CN111747448A - Preparation method of potassium tantalate niobate high-purity nanocrystal with adjustable forbidden band width - Google Patents

Preparation method of potassium tantalate niobate high-purity nanocrystal with adjustable forbidden band width Download PDF

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CN111747448A
CN111747448A CN202010641677.9A CN202010641677A CN111747448A CN 111747448 A CN111747448 A CN 111747448A CN 202010641677 A CN202010641677 A CN 202010641677A CN 111747448 A CN111747448 A CN 111747448A
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purity
reaction
potassium tantalate
powder
ktn
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禹化健
王旭平
刘冰
邱程程
户延延
杨玉国
吴丰年
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New Material Institute of Shandong Academy of Sciences
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G35/00—Compounds of tantalum
    • C01G35/006—Compounds containing, besides tantalum, two or more other elements, with the exception of oxygen or hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
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    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/30—Three-dimensional structures
    • C01P2002/34—Three-dimensional structures perovskite-type (ABO3)
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/38—Particle morphology extending in three dimensions cube-like
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer

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Abstract

The invention relates to a synthesis preparation method of a high-purity potassium tantalate niobate nano powder material, which mainly utilizes hydrothermal reaction in a mixed solvent for synthesis. Mixing isopropanol and water as reaction solvent, and using KOH and Nb2O5And Ta2O5As a reactant, white KTN powder with uniform particles is synthesized by a high-pressure reaction kettle at a constant temperature of 200 ℃ for 30 hours, the granularity of the white KTN powder is 50-100 nm through characterization and calculation, and the white KTN powder has a cubic phase nanocrystalline appearance, good crystallization and high purity. According to KTa1‑ xNbxO3The Ta/Nb ratio is adjusted through chemical structure characteristics, KTNs with different components are synthesized, the forbidden bandwidth values are different through tests and are between 3.14eV and 3.46eV, and the band gap of the potassium tantalate-niobate material can be adjusted.

Description

Preparation method of potassium tantalate niobate high-purity nanocrystal with adjustable forbidden band width
Technical Field
The invention relates to the technical field of artificial synthesis of high-performance photoelectric material nano powder, in particular to a method for preparing potassium tantalate-niobate nano crystals with different forbidden band width values.
Background
Potassium tantalate niobate (KTa)1-xNbxO3(ii) a KTN) is an ABO3The perovskite-type ferroelectric material is a functional material with wide application, has a series of abundant physical properties for technical application, and has extremely wide application in the technical fields of dielectric, piezoelectric, ferroelectric, superconducting, nonlinear optics and the like. The KTN material is KTaO3And KNbO3The KTN has various forms such as powder, thin film, ceramic, single crystal and the like, and the single crystal material has important application prospect in the aspects of holographic storage, optical modulation, beam deflection, optical phase conjugation and the like due to excellent electro-optic and secondary electro-optic effects.
The potassium tantalate niobate material has great development potential, but the practical application of the material is difficult: the high-quality powder material is the basis and the premise of the preparation of ceramics and crystals thereof, the main preparation method of the KTN material at present needs high-temperature treatment, the problems of overlarge crystal grains, hard agglomeration and the like are easily caused by high-temperature calcination, the performance of the KTN material can be directly influenced, and the purity of the prepared material is difficult to ensure; the synthesis preparation of uniform KTN powder, large-size and high-quality KTN transparent ceramics and single crystals is difficult, which limits the application of the KTN powder and the KTN transparent ceramics and the single crystals on devices such as electro-optical devices, semiconductors and the like; in addition, the semiconductor device has strict requirements on the forbidden bandwidth value of the material, and the adjustability of the forbidden bandwidth has great significance for the semiconductor application of the KTN material. With the development of low dimension of various devices, the low dimension ferroelectric nano material receives extensive attention due to its unique properties.
The forbidden band width is an important characteristic parameter of a semiconductor, and the size of the forbidden band width is mainly determined by the energy band structure of the semiconductor, namely, the forbidden band width is related to the combination property of a crystal structure and atoms and the like. A large number of electrons in the semiconductor valence band are valence electrons, are not carriers, and cannot conduct electricity. Conduction is only possible when valence electrons transition to the conduction band to generate free electrons and holes. A hole is actually a valence vacancy left by the transition of a valence electron to the conduction band, that is, the movement of one hole is equivalent to the movement of a large group of valence electrons. The forbidden bandwidth actually reflects the degree to which the valence electrons are strongly and weakly bound, i.e., the minimum energy required for their intrinsic excitation. Therefore, the size of the forbidden band width and the adjustable degree of the forbidden band width will affect the photoelectric performance of the material, and further affect the application of the material.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a preparation method of a potassium tantalate niobate high-purity nanocrystalline material, the forbidden bandwidth of the material can be adjusted by adjusting a synthesis process and a component proportion, the high-purity nano powder material can provide a good foundation for the preparation of potassium tantalate niobate ceramics and single crystals, and the adjustment of the forbidden bandwidth of the material can meet the requirements of corresponding semiconductor devices.
The technical scheme adopted by the invention is as follows:
the method is characterized in that the high-purity potassium tantalate-niobate nanocrystalline is synthesized by a hydrothermal reaction in a mixed solvent, the specific synthesis reaction is carried out in a stainless steel high-pressure reaction kettle, the capacity of a polytetrafluoroethylene lining is 100ml, and the reaction volume rate in the lining is controlled to be 60%. Firstly, weighing a high-purity KOH reagent according to a proper concentration, dissolving the high-purity KOH reagent in deionized water with a certain volume, adding an isopropanol solution, and uniformly mixing to obtain a reaction solvent, wherein KOH serves as a reactant and a mineralizer in the hydrothermal reaction process. Press KTa1- xNbxO3Chemical formula metering proportion separately weighing analytical pure Nb2O5Reagent and Ta2O5Taking a reagent as a reactant, sequentially adding reaction raw materials into a mixed solvent, then placing the mixture into a magnetic stirrer for stirring, fully and uniformly mixing the raw materials in the solvent, and pouring the uniform mixed solution into a polytetrafluoroethylene lining. And tightly covering and sealing the lining, placing the lining into a reaction kettle, screwing the reaction kettle, and placing the reaction kettle into a sintering furnace at 200 ℃ for constant-temperature reaction. And naturally cooling to room temperature after the synthesis reaction is finished, repeatedly centrifuging, washing, and drying in a drying box to obtain white KTN powder with fine and uniform particles.
Tantalic acidPotassium (KTaO)3) Has a forbidden band width of 3.46eV and potassium niobate (KNbO)3) The forbidden band width value is 3.14eV, and the potassium tantalate niobate is KTaO3And KNbO3Is KTa of the chemical formula1-xNbxO3The physical properties of the material are different with the content ratio of Ta/Nb components, so that the difference of x values in the chemical formula also causes the difference of forbidden bandwidth values of potassium tantalate niobate materials, and different x values are taken to determine Nb2O5And Ta2O5Respectively carrying out reaction synthesis experiments according to different proportions to prepare the corresponding KTN nano powder material.
The phase structure of the potassium tantalate niobate nano powder is tested by an EMPYREAN X-ray diffractometer produced by Dutch Pasacaceae; the size of the product grains was determined by MDI jade5.0 analysis software based on XRD data; the appearance of the crystal grains is characterized by SUPRA55 scanning electron microscope test produced by Germany Zeiss company; measuring the ultraviolet-visible diffuse reflection spectrum (DRUVS) of the powder by an ultraviolet-visible spectrophotometer, and extending to a point on an X axis (energy) along band-edge wavelength after fitting by a straight line extrapolation method according to a Kubelka-Munk function and the relation between the wavelength and the energy to obtain the forbidden band width value of the product.
According to the results of test characterization, the average particle size of the KTN powder prepared by the method is 50-100 nm and is in a nanometer level; the purity of the nano particles is high, and the crystallization is good; 4 groups of KTN nanocrystals with different Ta/Nb components are prepared, the forbidden band width values are different and are between KTaO3And KNbO3The band gap of the potassium tantalate niobate material can be adjusted. Compared with the prior art, the invention has the following beneficial effects and progresses: the reaction synthesis temperature of the KTN nanocrystals is reduced by utilizing the high-pressure condition in the high-pressure reaction kettle; the reaction environment for manufacturing a proper mixed solvent ensures the nanometer granularity of the KTN material, and greatly improves the purity of the product; the forbidden bandwidth value of the KTN material is adjusted by adjusting the stoichiometric proportion of the reaction raw materials, the regularity between the KTN material and the KTN material is obtained by repeated experiments, and the potassium sodium tantalate niobate with the corresponding band gap can be prepared according to the requirements of semiconductor devicesRice material.
Drawings
Fig. 1 is an XRD spectrum of KTN nanopowder of different compositions prepared by the present invention. Fig. 2 is a nano micrograph of KTN powder obtained by scanning electron microscopy.
Fig. 3 shows the forbidden bandwidth value of the KTN powder material obtained by extrapolation. On the basis of an ultraviolet visible diffuse reflection test result, according to a Kubelka-Munk function and a relation between wavelength and energy, a forbidden bandwidth value of a product is obtained by extending to a point on an X axis (energy) along band edge wavelength after fitting by a straight line extrapolation method, and specific forbidden bandwidth values of potassium tantalate-niobate powder with different components are obtained in a figure.
Detailed Description
The invention is further described below with reference to the accompanying drawings.
Example 1
The KTN nanocrystalline material is prepared by adopting a hydrothermal reaction method in a mixed solvent:
weighing a proper amount of KOH, dissolving the KOH in 30ml of deionized water, preparing a KOH solution with the concentration of 4mol/L, weighing 30ml of isopropanol, pouring the isopropanol into the mixture, and uniformly mixing to obtain a mixed solvent. According to formula KTa0.2Nb0.8O3Weighing 0.002mol of high-purity Ta according to the stoichiometric ratio of chemical reaction2O5Reagent 0.884g and 0.008mol of high-purity Nb2O52.126g of reagent. Weighing Nb2O5And Ta2O5And sequentially putting the powder into the prepared mixed solvent, and then putting the powder into a magnetic stirrer to stir for 3 hours to fully and uniformly mix the raw materials. Pouring the mixed solution into a polytetrafluoroethylene lining with the volume of 100ml, sealing the lining, putting the lining into a stainless steel high-pressure reaction kettle, screwing the reaction kettle, putting the reaction kettle into a sintering furnace, and carrying out constant-temperature reaction for 30 hours at the temperature of 200 ℃. Naturally cooling to room temperature after the reaction is finished, taking out the reactant and the mixed solvent in the lining, putting the reactant and the mixed solvent into a centrifuge, repeatedly centrifuging and washing the precipitated reactant for 5 times, and finally drying the reactant in an oven at 80 ℃ for 20 hours to obtain white KTa with uniform particles0.2Nb0.8O3And (3) powder. The average particle size of the sample was calculated from the XRD test results to be 78.7nm as measured by DRUVSTest results the forbidden band width value of the sample is calculated to be 3.202 eV.
Example 2
The material was prepared according to the procedure described above, according to formula KTa0.4Nb0.6O3Weighing 0.004mol of high-purity Ta according to the stoichiometric ratio of chemical reaction2O51.767g of reagent and 0.006mol of high-purity Nb2O51.595g of reagent. Finally KTa is obtained0.4Nb0.6O3And (3) powder. The average particle size of the sample was calculated from the XRD test results to be 69.5nm, and the forbidden bandwidth value of the sample was calculated from the DRUVS test results to be 3.237 eV.
Example 3
The material was prepared by the same procedure as above except that it was prepared according to formula KTa0.6Nb0.4O3Weighing 0.006mol of high-purity Ta according to the stoichiometric ratio of chemical reaction2O52.651g of reagent and 0.004mol of high-purity Nb2O5Reagent 1.063 g. Finally KTa is obtained0.6Nb0.4O3And (3) powder. The average particle size of the sample was calculated to be 65.3nm from the XRD test results, and the forbidden bandwidth value of the sample was calculated to be 3.275eV from the DRUVS test results.
Example 4
The material was prepared by the same procedure as above except that it was prepared according to formula KTa0.8Nb0.2O3Weighing 0.008mol of high-purity Ta according to the stoichiometric ratio of chemical reaction2O5Reagent 3.534g and 0.002mol of high-purity Nb2O50.532g of reagent. Finally KTa is obtained0.8Nb0.2O3And (3) powder. The average particle size of the sample was calculated from the XRD test results to be 83.4nm, and the forbidden bandwidth value of the sample was calculated from the DRUVS test results to be 3.426 eV.

Claims (4)

1. A potassium tantalate niobate high-purity nanocrystal with adjustable forbidden band width is characterized in that: KTa as described1-xNbxO3(X is more than or equal to 0.2 and less than or equal to 0.8), and the forbidden band width value is 3.202-3.426 eV; the granularity of the potassium tantalate niobate powder is nano and the cubic phase nanocrystalline morphology.
2. A method for preparing high-purity potassium tantalate niobate nanocrystals according to claim 1, which is characterized by comprising the following steps: the mixed solvent hydrothermal reaction method utilizes a stainless steel high-pressure reaction kettle, the volume of an inner lining of the stainless steel high-pressure reaction kettle is 100ml, the reaction volume ratio is 60%, the reaction temperature is 200 ℃, and the constant-temperature reaction time is 30 hours.
3. The method for preparing high-purity potassium tantalate niobate nanocrystals according to claim 2, wherein the ratio of the mixed solvent is composed of 30ml of isopropanol solution and 30ml of deionized water.
4. The method for preparing high-purity potassium tantalate niobate nanocrystals according to claim 3, wherein the reaction reagents used in the synthesis of the material are KOH and Nb2O5And Ta2O5Wherein KOH is used as a reactant and a mineralizer in the reaction process, and the concentration of the prepared KOH solution is 4 mol/L.
CN202010641677.9A 2020-07-06 2020-07-06 Preparation method of potassium tantalate niobate high-purity nanocrystal with adjustable forbidden band width Pending CN111747448A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112275298A (en) * 2020-11-23 2021-01-29 浙江师范大学 Bismuth sulfide composite potassium tantalate niobate catalyst, preparation method and application thereof

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CN102205988A (en) * 2011-03-15 2011-10-05 陕西科技大学 Method for preparing lithium-doped potassium sodium niobate-based lead-less piezoelectric ceramic powder by microwave water heating way
CN102180671A (en) * 2011-03-16 2011-09-14 南京航空航天大学 Nano functional ceramic material and preparation method thereof
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112275298A (en) * 2020-11-23 2021-01-29 浙江师范大学 Bismuth sulfide composite potassium tantalate niobate catalyst, preparation method and application thereof
CN112275298B (en) * 2020-11-23 2023-03-14 浙江师范大学 Bismuth sulfide composite potassium tantalate niobate catalyst, preparation method and application thereof

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Application publication date: 20201009