WO2016119159A1 - Procédé de préparation d'un monocristal - Google Patents

Procédé de préparation d'un monocristal Download PDF

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Publication number
WO2016119159A1
WO2016119159A1 PCT/CN2015/071800 CN2015071800W WO2016119159A1 WO 2016119159 A1 WO2016119159 A1 WO 2016119159A1 CN 2015071800 W CN2015071800 W CN 2015071800W WO 2016119159 A1 WO2016119159 A1 WO 2016119159A1
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Prior art keywords
crystal
hours
crucible
mgnb
pyroelectric
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PCT/CN2015/071800
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English (en)
Chinese (zh)
Inventor
罗豪甦
杨林荣
徐海清
李晓兵
赵祥永
王升
王西安
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上海硅酸盐研究所中试基地
中国科学院上海硅酸盐研究所
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Priority to PCT/CN2015/071800 priority Critical patent/WO2016119159A1/fr
Publication of WO2016119159A1 publication Critical patent/WO2016119159A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B11/00—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/16—Oxides
    • C30B29/22—Complex oxides
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/16—Oxides
    • C30B29/22—Complex oxides
    • C30B29/32—Titanates; Germanates; Molybdates; Tungstates

Definitions

  • the invention relates to a method for suppressing crack initiation and cracking of a manganese-doped pyroelectric single crystal, in particular to a method for preparing a manganese-doped lead indium bismuth hydride-lead-magnesium titanate-titanate by a modified Bridgman method
  • the method of lead ternary pyroelectric single crystal belongs to the field of crystal growth technology.
  • Infrared detectors are mainly divided into photon type infrared detectors and thermal infrared detectors.
  • the common photon-type infrared detector mainly uses a narrow band gap semiconductor material represented by mercury cadmium telluride and an optoelectronic semiconductor material represented by gallium arsenide.
  • semiconductor infrared devices generally require low-temperature refrigeration, which is bulky, costly, and consumes a lot of power.
  • the pyroelectric infrared detector developed by the pyroelectric effect of the material has a flat spectral response in the ultraviolet, visible and infrared bands, and has no need for refrigeration, low power consumption, low noise bandwidth, compact structure and convenience.
  • the advantages of carrying and low cost have become one of the most eye-catching focuses in the field of infrared technology.
  • pyroelectric infrared detectors for low cost, low power consumption and miniaturization, pyroelectric infrared detectors are rapidly expanding from the military market to the civilian market, especially in human body detection, fire warning, gas analysis, infrared spectrometers. And the field of infrared thermal imaging has played an important role, while reflecting the huge market potential.
  • the materials currently used in pyroelectric infrared detectors mainly include lead zirconate titanate (PZT), barium titanate (BST) and lead citrate (PST), etc., and the main limitations of materials for pyroelectric unit detectors. Lithium niobate (LiTaO 3 ), triglyceride sulfate (TGS), and the like.
  • PZT lead zirconate titanate
  • BST barium titanate
  • PST lead citrate
  • TGS triglyceride sulfate
  • these traditional materials have shortcomings such as low pyroelectric coefficient, large dielectric loss, and unstable physical properties, which are difficult to meet the application requirements of high-performance pyroelectric infrared detectors and their extended products.
  • the more mature commercial LiTaO 3 infrared detectors have a detection level of only 1 ⁇ 10 8 cm (Hz) 1/2 /W to 4 ⁇ 10 8 cm (Hz) 1/2 /W. Therefore, at the same time, overcoming the shortcomings of the above materials, exploring new pyroelectric materials with high detection value has become an urgent need for the development of uncooled infrared devices.
  • Crystals without cracks or microcracks are important guarantees for the preparation of high-performance pyroelectric detectors.
  • cracks lead to the decrease in the availability of pyroelectric crystals and wafer yield, and on the other hand, pyroelectrics in practical applications. Cracks hidden in the wafer, resulting in cracking of crystal properties, poor performance under service conditions, and low stability.
  • Mn-doped PMNT and PIMNT pyroelectric crystals are easy to form cracks and cracks, which is related to the formation of defects during crystal growth due to the ion distribution caused by the addition of Mn.
  • no publication has publicly reported a process for suppressing the generation and cracking of cracks in manganese-doped pyroelectric single crystals.
  • Patent literature
  • Patent Document 1 Chinese patent CN 1080777C.
  • the invention provides a good quality, non-cracking and crack-free manganese-doped PMNT, Mn-doped PIMNT pyroelectric single crystal prepared by the improved enthalpy drop method, to solve the prior art Mn-doped pyroelectricity
  • the present application reduces the temperature gradient and growth rate to improve uniformity compared to conventional preparation methods, while at the same time suppressing the resulting generation of segregation expansion by reducing the thickness of the crucible.
  • Step 1 Obtain high-purity Pb(Mn 1/3 Nb 2/3 )O 3 , MgNb 2 O 6 and InNbO 4 , PbO, TiO 2 for 20 to 30 hours, and then pre-burn for 5 to 8 hours at 1100 to 1350 degrees Celsius.
  • Starting material for crystal growth
  • Step 2 Fixing the starting material with a crystal of PMNT (lead bismuth magnesium silicate-lead titanate) or PIMNT (lead bismuth indium hydride-lead bismuth magnesium silicate-lead titanate) as a seed crystal
  • PMNT lead bismuth magnesium silicate-lead titanate
  • PIMNT lead bismuth indium hydride-lead bismuth magnesium silicate-lead titanate
  • the seed crystal and the starting material are enclosed in a crucible and then placed in a modified crystal growth furnace (Fig. 3), and the inoculation position is adjusted to a predetermined inoculation temperature and temperature gradient and then started to fall to achieve crystal growth.
  • the temperature gradient of the solid-liquid interface is controlled to be 30 to 70 ° C / cm, and the rate of decline is less than 0.5 mm / hr.
  • a single layer or a double layer of ruthenium having a thickness of 0.8 to 2.0 mm, or a layer of ruthenium having a single layer thickness of 0.1 to 0.5 mm is used as a growth container, or a combination of two layers of different thicknesses is used.
  • the inoculation time of crystal inoculation is 6 to 10 hours.
  • the seed crystal has a length of 30 to 60 mm and a diameter smaller than or equal to the diameter of the grown crystal, and preferably has a seed crystal diameter of 20 to 50 mm.
  • the furnace temperature is controlled at 1250 ⁇ 1500 °C.
  • the material of bismuth is platinum.
  • the second aspect of the present application is also a method for providing high purity Pb(Mn 1/3 Nb 2/3 )O 3 , MgNb 2 O 6 and InNbO 4 , as follows:
  • Step a preparing InNbO 4 : weighing 1:1 to weigh In 2 O 3 and Nb 2 O 5 , mixing for 20 to 30 hours, and then pre-burning at 1100 to 1350 degrees Celsius for 10 to 13 hours to obtain InNbO 4 ,
  • Step b preparing Pb(Mn 1/3 Nb 2/3 )O 3 : molar ratio 1:1 weighs MnO 2 and Nb 2 O 5 , mixes for 20-30 hours, and then in a vacuum atmosphere 900-1100 degrees Celsius The calcination was carried out for 10 to 13 hours to obtain MnNb 2 O 6 .
  • the prepared MnNb 2 O 6 is ground into a powder, and the MnNb 2 O 6 and PbO are accurately weighed by a molar ratio of 1:5 to 6, mixed for 20 to 30 hours, and then calcined at 1100 to 1300 degrees Celsius for 10 to 13 hours.
  • Pb(Mn 1/3 Nb 2/3 )O 3 molar ratio 1:1 weighs MnO 2 and Nb 2 O 5 , mixes for 20-30 hours, and then in a vacuum atmosphere 900-1100 degrees Celsius The calcination was carried out for 10 to 13 hours to obtain MnNb 2 O 6 .
  • the prepared MnNb 2 O 6 is ground into a powder,
  • Step c preparing MgNb 2 O 6 : weighing 1:1 to weigh MgO and Nb 2 O 5 , mixing for 20-30 hours, and then calcining at 900-1100 degrees Celsius for 12-16 hours to obtain MgNb 2 O 6 .
  • the inventors of the present application specifically improve the following: through the step b, the Mn element can be present in the +2 valence state, thereby achieving the purpose of reducing the dielectric properties such as dielectric loss of the material; b, can make the Mn element occupy the B position of the perovskite structure ABO 3 according to the material design requirements, and avoid the erosion of the free lead and manganese during the melting process of the raw material.
  • the raw material is prepared by the synthesis method of the present application, so that the growth precursor exists in the form of pure perovskite phase, especially Pb(Mn 1/3 Nb 2/3 )O 3 , which avoids direct oxidation of the original raw material.
  • Manganese is placed in a growth furnace, and the valence state of manganese ions in manganese oxide at high temperatures and the formation of hetero phases or inclusions in the crystal, resulting in the possibility of crystal cracking, greatly improving the crystal integrity of the crystal.
  • the present invention adopts a single layer or double layer of germanium having a thickness of 0.8 to 2.0 mm, or a thickness of 0.1 to More than 3 layers of 0.5 mm are used as growth vessels, or a combination of two layers of different thicknesses is used.
  • the invention finds that the thickness of the germanium technology can match the stress generated by the growth process of the Mn-doped pyroelectric crystal, on the one hand, the more stress can be released, on the other hand, the stable control of the crystal shape can be realized, and the interface can be avoided. Fluctuations generate macroscopic defects from the place where the crystal is in contact with the crucible wall, and crystal cracks caused by expansion into the interior of the crystal.
  • the key point of the temperature field of the crystal growth furnace used in the present invention is that the temperature gradient of the temperature gradient in the descending direction when the crucible starts to fall is 30 to 70 ° C / cm, and the temperature gradient is too large, which may cause the crystal crystallization process to be easily cracked. Too small will cause polycrystals to appear and cause grain boundary defects.
  • the key point of the crystal growth rate employed in the present invention is that, corresponding to the above temperature gradient, the crystal growth rate used is less than 0.5 mm/hr, which is lower than that of the conventionally grown crystal, which is related to the Mn-doped pyrolysis.
  • the kinetic effect of the manganese-octahedral element in the high-temperature melt is superimposed on the growth interface, thereby avoiding defects such as raw material encapsulation caused by excessive growth rate or cracks formed by unstable growth interface.
  • the seed inoculation time of the crystal inoculation is 6 to 10 hours, thereby effectively eliminating the opportunity for the possible cracks in the seed crystal to diffuse into the newly solidified crystal.
  • Example 1 is a photograph of a crack-free manganese-doped pyroelectric crystal prepared in Example 1, and b) a manganese-doped pyroelectric crystal prepared by a conventional method under strong light;
  • FIG 3 is a schematic view showing the structure of a melting zone of a Mn-doped relaxation ferroelectric single crystal growth furnace.
  • MnO 2 and Nb 2 O 5 were accurately weighed in a molar ratio of 1:1, mixed for 25 hours, and then calcined at 1000 degrees for 12 hours in a vacuum atmosphere to obtain MnNb 2 O 6 .
  • the MnNb 2 O 6 prepared as described above is ground into a powder, and the MnNb 2 O 6 and PbO are accurately weighed at a molar ratio of 1:5, mixed for 25 hours, and then calcined at 1250 degrees for 12 hours to obtain Pb (Mn 1/3 Nb 2 ). /3 )O 3 . (Step b)
  • a crystal of PIMNT (length 50 mm, diameter 30 mm) in the direction of ⁇ 001> is used as a seed crystal in a platinum crucible (the structure is shown in Fig. 3), and the diameter of the crystal growth portion is 75 mm and the thickness is 1 mm;
  • the pre-fired starting material is charged and closed. Then, it was placed in a modified crystal growth furnace, the furnace temperature was controlled at 1400 ° C, the melting time was 5 hours, and the inoculation position was adjusted to reach a predetermined inoculation temperature and temperature gradient, and then began to fall to achieve crystal growth.
  • the temperature gradient of the solid-liquid interface was controlled to be 45 ° C / cm, and the crystal growth rate was 0.4 mm / hr.
  • a pyroelectric single crystal is produced, as shown in FIG.
  • FIG. 1 is a photograph of a) crack-free manganese-doped pyroelectric crystal prepared in Example 1, and b) a manganese-doped pyroelectric crystal prepared by a conventional method under strong light.
  • the crystals prepared by the method provided by the present application avoid the problems of perforation, cracking and the like which may be caused by the conventional preparation method.
  • the surface is smooth, crack-free, crack-like, and the like.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)

Abstract

L'invention concerne un procédé de traitement visant à inhiber la formation de fissures et la fissuration d'un monocristal pyroélectrique dopé au manganèse, dans lequel la composition chimique du monocristal pyroélectrique dopé au manganèse est Mn-(1-x-y)Pb(In 1/2Nb 1/2)O 3-yPb(Mg 1/3Nb 2/3)O 3-xPbTiO 3, dans laquelle x = 0,35 à 0,42, y = 0,30 à 0,45, 1-x-y ＝ 0,20 à 0,29, et le niveau de dopage en Mn varie de 0 à 5,0 %. Le procédé de préparation de ce matériau consiste en un procédé Bridgman amélioré, comprenant les étapes de synthèse d'une matière première, de chauffage et de fusion, d'ensemencement à l'aide d'un germe cristallin et de croissance d'un cristal. Ce procédé permet d'éviter les inconvénients que l'on rencontre dans l'état de la technique, à savoir la formation trop facile de fissures dans un cristal et la fissuration d'un cristal du fait d'un dopage au Mn, et l'invention concerne, donc, selon un mode de réalisation, un procédé de préparation d'un monocristal pyroélectrique de grande taille et de qualité élevée, avec un rendement accru et une plus grande fiabilité de résultat.
PCT/CN2015/071800 2015-01-29 2015-01-29 Procédé de préparation d'un monocristal WO2016119159A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106637407A (zh) * 2017-01-06 2017-05-10 福建福晶科技股份有限公司 一种防止cbo晶体生长过程掉入熔体的方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101985775A (zh) * 2010-11-29 2011-03-16 中国科学院上海硅酸盐研究所 一种三元系弛豫铁电单晶材料及其制备方法
US20120037839A1 (en) * 2010-08-10 2012-02-16 Trs Technologies, Inc. Temperature and field stable relaxor-pt piezoelectric single crystals
CN102925959A (zh) * 2012-10-14 2013-02-13 宁波大学 新型弛豫铁电单晶pimnt的生长工艺
CN103866386A (zh) * 2014-03-04 2014-06-18 西安交通大学 一种新型三元压电晶体单相原料的制备方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120037839A1 (en) * 2010-08-10 2012-02-16 Trs Technologies, Inc. Temperature and field stable relaxor-pt piezoelectric single crystals
CN101985775A (zh) * 2010-11-29 2011-03-16 中国科学院上海硅酸盐研究所 一种三元系弛豫铁电单晶材料及其制备方法
CN102925959A (zh) * 2012-10-14 2013-02-13 宁波大学 新型弛豫铁电单晶pimnt的生长工艺
CN103866386A (zh) * 2014-03-04 2014-06-18 西安交通大学 一种新型三元压电晶体单相原料的制备方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106637407A (zh) * 2017-01-06 2017-05-10 福建福晶科技股份有限公司 一种防止cbo晶体生长过程掉入熔体的方法

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