CN101746960B - Preparation method of transparent metal oxide strontium titanate lanthanum film - Google Patents
Preparation method of transparent metal oxide strontium titanate lanthanum film Download PDFInfo
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- 229910052746 lanthanum Inorganic materials 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 22
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- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 title claims abstract description 12
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical compound [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 claims abstract description 56
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims abstract description 54
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000002243 precursor Substances 0.000 claims abstract description 41
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 31
- RXSHXLOMRZJCLB-UHFFFAOYSA-L strontium;diacetate Chemical compound [Sr+2].CC([O-])=O.CC([O-])=O RXSHXLOMRZJCLB-UHFFFAOYSA-L 0.000 claims abstract description 31
- 239000000758 substrate Substances 0.000 claims abstract description 29
- 239000010453 quartz Substances 0.000 claims abstract description 28
- 235000019260 propionic acid Nutrition 0.000 claims abstract description 27
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims abstract description 27
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- 238000000197 pyrolysis Methods 0.000 claims abstract description 9
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- 238000005303 weighing Methods 0.000 claims abstract description 7
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- 235000012239 silicon dioxide Nutrition 0.000 claims description 27
- 230000004888 barrier function Effects 0.000 claims description 25
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 23
- PACGUUNWTMTWCF-UHFFFAOYSA-N [Sr].[La] Chemical compound [Sr].[La] PACGUUNWTMTWCF-UHFFFAOYSA-N 0.000 claims description 19
- 239000011259 mixed solution Substances 0.000 claims description 19
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 18
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 18
- 229910010252 TiO3 Inorganic materials 0.000 claims description 17
- 238000009987 spinning Methods 0.000 claims description 14
- 239000011863 silicon-based powder Substances 0.000 claims description 13
- -1 lanthanum aluminate Chemical class 0.000 claims description 11
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 9
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 9
- 229910052712 strontium Inorganic materials 0.000 claims description 8
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 8
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
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- IQONKZQQCCPWMS-UHFFFAOYSA-N barium lanthanum Chemical compound [Ba].[La] IQONKZQQCCPWMS-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a preparation method of a transparent metal oxide strontium titanate lanthanum film. The preparation method comprises the following steps: weighing lanthanum acetate, strontium acetate and titanium n-butyl alcohol according to the component ratio of La0.5Sr0.5TiO3, then adding the lanthanum acetate, strontium acetate and titanium n-butyl alcohol into propionic acid as a solvent in sequence, respectively stirring at the temperature of 70 to 80 DEG C, and then adjusting the concentration thereof to be 0.15 to 0.25M by adding or evaporating the propionic acid so as to obtain precursor solution; later, the precursor solution is arranged on a rotating substrate to form a gel film by throwing films, putting the gel film into the environment with the temperature of 250 to 350 DEG C for pyrolysis for 20 to 30min, and repeating the process till a pyrolytic film with needed thickness is obtained; and finally, putting the pyrolytic film into the environment with the temperature of 900 to 1000 DEG C for annealing for 15 to 20h to obtain an initial film, then sealing the initiate film, a power-shaped blocking layer and power-shaped recovery precursor into a quartz tube, then putting the quartz tube into the environment with the temperature of 850 to 900 DEG C for annealing for at least 20h to obtain the transparent metal oxide strontium titanate lanthanum film. The product of the invention can be widely used for liquid crystal displays, organic light emitting diodes and transparent electrodes of a solar battery.
Description
Technical Field
The invention relates to a preparation method of a strontium lanthanum titanate film, in particular to a preparation method of a transparent metal oxide strontium lanthanum titanate film.
Background
At present, transparent conductive oxide thin films are widely used for transparent electrodes of liquid crystal displays, organic light emitting diodes, and solar cells; perovskite type oxides, an important class of materials, possess many excellent physical properties, and thus, it is necessary to obtain transparent conductive oxide thin films of perovskite structure. Recently, it was found that La1-xSrxTiO3The film is not only transparent, but also exhibits metallic behavior. And La0.5Sr0.5TiO3And is La1-xSrxTiO3The material has the highest conductivity and thus can be used as a transparent conductor. In order to obtain high conductivity La0.5Sr0.5TiO3Thin films, various attempts and efforts have been made, such as "an integratable multifunctional wet photosensitive element and a method for manufacturing the same" disclosed in chinese patent application publication No. CN 1205555a published on 20/1/1999. It is intended to provide an integratable multifunctional wet photosensitive element which has more stable chemical and physical properties, is small in volume, is convenient for industrial production, and can be miniaturized, and a manufacturing method thereof; the wet photosensitive element is formed by packaging an aluminum electrode, a tube seat electrode, a sensitive film, a silicon dioxide layer, a silicon epitaxial layer, a silicon substrate, a gold film layer and a tube seat together; the manufacturing method is that a composite structure comprising an MIOS capacitor and a film planar resistor is manufactured on a silicon epitaxial wafer or a silicon single crystal wafer by adopting the compatibility of an argon ion coating technology and a silicon planar process, and a sensitive film of the composite structure is formed on SiO2And coating lanthanum strontium titanate or lanthanum barium titanate on the Si substrate by using an argon ion coating technology. However, both the wet photosensor and the manufacturing method thereof have disadvantages in that, firstly, the wet photosensor cannot be used as a transparent conductor and is difficult to be used as a transparent electrode for liquid crystal displays, organic light emitting diodes, and solar cells; secondly, the manufacturing method uses argon ion plating technology to deposit on SiO2Although the lanthanum strontium titanate film can be plated on the Si substrate, the defects of complex equipment and higher production cost required by film plating are overcome.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a preparation method of a transparent metal oxide strontium lanthanum titanate film, which is low in cost and simple and convenient to operate.
The invention aims to solve another technical problem of providing an annealing device for the preparation method of the transparent metal oxide strontium lanthanum titanate film.
In order to solve the technical problem of the invention, the adopted technical scheme is as follows: the preparation method of the transparent metal oxide strontium titanate lanthanum film comprises a topological reduction method, and particularly comprises the following steps:
and 4, annealing the pyrolytic film at 900-1000 ℃ for 15-20 h to obtain an initial film, sealing the initial film, the powdery barrier layer and the powdery reduction precursor in a quartz tube, and annealing at 850-900 ℃ for at least 20h to obtain the transparent metal oxide strontium titanate lanthanum film.
As a further improvement of the preparation method of the transparent metal oxide strontium lanthanum titanate film, lanthanum acetate, strontium acetate and titanium n-butoxide are weighed according to the molar ratio of lanthanum to strontium to titanium of 1: 2; the substrate is lanthanum aluminate or strontium titanate or YSZ (yttria stabilized zirconia) or alumina; the rotating speed of the substrate during film spinning is 4000-6000 r/min, and the time is 30-60 s; the powdery barrier layer is alumina powder or zirconia powder or silicon dioxide powder; the particle size of the alumina powder or the zirconia powder or the silicon dioxide powder is 1-900 mu m; the powdery reduction precursor is silicon powder or boron powder or zirconium powder or titanium powder; the particle size of the silicon powder or the boron powder or the zirconium powder or the titanium powder is 1-900 μm.
In order to solve another technical problem of the present invention, another technical solution is adopted: the annealing device of the preparation method of the transparent metal oxide strontium titanate lanthanum thin film comprises an annealing source and a quartz tube therein, and particularly comprises the following steps:
the quartz tube is nested with an inner layer and an outer layer;
the inner-layer quartz tube is divided into two sections, wherein one end of one section with the built-in initial film is closed, the other end of the one section with the built-in initial film is connected with one section with the built-in powdery barrier layer through a capillary tube, and the other end of the one section with the built-in powdery barrier layer of the inner-layer quartz tube is open;
the outer-layer quartz tube is in a sealed state, and a powdery reduction precursor is arranged in the sealed outer-layer quartz tube.
The annealing device used as the preparation method of the transparent metal oxide strontium lanthanum titanate film is further improved, and the diameter of the capillary tube is less than or equal to the grain diameter of the powdery barrier layer.
The first advantageous effect of the present invention is that the obtained thin film is characterized by using an X-ray diffractometer, an atomic force microscope, a resistivity meter of a physical property measurement system, and a spectrometer, respectively, and as a result, it is found that the thin film is formed of La having a high (h00) crystal grain orientation0.5Sr0.5TiO3The structure is compact and the roughness is small. The resistivity of the film is small. The film has good permeability in the visible light range even though the film is subjected to topological reduction annealing. The film is used as a transparent conductor and can be fully used as a transparent electrode of a liquid crystal display, an organic light-emitting diode and a solar cell; secondly, the equipment required in the preparation process is simple. Simplification by topological reduction in the preparation of thin filmsThe preparation process reduces the reduction temperature, thereby reducing the production cost, and has the characteristics of simple and easily mastered process, manually accurate control of the stoichiometric ratio of the film material, low preparation cost and contribution to large-scale industrial production; thirdly, the annealing device is simple and easy to manufacture, and the realization performance of the topology reduction function is good.
As a further embodiment of the beneficial effect, lanthanum acetate, strontium acetate and titanium n-butoxide are preferably weighed in a molar ratio of lanthanum to strontium to titanium of 1: 2, which facilitates La0.5Sr0.5TiO3Forming a thin film; the second is that the substrate is preferably lanthanum aluminate or strontium titanate or YSZ (yttria stabilized zirconia) or alumina, and La with high (h00) grain orientation is favorable0.5Sr0.5TiO3Generating a thin film; thirdly, the rotation speed of the substrate is preferably 4000-6000 r/min and the time is preferably 30-60 s during film spinning, so that the precursor solution is easy to spin into a gel film, and the film body of the gel film is uniform; fourthly, the powdery barrier layer is preferably alumina powder, zirconia powder or silicon dioxide powder, the grain size of the alumina powder, the zirconia powder or the silicon dioxide powder is preferably 1-900 microns, the characteristic of good stability of the alumina powder, the zirconia powder or the silicon dioxide powder is fully utilized, and not only can the initial film be physically blocked with the powdery reduction precursor, but also the chemical reaction between the initial film and the powdery reduction precursor is not influenced; and fifthly, the powdery reduction precursor is preferably silicon powder, boron powder, zirconium powder or titanium powder, wherein the particle size of the silicon powder, the boron powder, the zirconium powder or the titanium powder is preferably 1-900 microns, the activity of the silicon powder, the boron powder, the zirconium powder or the titanium powder is fully exerted, and the active reaction of oxygen released from the initial film and the active reaction of the oxygen is quick and complete.
Drawings
Preferred embodiments of the present invention will be described in further detail below with reference to the accompanying drawings.
FIG. 1 shows the use of Phillips X' Pe for the films obtainedAn XRD pattern obtained after an rt type X-ray diffraction (XRD) instrument is tested, wherein the abscissa in the pattern is a diffraction angle, the ordinate is the relative intensity of a diffraction peak, and S600Represents the final product, S, obtained at a topological reduction temperature of 600 DEG C700，S800，S900And so on. From the position and relative intensity of each diffraction peak in the XRD pattern, the film was La with highly (h00) oriented grains0.5Sr0.5TiO3A film;
FIG. 2 is an atomic force microscope photograph of the obtained film observed with an Autoprobe CP type atomic force microscope. La was observed from the atomic force microscope photograph0.5Sr0.5TiO3The film is relatively compact;
FIG. 3 is a graph showing the change of resistivity with temperature of the obtained film after the film was tested using a Physical Properties Measuring System (PPMS) of Quantum Design, USA, and it can be seen that the resistivity of the film at 300K is only 2.43 mOhm cm;
FIG. 4 is a graph showing the change in transmittance with the wavelength of incident light obtained after the obtained film was tested using a Varian CRAY-5E spectrometer, from which La can be seen0.5Sr0.5TiO3The film has good permeability in a visible light range, and topological reduction annealing has little influence on the permeability of the film;
fig. 5 is a schematic diagram of a basic structure of a quartz tube in an annealing apparatus for realizing topology reduction, in which reference numeral 1 in fig. 5 is an outer-layer quartz tube, 2 is an inner-layer quartz tube, 3 is a powdered barrier layer, 4 is a capillary tube, 5 is an initial thin film, and 6 is a reduction precursor.
Detailed Description
Firstly, lanthanum acetate, strontium acetate, titanium n-butoxide and propionic acid are prepared by a conventional method or commercially available, lanthanum aluminate, strontium titanate, YSZ (yttria-stabilized zirconia), alumina as a substrate, alumina powder, zirconia powder, silica powder as a powdery barrier layer, silicon powder, boron powder, zirconium powder, titanium powder as a powdery reduction precursor; the annealing device used as the preparation method comprises an annealing source and a quartz tube therein, wherein the quartz tube is nested as shown in figure 5 and comprises an inner layer and an outer layer, the inner layer quartz tube 2 is divided into two sections, one end of one section with an initial film 5 arranged therein is closed, the other end of the one section with the initial film 5 arranged therein is connected with one section with a powder barrier layer 3 arranged therein through a capillary tube 4, the diameter of the capillary tube 4 is less than or equal to the grain diameter of the powder barrier layer 3, the other end of the inner layer quartz tube 2 with one section with the powder barrier layer 3 arranged therein is an open port, the outer layer quartz tube 1 is sealed, and a powder reduction precursor 6 is arranged in the sealed outer layer. Then, the process of the present invention is carried out,
example 1
The preparation method comprises the following specific steps: step 1, according to La0.5Sr0.5TiO3Weighing lanthanum acetate, strontium acetate and titanium n-butoxide; wherein, lanthanum acetate, strontium acetate and titanium n-butoxide are weighed according to the molar ratio of lanthanum to strontium to titanium of 1: 2.
And 4, annealing the pyrolytic film at 900 ℃ for 20 hours to obtain an initial film. Sealing the initial film, the powdery barrier layer and the powdery reduction precursor in a quartz tube, and annealing at 850 ℃ for 24 hours; wherein the powdery barrier layer is alumina powder with the grain diameter of 1 μm, and the powdery reduction precursor is silicon powder with the grain diameter of 900 μm. A transparent metal oxide lanthanum strontium titanate thin film as shown in fig. 2, and as shown in the graphs of fig. 1, 3 and 4 was produced.
Example 2
The preparation method comprises the following specific steps: step 1, according to La0.5Sr0.5TiO3Weighing lanthanum acetate, strontium acetate and titanium n-butoxide; wherein, lanthanum acetate, strontium acetate and titanium n-butoxide are weighed according to the molar ratio of lanthanum to strontium to titanium of 1: 2.
And 4, annealing the pyrolytic film at 930 ℃ for 19 hours to obtain an initial film. Sealing the initial film, the powdery barrier layer and the powdery reduction precursor in a quartz tube, and annealing at 860 ℃ for 23 hours; wherein the powdery barrier layer is alumina powder with the grain diameter of 200 μm, and the powdery reduction precursor is silicon powder with the grain diameter of 700 μm. A transparent metal oxide lanthanum strontium titanate thin film as shown in fig. 2, and as shown in the graphs of fig. 1, 3 and 4 was produced.
Example 3
The preparation method comprises the following specific steps: step 1, according to La0.5Sr0.5TiO3Weighing lanthanum acetate, strontium acetate and titanium n-butoxide; wherein, lanthanum acetate, strontium acetate and titanium n-butoxide are weighed according to the molar ratio of lanthanum to strontium to titanium of 1: 2.
And 4, annealing the pyrolytic film at 950 ℃ for 17 hours to obtain an initial film. Sealing the initial film, the powdery barrier layer and the powdery reduction precursor in a quartz tube, and annealing at 870 ℃ for 22 h; wherein the powdery barrier layer is alumina powder with the grain diameter of 500 mu m, and the powdery reduction precursor is silicon powder with the grain diameter of 500 mu m. A transparent metal oxide lanthanum strontium titanate thin film as shown in fig. 2, and as shown in the graphs of fig. 1, 3 and 4 was produced.
Example 4
The preparation method comprises the following specific steps: step 1, according to La0.5Sr0.5TiO3The component ratio of (A) to (B) in the above-mentioned reaction mixture, lanthanum acetate and acetic acid were weighedStrontium and titanium n-butoxide; wherein, lanthanum acetate, strontium acetate and titanium n-butoxide are weighed according to the molar ratio of lanthanum to strontium to titanium of 1: 2.
And 4, annealing the pyrolytic film at 980 ℃ for 16h to obtain an initial film. Sealing the initial film, the powdery barrier layer and the powdery reduction precursor in a quartz tube, and annealing at 890 ℃ for 21 h; wherein the powdery barrier layer is alumina powder with the grain diameter of 700 mu m, and the powdery reduction precursor is silicon powder with the grain diameter of 200 mu m. A transparent metal oxide lanthanum strontium titanate thin film as shown in fig. 2, and as shown in the graphs of fig. 1, 3 and 4 was produced.
Example 5
The preparation method comprises the following specific steps: step 1, according to La0.5Sr0.5TiO3Weighing lanthanum acetate, strontium acetate and titanium n-butoxide; wherein, lanthanum acetate, strontium acetate and titanium n-butoxide are weighed according to the molar ratio of lanthanum to strontium to titanium of 1: 2.
And 4, annealing the pyrolytic film at 1000 ℃ for 15 hours to obtain an initial film. Sealing the initial film, the powdery barrier layer and the powdery reduction precursor in a quartz tube, and annealing at 900 ℃ for 20 hours; wherein the powdery barrier layer is alumina powder with the grain diameter of 900 μm, and the powdery reduction precursor is silicon powder with the grain diameter of 1 μm. A transparent metal oxide lanthanum strontium titanate thin film as shown in fig. 2, and as shown in the graphs of fig. 1, 3 and 4 was produced.
Then, strontium titanate or YSZ (yttria stabilized zirconia) or alumina as a substrate, zirconia powder or silica powder as a powdery barrier layer, and boron powder or zirconium powder or titanium powder as a powdery reduction precursor are respectively selected. The above examples 1 to 5 were repeated to obtain the transparent metal oxide strontium lanthanum titanate thin film shown in fig. 2 and the curves shown in fig. 1, 3 and 4.
It is apparent that those skilled in the art can make various changes and modifications to the method for preparing the transparent metal oxide strontium lanthanum titanate thin film of the present invention without departing from the spirit and scope of the present invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is intended to include such modifications and variations.
Claims (7)
1. A preparation method of a transparent metal oxide strontium lanthanum titanate film comprises a topological reduction method and is characterized by comprising the following steps:
step 1, according to La0.5Sr0.5TiO3Weighing lanthanum acetate, strontium acetate and titanium n-butoxide;
step 2, taking propionic acid as a solvent, adding lanthanum acetate into the solution, placing the solution at 70-80 ℃ and stirring until lanthanum acetate is completely dissolved to obtain a lanthanum acetate solution, adding strontium acetate into the lanthanum acetate solution, placing the solution at 70-80 ℃ and continuously stirring until strontium acetate is dissolved to obtain a mixed solution, then adding titanium n-butoxide into the mixed solution, placing the solution at 70-80 ℃ and stirring for 0.5-1 h, placing the solution at room temperature and stirring for 10-20 h, and adding or evaporating propionic acid to adjust the concentration of the solution to 0.15-0.25M to obtain a precursor solution;
step 3, firstly, placing the precursor solution on a rotating substrate, forming a gel film through film spinning, then, placing the gel film at 250-350 ℃ for pyrolysis for 20-30 min, and repeating the process until a pyrolysis film with the required thickness is obtained;
step 4, annealing the pyrolytic film at 900-1000 ℃ for 15-20 h to obtain an initial film, sealing the initial film, the powdery barrier layer and the powdery reduction precursor in a quartz tube, and annealing at 850-900 ℃ for at least 20h to obtain a transparent metal oxide strontium titanate lanthanum film; wherein,
the powdery barrier layer is alumina powder, or zirconia powder, or silicon dioxide powder,
the powdery reduction precursor is silicon powder, or boron powder, or zirconium powder, or titanium powder,
the quartz tube is a nested inner layer and a nested outer layer, the inner layer quartz tube is divided into two sections, one end of one section with an initial film is closed, the other end of the section with the initial film is connected with one section with a powder blocking layer through a capillary tube, the other end of the inner layer quartz tube with the section with the powder blocking layer is open, the outer layer quartz tube is sealed, and a powder reduction precursor is arranged in the sealed outer layer quartz tube.
2. The method for preparing a transparent metal oxide strontium lanthanum titanate film according to claim 1, wherein lanthanum acetate, strontium acetate and titanium n-butoxide are weighed according to the molar ratio of lanthanum to strontium to titanium of 1: 2.
3. The method of claim 1, wherein the substrate is lanthanum aluminate, strontium titanate, YSZ, or alumina.
4. The method for preparing the transparent strontium lanthanum titanate film as claimed in claim 1, wherein the substrate is spun at 4000-6000 r/min for 30-60 s.
5. The method as claimed in claim 1, wherein the grain size of the alumina powder or zirconia powder or silica powder is 1-900 μm.
6. The method of claim 1, wherein the grain size of the silicon powder, the boron powder, the zirconium powder, or the titanium powder is 1-900 μm.
7. The method of claim 1, wherein the diameter of the capillary tube is not greater than the diameter of the barrier layer.
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| CN1205555A (en) * | 1998-05-26 | 1999-01-20 | 华南理工大学 | Integrable multifunctional wet light activated element and its mfg. method |
| CN101074491A (en) * | 2007-03-29 | 2007-11-21 | 上海大学 | Method for growing barium strontium titanate on metal titanium-based substrate |
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| CN1205555A (en) * | 1998-05-26 | 1999-01-20 | 华南理工大学 | Integrable multifunctional wet light activated element and its mfg. method |
| CN101074491A (en) * | 2007-03-29 | 2007-11-21 | 上海大学 | Method for growing barium strontium titanate on metal titanium-based substrate |
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