CN1702887A - Process for preparing carbon electrode array with high surface area and high gap filling capacity - Google Patents
Process for preparing carbon electrode array with high surface area and high gap filling capacity Download PDFInfo
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- CN1702887A CN1702887A CNA2005100708529A CN200510070852A CN1702887A CN 1702887 A CN1702887 A CN 1702887A CN A2005100708529 A CNA2005100708529 A CN A2005100708529A CN 200510070852 A CN200510070852 A CN 200510070852A CN 1702887 A CN1702887 A CN 1702887A
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- filling capacity
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 33
- 238000011049 filling Methods 0.000 title claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 title description 3
- 229920000642 polymer Polymers 0.000 claims abstract description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 7
- 239000010703 silicon Substances 0.000 claims abstract description 7
- 229910052581 Si3N4 Inorganic materials 0.000 claims abstract description 4
- 229910052751 metal Inorganic materials 0.000 claims abstract description 4
- 239000002184 metal Substances 0.000 claims abstract description 4
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229920002120 photoresistant polymer Polymers 0.000 claims description 29
- 239000004005 microsphere Substances 0.000 claims description 17
- 239000003792 electrolyte Substances 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 238000000197 pyrolysis Methods 0.000 claims description 9
- 238000003763 carbonization Methods 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 claims description 6
- 238000001459 lithography Methods 0.000 claims description 6
- 238000011161 development Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 5
- 238000001259 photo etching Methods 0.000 claims description 5
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 4
- -1 ethenylidene chlorine Chemical compound 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001282 iso-butane Substances 0.000 claims description 4
- 235000013847 iso-butane Nutrition 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 230000002427 irreversible effect Effects 0.000 claims description 3
- 239000003595 mist Substances 0.000 claims description 3
- 230000000630 rising effect Effects 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- HGINCPLSRVDWNT-UHFFFAOYSA-N acrylaldehyde Natural products C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 claims 1
- 239000003292 glue Substances 0.000 abstract description 4
- 238000012545 processing Methods 0.000 abstract description 2
- 238000005530 etching Methods 0.000 abstract 3
- 239000003990 capacitor Substances 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 229920001486 SU-8 photoresist Polymers 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 238000012827 research and development Methods 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229920000103 Expandable microsphere Polymers 0.000 description 1
- 239000003708 ampul Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000747 cardiac effect Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 210000004904 fingernail bed Anatomy 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910021437 lithium-transition metal oxide Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000005469 synchrotron radiation Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Battery Electrode And Active Subsutance (AREA)
Abstract
This invention relates to carbon electrode array process method with large surface area and filling capacity in the field of micro machine system and micro battery, which comprises the following steps: adding some percentage of highly polymers expansion balls into the light etching glue and mixing them evenly; then coating it evenly on silicon slice, silicon nitride, earth silicon, quartz glass or metal underlay bottom surfaces; through drying, exploring, developing procedures; forming one graph thick film etching glue layer with certain deepness to width proportion; then processing light etching glue thermal carbon and forming hollow hole on the carbon electrode array; finally forming carbon electrode array structure with large surface area and filling capacitor.
Description
Technical field
The invention belongs to MEMS (micro electro mechanical system) (MEMS) and minicell field, it is simple, with low cost to be particularly related to technology, and a kind of preparation method with carbon electrode array of high surface and high gap filling capacity that surface area and gap filling capacity are improved significantly simultaneously.
Background technology
Lithium ion battery is a kind of very environmental type rechargeable battery of high-energy-density that has.At present, the positive electrode of the lithium ion battery of industrialized production mainly is the embedding lithium transition-metal oxide, and negative material all is carbon materials basically, and anodal and negative pole is parallel to each other, and the centre is an electrolyte; Charge and discharge process realizes that by chemical reaction the size that produces electric current depends on the degree that chemical reaction takes place, and electrolytical capacity is closely related in the surface area of the latter and electrode and the battery.The report that now relevant lithium ion battery has a high-energy-density very is normally based on the performance up to the large-sized battery of several ampere-hours.Because the hardware of encapsulation and inside battery has determined the size and the volume of entire cell to a great extent, for the minicell in can be used for microminiature electronic equipments such as cardiac pacemaker, smart card, hearing aids, remotely monitored sensor, available power and energy density can't be according to the such proportional variations of our expectation, just basic challenge has been proposed in the microminaturization of lithium ion battery development: should the expansion electrode size in very limited space to increase surface area, improve the electrolyte capacity simultaneously again.Different with macrocell, the positive and negative electrode of minicell is carbon film material usually, belong to two-dimentional battery, people generally are designed to them the structure of overlapping mutually, though increased electrode surface areas like this, might produce strong pulse current, but not change the little situation of electrolyte capacity, the electric energy of storage is still very limited.
In order to solve above-mentioned two-dimentional carbon film minicell in the deficiency aspect electrode size, electrolyte capacity and the energy density, the three-dimensional micro battery structure of being made up of high-aspect-ratio three-diemsnional electrode array has become an international in recent years research and development focus.Very distinctive in this respect at present is at document " C.L.Wang; L.Taherabadi; G.Jia; Marc Madou; etal.C-MEMS for the Manufacture of 3D Microbatteries.Electrochemical and Solid-State Letters; 7 (11): A435,2004 " California, USA university Irving branch school (UCI) the professor Madou leader's of report laboratory in; to be material with carbon carried out the work of a series of initiatives being referred to as the C-MEMS field for they; and in the research and development that are applied to three-dimensional lithium ion minicell recently; obtained compelling achievement: at first adopt the thick resist lithography technology of high-aspect-ratio to make the SU-8 photoresist that has tens～hundreds of micron thickness on silicon chip or the vitreous silica graphically form the three-dimensional photoetching plastic structure; under various atmosphere, to heat then, make the photoresist pyrolysis change three-dimensional carbon structure into; Adopt this method to develop the carbon post array electrode structure that looks like nail bed shape of moulding uniqueness, in the experiment of water and non-aqueous eletrolyte electrochemical reaction was arranged, the electrochemical response of they and glassy carbon material was suitable, embedding that can be reversible and deviate from lithium; Different rows' interlaced negative electrode and the anode of forming respectively of carbon post in the array, they not only can make the surface area of electrode increase greatly under the same projection area, also provide more space for electrolyte.This three-diemsnional electrode structure immersion is contained in the lithium electrolyte, and experimental result shows that it can be than voluminous living 78% the electric energy of the two-dimentional minicell of same size.
Now the C-MEM technology is applied to the three-dimensional micro battery and is badly in need of a key issue of solution is how to obtain more high-aspect-ratio and thicker electrode, so that further improve the surface area and the electrolyte capacity of carbon post array.Though utilize the LIGA technology can realize that thickness can reach several millimeters high-aspect-ratio photoresist structure, it needs very expensive synchrotron radiation X-ray light source and X ray mask plate, thereby makes processing and application be subjected to limiting greatly.For the MEMS device of making high-aspect-ratio with reduce R﹠D costs greatly, people's general choice at present be the thick resist lithography technology, its uses conventional mask aligner and mask plate just can form than higher depth-to-width ratio structure in SU-8 uniform thickness glue photoresist.At present, professor Madou leader's laboratory utilizes SU-8 thick resist lithography technology can produce thickness can to reach 275 microns, depth-to-width ratio and reach 10: 1 carbon electrode array, yet adopt this technology to desire further to improve photoresist thickness and reach more satisfactory depth-to-width ratio will be faced with formidable challenges undoubtedly.
Summary of the invention
The objective of the invention is to propose a kind of preparation method with carbon electrode array of high surface and high gap filling capacity.It is characterized in that: its implementation comprises three steps:
1) the high polymer expended microsphere is joined carries out thick resist lithography in the photoresist
The adding percent by volume is 0.1～30% high polymer expended microsphere and evenly mixes in photoresist earlier, then its even Tu is overlayed on substrate surfaces such as silicon chip, silicon nitride, silicon dioxide, quartz glass or metal, about tens～hundreds of the micron of thickness, after photoetching processes such as preceding baking, exposure, development, form patterned photoresist structure with certain depth-to-width ratio;
2) add thermal expansion
Baking before placing above-mentioned photoresist structure under 80～300 ℃ of temperature, get rid of the organic solvent in the photoresist so on the one hand, on the other hand, because the expended microsphere expanded by heating can form irreversible hollow structure, wherein, during preceding baking, the control temperature upper limit is 300 ℃, significantly expand because microballoon is heated, thereby can obviously increase the thickness of graphical photoresist;
3) pyrolysis carbonization
Said structure is placed 850～1150 ℃ of temperature and in a vacuum or carry out the pyrolysis carbonization treatment of photoresist under the non-oxidizing gas atmosphere, because the hollow structure of high polymer expended microsphere is destroyed, will in the carbon electrode array that forms, form the cavity, thereby further increased the surface area and the electrolyte volume of carbon electrode array, formed carbon resistance rod array structure at last with high surface and calking volume.
Described high polymer expended microsphere is made up of thermoplasticity shell and inner heat thereof the agent two parts that rise; Wherein shell is the copolymer of monomers such as acrylonitrile and ethenylidene chlorine, and the heat agent of rising is generally iso-butane or isopentane.
Described non-oxidizing gas is the mist of nitrogen, argon gas or they and hydrogen.
The invention has the beneficial effects as follows on the one hand, because the expended microsphere expanded by heating can form, thereby can obviously increase the thickness of graphical photoresist, for the surface area and the electrolyte volume that improve the device carbon electrode array are laid a good foundation; On the other hand, in the pyrolysis carbonisation of photoresist subsequently, the expandable microspheres hollow structure suffers that destruction can form the cavity in the carbon electrode array that forms, thereby has further increased the surface area and the electrolyte volume of carbon electrode array.This programme does not need extra technology just can realize the surface area of carbon post array and increasing substantially of electrolyte capacity simultaneously, thereby obviously strengthens energy storage capacity.The present invention has flexible design, makes simple and easy, low cost and other advantages.
Description of drawings
Fig. 1 is the carbon electrode array structural representation.
Embodiment
The present invention proposes a kind of preparation method with carbon electrode array of high surface and high gap filling capacity.Its implementation comprises three steps:
1) will be by thermoplasticity shell and inner heat thereof the agent high polymer expended microsphere dimerous that rise.Wherein shell is the copolymer of monomers such as acrylonitrile and ethenylidene chlorine, and the heat agent of rising is generally iso-butane or isopentane.Join and carry out thick resist lithography in the photoresist:
The adding percent by volume is 0.1～30% high polymer expended microsphere and evenly mixes in photoresist earlier, then its even Tu is overlayed on substrate surfaces such as silicon chip, silicon nitride, silicon dioxide, quartz glass or metal, about tens～hundreds of the micron of thickness, after photoetching processes such as preceding baking, exposure, development, form patterned photoresist structure with certain depth-to-width ratio;
2) add thermal expansion
Baking before placing above-mentioned photoresist structure under 80～300 ℃ of temperature, get rid of the organic solvent in the photoresist so on the one hand, on the other hand, because the expended microsphere expanded by heating can form irreversible hollow structure, wherein, during preceding baking, the control temperature upper limit is 300 ℃, significantly expand because microballoon is heated, thereby can obviously increase the thickness of graphical photoresist;
3) pyrolysis carbonization
Said structure placed 850～1150 ℃ of temperature and carry out the pyrolysis carbonization treatment of photoresist at vacuum or non-oxidizing gas (nitrogen,, the mixed atmosphere of argon gas or they and hydrogen), because the hollow structure of high polymer expended microsphere is destroyed, will in the carbon electrode array that forms, form the cavity, thereby further increased the surface area and the electrolyte volume of carbon electrode array, formation at last has the carbon electrode array structure of high surface and calking volume.
Exemplifying embodiment is below further specified.
Embodiment
With diameter is 6 microns 5% being joined in the SU-8 photoresist by volume by the thermoplasticity shell of the copolymer of monomers such as acrylonitrile and ethenylidene chlorine and the iso-butane heat high polymer expended microsphere that agent forms that rises, mix, then its even Tu is overlayed on the silicon chip substrate surface, about tens～hundreds of the micron of thickness, through preceding baking, exposure, after the photoetching processes such as development, baking before placing under 80～300 ℃ of temperature, the control temperature upper limit is 300 ℃, get rid of the organic solvent in the photoresist, and place uncovered quartz ampoule heating furnace, the nitrogen of feeding 2000sccm rises to 900 ℃ of temperature with the firing rate of 10 ℃/min, changes logical 5%H then
2And N
2Mist 2000sccm insulation 1 hour, the nitrogen that changes logical 2000sccm at last is cooled to room temperature, carries out the pyrolysis carbonization treatment of photoresist, and diameter reaches 20 microns behind the expended microsphere expanded by heating, and electrode surface area increases by 35%, and the electrolyte capacity improves 20%.
Claims (3)
1. preparation method with carbon electrode array of high surface and high gap filling capacity, it is characterized in that: its implementation comprises three steps:
1) the high polymer expended microsphere is joined carries out thick resist lithography in the photoresist
The adding percent by volume is 0.1～30% high polymer expended microsphere and evenly mixes in photoresist earlier, then it evenly is coated in silicon chip, silicon nitride, silicon dioxide, quartz glass or metal substrate surface, about tens～hundreds of the micron of thickness, after the photoetching process through preceding baking, exposure, development, form patterned photoresist structure with certain depth-to-width ratio;
2) add thermal expansion
Baking before placing above-mentioned photoresist structure under 80～300 ℃ of temperature, get rid of the organic solvent in the photoresist so on the one hand, on the other hand, because the expended microsphere expanded by heating can form irreversible hollow structure, wherein, during preceding baking, the control temperature upper limit is 300 ℃, significantly expand because microballoon is heated, thereby can obviously increase the thickness of graphical photoresist;
3) pyrolysis carbonization
Said structure is placed the pyrolysis carbonization treatment of carrying out photoresist under 850～1150 ℃ of temperature and the non-oxidizing gas atmosphere, because the hollow structure of high polymer expended microsphere is destroyed, will in the carbon electrode array that forms, form the cavity, thereby further increased the surface area and the electrolyte volume of carbon electrode array, formed carbon resistance rod array structure at last with high surface and high calking volume.
2. according to the described preparation method with carbon electrode array of high surface and high gap filling capacity of claim 1, it is characterized in that: described high polymer expended microsphere is made up of thermoplasticity shell and inner heat thereof the agent two parts that rise; Wherein shell is the copolymer of acrylon and ethenylidene chlorine monomer, and the heat agent of rising is iso-butane or isopentane.
3. according to the described preparation method with carbon electrode array of high surface and high gap filling capacity of claim 1, it is characterized in that: described non-oxidizing gas is the mist of nitrogen, argon gas or they and hydrogen.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2005100708529A CN1322608C (en) | 2005-05-20 | 2005-05-20 | Process for preparing carbon electrode array with high surface area and high gap filling capacity |
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|---|---|---|---|
| CNB2005100708529A CN1322608C (en) | 2005-05-20 | 2005-05-20 | Process for preparing carbon electrode array with high surface area and high gap filling capacity |
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| CN1702887A true CN1702887A (en) | 2005-11-30 |
| CN1322608C CN1322608C (en) | 2007-06-20 |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101877362B (en) * | 2009-04-30 | 2013-03-06 | 和椿科技股份有限公司 | Silicon substrate with period structure |
| CN103072938A (en) * | 2012-12-18 | 2013-05-01 | 厦门大学 | Preparation method of planar carbon film electrode |
| CN103342336A (en) * | 2013-06-27 | 2013-10-09 | 哈尔滨工业大学 | Preparation method of three-dimensional ordered macropore microelectrode |
| CN103487467A (en) * | 2013-09-06 | 2014-01-01 | 华中科技大学 | Manufacturing process of minitype gas-sensitive sensor of integrated heating element |
| CN104681308A (en) * | 2015-03-20 | 2015-06-03 | 太原理工大学 | Method for preparing aperture controllable three-dimensional microelectrode of super capacitor |
| CN104701020A (en) * | 2015-03-20 | 2015-06-10 | 太原理工大学 | Preparation method of SU-8 photoresist-based three-dimensional microelectrode |
| CN105047877A (en) * | 2015-07-08 | 2015-11-11 | 清华大学 | Negative active material and preparation method and application thereof |
| CN106744653A (en) * | 2016-11-07 | 2017-05-31 | 西南交通大学 | A kind of carbon-based micro-nano hierarchy array with endoporus and preparation method thereof |
| CN108370023A (en) * | 2015-12-09 | 2018-08-03 | Lg 化学株式会社 | The engraving method of electrode and the secondary cell for including the electrode etched by this method |
| CN112687802A (en) * | 2020-12-24 | 2021-04-20 | 亚洲硅业(青海)股份有限公司 | Electronic transmission layer of perovskite battery, preparation method of electronic transmission layer and perovskite battery |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5821033A (en) * | 1992-09-18 | 1998-10-13 | Pinnacle Research Institute, Inc. | Photolithographic production of microprotrusions for use as a space separator in an electrical storage device |
| IL122937A (en) * | 1998-01-14 | 2003-05-29 | Technion Res & Dev Foundation | Process and apparatus for etching a semiconductor material |
| JP3697426B2 (en) * | 2002-04-24 | 2005-09-21 | 株式会社東芝 | Pattern forming method and semiconductor device manufacturing method |
| CN1321054C (en) * | 2004-07-06 | 2007-06-13 | 华东师范大学 | Preparation method of silicon-based micro mechanical photomodulator chip |
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2005
- 2005-05-20 CN CNB2005100708529A patent/CN1322608C/en not_active Expired - Fee Related
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101877362B (en) * | 2009-04-30 | 2013-03-06 | 和椿科技股份有限公司 | Silicon substrate with period structure |
| CN103072938B (en) * | 2012-12-18 | 2015-07-08 | 厦门大学 | Preparation method of planar carbon film electrode |
| CN103072938A (en) * | 2012-12-18 | 2013-05-01 | 厦门大学 | Preparation method of planar carbon film electrode |
| CN103342336B (en) * | 2013-06-27 | 2016-03-16 | 哈尔滨工业大学 | A kind of preparation method of three-dimensional ordered macroporous microelectrode |
| CN103342336A (en) * | 2013-06-27 | 2013-10-09 | 哈尔滨工业大学 | Preparation method of three-dimensional ordered macropore microelectrode |
| CN103487467A (en) * | 2013-09-06 | 2014-01-01 | 华中科技大学 | Manufacturing process of minitype gas-sensitive sensor of integrated heating element |
| CN103487467B (en) * | 2013-09-06 | 2016-03-02 | 华中科技大学 | A kind of manufacture craft of miniature gas-sensitive sensor of integrated heating parts |
| CN104681308A (en) * | 2015-03-20 | 2015-06-03 | 太原理工大学 | Method for preparing aperture controllable three-dimensional microelectrode of super capacitor |
| CN104701020A (en) * | 2015-03-20 | 2015-06-10 | 太原理工大学 | Preparation method of SU-8 photoresist-based three-dimensional microelectrode |
| CN104701020B (en) * | 2015-03-20 | 2017-10-31 | 太原理工大学 | Three-dimensional micro-electrode preparation method based on the photoresists of SU 8 |
| CN105047877A (en) * | 2015-07-08 | 2015-11-11 | 清华大学 | Negative active material and preparation method and application thereof |
| CN108370023A (en) * | 2015-12-09 | 2018-08-03 | Lg 化学株式会社 | The engraving method of electrode and the secondary cell for including the electrode etched by this method |
| CN106744653A (en) * | 2016-11-07 | 2017-05-31 | 西南交通大学 | A kind of carbon-based micro-nano hierarchy array with endoporus and preparation method thereof |
| CN112687802A (en) * | 2020-12-24 | 2021-04-20 | 亚洲硅业(青海)股份有限公司 | Electronic transmission layer of perovskite battery, preparation method of electronic transmission layer and perovskite battery |
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| Publication number | Publication date |
|---|---|
| CN1322608C (en) | 2007-06-20 |
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