CN100395376C

CN100395376C - New CuI Crystal and growing method thereof

Info

Publication number: CN100395376C
Application number: CNB2004100665463A
Authority: CN
Inventors: 顾牡; 张睿; 汪大祥; 刘小林
Original assignee: Tongji University
Current assignee: Tongji University
Priority date: 2004-09-21
Filing date: 2004-09-21
Publication date: 2008-06-18
Anticipated expiration: 2024-09-21
Also published as: CN1609285A

Abstract

The present invention discloses a CuI crystal and a growing method thereof. The CuI crystal is in a regular gamma-phase tetrahedral structure, and the size is larger than 2mm. In the growing method, a method combining a concentration control technology and a complexing-decomplexing method is adopted. The growing method combining a concentration descending control technology and a complexing-decomplexing method adopted by the present invention has the advantages of simple equipment, low price, low growth temperature, easy adjustment and control of growth process, etc. The grown gamma-phase CuI crystal has the advantages of high purity, less stress, few disadvantages, good appearance and relatively large size. Thus, as a new generation of ultra-fast scintillator, the CuI crystal has an important application value in the aspects of high-speed X-ray counting and gamma ray counting, cathode beam measurement, etc. Simultaneously, the CuI crystal can also be used as a fast ionic conductor.

Description

New CuI Crystal and growth method thereof

Technical field

The present invention relates to the method for crystal growth, be specifically related to a kind of CuI crystalline growth method.

Background technology

Along with the fast development of high energy physics, nuclear physics and Application of Nuclear Technology, common inorganic scintillation crystal will be difficult to satisfy the needs of superelevation counting rate in measuring, and various countries are actively developing the research of novel fast flashing body in recent years for this reason.Semiconductor material with wide forbidden band cuprous iodide (CuI) crystal at room temperature has the blinking characteristic that is exceedingly fast, its luminescence decay time only is 90ps, and there is not slow composition, be people's the fastest inorganic scintillation crystal known today, thereby, all there is important use to be worth at aspects such as superelevation counting rate X-ray, gamma-rays and electron beam measurements as fast flashing body of new generation.CuI crystalline photoyield is BaF ₂/ 4th of a fast composition luminous intensity of crystal, but its time response wants fast 6-7 doubly, wherein accounts for the over half of total number of photons in the number of photons that t≤0.1ns sent in the time.Although CuI crystalline photoyield is higher 40 times than CsI (T1) crystalline in the number of photons that t≤0.1ns sent in the time than low two magnitudes of CsI (T1) crystalline.Exactly because CuI crystalline fast flashing characteristic has caused that people greatly pay close attention to, but the crystal growth difficulty is the bottleneck of its application of restriction.Multiple growing method has been applied to the growth of CuI crystalline at present both at home and abroad, crystalline size is also all in the millimeter magnitude.For example, people such as T.Goto are at J.Phys.Soc.Japan, and 1968, Vol.24, the article of delivering on the P314 is pointed out, adopts subliming method to obtain size and reaches 9mm ³Crystal, but the crystalline defective is more.The sol-gel crystal technique has ionic reaction and two kinds of methods of complexing-decomplexing usually.People such as I.Nakada are at Japan.J.Appl.Phys., and 1976, Vol.15, the article of delivering on the P919 is to adopt the ionic reaction method, having obtained volume is 5 * 5 * 1mm ³The CuI crystal.A.F.Armington and J.J.O ' Connor are at J.Crysal Growth, 1968, Vol.3/4, P367 and Mater.Res.Bull., 1971, Vol.6 has delivered two pieces of relevant complexings-decomplexing method growth CuI crystalline article on the P765, though the crystal purity that is grown is higher, the crystalline pattern is not good.

In complexing-decomplexing crystal growth, crystal be complex compound by CuI and HI in gel decomplexing and generate.Therefore the crystal of this method growth have cheap, equipment is simple, growth temperature is low, the purity advantages of higher, its process of growth is regulation and control easily also, thereby particularly suitable growth purity height, stress is little and defective is few crystal, but be difficult to obtain the crystal of pattern rule.Concentration control is a kind of common technology in the crystal growth.This technology is convenient to control nucleation rate, keeps stable crystalline growth velocity, can grow good, the larger-size crystal of pattern.Up to now, yet there are no the relevant report that in complexing-decomplexing method growth CuI crystal, adopts the concentration control techniques both at home and abroad.

Summary of the invention

One of purpose of the present invention is to provide a kind of ultrafast CuI scintillation crystal;

Another object of the present invention is to provide this crystalline growth method.

The present invention is exactly in order to overcome the deficiency in the above-mentioned growing technology, adopt concentration control techniques and method that complexing-the decomplexing method combines, grow the purity height, stress is little, defective is few, pattern good (tetrahedral structure that is rule), larger-size γ phase CuI crystal.

It is the growth method that concentration control techniques and complexing-decomplexing combine.Select for use analytically pure water glass, ionized water, acetate for preparing the raw material of gel, analytically pure hydroiodic acid HI is that complexing agent, CuI powder are raw material growth CuI crystal.

Its preparation method is as follows:

Earlier water glass is dissolved in the ionized water, add acetate and fully stirring, can obtain the required gel of crystal growth after leaving standstill, again the CuI powder is dissolved in the complexing agent hydroiodic acid HI of different amounts, form the complex compound CuI-HI saturated solution of different saturation, the CuI-HI complex compound spreads in gel will separate out the CuI crystal.Be different from common concentration control techniques-concentration and increase progressively, in the CuI crystal growing process, the method that adopts concentration to successively decrease promptly regularly replaced the high CuI-HI saturated solution of last concentration with the low CuI-HI saturated solution of concentration every 24 hours.Use Na afterwards ₂SO ₃Solution replaces the CuI-HI saturated solution of minimum concentration.

At last it is rested on 25 ± 0.5 ℃ shockproof growth case, crystal is grown up gradually.

The concentration that the present invention adopts successively decreases that growth method that control techniques and complexing-decomplexing combine has that equipment is simple, cheap, growth temperature is low and process of growth advantage such as regulation and control easily, the γ phase CuI crystal purity height of being grown, stress is little, defective is few, pattern good (be rule tetrahedral structure) and size are bigger, thereby as fast flashing body of new generation, all there is important use to be worth at aspects such as superelevation counting rate X-ray, gamma-rays and electron beam measurements, can also be used as fast-ionic conductor simultaneously.

Embodiment

How further specify the present invention below in conjunction with specific embodiment realizes:

Embodiment

Select for use analytically pure water glass, ionized water, acetate for preparing the raw material of gel, analytically pure hydroiodic acid HI is that complexing agent, CuI powder are raw material growth CuI crystal.106 gram water glass are dissolved in the deionized water of 250 grams, treat to dissolve fully after-filtration.Further dilute above-mentioned sodium silicate aqueous solution with deionized water again, and the acetate of adding 2M, sodium silicate aqueous solution, deionized water, acetate three's volume ratio is 7: 8: 15 (as 70ml water glass, 80ml deionized water, a 150ml acetate), constantly stirs in the solution process for preparation.Pour the solution of being prepared the U type pipe of diameter 3cm, high 25cm, wide 20cm into, after leaving standstill 48 hours under 25 ± 0.5 ℃ the temperature environment, be formed for the gel of crystal growth.

The CuI powder is dissolved in the 7M hydroiodic acid HI of different amounts, obtains the CuI-HI complex liquid that saturation ratio is respectively 1M, 0.86M, 0.72M, 0.57M, 0.43M, 0.28M, 0.14M.Above the gel of U type Guan Yiduan, add the hydroiodic acid HI 1ml of 7M, make it prediffusion in gel.After prediffusion in 4 hours, replace the hydroiodic acid HI of gel top with the complex liquid 10mzl of 1M.Complex liquid 10ml with 0.86M after 24 hours replaces 1 original M complex liquid of gel top.Afterwards every 24 hours, all use the lower complex liquid of equivalent concentration to replace the higher complex liquid of concentration, promptly use the complex liquid of the complex liquid replacement 0.86M of 0.72M, the complex liquid of 0.57M to replace the complex liquid of 0.72M, replace successively, till the complex liquid with 0.14M replaces the complex liquid of 0.28M.Again through 24 hours, with the Na of 0.1M ₂SO ₃Solution replaces the complex liquid of 0.14M.At last, U type pipe rested in 25 ± 0.5 ℃ the shockproof growth case, the CuI crystal is grown up gradually.

The CuI crystal morphology that is grown out is that regular tetrahedron, purity height, stress are little, size is greater than 2mm.The result that Brucker D8 type x-ray diffractometer is measured shows that the CuI crystal is the γ phase, has the ultrafast characteristics of luminescence.

Claims

1. the preparation method of a New CuI Crystal is as follows:

A, elder generation are dissolved in water glass in the ionized water, add acetate and fully stirring, can obtain the required gel of crystal growth after leaving standstill, again the CuI powder is dissolved in the complexing agent hydroiodic acid HI of different content, form the complex compound CuI-HI saturated solution of different saturation, the CuI-HI complex compound spreads in gel will separate out the CuI crystal, and the method that adopts concentration to successively decrease promptly regularly replaced the high CuI-HI saturated solution of last concentration with the low CuI-HI saturated solution of concentration every 24 hours;

B, use Na at last ₂SO ₃Solution replaces the CuI-HI saturated solution;

C, will use Na ₂SO ₃CuI-HI saturated solution after solution replaces rests on 25 ± 0.5 ℃ shockproof growth case, and crystal is grown up gradually.

2. the preparation method of New CuI Crystal as claimed in claim 1, it is characterized in that: selected preparation gel sodium silicate raw material, ionized water, acetate are analytically pure raw material, and the complexing agent hydroiodic acid HI is the analytical pure hydroiodic acid HI.

3. according to the New CuI Crystal of claim 1 or 2 described methods acquisitions, it is characterized in that: described CuI crystal is the regular tetrahedral structure of γ phase, and size is greater than 2mm.