CN105130428A - Ce<1-x>Zr<x>O2 buffer layer and preparation method thereof - Google Patents

Abstract

The invention discloses a Ce<1-x>Zr<x>O2 buffer layer of which the chemical composition is Ce<1-x>Zr<x>O2. The buffer layer is prepared through extension phase forming thermal treatment, wherein 0.1 <= x <= 0.3. The invention also discloses a preparation method of the buffer layer, comprising the following steps: (1) dissolving Ce(NO3)3.6H2O and ZrOCl2.8H2O in a solvent according to the molar ratio of Ce:Zr=(1-x):x, and regulating the addition quantity of the solvent according to the total mole number of metal ions to obtain a precursor solution being 0.1-0.6 mol/L in metal ion concentration; and (2) coating a NiW metal base bar by the precursor solution and performing thermal treatment to prepare the Ce<1-x>Zr<x>O2 buffer layer. The invention provides a template for growing a superconductive layer YBCO, and furthermore, a series of new oxides Ce<1-x>Zr<x>O2 substitutional solid solution is obtained. The method is low in raw material cost, is wide in raw material source, is simple in process and is beneficial to industrial large-scale production.

Description

A kind of Ce 1-Xzr xo 2buffer layer and preparation method thereof

Technical field

The invention belongs to high temperature superconducting materia preparing technical field, relate to a kind of Ce _1-xzr _xo ₂buffer layer, the invention still further relates to the preparation method of above-mentioned buffer layer.

Background technology

S-generation conductor of high-temperature superconductor coat becomes the focus of high temperature superconducting materia research with its high critical current densities and excellent upfield performance.Coating conductor is primarily of substrate, buffer layer, superconducting layer, protective layer four part composition.Wherein the effect of buffer layer reduces metal base and high-temp. superconducting layer YBa ₂cu ₃o _7-xlattice mismatch between (i.e. YBCO), realizes texture transmission; There is chemical reaction between barrier metal substrate simultaneously and superconducting layer YBCO to spread.

Up to the present, research and the preparation of conductor of high-temperature superconductor coat have had certain scale, but the production cost of costliness restricts practical major influence factors.The buffer layer of main research has at present: CeO ₂, YSZ, Y ₂o ₃, La ₂zr ₂o ₇, SrTiO ₃deng.CeO ₂due to its chemistry and Heat stability is good, there is no obvious chemical reaction with YBCO, and the lattice mismatch of its lattice and YBCO is only 0.52%.ZrO ₂there is planarization and compactness, and ZrO ₂as diffusing barrier, effect obviously.Therefore the CeO of Zr doping ₂be expected to the effect simultaneously realizing template layer, blocking layer, Seed Layer, simplify buffer layer preparation technology.

But, current high-performance high temperature coating conductor buffer layer adopts physical deposition techniques to prepare usually, as pulsed laser deposition, magnetron sputtering, but these technology need be carried out under vacuum conditions, therefore expensive vacuum apparatus is wanted, the preparation cost of film is higher, is unfavorable for extensive, the suitability for industrialized production of coating conductor.

Summary of the invention

The object of this invention is to provide a kind of Ce _1-xzr _xo ₂buffer layer, has form compact and stable structure and even curface;

Another object of the present invention is to provide the preparation method of above-mentioned buffer layer, solves the problem that existing technology of preparing need be carried out in vacuum environment.

Technical scheme of the present invention is, a kind of Ce _1-xzr _xo ₂buffer layer, the chemical constitution of this buffer layer is Ce _1-xzr _xo ₂, by CeO ₂and ZrO ₂extension becomes phase thermal treatment to obtain, wherein 0.1≤x≤0.3.

Another technical scheme of the present invention is, the preparation method of above-mentioned buffer layer specifically implements according to following steps:

Step 1, colloid are prepared: be dissolved in solvent by six water cerous nitrates and eight water zirconium oxychlorides according to the mol ratio of Ce: Zr=(1-x): x, calculate by the total mole number of metal ion, regulate the add-on of solvent, obtain the precursor aqueous solution that concentration of metal ions is 0.1 ~ 0.6mol/L;

Step 2, precursor liquid obtained for step 1 is coated on NiW metal base band and heat-treats, obtained Ce _1-xzr _xo ₂buffer layer, wherein the span of x is 0.1 ~ 0.3.

Feature of the present invention is also,

In step 1, solvent is anhydrous methanol or ethylene glycol monomethyl ether, the mixed solution of methyl alcohol or the mixed solution of ethylene glycol monomethyl ether, methyl alcohol and methyl ethyl diketone.

The concrete implementation step of step 2 is:

Step 2.1, adopt dip coating to be coated on NiW metal base band by precursor liquid obtained for step 1, then by be coated with precursor liquid NiW metal base band in retort furnace with 150 ~ 220 DEG C of pre-treatment 10 ~ 20min;

Step 2.2, the precursor liquid processed is put into quartz tube type sintering oven heat-treat through step 2.1, under reducing atmosphere protection, with the temperature rise rate of 3 ~ 10 DEG C/min in-furnace temperature be elevated to 300 DEG C and be incubated 8 ~ 12min;

Step 2.3, the precursor liquid processed through step 2.2 is cooled to 220 ~ 250 DEG C with stove, then with the ramp of 10 ~ 20 DEG C/min to 950 ~ 1100 DEG C, and be incubated 0.5 ~ 1h, take out after cooling to room temperature with the furnace, namely on NiW metal base band, obtain textured Ce _1-xzr _xo ₂buffer layer.

In step 2.2, reducing atmosphere is volume fraction 96%Ar and 4%H ₂gas mixture.

The invention has the beneficial effects as follows,

1) a kind of Ce _1-xzr _xo ₂buffer layer, has form compact and stable structure, and smooth surface is smooth, flawless, is conducive to the epitaxy of follow-up YBCO superconducting layer;

2) Ce _1-xzr _xo ₂the preparation method of buffer layer, by substituting with Zr atom pairs Ce atom, makes CeO ₂the atomic environment of buffer layer and lattice parameter produce fine setting, thus adjustment CeO ₂buffer layer and NiW substrate and YBa ₂cu ₃o _7-x(YBCO) lattice mismatch between superconducting layer, for superconducting layer YBCO growth provides template, and then obtains a series of new oxide compound Ce _1-xzr _xo ₂substitutional solid solution; And raw materials cost is low, wide material sources, preparation technology is simple, is convenient to industrialization scale operation.

Accompanying drawing explanation

Fig. 1 is Ce prepared by inventive embodiments 1 _0.7zr _0.3o ₂x-ray diffraction θ-2 θ of buffer layer scans spectrogram;

Fig. 2 is Ce prepared by inventive embodiments 1 _0.7zr _0.3o ₂the laser co-focusing Photomicrograph of buffer layer;

Fig. 3 is Ce prepared by inventive embodiments 2 _0.8zr _0.2o ₂x-ray diffraction θ-2 θ of buffer layer scans spectrogram;

Fig. 4 is Ce prepared by inventive embodiments 2 _0.8zr _0.2o ₂the X-ray diffraction ω of buffer layer scans spectrogram;

Fig. 5 is Ce prepared by inventive embodiments 4 _0.9zr _0.1o ₂x-ray diffraction θ-2 θ of buffer layer scans spectrogram;

Fig. 6 is Ce prepared by inventive embodiments 4 _0.9zr _0.1o ₂the X-ray diffraction of buffer layer scanning spectrogram.

Embodiment

Below in conjunction with embodiment, the present invention is described in detail.

A kind of Ce of the present invention _1-xzr _xo ₂the preparation method of buffer layer, specifically implements according to following steps:

Step 1, colloid are prepared: be dissolved in solvent by six water cerous nitrates and eight water zirconium oxychlorides according to the mol ratio of Ce: Zr=(1-x): x, solvent is anhydrous methanol or ethylene glycol monomethyl ether, the mixed solution of methyl alcohol or the mixed solution of ethylene glycol monomethyl ether, methyl alcohol and methyl ethyl diketone; Calculate by the total mole number of metal ion, regulate the add-on of solvent, obtain the precursor aqueous solution that concentration of metal ions is 0.1 ~ 0.6mol/L;

Step 2.1, adopt dip coating to be coated on NiW metal base band by precursor liquid obtained for step 1, then by be coated with precursor liquid NiW metal base band in retort furnace with 150 ~ 220 DEG C of pre-treatment 10 ~ 20min;

Step 2.2, the precursor liquid processed is put into quartz tube type sintering oven heat-treat through step 2.1; under reducing atmosphere protection; with the temperature rise rate of 3 ~ 10 DEG C/min in-furnace temperature be elevated to 300 DEG C and be incubated 8 ~ 12min, wherein, reducing atmosphere is volume fraction 96%Ar and 4%H ₂gas mixture;

Step 2.3, the precursor liquid processed through step 2.2 is cooled to 220 ~ 250 DEG C with stove, then with the ramp of 10 ~ 20 DEG C/min to 950 ~ 1100 DEG C, and be incubated 0.5 ~ 1h, take out after cooling to room temperature with the furnace, namely on NiW metal base band, obtain textured Ce _1-xzr _xo ₂buffer layer, wherein the span of x is 0.1 ~ 0.3.

Embodiment 1

Ce _0.7zr _0.3o ₂the preparation of buffer layer:

Getting x value is 0.3, by six water cerous nitrates and eight water zirconium oxychlorides according to Ce: Zr=0.7: 0.3 mol ratio be dissolved in solvent, solvent is anhydrous methanol; Calculate by the total mole number of metal ion, regulate the add-on of solvent, obtain the precursor aqueous solution that concentration of metal ions is 0.1mol/L; Adopt dip coating to be coated on NiW metal base band by obtained precursor liquid, then by be coated with precursor liquid NiW metal base band in retort furnace with 150 DEG C of pre-treatment 10min; The precursor liquid of process is put into quartz tube type sintering oven heat-treat, under reducing atmosphere protection, with the temperature rise rate of 3 DEG C/min in-furnace temperature be elevated to 300 DEG C and be incubated 8min, wherein, reducing atmosphere is volume fraction 96%Ar and 4%H ₂gas mixture; The precursor liquid of process is cooled to 220 DEG C with stove, then with the ramp of 10 DEG C/min to 950 DEG C, and be incubated 0.5h, take out after cooling to room temperature with the furnace, namely on NiW metal base band, obtain textured Ce _0.7zr _0.3o ₂buffer layer.

As can be seen from Figure 1, the Ce prepared by NiW substrate _0.7zr _0.3o ₂buffer layer thin film has good C axle orientation.

Ce can be found out from the laser co-focusing Photomicrograph of Fig. 2 _0.7zr _0.3o ₂the fine and close flawless of buffer layer thin film smooth surface.

Embodiment 2

Ce _0.8zr _0.2o ₂the preparation of buffer layer:

To get x value be 0.2, six water cerous nitrates and eight water zirconium oxychlorides according to Ce: Zr=0.8: 0.2 mol ratio be dissolved in solvent, solvent is the mixed solution of ethylene glycol monomethyl ether and methyl alcohol; Calculate by the total mole number of metal ion, regulate the add-on of solvent, obtain the precursor aqueous solution that concentration of metal ions is 0.3mol/L; Adopt dip coating to be coated on NiW metal base band by obtained precursor liquid, then by be coated with precursor liquid NiW metal base band in retort furnace with 180 DEG C of pre-treatment 13min; The precursor liquid of process is put into quartz tube type sintering oven heat-treat, under reducing atmosphere protection, with the temperature rise rate of 5 DEG C/min in-furnace temperature be elevated to 300 DEG C and be incubated 9min, wherein, reducing atmosphere is volume fraction 96%Ar and 4%H ₂gas mixture; The precursor liquid of process is cooled to 230 DEG C with stove, then with the ramp of 12 DEG C/min to 1000 DEG C, and be incubated 0.8h, take out after cooling to room temperature with the furnace, namely on NiW metal base band, obtain textured Ce _0.8zr _0.2o ₂buffer layer.

As can be seen from Figure 3, the Ce prepared by NiW substrate _0.8zr _0.2o ₂buffer layer thin film has good C axle orientation.

As can be seen from Figure 4, the halfwidth of XRD-Omega is 5.413 °, has orientation outside good face.

Embodiment 3

Ce _0.9zr _0.1o ₂the preparation of buffer layer:

Getting x value is 0.1, six water cerous nitrates and eight water zirconium oxychlorides are dissolved in solvent according to the mol ratio of Ce: Zr=0.9: 0.1, solvent is in the mixed solvent of methyl alcohol, ethylene glycol monomethyl ether and methyl ethyl diketone, wherein methyl alcohol: ethylene glycol monomethyl ether: the mass ratio of methyl ethyl diketone is 9:4:1; Calculate by the total mole number of metal ion, regulate the add-on of solvent, obtain the precursor aqueous solution that concentration of metal ions is 0.4mol/L; Adopt dip coating to be coated on NiW metal base band by obtained precursor liquid, then by be coated with precursor liquid NiW metal base band in retort furnace with 200 DEG C of pre-treatment 15min; The precursor liquid of process is put into quartz tube type sintering oven heat-treat, under reducing atmosphere protection, with the temperature rise rate of 7 DEG C/min in-furnace temperature be elevated to 300 DEG C and be incubated 10min, wherein, reducing atmosphere is volume fraction 96%Ar and 4%H ₂gas mixture; The precursor liquid of process is cooled to 240 DEG C with stove, then with the ramp of 15 DEG C/min to 1050 DEG C, and be incubated 1h, take out after cooling to room temperature with the furnace, namely on NiW metal base band, obtain textured Ce _0.9zr _0.1o ₂buffer layer.

Embodiment 4

Ce _0.9zr _0.1o ₂the preparation of buffer layer:

To get x value be 0.1, six water cerous nitrates and eight water zirconium oxychlorides according to Ce: Zr=0.9: 0.1 mol ratio be dissolved in solvent, solvent is the mixed solution of ethylene glycol monomethyl ether and methyl alcohol, and wherein the mass ratio of methyl alcohol and ethylene glycol monomethyl ether is 2:1; Calculate by the total mole number of metal ion, regulate the add-on of solvent, obtain the precursor aqueous solution that concentration of metal ions is 0.6mol/L; Adopt dip coating to be coated on NiW metal base band by obtained precursor liquid, then by be coated with precursor liquid NiW metal base band in retort furnace with 220 DEG C of pre-treatment 20min; The precursor liquid of process is put into quartz tube type sintering oven heat-treat, under reducing atmosphere protection, with the temperature rise rate of 10 DEG C/min in-furnace temperature be elevated to 300 DEG C and be incubated 12min, wherein, reducing atmosphere is volume fraction 96%Ar and 4%H ₂gas mixture; The precursor liquid of process is cooled to 250 DEG C with stove, then with the ramp of 20 DEG C/min to 1100 DEG C, and be incubated 1h, take out after cooling to room temperature with the furnace, namely on NiW metal base band, obtain textured Ce _0.9zr _0.1o ₂buffer layer.

As can be seen from Figure 5, the Ce prepared by NiW substrate _0.9zr _0.1o ₂buffer layer thin film has good C axle orientation.

As can be seen from Figure 6, the halfwidth of XRD-Phi is 5.242 °, has orientation in good face.

Claims (5)

1. a Ce _1-xzr _xo ₂buffer layer, is characterized in that, the chemical constitution of this buffer layer is Ce _1-xzr _xo ₂, by CeO ₂and ZrO ₂extension becomes phase thermal treatment to obtain, 0.1≤x≤0.3.

2. a Ce _1-xzr _xo ₂the preparation method of buffer layer, is characterized in that, specifically implements according to following steps:

Step 1, colloid are prepared: be dissolved in solvent by six water cerous nitrates and eight water zirconium oxychlorides according to the mol ratio of Ce: Zr=(1-x): x, calculate by the total mole number of metal ion, regulate the add-on of solvent, obtain the precursor aqueous solution that concentration of metal ions is 0.1 ~ 0.6mol/L;

Step 2, precursor liquid obtained for step 1 is coated on NiW metal base band and heat-treats, obtained Ce _1-xzr _xo ₂buffer layer, wherein the span of x is 0.1 ~ 0.3.

3. Ce according to claim 2 _1-xzr _xo ₂the preparation method of buffer layer, is characterized in that, in described step 1, solvent is anhydrous methanol or ethylene glycol monomethyl ether, the mixed solution of methyl alcohol or the mixed solution of ethylene glycol monomethyl ether, methyl alcohol and methyl ethyl diketone.

4. Ce according to claim 2 _1-xzr _xo ₂the preparation method of buffer layer, is characterized in that, the concrete implementation step of described step 2 is:

Step 2.1, adopt dip coating to be coated on NiW metal base band by precursor liquid obtained for step 1, then by be coated with precursor liquid NiW metal base band in retort furnace with 150 ~ 220 DEG C of pre-treatment 10 ~ 20min;

Step 2.2, the precursor liquid processed is put into quartz tube type sintering oven heat-treat through step 2.1, under reducing atmosphere protection, with the temperature rise rate of 3 ~ 10 DEG C/min in-furnace temperature be elevated to 300 DEG C and be incubated 8 ~ 12min;

Step 2.3, the precursor liquid processed through step 2.2 is cooled to 220 ~ 250 DEG C with stove, then with the ramp of 10 ~ 20 DEG C/min to 950 ~ 1100 DEG C, and be incubated 0.5 ~ 1h, take out after cooling to room temperature with the furnace, namely on NiW metal base band, obtain textured Ce _1-xzr _xo ₂buffer layer.

5. Ce according to claim 4 _1-xzr _xo ₂the preparation method of buffer layer, is characterized in that, in described step 2.2, reducing atmosphere is volume fraction 96%Ar and 4%H ₂gas mixture.