CN106653360B - 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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- 239000003990 capacitor Substances 0.000 title claims abstract description 68
- 239000010409 thin film Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 239000010408 film Substances 0.000 claims abstract description 131
- 238000000034 method Methods 0.000 claims abstract description 38
- 229910052751 metal Inorganic materials 0.000 claims abstract description 31
- 239000002184 metal Substances 0.000 claims abstract description 31
- 239000000758 substrate Substances 0.000 claims abstract description 22
- 238000001704 evaporation Methods 0.000 claims abstract description 16
- 238000000151 deposition Methods 0.000 claims abstract description 12
- 230000008020 evaporation Effects 0.000 claims abstract description 12
- 230000008021 deposition Effects 0.000 claims abstract description 7
- 238000005566 electron beam evaporation Methods 0.000 claims description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 16
- 229910052760 oxygen Inorganic materials 0.000 claims description 16
- 239000001301 oxygen Substances 0.000 claims description 16
- 239000010936 titanium Substances 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 12
- 230000005611 electricity Effects 0.000 claims description 11
- 229910000807 Ga alloy Inorganic materials 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- 238000005137 deposition process Methods 0.000 claims description 9
- 239000011575 calcium Substances 0.000 claims description 8
- 239000012528 membrane Substances 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 238000005520 cutting process Methods 0.000 claims description 5
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 5
- 150000002602 lanthanoids Chemical class 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 238000010884 ion-beam technique Methods 0.000 claims description 4
- 229910021076 Pd—Pd Inorganic materials 0.000 claims description 3
- HAUBPZADNMBYMB-UHFFFAOYSA-N calcium copper Chemical compound [Ca].[Cu] HAUBPZADNMBYMB-UHFFFAOYSA-N 0.000 claims description 3
- 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
- 239000011572 manganese Substances 0.000 description 21
- 229910004247 CaCu Inorganic materials 0.000 description 7
- 229910002966 CaCu3Ti4O12 Inorganic materials 0.000 description 5
- 238000005516 engineering process Methods 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
- 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
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 229910052737 gold Inorganic materials 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
- 230000005389 magnetism Effects 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- UPWOEMHINGJHOB-UHFFFAOYSA-N oxo(oxocobaltiooxy)cobalt Chemical compound O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 description 2
- 230000001737 promoting effect Effects 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
- -1 Co2O3 Chemical class 0.000 description 1
- 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
- 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
- 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
- 230000002708 enhancing effect Effects 0.000 description 1
- 229910052733 gallium Inorganic materials 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
- 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
- 238000003860 storage Methods 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 fields, more particularly to a kind of high-energy density thin-film capacitor and its preparation side
Method.
Background technique
Currently, the energy storage density of capacitor depends mainly on capacitance and breakdown voltage, E=1/2CV2.Capacitor at present
Part (including conventional capacitive and supercapacitor etc.) mainly improves electricity by reducing interelectrode distance, increase electrode specific surface area
Capacitance and energy density.On this basis, dielectric dielectric property is changed by selection, improves its breakdown voltage and opposite dielectric
Constant is also the effective way for improving capacitive energy density.
Patent (CN200910134160.4 and CN200910145423.1) proposes the concept of magnetocapacitance energy storage, passes through magnetic
Field influences dielectric dielectric property.Structure based on plane-parallel capacitor, the positive and negative electrode of capacitor is two layers of magnetic in the patent
Property metal material, centre be dielectric layer.Magnetic metal provides the magnetic field perpendicular to dielectric direction, the work in some strength magnetic field
With dielectric dielectric property is changed, the charge density for storing electrode and dielectric interface increases, 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 the report having an impact about magnetic field to above-mentioned material electricity and dielectric property.The patent
There is no thin dielectric film and magnetic membrane material and its property is clearly proposed, also the preparation process of thin-film capacitor is not proposed
Relevant claim.
Improving dielectric Constant is one of the technological approaches for obtaining High energy density capacitive.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 process of capacitor, previously
Patent (application number: CN201610031323.6, CN201310743770.0) mostly uses solwution method to prepare calcium titanate Copper thin film, with
LaAlO3As base material, the precursor liquid containing calcium copper titanium is spun in substrate, finally heat treatment forms film again.On
State process advantage be it is low in cost, do not need complex device, but be readily incorporated in thin dielectric film preparation process miscellaneous
Matter, is not suitable for the serialization preparation of large area film, and exists and be not easy compatible, substrate material with thin magnetic film preparation process
The problems such as expecting also costly.
Summary of the invention
The present invention be solve technical problem present in well-known technique 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 structure is similar to plane-parallel capacitor, upper layer and lower layer metal
Membrane electrode, middle section are made of thin dielectric film and one layer of nanometer magnetic metal film.Magnetic metallic film can hang down
Directly in providing the magnetic field of sufficient intensity on dielectric direction, changes dielectric dielectric polarization, effectively improve dielectric electricity
Capacity is expected to obtain the novel thin film capacitor of higher energy density.It is to be doped with magnetic member that this patent, which clearly proposes dielectric,
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/buffer layer/thin magnetic film/
Metal electrode.Magnetic metallic film is provided perpendicular to dielectric direction, some strength magnetic field, be can be changed and is situated between inside dielectric
Electric polarization effectively improves dielectric capacitance and energy density.In the capacitance structure that this patent proposes, thin dielectric film,
Thin magnetic film and electrode are all made of evaporation technology preparation, realize the serialization preparation of each layer film of capacitor element, and can
To obtain the thin magnetic film of the thin dielectric film and stronger perpendicular magnetic anisotropic with good dielectric property, meet preparation 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
The high-energy density thin-film capacitor for the features such as pressure is high, low in cost, has 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, its main feature is that: high-energy density thin-film capacitor structure is Si substrate/metal electricity
Pole/thin dielectric film/buffer layer/thin magnetic film/metal electrode；Thin dielectric film, thin magnetic film and electrode are all made of evaporation
Process deposits form, and buffer layer is located at thin magnetic film and thin dielectric membrane interface.
High-energy density thin-film capacitor of the present invention can also adopt the following technical scheme that
The high-energy density thin-film capacitor, its main feature is that: thin dielectric film is the CaCu 3 Ti 4 O of doped magnetic element,
For thin dielectric film with a thickness of 0.3 μm -3 μm, the valent state of doped chemical, part substitutes Ca or Ti, occupies corresponding lattice position
It sets.
The high-energy density thin-film capacitor, its main feature is that: the magnetic element of doping is Ni, Co, Mn, La or group of the lanthanides member
Element, doping concentration mole ratio is less than 5%.
The high-energy density thin-film capacitor, its main feature is that: buffer layer is Pt (001) or Pd (001) film, with a thickness of
0.1-0.3μm。
The high-energy density thin-film capacitor, its main feature is that: magnetic membrane material MnxGa alloy, 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 to have simple process, capacitor element serialization preparation is advantageously implemented
The system of the high-energy density thin-film capacitor for the features such as mass production, product power density is high, and energy density is high, 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, its main feature is that: preparation Si substrate/metal electrode/buffer layer/
When 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, and being passed through oxygen flow is 10sccm-60sccm.
The preparation method of high-energy density thin-film capacitor of the present invention can also adopt the following technical scheme that
The preparation method of the high-energy density thin-film capacitor, its main feature is that: electron beam evaporation process prepares dielectric
When film, electron beam evaporation process is used in thin dielectric film surface to deposit a layer thickness first thin for 0.05 μm of Au or Pd
Then film obtains 0.1-0.3 μm of a layer thickness of Pt or Pd buffer layer thin film by ion beam cutting technique, and by Au-Pt,
Pd-Pd metal bonding is transferred on thin dielectric film.
The preparation method of the high-energy density thin-film capacitor, its main feature is that: use vacuum evaporation technology deposited magnetic
Film, thin magnetic film MnxGa alloy, x=1.1-1.9, underlayer temperature is 150 DEG C -380 DEG C in deposition process, the source Mn and Ga
The evaporating temperature in source is respectively 960 DEG C -990 DEG C and 1000 DEG C -1060 DEG C.
The thin-film capacitor and preparation method thereof that technology of the invention includes:
1. the present invention proposes high-energy density thin-film capacitor structure are as follows: substrate/metal electrode/thin dielectric film/buffer layer/
Thin magnetic film/metal electrode.Wherein, dielectric layer uses the calcium copper titanate film (M- for adulterating a certain amount of magnetic element
CaCu3Ti4O12, M represents magnetic element), the magnetic element of doping includes Ni, Co, Mn, La and lanthanide series etc., and film is thick
Degree is 0.3 μm -3 μm.According to the valent state of doped chemical, 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, keep dielectric micro-
The dielectric polarization enhancing of structure is seen, the relative dielectric constant and magnitude of the stored charge for improving dielectric layer are, it can be achieved that high-energy density
Thin-film capacitor.By optimization doped magnetic element mole and doped chemical valence state, foreign atom is effectively controlled in lattice
Position, can be changed the microcosmic electrical properties of dielectric, reduce dielectric loss.
Magnetic membrane material is MnxGa alloy (x=1.1-1.9), thickness are about 0.05 μm -0.5 μm.It is logical to adjust containing for Mn
(x value) and thin magnetic film sedimentary condition are measured, the size and Orientation of net saturation magnetic moment is controlled, makes film that there is very strong perpendicular magnetic
Anisotropy, the magnetic field strength provided is in 0.1T-1T range.
The 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 as buffer layer.Due to MnxThe perpendicular magnetic anisotropic and magnetic field strength of Ga thin magnetic film and the surface texture in base
Closely related, Pt film has splendid flatness, by growing one layer of Pt (001) transition zone to optimization in dielectric surface
MnxThe perpendicular magnetic anisotropic of Ga film plays a significant role.
The metal electrode material of capacitor is made of one or more of metals such as Au, Ag, Pd, Pt, thickness of electrode about 0.1-0.5
μm。
2. the preparation method that the present invention proposes thin-film capacitor.Each layer membrane materials of capacitor (including electrode) are all made of evaporator man
Skill preparation.To be commercialized silicon wafer as substrate (300 μm -400 μm of thickness), first using electron beam evaporation process deposited metal electricity
Pole.Second step still uses electron beam evaporation process, co-evaporates CuO, CaO, TiO2And magnetic metal oxide (such as Co2O3,
NiO, La2O3Deng), while the oxygen of certain flow, thin dielectric film deposition process are nearby passed through to the indoor evaporation boat of evaporation cavity
Middle underlayer temperature is maintained at constant within the scope 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, keep underlayer temperature at 300 DEG C -500
It is DEG C constant, the Au film that a layer thickness is about 0.05 μm is deposited in dielectric surface using electron beam evaporation process.Third step is led to
It crosses ion cutting technique 0.1 μm -0.3 μm of a layer thickness of Pt (001) or Pd (001) film are transferred on thin dielectric film,
Epitaxial substrate as 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 film.Finally, preparing Au top electrode using electron beam evaporation.
The advantages and positive effects of the present invention are:
High-energy density thin-film capacitor and preparation method thereof is due to using the completely new technical solution of the present invention, with existing skill
Art is compared, the invention has the characteristics that:
1, the present invention proposes in thin-film capacitor structure, and dielectric layer uses magnetic-doped M-CaCu3Ti4O12Film, room temperature
Under relative dielectric constant be 103-104Magnitude, and relative dielectric constant is hardly influenced by frequency and temperature.Pass through magnetic
Field action can further improve its relative dielectric constant, to increase capacitance.Pass through control doped chemical mole and chemistry
Dielectric loss can be effectively reduced in valence state.Meanwhile CaCu 3 Ti 4 O sill has good dielectric strength (foreign countries' report thickness
Breakdown voltage for 0.5 μm of dielectric film is more than 10V).Therefore, magnetic-doped M-CaCu3Ti4O12Film is highly suitable as
Dielectric is, it can be achieved that high power density, high-energy density and the thin-film capacitor of long-life, practical ranges are extensive.
2, the present invention proposes the Mn that one layer of nanoscale is inserted into the capacitor of parallel-plate structurexGa alloy firm, provides
Some strength, magnetic field perpendicular to dielectric direction.The magnetic of thin-film capacitor is realized using relatively simple device architecture
Built in.
3, the present invention is in one layer of Pt (001) of thin magnetic film and thin dielectric film interface or Pd (001) film as slow
Layer is rushed, Mn is assistedxThe epitaxial growth of Ga thin magnetic film, avoids MnxThe perpendicular magnetic anisotropic of Ga film is by thin dielectric film
It influences.
4, the present invention prepares dielectric, thin magnetic film and electrode layer using evaporation technology technology, and it is each to realize capacitor element
Prepared by the serialization of layer film, be advantageously implemented the mass production of high performance thin film storage capacitor.
Detailed description of the invention
Fig. 1 is high-energy density thin-film capacitor structural schematic diagram of the present invention；
In figure, 1-Si piece substrate, 300 μm -400 μm of thickness；2- hearth electrode Au-Ag alloy, 0.1 μm -0.3 μm of thickness；3-
Dielectric M-CaCu3Ti4O12Film, 0.3 μm -3 μm of thickness；4- buffer layer Pt or Pd film, 0.1 μm -0.3 μm of thickness；5- magnetic
Property layer, MnxGa alloy firm, 0.05 μm -0.5 μm of thickness；6- top electrode layer, Au-Ag alloy, 0.1 μm -0.3 μm of thickness；7-
Metal electrode contact point；Magnetic field H built in 8-, perpendicular to dielectric layer direction.
Fig. 2 is dielectric substance preparation process flow schematic diagram.
Specific embodiment
In order to further understand the content, features and effects of the present invention, the following examples are hereby given, and cooperate attached drawing
Detailed description are as follows:
Refering to attached drawing 1 and Fig. 2.
Embodiment 1
A kind of high-energy density thin-film capacitor, structure are as follows: substrate/metal electrode/thin dielectric film/buffer layer/magnetism
Film/metal electrode.Each layers such as metal electrode, thin dielectric film and thin magnetic film in capacitance structure be thin are all made of evaporator man
Skill is prepared.
The present embodiment preparation process:
Step 1 successively uses acetone and deionized water to be commercialized Si piece as substrate -1 (300 μm -400 μm of thickness)
Si piece is cleaned, the substrate with clean surface is obtained.
Step 2, the Au film for being about 0.1 μm -0.3 μm using electron beam evaporation process deposition thickness, the bottom as capacitor
Electrode -2.Background vacuum pressure is 10-4Pa controls hearth electrode thickness by control beam power, and evaporation power is about
The substrate of 1250W-1400W, evaporation process process do not heat.
Step 3, the same thin dielectric film -3 for being about 0.3 μm -3 μm using electron beam evaporation process deposition thickness.Electricity is situated between
Matter thin-film material is the CaCu 3 Ti 4 O for adulterating 3%Ni, i.e. CaCu3NixTi4-xO12-2x(x=0.6).Background vacuum pressure reaches 10-4Oxygen is passed through after Pa in vacuum chamber, flow 10sccm-60sccm co-evaporates CuO, CaO, TiO under oxygen atmosphere2With
And NiO, beam power control Cu, Ti, Ca by adjusting the beam power of different oxide sources in 150W-750W range
With the component ratio and film integral thickness of Ni.The oxygen being passed through is for promoting the combination reaction between different oxides abundant
It carries out, the CaCu guaranteed3NixTi4-xO12-2xOxygen element content composite chemical measures ratio.In thin dielectric film deposition process
Middle underlayer temperature is maintained at constant within the scope of 600 DEG C -900 DEG C.After depositing operation, electron beam and silicon are closed, after
It is continuous to be passed through oxygen, so that thin dielectric film is cooled down under oxygen atmosphere.
It is thin in thin dielectric film surface to deposit the Au that a layer thickness is about 0.05 μm using electron beam evaporation first for step 4
Film, sedimentary condition is essentially identical with step 2, and the thickness of Au is controlled by reducing sedimentation time.Pass through ion beam cutting technique etc.
To 0.1-0.3 μm of a layer thickness of Pt (001) buffer layer thin film -4, and thin dielectric film is transferred to by Au-Pt metal bonding
On, the epitaxial substrate as thin magnetic film.
Step 5, the Mn for being about 0.05 μm -0.5 μm using high vacuum evaporation process deposits thicknessxGa alloy (x=1.1-
1.9) film -5.Vacuum pressure during whole is maintained at 10-6Pa-10-7Pa magnitude, underlayer temperature are about 150 DEG C -380 DEG C.
The evaporating temperature in the source Mn and the source Ga is respectively 960 DEG C -990 DEG C and 1000 DEG C -1060 DEG C.The logical content (x value) for adjusting Mn and
The conditions such as depositing temperature, the size and Orientation in the magnetic field -8 that control film provides, make film have very strong perpendicular magnetic respectively to different
Property.The magnetic field strength that film provides can reach 0.1T-1T.
Step 6 deposits the Au that a layer thickness is about 0.1-0.3 μm on thin magnetic film surface using electron beam evaporation process
Film, the top electrode -6 as capacitor.Deposition process conditions are identical as step 2.
Embodiment 2
A kind of high-energy density thin-film capacitor, structure are as follows: substrate/metal electrode/thin dielectric film/buffer layer/magnetism
Film/metal electrode.Detailed process is as follows by the present embodiment capacitor element preparation process:
Step 1 successively uses acetone and deionized water to be commercialized Si piece as substrate -1 (300 μm -400 μm of thickness)
Si piece is cleaned, the substrate with clean surface is obtained.
Step 2, the Au-Ag alloy firm for being about 0.1 μm -0.3 μm using electron beam evaporation process deposition thickness, as
The hearth electrode -2 of capacitor.Background vacuum pressure is 10-4Pa controls hearth electrode thickness, evaporation power by control beam power
The substrate of about 1250W-1400W, evaporation process process do not heat.
Step 3, the same thin dielectric film -3 for being about 0.3 μm -3 μm using electron beam evaporation process deposition thickness.Electricity is situated between
Matter thin-film material is the CaCu 3 Ti 4 O for adulterating 1%La, i.e. Ca1-xLaxCu3Ti4O12+x/2(x=0.2).Background vacuum pressure reaches
10-4Oxygen is passed through after Pa in vacuum chamber, flow 10sccm-60sccm co-evaporates CuO, CaO, TiO under oxygen atmosphere2
And La2O3, beam power is in 150W-900W range, by adjusting the beam power of different oxide sources, control Cu,
The component ratio and film integral thickness of Ti, Ca and La.The oxygen being passed through is for promoting the chemical combination between different oxides anti-
It should sufficiently carry out, the Ca guaranteed1-xLaxCu3Ti4O12+x/2(x=0.2) oxygen element content composite chemical measures ratio.It is situated between in electricity
Underlayer temperature is maintained at constant within the scope of 600 DEG C -900 DEG C in matter film deposition process.After depositing operation, electron beam is closed
And silicon, continue to be passed through oxygen, thin dielectric film is made to cool down under oxygen atmosphere.
It is thin in thin dielectric film surface to deposit the Pd that a layer thickness is about 0.05 μm using electron beam evaporation first for step 4
Film, deposition process is essentially identical with step 2, and the thickness of Pd is controlled by adjusting beam power.Pass through ion beam cutting technique
Until 0.1-0.3 μm of a layer thickness of Pd (001) buffer layer thin film -4, and thin dielectric is transferred to by Pd-Pd metal bonding
Epitaxial substrate on film, as thin magnetic film.
Step 5, the Mn for being about 0.05 μm -0.5 μm using high vacuum evaporation process deposits thicknessxGa alloy (x=1.1-
1.9) film -5.Vacuum pressure during whole is maintained at 10-6Pa-10-7Pa magnitude, underlayer temperature are about 150 DEG C -380 DEG C.
The evaporating temperature in the source Mn and the source Ga is respectively 960 DEG C -990 DEG C and 1000 DEG C -1060 DEG C.The logical content (x value) for adjusting Mn and
The conditions such as depositing temperature, the size and Orientation in the magnetic field -8 that control film provides, make film have very strong perpendicular magnetic respectively to different
Property.
Step 6 deposits the Au that a layer thickness is about 0.1-0.3 μm on thin magnetic film surface using electron beam evaporation process
Film, the top electrode -6 as capacitor.Deposition process conditions are identical as step 2.
The present embodiment has the power density high, and energy density is high, long-life energy storage, and operating voltage is high, at low cost
It is honest and clean, it has wide range of applications, capacitor element continuous preparation process is advantageously implemented the good effects such as mass production.
Claims (4)
1. a kind of high-energy density thin-film capacitor, it is characterized in that: high-energy density thin-film capacitor structure is Si substrate/metal electricity
Pole/thin dielectric film/buffer layer/thin magnetic film/metal electrode；Thin dielectric film, thin magnetic film and electrode are all made of evaporation
Process deposits form, and buffer layer is located at thin magnetic film and thin dielectric membrane interface；Thin dielectric film is the titanium of doped magnetic element
Sour copper calcium, for thin dielectric film with a thickness of 0.3 μm -3 μm, the valent state of doped chemical, part substitutes Ca or Ti, occupies corresponding
Lattice position；The magnetic element of doping is Ni, Co, Mn or lanthanide series, and doping concentration mole ratio is less than 5%；Buffer layer
For Pt or Pd film, with a thickness of 0.1-0.3 μm.
2. high-energy density thin-film capacitor according to claim 1, it is characterized in that: magnetic membrane material is MnxGa alloy, x
=1.1-1.9, magnetic film thickness are 0.05 μm -0.5 μm.
3. a kind of preparation method of high-energy density thin-film capacitor, it is characterized in that: preparation Si substrate/metal electrode/thin dielectric
When film/buffer layer/thin magnetic film/metal electrode structure thin-film capacitor, thin dielectric film is prepared using electron beam evaporation process, electricity
Dielectric layer uses the calcium copper titanate film for adulterating a certain amount of magnetic element, and the magnetic element of doping is Ni, Co, Mn or group of the lanthanides member
Element, according to the valent state of doped chemical, part substitutes Ca or Ti, occupies corresponding lattice position；Thin dielectric film deposition
Underlayer temperature in the process is 600 DEG C -900 DEG C, and being passed through oxygen flow is 10sccm-60sccm；Electron beam evaporation process preparation
When thin dielectric film, use first electron beam evaporation process thin dielectric film surface deposit a layer thickness for 0.05 μm Au or
Pd film, then by ion beam cutting technique obtain 0.1-0.3 μm of a layer thickness Pt (001) or Pd (001) buffer layer it is thin
Film, and be transferred on thin dielectric film by Au-Pt, Pd-Pd metal bonding.
4. the preparation method of high-energy density thin-film capacitor according to claim 3, it is characterized in that: using work is evaporated in vacuo
Skill depositing magnetic film, thin magnetic film MnxGa alloy, x=1.1-1.9, underlayer temperature is 150 DEG C -380 in deposition process
DEG C, the evaporating temperature in the source Mn and the source Ga is respectively 960 DEG C -990 DEG C and 1000 DEG C -1060 DEG C.
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