutes by seed crystal at the top of crystal growing furnace, then mixed molten liquid liquid level or mixed will be extremely contacted under seed crystal
Close in liquation and carry out melt back, constant temperature 5-60 minutes, be quickly down to 580-810 DEG C of temperature；
E, crystal is carried out with 0-100rpm rotating speeds rotary seed crystal rod with the speed slow cooling of 0.1-3 DEG C/day of temperature again
Growth, after crystal growth yardstick needed for, room is down to by crystal lift-off mixed molten liquid surface, and with temperature 1-80 DEG C/h speed
Temperature, then crystal is taken out from burner hearth, you can obtain caesium lead phosphorus oxygen optical crystal.
Containing cesium compound it is Cs described in step a2CO3Or CsNO3, lead-containing compounds PbO, PbCO3Or Pb (NO3)2, it is phosphorous
Compound be (NH4)2HPO4Or (NH4)H2PO4。
Fluxing agent described in step b is PbO, PbF2-PbO、H3BO3-PbO、H3BO3-PbF2Or H3BO3-PbF2-PbO。
Fluxing agent H3BO3-PbO、H3BO3-PbF2Or H3BO3-PbF2H in-PbO systems3BO3With lead-containing compounds PbO, PbF2
Mol ratio be 1-6:1-5.
Window material of the described caesium lead phosphorus oxygen optical crystal in detector, aircraft, head-shield, radome fairing is prepared, or
The purposes in prism in convex lens in microscope, telescope, or periscope, binocular, spectrometer.
Caesium lead phosphorus oxygen optical crystal of the present invention and preparation method, in principle, using general chemical synthesis process all
Can be with prepare compound CsPbPO4, existing preferred solid reaction process, the compound has and following can typically obtain CsPbPO4
The chemical equation of compound：
(1)Cs2CO3+2PbO+2(NH4)H2PO4→2CsPbPO4+CO2↑+2NH3↑+3H2O↑
(2)Cs2CO3+2PbCO3+2(NH4)H2PO4→2CsPbPO4+3CO2↑+2NH3↑+3H2O↑
(3)Cs2CO3+2Pb(NO3)2+2(NH4)H2PO4→2CsPbPO4+CO2↑+4NO2↑+O2↑+2NH3↑+3H2O↑
(4)CsNO3+PbO+(NH4)H2PO4→CsPbPO4+NO2↑+NH3↑+3/2H2O↑+1/4O2↑
(5)CsNO3+PbCO3+(NH4)H2PO4→CsPbPO4+CO2↑+NO2↑+NH3↑+3/2H2O↑+1/4O2↑
(6)CsNO3+Pb(NO3)2+(NH4)H2PO4→CsPbPO4+3NO2↑+3/4O2↑+NH3↑+3/2H2O↑
(7)Cs2CO3+2PbO+2(NH4)2HPO4→2CsPbPO4+CO2↑+4NH3↑+3H2O↑
(8)Cs2CO3+2PbCO3+2(NH4)2HPO4→2CsPbPO4+3CO2↑+4NH3↑+3H2O↑
(9)CsNO3+PbO+(NH4)2HPO4→CsPbPO4+NO2↑+2NH3↑+3/2H2O↑+1/4O2↑
The present invention provides caesium lead phosphorus oxygen optical crystal, and the chemical formula of the crystal is CsPbPO4, molecular weight 435.07, category
In rhombic system, space group Pnma.
The present invention provides CsPbPO4The preparation method of optical crystal, crystal is grown using flux growth metrhod, can obtain size is
The CsPbPO of Centimeter Level4.The crystal mechanical hardness is moderate, is easy to cutting, polishing, suitable for making window, lens and rib
The optics such as mirror.Such as：Window, head-shield or radome fairing in infrared detector and aircraft etc.；For microscope and
Convex lens in telescope；Prism of travel direction for changing light in the instruments such as periscope, binocular etc..
Brief description of the drawings
Fig. 1 is CsPbPO of the present invention4The x-ray diffraction pattern of powder；
Fig. 2 is CsPbPO of the present invention4Crystal structure figure；
Fig. 3 is that window of the present invention uses schematic diagram, wherein 1 is protection cap, 2 be flange base, and 3 be crystalline material (window
Mouthful), 4 be sealing ring, and 5 be sealing ring, and 6 be outward turning trim ring；
Fig. 4 is convex lens principle schematic of the present invention；
Fig. 5 is that prism of the present invention uses schematic diagram.
Embodiment
Below in conjunction with drawings and examples, the present invention is described in detail：
Embodiment 1：
By reaction equation:(1)Cs2CO3+2PbO+2(NH4)H2PO4→2CsPbPO4+CO2↑+2NH3↑+3H2O ↑ synthesis
CsPbPO4Compound；
By Cs2CO3、PbO、(NH4)H2PO4In molar ratio 1:2:2, which weigh raw material, is put into mortar, mixes and carefully grinds,
It is then charged into Φ 100mm × 100mm opening corundum crucible, is put into Muffle furnace, is to slowly warm up to 400 DEG C, constant temperature 12 is small
When, crucible is taken out after cooling, sample is ground uniformly, then be placed in crucible, Muffle furnace is warming up to 700 DEG C, constant temperature 48 hours
Sample is taken out afterwards, carefully grinding is put into mortar and obtains caesium lead phosphoric-oxygenic compound single-phase polycrystalline powder, then to the polycrystal powder
Carry out X-ray analysis, gained X-ray spectrogram and CsPbPO4Monocrystalline last X-ray spectrogram of pulverizing is consistent；
Cesium carbonate in reaction equation is replaced by cesium nitrate, and lead oxide is replaced by ceruse, plumbi nitras, and ammonium dihydrogen phosphate is by phosphorus
The sour ammonium of hydrogen two is replaced；
By the caesium lead phosphorus oxygen CsPbPO of synthesis4Compound and fluxing agent PbO in molar ratio 1:3 carry out mixture, load Φ
In 80mm × 80mm opening platinum crucible, 850 DEG C of temperature is heated to temperature 50 C/h heating rate, constant temperature 24 hours,
Obtain caesium lead phosphorus oxygen mixed molten liquid；
Mixed molten liquid is cooled to 790 DEG C again, seed rod is quickly stretched into below liquid level, is delayed with 2 DEG C/h of temperature speed
Slowly 700 DEG C are down to, seed rod are proposed into liquid level, aggregation is had on seed rod, then room temperature is down to temperature 50 C/h speed,
Obtain CsPbPO4Seed crystal；
Crystal is grown in compound liquation：Obtained caesium lead phosphorus oxygen mixed molten liquid is down to 780 DEG C of temperature, then will be obtained
Caesium lead phosphorus oxygen seed crystal be fixed on seed rod, the lower seed crystal at the top of the crystal growing furnace, first seed crystal is preheated 10 minutes, then will
Melt back is carried out to contact mixed molten liquid liquid level under seed crystal, constant temperature 10 minutes, is quickly down to 770 DEG C of temperature；
Cooled again with the speed of DEG C/day of temperature 2, with 80rpm rotating speed rotary seed crystal rod, after crystal growth terminates, made
Crystal departs from liquid level, is down to room temperature with temperature 50 C/h speed, then takes out crystal from burner hearth, you can obtaining yardstick is
22mm × 21mm × 18mm CsPbPO4Crystal.
Embodiment 2：
By reaction equation：(2)Cs2CO3+2PbCO3+2(NH4)H2PO4→2CsPbPO4+3CO2↑+2NH3↑+3H2O ↑ preparation
CsPbPO4Compound；
By Cs2CO3、PbCO3、(NH4)H2PO4In molar ratio 1:2:2 directly weigh raw material, with fluxing agent PbO in molar ratio
1:2 carry out mixture, are fitted into Φ 80mm × 80mm opening platinum crucible, temperature is heated to 80 DEG C/h of temperature heating rate
880 DEG C, constant temperature 30 hours, obtain caesium lead phosphorus oxygen mixed molten liquid；
Mixed molten liquid is down to 830 DEG C of temperature, seed rod is quickly stretched under liquid level, it is slow with 2 DEG C/h of temperature speed
750 DEG C are down to, seed rod is proposed into liquid level, aggregation is had on seed rod, then room temperature is down to temperature 50 C/h speed, is obtained
Obtain CsPbPO4Seed crystal；
Crystal is grown in compound liquation：Obtained caesium lead phosphorus oxygen mixed molten liquid is down to 820 DEG C of temperature, by acquisition
CsPbPO4Seed crystal is fixed on seed rod, from the lower seed crystal in crystal growing furnace top, is first preheated seed crystal 10 minutes, then by seed
Melt back is carried out under crystalline substance into mixed molten liquid, constant temperature 10 minutes, is quickly down to 810 DEG C of temperature；
Again with the speed slow cooling of DEG C/day of temperature 1.5, with 50rpm rotating speed rotary seed crystal rod, treat crystal growth to institute
After needing yardstick, by crystal lift-off molten surface, room temperature is down to temperature 10 DEG C/h speed, then taken out crystal from burner hearth,
The CsPbPO that yardstick is 24mm × 18mm × 12mm can be obtained4Crystal；
Cesium carbonate in reaction equation is replaced by cesium nitrate, and ceruse is replaced by lead oxide, plumbi nitras, and ammonium dihydrogen phosphate is by phosphorus
The sour ammonium of hydrogen two is replaced.
Embodiment 3：
By reaction equation：(3)Cs2CO3+2Pb(NO3)2+2(NH4)H2PO4→2CsPbPO4+CO2↑+4NO2↑+O2↑+2NH3↑+
3H2O ↑ synthesis CsPbPO4 compounds；
By Cs2CO3、Pb(NO3)2、(NH4)H2PO4In molar ratio 1:2:2 are put into mortar, mix and carefully grind, then
It is fitted into Φ 100mm × 100mm opening corundum crucible, is put into Muffle furnace, is to slowly warm up to 400 DEG C, constant temperature 12 hours is cold
But crucible is taken out afterwards, sample is ground uniformly, then is placed in crucible, Muffle furnace is warming up to 700 DEG C, constant temperature is after 48 hours by sample
Product take out, and are put into mortar carefully grinding and obtain caesium lead phosphoric-oxygenic compound single-phase polycrystalline powder, then carry out X to the polycrystal powder and penetrate
Line analysis, gained X-ray spectrogram and CsPbPO4Monocrystalline last X-ray spectrogram of pulverizing is consistent；
Cesium carbonate in reaction equation is replaced by cesium nitrate, and plumbi nitras is replaced by ceruse, lead oxide, and ammonium dihydrogen phosphate is by phosphorus
The sour ammonium of hydrogen two is replaced；
By the caesium lead phosphorus oxygen CsPbPO of synthesis4Compound and fluxing agent PbO-H3BO3In molar ratio 1:2 carry out mixture, wherein
PbO and H3BO3Mol ratio be 1:1, it is fitted into Φ 80mm × 80mm opening platinum crucible, with temperature 70 C/h heating speed
Rate is heated to 840 DEG C, constant temperature 48 hours, obtains caesium lead phosphorus oxygen liquation；
Mixed molten liquid is cooled to 780 DEG C again, seed rod is quickly stretched into below liquid level, is delayed with 1 DEG C/h of temperature speed
Slowly 685 DEG C are down to, seed rod are proposed into liquid level, aggregation is had on seed rod, then room temperature is down to 20 DEG C/h of temperature speed,
Obtain CsPbPO4Seed crystal；
Crystal is grown in compound liquation：Obtained caesium lead phosphorus oxygen mixed molten liquid is down to 770 DEG C of temperature, by acquisition
CsPbPO4Seed crystal is fixed on seed rod, from the lower seed crystal in crystal growing furnace top, is first preheated seed crystal 5 minutes, then by seed crystal
It is lower to carry out melt back to contact mixed molten liquid liquid level, constant temperature 5 minutes, quickly it is down to 760 DEG C of temperature；
Cooled again with the speed of DEG C/day of temperature 1, with 25rpm rotating speed rotary seed crystal rod, after crystal growth terminates, made
Crystal departs from liquid level, is down to room temperature with 20 DEG C/h of temperature speed, then takes out crystal from burner hearth, you can obtaining yardstick is
27mm × 24mm × 18mm CsPbPO4Crystal.
Embodiment 4：
By reaction equation：(4)CsNO3+PbO+(NH4)H2PO4→CsPbPO4+NO2↑+NH3↑+3/2H2O↑+1/4O2↑ synthesis
CsPbPO4Compound；
By CsNO3、PbO、(NH4)H2PO4In molar ratio 1:1:1 directly weighs raw material, with fluxing agent PbO-H3BO3By mole
Than 1:3 carry out mixture, wherein PbO and H3BO3Mol ratio be 1:1, it is fitted into Φ 80mm × 80mm opening platinum crucible, with
1 DEG C/h of temperature heating rate is heated to 790 DEG C of temperature, constant temperature 12 hours, obtains caesium lead phosphorus oxygen mixed molten liquid；
Mixed molten liquid is cooled to 730 DEG C, seed rod is quickly stretched under liquid level, is slowly dropped with 3 DEG C/h of temperature speed
To 640 DEG C, seed rod is proposed into liquid level, aggregation is had on seed rod, then room temperature is down to 40 DEG C/h of temperature speed, is obtained
CsPbPO4Seed crystal；
Crystal is grown in compound liquation：Obtained caesium lead phosphorus oxygen mixed molten liquid is down to 720 DEG C of temperature, by acquisition
CsPbPO4Seed crystal is fixed on seed rod, from the lower seed crystal in crystal growing furnace top, is first preheated seed crystal 15 minutes, then by seed
Crystalline substance is lower to carry out melt back to contact mixed molten liquid liquid level, constant temperature 15 minutes, is quickly down to 710 DEG C of temperature；
Again with the speed slow cooling of DEG C/day of temperature 3, with 10rpm rotating speed rotary seed crystal rod, treat crystal growth needed for
After yardstick, by crystal lift-off molten surface, room temperature is down to temperature 40 DEG C/h speed, then taken out crystal from burner hearth, i.e.,
The CsPbPO that yardstick is 25mm × 22mm × 17mm can be obtained4Crystal；
Cesium nitrate in reaction equation is replaced by cesium carbonate, and lead oxide is replaced by ceruse, plumbi nitras, and ammonium dihydrogen phosphate is by phosphorus
The sour ammonium of hydrogen two is replaced.
Embodiment 5：
By reaction equation：(5)CsNO3+PbCO3+(NH4)H2PO4→CsPbPO4+CO2↑+NO2↑+NH3↑+3/2H2O↑+1/4O2↑
Prepare CsPbPO4Compound；
By CsNO3、PbCO3、(NH4)H2PO4In molar ratio 1:1:1 directly weighs raw material, with fluxing agent PbO-H3BO3Massage
That ratio 1:4 carry out mixture, wherein PbO and H3BO3Mol ratio be 1:1.5, load Φ 80mm × 80mm opening platinum crucible
In, 760 DEG C of temperature is heated to 20 DEG C/h of temperature heating rate, constant temperature 50 hours, obtains caesium lead phosphorus oxygen mixed molten liquid；
Mixed molten liquid is down to 695 DEG C of temperature, seed rod is quickly stretched under liquid level, is delayed with 1.5 DEG C/h of temperature speed
Slowly 600 DEG C are down to, seed rod are proposed into liquid level, aggregation is had on seed rod, then room temperature is down to 30 DEG C/h of temperature speed,
Obtain caesium lead phosphorus oxygen seed crystal；
Crystal is grown in compound liquation：Obtained caesium lead phosphorus oxygen mixed molten liquid is down to 685 DEG C of temperature, by acquisition
CsPbPO4Seed crystal is fixed on seed rod, from the lower seed crystal in crystal growing furnace top, is first preheated seed crystal 40 minutes, then by seed
Melt back is carried out under crystalline substance into mixed molten liquid, constant temperature 40 minutes, is quickly down to 675 DEG C of temperature；
Again with the speed slow cooling of DEG C/day of temperature 1.5, with 0rpm rotating speed not rotary seed crystal rod, treat that crystal growth arrives
After required yardstick, by crystal lift-off molten surface, room temperature is down to temperature 30 DEG C/h speed, then taken crystal from burner hearth
Go out, you can acquisition yardstick is 25mm × 21mm × 17mm CsPbPO4Crystal；
Embodiment 6：
By reaction equation：(6)CsNO3+Pb(NO3)2+(NH4)H2PO4→CsPbPO4+3NO2↑+3/4O2↑+NH3↑+3/2H2O↑
Synthesize CsPbPO4Compound；
By CsNO3、Pb(NO3)2、(NH4)H2PO4In molar ratio 1:1:1 is put into mortar, mixes and carefully grinds, then
It is fitted into Φ 100mm × 100mm opening corundum crucible, is put into Muffle furnace, is to slowly warm up to 400 DEG C, constant temperature 12 hours is cold
But crucible is taken out afterwards, sample is ground uniformly, then is placed in crucible, Muffle furnace is warming up to 700 DEG C, constant temperature is after 48 hours by sample
Product take out, and are put into mortar carefully grinding and obtain caesium lead phosphoric-oxygenic compound single-phase polycrystalline powder, then carry out X to the polycrystal powder and penetrate
Line analysis, gained X-ray spectrogram and CsPbPO4Monocrystalline last X-ray spectrogram of pulverizing is consistent；
Cesium nitrate in reaction equation is replaced by cesium carbonate, and plumbi nitras is replaced by ceruse, lead oxide, and ammonium dihydrogen phosphate is by phosphorus
The sour ammonium of hydrogen two is replaced；
By the caesium lead phosphorus oxygen CsPbPO of synthesis4Compound and fluxing agent PbO-H3BO3In molar ratio 1:3.5 carry out mixture, its
Middle PbO and H3BO3Mol ratio be 1:3, it is fitted into Φ 80mm × 80mm opening platinum crucible, with 5 DEG C/h of temperature heating speed
Rate is heated to 750 DEG C of temperature, constant temperature 60 hours, obtains caesium lead phosphorus oxygen liquation；
Mixed molten liquid is down to 690 DEG C of temperature, seed rod is quickly stretched under liquid level, it is slow with 4 DEG C/h of temperature speed
610 DEG C are down to, seed rod is proposed into liquid level, aggregation is had on seed rod, then room temperature is down to temperature 60 C/h speed, is obtained
Obtain caesium lead phosphorus oxygen seed crystal；
Crystal is grown in compound liquation：Obtained caesium lead phosphorus oxygen mixed molten liquid is down to 680 DEG C of temperature, by acquisition
CsPbPO4Seed crystal is fixed on seed rod, from the lower seed crystal in crystal growing furnace top, is first preheated seed crystal 25 minutes, then by seed
Melt back is carried out under crystalline substance into mixed molten liquid, constant temperature 25 minutes, is quickly down to 670 DEG C of temperature；
Again with the speed slow cooling of DEG C/day of temperature 2.5, with 40rpm rotating speed rotary seed crystal rod, treat crystal growth to institute
After needing yardstick, by crystal lift-off molten surface, room temperature is down to temperature 60 C/h speed, then taken out crystal from burner hearth,
The CsPbPO that yardstick is 23mm × 18mm × 12mm can be obtained4Crystal.
Embodiment 7：
By reaction equation：(7)Cs2CO3+2PbO+2(NH4)2HPO4→2CsPbPO4+CO2↑+4NH3↑+3H2O ↑ synthesis
CsPbPO4Compound；
By Cs2CO3、PbO、(NH4)2HPO4In molar ratio 1:2:2 are put into mortar, mix and carefully grind, are then charged into
In Φ 100mm × 100mm opening corundum crucible, it is put into Muffle furnace, is slowly increased to 400 DEG C of temperature, constant temperature 12 hours, cooling
After take out crucible, sample is ground uniform, then is placed in crucible, Muffle furnace is risen into 700 DEG C of temperature, constant temperature is after 48 hours by sample
Product take out, and are put into mortar carefully grinding and obtain caesium lead phosphoric-oxygenic compound single-phase polycrystalline powder, then carry out X to the polycrystal powder and penetrate
Line analysis, gained X-ray spectrogram and CsPbPO4Monocrystalline last X-ray spectrogram of pulverizing is consistent；
Cesium carbonate in reaction equation is replaced by cesium nitrate, and lead oxide is replaced by ceruse, plumbi nitras, and diammonium hydrogen phosphate is by phosphorus
Acid dihydride ammonium is replaced；
By the caesium lead phosphoric-oxygenic compound of synthesis and fluxing agent H3BO3-PbF2In molar ratio 1:3 carry out mixture, wherein H3BO3With
PbF2Mol ratio be 2:1, it is fitted into Φ 80mm × 80mm opening platinum crucible, is heated with 35 DEG C/h of temperature heating rate
To 800 DEG C of temperature, constant temperature 32 hours, caesium lead phosphorus oxygen liquation is obtained；
Mixed molten liquid is down to 745 DEG C of temperature, seed rod is quickly stretched under liquid level, is delayed with 2.5 DEG C/h of temperature speed
Slowly 640 DEG C are down to, seed rod are proposed into liquid level, aggregation is had on seed rod, then room temperature is down to temperature 45 C/h speed,
Obtain caesium lead phosphorus oxygen seed crystal；
Crystal is grown in compound liquation：Obtained caesium lead phosphorus oxygen mixed molten liquid is down to 735 DEG C of temperature, by acquisition
CsPbPO4Seed crystal is fixed on seed rod, from the lower seed crystal in crystal growing furnace top, is first preheated seed crystal 15 minutes, then by seed
Melt back is carried out under crystalline substance into mixed molten liquid, constant temperature 15 minutes, is quickly down to 725 DEG C of temperature；
Again with the speed slow cooling of DEG C/day of temperature 0.5, with 35rpm rotating speed rotary seed crystal rod, treat crystal growth to institute
After needing yardstick, by crystal lift-off molten surface, room temperature is down to temperature 65 DEG C/h speed, then taken out crystal from burner hearth,
The CsPbPO that yardstick is 20mm × 15mm × 10mm can be obtained4Crystal.
Embodiment 8：
By reaction equation：(8)Cs2CO3+2PbCO3+2(NH4)2HPO4→2CsPbPO4+3CO2↑+4NH3↑+3H2O ↑ synthesis
CsPbPO4Compound；
By Cs2CO3、PbCO3、(NH4)2HPO4In molar ratio 1:2:2 directly weigh raw material, with fluxing agent H3BO3-PbF2Press
Mol ratio 1:1 carries out mixture, wherein H3BO3With PbF2Mol ratio be 6:1, load Φ 80mm × 80mm opening platinum crucible
In, 850 DEG C of temperature is heated to 15 DEG C/h of temperature heating rate, constant temperature 50 hours, obtains caesium lead phosphorus oxygen mixed molten liquid；
Mixed molten liquid is down to 790 DEG C of temperature, seed rod is quickly stretched under liquid level, it is slow with 1 DEG C/h of temperature speed
680 DEG C are down to, seed rod is proposed into liquid level, aggregation is had on seed rod, then room temperature is down to 25 DEG C/h of temperature speed, is obtained
Obtain caesium lead phosphorus oxygen seed crystal；
Crystal is grown in compound liquation：Obtained caesium lead phosphorus oxygen mixed molten liquid is down to 780 DEG C of temperature, by acquisition
CsPbPO4Seed crystal is fixed on seed rod, from the lower seed crystal in crystal growing furnace top, is first preheated seed crystal 60 minutes, then by seed
Melt back is carried out under crystalline substance into mixed molten liquid, constant temperature 60 minutes, is quickly down to 770 DEG C of temperature；
Again with the speed slow cooling of DEG C/day of temperature 1.5, with 65rpm rotating speed rotary seed crystal rod, treat crystal growth to institute
After needing yardstick, by crystal lift-off molten surface, room temperature is down to temperature 45 C/h speed, then taken out crystal from burner hearth,
The CsPbPO that yardstick is 18mm × 14mm × 10mm can be obtained4Crystal；
Cesium carbonate in reaction equation is replaced by cesium nitrate, and ceruse is replaced by lead oxide, plumbi nitras, and diammonium hydrogen phosphate is by phosphorus
Acid dihydride ammonium is replaced.
Embodiment 9：
By reaction equation：(9)CsNO3+PbO+(NH4)2HPO4→CsPbPO4+NO2↑+2NH3↑+3/2H2O↑+1/4O2↑ synthesis
CsPbPO4Compound；
By CsNO3、PbO、(NH4)2HPO4In molar ratio 1:1:1 is put into mortar, mixes and carefully grinds, is then charged into
In Φ 100mm × 100mm opening corundum crucible, it is put into Muffle furnace, is slowly increased to 400 DEG C of temperature, constant temperature 12 hours, cooling
After take out crucible, sample is ground uniform, then is placed in crucible, Muffle furnace is risen into 700 DEG C of temperature, constant temperature is after 48 hours by sample
Product take out, and are put into mortar carefully grinding and obtain caesium lead phosphoric-oxygenic compound single-phase polycrystalline powder, then carry out X to the polycrystal powder and penetrate
Line analysis, gained X-ray spectrogram and CsPbPO4Monocrystalline last X-ray spectrogram of pulverizing is consistent；
Cesium nitrate in reaction equation is replaced by cesium carbonate, and lead oxide is replaced by ceruse, plumbi nitras, and diammonium hydrogen phosphate is by phosphorus
Acid dihydride ammonium is replaced；
By the caesium lead phosphorus oxygen CsPbPO of synthesis4Compound and fluxing agent H3BO3-PbF2In molar ratio 1:8 carry out mixture, its
Middle H3BO3With PbF2Mol ratio be 1:5, it is fitted into Φ 80mm × 80mm opening platinum crucible, with 80 DEG C/h of temperature heating
Speed is heated to 650 DEG C of temperature, constant temperature 100 hours, obtains caesium lead phosphorus oxygen mixed molten liquid；
Mixed molten liquid is down to 600 DEG C of temperature, seed rod is quickly stretched under liquid level, is delayed with 0.5 DEG C/h of temperature speed
Slowly 595 DEG C are down to, seed rod are proposed into liquid level, aggregation is had on seed rod, then room temperature is down to 1 DEG C/h of temperature speed,
Obtain caesium lead phosphorus oxygen seed crystal；
Crystal is grown in compound liquation：Obtained caesium lead phosphorus oxygen mixed molten liquid is down to 595 DEG C of temperature, by acquisition
CsPbPO4Seed crystal is fixed on seed rod, from the lower seed crystal in crystal growing furnace top, is first preheated seed crystal 45 minutes, then by seed
Melt back is carried out under crystalline substance into mixed molten liquid, constant temperature 45 minutes, is quickly down to 590 DEG C of temperature；
Again with the speed slow cooling of DEG C/day of temperature 1, with 30rpm rotating speed rotary seed crystal rod, treat crystal growth needed for
After yardstick, by crystal lift-off molten surface, room temperature is down to temperature 35 DEG C/h speed, then taken out crystal from burner hearth, i.e.,
The CsPbPO that yardstick is 20mm × 11mm × 8mm can be obtained4Crystal.
Embodiment 10：
Arbitrary CsPbPO obtained by embodiment 1-94Crystal, for preparing in detector, aircraft, head-shield, radome fairing
Window material (as shown in Figure 3)；For preparing the convex lens in microscope and telescope (as shown in Figure 4)；Used for preparing
CsPbPO4One prism of crystal pro cessing, change the travel direction of light in the instruments such as periscope, binocular, so as to adjust
Complex light, spectrum is decomposed into spectral instrument by its image space (as shown in Figure 5) by dispersion.
Claims (6)
1. a kind of caesium lead phosphorus oxygen optical crystal, it is characterised in that the chemical formula of the crystal is CsPbPO4, molecular weight 435.07, category
In rhombic system, space group isPNma, cell parameter area=9.930 (9),b=5.655 (5),c = 8.954(8)
, V=502.8 (8)3,Z=4, crystal is grown using pyrosol.
2. the preparation method of caesium lead phosphorus oxygen optical crystal according to claim 1, it is characterised in that using solid reaction process
Compound is synthesized, crystal is grown using pyrosol, concrete operations follow these steps to carry out：
A, using solid reaction process, Cs in molar ratio:Pb:P = 1:1:1, which weighs raw material, is put into mortar, is put into after grinding uniformly
Corundum crucible, corundum crucible is placed in Muffle furnace, is to slowly warm up to 400 DEG C, constant temperature 12 hours, crucible is taken out after cooling, will
Sample grinding is uniform, then is placed in crucible, Muffle furnace is warming up into 700 DEG C, constant temperature took out sample after 48 hours, was put into mortar
In carefully grinding obtain caesium lead phosphoric-oxygenic compound single-phase polycrystalline powder, then X-ray analysis is carried out to the polycrystal powder, gained X is penetrated
Line spectrum figure and CsPbPO4Monocrystalline last X-ray spectrogram of pulverizing is consistent；
B, the caesium lead phosphoric-oxygenic compound single-phase polycrystalline powder for preparing step a and fluxing agent in molar ratio 1:1-8 is uniformly mixed,
It is fitted into platinum crucible, 650-880 DEG C of temperature is heated to 1-80 DEG C/h heating rate, constant temperature 6-100 hours, mixed
Liquation；
Or Cs in molar ratio:Pb:P = 1:1:1 directly weighs raw material, is well mixed with fluxing agent, with 1-80 DEG C/h heating speed
Rate is heated to 650-880 DEG C of temperature, constant temperature 6-100 hours, obtains mixed molten liquid；
C, the obtained mixed molten liquids of step b are cooled to 595-830 DEG C, seed rod is stretched into below liquid level, with 0.5-5 DEG C/h's
5-100 DEG C of speed slow cooling, seed rod is proposed into liquid level, aggregation is had on seed rod, then drop with 1-80 DEG C/h speed
To room temperature, caesium lead phosphorus oxygen seed crystal is obtained；
D, step b mixed molten liquid is cooled to 590-820 DEG C, the obtained seed crystals of step c is fixed on seed rod, from crystal
Lower seed crystal, first preheats 5-60 minutes by seed crystal at the top of growth furnace, then will be molten to contact mixed molten liquid liquid level or mixing under seed crystal
Melt back is carried out in liquid, constant temperature 5-60 minutes, is quickly down to 780-810 DEG C of temperature；
E, the growth of crystal is carried out with 0-100rpm rotating speeds rotary seed crystal rod, is treated with 0.1-3 DEG C/day of speed slow cooling again
After crystal growth yardstick needed for, room temperature is down to by crystal lift-off mixed molten liquid surface, and with 1-80 DEG C/h speed, then by crystalline substance
Body takes out from burner hearth, you can obtains caesium lead phosphorus oxygen optical crystal.
3. according to the method for claim 2, it is characterised in that containing cesium compound be Cs in step a2CO3Or CsNO3, it is leaded
Compound is PbO, PbCO3Or Pb (NO3)2, phosphorous compound is (NH4)2HPO4Or (NH4)H2PO4。
4. according to the method for claim 2, it is characterised in that fluxing agent described in step b is PbO, PbF2-PbO、H3BO3-
PbO、H3BO3-PbF2Or H3BO3-PbF2-PbO。
5. method according to claim 4, it is characterised in that fluxing agent H3BO3-PbO、H3BO3-PbF2Or H3BO3-PbF2-PbO
H in system3BO3With lead-containing compounds PbO, PbF2Mol ratio be 1-6:1-5.
6. caesium lead phosphorus oxygen optical crystal according to claim 1 is in detector, aircraft, head-shield, radome fairing is prepared
The use in prism in convex lens in window material, or microscope, telescope, or periscope, binocular, spectrometer
On the way.
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| CN101876772A (en) * | 2009-11-19 | 2010-11-03 | 中国科学院新疆理化技术研究所 | Compound potassium lead borophosphate nonlinear optical crystal as well as preparation method and application thereof |
| CN103628136A (en) * | 2012-08-23 | 2014-03-12 | 中国科学院新疆理化技术研究所 | Compound lead rubidium borophosphate and non-linear optical crystal of lead rubidium borophosphate, preparation method and applications thereof |
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| CN101876772A (en) * | 2009-11-19 | 2010-11-03 | 中国科学院新疆理化技术研究所 | Compound potassium lead borophosphate nonlinear optical crystal as well as preparation method and application thereof |
| CN103628136A (en) * | 2012-08-23 | 2014-03-12 | 中国科学院新疆理化技术研究所 | Compound lead rubidium borophosphate and non-linear optical crystal of lead rubidium borophosphate, preparation method and applications thereof |
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| Study of phase transitions in the system ABPO4 with A=Li,Rb and B=Mg,Ca,Sr,Ba,Zn,Cd,Pb;L.ELAMMARI et al.;《Phase Transitions》;19881231;第13卷;全文 * |
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