CN101148781A - Process for preparing zinc oxide ferro-electricity film - Google Patents
Process for preparing zinc oxide ferro-electricity film Download PDFInfo
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- CN101148781A CN101148781A CNA2007101196527A CN200710119652A CN101148781A CN 101148781 A CN101148781 A CN 101148781A CN A2007101196527 A CNA2007101196527 A CN A2007101196527A CN 200710119652 A CN200710119652 A CN 200710119652A CN 101148781 A CN101148781 A CN 101148781A
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Abstract
The preparation process of ferroelectric zinc oxide film includes the following steps: 1. washing zinc chip, eliminating surface oxide and leveling; 2. anode oxidizing zinc chip in water solution of lithium hydroxide of 0.3-0.5 mol/l concentration as the electrolyte; and 3. flushing the taken out zinc chip with deionized water to obtain porous ferroelectric lithium doped zinc oxide film in 10 micron thickness on the surface of zinc chip. The process is simple and controllable, and realizes the conversion of zinc oxide from piezoelectric material to ferroelectric material.
Description
Technical field
The present invention relates to the film growth field, particularly zinc oxide ferro-electricity film and preparation method thereof.
Background technology
Ferroelectric material is a kind of application functional materials very widely.Ferroelectric material often has very big specific inductivity, is the main raw material of making electrical condenser.Ferroelectric material after the polarization is good piezoelectric, is widely used in the making of the various underwater sounds and ultrasonic transducer.Ferroelectric material occupies an important position in development of new techniques.Over nearly 10 years, the development of ferroelectric thin-flim materials is very rapid, and its application is increasingly extensive.Fields such as pyroelectric infrared detector, micromechanics electronic system device and non-volatile ferroelectric RAM become the focus of present research.Because the application of ferroelectric material is very extensive, different application has proposed different requirements to ferroelectric material, and existing ferroelectric material is difficult to satisfy fully the requirement of using, and therefore, explores the novel ferroelectric material of development and has very important significance.
Zinc oxide is a kind of typical II-VI group iii v compound semiconductor material, has very wide band gap (3.37eV), very big exciton bound energy (exciton binding energy, 60meV under the room temperature), well chemical stability and biocompatibility.In addition, the nano structure of zinc oxide of various forms is easy to preparation.This is indicating that zinc oxide will bring into play high using value in a lot of fields.Although zinc oxide is a kind of piezoelectric, it does not have ferroelectricity.In case zinc oxide has ferroelectricity, will produce promoter action to the application of zinc oxide.At present, existing investigator attempts the ferroelectric zinc-oxide film of preparation by adulterated method.Its principle is such: zincite crystal belongs to wurtzite structure.Each zinc atom links to each other with four Sauerstoffatoms, and four Sauerstoffatoms constitute a positive tetrahedron structure, and zinc atom is positioned at the center of positive tetrahedron.Same each Sauerstoffatom links to each other with four zinc atoms, and Sauerstoffatom is positioned at the center of the positive tetrahedron of zinc atom formation.After zinc atom was replaced by the atom (for example lithium atom) littler than it, this atom can depart to the bottom surface of positive tetrahedron.So just produce electric dipole moment, also just produced electricdomain, made zinc oxide have ferroelectric property.
At present, the technology of preparation ferroelectricity zinc oxide is also very limited, and most doping is the method that adopts vapour deposition.For example, the method of employing pulsed laser depositions such as M.Joseph prepares zinc-oxide film, and test its ferroelectric properties (M.Joseph, H.Tabata, and T.Kawai, Ferroelectric behavior of Li-doped ZnO thin films on si (100) by pulsedlaser deposition, Applied Physics Letters, Volume 34, and Number 17, and Page 2534).Preparation is carried out in vacuum chamber.The vacuum tightness of vacuum chamber can remain on 1 * 10 under the suction of turbomolecular pump
-5Torr.To the vacuum chamber aerating oxygen, the pressure of oxygen remains on 6 * 10
-4Torr.The heating silicon base, temperature remains on 550 ℃.Use pulsed laser bombardment target (Zn
1-xLi
xO) make it to deposit in the substrate, in substrate, generate zinc-oxide film with ferroelectric property.
Solution method is a kind of important means of zinc oxide films membrane prepare.Compare with vapor phase process, the solution method characteristics are that experimental installation is simple, and stability is high, are fit to large-area preparation.If in solution, realize the lithium doping of zinc oxide, prepare and have ferroelectric zinc-oxide film, will produce tremendous influence to the application of zinc oxide.
Summary of the invention
At the problems referred to above, the purpose of this invention is to provide a kind of method for preparing zinc oxide ferro-electricity film.
Technical scheme of the present invention is that the employing anodic oxidation is means, and lithium hydroxide prepares zinc-oxide film as electrolytic solution, has realized the lithium doping of zinc oxide in the solution growth process, has obtained to have the zinc-oxide film of ferroelectric property.Specifically comprise following step:
(1) cleans zinc metal sheet, remove the oxide compound on zinc metal sheet top layer and make it smooth;
(2) with the lithium hydroxide aqueous solution of 0.3～0.5 mol as electrolytic solution, the anodic oxidation zinc metal sheet forms the zinc-oxide film of lithium doping on the zinc metal sheet surface;
(3) will from electrolytic solution, take out with the zinc metal sheet of zinc oxide ferro-electricity film, rinse well with deionized water.
Above-mentioned steps (1) can adopt the method for electropolishing to remove the oxide compound on zinc metal sheet top layer, and makes the zinc metal sheet surface be tending towards smooth.To form two-level structure in high-purity zinc metal sheet and another tinsel (as platinum) insertion polishing fluid, zinc metal sheet links to each other with the positive pole of power supply, and the negative pole of power supply links to each other with described tinsel, and galvanization 0.6～1A got final product in about 3～5 minutes.After electropolishing finishes, zinc metal sheet is taken out, rinse well with deionized water.It is 35% phosphoric acid ethanol solution that used polishing fluid is generally weight percent.
The anodic oxidation of above-mentioned steps (2) zinc metal sheet is that the zinc metal sheet after cleaning is linked to each other with the anode of electro-chemical test system, and another tinsel (as platinized platinum) is linked to each other with the negative electrode of test macro, and the two contacts with electrolytic solution.Start test macro, holding current 30～50mA, reaction begins to carry out:
At first, zinc loses electronics becomes zine ion.
Zn-2e→Zn
2+
Then, some zine ion enters in the solution, and the oxonium ion in the solution enters under effect of electric field in the zinc metal sheet top layer and zine ion in conjunction with generating zinc oxide.
Zn
2+O
2-→ZnO
Along with zine ion and oxonium ion move in the opposite direction, zinc-oxide film forms on the surface of zinc metal sheet.Zinc oxide is intermediate oxide, can be dissolved in the lithium hydroxide solution, has formed cell texture.
ZnO+OH
-→[Zn(OH)
4]
2-
Guarantee that so also solution can contact by a direct sum zinc, reaction is continued, film constantly thickens.After reaction proceeded to 8～12 hours, oxidation and dissolving reached balance substantially, and film thickness no longer includes obvious variation.
Reaction is taken out sample after finishing immediately from electrolytic solution, rinse well with deionized water.If untimely sample is taken out from electrolytic solution, perhaps flushing is not thorough, and electrolytic solution can disruptive oxidation zinc film planeness.
Anodic oxidation is the common method of preparation metal oxide film, but seldom is used to prepare zinc-oxide film.Document few in number mostly adopts hydrofluoric acid as electrolytic solution (Sung-Sik Chang for example, Shu Kurokawa and AkiraSaka Properties of annealed anodically etched porous Zn studied by scanning tunnelingmicroscopy Applied Surface Science, Volume 217, Issues 1-4,15 July 2003, Pages 50-55), prepared film does not have ferroelectric property.The present invention as electrolytic solution, adopts anodised method to prepare zinc-oxide film with lithium hydroxide solution, makes to be entrained in the solution to be achieved, and film presents ferroelectric property.Observe by scanning electronic microscope (SEM), this zinc-oxide film is a cell texture, surfacing, and thickness can reach 10 microns (referring to Fig. 1,7,8).Its cavernous structure distribution gradient, outer field hole is less, about tens nanometers of internal diameter, the hole of internal layer is bigger, the about 100-200 nanometer of internal diameter, thickness can reach about 10 microns.X-ray diffraction spectrum (XRD) shows that this film is the single crystal structure (see figure 2) of zinc oxide.Contain the lithium ion (see figure 3) in second ion mass spectroscopy (SIMS) the demonstration film, and Raman spectrum is at 573cm
-1Near the peak value (see figure 4) appears, illustrate in the lithium ion doped lattice that enters zinc oxide, rather than between the gap of lattice.By the electric hysteresis of the having tested zinc-oxide film of the present invention curve of whirling, prove that sample has tangible ferroelectric property (see figure 5).
The method for preparing zinc oxide ferro-electricity film of the present invention prepares the desired raw material cheapness, and equipment used and step are simple, and preparation parameter is controlled easily, has realized that zinc oxide is by the conversion of general piezoelectric to ferroelectric material.
Description of drawings
Fig. 1 is the image of the porous zinc bloom film of embodiment one preparation of arriving with scanning electron microscopic observation, and wherein: A is the image of film surface; B is the image of a section of film.
Fig. 2 is the X-ray diffraction spectrum (XRD) of porous zinc bloom film of the present invention.
Fig. 3 is the second ion mass spectroscopy of porous zinc bloom film of the present invention.
Fig. 4 is the Raman spectrum of porous zinc bloom film of the present invention.
Fig. 5 is the electric hysteresis of the porous zinc bloom film of the present invention line of whirling.
Fig. 6 is the experimental installation synoptic diagram that the embodiment of the invention is used to prepare the porous zinc bloom ferroelectric membranc, wherein:
1---electrolytic solution 2---zinc metal sheet 3---ring flange 4---platinized platinum
5---the electro-chemical test system
Fig. 7 is the image of the porous zinc bloom film of embodiment two preparations of arriving with scanning electron microscopic observation.
Fig. 8 is the image of the porous zinc bloom film of embodiment three preparations of arriving with scanning electron microscopic observation.
Embodiment
Embodiment one: anonizing prepares ferroelectric zinc-oxide film
The concentration that this example is implemented used electrolytic solution is the lithium hydroxide of 0.4 mol, and the electric current that is adopted is 30 milliamperes.
(1) preparation electrolytic solution and polishing fluid.Compound concentration is that the lithium hydroxide aqueous solution of 0.4 mol is as electrolytic solution; The preparation weight percent is that 35% phosphoric acid ethanol solution is a polishing fluid.
(2) electropolishing of zinc metal sheet.Electropolishing can be removed the oxide compound on zinc metal sheet top layer, and makes the zinc metal sheet surface be tending towards smooth.With 0.3 mm thick, purity is the square that 99.99% zinc metal sheet is cut into 3.3 centimetres of 3.3 cm x.To form two-level structure in zinc metal sheet and the platinized platinum insertion polishing fluid, zinc metal sheet links to each other with the positive pole of power supply, and the negative pole of power supply links to each other with platinized platinum.The used power supply of electropolishing is the DH1720A-2 type power supply that big magnificent company produces.Power work is at the voltage stabilizing state, and voltage is 18 volts, and electric current is about 0.8 peace, and polishing time is about 3 minutes.After electropolishing finishes, zinc metal sheet is taken out, rinse well with deionized water.
(3) anodic oxidation of zinc metal sheet.Zinc metal sheet after the polishing is installed on the container shown in Figure 6.Container is the vial of 250 milliliters of circles, and circular open is arranged on the vial, and opening links to each other with the ring flange of being made by tetrafluoroethylene 3, and the bore of ring flange is 2.2 centimetres.Zinc metal sheet 2 is fixed on the ring flange, has only one side to contact with electrolytic solution.The electrolytic solution 1 for preparing is poured in the container, the anode of zinc metal sheet with CS300 electro-chemical test system 5 (buying in the Central China University of Science and Technology) linked to each other, one platinized platinum 4 is linked to each other with the negative electrode of test macro, and insert in the electrolytic solution or the same, contact with electrolytic solution with the fixing back of ring flange one side with zinc metal sheet.Test macro is placed under the operating mode of continuous current, current settings is 30 milliamperes, and the time is 8 hours 20 minutes, starts test macro, and reaction begins to carry out.
(4) reaction is taken out zinc metal sheet after finishing immediately from solution, and rinses well with deionized water.
The image of the zinc-oxide film that forms on zinc metal sheet surface by scanning electron microscopic observation (Figure 1A, B), wherein A shows that film is a cell texture, surperficial opposed flattened; What B showed is a section of film, shows that whole film is cell texture from outside to inside.
Embodiment two:
In the present embodiment, the step of being implemented is identical with embodiment one, and different is, the concentration of used electrolytic solution is the lithium hydroxide of 0.3 mol, and the electric current that is adopted is 30 milliamperes.Prepared zinc-oxide film is a cell texture, the surfacing (see figure 7).
Embodiment three:
In the present embodiment, the step of being implemented is identical with embodiment one, and different is, the concentration of used electrolytic solution is the lithium hydroxide of 0.3 mol, and the electric current that is adopted is 50 milliamperes.Prepared zinc-oxide film is a cell texture, the surfacing (see figure 8).
From above three embodiment as can be seen, as long as the concentration and the electric current of electrolytic solution remain in certain scope, the ferroelectric zinc oxide that makes just has identical pattern, and all has ferroelectric property after tested.
More than by embodiment the present invention is described in detail, those skilled in the art is to be understood that, in the scope that does not exceed spirit of the present invention and essence, the present invention is made certain modification and distortion, such as replace with other purging methods content embodiment of the present invention used to zinc metal sheet electropolishing, perhaps power supply such as constant voltage mode, still can be realized purpose of the present invention with other operation mode.In addition, set different parameters such as temperature and time, still might realize result of the present invention.
Claims (10)
1. the preparation method of a zinc oxide ferro-electricity film may further comprise the steps:
A. clean zinc metal sheet, remove the oxide compound on zinc metal sheet top layer and make it smooth;
B. with the lithium hydroxide aqueous solution of 0.3～0.5 mol as electrolytic solution, the anodic oxidation zinc metal sheet forms the zinc-oxide film of lithium doping on the zinc metal sheet surface;
C. take out zinc metal sheet, rinse well, obtain zinc oxide ferro-electricity film on the zinc metal sheet surface with deionized water.
2. preparation method according to claim 1 is characterized in that: described step a adopts the method for electropolishing to clean zinc metal sheet.
3. preparation method according to claim 2, it is characterized in that: described step a will form two-level structure in zinc metal sheet and another tinsel insertion polishing fluid, zinc metal sheet links to each other with the positive pole of power supply, described another tinsel links to each other with the negative pole of power supply, logical 0.6～1A electric current 3～5 minutes, take out zinc metal sheet then, rinse well with deionized water.
4. preparation method according to claim 3 is characterized in that: be weight percentage 35% phosphoric acid ethanol solution of described step polishing fluid.
5. preparation method according to claim 3 is characterized in that: described another tinsel is a platinized platinum.
6. preparation method according to claim 1, it is characterized in that: described step b links to each other with the anode of electro-chemical test system the zinc metal sheet after cleaning respectively with another tinsel with negative electrode, and contact holding current 30～50mA reaction 8～12 hours with electrolytic solution.
7. preparation method according to claim 6 is characterized in that: described another tinsel is a platinized platinum.
8. according to claim 1 or 6 described preparation methods, it is characterized in that: described electrolytic solution is the lithium hydroxide aqueous solution of 0.4 mol.
9. according to claim 1 or 6 described preparation methods, it is characterized in that: have only one side to contact with electrolytic solution at zinc metal sheet described in the step b.
10. preparation method according to claim 9 is characterized in that: holding the container upper shed of electrolytic solution, this opening links to each other with the ring flange of being made by tetrafluoroethylene, and zinc metal sheet is fixed on the ring flange, has only one side to contact with electrolytic solution.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106065493A (en) * | 2016-07-29 | 2016-11-02 | 中山大学 | A kind of high resistivity single-crystal zinc-oxide and its preparation method and application |
| CN112002799A (en) * | 2020-09-04 | 2020-11-27 | 哈尔滨工业大学 | Iron-lithium ion pair doped modified high-piezoelectric-coefficient zinc oxide-based piezoelectric film and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1317749C (en) * | 2005-04-05 | 2007-05-23 | 中国科学院物理研究所 | Three-dopant contained P-type zinc oxide film and method for making same |
| CN1316076C (en) * | 2005-10-26 | 2007-05-16 | 浙江大学 | Process for Li-N codoping growth P type ZnO crystal film |
| CN1328418C (en) * | 2005-10-26 | 2007-07-25 | 浙江大学 | Process for Li doping growing P type ZnO Single Crystal film |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106065493A (en) * | 2016-07-29 | 2016-11-02 | 中山大学 | A kind of high resistivity single-crystal zinc-oxide and its preparation method and application |
| CN112002799A (en) * | 2020-09-04 | 2020-11-27 | 哈尔滨工业大学 | Iron-lithium ion pair doped modified high-piezoelectric-coefficient zinc oxide-based piezoelectric film and preparation method thereof |
| CN112002799B (en) * | 2020-09-04 | 2022-08-30 | 哈尔滨工业大学 | Iron-lithium ion pair doping modified high-piezoelectric coefficient zinc oxide-based piezoelectric film and preparation method thereof |
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