CN102751104B - Based on thick resist lithography electroforming process three-dimensional MEMS ultracapacitor manufacture method - Google Patents
Based on thick resist lithography electroforming process three-dimensional MEMS ultracapacitor manufacture method Download PDFInfo
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Abstract
The present invention relates to a kind of based on thick resist lithography eletroforming technique three-dimensional MEMS ultracapacitor manufacture method. This ultracapacitor has comb teeth-shaped and inserts finger structure, on at the bottom of silicon wafer-based, use SU-8 thick resist lithography as template, use electroforming process in template, to deposit collector, then on collector, electrochemical polymerization conducting polymer, as ultracapacitor active electrode material, finally covers one deck solid electrolyte. This ultracapacitor, owing to having three-dimensional structure, has effectively increased the surface area of electrode, has therefore greatly improved energy density and power density with respect to slab construction. In addition, the use of solid electrolyte has improved its security performance.
Description
Technical field
The present invention relates to a kind of MEMS ultracapacitor manufacture method based on thick resist lithography electroforming process.
Background technology
Ultracapacitor (electrochemical capacitance) is a kind of Novel energy storage apparatus between traditional capacitor and battery, has the advantages such as power density is large, the time that discharges and recharges is short, have extended cycle life, cryogenic property is good. The dual-use application of electrochemical capacitance is very extensive, the little wireless senser to micron level, and the starting drive that arrives greatly rocket satellite all be unable to do without electrochemical capacitance. Current research according to Lux shows, ultra-capacitor has huge market potential, and whole ultra-capacitor market income is expected to break through to 8.77 hundred million dollars in 2014 from 2.08 hundred million dollars of 2008.
Small-sized electrochemical capacitance can be integrated due to portable electric appts etc. with IC circuit. The electrochemical capacitance integrated with IC electric current can be used as stand-by power supply, and in the time of the power supply of main power source cut or voltage dip, ultracapacitor can start to memory, micro calculator, mainboard, these critical component power supplies such as clock; In addition, can provide pulse current that battery can not provide to meet high power requirements with the integrated electrochemical capacitance of IC circuit, there is continuous flash of light ability such as the electrochemical capacitance in camera flash system makes camera; In addition, can be used as the storing apparatus of energy collecting system with the integrated electrochemical capacitance of IC circuit, after a solar energy wrist-watch with electrochemical capacitance is full of electricity by day, can work up to a hundred hours, and this solar energy wrist-watch need not be changed electrochemical capacitance throughout one's life. Except aspect consumer electronics, the electrochemical capacitance of miniaturization is due to its high power density, and the advantages such as long-life, also have quite high using value aspect military or civilian wireless telecommunications and wireless senser.
Electrochemical capacitance has application so widely and comes from the advantages such as its power density is large, the time that discharges and recharges is short, have extended cycle life, cryogenic property is good. The major defect of electrochemical capacitance is that its energy density is only 5～7% of lithium ion battery. Therefore, how to improve the performance of electrochemical capacitance, especially energy density, becomes the major subjects that electrochemical capacitance is studied.
As a rule, according to charge-storage mechanism, ultra-capacitor can be divided into two kinds of electric double layer capacitance and electrochemical capacitors. The electric capacity of electric double layer derives from the electrostatic attraction (similar traditional capacitor) of physics, and the capacity of electrochemical capacitor is from redox reaction (similar battery). The capacity density of the electrochemical capacitance of every type all with the effective area positive correlation of electrode material, therefore about introducing nanometer technology, to improve the research of performance of electrochemical capacitance very extensive, especially improves the performance of electrochemical capacitance by preparing nano-electrode material. Wherein CNT is as the electrode material most study of electric double layer capacitance, metal nanoparticle also can be used as the electrode of electrochemical capacitance, it is studied that the typical electrode materials conducting polymer of electrochemistry electrochemical capacitance is also made into nanostructured, metal oxide has also improved performance by nano modification as the material of another electrochemistry electrochemical capacitance, in addition researchers have also prepared carbon nano tube/conducting polymer compound film electrode, attempt to bring into play the double action of electric double layer capacitance and electrochemical capacitor.
But, electrode material is only a key component of electrochemical capacitance system, how selects suitable electrochemical capacitance system (comprising electrochemical capacitance structure, electrolyte, collector etc.), preparation processing method according to electrode material and is also the especially major issue of electrochemical capacitance application of research electrochemical capacitance with integrated (the comprising the integrated of the integrated of small-size chips level and large scale hybrid energy system) of circuit. Increasingly mature MEMS(MEMS) the technology chip-scale that is electrochemical capacitance and other function elements is integrated that good condition is provided. But now for the integrated electrochemical capacitance of chip of silicon chip level technology or to be integrated in the electrochemical capacitance research of printed circuit board (PCB) very limited. Korea S Sung has prepared all solid state electrochemical capacitance of plane comb structure based on silicon base, but because structure is too simple, does not effectively carry out space utilization and cause this electrochemical capacitance performance not high. Y.Q.Jiang has prepared CNT forest that 80 μ m the are high electrode as electrochemical capacitance on silicon chip, has obtained 428 μ Fcm-2Specific capacity and 0.28mWcm-2The electric double layer electrochemical capacitance of specific power, its energy density is still limited, and liquid electrolyte has increased its integrated difficulty and the occasion that has limited its application in addition. For the problem of electrochemical capacitance and the integrated aspect of plated circuit, once had two Americans to study the circuit board integral printing of ultra-capacitor, but without any technical data and scientific and technical literature publish.
Summary of the invention
The present invention proposes a kind of novel three-dimensional MEMS electrochemical capacitance, and this electrochemical capacitance utilizes the manufacture of MEMS processing method to form. Adopt the MEMS processing technology of existing maturation, in silicon or substrate of glass, utilize nanometer technique to process the very large three-dimensional structure of specific area, combined with electrochemical conducting polymer electrode preparation technology realizes high power density, high-energy-density and long cycle lie. The all processing process of the present invention and printed circuit board (PCB) or other MEMS device fabrication compatibilities, therefore both can form hybrid energy system with energy harvester or micro cell, can embed again electronic circuit system and be applied to consumer electronics and wireless device.
The technical solution used in the present invention is:
Comprise the following steps based on thick resist lithography electroforming process three-dimensional MEMS ultracapacitor manufacture method:
(1) Wafer Cleaning, cleaning step is for being followed successively by organic oil removing, and inorganic oil removing, removes oxide-film and removes metal ion.
(2) put cleaned silicon chip in step (1) into oxidation furnace and carry out thermal oxide, the oxide-film of formation is as the electric insulation layer of two electrodes of ultracapacitor.
(3) put well-oxygenated silicon chip in step (2) into vacuum sputter system sputter electroforming Seed Layer.
(4) in step (3), have on the silicon chip of electroforming Seed Layer and adopt the method for the even glue of rotation to coat thick layer photoresist, exposure, develops, and after solidifying, forms three-dimensional broach template.
(5) silicon chip in step (4) with the three-dimensional broach template of thick glue is put in electroplating pool and carried out electroforming until fill full whole broach template, then remove the Seed Layer below thick glue pattern plate and template by the method for chemical attack, insert thereby form to have the collector that refers to structure on silicon chip.
(6) silicon chip in step (5) with slotting finger structure collector is put in electrochemical reaction cell and carried out electrochemical polymerization, form conducting polymer electrode at collection liquid surface.
(7) in step (6), have and on the silicon chip of conducting polymer electrode, apply one deck solid electrolyte and form three-dimensional MEMS ultracapacitor device.
In described step (1), cleaning is silicon chip standard cleaning technique.
In described step (2), thermal oxide is means of wet thermal oxidation, and thickness is 0.5-1.5 micron.
Electroforming Seed Layer in described step (3) is the one of gold, platinum, nickel, and thickness is 100-500 nanometer.
Photoresist in described step (4) can be negative glue SU-8 or positive glue PMMA(polymethyl methacrylate), three-dimensional structure width is 5-200 micron, and thickness is 100-1000 micron, and solidification temperature is 80-100 degree Celsius.
The removal method of the photoresist template in described step (4) is chemical attack.
Collector in described step (5) is the one of gold, copper or nickel, and electroforming current density is 10-50mAcm-2, temperature is 30-90 degree Celsius.
Conducting polymer in described step (6) is polypyrrole, polyaniline, and one or both of polythiophene or its derivative, also can be composite conductive high molecular.
Electrochemical polymerization solution in described step (6) contains large-scale anion, and current density is 0.1-10mAcm-2。
Solid electrolyte in described step (7) is gel state electrolyte, contains the anion that size is relatively little.
Advantage of the present invention is: in whole device fabrication process, technique used is compatible mutually with ripe MEMS technique, three-dimensional micro-electrode structure of the present invention effectively raises the effective surface area of unit area basis area, thereby improves specific energy and the specific power of ultracapacitor device. In addition, the application of solid electrolyte has improved the security performance of ultracapacitor.
Brief description of the drawings
Fig. 1 is the structural representation of ultracapacitor example of the present invention; SiO in figure2/ SiSubstrate is SiO2/ Si substrate; Solidstateelectrolyte is solid electrolyte; Output is output;
Fig. 2 is the processing process figure of example of the present invention.
Detailed description of the invention
The structural representation of ultracapacitor example of the present invention as shown in Figure 1.
As shown in Figure 2, based on thick resist lithography electroforming process three-dimensional MEMS ultracapacitor manufacture method, comprise the following steps:
(1) choose 4 cun of silicon chips as substrate, silicon chip cleans with wipe oil successively in dimethylbenzene, acetone, alcohol, sulfuric acid/hydrogen peroxide, ammoniacal liquor/hydrogen peroxide, hydrochloric acid/hydrogen peroxide solution, oxide-film and metal ion.
(2) put cleaned silicon chip in step (1) into oxidation furnace and carry out means of wet thermal oxidation 10 hours, oxidated layer thickness is 1.5 microns.
(3) in step (2), on well-oxygenated silicon chip, rf magnetron sputtering a layer thickness is that the nickel of 300 nanometers is as electroforming Seed Layer.
(4) on the nickel dam in step (3), adopt the method for the even glue of rotation to be coated with the SU-8 photoresist of last layer Microchem company, leave standstill after bubble collapse 95 degrees Celsius of front bakings 4 hours, expose 320 seconds, develop 4 hours, after 95 degrees Celsius, dry and solidify that after 4 hours, to form thickness be the three-dimensional comb structure of 450 microns.
(5) using the three-dimensional comb structure in step (4) as template, carry out the collector of electroformed nickel as ultracapacitor thereon, current density is 20mAcm-2, the electroforming time is about 20 hours, and electroforming solution is the watt electroplate liquid of improveing. In the time that the thickness of electroformed nickel reaches template thickness, stop electroforming, erode the Seed Layer below template and template, insert thereby form to have the nickel collector that refers to structure on silicon chip.
(6) in step (5), on nickel collector, in electrolytic cell, carry out polypyrrole (PPy) electrochemical polymerization, electrolyte ph is 4 and contains the mix ion of p-methyl benzenesulfonic acid anion as polypyrrole, and polymerization current density is 1mAcm-2, polymerization temperature is 25 degrees Celsius, polymerization time is 30 minutes.
(7) POLYPROPYLENE GLYCOL/lithium perchlorate/water that applies layer of gel state on step (6) Platinum completes the encapsulation of whole three-dimensional MEMS ultracapacitor as the solid electrolyte of this ultracapacitor.
As above the three-dimensional MEMS ultracapacitor processed is tested on electrochemical workstation, at 5mAcm-2Under discharge rate, recording its specific capacity is 0.029Fcm-2。
The present invention has improved the surface area of electrode of super capacitor by micro fabrication, thereby has improved energy density and the power density of ultracapacitor. All processing technologys in the present invention are compatible mutually with the processing technology of other MEMS devices such as pressure sensor, energy harvester etc., therefore have very high integration, have a wide range of applications in microelectronics, sensor field.
Claims (8)
1. the three-dimensional MEMS ultracapacitor manufacture method based on thick resist lithography electroforming process, is characterized in that, comprises the following steps:
(1) Wafer Cleaning, cleaning step is for being followed successively by organic oil removing, and inorganic oil removing, removes oxide-film and removes metal ion;
(2) put cleaned silicon chip in step (1) into oxidation furnace and carry out thermal oxide, the oxide-film of formation is as the electric insulation layer of two electrodes of ultracapacitor;
(3) put well-oxygenated silicon chip in step (2) into vacuum sputter system sputter electroforming Seed Layer;
(4) in step (3), have on the silicon chip of electroforming Seed Layer and adopt the method for the even glue of rotation to coat thick layer photoresist, exposure, develops, and after solidifying, forms three-dimensional broach template; Three-dimensional structure width is 5-200 micron, and thickness is 100-1000 micron;
(5) silicon chip in step (4) with the three-dimensional broach template of thick glue is put in electroplating pool and carried out electroforming until fill full whole broach template, then remove the Seed Layer below thick glue pattern plate and template by chemical method, insert thereby form to have the collector that refers to structure on silicon chip;
(6) silicon chip in step (5) with slotting finger structure collector is put in electrochemical reaction cell and carried out electrochemical polymerization, form conducting polymer electrode at collection liquid surface;
(7) in step (6), have and on the silicon chip of conducting polymer electrode, apply one deck solid electrolyte and form three-dimensional MEMS ultracapacitor device.
2. the three-dimensional MEMS ultracapacitor manufacture method based on thick resist lithography electroforming process according to claim 1, is characterized in that, in described step (3), electroforming Seed Layer is the one of metallic gold, platinum or nickel, and thickness is 100-500 nanometer.
3. the three-dimensional MEMS ultracapacitor manufacture method based on thick resist lithography electroforming process according to claim 1, it is characterized in that, photoresist in described step (4) can be negative glue SU-8 or positive glue polymetylmethacrylate, and solidification temperature is 80-100 degree Celsius.
4. the three-dimensional MEMS ultracapacitor manufacture method based on thick resist lithography electroforming process according to claim 1, is characterized in that, the removal method of the photoresist template in described step (4) is chemical attack.
5. the three-dimensional MEMS ultracapacitor manufacture method based on thick resist lithography electroforming process according to claim 1, is characterized in that, the collector in described step (5) is the one of gold, copper or nickel, and electroforming current density is 10-50mAcm-2, temperature is 30-90 degree Celsius.
6. the three-dimensional MEMS ultracapacitor manufacture method based on thick resist lithography electroforming process according to claim 1, it is characterized in that, the conducting polymer in described step (6) is polypyrrole, polyaniline, one or both of polythiophene or its derivative, also can be composite conductive high molecular.
7. the three-dimensional MEMS ultracapacitor manufacture method based on thick resist lithography electroforming process according to claim 1, is characterized in that, the electrochemical polymerization solution in described step (6) contains large-scale anion, and current density is 0.1-10mAcm-2。
8. the three-dimensional MEMS ultracapacitor manufacture method based on thick resist lithography electroforming process according to claim 1, is characterized in that, the solid electrolyte in described step (7) is gel state electrolyte, contains the anion that size is relatively little.
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| CN104810163B (en) * | 2014-07-18 | 2017-08-08 | 纳米新能源（唐山）有限责任公司 | Preparation method, graphene ultracapacitor and the energy-storage system of graphene ultracapacitor |
| CN104465125B (en) * | 2014-11-28 | 2017-12-01 | 太原理工大学 | TiO2Three-dimensional interdigital microelectrodes of/NiO and preparation method thereof |
| CN104599864B (en) * | 2015-01-22 | 2017-10-24 | 太原理工大学 | It is a kind of to increase the skew ray carving method of MEMS supercapacitor electrode specific surface area |
| CN104681304B (en) * | 2015-03-20 | 2017-08-25 | 太原理工大学 | A kind of Asymmetric Supercapacitor preparation method |
| CN104701030B (en) * | 2015-03-24 | 2017-09-29 | 武汉理工大学 | All solid state symmetric three-dimensional spiral micro super capacitor and preparation method thereof |
| CN108751125A (en) * | 2018-06-07 | 2018-11-06 | 皖西学院 | A method of improving photoresist glue-line and electroforming metal bed boundary binding force |
| CN109659153A (en) * | 2018-12-18 | 2019-04-19 | 清华大学 | A kind of metal oxide and the compound micro comb energy storage electrode of carbon nanotube |
| CN109809359A (en) * | 2019-01-10 | 2019-05-28 | 北方工业大学 | 2.5D interdigital electrode manufacturing method and interdigital electrode |
| CN111063548A (en) * | 2019-12-13 | 2020-04-24 | 江苏大学 | Three-dimensional silicon structure/polyaniline-based composite electrode material and preparation method thereof |
| CN112382511B (en) * | 2020-10-14 | 2021-08-13 | 北京理工大学 | Self-charging micro optical capacitor device and preparation method thereof |
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| CN101325130A (en) * | 2008-05-22 | 2008-12-17 | 清华大学 | Poly-pyrrole minisize super capacitor based on MEMS technique and method for manufacturing the same |
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