CN1260407C - Growth process for DADP photoelectric crystal - Google Patents
Growth process for DADP photoelectric crystal Download PDFInfo
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- CN1260407C CN1260407C CN 01143234 CN01143234A CN1260407C CN 1260407 C CN1260407 C CN 1260407C CN 01143234 CN01143234 CN 01143234 CN 01143234 A CN01143234 A CN 01143234A CN 1260407 C CN1260407 C CN 1260407C
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Abstract
The present invention relates to a growing method of a deuteration ammonium dideuterium phosphate (DADP) electrooptic crystal, which belongs to the field of crystal growth. The present invention uses NH4H2PO4 and heavy water as raw material, and grows a crystal by using a solution temperature falling method, wherein the growth condition of the crystal satisfies that the pH value of solution is from 4 to 5, growth temperature is from 60 DEG C to room temperature, a seed crystal uses a Z cutting direction, growth speed is controlled at 1 to 3 mm/d at z direction, temperature control accuracy is (+/-)0.01 DEG C, and the forward backward rotary speed of the crystal is from 50 to 60 revolutions per minute. The growing method of the DADP crystal adopted by the present invention has the advantages of simple device, convenient operation and high growth velocity of the crystals, and has high success ratio for obtaining the crystals with high optical quality.
Description
The present invention relates to field of crystal growth, particularly relate to a kind of growth method of electro-optic crystal.
DADP (ND
4D
2PO
4, be called for short DADP or AD
*P) crystal is KDP (potassium primary phosphate) type (KDP, DKDP, ADP, DADP) a kind of good electrooptic nonlinear optical crystal material in.Be electrooptical switching, modulated laser high-tech sector electrooptical material commonly used at 400～1100nm wave band.As KDP (KH
2PO
4) two hydrogen of deuterate become DKDP (KD
2PO
4) crystal is the same, ADP (NH
4H
2PO
4) six hydrogen of deuterate and become DADP, crystalline optics, electric property is similar to the ADP crystal but its semi-wave modulated voltage is minimum in the above-mentioned KDP N-type waferN material, near infrared sees through wave band and also widens nearly 300nm than ADP crystal, causes the DADP crystal at making high frequency, high-sensitive electro-optical modulation device proper value to be arranged more.DADP crystalline structure (Piltz.R.O.McMahon, et.al.Deuteration and pressure effects on the crystal structure ofparaelectric NH
4H
2PO
4Zeitschrift fueer kristallographic, 195 (1991) 241-249.), its light,, calorifics, character such as phase transformation (R.S.Adhavand A.D.Vlassopoules, J.QuantumnElectron 10,688 (1974)) research is all arranged abroad, American I nrad INC. company (QuantumnTechnology Inc.EO Modulation System specifications.) is relevant for the electro-optical device product introduction of KDP type crystals, but the raw material that does not find relevant DADP as yet is synthetic and bibliographical information (the A.opilaki and J.Szuber of crystal growth aspect, Journal of Crystal growth 29 (1975) 173-175.), domesticly do not carry out this crystalline research work yet.
Because the DADP crystal is the good electric luminescent crystal material that has important application and exploitation to be worth, so purpose of the present invention is exactly the method that discloses a kind of DADP feedstock production and crystal growth.Make and to obtain to reach electro-optical device size 20 * 20 * 20mm in this way
3Crystalline material with specification of quality.
Realize that technical scheme of the present invention is as follows:
1.DADP the crystal growth raw material is synthetic
With reference to ADA (NH
4H
2AsO
4) deuterate is DADA (ND
4D
2AsO
4) synthetic method (A.pilaki and J.Szuber, Journal of Crystal growth 29 (1975) 173-175), promptly three recrystallizations obtain six reactive hydrogen deuterates among the ADA DADA crystallization of higher deuterate rate in excessive heavy water.ADP also can adopt this method, uses the pure NH of top grade
4H
2PO
4(content＞99.5%) and heavy water (purity＞99.5%) are raw material, through three recrystallizations, obtain to contain the crystallization raw material of deuterium amount＞95% in heavy water, different is except adopting low temperature crystallization to increase the way of the crystallization amount of separating out, also the mother liquor after the crystallization is distilled concentratedly, improve D
2The degree of supersaturation of O-DADP solution increases the crystallization yields of DADP significantly.
2. growing method and condition
According to the mensuration of DADP solubleness in heavy water, be 88.4 gram/100ml (D2O) 42 ℃ solubleness.To the saturated solution of 1000ml, every increase 10gDADP can make temperature of saturation improve 1 ℃, illustrates that DADP is at D
2Bigger solubleness and temperature factor are arranged, so available aqueous solution cooling method growth DADP crystal among the O.
Adopt the DADP crystallization (contain deuterium amount＞95%) of above-mentioned ADP after three deuterates of heavy water to be the crystal growth raw material, heavy water is a solvent.With ADP crystal z section is seed crystal, is fixed in the synthetic glass disk, along axially unidirectional growth down of z.The potential of hydrogen PH=4 of solution～5, growth start-stop temperature is 60 a ℃～room temperature, the temperature-controlled precision of aqueous solution thermostatic bath reaches ± and 0.01 ℃.The forward and reverse velocity of rotation of crystalline is 50～60 rev/mins, and crystal was controlled at 1～3mm/ days along the axial speed of growth of z.
3. the technological step of crystal growth (comprises DADP-D
2The preparation of O saturated solution and crystal growing process)
(1) preparation of saturated solution: dissolve → hang brilliant method and measure temperature of saturation → 0.25 μ m millipore filtration → solution Overheating Treatment (10 ℃, 24 hours).
(2) crystal growing process: z cuts the manufacturing of ADP seed crystal → seed crystal and is preheated to temperature of saturation → seed crystal and moves into saturated solution → one-tenths awl → programmed cooling and control crystal growth → crystal annealing and take out to room temperature.
Through the growth in 1～2 month cycle, what can obtain to reach crystal current optical device specification of quality contains the transparent complete DADP crystal of deuterium amount＞95%.
The present invention compares the beneficial effect that is had with background technology: DADP crystal raw material of the present invention preparation and growing method are compared with DKDP crystal of the same type, raw material synthetic aspect, with ADP directly and heavy water carry out the deuterate recrystallization, the purity of raw material is higher, improve crystallization yields in conjunction with adopting the mother liquor distillation to concentrate, also reduced the cost of raw material.The monocline that occurs influencing crystalline growth velocity and quality easily in the growth under than the high degree of supersaturation condition of DKDP crystal aspect the crystal growth is problem mutually, and monocline phase problem does not appear in DADP crystal growth of the present invention, so can improve the crystalline speed of growth and quality.DADP growing method of the present invention has that equipment is simple, easy to operate, and crystalline growth velocity is fast, obtains the high advantage of high optical quality crystalline success ratio.
Now enumerate and realize exemplary embodiments of the present invention:
1, raw material: use the pure NH of homemade top grade
4H
2PO
4(content 99.5%) obtains containing the deuterium amount greater than 95% DADP crystal raw material through three deuterate recrystallizations of heavy water (containing deuterium amount＞99.5%).
2, the preparation of growth solution: 1000cm
3The K9 ground glass educate in the brilliant bottle DADP crystallization raw material with 600ml heavy water dissolving 650g.With hanging the saturation point that brilliant method records solution is 54.8 ℃, with 0.25 μ m filtering with microporous membrane solution, crosses 24 hours postcooling to 55.7 of hot solution ℃ for 65 ℃, and the pH value of solution is 4.3.
3, seed crystal is prepared: adopt ADP crystal Z to the wafer that cuts out 21 * 21 * 4 (mm), through grinding, tiing up on synthetic glass disk carrier crystal stand with nylon wire after the boring, clean, move into above-mentioned solution and carry out the growth of crystal temperature control after preheating.
4, crystal growth condition:
Constant temperature water bath groove temperature-controlled precision is ± 0.01 ℃, and the crystal rotating speed is 50 rev/mins, and the average speed of growth of Z direction is 1.7mm/ days, x (y) direction average speed of growth 0.26mm/ days, and crystal is grown along the Z-direction half cone downwards.
Obtain being of a size of the transparent complete uniform DADP monocrystalline of 29 * 29 * 62 (mm) through 34 days growth cycles.This crystal does not have scattering phenomenon under the He-Ne Lasers radiation, illustrate that crystal has good optical quality.
Claims (2)
1. the growth method of a DADP electro-optic crystal comprises synthesizing and crystalline growth method two portions of crystallization raw material, it is characterized in that:
(1) DADP is the synthetic of DADP crystallization raw material: the NH that uses pure content＞99.5% of top grade
4H
2PO
4The heavy water of reagent and purity＞99.5% is a raw material, adopts three recrystallization deuterated methods to obtain containing the deuterium amount greater than 95% DADP crystal raw material in heavy aqueous solution;
(2) DADP crystalline growth method adopts aqueous solution cooling method, and its growth conditions is:
The potential of hydrogen of growth solution is pure state PH=4～5;
DADP crystalline growth temperature is 60 a ℃～room temperature;
The ADP crystal that seed crystal uses Z to cut is fixed in the synthetic glass rotary disk, makes it downward half cone growth;
The temperature-controlled precision of constant temperature water bath groove is ± 0.01 ℃, and the forward and reverse rotating speed of crystal is 50～60 rev/mins;
Crystal was controlled at 1～3mm/ days along the average speed of growth of Z direction.
2. the growth method of DADP electro-optic crystal as claimed in claim 1 is characterized in that: in raw material is synthetic, distill the mother liquor after the crystallization concentrated.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01143234 CN1260407C (en) | 2001-12-14 | 2001-12-14 | Growth process for DADP photoelectric crystal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01143234 CN1260407C (en) | 2001-12-14 | 2001-12-14 | Growth process for DADP photoelectric crystal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1424439A CN1424439A (en) | 2003-06-18 |
| CN1260407C true CN1260407C (en) | 2006-06-21 |
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ID=4677089
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 01143234 Expired - Fee Related CN1260407C (en) | 2001-12-14 | 2001-12-14 | Growth process for DADP photoelectric crystal |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100453709C (en) * | 2004-07-29 | 2009-01-21 | 中国科学院福建物质结构研究所 | Method for developing monocrystal of potassium dihydrogen phosphate in large aperture rapidly |
| CA2691554A1 (en) * | 2010-02-01 | 2011-08-01 | Michael Krautter | Crystal growing device |
| CN102560651B (en) * | 2010-12-16 | 2016-06-29 | 中国科学院福建物质结构研究所 | A kind of dielectric crystal two hydration boric acid mandelic acid sodium salt and its production and use |
| CN102534778A (en) * | 2012-03-14 | 2012-07-04 | 青岛大学 | Omnibearing growing method for KDP (Potassium Dihydrogen Phosphate) crystals |
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2001
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