CN106653360A - High-energy-density thin film capacitor and preparation method thereof - Google Patents
High-energy-density thin film capacitor and preparation method thereof Download PDFInfo
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- CN106653360A CN106653360A CN201611226336.5A CN201611226336A CN106653360A CN 106653360 A CN106653360 A CN 106653360A CN 201611226336 A CN201611226336 A CN 201611226336A CN 106653360 A CN106653360 A CN 106653360A
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- 239000010409 thin film Substances 0.000 title claims abstract description 62
- 239000003990 capacitor Substances 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000010408 film Substances 0.000 claims abstract description 128
- 238000000034 method Methods 0.000 claims abstract description 36
- 229910052751 metal Inorganic materials 0.000 claims abstract description 31
- 239000002184 metal Substances 0.000 claims abstract description 31
- 230000008569 process Effects 0.000 claims abstract description 28
- 239000000758 substrate Substances 0.000 claims abstract description 22
- 238000001704 evaporation Methods 0.000 claims abstract description 16
- 230000008020 evaporation Effects 0.000 claims abstract description 12
- 238000005566 electron beam evaporation Methods 0.000 claims description 18
- 229910052760 oxygen Inorganic materials 0.000 claims description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 16
- 239000001301 oxygen Substances 0.000 claims description 16
- 230000005611 electricity Effects 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 11
- 229910000807 Ga alloy Inorganic materials 0.000 claims description 10
- 238000005137 deposition process Methods 0.000 claims description 10
- 229910004247 CaCu Inorganic materials 0.000 claims description 8
- 239000012528 membrane Substances 0.000 claims description 8
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- 238000005520 cutting process Methods 0.000 claims description 5
- 150000002602 lanthanoids Chemical class 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 238000010884 ion-beam technique Methods 0.000 claims description 4
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 229910021076 Pd—Pd Inorganic materials 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 230000003139 buffering effect Effects 0.000 claims 1
- 238000000151 deposition Methods 0.000 abstract description 8
- 238000004146 energy storage Methods 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 230000010287 polarization Effects 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 230000008021 deposition Effects 0.000 abstract description 2
- 239000011572 manganese Substances 0.000 description 21
- 238000005516 engineering process Methods 0.000 description 12
- 239000010936 titanium Substances 0.000 description 12
- 239000011575 calcium Substances 0.000 description 6
- 229910002966 CaCu3Ti4O12 Inorganic materials 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 238000007738 vacuum evaporation Methods 0.000 description 4
- 229910001316 Ag alloy Inorganic materials 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 229910052746 lanthanum Inorganic materials 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- UPWOEMHINGJHOB-UHFFFAOYSA-N oxo(oxocobaltiooxy)cobalt Chemical compound O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910002244 LaAlO3 Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical group [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- KPWQKEUUJCLATM-UHFFFAOYSA-N [Ca].[Cu].[Ti] Chemical compound [Ca].[Cu].[Ti] KPWQKEUUJCLATM-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- HAUBPZADNMBYMB-UHFFFAOYSA-N calcium copper Chemical compound [Ca].[Cu] HAUBPZADNMBYMB-UHFFFAOYSA-N 0.000 description 1
- AOWKSNWVBZGMTJ-UHFFFAOYSA-N calcium titanate Chemical compound [Ca+2].[O-][Ti]([O-])=O AOWKSNWVBZGMTJ-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000001451 molecular beam epitaxy Methods 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N nickel(II) oxide Inorganic materials [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/33—Thin- or thick-film capacitors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G13/00—Apparatus specially adapted for manufacturing capacitors; Processes specially adapted for manufacturing capacitors not provided for in groups H01G4/00 - H01G11/00
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
- H01G4/08—Inorganic dielectrics
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
Abstract
The invention relates to a high-energy-density thin-film capacitor and a preparation method thereof. The invention belongs to the technical field of physical power supplies. A high energy density film capacitor is characterized in that: the high energy density thin film capacitor structure is Si substrate/metal electrode/dielectric film/buffer layer/magnetic film/metal electrode; the magnetic film provides a magnetic field with certain intensity perpendicular to the dielectric medium direction, so that the dielectric polarization in the dielectric medium film is enhanced, and the capacitance and the energy density can be effectively improved. The buffer layer metal film is used for assisting the epitaxial growth of the magnetic film and ensuring that the magnetic film has better magnetic anisotropy in the vertical direction. When the thin film capacitor with the structure is prepared, the dielectric thin film, the magnetic thin film and the electrode are deposited by adopting an evaporation process, and the continuous deposition of a capacitor device can be realized. The thin film capacitor has the advantages of high power density, high energy density, long service life, high energy storage, high working voltage, wide application range, continuous preparation of capacitor devices, mass production and the like.
Description
Technical field
The invention belongs to physical power source technical field, more particularly to a kind of high-energy-density thin-film capacitor and its preparation side
Method.
Background technology
At present, the energy storage density of electric capacity depends mainly on capacitance and breakdown voltage, E=1/2CV2.Current capacitor
Part (including conventional capacitive and ultracapacitor etc.) is main to improve electricity by reducing interelectrode distance, increase electrode specific surface area
Capacitance and energy density.On this basis, by selecting to change dielectric dielectric property, its breakdown voltage and relative dielectric are improved
Constant is also the effective way for improving capacitive energy density.
Patent (CN200910134160.4 and CN200910145423.1) proposes the concept of magnetocapacitance energy storage, by magnetic
Field affects dielectric dielectric property.Based on the structure of plane-parallel capacitor, the positive and negative electrode of electric capacity is two-layer magnetic in the patent
Property metal material, centre be dielectric layer.Magnetic metal is provided perpendicular to the magnetic field in dielectric direction, the work in some strength magnetic field
With dielectric dielectric property is changed, the charge density increase of electrode and dielectric interface storage is made, so as to improve capacitance
And energy density.The patent proposes that dielectric substance used is TiO2Or barium titanate.However, the dielectric substance (titanate)
And magnetic element is not contained, also have no and the report for affecting is produced on above-mentioned material electricity and dielectric property with regard to magnetic field.The patent
Thin dielectric film and magnetic membrane material and its property are not clearly proposed, does not have to be proposed with regard to the preparation technology of thin-film capacitor yet
Related claim.
It is one of technological approaches of acquisition High energy density capacitive to improve dielectric Constant.Research is it has proven convenient that one
Under fixed condition, magnetic field will affect dielectric electrical properties and dielectric properties.For the core material preparation technology of electric capacity, previously
Patent (application number：CN201610031323.6, CN201310743770.0) more calcium titanate Copper thin film is prepared using solwution method, with
LaAlO3As base material, the precursor liquid containing calcium copper titanium is spun in substrate, finally again heat treatment forms film.On
The advantage for stating process is with low cost, it is not necessary to complex device, but is readily incorporated in thin dielectric film preparation process miscellaneous
Prepared by matter, the serialization for being not suitable for large area film, and presence is not easy compatible, substrate material with thin magnetic film preparation technology
Material also costly the problems such as.
The content of the invention
The present invention for solve known technology present in technical problem and provide a kind of high-energy-density thin-film capacitor and its
Preparation method.
This patent goes out a kind of high-energy-density thin-film capacitor, and it is similar to that plane-parallel capacitor, upper and lower double layer of metal
Membrane electrode, mid portion is made up of thin dielectric film with one layer of nanometer magnetic metal film.Magnetic metallic film can hang down
The straight magnetic field that sufficient intensity is provided on dielectric direction, changes dielectric dielectric polarization, effectively improves dielectric electricity
Capacity, is expected to obtain the novel thin film electric capacity of higher energy density.This patent clearly proposes dielectric to be doped with magnetic unit
CaCu 3 Ti 4 O (the M-CaCu of element3Ti4O12, the magnetic element of M representative doping) and film, magnetic metallic film is manganese gallium alloy.
Thin-film capacitor structure proposed by the present invention is：Substrate/metal electrode/thin dielectric film/cushion/thin magnetic film/
Metal electrode.Magnetic metallic film is provided perpendicular to dielectric direction, some strength magnetic field, can be changed dielectric inside and is situated between
Electric polarization, effectively improves dielectric capacitance and energy density.In the capacitance structure that this patent is proposed, thin dielectric film,
Thin magnetic film and electrode are prepared using evaporation technology, and prepared by the serialization for realizing each layer film of capacitor element, and can
To obtain the thin magnetic film of the thin dielectric film with good dielectric property and stronger perpendicular magnetic anisotropic, meet and prepare Gao Gong
The requirement of rate density, high-energy-density and long-life energy storage thin-film capacitor.
An object of the present invention is to provide a kind of high with power density, energy density height, long-life energy storage, work electricity
Pressure is high, with low cost, high-energy-density thin-film capacitor the features such as have wide range of applications.
High-energy-density thin-film capacitor of the present invention is adopted the technical scheme that：
A kind of high-energy-density thin-film capacitor, is characterized in：High-energy-density thin-film capacitor structure is Si substrates/metal electricity
Pole/thin dielectric film/cushion/thin magnetic film/metal electrode；Thin dielectric film, thin magnetic film and electrode are using evaporation
Process deposits are formed, and cushion is located at thin magnetic film and thin dielectric membrane interface.
High-energy-density thin-film capacitor of the present invention can also be adopted the following technical scheme that：
Described high-energy-density thin-film capacitor, is characterized in：Thin dielectric film is the CaCu 3 Ti 4 O of doped magnetic element,
Thin dielectric film thickness is 0.3 μm -3 μm, and the valent state of doped chemical, part substitutes Ca or Ti, occupies corresponding lattice position
Put.
Described high-energy-density thin-film capacitor, is characterized in：The magnetic element of doping is Ni, Co, Mn, La or group of the lanthanides unit
Element, doping content mole ratio is less than 5%.
Described high-energy-density thin-film capacitor, is characterized in：Cushion is Pt (001) or Pd (001) film, and thickness is
0.1-0.3μm。
Described high-energy-density thin-film capacitor, is characterized in：Magnetic membrane material is MnxGa alloys, x=1.1-1.9,
Magnetic film thickness is 0.05 μm -0.5 μm.
The second object of the present invention is to provide one kind and has process is simple, and capacitor element serialization is prepared, is advantageously implemented
The system of the high-energy-density thin-film capacitor of the features such as mass production, product power density height, energy density height, long-life energy storage
Preparation Method.
The preparation method of high-energy-density thin-film capacitor of the present invention is adopted the technical scheme that：
A kind of preparation method of high-energy-density thin-film capacitor, is characterized in：Preparation Si substrates/metal electrode/cushion/
During thin dielectric film/thin magnetic film/metal electrode structure thin-film capacitor, thin dielectric film is prepared using electron beam evaporation process,
Underlayer temperature in thin dielectric film deposition process is 600 DEG C -900 DEG C, is passed through oxygen flow for 10sccm-60sccm.
The preparation method of high-energy-density thin-film capacitor of the present invention can also be adopted the following technical scheme that：
The preparation method of described high-energy-density thin-film capacitor, is characterized in：Electron beam evaporation process prepares dielectric
During film, deposit the Au that a layer thickness is 0.05 μm on thin dielectric film surface initially with electron beam evaporation process or Pd is thin
Film, then obtains Pt the or Pd buffer layer thin films of a layer thickness 0.1-0.3 μm by ion beam cutting technique, and by Au-Pt,
Pd-Pd metal bondings are transferred on thin dielectric film.
The preparation method of described high-energy-density thin-film capacitor, is characterized in：Using vacuum evaporation technology deposited magnetic
Film, thin magnetic film is MnxGa alloys, x=1.1-1.9, underlayer temperature is 150 DEG C -380 DEG C in deposition process, Mn sources and Ga
The evaporating temperature in source is respectively 960 DEG C -990 DEG C and 1000 DEG C -1060 DEG C.
Thin-film capacitor that the technology of the present invention includes and preparation method thereof：
1. the present invention proposes that high-energy-density thin-film capacitor structure is：Substrate/metal electrode/thin dielectric film/cushion/
Thin magnetic film/metal electrode.Wherein, dielectric layer employs the calcium copper titanate film (M- of a certain amount of magnetic element of adulterating
CaCu3Ti4O12, M represents magnetic element), the magnetic element of doping includes Ni, Co, Mn, La and lanthanide series etc., and film is thick
Spend for 0.3 μm -3 μm.According to the valent state of doped chemical, its part substitutes Ca or Ti, occupies corresponding lattice position, adulterates
Concentration is generally less than 5% (mole ratio).By apply some strength, perpendicular to dielectric magnetic field, make dielectric micro-
Seeing the dielectric polarization of structure strengthens, and improves the relative dielectric constant and magnitude of the stored charge of dielectric layer, is capable of achieving high-energy-density
Thin-film capacitor.By optimizing doped magnetic element mole and doped chemical valence state, effective control foreign atom is in lattice
Position, can change dielectric microcosmic electrical properties, reduce dielectric loss.
Magnetic membrane material is MnxGa alloys (x=1.1-1.9), thickness is about 0.05 μm -0.5 μm.It is logical to adjust containing for Mn
Amount (x values) and thin magnetic film sedimentary condition, control the size and Orientation of net saturation magnetic moment, make film have very strong perpendicular magnetic
Anisotropy, there is provided magnetic field intensity in 0.1T-1T scopes.
Pt (001) or Pd (001) that a layer thickness is about 0.1-0.3 μm are designed between thin magnetic film and thin dielectric film
Film is used as cushion.Due to MnxThe perpendicular magnetic anisotropic and magnetic field intensity of Ga thin magnetic films and the surface texture in base
Closely related, Pt films have splendid flatness, by growing one layer of Pt (001) transition zone to optimization in dielectric surface
MnxThe perpendicular magnetic anisotropic of Ga films has important function.
By Au, Ag, Pd, Pt etc., one or more metals are constituted the metal electrode material of electric capacity, thickness of electrode about 0.1-0.5
μm。
2. the present invention proposes the preparation method of thin-film capacitor.The each layer membrane materials of electric capacity (including electrode) adopts evaporator man
It is prepared by skill.To be commercialized silicon chip as substrate (300 μm -400 μm of thickness), initially with electron beam evaporation process deposited metal electricity
Pole.Second step, still using electron beam evaporation process, co-evaporates CuO, CaO, TiO2And magnetic metal oxide is (such as Co2O3,
NiO, La2O3Deng), while the oxygen of certain flow is passed through near the evaporation boat of evaporation within the chamber, thin dielectric film deposition process
Middle underlayer temperature is maintained at constant in the range of 600 DEG C -900 DEG C.By the evaporation speed for adjusting oxygen flow and different compounds
Rate, controls M-CaCu3Ti4O12Component ratio.After thin dielectric film deposition is finished, underlayer temperature is kept at 300 DEG C -500
It is DEG C constant, the Au films that a layer thickness is about 0.05 μm are deposited in dielectric surface using electron beam evaporation process.3rd step, leads to
Cross ion cutting technique the Pt (001) or Pd (001) film of 0.1 μm -0.3 μm of a layer thickness are transferred on thin dielectric film,
As the epitaxial substrate of thin magnetic film.4th step, is about using high vacuum evaporation technique (such as molecular beam epitaxy) growth thickness
0.05 μm -0.5 μm of MnxGa films.Finally, Au Top electrodes are prepared using electron beam evaporation.
The present invention has the advantages and positive effects that：
High-energy-density thin-film capacitor and preparation method thereof as a result of the brand-new technical scheme of the present invention, with existing skill
Art is compared, the invention has the characteristics that：
1st, the present invention proposes in thin-film capacitor structure that dielectric layer adopts magnetic-doped M-CaCu3Ti4O12Film, room temperature
Under relative dielectric constant be 103-104Magnitude, and relative dielectric constant hardly affected by frequency and temperature.By magnetic
Field action can further improve its relative dielectric constant, so as to increase capacitance.By controlling doped chemical mole and chemistry
Valence state, can effectively reduce dielectric loss.Meanwhile, CaCu 3 Ti 4 O sill has good dielectric strength (foreign countries' report thickness
For 0.5 μm of dielectric film breakdown voltage more than 10V).Therefore, magnetic-doped M-CaCu3Ti4O12Film is highly suitable as
Dielectric, is capable of achieving high power density, high-energy-density and long-life thin-film capacitor, and practical ranges are extensive.
2nd, the present invention proposes the Mn that one layer of nanoscale is inserted in the electric capacity of parallel-plate structurexGa alloy firms, there is provided
Some strength, magnetic field perpendicular to dielectric direction.Employ the magnetic that relatively simple device architecture realizes thin-film capacitor
Field is built-in.
3rd, the present invention in one layer of Pt (001) of thin magnetic film and thin dielectric film interface or Pd (001) films as delaying
Layer is rushed, Mn is aided inxThe epitaxial growth of Ga thin magnetic films, it is to avoid MnxThe perpendicular magnetic anisotropic of Ga films is by thin dielectric film
Affect.
4th, the present invention prepares dielectric, thin magnetic film and electrode layer using evaporation technology technology, realizes capacitor element each
Prepared by the serialization of layer film, be advantageously implemented the mass production of high performance thin film storage capacitor.
Description of the drawings
Fig. 1 is high-energy-density thin-film capacitor structural representation of the present invention；
In figure, 1-Si piece substrates, 300 μm -400 μm of thickness；2- hearth electrode Au-Ag alloys, 0.1 μm -0.3 μm of thickness；3-
Dielectric M-CaCu3Ti4O12Film, 0.3 μm -3 μm of thickness；4- cushion Pt or Pd films, 0.1 μm -0.3 μm of thickness；5- magnetic
Property layer, MnxGa alloy firms, 0.05 μm -0.5 μm of thickness；6- top electrode layers, Au-Ag alloys, 0.1 μm -0.3 μm of thickness；7-
Metal electrode contact point；The built-in magnetic field H of 8-, perpendicular to dielectric layer direction.
Fig. 2 is dielectric substance preparation technology schematic flow sheet.
Specific embodiment
For the content of the invention, feature and effect of the present invention can be further appreciated that, following examples are hereby enumerated, and coordinate accompanying drawing
Describe in detail as follows：
Refering to accompanying drawing 1 and Fig. 2.
Embodiment 1
A kind of high-energy-density thin-film capacitor, its structure is：Substrate/metal electrode/thin dielectric film/cushion/magnetic
Film/metal electrode.Metal electrode, thin dielectric film and thin magnetic film in capacitance structure be thin etc., and each layer adopts evaporator man
Skill is prepared from.
The present embodiment preparation process：
Step one, to be commercialized Si pieces as substrate -1 (300 μm -400 μm of thickness), successively using acetone and deionized water
Cleaning Si pieces, obtain the substrate with clean surface.
Step 2, is about 0.1 μm -0.3 μm of Au films, as the bottom of electric capacity using electron beam evaporation process deposit thickness
Electrode -2.Background vacuum pressure is 10-4Pa, by controlling beam power hearth electrode thickness is controlled, and evaporation power is about
1250W-1400W, the substrate of evaporation process process is not heated.
Step 3, the same thin dielectric film -3 for being about 0.3 μm -3 μm using electron beam evaporation process deposit thickness.Electricity is situated between
Matter thin-film material be adulterate 3%Ni CaCu 3 Ti 4 O, i.e. CaCu3NixTi4-xO12-2x(x=0.6).Background vacuum pressure reaches 10-4Oxygen is passed through toward in vacuum chamber after Pa, flow is 10sccm-60sccm, CuO, CaO, TiO are co-evaporated under oxygen atmosphere2With
And NiO, beam power by the beam power for adjusting different oxide sources, controls Cu, Ti, Ca in 150W-750W scopes
With the component ratio and film integral thickness of Ni.The oxygen being passed through is used to promote the combination reaction between different oxides abundant
Carry out, it is ensured that the CaCu for obtaining3NixTi4-xO12-2xOxygen element content composite chemical metering ratio.In thin dielectric film deposition process
Middle underlayer temperature is maintained at constant in the range of 600 DEG C -900 DEG C.After depositing operation terminates, electron beam and silicon are closed, after
It is continuous to be passed through oxygen, make thin dielectric film lower the temperature under oxygen atmosphere.
Step 4, depositing a layer thickness first on thin dielectric film surface using electron beam evaporation, to be about 0.05 μm of Au thin
Film, sedimentary condition is essentially identical with step 2, and the thickness of Au is controlled by reducing sedimentation time.By ion beam cutting technique etc.
To Pt (001) buffer layer thin film -4 of a layer thickness 0.1-0.3 μm, and thin dielectric film is transferred to by Au-Pt metal bondings
On, as the epitaxial substrate of thin magnetic film.
Step 5, using high vacuum evaporation process deposits thickness 0.05 μm -0.5 μm of Mn is aboutxGa alloy (x=1.1-
1.9) film -5.Vacuum pressure during whole is maintained at 10-6Pa-10-7Pa magnitudes, underlayer temperature is about 150 DEG C -380 DEG C.
The evaporating temperature in Mn sources and Ga sources is respectively 960 DEG C -990 DEG C and 1000 DEG C -1060 DEG C.The logical content (x values) for adjusting Mn and
The conditions such as depositing temperature, control the size and Orientation in the magnetic field -8 that film is provided, and make film have very strong perpendicular magnetic respectively to different
Property.The magnetic field intensity that film is provided can reach 0.1T-1T.
Step 6, the Au that a layer thickness is about 0.1-0.3 μm is deposited using electron beam evaporation process on thin magnetic film surface
Film, as the top electrode -6 of electric capacity.Deposition process conditions are identical with step 2.
Embodiment 2
A kind of high-energy-density thin-film capacitor, its structure is：Substrate/metal electrode/thin dielectric film/cushion/magnetic
Film/metal electrode.The present embodiment capacitor element preparation technology detailed process is as follows：
Step one, to be commercialized Si pieces as substrate -1 (300 μm -400 μm of thickness), successively using acetone and deionized water
Cleaning Si pieces, obtain the substrate with clean surface.
Step 2, using electron beam evaporation process deposit thickness 0.1 μm -0.3 μm of Au-Ag alloy firms are about, as
The hearth electrode -2 of electric capacity.Background vacuum pressure is 10-4Pa, by controlling beam power hearth electrode thickness, evaporation power are controlled
About 1250W-1400W, the substrate of evaporation process process is not heated.
Step 3, the same thin dielectric film -3 for being about 0.3 μm -3 μm using electron beam evaporation process deposit thickness.Electricity is situated between
Matter thin-film material be adulterate 1%La CaCu 3 Ti 4 O, i.e. Ca1-xLaxCu3Ti4O12+x/2(x=0.2).Background vacuum pressure reaches
10-4Oxygen is passed through toward in vacuum chamber after Pa, flow is 10sccm-60sccm, CuO, CaO, TiO are co-evaporated under oxygen atmosphere2
And La2O3, beam power in 150W-900W scopes, by the beam power for adjusting different oxide sources, control Cu,
The component ratio and film integral thickness of Ti, Ca and La.The oxygen being passed through is used to promote the chemical combination between different oxides anti-
Should fully carry out, it is ensured that the Ca for obtaining1-xLaxCu3Ti4O12+x/2(x=0.2) oxygen element content composite chemical metering ratio.In electricity Jie
Underlayer temperature is maintained at constant in the range of 600 DEG C -900 DEG C in matter film deposition process.After depositing operation terminates, electron beam is closed
And silicon, continue to be passed through oxygen, make thin dielectric film lower the temperature under oxygen atmosphere.
Step 4, depositing a layer thickness first on thin dielectric film surface using electron beam evaporation, to be about 0.05 μm of Pd thin
Film, deposition process is essentially identical with step 2, and the thickness of Pd is controlled by adjusting beam power.By ion beam cutting technique
When Pd (001) buffer layer thin film -4 of a layer thickness 0.1-0.3 μm, and thin dielectric is transferred to by Pd-Pd metal bondings
On film, as the epitaxial substrate of thin magnetic film.
Step 5, using high vacuum evaporation process deposits thickness 0.05 μm -0.5 μm of Mn is aboutxGa alloy (x=1.1-
1.9) film -5.Vacuum pressure during whole is maintained at 10-6Pa-10-7Pa magnitudes, underlayer temperature is about 150 DEG C -380 DEG C.
The evaporating temperature in Mn sources and Ga sources is respectively 960 DEG C -990 DEG C and 1000 DEG C -1060 DEG C.The logical content (x values) for adjusting Mn and
The conditions such as depositing temperature, control the size and Orientation in the magnetic field -8 that film is provided, and make film have very strong perpendicular magnetic respectively to different
Property.
Step 6, the Au that a layer thickness is about 0.1-0.3 μm is deposited using electron beam evaporation process on thin magnetic film surface
Film, as the top electrode -6 of electric capacity.Deposition process conditions are identical with step 2.
The present embodiment has described power density high, and energy density is high, long-life energy storage, and operating voltage is high, low cost
It is honest and clean, have wide range of applications, capacitor element continuous preparation process is advantageously implemented the good effects such as mass production.
Claims (8)
1. a kind of high-energy-density thin-film capacitor, is characterized in that：High-energy-density thin-film capacitor structure is Si substrates/metal electricity
Pole/thin dielectric film/cushion/thin magnetic film/metal electrode；Thin dielectric film, thin magnetic film and electrode are using evaporation
Process deposits are formed, and cushion is located at thin magnetic film and thin dielectric membrane interface.
2. high-energy-density thin-film capacitor according to claim 1, is characterized in that：Thin dielectric film is doped magnetic element
CaCu 3 Ti 4 O, thin dielectric film thickness be 0.3 μm -3 μm, the valent state of doped chemical, part substitute Ca or Ti, occupy phase
The lattice position answered.
3. high-energy-density thin-film capacitor according to claim 2, is characterized in that：The magnetic element of doping be Ni, Co,
Mn, La or lanthanide series, doping content mole ratio is less than 5%.
4. high-energy-density thin-film capacitor according to claim 1, is characterized in that：Cushion be Pt or Pd films, thickness
For 0.1-0.3 μm.
5. high-energy-density thin-film capacitor according to claim 1, is characterized in that：Magnetic membrane material is MnxGa alloys, x
=1.1-1.9, magnetic film thickness is 0.05 μm -0.5 μm.
6. a kind of preparation method of high-energy-density thin-film capacitor, is characterized in that：Prepare Si substrates/metal electrode/cushion/electricity
During dielectric film/thin magnetic film/metal electrode structure thin-film capacitor, thin dielectric film is prepared using electron beam evaporation process, electricity
Underlayer temperature in dielectric film deposition process is 600 DEG C -900 DEG C, is passed through oxygen flow for 10sccm-60sccm.
7. the preparation method of high-energy-density thin-film capacitor according to claim 6, is characterized in that：Electron beam evaporation process
When preparing thin dielectric film, it is 0.05 μm to deposit a layer thickness on thin dielectric film surface initially with electron beam evaporation process
Au or Pd films, then obtain Pt (001) or Pd (001) buffering of a layer thickness 0.1-0.3 μm by ion beam cutting technique
Layer film, and be transferred on thin dielectric film by Au-Pt, Pd-Pd metal bonding.
8. the preparation method of the high-energy-density thin-film capacitor according to claim 6 or 7, is characterized in that：Steamed using vacuum
Process deposits thin magnetic film is sent out, thin magnetic film is MnxGa alloys, x=1.1-1.9, in deposition process underlayer temperature be 150 DEG C-
380 DEG C, the evaporating temperature in Mn sources and Ga sources is respectively 960 DEG C -990 DEG C and 1000 DEG C -1060 DEG C.
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| CN111295463A (en) * | 2018-10-08 | 2020-06-16 | 深圳市汇顶科技股份有限公司 | Preparation method of calcium copper titanate film and calcium copper titanate film |
| CN112321298A (en) * | 2020-11-06 | 2021-02-05 | 中国科学院新疆理化技术研究所 | Perovskite-like thermistor material and preparation method thereof |
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| CN101826394A (en) * | 2009-02-24 | 2010-09-08 | 源泰投资股份有限公司 | Magnetic capacitor |
| CN103155063A (en) * | 2010-06-10 | 2013-06-12 | 日本硅电子技术株式会社 | Electrical energy storage device |
| US20140313637A1 (en) * | 2013-04-23 | 2014-10-23 | Alexander Mikhailovich Shukh | Magnetic Capacitor |
| US20150371777A1 (en) * | 2014-06-23 | 2015-12-24 | Industrial Technology Research Institute | Magnetic capacitor structures |
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| CN101826394A (en) * | 2009-02-24 | 2010-09-08 | 源泰投资股份有限公司 | Magnetic capacitor |
| CN103155063A (en) * | 2010-06-10 | 2013-06-12 | 日本硅电子技术株式会社 | Electrical energy storage device |
| US20140313637A1 (en) * | 2013-04-23 | 2014-10-23 | Alexander Mikhailovich Shukh | Magnetic Capacitor |
| US20150371777A1 (en) * | 2014-06-23 | 2015-12-24 | Industrial Technology Research Institute | Magnetic capacitor structures |
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| CN111295463A (en) * | 2018-10-08 | 2020-06-16 | 深圳市汇顶科技股份有限公司 | Preparation method of calcium copper titanate film and calcium copper titanate film |
| CN112321298A (en) * | 2020-11-06 | 2021-02-05 | 中国科学院新疆理化技术研究所 | Perovskite-like thermistor material and preparation method thereof |
| CN112321298B (en) * | 2020-11-06 | 2022-03-11 | 中国科学院新疆理化技术研究所 | Perovskite-like thermistor material and preparation method thereof |
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