CN109825874A - A kind of preparation method of monocrystalline lead titanate thin film - Google Patents
A kind of preparation method of monocrystalline lead titanate thin film Download PDFInfo
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- CN109825874A CN109825874A CN201910234845.XA CN201910234845A CN109825874A CN 109825874 A CN109825874 A CN 109825874A CN 201910234845 A CN201910234845 A CN 201910234845A CN 109825874 A CN109825874 A CN 109825874A
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Abstract
The invention discloses a kind of monocrystalline lead titanates (PbTiO3) film preparation method.This method is with plumbi nitras (Pb (NO3)2) and tetra-n-butyl titanate (TBOT) be used as primary raw material, potassium hydroxide (KOH) is used as mineralizer, by deploying the amount of every raw material, realizes monocrystalline PbTiO using hydro-thermal method3The synthesis of film.Present invention process is simple, easily controllable, at low cost, is suitble to large-scale production.The extension laminated film surface of acquisition is completely continuous, and interface is smooth, and PbTiO3The thickness of film is controllable.The lead titanate thin film of this high quality is expected in ferroelectric memory, and pyroelectric sensor and communication field have wide practical use.
Description
Technical field
The present invention relates to a kind of preparation methods of monocrystalline lead titanate thin film, belong to functional material preparation field.
Background technique
Information age, microelectronic component are pursued high density, high speed, low-loss, are mentioned to the integration and miniaturization of device
High request out, film material with function are developed into research hotspot.Perovskite oxide is because of its abundant and excellent physical chemistry
Property such as ferroelectricity, pyroelectric, piezoelectricity, ferromagnetism etc. receives significant attention, in high density data storage, high sensitivity
There is extremely wide application prospect in the fields such as sensing, high-frequency communication.PbTiO3As typical ABO3The oxidation of type perovskite
Object, has excellent ferroelectricity, piezoelectricity and pyroelectric property, and the spontaneous polarization strength of monocrystal can achieve 75 μ C/cm2.Its
Pyroelectric coefficient is about 6 × 108C·cm-2·K-1, it is good pyroelectricity material.Furthermore perovskite PbTiO3Opposite dielectric
Constant is small compared with other perovskite oxides, about 149 Fm-1。
Summary of the invention
The purpose of the present invention is to provide a kind of low cost, simple process, the easily controllable monocrystalline lead titanate thin films of process
Preparation method, can get high quality film surface and heterojunction boundary.
The preparation method of monocrystalline lead titanate thin film of the invention, comprising the following steps:
1) mineralizer KOH is added in reaction kettle liner, deionized water stirring is added, acquisition molar concentration is 3-6mol/L
KOH solution；
2) will tetra-n-butyl titanate (TBOT) be added step 1) acquired solution in, be mixed 10-20min, acquisition it is molten
The molar concentration of TBOT is 0.003-0.04mol/L in liquid；
3) by plumbi nitras (Pb (NO3)2) it is dissolved in deionized water stirring, adjust lead titanium molar ratio Pb/Ti=1-1.25；
4) step 3) acquired solution is slowly added dropwise into 2) acquired solution, strong stirring at least 2h；
5) by SrTiO3It after substrate Ar corona treatment, is vertically arranged in hydro-thermal reaction frame, uses acetone, second respectively
After alcohol, water, ethyl alcohol respectively clean at least 10min, 60 DEG C of dry 2h；
6) contain reactant solution and SrTiO for what step 5) was prepared3The reaction kettle liner of substrate is fitted into mating reaction kettle,
Sealing, reacts 2h-24h at 100-200 DEG C, then allows reaction kettle cooled to room temperature, after unloading kettle, with deionized water and nothing
Washing reaction product, filtering, drying obtain SrTiO to water-ethanol repeatedly3PbTiO in single crystal substrates3Monocrystal thin films.
The reaction kettle is polytetrafluoroethylliner liner, the closed reaction kettle of stainless steel external member.
It is pure that the purity of the potassium hydroxide, tetra-n-butyl titanate and plumbi nitras is all not less than chemistry.
The ion beam current energy of the Ar corona treatment is 3000eV, and beam current density is 50 μ A/cm2。
The SrTiO3Substrate is cube phase monocrystal, the polishing substrate of (100) orientation.
The hydro-thermal reaction frame is bracket made of polytetrafluoroethylene material.
The SrTiO that above-mentioned method obtains3The PbTiO grown in single crystal substrates3Monocrystal thin films, PbTiO3With a thickness of
100-500nm。
The present invention is prepared for a kind of PbTiO with high-quality surface and interface by simple hydro-thermal reaction3Monocrystalline is thin
Film.Compared to the PLD for preparing lead titanate thin film at present and generalling use, the physical deposition methods such as MBE, the hydro-thermal method that the present invention uses
The lead titanate thin film of stoichiometric ratio can be synthesized at a lower temperature.Simultaneously as reaction environment is liquid phase, it is advantageous to
The homogeneous nucleation and diffusion of crystallization reaction obtain the good product of crystal property.The present invention is with the SrTiO of monocrystalline3Substrate conduct
PbTiO has been prepared in carrier3Monocrystal thin films.SrTiO3And PbTiO3Crystal structure is identical, and cell parameter is very close,
PbTiO3{ 100 } crystal faceWith SrTiO3{ 100 } crystal faceLattice mismatch be only 0.03%.This
Invented technology process is simple, easily controllable, pollution-free, at low cost, is readily produced.
Detailed description of the invention
Fig. 1 is SrTiO prepared by the embodiment of the present invention 13(STO) PbTiO on substrate3(PTO) X-ray of monocrystal thin films
Diffraction (XRD) map；
Fig. 2 is SrTiO prepared by the embodiment of the present invention 13(STO) PbTiO on substrate3(PTO) the scanning electricity of monocrystal thin films
Sub- microscope (SEM) figure；
Fig. 3 is SrTiO prepared by the embodiment of the present invention 13(STO) PbTiO on substrate3(PTO) the transmission electricity of monocrystal thin films
Sub- microscope (TEM) figure.
Specific embodiment
Technical solution of the present invention is further illustrated below in conjunction with example.
Embodiment 1
1) mineralizer KOH is added in reaction kettle liner, 20ml deionized water is added, stir 5min, obtain molar concentration
For the KOH solution of 6mol/L；
2) tetra-n-butyl titanate (TBOT) is added in step 1) acquired solution, mixing 20min, in the solution of acquisition
The molar concentration of TBOT is 0.04mol/L；
3) by plumbi nitras (Pb (NO3)2) it is dissolved in 15ml deionized water, adjust lead titanium molar ratio Pb/Ti=1.25, stirring
20min；
4) step 3) acquired solution is slowly added dropwise into 2) acquired solution, strong stirring 2h；
5) by SrTiO3It after substrate Ar corona treatment, is vertically arranged in hydro-thermal reaction frame, uses acetone, second respectively
After alcohol, water, ethyl alcohol respectively clean 10min, 60 DEG C of dry 2h；
6) contain reactant solution and SrTiO for what step 5) was prepared3The reaction kettle liner of substrate is fitted into mating reaction kettle,
Sealing, reacts 12h at 200 DEG C, then allows reaction kettle cooled to room temperature, after unloading kettle, with deionized water and dehydrated alcohol
Washing reaction product repeatedly filters, and drying obtains SrTiO3PbTiO in single crystal substrates3Monocrystal thin films.
It can be seen that PbTiO from Fig. 1, Fig. 2 and Fig. 33For (001) orientation monocrystal thin films, have even curface and
The interface PTO/STO, PTO film thickness are about 480nm.
Embodiment 2
1) mineralizer KOH is added in reaction kettle liner, 20ml deionized water is added, stir 5min, obtain molar concentration
For the KOH solution of 6mol/L；
2) tetra-n-butyl titanate (TBOT) is added in step 1) acquired solution, mixing 20min, in the solution of acquisition
The molar concentration of TBOT is 0.04mol/L；
3) by plumbi nitras (Pb (NO3)2) it is dissolved in 15ml deionized water, adjust lead titanium molar ratio Pb/Ti=1.25, stirring
20min；
4) step 3) acquired solution is slowly added dropwise into 2) acquired solution, strong stirring 2h；
5) by SrTiO3It after substrate Ar corona treatment, is vertically arranged in hydro-thermal reaction frame, uses acetone, second respectively
After alcohol, water, ethyl alcohol respectively clean 10min, 60 DEG C of dry 2h；
6) contain reactant solution and SrTiO for what step 5) was prepared3The reaction kettle liner of substrate is fitted into mating reaction kettle,
Sealing, reacts 6h at 200 DEG C, then allows reaction kettle cooled to room temperature, anti-with deionized water and dehydrated alcohol after unloading kettle
Reaction product is washed in after backwashing, is filtered, and drying obtains SrTiO3PbTiO in single crystal substrates3Monocrystal thin films.
Embodiment 3
1) mineralizer KOH is added in reaction kettle liner, 20ml deionized water is added, stir 5min, obtain molar concentration
For the KOH solution of 6mol/L；
2) tetra-n-butyl titanate (TBOT) is added in step 1) acquired solution, mixing 20min, in the solution of acquisition
The molar concentration of TBOT is 0.02mol/L；
3) by plumbi nitras (Pb (NO3)2) it is dissolved in 15ml deionized water, adjust lead titanium molar ratio Pb/Ti=1.25, stirring
20min；
4) step 3) acquired solution is slowly added dropwise into 2) acquired solution, strong stirring 2h；
5) by SrTiO3It after substrate Ar corona treatment, is vertically arranged in hydro-thermal reaction frame, uses acetone, second respectively
After alcohol, water, ethyl alcohol respectively clean 10min, 60 DEG C of dry 2h；
6) contain reactant solution and SrTiO for what step 5) was prepared3The reaction kettle liner of substrate is fitted into mating reaction kettle,
Sealing, reacts 12h at 200 DEG C, then allows reaction kettle cooled to room temperature, after unloading kettle, with deionized water and dehydrated alcohol
Washing reaction product repeatedly filters, and drying obtains SrTiO3PbTiO in single crystal substrates3Monocrystal thin films.
Claims (7)
1. a kind of preparation method of monocrystalline lead titanate thin film, which comprises the following steps:
1) mineralizer KOH is added in reaction kettle liner, deionized water stirring is added, obtaining molar concentration is 3-6mol/L's
KOH solution；
2) tetra-n-butyl titanate (TBOT) is added in step 1) acquired solution, mixing 10-20min, in the solution of acquisition
The molar concentration of TBOT is 0.003-0.04mol/L；
3) by plumbi nitras (Pb (NO3)2) it is dissolved in deionized water stirring, adjust lead titanium molar ratio Pb/Ti=1-1.25；
4) step 3) acquired solution is added dropwise in 2) acquired solution, strong stirring at least 2h；
5) by SrTiO3After substrate Ar corona treatment, be vertically arranged in hydro-thermal reaction frame, respectively with acetone, ethyl alcohol,
After water, ethyl alcohol respectively clean at least 10min, 60 DEG C of dry 2h；
6) contain reactant solution and SrTiO for what step 5) was prepared3The reaction kettle liner of substrate is fitted into mating reaction kettle, sealing,
2h-24h is reacted at 100-200 DEG C, then allows reaction kettle cooled to room temperature, after unloading kettle, with deionized water and anhydrous second
Washing reaction product, filtering, drying obtain SrTiO to alcohol repeatedly3PbTiO in single crystal substrates3Monocrystal thin films.
2. the preparation method of monocrystalline lead titanate thin film according to claim 1, which is characterized in that the reaction kettle is poly-
Tetrafluoroethene liner, the closed reaction kettle of stainless steel external member.
3. the preparation method of monocrystalline lead titanate thin film according to claim 1, which is characterized in that described KOH, TBOT and
With Pb (NO3)2Purity be all not less than chemistry it is pure.
4. the preparation method of monocrystalline lead titanate thin film according to claim 1, which is characterized in that in the step 5)
The ion beam current energy of Ar corona treatment is 3000eV, and beam current density is 50 μ A/cm2。
5. the preparation method of monocrystalline lead titanate thin film according to claim 1, which is characterized in that in the step 5)
SrTiO3Substrate is cube phase monocrystal, the polishing substrate of (100) orientation.
6. the preparation method of monocrystalline lead titanate thin film according to claim 1, which is characterized in that in the step 5)
Hydro-thermal reaction frame is bracket made of polytetrafluoroethylene material.
7. a kind of monocrystalline lead titanate thin film, which is characterized in that be prepared into using as the method according to claim 1 to 6
It arrives, wherein being grown in SrTiO3PbTiO on substrate3With a thickness of 100-500nm.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113279062A (en) * | 2021-05-17 | 2021-08-20 | 浙江大学 | Nickel-doped lead titanate single crystal film and preparation and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1721582A (en) * | 2005-06-08 | 2006-01-18 | 中国科学院上海光学精密机械研究所 | Improve Hydrothermal Growth ZnO crystal growth efficiency and method for quality |
| CN102925979A (en) * | 2012-11-08 | 2013-02-13 | 浙江大学 | Method for preparing perovskite lead titanate crystal nanosheet |
| CN102923766A (en) * | 2012-11-14 | 2013-02-13 | 浙江大学 | Preparation method of lead-titanate ceramic single-crystal nanosheet |
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2019
- 2019-03-26 CN CN201910234845.XA patent/CN109825874A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1721582A (en) * | 2005-06-08 | 2006-01-18 | 中国科学院上海光学精密机械研究所 | Improve Hydrothermal Growth ZnO crystal growth efficiency and method for quality |
| CN102925979A (en) * | 2012-11-08 | 2013-02-13 | 浙江大学 | Method for preparing perovskite lead titanate crystal nanosheet |
| CN102923766A (en) * | 2012-11-14 | 2013-02-13 | 浙江大学 | Preparation method of lead-titanate ceramic single-crystal nanosheet |
Non-Patent Citations (1)
| Title |
|---|
| TAKESHI MORITA等: "Epitaxial PbTiO3 Thin Films on SrTiO3(100) and SrRuO3/SrTiO3(100) Substrates Deposited by a Hydrothermal Method", 《JAPANESE JOURNAL OF APPLIED PHYSICS》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113279062A (en) * | 2021-05-17 | 2021-08-20 | 浙江大学 | Nickel-doped lead titanate single crystal film and preparation and application thereof |
| CN113279062B (en) * | 2021-05-17 | 2022-07-08 | 浙江大学 | Nickel-doped lead titanate single crystal film and preparation and application thereof |
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Application publication date: 20190531 |