CN101800253A - Nano capacitor for storing energy and preparation method thereof - Google Patents
Nano capacitor for storing energy and preparation method thereof Download PDFInfo
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- CN101800253A CN101800253A CN 201010138066 CN201010138066A CN101800253A CN 101800253 A CN101800253 A CN 101800253A CN 201010138066 CN201010138066 CN 201010138066 CN 201010138066 A CN201010138066 A CN 201010138066A CN 101800253 A CN101800253 A CN 101800253A
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Abstract
The invention belongs to the technical field of energy storage devices, in particular to a nano capacitor for storing energy and a preparation method thereof. The preparation method of the nano capacitor includes the following steps: depositing a metal aluminium membrane on a silicon or glass substrate; anodizing the metal aluminium twice to obtain anodized aluminium cyclostyle; depositing a bottom metal electrode, a middle insulated medium and a top metal electrode in the nano gaps of cyclostyle through ALD method; depositing a metal aluminium layer on the surface of the top metal electrode to be used as a top current collector; and exposing a bottom current collector through photoetching technology and reactive ion etching, respectively leading out the top current collector and the bottom current collector through leads to be used as the two electrodes of the nano capacitor. The nano capacitor can have high power and energy density and is simple in fabrication process, low in cost and small in packaged volume.
Description
Technical field
The invention belongs to technical field of energy storage devices, be specifically related to a kind of MIM (metal-insulator medium-metal) nano capacitor based on AAO (anodised aluminium) template and ALD (atomic layer deposition) technology.
Background technology
Along with the appearance of energy shortage and ecological deterioration problem, how to make up resource-conserving and environmentally friendly society has been put on schedule.One time, a collection of new energy resource system emerged, as solar energy, water energy, wind energy, biological energy source etc.Yet there is the unsteadiness of self in these energy resource systems, so a kind of energy storage device must be arranged can be preserved these energy with the form of electric energy, this energy storage device can also provide high power density and energy density simultaneously, and environmentally safe, to satisfy energy-conservation and environmental protection requirement.
Traditional electrostatic capacitance is by the gathering stored energy of electric charge at electrode surface, and the speed that discharges and recharges is fast, and very high power density can be provided, yet limited electrode surface area makes its energy density very low, so can't be as power supply component.Therefore, the super capacitor based on electric double layer capacitance and faraday's electric capacity is proposed in succession.This is because super capacitor can provide very high energy density and power density, yet low mobility and the redox reaction of electric charge in electrolyte all limited further reducing of the time that discharges and recharges, thereby has limited the further raising of power density.
The separation of charge on the electrode/electrolyte interface of being based on electric double layer capacitance realizes the storage of energy, and faraday's electric capacity is based on the storage that pseudo-capacitance that surperficial quick, the reversible redox reaction of metal oxide or conducting polymer produces is realized energy.The high power density that how can have electrostatic capacitance can have the high-energy-density of super capacitor again, and the development of nanometer technology has brought solution for this problem.
Highly purified aluminium flake can form super-high density (10 at alumina surface through anodic oxidation
10Cm
-2) the loose structure arranged of high-sequential, hexagon, and can obtain different-diameter (30～80nm) and the hole of the degree of depth by control of process condition.This electrochemical process is known as anodised aluminium (AAO) technology.Therefore, adopt this nanostructure, can be easy to obtain to surpass 100 times surface area.If as making template, form mim capacitor structure on its surface with this aluminum oxide porous structure (AAO template), be directly proportional with capacitance according to energy, capacitance this rule that is directly proportional with electrode surface area again can obtain very big energy.And the hole density of superelevation makes this device very light in weight, thereby energy density will be very high.This device has adopted MIM electrostatic capacitance structure simultaneously, thereby can obtain very high power density.The present invention proposes to adopt the ALD method mim structure of growing, and not only thickness is easy to control, and the deep hole filling effect is good.
Summary of the invention
The objective of the invention is to propose a kind of MIM nano capacitor that is used for the energy storage, this nano capacitor can obtain high power density and energy density simultaneously, and manufacture craft is simple, and cost is low, and encapsulation volume is little.
For reaching above-mentioned purpose of the present invention, the present invention AAO (anodised aluminium) orderly to have, loose structure makes template.Adopt the method for ALD, deposit underlying metal electrode, middle insulated medium and top-level metallic electrode successively in the hole of AAO template, thus form mim capacitor structure.
In above-described mim structure, the underlying metal electrode material can be TiN, TaN or Ru, and the middle insulated medium material can be the Al with high dielectric constant
2O
3, HfO
2, Ta
2O
5Or ZrO
2, or several composite material among them, the top-level metallic electrode material can be TiN, TaN or Ru.
In the above-mentioned nano capacitor, in the described AAO template, the degree of depth in hole is 10～100 microns, and the diameter in hole is 30～80 nanometers.
In the above-mentioned nano capacitor, the thickness of described underlying metal electrode is 5～15 nanometers, and the thickness of middle insulated medium is 10～50 nanometers, and the thickness of top-level metallic electrode is 5～15 nanometers.
The invention allows for the above-mentioned manufacture method that is used for the nano capacitor of energy storage, this method comprises the following steps:
(1) deposit layer of metal aluminium film on monocrystalline silicon or glass substrate, thickness is 100～500 microns;
(2) metallic aluminium is carried out twice anodic oxidation and obtain the AAO template, contain the very big nano-pore of depth-to-width ratio in this template; For example, the degree of depth is 10～100 microns, and the diameter in hole is 30～80 nanometers
(3) adopt ALD method deposit underlying metal electrode in the nanoaperture of template, thickness is 5～15 nanometers;
(4) use ALD method deposit middle insulated medium on the underlying metal electrode, thickness is 10～50 nanometers;
(5) use ALD method deposit top-level metallic electrode on middle insulated medium, thickness is 5～15 nanometers;
(6) at top-level metallic electrode surface deposit layer of metal again aluminium film as the top layer collector, thickness is 200～500 nanometers;
(7) by photoetching process and reactive ion etching the bottom collector is come out, and with lead top layer and bottom collector are drawn respectively, as two electrodes of nanometer electric capacity.
The MIM nano capacitor that the present invention prepares has very high power density and energy density, and manufacture craft is simple, and cost is low, and encapsulation volume is little.
Description of drawings
Fig. 1: deposit layer of metal aluminium film on silicon substrate.
Fig. 2: metallic aluminium is carried out the AAO template that twice anodic oxidation obtains.
Fig. 3: in the nanoaperture of AAO template, obtain the underlying metal electrode by the ALD deposit.
Fig. 4: obtain middle insulated medium by the ALD deposit at the underlying metal electrode surface.
Fig. 5: obtain the top-level metallic electrode by the ALD deposit on the middle insulated medium surface.
Fig. 6: at the top-level metallic electrode surface deposit layer of metal again aluminium film of nano capacitor.
Fig. 7: expose bottom collector-aluminium film by photoetching process and reactive ion etching.
Fig. 8: with lead top layer and bottom collector are drawn respectively, as the electrode of nanometer electric capacity.
Embodiment
Below in conjunction with the drawings and specific embodiments the present invention is carried out detailed explanation.
Step 1: please refer to Fig. 1, put substrate 200 in electron beam evaporation system or magnetic control sputtering system deposit layer of metal 201, wherein 200 is monocrystalline silicon or glass, and thickness is 5 microns; The 201st, aluminium film (purity is 99.99%), thickness is 100～500 microns.
Step 2: please refer to Fig. 2, twice traditional anodic oxidation of 201 employings obtained 202, wherein 202 is aluminium oxide.Here twice anodised process conditions is identical, and all having adopted concentration is 0.3M, and temperature is 0 ℃ a sulfuric acid solution, adds the 25V direct voltage between anode and the negative electrode.Can obtain the degree of depth by the control anodizing time is 10～100 microns, and diameter is the hole of 30～80 nanometers.
Step 3: please refer to Fig. 3, the nano-pore inner surface 202 passes through ALD method deposit layer of metal 203,203rd, TiN, and its thickness is in 5～15 nanometer range.
Step 4: please refer to Fig. 5, the surface 203 is by ALD method deposit one deck dielectric 204,204th, Al
20
3, its thickness is in 10～50 nanometer range.
Step 5: please refer to Fig. 6, ALD deposit layer of metal 205,205th is passed through on the surface 204, TiN, and its thickness is in 5～15 nanometer range.Simultaneously, metal 203, dielectric 204, metal 205 three's thickness sums should be not less than the diameter of nano-pore.
Step 6: please refer to Fig. 6, the nano capacitor substrate that is manufactured with mim structure put into electron beam evaporation chamber or magnetron sputtering chamber, in 205 surface deposition layer of metal 206 as the top layer collector, the 206th, aluminium, its thickness are 200～500 nanometers.
Step 7: please refer to Fig. 7, expose bottom collector 201 by photoetching process and reactive ion etching.
Step 8: please refer to Fig. 8, extract 201 and 206 with lead respectively, be used for two electrodes of nanometer electric capacity.
Enforcement of the present invention can obtain a kind of nano capacitor that is used for the energy storage, can obtain high power density and high-energy-density.In addition, manufacture craft is simple, and cost is low, and encapsulation volume is little.
Claims (7)
1. one kind is used for the nano capacitor that energy is stored, it is characterized in that, this capacitor with have in order, the anodised aluminium of loose structure serves as to make template, adopts the ALD method, deposit underlying metal electrode, middle insulated medium and top-level metallic electrode and obtain successively in the micropore of template.
2. nano capacitor according to claim 1 is characterized in that described top-level metallic electrode material is TiN, TaN or Ru.
3. nano capacitor according to claim 1 is characterized in that described middle insulated medium material is Al
2O
3, HfO
2, Ta
2O
5Or ZrO
2
4. nano capacitor according to claim 1 is characterized in that described underlying metal electrode material is TiN, TaN or Ru.
5. nano capacitor according to claim 1, the degree of depth that it is characterized in that described anodic oxidation aluminium formwork mesopore is 10～100 microns, the diameter in hole is 30～80 nanometers.
6. nano capacitor according to claim 1, the thickness that it is characterized in that described underlying metal electrode is 5～15 nanometers, and the thickness of middle insulated medium is 10～50 nanometers, and the thickness of top-level metallic electrode is 5～15 nanometers.
7. one kind is used for the nano capacitor manufacture method that energy is stored, and it is characterized in that concrete steps are as follows:
(1) deposit layer of metal aluminium on silicon substrate, thickness is 100～500 microns;
(2) metallic aluminium is carried out twice anodic oxidation and obtain having anodic oxidation aluminium formwork orderly, loose structure;
(3) use ALD method deposit underlying metal electrode in the nano-pore of template, thickness is 5～15 nanometers;
(4) in underlying metal electrode surface ALD method deposit middle insulated medium, thickness is 10～50 nanometers;
(5) use ALD method deposit top-level metallic electrode on the middle insulated medium surface, thickness is 5～15 nanometers;
(6) at top-level metallic electrode surface deposit layer of metal aluminium as the top layer collector, thickness is 200～500 nanometers;
(7) by photoetching process and reactive ion etching the bottom collector is come out, and with lead top layer and bottom collector are drawn respectively, as two electrodes of nanometer electric capacity.
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| CN 201010138066 CN101800253A (en) | 2010-04-01 | 2010-04-01 | Nano capacitor for storing energy and preparation method thereof |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101996775A (en) * | 2010-11-16 | 2011-03-30 | 复旦大学 | Method for preparing solid-state ultracapacitor |
| CN102517558A (en) * | 2011-11-08 | 2012-06-27 | 复旦大学 | Porous metal/dielectric micro tube, and preparation method and application thereof |
| CN102568817A (en) * | 2012-03-01 | 2012-07-11 | 中北大学 | MEMS (Micro Electro Mechanical System) capacitor based on three-dimensional silicon micro structure and manufacturing method thereof |
| CN102623174A (en) * | 2012-04-17 | 2012-08-01 | 电子科技大学 | Method for preparing high energy density capacitor |
| CN102623184A (en) * | 2012-04-05 | 2012-08-01 | 清华大学 | Photoresist-diaphragm-based micro super-capacitor and manufacturing method thereof |
| CN102623175A (en) * | 2012-04-17 | 2012-08-01 | 电子科技大学 | Preparation method of nano capacitor |
| CN102623173A (en) * | 2012-04-17 | 2012-08-01 | 电子科技大学 | Method for preparing alumina ordered nanopore structure-based capacitor |
| CN105071545A (en) * | 2015-08-05 | 2015-11-18 | 国润金华（北京）国际能源投资有限公司 | Quantum physics storage battery and preparation method thereof |
| CN109585161A (en) * | 2017-09-29 | 2019-04-05 | 日月光半导体制造股份有限公司 | Capacitor arrangement |
| CN111933622A (en) * | 2020-07-08 | 2020-11-13 | 电子科技大学 | Preparation method of three-dimensional MIM capacitor |
| CN112151539A (en) * | 2020-09-10 | 2020-12-29 | 复旦大学 | High-storage-capacity nano-capacitor three-dimensional integrated structure and preparation method thereof |
| CN112151536A (en) * | 2020-08-17 | 2020-12-29 | 复旦大学 | Three-dimensional integrated structure of nano capacitor and preparation method thereof |
| CN112201655A (en) * | 2020-09-10 | 2021-01-08 | 复旦大学 | Three-dimensional integrated structure of nano capacitor and manufacturing method thereof |
-
2010
- 2010-04-01 CN CN 201010138066 patent/CN101800253A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| 《nature nanotechnology》 20090331 Parag Banerjee,Israel Perez,et.al Nanotubular metal-insulator-metal capacitor arrays for energy storage 292-296 1-7 第4卷, 2 * |
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101996775B (en) * | 2010-11-16 | 2012-07-04 | 复旦大学 | Method for preparing solid-state ultracapacitor |
| CN101996775A (en) * | 2010-11-16 | 2011-03-30 | 复旦大学 | Method for preparing solid-state ultracapacitor |
| CN102517558B (en) * | 2011-11-08 | 2013-07-10 | 复旦大学 | Porous metal/dielectric micro tube, and preparation method and application thereof |
| CN102517558A (en) * | 2011-11-08 | 2012-06-27 | 复旦大学 | Porous metal/dielectric micro tube, and preparation method and application thereof |
| CN102568817A (en) * | 2012-03-01 | 2012-07-11 | 中北大学 | MEMS (Micro Electro Mechanical System) capacitor based on three-dimensional silicon micro structure and manufacturing method thereof |
| CN102623184A (en) * | 2012-04-05 | 2012-08-01 | 清华大学 | Photoresist-diaphragm-based micro super-capacitor and manufacturing method thereof |
| CN102623174B (en) * | 2012-04-17 | 2014-06-25 | 电子科技大学 | Method for preparing high energy density capacitor |
| CN102623173A (en) * | 2012-04-17 | 2012-08-01 | 电子科技大学 | Method for preparing alumina ordered nanopore structure-based capacitor |
| CN102623175A (en) * | 2012-04-17 | 2012-08-01 | 电子科技大学 | Preparation method of nano capacitor |
| CN102623173B (en) * | 2012-04-17 | 2014-05-28 | 电子科技大学 | Method for preparing alumina ordered nanopore structure-based capacitor |
| CN102623174A (en) * | 2012-04-17 | 2012-08-01 | 电子科技大学 | Method for preparing high energy density capacitor |
| CN105071545A (en) * | 2015-08-05 | 2015-11-18 | 国润金华（北京）国际能源投资有限公司 | Quantum physics storage battery and preparation method thereof |
| CN109585161A (en) * | 2017-09-29 | 2019-04-05 | 日月光半导体制造股份有限公司 | Capacitor arrangement |
| CN111933622A (en) * | 2020-07-08 | 2020-11-13 | 电子科技大学 | Preparation method of three-dimensional MIM capacitor |
| CN111933622B (en) * | 2020-07-08 | 2022-07-29 | 电子科技大学 | Preparation method of three-dimensional MIM capacitor |
| CN112151536A (en) * | 2020-08-17 | 2020-12-29 | 复旦大学 | Three-dimensional integrated structure of nano capacitor and preparation method thereof |
| CN112151536B (en) * | 2020-08-17 | 2022-04-12 | 复旦大学 | Three-dimensional integrated structure of nano capacitor and preparation method thereof |
| CN112151539A (en) * | 2020-09-10 | 2020-12-29 | 复旦大学 | High-storage-capacity nano-capacitor three-dimensional integrated structure and preparation method thereof |
| CN112201655A (en) * | 2020-09-10 | 2021-01-08 | 复旦大学 | Three-dimensional integrated structure of nano capacitor and manufacturing method thereof |
| CN112151539B (en) * | 2020-09-10 | 2022-04-26 | 复旦大学 | High-storage-capacity nano-capacitor three-dimensional integrated structure and preparation method thereof |
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Application publication date: 20100811 |