WO2016119157A1 - Procédé pour préparer un monocristal pyroélectrique - Google Patents

Procédé pour préparer un monocristal pyroélectrique Download PDF

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WO2016119157A1
WO2016119157A1 PCT/CN2015/071798 CN2015071798W WO2016119157A1 WO 2016119157 A1 WO2016119157 A1 WO 2016119157A1 CN 2015071798 W CN2015071798 W CN 2015071798W WO 2016119157 A1 WO2016119157 A1 WO 2016119157A1
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crystal
hours
mgnb
innbo
crucible
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PCT/CN2015/071798
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English (en)
Chinese (zh)
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罗豪甦
王升
李晓兵
徐海清
赵祥永
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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/CN2015/071798 priority Critical patent/WO2016119157A1/fr
Publication of WO2016119157A1 publication Critical patent/WO2016119157A1/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
    • 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
    • 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
    • C30B29/30—Niobates; Vanadates; Tantalates
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N15/00—Thermoelectric devices without a junction of dissimilar materials; Thermomagnetic devices, e.g. using the Nernst-Ettingshausen effect
    • H10N15/10—Thermoelectric devices using thermal change of the dielectric constant, e.g. working above and below the Curie point

Definitions

  • the invention relates to a preparation method of a large-sized manganese-doped novel pyroelectric single crystal, in particular to a method for preparing a large-sized (diameter ⁇ three inches) manganese-doped lead indium bismuth-bismuth by a modified Bridgman method.
  • the method of lead magnesium titanate-titanate lead ternary pyroelectric single crystal belongs to the technical field of crystal growth.
  • 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 infrared thermal imaging, etc.
  • the field plays an important role and at the same time reflects 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.
  • the size of the single crystals prepared using the Bridgman method is less than 2 inches. In order to reduce the cost of the device, detector design and other factors, more and more larger wafers are needed.
  • the increase in the thickness of the crucible causes the internal stress of the crystal to increase, causing the crystal to crack, so that the crystal can not be subsequently applied, and the preparation cost is further Also greatly increased.
  • Patent literature
  • Patent Document 1 Chinese patent CN 1080777C;
  • the present invention provides a large-sized manganese-doped pyroelectric single crystal prepared by the modified Bridgman method to solve the defects in the prior art that large-sized Mn-doped pyroelectric single crystals are difficult to grow in batches.
  • An aspect of the present invention provides a method for preparing a single crystal, which is an improved method.
  • the Bridgman method includes the following specific steps:
  • Step 1 Obtain high-purity Pb(Mn 1/3 Nb 2/3 )O 3 , MgNb 2 O 6 , InNbO 4 , TiO 2 and PbO for 20 to 30 hours, then pre-burn at 6 to 1300 ° C for 6 to 10 Hour as the starting material for crystal growth;
  • Step 2 Fixing the bottom of the crucible with PMNT (lead magnesium niobate-lead titanate) or PIMNT (lead antimony lead indium niobate-lead magnesium niobate-lead titanate) or its Mn-doped crystal as a seed crystal
  • PMNT magnesium niobate-lead titanate
  • PIMNT lead indium niobate-lead magnesium niobate-lead titanate
  • Mn-doped crystal as a seed crystal
  • the starting material is charged and closed, and the crucible is placed in a crystal growth furnace, and the crystal growth furnace adopts a melting zone width of 10 to 25 mm, and the crucible is used for storing the original material.
  • the diameter is greater than three inches.
  • the ruthenium material is platinum, and the ruthenium has a thickness of 0.6 to 1.5 mm.
  • the seed crystal has a length of 50 to 70 mm, and the seed crystal diameter is less than or equal to the diameter of the grown crystal, and preferably the seed crystal diameter is 30 to 40 mm.
  • the crystallographic direction of the seed crystal is [001].
  • the furnace temperature is controlled at 1350 to 1400 °C.
  • the solid-liquid interface temperature gradient is 50 to 100 ° C / cm.
  • the falling speed is 7.0 to 10. mm/day.
  • the second aspect 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 Pb(Mn 1/3 Nb 2/3 )O 3 : mass ratio 1:1 weighs MnO 2 and Nb 2 O 5 , mixes for 20-30 hours, and then in a vacuum atmosphere 900-1000 degrees Celsius The calcination was carried out for 12 to 16 hours to obtain MnNb 2 O 6 .
  • Preparation of Pb(Mn 1/3 Nb 2/3 )O 3 The MnNb 2 O 6 prepared in the step a is ground into a powder, and the MnNb 2 O 6 and PbO are weighed at a molar ratio of 1:5, and mixed 20-30. After an hour, it is pre-fired at 1100 to 1300 ° C for 12 to 16 hours to obtain Pb(Mg 1/3 Nb 2/3 )O 3 .
  • step b MgNb 2 O 6 is prepared: MgO and Nb 2 O 5 are weighed in a molar ratio of 1:1, and after mixing for 20 to 30 hours, calcination is carried out at 900 to 1100 ° C for 12 to 16 hours to obtain MgNb 2 O 6 .
  • Step c preparing InNbO 4 : In 2 O 3 and Nb 2 O 5 are weighed in a molar ratio of 1:1, mixed for 20 to 30 hours, and then calcined at 1100 to 1350 ° C for 10 to 13 hours to obtain InNbO 4 .
  • the inventors of the present application specifically improve that through the step a, the Mn element can exist in the +2 valence state, thereby achieving the purpose of reducing the dielectric properties such as dielectric loss of the material; b, may be such that Mn element occupies a perovskite structure ABO B bit 3 of the material according to the design requirements, to avoid lead and manganese free state of erosion of the crucible material during melting; preparation of starting materials combined step b and step 1 Can avoid free lead and manganese.
  • the raw material is prepared by the synthesis method of the present application, so that the Mn element occupies the B position of the perovskite structure ABO 3 according to the material design requirement, and exists in the +2 valence state, thereby achieving the purpose of reducing the dielectric property loss and the like.
  • the raw material is completely present in the form of a pure perovskite phase, which avoids the erosion of free lead and manganese during the melting of the raw material.
  • the inventors of the present application found that another advantage of selecting a narrow melting zone is that it can increase the temperature gradient of the growth interface, since Mn needs to be bonded to the Mg, Ti, and Nb of the B site. More heat is released, so the narrow melting zone, that is, the large temperature gradient, facilitates the Mn ions to bond to the solid-liquid interface and enter the crystal, thereby avoiding the erosion of the free manganese during the melting of the raw material.
  • the conventional helium-down method growth relaxation ferroelectric crystal adopts the [111] direction seed crystal.
  • This method uses the [001] direction seed crystal growth tetragonal phase relaxation ferroelectric single crystal.
  • the optimal pyroelectric performance direction of the tetragonal phase relaxation ferroelectric single crystal for pyroelectric devices is the [001] direction, and the seed crystal growth in this direction can obtain large wafer uniformity, and the heat of the tetragonal phase large-sized crystal. The application of electricity is necessary.
  • Mn doping to eliminate defects caused by [001] direction growth and improve crystal integrity.
  • crystal growth in the [001] direction is advantageous for obtaining a wafer having uniform performance, point defects are generated to cause blackening of the crystal as compared with the conventional growth in the [111] direction.
  • the Mn doping regulates the dot defect structure in the crystal, inhibits crystal blackening, and improves wafer integrity.
  • FIG. 2 is a schematic view showing the structure of a melting zone of a Mn-doped relaxation ferroelectric single crystal growth furnace
  • Example 3 is a photograph of a three-inch manganese-doped pyroelectric crystal prepared in Example 1;
  • Example 4 is a graph showing the relationship between the dielectric constant ⁇ r of the ⁇ 001> oriented single crystal prepared in Example 1 after the polarization treatment at 1, 10, and 100 kHz, respectively.
  • MnO 2 and Nb 2 O 5 were weighed at a molar ratio of 1:1, and after mixing for 20 hours, they were calcined at 1000 ° C for 12 hours in a vacuum atmosphere (step a).
  • the obtained agglomerated MnNb 2 O 6 was ground into a powder, and MnNb 2 O 6 and PbO were weighed at a molar ratio of 1:5, mixed for 20 hours, and then calcined at 1200 ° C for 15 hours to obtain Pb (Mn 1/3 Nb). 2/3 ) O 3 (step a).
  • MgO and Nb 2 O 5 were weighed in a molar ratio of 1:1, and after mixing for 20 hours, calcination was carried out at 1000 ° C for 15 hours to obtain MgNb 2 O 6 (step b).
  • In 2 O 3 and Nb 2 O 5 were weighed in a molar ratio of 1:1, mixed for 20 hours, and then calcined at 1200 ° C for 12 hours to obtain InNbO 4 (step c).
  • a PMNT crystal having a diameter of 40 mm and a length of 50 mm in the [001] direction is used as a seed crystal, and is placed in a platinum crucible.
  • the crystal growth portion has a crucible diameter of 77 mm and a thickness of 1 mm; and the pre-fired starting material is further used. Load and close the ⁇ . Then, it is placed in a crystal growth furnace as shown in Fig. 2, the furnace temperature is controlled at 1350 to 1400 ° C, and the melting zone width is 15 mm. Crystal growth is achieved by adjusting the inoculation position to a predetermined inoculation temperature and temperature gradient and then starting to fall. The temperature gradient of the solid-liquid interface was controlled to be 60 ° C / cm, and the rate of decline was 0.7 mm / hr. The crystal shown in Figure 3 is finally obtained.
  • Line 4 in Figure 1 represents the valence state of the crystal prepared in Example 1 of the present application
  • lines 1, 2, 3, and 5 are the valence states of the material containing Mn element known in the prior art
  • the line 1 is the absorption edge of Mn in (Sr 0.97 Mn 0.03 )TiO 3
  • lines 2, 3 are absorption edges of Mn in Sr(Ti 0.97 Mn 0.03 )O 3 purchased from different companies
  • line 5 is Pb (Mn 1/2 Mn in Nb 1/2 )O 3
  • Line 4 is the absorption edge of Mn in the Mn-doped relaxed ferroelectric crystal obtained by the present method.
  • the structure of the crystal prepared by the present application is a pure perovskite structure in which the doped Mn is +2 valence and occupies the B site of the perovskite structure ABO 3 .
  • Figure 4 is a graph showing the dielectric constant ⁇ r of a Mn-doped PIMNT 29/29/42 single crystal at a frequency of 0.1 kHz, 1.0 kHz, and 10.0 kHz as a function of temperature.
  • the inner point is 258 degrees Celsius and the crystal is a tetragonal phase crystal.
  • the average dielectric constant of the same film is 240, and the dielectric constant fluctuation of different parts is ⁇ 4.0%, indicating that the crystal has high uniformity.

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

Abstract

L'invention concerne un procédé pour préparer un monocristal pyroélectrique de grande dimension, d'homogénéité élevée, dopé au manganèse. La composition chimique du monocristal pyroélectrique dopé au manganèse est la suivante : Mn-(1-x-y)Pb(In1/2Nb1/2)O3-yPb(Mg1/3Nb2/3)O3-xPbTiO3, dans laquelle x = 0,35-0,42, y = 0,30-0,45 et 1-x-y ＝ 0,20-0,29. La quantité de dopage de Mn est 0-5 %. Le procédé de préparation du matériau est un procédé Bridgman amélioré, qui comprend une synthèse de matière première, une sélection de cristal d'ensemencement, une régulation du procédé de croissance, une régulation et un contrôle des défauts, etc. La présente invention surmonte les inconvénients dans l'état de la technique, selon lesquels le dopage par l'élément Mn est difficile, le creuset fuit facilement et un défaut est facilement généré dans la direction [001], et concerne un procédé de mise en oeuvre pour la croissance industrielle de monocristaux pyroélectriques de grande dimension.
PCT/CN2015/071798 2015-01-29 2015-01-29 Procédé pour préparer un monocristal pyroélectrique WO2016119157A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113106548A (zh) * 2021-04-08 2021-07-13 东莞理工学院 一种pzn基大尺寸三元高性能单晶、生长方法及熔盐炉

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1294029A2 (fr) * 2001-09-13 2003-03-19 Ngk Insulators, Ltd. Dispositif à couche piézo-électrique/électrostrictive
US20110017937A1 (en) * 2009-03-17 2011-01-27 Trs Technologies, Inc. Relaxor-pt ferroelectric 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
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
CN104178802A (zh) * 2014-08-01 2014-12-03 西安交通大学 一种三元系弛豫铁电压电晶体及其多温区生长方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1294029A2 (fr) * 2001-09-13 2003-03-19 Ngk Insulators, Ltd. Dispositif à couche piézo-électrique/électrostrictive
US20110017937A1 (en) * 2009-03-17 2011-01-27 Trs Technologies, Inc. Relaxor-pt ferroelectric 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
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
CN104178802A (zh) * 2014-08-01 2014-12-03 西安交通大学 一种三元系弛豫铁电压电晶体及其多温区生长方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
LI, LONG ET AL.: "Pyroelectric Performance of Relaxor-based Ferroelectric Single Crystals and Their Application in Infrared Detector", JOURNAL OF THE CHINEST CERAMIC SOCIETY, vol. 42, no. 4, 30 April 2014 (2014-04-30), ISSN: 0454-5648 *
YANG, LINRONG ET AL.: "Pyroelectric Performance of Relaxor-based Ferroelectric Single Crystals and Their Application in Infrared Detector", PROCEEDINGS OF THE 19 TH ACADEMIC ANNUAL CONFERENCE OF SHANGHAI INFRARED AND REMOTE SENSING SOCIETY, 4 December 2014 (2014-12-04) *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113106548A (zh) * 2021-04-08 2021-07-13 东莞理工学院 一种pzn基大尺寸三元高性能单晶、生长方法及熔盐炉
CN113106548B (zh) * 2021-04-08 2021-09-14 东莞理工学院 一种pzn基大尺寸三元高性能单晶、生长方法及熔盐炉

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