CN112151357A - Barium titanate-based super-paraelectric film and low-and-medium-temperature preparation method and application thereof - Google Patents
Barium titanate-based super-paraelectric film and low-and-medium-temperature preparation method and application thereof Download PDFInfo
- Publication number
- CN112151357A CN112151357A CN202011015541.3A CN202011015541A CN112151357A CN 112151357 A CN112151357 A CN 112151357A CN 202011015541 A CN202011015541 A CN 202011015541A CN 112151357 A CN112151357 A CN 112151357A
- Authority
- CN
- China
- Prior art keywords
- barium titanate
- film
- sputtering
- electrode
- buffer layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910002113 barium titanate Inorganic materials 0.000 title claims abstract description 74
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims description 30
- 239000010408 film Substances 0.000 claims abstract description 109
- 238000004544 sputter deposition Methods 0.000 claims abstract description 40
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000000758 substrate Substances 0.000 claims abstract description 23
- 239000010409 thin film Substances 0.000 claims abstract description 19
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 17
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 17
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 17
- 239000010703 silicon Substances 0.000 claims abstract description 17
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 9
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 9
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 7
- 239000010936 titanium Substances 0.000 claims abstract description 7
- WOIHABYNKOEWFG-UHFFFAOYSA-N [Sr].[Ba] Chemical compound [Sr].[Ba] WOIHABYNKOEWFG-UHFFFAOYSA-N 0.000 claims description 23
- 239000003990 capacitor Substances 0.000 claims description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 238000000151 deposition Methods 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 229910052737 gold Inorganic materials 0.000 claims description 6
- 239000010931 gold Substances 0.000 claims description 6
- 229910052681 coesite Inorganic materials 0.000 claims description 5
- 229910052906 cristobalite Inorganic materials 0.000 claims description 5
- 230000008021 deposition Effects 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 229910052682 stishovite Inorganic materials 0.000 claims description 5
- 229910052905 tridymite Inorganic materials 0.000 claims description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- 239000004065 semiconductor Substances 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 229910021523 barium zirconate Inorganic materials 0.000 claims description 2
- DQBAOWPVHRWLJC-UHFFFAOYSA-N barium(2+);dioxido(oxo)zirconium Chemical compound [Ba+2].[O-][Zr]([O-])=O DQBAOWPVHRWLJC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 229910000510 noble metal Inorganic materials 0.000 claims description 2
- 238000004146 energy storage Methods 0.000 abstract description 34
- 239000000463 material Substances 0.000 abstract description 19
- 238000010438 heat treatment Methods 0.000 abstract description 7
- 230000010287 polarization Effects 0.000 description 7
- 238000005477 sputtering target Methods 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 5
- 239000013077 target material Substances 0.000 description 5
- 239000000919 ceramic Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 3
- 229910052454 barium strontium titanate Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000004377 microelectronic Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 238000000137 annealing Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000012612 commercial material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005621 ferroelectricity Effects 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- -1 platinum metals Chemical class 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 231100000701 toxic element Toxicity 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
- H01L21/02172—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
- H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02296—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer
- H01L21/02299—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer pre-treatment
- H01L21/02304—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer pre-treatment formation of intermediate layers, e.g. buffer layers, layers to improve adhesion, lattice match or diffusion barriers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Landscapes
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Semiconductor Integrated Circuits (AREA)
- Semiconductor Memories (AREA)
Abstract
The invention discloses a barium titanate-based super-cis-electric film material, a method for integrally preparing the barium titanate-based super-cis-electric film on a silicon substrate at a medium and low temperature and application thereof. The method comprises the following steps: the method comprises the steps of carrying out magnetron sputtering on a buffer layer and a barium titanate-based film from bottom to top on the surface of a base body plated with platinum and titanium at room temperature (without heating) or 150 ℃, carrying out magnetron sputtering on a top electrode on the surface of the barium titanate-based film, wherein the buffer layer is made of a conductive oxide lanthanum nickelate with a perovskite structure and capable of being matched with barium titanate-based lattices, and the sputtering mode is a continuous sputtering mode of the lanthanum nickelate buffer layer and the barium titanate-based film. The invention can reduce the temperature for preparing the barium titanate-based film material to room temperature or 150 ℃, and the barium titanate-based film material has a well dispersed nano polar region, high energy storage density and energy storage efficiency and high energy storage characteristic which are not changed along with the increase of the thickness. In addition, the thickness of the super-paraelectric film layer is reduced, the capacitance density and the dielectric constant are increased, and the requirement of the thin film transistor on the high dielectric constant of the dielectric layer is met.
Description
Technical Field
The invention relates to the technical field of electronic material development and thin film material preparation, in particular to a barium titanate-based super-paraelectric film and a medium-low temperature preparation method and application thereof.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
In recent years, with the rapid development of electronic devices such as capacitors, power tuning devices, pulse power systems, thin film transistors, and the like, there is a great demand for materials and devices with high capacitance density, high dielectric constant, high energy storage density, and high energy storage efficiency, and the materials and devices are one of the leading edges and hot spots of current scientific research.
Compared with other energy storage components such as a battery and a super capacitor, the dielectric film capacitor has the advantages of rapid charge and discharge, environmental friendliness, good heat resistance and fatigue resistance and longer service life. The dielectric super-paraelectric capacitor is a material with high dielectric constant and low charge-discharge loss at room temperature, the super-paraelectric film has a well-dispersed short-range ordered polarization region, and due to the special microstructure, compared with ferroelectric and paraelectric films, the super-paraelectric film removes an electric hysteresis loop while keeping high dielectric constant, so that the super-paraelectric capacitor has high energy storage density and high energy storage efficiency, and the dielectric constant of the super-paraelectric capacitor has good frequency and temperature stability. Meanwhile, due to the high dielectric constant and low dielectric loss, the silicon dioxide can be applied to the thin film transistor as a high dielectric constant dielectric layer instead of the traditional silicon dioxide, and the overall performance of the thin film transistor is improved. The excellent electrical properties determine that the super-paraelectric thin-film material has wide application prospects in the technical fields of capacitors, power tuning devices, pulse power systems, thin-film transistors and the like, and the possibility is provided for realizing integration, miniaturization and multiple functions of thin-film electronic devices.
The inventor finds that in the practical application of the dielectric capacitor, the problems of high preparation temperature, high energy storage density, high energy storage efficiency and the like cannot be achieved at the same time. High fabrication temperatures not only add additional thermal budget, process flow and cost expense, but also pose significant challenges to the compatibility of dielectric capacitors with CMOS-Si technology. In addition, the high temperature causes the crystal size (grain size) to become large, resulting in that the ferroelectric capacitor exhibits a nearly square hysteresis dielectric response ("ferroelectric hysteresis loop") under an external electric field, and the recoverable capacitance thereof has low energy density, poor charging and discharging efficiency, is difficult to be connected to the existing electric energy storage and conversion technology, and in severe cases, will cause device failure. In addition, with the development of integrated circuits, in the practical application of thin film transistors, the dielectric layer material thereof has the problems of high preparation temperature, low capacitance density and low dielectric constant, and the like, which seriously restrict the development of thin film transistors.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention provides a barium titanate-based superparaelectric film, a medium-low temperature preparation method and application thereof. In the preparation method of the super-cis-electric film, the film forming temperature is reduced to 150 ℃ or room temperature (without heating), any subsequent annealing process is not needed, and the super-cis-electric phase can be directly formed by cooling after preparation. The super-cis-electric film is highly compatible with CMOS-Si technology and large-scale integrated circuit technology, and the formed film material has high energy storage density and high energy storage efficiency, and the energy storage characteristic is not weakened along with the increase of the thickness. In addition, the capacitance density and the dielectric constant of the super-cis-electric film layer are increased by reducing the thickness of the super-cis-electric film layer, and the requirement of the thin film transistor on the high dielectric constant of the dielectric layer is met.
To solve the above technical problem, one or more of the following embodiments of the present invention provide the following technical solutions:
in a first aspect, the invention provides a medium-low temperature preparation method of a barium titanate-based superparamagnetic film, which comprises the following steps:
and sputtering and depositing a lanthanum nickelate buffer layer and a barium titanate base film on the silicon substrate sputtered with the bottom electrode in sequence, wherein the deposition temperature is 25-150 ℃, and the preparation method is obtained.
In a second aspect, the present invention provides a barium titanate-based superparamagnetic film, which is prepared by the above preparation method.
In a third aspect, the invention provides an electrode, wherein a silicon substrate, a bottom electrode, a buffer layer, a barium titanate-based film and a top electrode are sequentially arranged from the silicon substrate to the top electrode, and the buffer layer is made of a perovskite-structured conductive oxide lanthanum nickelate, which is in lattice match with the barium titanate-based film.
In a fourth aspect, the invention provides an application of the barium titanate-based superparaelectric film in preparing capacitors, power tuning devices, pulse power systems, silicon integrated circuits and thin film transistor devices.
Compared with the prior art, one or more technical schemes of the invention have the following beneficial effects:
1. the barium titanate-based film prepared by the invention has a well-dispersed nano polar region, high maximum polarization strength, small residual polarization strength, large dielectric constant and small dielectric loss, so that the barium titanate-based film has the characteristics of low preparation temperature, high energy storage density and energy storage efficiency and high energy storage characteristic which is not changed along with the increase of the thickness. In addition, the thickness of the super-paraelectric film layer is reduced, the capacitance density and the dielectric constant are increased, and the requirement of the thin film transistor on the high dielectric constant of the dielectric layer is met.
2. In the preparation process, the sputtering deposition temperature of the film on the silicon substrate is as low as room temperature (no heating), which is beneficial to the application in the fields of integrated circuits and microelectronics; the low preparation temperature greatly simplifies the production process flow, reduces the thermal budget in the production process, saves a large amount of cost, and obtains a membrane material with excellent energy storage property, and the recoverable energy density of the membrane material reaches 100J/cm3The energy storage efficiency reaches 90%, and the capacitance density and the dielectric constant of the capacitor have good frequency stability.
3. In the preparation process, the sputtering deposition temperature of the film on the silicon substrate is as low as room temperature (no heating), which is beneficial to the application in the fields of integrated circuits and microelectronics; the low preparation temperature greatly simplifies the production process flow of the thin film transistor, reduces the cost, and obtains the film material with high capacitance density and high dielectric constant, wherein the capacitance density reaches 2450nF/cm2The dielectric constant reached 304(@1 kHz).
4. The invention uses the conductive oxide lanthanum nickelate matched with the barium titanate-based material in lattice as the buffer layer, which is beneficial to improving the crystallinity of the barium titanate-based film under the condition of medium and low temperature and optimizing the electrical property of the barium titanate-based film.
5. The superparamagnetic ferroelectric barium titanate-based film material obtained by the invention is a low-cost commercial material, does not contain toxic elements, and is green and environment-friendly; the preparation process is simple, low in equipment cost and easy in device integration, and is suitable for industrial popularization and production.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 is a schematic view showing the structure of a barium titanate-based superparamagnetic film in example 1 of the present invention;
FIG. 2 is a high resolution TEM image of a barium strontium zirconate titanate film according to example 1 and a diffraction pattern of selected areas;
FIG. 3 is a single-sided hysteresis loop diagram (polarization intensity-applied electric field relationship diagram) of a barium strontium zirconate titanate film in example 1 of the present invention;
FIG. 4 is a graph of capacitance density versus frequency for a barium strontium zirconate titanate superparaelectric film in example 1 of the present invention;
FIG. 5 is a graph of dielectric constant versus frequency for a barium strontium zirconate titanate superparaelectric film in example 1 of the present invention;
FIG. 6 is a graph of capacitance density versus frequency for barium strontium zirconate titanate film (10 nm) in example 8 in accordance with the invention;
FIG. 7 is a graph of dielectric constant versus frequency for barium strontium zirconate titanate film (10 nm) in example 8 of the present invention.
Wherein, 1-basal body, 2-bottom electrode, 3-buffer layer, 4-barium titanate-based film and 5-top electrode.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
In a first aspect, the invention provides a medium-low temperature preparation method of a barium titanate-based superparamagnetic film, which comprises the following steps:
and sputtering and depositing a lanthanum nickelate buffer layer and a barium titanate base film on the silicon substrate sputtered with the bottom electrode in sequence, wherein the deposition temperature is 25-150 ℃, and the preparation method is obtained.
Earlier researches show that lanthanum nickelate can effectively reduce the crystallization temperature of a sputtered barium titanate-based film. When the sputtering temperature in the above step is 200 ℃ or above, the barium titanate-based film can form columnar nano-crystalline grains which are vertical to the film thickness, so that the barium titanate-based film is in a ferroelectric state, the bearable voltage (breakdown voltage) of the barium titanate-based film is reduced, the remanent polarization strength is increased, and the recoverable energy storage density and the energy storage efficiency are correspondingly lower. The invention reduces the sputtering temperature of barium titanate-based film and lanthanum nickelate buffer layer to below 150 deg.C, so that the barium titanate-based film has long nucleation and large dispersed nano-polar region (diameter is 2-3 nm), the macro ferroelectricity disappears, the material is converted into super-paraelectric phase, and the energy storage density, efficiency and stability are improved. And, by reducing the thickness of the super-cis-electricity film layer (to 10nm at the lowest), the super-cis-electricity film has better capacitance density and dielectric constant. The invention realizes the sputtering preparation of barium titanate-based super-cis-electric film at 150 ℃ and room temperature, and the prepared film has well dispersed nano-polar regions, meets the strict size interval of super-cis-electric and has excellent dielectric and energy storage properties.
According to the invention, the conductive oxide lanthanum nickelate with a perovskite structure matched with barium titanate base lattices is added as a buffer layer, and the crystallinity of the barium titanate base film at the sputtering temperature of 150 ℃ and at room temperature (without heating) can be enhanced, so that the super-cis electric barium titanate base film with a well-dispersed nano-polarity region is formed, and the super-cis electric barium titanate base film material prepared at room temperature has high energy storage density and energy storage efficiency and high energy storage property and is not changed along with the increase of thickness. In addition, the capacitance density and the dielectric constant of the super-cis-electric film layer are increased by reducing the thickness of the super-cis-electric film layer, and the requirement of the thin film transistor on the high dielectric constant of the dielectric layer is met.
In some embodiments, the barium titanate-based film is pure barium titanate, barium zirconate titanate, or barium strontium zirconate titanate.
In some embodiments, the atmosphere in magnetron sputtering of the barium titanate-based film is a mixed atmosphere of argon and oxygen.
In some embodiments, the pressure of the magnetron sputtering is 1.2 to 1.4Pa and the sputtering power is 96 to 100W when the barium titanate-based film is magnetron sputtered.
In some embodiments, the buffer layer is magnetron sputtered in a mixed atmosphere of argon and oxygen, the magnetron sputtering pressure is 0.3Pa, and the sputtering power is 100W.
In some embodiments, the bottom electrode is magnetron sputtered in an atmosphere of argon at a pressure of 0.3Pa and a sputtering power of 55W.
In a second aspect, the present invention provides a barium titanate-based superparamagnetic film, which is prepared by the above preparation method.
The barium titanate-based superparaelectric film material provided by the invention has a well-dispersed nano polar region, high maximum polarization strength, small residual polarization strength, large capacitance density, large dielectric constant and small dielectric loss, so that the barium titanate-based superparaelectric film material has the characteristics of low preparation temperature, high energy storage density, high energy storage efficiency and no change of energy storage characteristics along with the increase of thickness, and is beneficial to the improvement of the performances of electronic devices such as capacitors, power tuning devices, pulse power systems, thin film transistors and the like.
In some embodiments, the barium titanate-based superparamagnetic film has a thickness of 10 to 40 nm. By reducing the thickness of the super paraelectric film layer (to 10nm at the lowest), the capacitance density reaches 738-2450nF/cm2(ii) a The dielectric constant reaches 96-304(@1 kHz).
In a third aspect, the invention provides an electrode, wherein a silicon substrate, a bottom electrode, a buffer layer, a barium titanate-based film and a top electrode are sequentially arranged from the silicon substrate to the top electrode, and the buffer layer is made of a perovskite-structured conductive oxide lanthanum nickelate, which is in lattice match with the barium titanate-based film.
In some embodiments, the silicon substrate is a semiconductor Si/SiO2A substrate.
In some embodiments, the bottom electrode is an inert metal with a metal mobility lower than hydrogen.
Further, the bottom electrode is a composite electrode of one or two of copper, gold, silver, platinum and titanium.
Furthermore, the bottom electrode is a composite electrode of a titanium layer and a platinum layer.
Further, the thickness of the bottom electrode is 150 nm.
In some embodiments, the buffer layer has a thickness of 25-100 nm.
In some embodiments, the barium titanate-based film has a thickness in the range of 10nm to 900 nm.
In some embodiments, the top electrode is made of a noble metal.
Furthermore, the top electrode is made of gold, silver or platinum.
Furthermore, the top electrode is made of gold.
In a fourth aspect, the invention provides an application of the barium titanate-based superparaelectric film in preparing capacitors, power tuning devices, pulse power systems, silicon integrated circuits and thin film transistor devices.
Example 1
(a) Treatment of substrates
With semiconductor Si/SiO2Putting the substrate into a sample tray as a substrate, and finally putting the sample tray on a sample tray frame of a vacuum coating chamber;
vacuumizing: closing the vacuum chamber, vacuumizing to 2 × 10-4Pa；
Heating: introducing Ar gas into the chamber, heating the substrate to 300 ℃, and keeping the temperature stable.
(b) Preparation of bottom electrode
Titanium and platinum metals are used as sputtering targets, and a bottom electrode is deposited in a radio frequency magnetron sputtering mode. The sputtering pressure is adjusted to 0.3Pa, the sputtering power is 55W, and the sputtering pressure is adjusted to Si/SiO2Titanium and platinum are sequentially deposited on the substrate, and the total thickness of the bottom electrode is about 150 nm.
(c) Preparation of buffer layer
Using lanthanum nickelate ceramic as sputtering target material, and performing radio frequency magnetron sputtering on platinum-titanium-plated Si/SiO2A buffer layer is deposited on the substrate. The sputtering temperature is room temperature, and the sputtering atmosphere is Ar and O2Mixed atmosphere, Ar gas flow controlled at 60sccm, O2The gas flow is controlled at 15sccm, the sputtering pressure is 0.3Pa, the sputtering power is 100W, and the thickness of the lanthanum nickelate layer is about 100 nm.
(d) Preparation of barium strontium zirconate titanate film
The perovskite oxide barium strontium zirconate titanate ceramic is used as a sputtering target material, and a barium strontium zirconate titanate film is deposited in a radio frequency magnetron sputtering mode. The sputtering temperature is room temperature, and the sputtering atmosphere is Ar and O2Mixed atmosphere, Ar gas flow controlled at 60sccm, O2The gas flow is controlled at 15sccm, the sputtering pressure is 1.4Pa, the sputtering power is 96-98W, and the thickness of the barium strontium zirconate titanate film layer is 300 nm.
(e) Preparation of the Top electrode
And covering the mask plate on the super paraelectric barium strontium titanate dielectric film layer at room temperature, and depositing the top electrode by using a direct current sputtering mode by using a gold foil target as a sputtering target material. The sputtering atmosphere was air, the discharge current was 9mA, and the sputtering power was 80W. The top electrode diameter was 200 μm.
The prepared electrode structure is shown in fig. 1 and sequentially comprises a substrate 1, a bottom electrode 2, a buffer layer 3, a barium strontium zirconate titanate film 4 and a top electrode 5 from bottom to top.
As shown in fig. 2, the high-resolution transmission electron microscope and selective diffraction results of the barium strontium zirconate titanate film prepared in this example show that the barium strontium zirconate titanate film prepared at room temperature has well-dispersed nano-polar regions, and satisfies the grain size region with strict superparaelectric property.
The single-sided hysteresis loop result of the barium strontium zirconate titanate film prepared in the example is shown in FIG. 3, which is a thin-long hysteresis loop, and the recoverable energy density reaches 100J/cm through the calculation of the energy storage density3And the energy storage efficiency reaches 90 percent. The capacitance density and dielectric constant are shown in fig. 4 and 5, and both have good frequency stability.
Example 2
This example differs from example 1 in that: in the step (d), perovskite oxide barium titanate ceramic is used as a sputtering target material, the sputtering pressure is 1.2Pa, the sputtering power is 100W, the thickness of the barium titanate-based film is 350nm, and other steps and parameters are the same as those in the specific example 1.
Example 3
This example differs from example 1 in that: in the step (c), the sputtering temperature of the lanthanum nickelate buffer layer is 150 ℃; in the step (d), the sputtering temperature of the barium strontium zirconate titanate film is 150 ℃, and other steps and parameters are the same as those of the specific example 1.
Example 4
This example differs from example 1 in that: in the step (c), the sputtering temperature of the lanthanum nickelate buffer layer is 150 ℃; in the step (d), perovskite oxide barium titanate ceramic is used as a sputtering target material, the sputtering temperature of the barium titanate-based film is 150 ℃, the sputtering pressure is 1.2Pa, the sputtering power is 100W, the thickness of the barium titanate-based film is 350nm, and other steps and parameters are the same as those in the specific example 1.
Example 5
This example differs from example 1 in that: in the step (d), the thickness of the barium strontium zirconate titanate film was 900nm, and other steps and parameters were the same as those in embodiment 1.
Through electrical property tests, the barium titanate-based films prepared by various embodiments have thin and long ferroelectric hysteresis lines at the sputtering temperature of 150 ℃ and different thicknesses, the energy storage density and the energy storage efficiency of the barium titanate-based films are not greatly different from those of example 1, and the recoverable energy density is basically stable at 100J/cm3The energy storage efficiency is basically stabilized at about 90 percent. Both the capacitance density and the dielectric constant have good frequency stability. Other examples 2-5 performed similarly to example 1.
Example 6
This example differs from example 1 in that: in the step (d), the thickness of the barium strontium zirconate titanate film was 40nm, and other steps and parameters were the same as those in embodiment 1.
Example 7
This example differs from example 1 in that: in the step (d), the thickness of the barium strontium zirconate titanate film was 20nm, and other steps and parameters were the same as those in embodiment 1.
Example 8
This example differs from example 1 in that: in the step (d), the thickness of the barium strontium zirconate titanate film was 10nm, and other steps and parameters were the same as those in embodiment 1.
Through electrical property tests, the barium strontium titanate-based film prepared by the embodiment has larger capacitance density and dielectric constant, and the capacitance density and dielectric constant results are shown in fig. 6 and 7, and the capacitance density reaches 2450nF/cm2The dielectric constant reached 304(@1 kHz).
Example 9
In the step (c), the thickness of the lanthanum nickelate buffer layer is 25 nm; in the step (d), the thickness of the barium strontium zirconate titanate film is 10 nm.
Through electrical property tests, the capacitance density of the barium strontium zirconate titanate film prepared by the embodiment reaches 2440nF/cm2The dielectric constant reached 96(@1 kHz).
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The medium-low temperature preparation method of the barium titanate-based super-paramagnetic thin film is characterized by comprising the following steps of: the method comprises the following steps:
and sputtering and depositing a lanthanum nickelate buffer layer and a barium titanate base film on the silicon substrate sputtered with the bottom electrode in sequence, wherein the deposition temperature is 25-150 ℃, and the preparation method is obtained.
2. The method for medium-low temperature production of a barium titanate-based superparamagnetic film according to claim 1, characterized in that: when the barium titanate-based film is subjected to magnetron sputtering, the atmosphere is a mixed atmosphere of argon and oxygen;
further, the barium titanate-based film is made of pure barium titanate, barium zirconate titanate or barium strontium zirconate titanate.
3. The method for medium-low temperature production of a barium titanate-based superparamagnetic film according to claim 1, characterized in that: when the barium titanate-based film is subjected to magnetron sputtering, the pressure of magnetron sputtering is 1.2-1.4Pa, and the sputtering power is 96-100W.
4. The method for medium-low temperature production of a barium titanate-based superparamagnetic film according to claim 1, characterized in that: when the buffer layer is subjected to magnetron sputtering, the atmosphere is a mixed atmosphere of argon and oxygen, the pressure of magnetron sputtering is 0.3Pa, and the sputtering power is 100W;
or when the bottom electrode is sputtered by magnetron sputtering, the atmosphere is argon, the gas pressure is 0.3Pa, and the sputtering power is 55W.
5. A barium titanate-based superparamagnetic film, characterized by: prepared by the preparation method of any one of claims 1 to 4.
6. The barium titanate-based superparamagnetic film according to claim 5, wherein: the barium titanate-based superparamagnetic film has a thickness of 10 to 40 nm.
7. An electrode, characterized by: the silicon substrate, the bottom electrode, the buffer layer, the barium titanate-based film and the top electrode are sequentially arranged from the silicon substrate to the top electrode, and the buffer layer is made of a perovskite-structured conductive oxide lanthanum nickelate matched with the barium titanate-based film in a lattice mode.
8. The electrode of claim 7, wherein: the silicon substrate is semiconductor Si/SiO2A substrate;
or, the bottom electrode is an inert metal with metal activity lower than that of hydrogen;
further, the bottom electrode is a composite electrode of one or two of copper, gold, silver, platinum and titanium;
furthermore, the bottom electrode is a composite electrode of a titanium layer and a platinum layer;
further, the thickness of the bottom electrode is 150 nm.
9. The electrode of claim 6, wherein: the thickness of the buffer layer is 25-100 nm;
or, the barium titanate-based film has a thickness of 10 to 900 nm;
or the top electrode is made of noble metal;
furthermore, the top electrode is made of gold, silver or platinum;
furthermore, the top electrode is made of gold.
10. Use of the barium titanate-based superparaelectric film of claim 5 in the manufacture of capacitors, power tuning devices, pulsed power systems, silicon integrated circuits, and thin film transistor devices.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011015541.3A CN112151357B (en) | 2020-09-24 | 2020-09-24 | Barium titanate-based super-paraelectric film and low-and-medium-temperature sputtering preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011015541.3A CN112151357B (en) | 2020-09-24 | 2020-09-24 | Barium titanate-based super-paraelectric film and low-and-medium-temperature sputtering preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112151357A true CN112151357A (en) | 2020-12-29 |
| CN112151357B CN112151357B (en) | 2023-03-21 |
Family
ID=73896547
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011015541.3A Active CN112151357B (en) | 2020-09-24 | 2020-09-24 | Barium titanate-based super-paraelectric film and low-and-medium-temperature sputtering preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112151357B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112921288A (en) * | 2021-01-25 | 2021-06-08 | 齐鲁工业大学 | Preparation of high-energy-storage-density BaTiO3Ferroelectric thin film method, product and application thereof |
| CN114438450A (en) * | 2022-01-05 | 2022-05-06 | 上海交通大学 | Perovskite thin film and low-temperature preparation method and device thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001045864A1 (en) * | 1999-12-22 | 2001-06-28 | Advanced Technology Materials, Inc. | Low temperature process for high density thin film integrated capacitors, and amorphously frustrated ferroelectric materials therefor |
| US6255122B1 (en) * | 1999-04-27 | 2001-07-03 | International Business Machines Corporation | Amorphous dielectric capacitors on silicon |
| WO2002002842A2 (en) * | 2000-06-29 | 2002-01-10 | Applied Materials, Inc. | Low temperature cvd bst deposition |
| CN101084581A (en) * | 2004-12-21 | 2007-12-05 | 皇家飞利浦电子股份有限公司 | Semiconductor device with a superparaelectric gate insulator |
| CN104419895A (en) * | 2013-09-09 | 2015-03-18 | 中国科学院上海硅酸盐研究所 | Method for preparing strontium ruthenate film with highly (001) preferred orientation at low temperature |
| CN106601903A (en) * | 2016-12-06 | 2017-04-26 | 山东大学苏州研究院 | C axis height-oriented barium titanate film and in-situ preparation method of the same at medium and low temperature |
| US20180327317A1 (en) * | 2017-05-11 | 2018-11-15 | Korea Advanced Institute Of Science And Technology | Non-Ferroelectric High Dielectric and Preparation Method Thereof |
-
2020
- 2020-09-24 CN CN202011015541.3A patent/CN112151357B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6255122B1 (en) * | 1999-04-27 | 2001-07-03 | International Business Machines Corporation | Amorphous dielectric capacitors on silicon |
| WO2001045864A1 (en) * | 1999-12-22 | 2001-06-28 | Advanced Technology Materials, Inc. | Low temperature process for high density thin film integrated capacitors, and amorphously frustrated ferroelectric materials therefor |
| WO2002002842A2 (en) * | 2000-06-29 | 2002-01-10 | Applied Materials, Inc. | Low temperature cvd bst deposition |
| CN101084581A (en) * | 2004-12-21 | 2007-12-05 | 皇家飞利浦电子股份有限公司 | Semiconductor device with a superparaelectric gate insulator |
| CN104419895A (en) * | 2013-09-09 | 2015-03-18 | 中国科学院上海硅酸盐研究所 | Method for preparing strontium ruthenate film with highly (001) preferred orientation at low temperature |
| CN106601903A (en) * | 2016-12-06 | 2017-04-26 | 山东大学苏州研究院 | C axis height-oriented barium titanate film and in-situ preparation method of the same at medium and low temperature |
| US20180327317A1 (en) * | 2017-05-11 | 2018-11-15 | Korea Advanced Institute Of Science And Technology | Non-Ferroelectric High Dielectric and Preparation Method Thereof |
Non-Patent Citations (1)
| Title |
|---|
| KUN WANG,ETC.: "《Superparaelectric (Ba0.95,Sr0.05)(Zr0.2,Ti0.8)O3 Ultracapacitors》", 《ADVANCED ENERGY MATERIALS》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112921288A (en) * | 2021-01-25 | 2021-06-08 | 齐鲁工业大学 | Preparation of high-energy-storage-density BaTiO3Ferroelectric thin film method, product and application thereof |
| CN112921288B (en) * | 2021-01-25 | 2023-04-07 | 齐鲁工业大学 | Preparation of high-energy-storage-density BaTiO 3 Ferroelectric thin film method, product and application thereof |
| CN114438450A (en) * | 2022-01-05 | 2022-05-06 | 上海交通大学 | Perovskite thin film and low-temperature preparation method and device thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112151357B (en) | 2023-03-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhang et al. | ALD preparation of high-k HfO 2 thin films with enhanced energy density and efficient electrostatic energy storage | |
| CN112151357B (en) | Barium titanate-based super-paraelectric film and low-and-medium-temperature sputtering preparation method and application thereof | |
| JP2016029708A (en) | Thin-film dielectric and thin-film capacitor element | |
| US20210184100A1 (en) | Electret | |
| Zhang et al. | Flexible antiferroelectric thick film deposited on nickel foils for high energy‐storage capacitor | |
| Hou et al. | Significantly enhanced energy storage performance in BiFeO 3/BaTiO 3/BiFeO 3 sandwich-structured films through crystallinity regulation | |
| Yao et al. | Bi0· 5Na0· 5TiO3–Sr0. 85Bi0· 1TiO3 ceramics with high energy storage properties and extremely fast discharge speed via regulating relaxation temperature | |
| Shen et al. | Enhanced energy-storage performance of an all-inorganic flexible bilayer-like antiferroelectric thin film via using electric field engineering | |
| Nguyen et al. | High-performance energy storage and breakdown strength of low-temperature laser-deposited relaxor PLZT thin films on flexible Ti-foils | |
| US9506153B2 (en) | Integrated composite perovskite oxide heterostructure | |
| CN1755848A (en) | Dielectric thin film, thin film capacitor element, and method for manufacturing thin film capacitor element | |
| CN106601903A (en) | C axis height-oriented barium titanate film and in-situ preparation method of the same at medium and low temperature | |
| WO2021208276A1 (en) | Bismuth ferrite film material, method for integrally preparing bismuth ferrite film on silicon substrate at low temperature, and application | |
| Ye et al. | Dielectric and electrocaloric responses of Ba (Zr 0.2 Ti 0.8) O 3 bulk ceramics and thick films with sintering aids | |
| JP2007234726A (en) | Semiconductor device and its fabrication process | |
| CN105296946B (en) | A kind of the bismuth niobate calcium thin film material system and preparation method height-oriented with a axles | |
| Lamichhane et al. | Studies on energy storage properties of BFO/WO3 bilayer thin film capacitor | |
| CN110863184A (en) | Wide-working-temperature lead-free epitaxial film and preparation method thereof | |
| JP2006140136A (en) | Dielectric thin film, thin-film dielectric device, and its manufacturing method | |
| Li et al. | Preferred orientation and ferroelectric properties of lead zirconate titanate thin films | |
| CN100431157C (en) | Oxide ferroelectric memory cell and prepn process | |
| CN112921288B (en) | Preparation of high-energy-storage-density BaTiO 3 Ferroelectric thin film method, product and application thereof | |
| CN113718330B (en) | Low-dielectric-constant high-entropy film and preparation method thereof | |
| CN115959905B (en) | Lead zirconate titanate and magnesium oxide vertical self-assembled nano composite dielectric energy storage film and preparation method thereof | |
| CN117049597B (en) | Preparation method of high-energy-ratio dielectric capacitor and dielectric capacitor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20231113 Address after: 250353 University Road, Changqing District, Ji'nan, Shandong Province, No. 3501 Patentee after: OuYang Jun Patentee after: Qilu University of Technology (Shandong Academy of Sciences) Address before: 250353 University Road, Changqing District, Ji'nan, Shandong Province, No. 3501 Patentee before: OuYang Jun |
|
| TR01 | Transfer of patent right |