CN101200127A - Lanthanum zirconic acid/yttrium titanate film material and method for making same - Google Patents
Lanthanum zirconic acid/yttrium titanate film material and method for making same Download PDFInfo
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- CN101200127A CN101200127A CNA2006101614788A CN200610161478A CN101200127A CN 101200127 A CN101200127 A CN 101200127A CN A2006101614788 A CNA2006101614788 A CN A2006101614788A CN 200610161478 A CN200610161478 A CN 200610161478A CN 101200127 A CN101200127 A CN 101200127A
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Abstract
The invention discloses a Lanthanum zirconate / titanate Y film material and the preparation method of the Lanthanum zirconate / titanate Y film material. The material is the metal nickel of (100) axial orientation or the nickel alloy base covered in sequence with a Lanthanum zirconate seed layer of the (100) axial orientation, a Lanthanum zirconate layer of the (100) axis orientation, a titanate Y seed layer of (100) axial orientation and a titanate Y film of (100) axial orientation. In the preparation, according to the mol ratios of la: zieconim 1:1 and Y:Ti 1:1, the precursor colloid of the Lanthanum zirconate seed layer and the precursor colloid of the follow up layer of the Lanthanum zirconate seed layer are firstly respectively prepared. And then the metal nickel of (100) axial orientation or the nickel alloy base is coated in sequence with the above precursor colloid, which is also respectively and successively under the heat of 300 to 450 DEG C. for 15 to 30 minutes and in annealing under 850 to 1150 DEG C.for more than 15 minutes in a reduction atmosphere. Thus the Lanthanum zirconate / titanate Y film materal is produced. The material has high (100) axial orientation, which can be widely applied in catalysts, optical materials, superconducting materials and other fields.
Description
Technical field
The present invention relates to a kind of thin-film material and method for making, especially zirconic acid lanthanum/metatitanic acid yttrium thin-film material and preparation method thereof.
Background technology
Dielectric materials such as zirconic acid lanthanum, metatitanic acid yttrium have a wide range of applications at aspects such as catalyst, optical material and superconductors, people are in order to obtain it, multiple trial and effort have been done, as a kind of " the topological anion exchange sull and preparation method thereof " that discloses among the disclosed U.S. application for a patent for invention prospectus US 2006/0107891A1 on May 25th, 2006.It is intended to provide a kind of sull goods and its preparation method.The sull goods contain the zirconic acid lanthanum for to be covered with multilevel oxide on silicon chip in the oxide; What the preparation method adopted is ion-exchange, and processing step is elder generation's growing nitride film on silicon chip, is placed under the high-temperature oxygen atmosphere again, to remove the nitrogen in the nitride, makes it become oxidation film.But, this sull goods and preparation method thereof all exist weak point, at first, the sull goods are not zirconic acid lanthanum/metatitanic acid yttrium thin-film materials, particularly not the zirconic acid lanthanum/metatitanic acid yttrium thin-film material of height (100) axle orientation, more do not possess the excellent properties of the zirconic acid lanthanum/metatitanic acid yttrium thin-film material of height (100) axle orientation; Secondly, the preparation method both can not prepare the zirconic acid lanthanum/metatitanic acid yttrium thin-film material of height (100) axle orientation, again because of adopting metal non-oxidized substance salt such as nitride to be used as forerunner's raw material, and these metal non-oxidized substances forerunner raw material is except that needing preparation in a vacuum, also to make the high temperature denitrification and handle, thereby make it that defective that technology is too numerous and diverse and manufacturing cost is difficult to reduce be arranged.
Summary of the invention
The technical problem to be solved in the present invention is for overcoming weak point of the prior art, provides a kind of height (100) axle orientation of having, zirconic acid lanthanum easy to make/metatitanic acid yttrium thin-film material and preparation method thereof.
Zirconic acid lanthanum/metatitanic acid yttrium thin-film material comprises that substrate and the zirconic acid lanthanum layer, particularly (a) said substrate that are covered with on it are the metallic nickel or the nickel alloy base band of (100) axle orientation; (b) said zirconic acid lanthanum layer is the zirconic acid lanthanum layer of zirconic acid lanthanum Seed Layer and (100) axle orientation of (100) axle orientation; (c) be covered with the zirconic acid lanthanum Seed Layer of (100) axle orientation, the zirconic acid lanthanum layer of (100) axle orientation, the metatitanic acid yttrium Seed Layer of (100) axle orientation and the metatitanic acid yttrium film of (100) axle orientation on the metallic nickel of said (100) axle orientation or the nickel alloy base band successively.
Further improvement as zirconic acid lanthanum/metatitanic acid yttrium thin-film material, the thickness of the zirconic acid lanthanum Seed Layer of described (100) axle orientation is 1～90nm, (100) thickness of the zirconic acid lanthanum layer of axle orientation is 20～3000nm, (100) thickness of the metatitanic acid yttrium Seed Layer of axle orientation is 1～90nm, and the thickness of the metatitanic acid yttrium film of (100) axle orientation is 20～3000nm.
The preparation method of zirconic acid lanthanum/metatitanic acid yttrium thin-film material comprises chemical solution method, particularly it is finished according to the following steps: (a) according to lanthanum: zirconium is 1: 1 a mol ratio, difference weighing lanthanum acetate, each two parts of zirconium-n-propylates, earlier two parts of lanthanum acetates are dissolved in respectively in two parts of propionic acid solution, being stirred to lanthanum acetate at 50～90 ℃ dissolves fully, wherein, two parts propionic acid volume: the lanthanum acetate molal quantity is respectively 10～20 liters: 1 mole and 2.5～5 liters: 1 mole, again two parts of zirconium-n-propylates are added respectively to be stirred in the propionic acid solution of above-mentioned different volumes than molal quantity fully and dissolve, obtain zirconic acid lanthanum Seed Layer forerunner's colloid and zirconic acid lanthanum succeeding layer forerunner colloid respectively; (b) zirconic acid lanthanum Seed Layer forerunner colloid is coated on metallic nickel of (100) axle orientation or the nickel alloy base band and forms gel, again with it in 300～450 ℃ of following pyrolysis after 15～30 minutes, in reducing atmosphere, anneal more than 15 minutes in 950～1150 ℃, obtain the zirconic acid lanthanum Seed Layer of (100) axle orientation, afterwards, zirconic acid lanthanum succeeding layer forerunner colloid is coated to growth to be had on the metallic nickel of (100) axle orientation of zirconic acid lanthanum Seed Layer of (100) axle orientation or the nickel alloy base band and forms gel, again with it in 300～450 ℃ of following pyrolysis after 15～30 minutes, in reducing atmosphere, more than 15 minutes, obtain the zirconic acid lanthanum layer of (100) axle orientation in 950～1150 ℃ of annealing; (c) the latter half of process afterwards of repeating step (b) is until the zirconic acid lanthanum layer of (100) axle orientation that obtains desired thickness; (d) according to yttrium: titanium is 1: 1 a mol ratio, weighing yttrium acetate, n-butanol titanium are each two parts respectively, earlier two parts of yttrium acetates are dissolved in respectively in two parts of propionic acid solution, being stirred to yttrium acetate at 50～90 ℃ dissolves fully, wherein, two parts propionic acid volume: the yttrium acetate molal quantity is respectively 10～20 liters: 1 mole and 2.5～5 liters: 1 mole, again two parts of n-butanol titaniums are added respectively to be stirred in the propionic acid solution of above-mentioned different volumes than molal quantity fully and dissolve, obtain metatitanic acid yttrium Seed Layer forerunner's colloid and metatitanic acid yttrium succeeding layer forerunner colloid respectively; (e) metatitanic acid yttrium Seed Layer forerunner colloid being coated to successively growth has on the metallic nickel of (100) axle orientation of zirconic acid lanthanum layer of zirconic acid lanthanum Seed Layer of (100) axle orientation and (100) axle orientation or the nickel alloy base band and forms gel mould, again with it in 300～450 ℃ of following pyrolysis after 15～30 minutes, in reducing atmosphere, anneal more than 15 minutes down in 850～1150 ℃, obtain the metatitanic acid yttrium Seed Layer of (100) axle orientation, afterwards, metatitanic acid yttrium succeeding layer forerunner colloid is coated to the zirconic acid lanthanum Seed Layer that growth successively has (100) axle orientation, (100) form gel on the metallic nickel of (100) axle orientation of the metatitanic acid yttrium Seed Layer of the zirconic acid lanthanum layer of axle orientation and (100) axle orientation or the nickel alloy base band, again with it in 300～450 ℃ of following pyrolysis after 15～30 minutes, in reducing atmosphere, anneal more than 15 minutes metatitanic acid yttrium layer of acquisition (100) axle orientation down in 850～1150 ℃; (f) the latter half of process afterwards of repeating step (e) until the metatitanic acid yttrium film of (100) axle orientation that obtains desired thickness, thereby makes zirconic acid lanthanum/metatitanic acid yttrium thin-film material.
As the preparation method's of zirconic acid lanthanum/metatitanic acid yttrium thin-film material further improvement, described lanthanum acetate or yttrium acetate are dissolved in the propionic acid solution, stir more than 10 minutes at 50～90 ℃; Described reducing atmosphere is that the hydrogen that 3～5% hydrogen adds nitrogen or 3～5% adds argon gas; The heating rate that described pyrolysis temperature is warming up to annealing temperature is 5～500 ℃/minute.
Beneficial effect with respect to prior art is, one, select for use (100) metallic nickel that is orientated or nickel alloy base band as substrate, the zirconic acid lanthanum layer that adopts (100) zirconic acid lanthanum Seed Layer that is orientated and (100) axle orientation is as zirconic acid lanthanum layer, the necessary condition of oriented growth both was provided for the metatitanic acid yttrium, had established sufficient basis for the final metatitanic acid yttrium film that obtains height (100) axle orientation again; They are two years old, zirconic acid lanthanum layer that obtains and the thin-film material that makes are used x-ray diffractometer respectively, after field emission scanning electron microscope and AFM are tested and are observed, from the X-ray diffracting spectrum that obtains, stereoscan photograph and atomic force photo, and by analysis with calculate as can be known, thin-film material is by the zirconic acid lanthanum Seed Layer that is covered with (100) axle orientation on the metallic nickel of (100) axle orientation or the nickel alloy base band successively, (100) the zirconic acid lanthanum layer of axle orientation, (100) the metatitanic acid yttrium film of the metatitanic acid yttrium Seed Layer of axle orientation and (100) axle orientation constitutes, wherein, zirconic acid lanthanum layer and metatitanic acid yttrium film all have (100) grain orientation of height, and its surperficial compact structure, evenly; They are three years old, adopt the inventive method to prepare thin-film material, because of its stoichiometric proportion can accurately be controlled, so every layer thickness of thin-film material and total thickness all can be set and be made subsequently according to actual needs artificially in advance, expand the application scenario of thin-film material widely, greatly expanded its applicable scope; Its four, equipment required in the preparation process is few, technology is simple, operation and control are easily grasped, the cost of preparation is low, be beneficial to large-scale industrial production.
Further embodiment as beneficial effect, the one, the thickness of selecting zirconic acid lanthanum Seed Layer of (100) axle orientation for use is that the thickness of zirconic acid lanthanum layer of 1～90nm, (100) axle orientation is that the thickness of metatitanic acid yttrium Seed Layer of 20～3000nm, (100) axle orientation is that the thickness of metatitanic acid yttrium film of 1～90nm, (100) axle orientation is 20～3000nm, just can grow metatitanic acid yttrium film of height (100) axle orientation, in the time of satisfying actual use again fully to the needs of film thickness; The 2nd, lanthanum acetate or yttrium acetate are dissolved in the propionic acid solution, only need stir more than 10 minutes under 50～90 ℃, just be enough to make lanthanum acetate or yttrium acetate to dissolve fully; The 3rd, the hydrogen that reducing atmosphere adopts 3～5% hydrogen to add nitrogen or 3～5% adds argon gas, just can prevent the oxidation of metallic nickel or nickel alloy base band, thereby prevents the thin film alignment decline problem that causes because of the base band oxidation; The 4th, the heating rate that pyrolysis temperature is warming up to annealing temperature adopts 5～500 ℃/minute, can not only reach required annealing temperature with heating rate faster, also can favorable influence be arranged to the orientation of thin-film material.
Description of drawings
Below in conjunction with accompanying drawing optimal way of the present invention is described in further detail.
Fig. 1 uses the XRD figure spectrum that obtains after the test of Phillips X ' Pert type X-ray diffraction (XRD) instrument to the zirconic acid lanthanum layer that obtains; Wherein, abscissa is the angle of diffraction, and ordinate is the relative intensity of diffraction maximum.By the position of each diffraction maximum in the XRD figure and relative intensity as can be known, the material of being tested is the zirconic acid lanthanum, and it has (100) grain orientation of height;
Fig. 2 uses the XRD figure spectrum that obtains after the test of Phillips X ' Pert type X-ray diffraction (XRD) instrument to the zirconic acid lanthanum that makes/metatitanic acid yttrium thin-film material; Wherein, abscissa is the angle of diffraction, and ordinate is the relative intensity of diffraction maximum.By the position of each diffraction maximum in the XRD figure and relative intensity as can be known, the thin-film material that makes is zirconic acid lanthanum/metatitanic acid yttrium laminated film.And the orientation of the metatitanic acid yttrium film crystal grain of subsequent growth depend on before the orientation of zirconic acid lanthanum layer crystal grain of growth, promptly only on the zirconic acid lanthanum layer of height (100) orientation, just can make the metatitanic acid yttrium film of height (100) orientation;
Fig. 3 be to the zirconic acid lanthanum layer that obtains use take the photograph behind LEO 1530 type field emission scanning electron microscopes (FE-SEM) the observation surface topography the FE-SEM photo.Zirconic acid lanthanum layer has fine and close pattern as can be seen from photo;
Fig. 4 be to the zirconic acid lanthanum that makes/metatitanic acid yttrium thin-film material use take the photograph behind LEO 1530 type field emission scanning electron microscopes (FE-SEM) the observation surface topography the FE-SEM photo.Metatitanic acid yttrium layer surperficial dense in zirconic acid lanthanum/metatitanic acid yttrium thin-film material as can be seen from photo;
Fig. 5 be to the zirconic acid lanthanum layer that obtains use take the photograph after the observation of Autoprobe CP type AFM the atomic force electromicroscopic photograph, zirconic acid lanthanum layer has less surface roughness as can be seen from photo;
Fig. 6 be to the zirconic acid lanthanum that makes/metatitanic acid yttrium thin-film material use take the photograph after the observation of Autoprobe CP type AFM the atomic force electromicroscopic photograph, from photo as can be seen in zirconic acid lanthanum/metatitanic acid yttrium thin-film material the surface roughness of metatitanic acid yttrium layer also smaller.
The specific embodiment
At first make or buy the metallic nickel or the nickel alloy base band of height (100) axle orientation as substrate from market with conventional method, and lanthanum acetate, zirconium-n-propylate, propionic acid, yttrium acetate and n-butanol titanium.Then,
Embodiment 1: finish preparation according to the following steps successively: a) according to lanthanum: zirconium is 1: 1 a mol ratio, weighing lanthanum acetate, zirconium-n-propylate are each two parts respectively, earlier two parts of lanthanum acetates are dissolved in respectively in two parts of propionic acid solution, respectively stir at 50 ℃ and to dissolve fully to lanthanum acetate in 20 minutes, wherein, two parts propionic acid volume: the lanthanum acetate molal quantity is respectively 10 liters: 1 mole and 2.5 liters: 1 mole.Again two parts of zirconium-n-propylates are added respectively to be stirred in the propionic acid solution of above-mentioned different volumes than molal quantity fully and dissolve, obtain zirconic acid lanthanum Seed Layer forerunner's colloid and zirconic acid lanthanum succeeding layer forerunner colloid respectively.B) zirconic acid lanthanum Seed Layer forerunner colloid is coated on metallic nickel base band of (100) axle orientation and forms gel, again with it in 300 ℃ of following pyrolysis after 30 minutes, in reducing atmosphere, annealed 120 minutes in 950 ℃, wherein, reducing atmosphere is that 3% hydrogen adds nitrogen, the heating rate that pyrolysis temperature is warming up to annealing temperature is 500 ℃/minute, obtains the zirconic acid lanthanum Seed Layer of (100) axle orientation.Afterwards, zirconic acid lanthanum succeeding layer forerunner colloid is coated to growth to be had on metallic nickel base band of (100) axle orientation of zirconic acid lanthanum Seed Layer of (100) axle orientation and forms gel, again with it in 300 ℃ of following pyrolysis after 30 minutes, in reducing atmosphere, annealed 120 minutes in 950 ℃, wherein, reducing atmosphere is that 3% hydrogen adds nitrogen, and the heating rate that pyrolysis temperature is warming up to annealing temperature is 500 ℃/minute, obtains zirconic acid lanthanum layer that (100) axle as Fig. 1, Fig. 3 and Fig. 5 as shown in is orientated.C) the latter half of process afterwards of repeating step b is until the zirconic acid lanthanum layer of (100) axle orientation that obtains desired thickness.D) according to yttrium: titanium is 1: 1 a mol ratio, weighing yttrium acetate, n-butanol titanium are each two parts respectively, earlier two parts of yttrium acetates are dissolved in respectively in two parts of propionic acid solution, respectively stir at 50 ℃ and to dissolve fully to yttrium acetate in 20 minutes, wherein, two parts propionic acid volume: the yttrium acetate molal quantity is respectively 10 liters: 1 mole and 2.5 liters: 1 mole.Again two parts of n-butanol titaniums are added respectively to be stirred in the propionic acid solution of above-mentioned different volumes than molal quantity fully and dissolve, obtain metatitanic acid yttrium Seed Layer forerunner's colloid and metatitanic acid yttrium succeeding layer forerunner colloid respectively.E) metatitanic acid yttrium Seed Layer forerunner colloid being coated to successively growth has on metallic nickel base band of (100) axle orientation of zirconic acid lanthanum layer of zirconic acid lanthanum Seed Layer of (100) axle orientation and (100) axle orientation and forms gel mould, again with it in 300 ℃ of following pyrolysis after 30 minutes, in reducing atmosphere, annealed 120 minutes down in 850 ℃, wherein, reducing atmosphere is that 3% hydrogen adds nitrogen, the heating rate that pyrolysis temperature is warming up to annealing temperature is 500 ℃/minute, obtains the metatitanic acid yttrium Seed Layer of (100) axle orientation.Afterwards, metatitanic acid yttrium succeeding layer forerunner colloid is coated to successively growth to be had on metallic nickel base band of (100) axle orientation of metatitanic acid yttrium Seed Layer of zirconic acid lanthanum layer of zirconic acid lanthanum Seed Layer, (100) axle orientation of (100) axle orientation and (100) axle orientation and forms gel, again with it in 300 ℃ of following pyrolysis after 30 minutes, in reducing atmosphere, annealed 120 minutes down in 850 ℃, wherein, reducing atmosphere is that 3% hydrogen adds nitrogen, the heating rate that pyrolysis temperature is warming up to annealing temperature is 500 ℃/minute, obtains the metatitanic acid yttrium layer of (100) axle orientation.F) repeating step e after latter half of process, until the metatitanic acid yttrium film of (100) axle orientation that obtains desired thickness, thereby make zirconic acid lanthanum/metatitanic acid yttrium thin-film material as shown in Fig. 2, Fig. 4 and Fig. 6.
Embodiment 2: finish preparation according to the following steps successively: a) according to lanthanum: zirconium is 1: 1 a mol ratio, weighing lanthanum acetate, zirconium-n-propylate are each two parts respectively, earlier two parts of lanthanum acetates are dissolved in respectively in two parts of propionic acid solution, respectively stir at 60 ℃ and to dissolve fully to lanthanum acetate in 17 minutes, wherein, two parts propionic acid volume: the lanthanum acetate molal quantity is respectively 13 liters: 1 mole and 3 liters: 1 mole.Again two parts of zirconium-n-propylates are added respectively to be stirred in the propionic acid solution of above-mentioned different volumes than molal quantity fully and dissolve, obtain zirconic acid lanthanum Seed Layer forerunner's colloid and zirconic acid lanthanum succeeding layer forerunner colloid respectively.B) zirconic acid lanthanum Seed Layer forerunner colloid is coated on metallic nickel base band of (100) axle orientation and forms gel, again with it in 340 ℃ of following pyrolysis after 27 minutes, in reducing atmosphere, annealed 100 minutes in 1000 ℃, wherein, reducing atmosphere is that 3.5% hydrogen adds nitrogen, the heating rate that pyrolysis temperature is warming up to annealing temperature is 380 ℃/minute, obtains the zirconic acid lanthanum Seed Layer of (100) axle orientation.Afterwards, zirconic acid lanthanum succeeding layer forerunner colloid is coated to growth to be had on metallic nickel base band of (100) axle orientation of zirconic acid lanthanum Seed Layer of (100) axle orientation and forms gel, again with it in 340 ℃ of following pyrolysis after 27 minutes, in reducing atmosphere, annealed 100 minutes in 1000 ℃, wherein, reducing atmosphere is that 3.5% hydrogen adds nitrogen, and the heating rate that pyrolysis temperature is warming up to annealing temperature is 380 ℃/minute, obtains zirconic acid lanthanum layer that (100) axle as Fig. 1, Fig. 3 and Fig. 5 as shown in is orientated.C) the latter half of process afterwards of repeating step b is until the zirconic acid lanthanum layer of (100) axle orientation that obtains desired thickness.D) according to yttrium: titanium is 1: 1 a mol ratio, weighing yttrium acetate, n-butanol titanium are each two parts respectively, earlier two parts of yttrium acetates are dissolved in respectively in two parts of propionic acid solution, respectively stir at 60 ℃ and to dissolve fully to yttrium acetate in 17 minutes, wherein, two parts propionic acid volume: the yttrium acetate molal quantity is respectively 13 liters: 1 mole and 3 liters: 1 mole.Again two parts of n-butanol titaniums are added respectively to be stirred in the propionic acid solution of above-mentioned different volumes than molal quantity fully and dissolve, obtain metatitanic acid yttrium Seed Layer forerunner's colloid and metatitanic acid yttrium succeeding layer forerunner colloid respectively.E) metatitanic acid yttrium Seed Layer forerunner colloid being coated to successively growth has on metallic nickel base band of (100) axle orientation of zirconic acid lanthanum layer of zirconic acid lanthanum Seed Layer of (100) axle orientation and (100) axle orientation and forms gel mould, again with it in 340 ℃ of following pyrolysis after 27 minutes, in reducing atmosphere, annealed 100 minutes down in 930 ℃, wherein, reducing atmosphere is that 3.5% hydrogen adds nitrogen, the heating rate that pyrolysis temperature is warming up to annealing temperature is 380 ℃/minute, obtains the metatitanic acid yttrium Seed Layer of (100) axle orientation.Afterwards, metatitanic acid yttrium succeeding layer forerunner colloid is coated to successively growth to be had on metallic nickel base band of (100) axle orientation of metatitanic acid yttrium Seed Layer of zirconic acid lanthanum layer of zirconic acid lanthanum Seed Layer, (100) axle orientation of (100) axle orientation and (100) axle orientation and forms gel, again with it in 340 ℃ of following pyrolysis after 27 minutes, in reducing atmosphere, annealed 100 minutes down in 930 ℃, wherein, reducing atmosphere is that 3.5% hydrogen adds nitrogen, the heating rate that pyrolysis temperature is warming up to annealing temperature is 380 ℃/minute, obtains the metatitanic acid yttrium layer of (100) axle orientation.F) repeating step e after latter half of process, until the metatitanic acid yttrium film of (100) axle orientation that obtains desired thickness, thereby make zirconic acid lanthanum/metatitanic acid yttrium thin-film material as shown in Fig. 2, Fig. 4 and Fig. 6.
Embodiment 3: finish preparation according to the following steps successively: a) according to lanthanum: zirconium is 1: 1 a mol ratio, weighing lanthanum acetate, zirconium-n-propylate are each two parts respectively, earlier two parts of lanthanum acetates are dissolved in respectively in two parts of propionic acid solution, respectively stir at 70 ℃ and to dissolve fully to lanthanum acetate in 15 minutes, wherein, two parts propionic acid volume: the lanthanum acetate molal quantity is respectively 15 liters: 1 mole and 3.8 liters: 1 mole.Again two parts of zirconium-n-propylates are added respectively to be stirred in the propionic acid solution of above-mentioned different volumes than molal quantity fully and dissolve, obtain zirconic acid lanthanum Seed Layer forerunner's colloid and zirconic acid lanthanum succeeding layer forerunner colloid respectively.B) zirconic acid lanthanum Seed Layer forerunner colloid is coated on metallic nickel base band of (100) axle orientation and forms gel, again with it in 380 ℃ of following pyrolysis after 23 minutes, in reducing atmosphere, annealed 70 minutes in 1050 ℃, wherein, reducing atmosphere is that 4% hydrogen adds nitrogen, the heating rate that pyrolysis temperature is warming up to annealing temperature is 250 ℃/minute, obtains the zirconic acid lanthanum Seed Layer of (100) axle orientation.Afterwards, zirconic acid lanthanum succeeding layer forerunner colloid is coated to growth to be had on metallic nickel base band of (100) axle orientation of zirconic acid lanthanum Seed Layer of (100) axle orientation and forms gel, again with it in 380 ℃ of following pyrolysis after 23 minutes, in reducing atmosphere, annealed 70 minutes in 1050 ℃, wherein, reducing atmosphere is that 4% hydrogen adds nitrogen, and the heating rate that pyrolysis temperature is warming up to annealing temperature is 250 ℃/minute, obtains zirconic acid lanthanum layer that (100) axle as Fig. 1, Fig. 3 and Fig. 5 as shown in is orientated.C) the latter half of process afterwards of repeating step b is until the zirconic acid lanthanum layer of (100) axle orientation that obtains desired thickness.D) according to yttrium: titanium is 1: 1 a mol ratio, weighing yttrium acetate, n-butanol titanium are each two parts respectively, earlier two parts of yttrium acetates are dissolved in respectively in two parts of propionic acid solution, respectively stir at 70 ℃ and to dissolve fully to yttrium acetate in 15 minutes, wherein, two parts propionic acid volume: the yttrium acetate molal quantity is respectively 15 liters: 1 mole and 3.8 liters: 1 mole.Again two parts of n-butanol titaniums are added respectively to be stirred in the propionic acid solution of above-mentioned different volumes than molal quantity fully and dissolve, obtain metatitanic acid yttrium Seed Layer forerunner's colloid and metatitanic acid yttrium succeeding layer forerunner colloid respectively.E) metatitanic acid yttrium Seed Layer forerunner colloid being coated to successively growth has on metallic nickel base band of (100) axle orientation of zirconic acid lanthanum layer of zirconic acid lanthanum Seed Layer of (100) axle orientation and (100) axle orientation and forms gel mould, again with it in 380 ℃ of following pyrolysis after 23 minutes, in reducing atmosphere, annealed 70 minutes down in 1000 ℃, wherein, reducing atmosphere is that 4% hydrogen adds nitrogen, the heating rate that pyrolysis temperature is warming up to annealing temperature is 250 ℃/minute, obtains the metatitanic acid yttrium Seed Layer of (100) axle orientation.Afterwards, metatitanic acid yttrium succeeding layer forerunner colloid is coated to successively growth to be had on metallic nickel base band of (100) axle orientation of metatitanic acid yttrium Seed Layer of zirconic acid lanthanum layer of zirconic acid lanthanum Seed Layer, (100) axle orientation of (100) axle orientation and (100) axle orientation and forms gel, again with it in 380 ℃ of following pyrolysis after 23 minutes, in reducing atmosphere, annealed 70 minutes down in 1000 ℃, wherein, reducing atmosphere is that 4% hydrogen adds nitrogen, the heating rate that pyrolysis temperature is warming up to annealing temperature is 250 ℃/minute, obtains the metatitanic acid yttrium layer of (100) axle orientation.F) repeating step e after latter half of process, until the metatitanic acid yttrium film of (100) axle orientation that obtains desired thickness, thereby make zirconic acid lanthanum/metatitanic acid yttrium thin-film material as shown in Fig. 2, Fig. 4 and Fig. 6.
Embodiment 4: finish preparation according to the following steps successively: a) according to lanthanum: zirconium is 1: 1 a mol ratio, weighing lanthanum acetate, zirconium-n-propylate are each two parts respectively, earlier two parts of lanthanum acetates are dissolved in respectively in two parts of propionic acid solution, respectively stir at 80 ℃ and to dissolve fully to lanthanum acetate in 13 minutes, wherein, two parts propionic acid volume: the lanthanum acetate molal quantity is respectively 17 liters: 1 mole and 4.4 liters: 1 mole.Again two parts of zirconium-n-propylates are added respectively to be stirred in the propionic acid solution of above-mentioned different volumes than molal quantity fully and dissolve, obtain zirconic acid lanthanum Seed Layer forerunner's colloid and zirconic acid lanthanum succeeding layer forerunner colloid respectively.B) zirconic acid lanthanum Seed Layer forerunner colloid is coated on metallic nickel base band of (100) axle orientation and forms gel, again with it in 410 ℃ of following pyrolysis after 19 minutes, in reducing atmosphere, annealed 40 minutes in 1100 ℃, wherein, reducing atmosphere is that 4.5% hydrogen adds nitrogen, the heating rate that pyrolysis temperature is warming up to annealing temperature is 130 ℃/minute, obtains the zirconic acid lanthanum Seed Layer of (100) axle orientation.Afterwards, zirconic acid lanthanum succeeding layer forerunner colloid is coated to growth to be had on metallic nickel base band of (100) axle orientation of zirconic acid lanthanum Seed Layer of (100) axle orientation and forms gel, again with it in 410 ℃ of following pyrolysis after 19 minutes, in reducing atmosphere, annealed 40 minutes in 1100 ℃, wherein, reducing atmosphere is that 4.5% hydrogen adds nitrogen, and the heating rate that pyrolysis temperature is warming up to annealing temperature is 130 ℃/minute, obtains zirconic acid lanthanum layer that (100) axle as Fig. 1, Fig. 3 and Fig. 5 as shown in is orientated.C) the latter half of process afterwards of repeating step b is until the zirconic acid lanthanum layer of (100) axle orientation that obtains desired thickness.D) according to yttrium: titanium is 1: 1 a mol ratio, weighing yttrium acetate, n-butanol titanium are each two parts respectively, earlier two parts of yttrium acetates are dissolved in respectively in two parts of propionic acid solution, respectively stir at 80 ℃ and to dissolve fully to yttrium acetate in 13 minutes, wherein, two parts propionic acid volume: the yttrium acetate molal quantity is respectively 17 liters: 1 mole and 4.4 liters: 1 mole.Again two parts of n-butanol titaniums are added respectively to be stirred in the propionic acid solution of above-mentioned different volumes than molal quantity fully and dissolve, obtain metatitanic acid yttrium Seed Layer forerunner's colloid and metatitanic acid yttrium succeeding layer forerunner colloid respectively.E) metatitanic acid yttrium Seed Layer forerunner colloid being coated to successively growth has on metallic nickel base band of (100) axle orientation of zirconic acid lanthanum layer of zirconic acid lanthanum Seed Layer of (100) axle orientation and (100) axle orientation and forms gel mould, again with it in 410 ℃ of following pyrolysis after 19 minutes, in reducing atmosphere, annealed 40 minutes down in 1080 ℃, wherein, reducing atmosphere is that 4.5% hydrogen adds nitrogen, the heating rate that pyrolysis temperature is warming up to annealing temperature is 130 ℃/minute, obtains the metatitanic acid yttrium Seed Layer of (100) axle orientation.Afterwards, metatitanic acid yttrium succeeding layer forerunner colloid is coated to successively growth to be had on metallic nickel base band of (100) axle orientation of metatitanic acid yttrium Seed Layer of zirconic acid lanthanum layer of zirconic acid lanthanum Seed Layer, (100) axle orientation of (100) axle orientation and (100) axle orientation and forms gel, again with it in 410 ℃ of following pyrolysis after 19 minutes, in reducing atmosphere, annealed 40 minutes down in 1080 ℃, wherein, reducing atmosphere is that 4.5% hydrogen adds nitrogen, the heating rate that pyrolysis temperature is warming up to annealing temperature is 130 ℃/minute, obtains the metatitanic acid yttrium layer of (100) axle orientation.F) repeating step e after latter half of process, until the metatitanic acid yttrium film of (100) axle orientation that obtains desired thickness, thereby make zirconic acid lanthanum/metatitanic acid yttrium thin-film material as shown in Fig. 2, Fig. 4 and Fig. 6.
Embodiment 5: finish preparation according to the following steps successively: a) according to lanthanum: zirconium is 1: 1 a mol ratio, weighing lanthanum acetate, zirconium-n-propylate are each two parts respectively, earlier two parts of lanthanum acetates are dissolved in respectively in two parts of propionic acid solution, respectively stir at 90 ℃ and to dissolve fully to lanthanum acetate in 10 minutes, wherein, two parts propionic acid volume: the lanthanum acetate molal quantity is respectively 20 liters: 1 mole and 5 liters: 1 mole.Again two parts of zirconium-n-propylates are added respectively to be stirred in the propionic acid solution of above-mentioned different volumes than molal quantity fully and dissolve, obtain zirconic acid lanthanum Seed Layer forerunner's colloid and zirconic acid lanthanum succeeding layer forerunner colloid respectively.B) zirconic acid lanthanum Seed Layer forerunner colloid is coated on metallic nickel base band of (100) axle orientation and forms gel, again with it in 450 ℃ of following pyrolysis after 15 minutes, in reducing atmosphere, annealed 15 minutes in 1150 ℃, wherein, reducing atmosphere is that 5% hydrogen adds nitrogen, the heating rate that pyrolysis temperature is warming up to annealing temperature is 5 ℃/minute, obtains the zirconic acid lanthanum Seed Layer of (100) axle orientation.Afterwards, zirconic acid lanthanum succeeding layer forerunner colloid is coated to growth to be had on metallic nickel base band of (100) axle orientation of zirconic acid lanthanum Seed Layer of (100) axle orientation and forms gel, again with it in 450 ℃ of following pyrolysis after 15 minutes, in reducing atmosphere, annealed 15 minutes in 1150 ℃, wherein, reducing atmosphere is that 5% hydrogen adds nitrogen, and the heating rate that pyrolysis temperature is warming up to annealing temperature is 5 ℃/minute, obtains zirconic acid lanthanum layer that (100) axle as Fig. 1, Fig. 3 and Fig. 5 as shown in is orientated.C) the latter half of process afterwards of repeating step b is until the zirconic acid lanthanum layer of (100) axle orientation that obtains desired thickness.D) according to yttrium: titanium is 1: 1 a mol ratio, weighing yttrium acetate, n-butanol titanium are each two parts respectively, earlier two parts of yttrium acetates are dissolved in respectively in two parts of propionic acid solution, respectively stir at 90 ℃ and to dissolve fully to yttrium acetate in 10 minutes, wherein, two parts propionic acid volume: the yttrium acetate molal quantity is respectively 20 liters: 1 mole and 5 liters: 1 mole.Again two parts of n-butanol titaniums are added respectively to be stirred in the propionic acid solution of above-mentioned different volumes than molal quantity fully and dissolve, obtain metatitanic acid yttrium Seed Layer forerunner's colloid and metatitanic acid yttrium succeeding layer forerunner colloid respectively.E) metatitanic acid yttrium Seed Layer forerunner colloid being coated to successively growth has on metallic nickel base band of (100) axle orientation of zirconic acid lanthanum layer of zirconic acid lanthanum Seed Layer of (100) axle orientation and (100) axle orientation and forms gel mould, again with it in 450 ℃ of following pyrolysis after 15 minutes, in reducing atmosphere, annealed 15 minutes down in 1150 ℃, wherein, reducing atmosphere is that 5% hydrogen adds nitrogen, the heating rate that pyrolysis temperature is warming up to annealing temperature is 5 ℃/minute, obtains the metatitanic acid yttrium Seed Layer of (100) axle orientation.Afterwards, metatitanic acid yttrium succeeding layer forerunner colloid is coated to successively growth to be had on metallic nickel base band of (100) axle orientation of metatitanic acid yttrium Seed Layer of zirconic acid lanthanum layer of zirconic acid lanthanum Seed Layer, (100) axle orientation of (100) axle orientation and (100) axle orientation and forms gel, again with it in 450 ℃ of following pyrolysis after 15 minutes, in reducing atmosphere, annealed 15 minutes down in 1150 ℃, wherein, reducing atmosphere is that 5% hydrogen adds nitrogen, the heating rate that pyrolysis temperature is warming up to annealing temperature is 5 ℃/minute, obtains the metatitanic acid yttrium layer of (100) axle orientation.F) repeating step e after latter half of process, until the metatitanic acid yttrium film of (100) axle orientation that obtains desired thickness, thereby make zirconic acid lanthanum/metatitanic acid yttrium thin-film material as shown in Fig. 2, Fig. 4 and Fig. 6.
Selecting base band more respectively for use is that nickel alloy, reducing atmosphere are that 3～5% hydrogen adds argon gas, repeat the foregoing description 1～5, make the zirconic acid lanthanum layer and the zirconic acid lanthanum as shown in Fig. 2, Fig. 4 and Fig. 6/metatitanic acid yttrium thin-film material of (100) axle orientation as shown in Fig. 1, Fig. 3 and Fig. 5 equally.
Obviously, those skilled in the art can carry out various changes and modification to zirconic acid lanthanum of the present invention/metatitanic acid yttrium thin-film material and preparation method thereof and not break away from the spirit and scope of the present invention.Like this, if of the present invention these are revised and modification belongs within the scope of claim of the present invention and equivalent technologies thereof, then the present invention also is intended to comprise these changes and modification interior.
Claims (6)
1. zirconic acid lanthanum/metatitanic acid yttrium thin-film material comprises substrate and the zirconic acid lanthanum layer that is covered with on it, it is characterized in that:
(a) said substrate is the metallic nickel or the nickel alloy base band of (100) axle orientation;
(b) said zirconic acid lanthanum layer is the zirconic acid lanthanum layer of zirconic acid lanthanum Seed Layer and (100) axle orientation of (100) axle orientation;
(c) be covered with the zirconic acid lanthanum Seed Layer of (100) axle orientation, the zirconic acid lanthanum layer of (100) axle orientation, the metatitanic acid yttrium Seed Layer of (100) axle orientation and the metatitanic acid yttrium film of (100) axle orientation on the metallic nickel of said (100) axle orientation or the nickel alloy base band successively.
2. zirconic acid lanthanum according to claim 1/metatitanic acid yttrium thin-film material, the thickness that it is characterized in that the zirconic acid lanthanum Seed Layer of (100) axle orientation is 1～90nm, (100) thickness of the zirconic acid lanthanum layer of axle orientation is 20～3000nm, (100) thickness of the metatitanic acid yttrium Seed Layer of axle orientation is 1～90nm, and the thickness of the metatitanic acid yttrium film of (100) axle orientation is 20～3000nm.
3. the preparation method of zirconic acid lanthanum according to claim 1/metatitanic acid yttrium thin-film material comprises chemical solution method, it is characterized in that finishing according to the following steps:
(a) according to lanthanum: zirconium is 1: 1 a mol ratio, weighing lanthanum acetate, zirconium-n-propylate are each two parts respectively, earlier two parts of lanthanum acetates are dissolved in respectively in two parts of propionic acid solution, being stirred to lanthanum acetate at 50～90 ℃ dissolves fully, wherein, two parts propionic acid volume: the lanthanum acetate molal quantity is respectively 10～20 liters: 1 mole and 2.5～5 liters: 1 mole, again two parts of zirconium-n-propylates are added respectively to be stirred in the propionic acid solution of above-mentioned different volumes than molal quantity fully and dissolve, obtain zirconic acid lanthanum Seed Layer forerunner's colloid and zirconic acid lanthanum succeeding layer forerunner colloid respectively;
(b) zirconic acid lanthanum Seed Layer forerunner colloid is coated on metallic nickel of (100) axle orientation or the nickel alloy base band and forms gel, again with it in 300～450 ℃ of following pyrolysis after 15～30 minutes, in reducing atmosphere, anneal more than 15 minutes in 950～1150 ℃, obtain the zirconic acid lanthanum Seed Layer of (100) axle orientation, afterwards, zirconic acid lanthanum succeeding layer forerunner colloid is coated to growth to be had on the metallic nickel of (100) axle orientation of zirconic acid lanthanum Seed Layer of (100) axle orientation or the nickel alloy base band and forms gel, again with it in 300～450 ℃ of following pyrolysis after 15～30 minutes, in reducing atmosphere, more than 15 minutes, obtain the zirconic acid lanthanum layer of (100) axle orientation in 950～1150 ℃ of annealing;
(c) the latter half of process afterwards of repeating step (b) is until the zirconic acid lanthanum layer of (100) axle orientation that obtains desired thickness;
(d) according to yttrium: titanium is 1: 1 a mol ratio, weighing yttrium acetate, n-butanol titanium are each two parts respectively, earlier two parts of yttrium acetates are dissolved in respectively in two parts of propionic acid solution, being stirred to yttrium acetate at 50～90 ℃ dissolves fully, wherein, two parts propionic acid volume: the yttrium acetate molal quantity is respectively 10～20 liters: 1 mole and 2.5～5 liters: 1 mole, again two parts of n-butanol titaniums are added respectively to be stirred in the propionic acid solution of above-mentioned different volumes than molal quantity fully and dissolve, obtain metatitanic acid yttrium Seed Layer forerunner's colloid and metatitanic acid yttrium succeeding layer forerunner colloid respectively;
(e) metatitanic acid yttrium Seed Layer forerunner colloid being coated to successively growth has on the metallic nickel of (100) axle orientation of zirconic acid lanthanum layer of zirconic acid lanthanum Seed Layer of (100) axle orientation and (100) axle orientation or the nickel alloy base band and forms gel mould, again with it in 300～450 ℃ of following pyrolysis after 15～30 minutes, in reducing atmosphere, anneal more than 15 minutes down in 850～1150 ℃, obtain the metatitanic acid yttrium Seed Layer of (100) axle orientation, afterwards, metatitanic acid yttrium succeeding layer forerunner colloid is coated to the zirconic acid lanthanum Seed Layer that growth successively has (100) axle orientation, (100) form gel on the metallic nickel of (100) axle orientation of the metatitanic acid yttrium Seed Layer of the zirconic acid lanthanum layer of axle orientation and (100) axle orientation or the nickel alloy base band, again with it in 300～450 ℃ of following pyrolysis after 15～30 minutes, in reducing atmosphere, anneal more than 15 minutes metatitanic acid yttrium layer of acquisition (100) axle orientation down in 850～1150 ℃;
(f) the latter half of process afterwards of repeating step (e) until the metatitanic acid yttrium film of (100) axle orientation that obtains desired thickness, thereby makes zirconic acid lanthanum/metatitanic acid yttrium thin-film material.
4. the preparation method of zirconic acid lanthanum according to claim 3/metatitanic acid yttrium thin-film material is characterized in that lanthanum acetate or yttrium acetate are dissolved in the propionic acid solution, stirs more than 10 minutes at 50～90 ℃.
5. the preparation method of zirconic acid lanthanum according to claim 3/metatitanic acid yttrium thin-film material is characterized in that reducing atmosphere is that the hydrogen that 3～5% hydrogen adds nitrogen or 3～5% adds argon gas.
6. the preparation method of zirconic acid lanthanum according to claim 3/metatitanic acid yttrium thin-film material is characterized in that the heating rate that pyrolysis temperature is warming up to annealing temperature is 5～500 ℃/minute.
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| CN106395889A (en) * | 2016-09-12 | 2017-02-15 | 渤海大学 | Porous spherical yttrium titanate nano material preparation method |
| CN106830074A (en) * | 2017-01-17 | 2017-06-13 | 北京工业大学 | A kind of preparation method of two generations high-temperature superconductor transition zone zirconic acid lanthanum |
| CN113087729A (en) * | 2021-04-01 | 2021-07-09 | 山东大学 | Lanthanum complex precursor, lanthanum oxide fiber and preparation method and application of lanthanum zirconate fiber derived from lanthanum oxide fiber |
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| US6573209B1 (en) * | 2000-10-13 | 2003-06-03 | Applied Thin Films, Inc. | Zirconium nitride and yttrium nitride solid solution composition |
| CN1238575C (en) * | 2001-10-26 | 2006-01-25 | 旺宏电子股份有限公司 | Method of building crystal to grow lead zirconate titanate film |
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| CN106395889A (en) * | 2016-09-12 | 2017-02-15 | 渤海大学 | Porous spherical yttrium titanate nano material preparation method |
| CN106395889B (en) * | 2016-09-12 | 2018-05-18 | 渤海大学 | A kind of preparation method of porous spherical metatitanic acid yttrium nano material |
| CN106830074A (en) * | 2017-01-17 | 2017-06-13 | 北京工业大学 | A kind of preparation method of two generations high-temperature superconductor transition zone zirconic acid lanthanum |
| CN113087729A (en) * | 2021-04-01 | 2021-07-09 | 山东大学 | Lanthanum complex precursor, lanthanum oxide fiber and preparation method and application of lanthanum zirconate fiber derived from lanthanum oxide fiber |
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