CN103044492A - Ferroelectric organometallic compound, as well as preparation method and application thereof - Google Patents

Ferroelectric organometallic compound, as well as preparation method and application thereof Download PDF

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Publication number
CN103044492A
CN103044492A CN201210511721XA CN201210511721A CN103044492A CN 103044492 A CN103044492 A CN 103044492A CN 201210511721X A CN201210511721X A CN 201210511721XA CN 201210511721 A CN201210511721 A CN 201210511721A CN 103044492 A CN103044492 A CN 103044492A
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ferroelectric
preparation
coo
angstroms
organometallic complex
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潘春阳
麦海登
赵丰华
李大光
杨红梅
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Guangdong University of Technology
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Guangdong University of Technology
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Abstract

The invention discloses a ferroelectric organometallic compound, as well as a preparation method and an application thereof. The compound adopts hydrothermal reaction to obtain crystals; and the compound molecular formula is C4H13N2B2P3CoO13, the space group is Ima2(No.46), cell parameters are that a =12.4820(8) angstroms, b=9.4146(3) angstroms, c=11.4646(2) angstroms, alpha=beta=gamma=90.00 degrees, Z=4, and the unit cell volume V=1347.2(1) angstroms<3>. The compound is applied to pagination devices and ferrum electro-optic valve arrays for storing and recovering information, transmitting optical information, displaying images and holography to be used as a holographic memory, and is mainly applied to an electronic technology, a laser technology, an infrared detection technology, an ultrasonic technology, a solid-state memory and display technology and other engineering technologies.

Description

A kind of ferroelectric material organometallic complex and preparation method thereof and application
Technical field
The present invention relates to a kind of ferroelectric material organometallic complex and preparation method thereof and application.
Background technology
Ferroelectric material is a kind of multifunctional material that has simultaneously the performances such as ferroelectric, piezoelectricity, pyroelectricity, electric light, nonlinear optics.So-called ferroelectric material refers to that crystalline structure just has the spontaneous polarization phenomenon when not adding external electric field, the material that the direction of its spontaneous polarization can be reversed or redirect by extra electric field.This specific character of material is called as " ferroelectricity " or " ferroelectric effect ".In the last few years, the ferroelectric material development is very rapid, electronic technology, laser technology, infrared detection technique, ultrasonic (and microwave acoustics) technology, Solid State memory and technique of display and Other Engineering technical elements have been widely used in, and the ferroelectric material of research and production excellent property is again the basis of the functional devices such as various ferroelectric, the piezoelectricity of development, thermoelectricity and electric light.Therefore, very active to development and the exploration of ferroelectric material in the world at present.
People mainly concentrate on the inorganic materials research and the application of ferroelectric material at present.The inorganic iron electric material owing to have high strength, high rigidity, the advantages such as high temperature resistant, performance is steady in a long-term, long service life are widely used, but because the making of inorganic iron conductive film needs the condition of high vacuum comparatively high temps, make cost of manufacture comparatively expensive, be difficult for making large area film and need to adopt mechanically resistant material to make substrate, limited significantly its application.In recent years, the organic ferroelectric film also gains great popularity, mainly be owing to comparing with the inorganic iron electric material, it has makes easily that large area film, cost of manufacture are low, low temperature manufacturing conditions, relatively large molecular hyperpolarizability, large Electrostrictive strain ability, with the anti-acoustic resistance matching of air unique advantages such as superiority is arranged, simultaneously because its low temperature manufacturing conditions and can make substrate with the plastics of softness.But because the ferroelectric percentage coupling of Organic Iron electric material is lower, relative permittivity is less, the permanent stability relative mistake of performance, function some, thereby make its application be subject to larger restriction.Therefore, research novel ferroelectric material has become the research emphasis of current ferroelectric material with the inherent defect that overcomes inorganic or Organic Iron electric material.
In recent years, organically templated metal boron phosphate with ferroelectric effect has caused people's very big research interest, this is because this class hybrid material process is well-designed and regulation and control, can reach and raise the separately effect of growing and keeping away short " heterosis, hybrid vigor " of its shortcoming of advantage of inorganic materials and organic materials, and the interaction between Inorganic Boron oxygen metallic framework and the organic formwork component, can make materials present novel character.
Summary of the invention
Purpose of the present invention just is to provide a kind of ferroelectric material organometallic complex and preparation method thereof and application, and its technical scheme is as follows:
A kind of ferroelectric material organometallic complex provided by the invention, this complex molecule formula is C 4H 13N 2B 2P 3CoO 13, spacer is Im A2(No.46), cell parameter is a=12.4820 (8), b=9.4146 (3), c=11.4646 (2), α= β= γ=90.00 o, Z=4, unit-cell volume V=1347.2 (1) 3
The present invention also provides a kind of preparation method of ferroelectric material organometallic complex, under hydrothermal condition, and reactant cobaltous acetate (Co (CH 3COO) 2), boric acid (H 3BO 3), piperazine (C 4H 10N 2), phosphoric acid (H 3PO 4) as raw material, its mol ratio is 0.5～5:1～3:0.5～3:1.5～6, adopts water as solvent, hydro-thermal reaction is warming up to 140～220 ℃, and naturally cooling under the room temperature obtains C 4H 13N 2B 2P 3CoO 13
Above-mentioned cobaltous acetate is replaced by the Cobaltous nitrate hexahydrate of jljl quality, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, rose vitriol or cobalt chloride.
The present invention also provides a kind of purposes of ferroelectric material organometallic complex, this material is applied to store and recovery information, transmission light information, image show or holographic in pagination device, the storage that ferroelectric light valve array is made holographic.
We select cobaltous acetate (Co (CH 3COO) 2), boric acid (H 3BO 3), piperazine (C 4H 10N 2), phosphoric acid (H 3PO 4) as raw material, its mol ratio is 0.5～2.5:1.5～2.5:0.5～1.5:1.5～4.5, adopts water as solvent, under hydrothermal reaction condition, boric acid, cobaltous acetate, piperazine and phosphoric acid generation chemical reaction, the monocrystalline of the organically templated metal cobalt borophosphate of having grown.
We record the crystalline structure of this organically templated metal cobalt borophosphate, and structural parameter are as follows:
Molecular formula is C 4H 13N 2B 2P 3CoO 13, spacer is Ima2(No.46), cell parameter is a=12.4820 (8), b=9.4146 (3), c=11.4646 (2), α= β= γ=90.00 o, Z=4, unit-cell volume V=1347.2 (1) 3
The advantage of this material is not to be soluble in general solvent, and heat decomposition temperature point is high (can be stabilized to 250 in the air atmosphere oC), crystal grain is even.
Beneficial effect of the present invention:
Organically templated metal cobalt borophosphate provided by the invention is the crystal that grows at solvent process for thermosynthesizing.The material preparation process that adopts is simple, productive rate is high and good reproducibility.
The advantage of this material is that spontaneous polarization produces by hydrogen bond, and polarization mode is stable, has preferably using value.
The important ferroelectric properties that this material has is: at room temperature its electricity causes the Pr=0.029 μ C/cm of curve 2, Ps=0.055 μ C/cm 2But the temperature rising gradually along with the external world, its spontaneous polarizability Ps and residual polarization rate can weaken accordingly, and this ferroelectric property that causes that varies with temperature changes, and might be utilized on some novel electronics, laser or the infrared acquisition electron device.This specific character has in known ferroelectrics uncommon.
Embodiment
1, the preparation of compound
Take by weighing cobaltous acetate (Co (CH 3COO) 2) 0.088 to 0.880g, boric acid (H 3BO 3) 0.062 to 0.186g, piperazine (C 4H 10N 2) 0.048 to 0.258, measure 0.18 to 0.72ml phosphate aqueous solution (H 3PO 4, mass concentration 85%), water (H 2O) 3.0 to 9.0ml, its mol ratio is 0.5～5:1～3:0.5～3:1.5～6:16～50, stirs 20min, pack in the reactor of 28 airtight mL, be warming up to 140～220 ℃, constant temperature 1 to 7 day, naturally cooling at ambient temperature after the taking-up just can obtain crystal.Analyze through the X ray single crystal diffraction, determine that this crystal is C 4H 13N 2B 2P 3CoO 13Cobaltous acetate is replaced by the Cobaltous nitrate hexahydrate of jljl quality, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, rose vitriol or cobalt chloride, can obtain identical C 4H 13N 2B 2P 3CoO 13Compound.
Concrete reactant embodiment is as follows:
（1）Co：H 3BO 3：C 4H 10N 2：H 3PO 4：H 2O＝0.5：1：0.5：1.5：16，
（2）Co：H 3BO 3：C 4H 10N 2：H 3PO 4：H 2O＝2：2：1：4：35，
（3）Co：H 3BO 3：C 4H 10N 2：H 3PO 4：H 2O＝0.5：3：3：6：50，
（4）Co：H 3BO 3：C 4H 10N 2：H 3PO 4：H 2O＝1：3：2：3：40，
（5）Co：H 3BO 3：C 4H 10N 2：H 3PO 4：H 2O＝0.5：3：3：6：16，
（6）Co：H 3BO 3：C 4H 10N 2：H 3PO 4：H 2O＝5：1：3：6：16，
（7）Co：H 3BO 3：C 4H 10N 2：H 3PO 4：H 2O＝0.5：1：0.5：6：16，
（8）Co：H 3BO 3：C 4H 10N 2：H 3PO 4：H 2O＝0.5：3：0.5：?6：50，
（9）Co：H 3BO 3：C 4H 10N 2：H 3PO 4：H 2O＝5：3：3：6：16，
（10）Co：H 3BO 3：C 4H 10N 2：H 3PO 4：H 2O＝5：3：0.5：1.5：16，
（11）Co：H 3BO 3：C 4H 10N 2：H 3PO 4：H 2O＝3：2：3：5：45，
（12）Co：H 3BO 3：C 4H 10N 2：H 3PO 4：H 2O＝5：1：3：6：50，
（13）Co：H 3BO 3：C 4H 10N 2：H 3PO 4：H 2O＝5：1：0.5：1.5：50。
2, structure elucidation
Choose the colourless particulate state monocrystalline of suitable dimension, with Siemens Smart CCD diffractometer in 293(± 2) use through the Mo of graphite monochromatization K alpha-ray (λ=0.071073 nm) under the K and collect the diffracted intensity data.Raw data is carried out absorption correction with the ABSOR program, adopts direct method to determine the original texture model of crystal.At last, expand initial model with difference Fourier analysis and method of least squares, and position and the anisotropic temperature factor of all non-hydrogen atoms carried out refine (SHELXTL-97).The result shows, molecular formula is C 4H 13N 2B 2P 3CoO 13, spacer is Im A2(No.46), cell parameter is a=12.4820 (8), b=9.4146 (3), c=11.4646 (2), α= β= γ=90.00 o, Z=4, V=1347.2 (1) 3
3, performance test
Choose an amount of sample, under tabletting machine, be processed as the circular testing sample of thickness 0.6mm, in the up and down both sides of compressing tablet, coat conductive silver glue.Then test at the ferroelectric tester of aix-ACCT TF2000.We study discovery to the organically templated metal cobalt borophosphate that obtains: the polarizability P of this title complex shows to have obvious ferroelectric effect, Pr=0.029 μ C/cm with the relation curve of executing electric field strength E outward 2, Ps=0.055 μ C/cm 2The alternating temperature polarization curve is according to every rising 10K, and recording once, electricity causes curve.Can be observed obvious Pr and Ps value, vary with temperature and gradually reduction.

Claims (4)

1. ferroelectric material organometallic complex, it is characterized in that: this complex molecule formula is C 4H 13N 2B 2P 3CoO 13, spacer is Im A2(No.46), cell parameter is a=12.4820 (8), b=9.4146 (3), c=11.4646 (2), α= β= γ=90.00 o, Z=4, unit-cell volume V=1347.2 (1) 3
2. the preparation method of the described ferroelectric material organometallic complex of claim 1 is characterized in that: under hydrothermal condition, and reactant cobaltous acetate (Co (CH 3COO) 2), boric acid (H 3BO 3), piperazine (C 4H 10N 2), phosphoric acid (H 3PO 4) as raw material, its mol ratio is 0.5～5:1～3:0.5～3:1.5～6, adopts water as solvent, hydro-thermal reaction is warming up to 140～220 ℃, and naturally cooling under the room temperature obtains C 4H 13N 2B 2P 3CoO 13
3. the preparation method of ferroelectric material organometallic complex as claimed in claim 2, it is characterized in that: above-mentioned cobaltous acetate is replaced by the Cobaltous nitrate hexahydrate of jljl quality, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, rose vitriol or cobalt chloride.
4. the purposes of the described ferroelectric material organometallic complex of claim 1 is characterized in that: this material is applied to store and recovery information, transmission light information, image show or holographic in pagination device, the storage that ferroelectric light valve array is made holographic.
CN201210511721XA 2012-12-04 2012-12-04 Ferroelectric organometallic compound, as well as preparation method and application thereof Pending CN103044492A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106565754A (en) * 2015-10-10 2017-04-19 宁波大学 Hydration L-malic acid NdB ferroelectric function material and preparation method thereof
CN109659570A (en) * 2019-01-09 2019-04-19 长江大学 The application of the metal organic framework compound hollow microsphere of load iron cobalt sulfide

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101691386A (en) * 2009-10-16 2010-04-07 广东工业大学 Ferroelectric material organically templated metal boron phosphate and preparation method and application thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101691386A (en) * 2009-10-16 2010-04-07 广东工业大学 Ferroelectric material organically templated metal boron phosphate and preparation method and application thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106565754A (en) * 2015-10-10 2017-04-19 宁波大学 Hydration L-malic acid NdB ferroelectric function material and preparation method thereof
CN109659570A (en) * 2019-01-09 2019-04-19 长江大学 The application of the metal organic framework compound hollow microsphere of load iron cobalt sulfide

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Application publication date: 20130417