CN106876141A - A kind of preparation method of high-sequential platinum silicon nanowires to electrode - Google Patents
A kind of preparation method of high-sequential platinum silicon nanowires to electrode Download PDFInfo
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- CN106876141A CN106876141A CN201510932381.1A CN201510932381A CN106876141A CN 106876141 A CN106876141 A CN 106876141A CN 201510932381 A CN201510932381 A CN 201510932381A CN 106876141 A CN106876141 A CN 106876141A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/0029—Processes of manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
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- H01G9/04—Electrodes or formation of dielectric layers thereon
- H01G9/042—Electrodes or formation of dielectric layers thereon characterised by the material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
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- 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
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
Abstract
The invention discloses a kind of high-sequential platinum/silicon nanowires to the preparation method of electrode, belong to DSSC technical field, the present invention be using high-sequential silicon nanowires substrate and by electroless plating techniques Pt nanoparticle uniformly sink be plated on the side wall of silicon nanowires, on the one hand the technique and traditional integrated circuit process compatible, it is easy to prepare integrable miniature DSSC batteries, on the other hand the high-sequential platinum-silicon nanowires has big specific surface area to electrode, its ordered nano linear structure in electrode electron transport one-dimensional path is provided, the catalytic reduction efficiency of I3- ions in electrolyte is greatly improved, based on this DSSC to electrode composition, energy conversion efficiency is obviously improved.
Description
Technical field
The present invention relates to a kind of high-sequential platinum/silicon nanowires to the preparation method of electrode, belong to DSSC technical field.
Background technology
From 1991And O ' Regan propose that DSSC is because have on DSSC (DSSC) report
Potential low cost, abundant raw materials, be easy to large-scale production, can flexible manufacturing and the advantages of photoelectric efficiency higher, as renewable new
Energy battery is attracted wide attention.Typical DSSC is made up of the sandwich that two pieces of fluorine-doped tin oxide (FTO) glass plates are constituted：One
Used as galvanic anode, applied atop has nano TiO 2 and sensitization organic dyestuff to block FTO glass plates, and the dyestuff absorbs visible ray, and catalysis is simultaneously
Release electronics is in nanocrystalline TiO2 thin layers.Used as to electrode, applied atop has noble metal platinum (Pt) thin layer to another piece of FTO glass plate,
On the one hand electric current is conducted as cell cathode, the I3- in another aspect catalytic electrolysis matter receives electron reduction for I- on to electrode.Platinum DSSC
The catalyst commonly used to electrode in battery., to electrode generally by sputtering method, prepared by the method such as thermal decomposition method and electrochemical deposition, electrochemistry for platinum base
Deposition can make the coating have a good uniformity, controllable thickness, and the features such as large-scale production.Silicon-based nano cable architecture can provide bigger
Specific surface area come the dispersion that supports effective catalyst good, while silicon-based substrate material also allow for traditional integrated circuit process compatible, being can be integrated
Miniature dye-sensitized solar battery lays the foundation.
The content of the invention
The invention provides a kind of high-sequential platinum/silicon nanowires to the preparation method of electrode, electrode is improved using the high-sequential platinum silicon nanowires
The opto-electronic conversion performance of DSSC.
The technical solution adopted for the present invention to solve the technical problems is：A kind of high-sequential platinum/silicon nanowires is wrapped to the preparation method of electrode
Include following steps：
The first step, silicon nanowires is prepared using metal inducement selective wet chemical etching
1st, print cutting：Using single-sided polishing, N-shaped<100>Crystal orientation silicon chip, cuts into 1cm × 1cm prints.
2nd, print cleaning：Acetone soln is cleaned by ultrasonic organic stained particles such as 10-20min, removal surface dirt, greasy dirt and wax first；
Then ethylene glycol solution is cleaned by ultrasonic 10-20min, removes the residual of surface organic matter；Afterwards by going to be rinsed from water, removal surface is organic
Solvent；Afterwards by H2SO4: heated up in H2O2=3: 1 (volume ratio) solution and boil 10-20min, to remove
Metallic simultaneously generates hydrophilic thin oxide layer in silicon chip surface；Last print be cleaned by ultrasonic in a large amount of deionized waters remove removal of residue after taking-up nitrogen
Air-blowing is done standby.
3rd, prepared by high-sequential silicon nanowires (SiNWs) array：Print is polished upwardly, is immersed in AgNO3+HF+ deionized waters and is mixed
Close in solution, wherein AgNO3 concentration is 0.5-1.0mM, HF concentration is 1-2M, ultrasonic reaction time 30-40min, makes silver
Grain uniform deposition is to silicon chip surface；Print is taken out, polishing upwardly, is immersed in HF: H2O2=1: 1 (volume ratio) solution
In, room temperature etching 40-60min prepares high-sequential silicon nanowires (SiNWs) array substrate, the unnecessary Ag particles dilute nitre of 20-30%
Acid solution clean and reuse.
Second step, silicon nanowire array substrate pre-treatment：In the TritonX-100 solution of silicon nanowires substrate print immersion concentration 3%
30-60s, with the wellability for reducing internal pressure stress and improving SiNWs, is rinsed well after taking-up with deionized water.
3rd step, plating prepares platinum-silicon nanowires to electrode：KCL solution is electrolyte, and concentration is 0.1-0.2M；H2PtCl6
Used as platinum source, concentration is 2-4mM, and ethylenediamine tetra-acetic acid (EDTA) is complexing agent, concentration 10-15mg L-1；55-85 DEG C of magnetic agitation
Water-bath；PH value is adjusted being maintained at 8.0-9.0 by adding ammoniacal liquor；Two electrode systems, working electrode is silicon nanowire array substrate,
To electrode be platinum plate electrode, working pulse voltage waveform be triangular wave, high level 0.5V, low level -0.4V, sweep speed 100mVs-1,
Continue 100-200 circulations.
4th step, platinum-silicon nanowires is to electrode thermal anneal process：Nitrogen atmosphere protection, nitrogen flow 1-1.5Lmin-1,400-500 DEG C
Rapid thermal annealing 400-600s.
Through above-mentioned technical process, the silicon nanowires pattern of preparation than more uniform, high-sequential, line footpath 70-300nm, about 70-80 μm of height,
Pt nanoparticle is plated on the side wall of silicon nanowires by electrochemistry electro-plating method by uniform sinking.The diameter range of platinum grain is received tens to hundreds of
Between rice, platinum particles uniform deposition is in whole silicon nanowires side wall and bottom.
The beneficial effects of the invention are as follows：
1) platinum/silicon nanowires of the invention is high-sequential, moderate length, and line footpath is uniform, platinum grain uniform deposition in surface of silicon nanowires,
Good dispersion, specific surface area is big, high catalytic efficiency.
2) preparation method and traditional integrated circuit process compatible of platinum modification silicon nanowires nano structure electrode of the invention, mainly using electrochemistry
Processing procedure, low cost is simple to operate, and process conditions are gentle, and it is easy to realize.
3) silicon nanowire array substrate fabrication method of the invention uses metal inducement selective wet chemical etching technology, by pre-deposition argent
Grain mask and H2O2+HF mixed solutions prepare uniform silicon nanowire array, while silver nitrate is recyclable being used for multiple times.The method technique
It is mild condition, easy to operate, be can popularization and application a kind of low-cost silicon micro-processing technology.
4) plating solution of electroplatinizing prepares simple in the preparation method of platinum modification silicon nanowires nanostructured of the invention, and agents useful for same is common, valency
Lattice are cheap, low cost, and the platinum film of deposition is evenly distributed, and through quick thermal annealing process, platinum silicon nanowires contact layer process based prediction model is steady
It is fixed.
5) platinum/silicon nanowires has more catalysis activity than plane platinum film, platinum nanometer of its higher catalytic activity from not only homogeneous branch
Cluster Structures, the micro-nano spacing effect of silicon nanowire array substrate is relevant, also with rapid thermal annealing after platinum-silicon nanowires contact layer Xiao Te
Base Electric Field Distribution is relevant with the electrons transport property of the contact layer.Up to 8.30% can be obtained to the dye-sensitized cell of electrode based on platinum/silicon nanowires
Energy conversion efficiency, it is more taller than by sputtering the energy conversion efficiency that is obtained in the dye-sensitized cell that constitutes of Pt/ silicon planar counter electrodes.
Specific embodiment
A kind of high-sequential platinum/silicon nanowires comprises the following steps to the preparation method of electrode：
The first step, silicon nanowires is prepared using metal inducement selective wet chemical etching
1st, print cutting：Using single-sided polishing, N-shaped<100>Crystal orientation silicon chip, cuts into 1cm × 1cm prints.
2nd, print cleaning：Acetone soln is cleaned by ultrasonic organic stained particles such as 10-20min, removal surface dirt, greasy dirt and wax first；
Then ethylene glycol solution is cleaned by ultrasonic 10-20min, removes the residual of surface organic matter；Afterwards by going to be rinsed from water, removal surface is organic
Solvent；Afterwards by H2SO4: heated up in H2O2=3: 1 (volume ratio) solution and boil 10-20min, to remove
Metallic simultaneously generates hydrophilic thin oxide layer in silicon chip surface；Last print be cleaned by ultrasonic in a large amount of deionized waters remove removal of residue after taking-up nitrogen
Air-blowing is done standby.
3rd, prepared by high-sequential silicon nanowires (SiNWs) array：Print is polished upwardly, is immersed in AgNO3+HF+ deionized waters and is mixed
Close in solution, wherein AgNO3 concentration is 0.5-1.0mM, HF concentration is 1-2M, ultrasonic reaction time 30-40min, makes silver
Grain uniform deposition is to silicon chip surface；Print is taken out, polishing upwardly, is immersed in HF: H2O2=1: 1 (volume ratio) solution
In, room temperature etching 40-60min prepares high-sequential silicon nanowires (SiNWs) array substrate, the unnecessary Ag particles dilute nitre of 20-30%
Acid solution clean and reuse.
Second step, silicon nanowire array substrate pre-treatment：In the TritonX-100 solution of silicon nanowires substrate print immersion concentration 3%
30-60s, with the wellability for reducing internal pressure stress and improving SiNWs, is rinsed well after taking-up with deionized water.
3rd step, plating prepares platinum-silicon nanowires to electrode：KCL solution is electrolyte, and concentration is 0.1-0.2M；H2PtCl6
Used as platinum source, concentration is 2-4mM, and ethylenediamine tetra-acetic acid (EDTA) is complexing agent, concentration 10-15mg L-1；55-85 DEG C of magnetic agitation
Water-bath；PH value is adjusted being maintained at 8.0-9.0 by adding ammoniacal liquor；Two electrode systems, working electrode is silicon nanowire array substrate,
To electrode be platinum plate electrode, working pulse voltage waveform be triangular wave, high level 0.5V, low level -0.4V, sweep speed 100mVs-1,
Continue 100-200 circulations.
4th step, platinum-silicon nanowires is to electrode thermal anneal process：Nitrogen atmosphere protection, nitrogen flow 1-1.5Lmin-1,400-500 DEG C
Rapid thermal annealing 400-600s.
Through above-mentioned technical process, the silicon nanowires pattern of preparation than more uniform, high-sequential, line footpath 70-300nm, about 70-80 μm of height,
Pt nanoparticle is plated on the side wall of silicon nanowires by electrochemistry electro-plating method by uniform sinking.The diameter range of platinum grain is received tens to hundreds of
Between rice, platinum particles uniform deposition is in whole silicon nanowires side wall and bottom.
Claims (3)
1. preparation method of a kind of high-sequential platinum silicon nanowires to electrode, it is characterised in that：Its preparation method following steps：
1) print cutting：Using single-sided polishing, N-shaped<100>Crystal orientation silicon chip, cuts into 1cm × 1cm prints；
2) print cleaning：Acetone soln is cleaned by ultrasonic organic stained particles such as 10-20min, removal surface dirt, greasy dirt and wax；Then second
Glycol solution is cleaned by ultrasonic 10-20min, removes the residual of surface organic matter；Afterwards by deionized water rinsing, surface organic solvent is removed；
Afterwards by H2SO4: heated up in H2O2=3: 1 (volume ratio) solution and boil 10-20min, remove metallic and in silicon
The hydrophilic thin oxide layer of piece Surface Creation；Last print be cleaned by ultrasonic in a large amount of deionized waters remove removal of residue after the drying of taking-up nitrogen it is standby；
3) prepared by metal inducement selective wet chemical etching silicon nanowire array substrate：Print is polished upwardly, is immersed in AgNO 3+HF+ deionized waters
In mixed solution, wherein the concentration of AgNO 3 is 0.5-1.0mM, and HF concentration is 1-2M, ultrasonic reaction time 30-40min, makes silver
Grain uniform deposition is to silicon chip surface；Print is taken out, polishing upwardly, is immersed in HF: in H2O2=1: 1 (volume ratio) solution,
Room temperature etches 40-60min, prepares high-sequential silicon nanowires (SiNWs) array substrate, and unnecessary Ag particles are molten with 20-30% dust technologies
Liquid clean and reuse；
4) platinum-silicon nanowires is prepared to electrode：30-60s in the Triton X-100 solution of substrate print immersion concentration 3%, to reduce internal pressure
The wellability of stress and raising SiNWs, is rinsed well after taking-up with deionized water；KCL solution is electrolyte, and concentration is 0.1-0.2M；
Used as platinum source, concentration is 2-4mM to H2 PtCl 6, and ethylenediamine tetra-acetic acid (EDTA) is complexing agent, concentration 10-15mg L-1；Magnetic force
55-85 DEG C of water-bath of stirring；PH value is adjusted being maintained at 8.0-9.0 by adding ammoniacal liquor；Two electrode systems, working electrode is silicon nanowires
Array substrate, is platinum plate electrode to electrode, and working pulse voltage waveform is triangular wave, high level 0.5V, low level -0.4V, scanning speed
Rate 100mVs-1, continues 100-200 circulations；Platinum-silicon nanowires to electrode nitrogen atmosphere protection, nitrogen flow 1-1.5Lmin-1,
400-500 DEG C of rapid thermal annealing 400-600s.
2. preparation method of a kind of high-sequential platinum silicon nanowires according to claim 1 to electrode, it is characterised in that：Described metal inducement
Learn wet etching silicon nanowire array substrate fabrication method：
1) metal inducement mask pretreatment：Print is polished upwardly, is immersed in AgNO 3+HF+ deionized water mixed solutions, wherein
The concentration of AgNO 3 is 0.5-1.0mM, and HF concentration is 1-2M, ultrasonic reaction time 30-40min, makes Argent grain uniform deposition to silicon chip
Surface；
2) prepared by metal inducement selective wet chemical etching silicon nanowires：Print is polished upwardly, is immersed in HF: H2O2=1: 1 (volume ratio) is molten
In liquid, room temperature etching 40-60min prepares high-sequential silicon nanowires (SiNWs) array substrate, and unnecessary Ag particles are dilute with 20-30%
Salpeter solution clean and reuse.
3. preparation method of a kind of high-sequential platinum silicon nanowires according to claim 1 to electrode, it is characterised in that：Described platinum-silicon nanometer
Line is prepared as electrochemistry pulsed deposition to electrode, and electroplating bath components and preceding final treatment techniques are：
1) 30-60s carries out plating pretreatment in the Triton X-100 solution of substrate print immersion concentration 3%, to reduce internal pressure stress and improve SiNWs
Wellability；
2) electrolyte composition：KCL solution is electrolyte, and concentration is 0.1-0.2M；Used as platinum source, concentration is 2-4mM to H2 PtCl 6,
Ethylenediamine tetra-acetic acid (EDTA) is complexing agent, concentration 10-15mg L-1；55-85 DEG C of water-bath of magnetic agitation；PH value is by adding ammonia
Water is adjusted being maintained at 8.0-9.0；Two electrode systems, working electrode is silicon nanowire array substrate, and to electrode platinum plate electrode, work arteries and veins
Voltage waveform is rushed for triangular wave, high level 0.5V, low level -0.4V, sweep speed 100mVs-1 continue 100-200 circulations；Platinum
- silicon nanowires is to electrode nitrogen atmosphere protection, nitrogen flow 1-1.5Lmin-1,400-500 DEG C of rapid thermal annealing 400-600s.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109087852A (en) * | 2018-08-10 | 2018-12-25 | 深圳市华星光电技术有限公司 | The production method of transistor metal electrode structure |
| CN109324090A (en) * | 2017-07-31 | 2019-02-12 | 天津大学 | One-dimensional silicon based array micro-structure and preparation method thereof and the application in gas sensor |
| CN113027664A (en) * | 2021-03-23 | 2021-06-25 | 华中科技大学 | Wave energy recovery device and method based on electrochemical principle |
-
2015
- 2015-12-13 CN CN201510932381.1A patent/CN106876141A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109324090A (en) * | 2017-07-31 | 2019-02-12 | 天津大学 | One-dimensional silicon based array micro-structure and preparation method thereof and the application in gas sensor |
| CN109087852A (en) * | 2018-08-10 | 2018-12-25 | 深圳市华星光电技术有限公司 | The production method of transistor metal electrode structure |
| CN109087852B (en) * | 2018-08-10 | 2020-09-08 | 深圳市华星光电技术有限公司 | Method for manufacturing transistor metal electrode structure |
| CN113027664A (en) * | 2021-03-23 | 2021-06-25 | 华中科技大学 | Wave energy recovery device and method based on electrochemical principle |
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