CN110993332B - Preparation method of lead hafnate antiferroelectric thin film capacitor - Google Patents
Preparation method of lead hafnate antiferroelectric thin film capacitor Download PDFInfo
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- 239000003990 capacitor Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000010409 thin film Substances 0.000 title abstract description 32
- 239000002243 precursor Substances 0.000 claims abstract description 51
- 239000000758 substrate Substances 0.000 claims abstract description 33
- 238000000137 annealing Methods 0.000 claims abstract description 30
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 28
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000243 solution Substances 0.000 claims abstract description 25
- 239000011521 glass Substances 0.000 claims abstract description 18
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229960000583 acetic acid Drugs 0.000 claims abstract description 14
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 14
- MCFIMQJAFAOJPD-MTOQALJVSA-J hafnium(4+) (Z)-4-oxopent-2-en-2-olate Chemical compound [Hf+4].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O MCFIMQJAFAOJPD-MTOQALJVSA-J 0.000 claims abstract description 14
- 229940046892 lead acetate Drugs 0.000 claims abstract description 14
- 238000007747 plating Methods 0.000 claims abstract description 12
- 239000011259 mixed solution Substances 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 238000009987 spinning Methods 0.000 claims abstract description 6
- 238000004528 spin coating Methods 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 11
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000010408 film Substances 0.000 abstract description 82
- 238000003980 solgel method Methods 0.000 abstract description 3
- 238000004146 energy storage Methods 0.000 description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- 230000005684 electric field Effects 0.000 description 10
- 230000010287 polarization Effects 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- 229910052681 coesite Inorganic materials 0.000 description 6
- 229910052906 cristobalite Inorganic materials 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000004544 sputter deposition Methods 0.000 description 6
- 229910052682 stishovite Inorganic materials 0.000 description 6
- 229910052905 tridymite Inorganic materials 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910021650 platinized titanium dioxide Inorganic materials 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052735 hafnium Inorganic materials 0.000 description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 2
- 238000004377 microelectronic Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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Abstract
The invention provides a preparation method of a lead hafnate antiferroelectric film capacitor, which comprises the following steps: A) dissolving hafnium acetylacetonate and lead acetate in a mixed solution consisting of ethylene glycol monomethyl ether, glacial acetic acid and acetylacetone to obtain PbHfO3A precursor solution; B) the PbHfO is added3The precursor liquid is coated on the surface of the FTO glass substrate in a spinning mode and then dried to obtain a precursor film; C) performing high-temperature annealing on the precursor film in an air atmosphere to obtain a lead hafnate antiferroelectric film; D) and plating a top electrode on the surface of the lead hafnate anti-ferroelectric film to obtain the lead hafnate anti-ferroelectric film capacitor. PbHfO is firstly synthesized by a sol-gel method under proper annealing temperature and annealing time3The thin film, the antiferroelectric thin film capacitor prepared on FTO glass, has good antiferroelectric performance.
Description
Technical Field
The invention belongs to the technical field of microelectronics, and particularly relates to a preparation method of a lead hafnate antiferroelectric thin film capacitor.
Background
In recent years, with the continuous development of science and technology, thin film devices are receiving increasing attention, and have been developed in various fields, and an antiferroelectric thin film capacitor with high energy storage density is one of the directions with great development prospects.
The antiferroelectric material is different from the ferroelectric material in that adjacent dipoles in the antiferroelectric material are arranged in an antiparallel manner, and the net polarization strength is zero in a zero electric field. If an electric field higher than the antiferroelectric-ferroelectric phase transition electric field is applied, it will change into a ferroelectric phase and macroscopic polarization occurs. Antiferroelectric materials have very important application prospects in the field of microelectronic technology, such as being used for energy storage capacitors, piezoelectric devices, pyroelectric detectors and the like, so more and more researchers pay attention to developing antiferroelectric materials and devices thereof with stable and efficient performances.
Lead hafnium (PbHfO)3) With lead zirconate (PbZrO)3) All belong to antiferroelectric materials, which are structurally similar, chambersWhen the temperature is in an orthogonal phase, the ferroelectric material has antiferroelectric performance. Currently lead hafnium (PbHfO)3) The single crystal and ceramic of (2) have been successfully synthesized, however, the thin film and the device thereof have not been reported.
Disclosure of Invention
The invention aims to provide a preparation method of a lead hafnate antiferroelectric film capacitor, and PbHfO is synthesized for the first time by the method3The anti-ferroelectric film has outstanding performance.
The invention provides a preparation method of a lead hafnate antiferroelectric film capacitor, which comprises the following steps:
A) dissolving hafnium acetylacetonate and lead acetate in a mixed solution consisting of ethylene glycol monomethyl ether, glacial acetic acid and acetylacetone to obtain PbHfO3A precursor solution;
B) the PbHfO is added3The precursor liquid is coated on the surface of the FTO glass substrate in a spinning mode and then dried to obtain a precursor film;
C) performing high-temperature annealing on the precursor film in an air atmosphere to obtain a lead hafnate antiferroelectric film;
D) and plating a top electrode on the surface of the lead hafnate anti-ferroelectric film to obtain the lead hafnate anti-ferroelectric film capacitor.
Preferably, the molar ratio of the hafnium acetylacetonate to the lead acetate is 1: (1-1.2).
Preferably, the PbHfO3PbHfO in precursor solution3The concentration of (b) is 0.1 to 0.3 mol/L.
Preferably, the volume ratio of the ethylene glycol methyl ether to the glacial acetic acid to the acetylacetone is (1-10): 1.
Preferably, the spin coating in the step B) is performed according to the following steps:
the PbHfO is added3The precursor solution is spin-coated for 5-20 s at a rotation speed of 600-900 rpm, and then spin-coated for 10-30 s at a rotation speed of 5000-7000 rpm.
Preferably, the drying temperature in the step B) is 300-400 ℃;
the drying time in the step B) is 5-20 min.
Preferably, the temperature of the high-temperature annealing in the step C) is 650-700 ℃;
and C), the high-temperature annealing time in the step C) is 10-20 min.
Preferably, the top electrode is Au, Ti, Al, Ag, W, TiN or Pt.
Preferably, the thickness of the lead hafnate antiferroelectric film is 300-600 nm.
Preferably, in the step B), spin coating and drying can be repeated for 6-12 times to obtain a precursor film with a required thickness.
The invention provides a preparation method of a lead hafnate antiferroelectric film capacitor, which comprises the following steps: A) dissolving hafnium acetylacetonate and lead acetate in a mixed solution consisting of ethylene glycol monomethyl ether, glacial acetic acid and acetylacetone to obtain PbHfO3A precursor solution; B) the PbHfO is added3The precursor liquid is coated on the surface of the FTO glass substrate in a spinning mode and then dried to obtain a precursor film; C) performing high-temperature annealing on the precursor film in an air atmosphere to obtain a lead hafnate antiferroelectric film; D) and plating a top electrode on the surface of the lead hafnate anti-ferroelectric film to obtain the lead hafnate anti-ferroelectric film capacitor.
Compared with the prior art, the invention has the following beneficial effects:
1) PbHfO is firstly synthesized by a sol-gel method under proper annealing temperature and annealing time3A thin film having good antiferroelectric properties.
2) The antiferroelectric thin film capacitor prepared on the FTO glass has higher energy storage density and efficiency and stable performance.
3) The invention has simple preparation process and stable antiferroelectric performance, and can be used as energy storage elements, electrostrictive devices, piezoelectric devices, pyroelectric devices and the like.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 shows PbHfO in the present invention3The structure schematic diagram of the antiferroelectric thin film capacitor;
wherein, 1 is a top electrode, 2 is a lead hafnate antiferroelectric film, 3 is an FTO bottom electrode, and 4 is a glass substrate;
FIG. 2 shows PbHfO in example 1 of the present invention and comparative example 13An X-ray diffraction pattern of the antiferroelectric thin film capacitor;
FIG. 3 shows PbHfO in example 1 of the present invention3The ferroelectric thin film capacitor has a hysteresis loop and a polarization current curve under an external electric field of 1000 kV/cm;
FIG. 4 shows PbHfO in example 1 of the present invention3The energy storage density and the energy storage efficiency of the antiferroelectric thin film capacitor under different external electric fields;
FIG. 5 shows PbHfO in comparative example 1 of the present invention3A hysteresis loop and a polarization current curve of the film capacitor under an external electric field of 1000 kV/cm;
FIG. 6 shows PbHfO in comparative example 2 of the present invention3The thin film capacitor has a hysteresis loop and polarization current curve under an external electric field of 1000 kV/cm.
Detailed Description
The invention provides a preparation method of a lead hafnate antiferroelectric film capacitor, which comprises the following steps:
A) dissolving hafnium acetylacetonate and lead acetate in a mixed solution consisting of ethylene glycol monomethyl ether, glacial acetic acid and acetylacetone to obtain PbHfO3A precursor solution;
B) the PbHfO is added3The precursor liquid is coated on the surface of the FTO glass substrate in a spinning mode and then dried to obtain a precursor film;
C) performing high-temperature annealing on the precursor film in an air atmosphere to obtain a lead hafnate antiferroelectric film;
D) and plating a top electrode on the surface of the lead hafnate anti-ferroelectric film to obtain the lead hafnate anti-ferroelectric film capacitor.
In the present invention, the molar ratio of the hafnium acetylacetonate to the lead acetate is preferably 1: (1E >1.2), more preferably 1: (1-1.1), most preferably 1: 1.1; the volume ratio of the ethylene glycol monomethyl ether to the glacial acetic acid to the acetylacetone is preferably (1-10): 1, and more preferably (3-8): (3-8): 1, most preferably 5:5: 1; the PbHfO3The concentration of the precursor solution is preferably 0.1 to 0.3mol/L, and more preferably 0.2 to 0.3 mol/L.
Obtaining PbHfO3After the precursor solution, PbHfO is preferably added in the invention3The precursor solution is used after standing for one day, and the PbHfO is mixed by a spin coater3And spin-coating the precursor solution on an FTO glass substrate to obtain a wet film, and then drying the wet film to obtain a precursor film. If a lead hafnate antiferroelectric film with a specific thickness is required, the steps of spin coating and drying can be repeated several times to obtain a precursor film with a required thickness.
The invention preferably uses the PbHfO3The method comprises the following steps of firstly carrying out low-speed spin coating on a precursor solution, and then carrying out high-speed spin coating, wherein the low-speed spin coating speed is preferably 600-900 rpm/s, and more preferably 700-800 rpm/s; the time of the low-speed spin coating is preferably 5-20 s, and more preferably 10-15 s; the high-speed spin coating speed is preferably 5000-7000 r/s, and more preferably 6000-6500 r/s; the high-speed spin coating time is preferably 10-30 s, more preferably 15-25 s, and most preferably 20 s.
In the invention, the drying temperature is preferably 300-400 ℃, and more preferably 350 ℃; the drying time is preferably 5-20 min, and more preferably 10-15 min. The FTO glass substrate compounded with the precursor film is preferably placed on a heating platform for drying.
Research shows that only PbHfO is spin-coated on FTO glass substrate3The lead hafnate film obtained from the precursor solution has antiferroelectric property, high energy storage density and high efficiency, and can be used for other substrates, such as Pt/Ti/SiO2a/Si substrate, resulting PbHfO3The crystal structure of the film is mainly tetragonal phase, and PbHfO is prepared on an FTO substrate3The film has different crystal structures and does not have obvious antiferroelectric performance.
After the precursor film is obtained, the invention preferably carries out high-temperature annealing on the precursor film in an air atmosphere to obtain the lead hafnate antiferroelectric film.
In the invention, the high-temperature annealing temperature is preferably 650-700 ℃; the time of the high-temperature annealing is preferably 10-20 min.
After the lead hafnate antiferroelectric film is obtained, the invention records that the surface of the lead hafnate antiferroelectric film is plated with a top electrode, and the lead hafnate antiferroelectric film capacitor is obtained.
In the present invention, the top electrode is preferably Au, Ti, Al, Ag, W, TiN or Pt. The method for plating the top electrode is not particularly limited, and the method for plating the electrode commonly used by the person skilled in the art can be adopted, and the method for plating the top electrode is preferably adopted by a small-sized ion sputtering instrument.
The invention also provides a lead hafnate antiferroelectric film capacitor, which comprises a top electrode, an antiferroelectric film and a substrate; the top electrode is one of Au, Ti, Al, Ag, W, TiN or Pt, the thickness of the antiferroelectric film is 300-600 nm, and the substrate is FTO glass. Prepared according to the preparation method.
The invention provides a preparation method of a lead hafnate antiferroelectric film capacitor, which comprises the following steps: A) dissolving hafnium acetylacetonate and lead acetate in a mixed solution consisting of ethylene glycol monomethyl ether, glacial acetic acid and acetylacetone to obtain PbHfO3A precursor solution; B) the PbHfO is added3The precursor liquid is coated on the surface of the FTO glass substrate in a spinning mode and then dried to obtain a precursor film; C) performing high-temperature annealing on the precursor film in an air atmosphere to obtain a lead hafnate antiferroelectric film; D) and plating a top electrode on the surface of the lead hafnate anti-ferroelectric film to obtain the lead hafnate anti-ferroelectric film capacitor.
Compared with the prior art, the invention has the following beneficial effects:
1) PbHfO is firstly synthesized by a sol-gel method under proper annealing temperature and annealing time3A thin film having good antiferroelectric properties.
2) The antiferroelectric thin film capacitor prepared on the FTO glass has higher energy storage density and efficiency and stable performance.
3) The invention has simple preparation process and stable antiferroelectric performance, and can be used as energy storage elements, electrostrictive devices, piezoelectric devices, pyroelectric devices and the like.
In order to further illustrate the present invention, the following will describe in detail the method for preparing a lead hafnate antiferroelectric thin film capacitor provided by the present invention with reference to the following examples, which should not be construed as limiting the scope of the present invention.
Example 1
Dissolving hafnium acetylacetonate and lead acetate into a mixed solution of ethylene glycol monomethyl ether, glacial acetic acid and acetylacetone according to a molar ratio of 1:1.1 to obtain 0.3mol/L PbHfO3The precursor solution is used after standing for one day.
And ultrasonically cleaning the substrate by using acetone and absolute ethyl alcohol to remove oil stains and other impurities on the surface of the substrate.
Using a spin coater to spin PbHfO3The precursor solution is spin-coated on an FTO glass substrate to obtain a wet film, then the wet film is dried on a heating platform at 350 ℃ for 10min, and the spin-coating and drying are repeated for 9 times.
And (3) putting the film into a 700 ℃ rapid annealing furnace, and annealing for 10min at high temperature in an air atmosphere to obtain the film with the thickness of about 450 nm.
Plating Au top electrode on the annealed film by using a small ion sputtering instrument to obtain the PbHfO with high energy storage density3An antiferroelectric thin film capacitor.
FIG. 2 shows PbHfO in example 1 of the present invention3X-ray diffraction pattern of the antiferroelectric thin film capacitor. The antiferroelectric thin film capacitor comprises an Au top electrode and PbHfO3Thin films and FTO glasses.
FIG. 3 shows PbHfO in this example3And (3) a hysteresis loop and a polarization current curve of the antiferroelectric thin film capacitor under an external electric field of 1000 kV/cm. The results show that PbHfO3The film has good antiferroelectric performance, and the maximum polarization value of the film reaches 91.78 mu C/cm2And the remanent polarization is only 7.84. mu.C/cm2. In addition, the polarization current curve of the film also exhibits four asymmetric peaks.
FIG. 4 shows PbHfO in this example3Antiferroelectric thin film electricThe energy storage density and the energy storage efficiency of the container under different external electric fields. Along with the increase of the external electric field, the energy storage density is gradually improved, and the energy storage efficiency is slightly changed. The highest reversible energy storage density tested reaches 36.465J/cm3。
Example 2
Dissolving hafnium acetylacetonate and lead acetate into a mixed solution of ethylene glycol monomethyl ether, glacial acetic acid and acetylacetone according to a molar ratio of 1:1.1 to obtain 0.3mol/L PbHfO3The precursor solution is used after standing for one day.
And ultrasonically cleaning the substrate by using acetone and absolute ethyl alcohol to remove oil stains and other impurities on the surface of the substrate.
Using a spin coater to spin PbHfO3And spin-coating the precursor solution on an FTO glass substrate to obtain a wet film, drying the wet film on a heating platform at 350 ℃ for 10min, and repeating spin-coating and drying for 6 times.
And (3) putting the film into a 700 ℃ rapid annealing furnace, and annealing for 10min at high temperature in an air atmosphere to obtain the film with the thickness of about 300 nm.
Plating Au top electrode on the annealed film by using a small ion sputtering instrument to obtain the PbHfO with high energy storage density3An antiferroelectric thin film capacitor.
Example 3
Dissolving hafnium acetylacetonate and lead acetate into a mixed solution of ethylene glycol monomethyl ether, glacial acetic acid and acetylacetone according to a molar ratio of 1:1.1 to obtain 0.3mol/L PbHfO3The precursor solution is used after standing for one day.
And ultrasonically cleaning the substrate by using acetone and absolute ethyl alcohol to remove oil stains and other impurities on the surface of the substrate.
Using a spin coater to spin PbHfO3The precursor solution is spin-coated on an FTO glass substrate to obtain a wet film, then the wet film is dried on a heating platform at 350 ℃ for 10min, and the spin-coating and drying are repeated for 9 times.
And (3) putting the film into a 650 ℃ rapid annealing furnace, and annealing at high temperature for 20min in an air atmosphere to obtain the film with the thickness of about 450 nm.
Plating Au top electrode on the annealed film by using a small ion sputtering instrument to obtain the PbHfO with high energy storage density3Counter ironAn electric thin film capacitor.
Comparative example 1
Dissolving hafnium acetylacetonate and lead acetate into a mixed solution of ethylene glycol monomethyl ether, glacial acetic acid and acetylacetone according to a molar ratio of 1:1.1 to obtain 0.3mol/L PbHfO3The precursor solution is used after standing for one day.
And ultrasonically cleaning the substrate by using acetone and absolute ethyl alcohol to remove oil stains and other impurities on the surface of the substrate.
Using a spin coater to spin PbHfO3The precursor liquid is coated on Pt/TiO in a rotating way2/SiO2The wet film was obtained on a Si substrate, then dried on a heated platen at 350 ℃ for 10min, and spin coating and drying were repeated 4 times.
And (3) putting the film into a 700 ℃ rapid annealing furnace, and annealing for 10min at high temperature in an air atmosphere to obtain the film with the thickness of about 200 nm.
The annealed film was plated with an Au top electrode using a small ion sputtering apparatus, and the test results showed that the film was Pt/TiO2/SiO2PbHfO prepared on Si substrate3The film has no antiferroelectric property, and the XRD result shows that the film is prepared on Pt/TiO2/SiO2PbHfO on/Si substrate3The crystallinity of the thin film crystal is poor, and thus the antiferroelectric properties of the thin film are not sufficiently pronounced.
Comparative example 2
Dissolving hafnium acetylacetonate and lead acetate into a mixed solution of ethylene glycol monomethyl ether, glacial acetic acid and acetylacetone according to a molar ratio of 1:1.1 to obtain 0.3mol/L PbHfO3The precursor solution is used after standing for one day.
And ultrasonically cleaning the substrate by using acetone and absolute ethyl alcohol to remove oil stains and other impurities on the surface of the substrate.
Using a spin coater to spin PbHfO3The precursor liquid is coated on Pt/TiO in a rotating way2/SiO2The wet film was obtained on a Si substrate, then dried on a heated platen at 350 ℃ for 10min, and spin coating and drying were repeated 4 times.
And (3) putting the film into a 750 ℃ rapid annealing furnace, and annealing for 10min at high temperature in an air atmosphere to obtain the film with the thickness of about 200 nm.
After annealing by a small ion sputtering apparatusThe thin film of (2) was plated with an Au top electrode, and the test results are shown in FIG. 6. it can be seen from FIG. 6 that Pt/TiO2/SiO2PbHfO prepared on Si substrate3The antiferroelectric property of the thin film is poor, and the specific reason can be that the lead in the thin film is volatilized due to too high temperature, so that the crystallinity of the thin film is reduced, and the antiferroelectric property is poor.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (9)
1. A preparation method of a lead hafnate antiferroelectric film capacitor comprises the following steps:
A) dissolving hafnium acetylacetonate and lead acetate in a mixed solution consisting of ethylene glycol monomethyl ether, glacial acetic acid and acetylacetone to obtain PbHfO3A precursor solution;
B) the PbHfO is added3The precursor liquid is coated on the surface of the FTO glass substrate in a spinning mode and then dried to obtain a precursor film;
C) performing high-temperature annealing on the precursor film in an air atmosphere to obtain a lead hafnate antiferroelectric film;
the temperature of high-temperature annealing in the step C) is 650-700 ℃; the time of high-temperature annealing in the step C) is 10-20 min;
D) and plating a top electrode on the surface of the lead hafnate anti-ferroelectric film to obtain the lead hafnate anti-ferroelectric film capacitor.
2. The method according to claim 1, wherein the molar ratio of hafnium acetylacetonate to lead acetate is 1: (1-1.2).
3. The method for preparing according to claim 1, wherein the PbHfO is3PbHfO in precursor solution3The concentration of (b) is 0.1 to 0.3 mol/L.
4. The method according to claim 1, wherein the volume ratio of the ethylene glycol methyl ether, the glacial acetic acid and the acetylacetone is (1-10): 1.
5. The production method according to claim 1, wherein the spin coating in step B) is performed according to the following steps:
the PbHfO is added3The precursor solution is spin-coated for 5-20 s at a rotation speed of 600-900 rpm, and then spin-coated for 10-30 s at a rotation speed of 5000-7000 rpm.
6. The preparation method according to claim 1, wherein the drying temperature in the step B) is 300-400 ℃;
the drying time in the step B) is 5-20 min.
7. The method of claim 1, wherein the top electrode is Au, Ti, Al, Ag, W, TiN, or Pt.
8. The method according to claim 1, wherein the thickness of the lead hafnate antiferroelectric film is 300 to 600 nm.
9. The preparation method according to claim 1, wherein in the step B), spin coating and drying can be repeated for 6-12 times to obtain the precursor film with the required thickness.
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