CN107871613A - 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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- CN107871613A CN107871613A CN201610852108.2A CN201610852108A CN107871613A CN 107871613 A CN107871613 A CN 107871613A CN 201610852108 A CN201610852108 A CN 201610852108A CN 107871613 A CN107871613 A CN 107871613A
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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
- H01G9/2022—Light-sensitive devices characterized by he counter electrode
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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
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
A kind of preparation method the invention discloses high-sequential platinum/silicon nanowires to electrode, belong to DSSC technical field, the present invention is to use high-sequential silicon nanowires substrate and uniformly sink Pt nanoparticle by electroless plating techniques to be plated in 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 provides one-dimensional path for electron transport in electrode, the catalytic reduction efficiency of the ions of I 3 in electrolyte is greatly improved, DSSC based on this 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 dye sensitization of solar
Cell art.
Background technology
Since 1991And O ' Regan propose on DSSC (DSSC) report, DSSC because
With potential low cost, abundant raw materials, it is easy to the advantages that large-scale production, energy flexible manufacturing and higher photoelectric efficiency,
Attracted wide attention as renewable new energy battery.Typical DSSC is by two pieces of fluorine-doped tin oxide (FTO) glass plate groups
Into sandwich composition：For one piece of FTO glass plate as galvanic anode, applied atop has nano TiO 2 and sensitization organic dyestuff,
The dyestuff absorbs visible ray, is catalyzed and discharges electronics into nanocrystalline TiO2 thin layers.Another piece of FTO glass plate is used as to electrode,
Applied atop has noble metal platinum (Pt) thin layer, on the one hand electric current is conducted as cell cathode, in another aspect catalytic electrolysis matter
It is I- that I3- receives electron reduction on to electrode.The catalyst commonly used in platinum DSSC batteries to electrode.Platinum base is generally logical to electrode
Prepared by the methods of crossing sputtering method, thermal decomposition method and electrochemical deposition, electrochemical deposition can make coating have good uniformity,
Controllable thickness, and the features such as large-scale production.Silicon-based nano cable architecture can provide more bigger serface to support effective catalysis
Good scattered of agent, at the same silicon-based substrate material also allow for traditional integrated circuit process compatible, it is quick too for integrable miniature dye
Positive energy battery lays the foundation.
The content of the invention
Preparation method the invention provides a kind of high-sequential platinum/silicon nanowires to electrode, using the high-sequential platinum
Silicon nanowires improves the opto-electronic conversion performance of DSSC to electrode.
The technical solution adopted for the present invention to solve the technical problems is：A kind of high-sequential platinum/silicon nanowires is to electrode
Preparation method, comprise the following steps：
The first step, silicon nanowires is prepared using metal inducement selective wet chemical etching
1st, print is cut：Using single-sided polishing, n-type<100>Crystal orientation silicon chip, cut into 1cm × 1cm prints.
2nd, print cleans：Acetone soln is cleaned by ultrasonic 10-20min first, removes organic flaws such as surface dirt, greasy dirt and wax
Dirty particle；Then ethylene glycol solution is cleaned by ultrasonic 10-20min, removes the residual of surface organic matter；Afterwards by going to rush from water
Wash, remove surface organic solvent；10-20min is boiled by being heated up in H2SO4: H2O2=3: 1 (volume ratio) solution afterwards,
To remove metallic and to generate hydrophilic thin oxide layer in silicon chip surface；Last print is cleaned by ultrasonic in a large amount of deionized waters
The drying of taking-up nitrogen is standby after removing removal of residue.
3rd, prepared by high-sequential silicon nanowires (SiNWs) array：Print polish upwardly, be immersed in AgNO3+HF+ go from
In sub- water mixed solution, wherein AgNO3 concentration is 0.5-1.0mM, and HF concentration is 1-2M, ultrasonic reaction time 30-40min, is made
Argent 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, high-sequential silicon nanowires (SiNWs) array substrate is prepared, unnecessary Ag particles are dilute with 20-30%
Salpeter solution clean and reuse.
Second step, silicon nanowire array substrate pre-treatment：Silicon nanowires substrate print immerses the TritonX- of concentration 3%
30-60s in 100 solution, with the wellability for reducing internal pressure stress and improving SiNWs, rinsed well after taking-up with deionized water.
3rd step, plating prepare platinum-silicon nanowires to electrode：KCL solution is electrolyte, concentration 0.1-0.2M；
H2PtCl6 is as platinum source, concentration 2-4mM, and ethylenediamine tetra-acetic acid (EDTA) is complexing agent, concentration 10-15mg L-1；Magnetic force stirs
Mix 55-85 DEG C of water-bath；PH value is adjusted by adding ammoniacal liquor and is maintained at 8.0-9.0；Two electrode systems, working electrode are received for silicon
Nanowire arrays substrate, is platinum plate electrode to electrode, and working pulse voltage waveform is 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 of rapid thermal annealing 400-600s.
Through above-mentioned technical process, the silicon nanowires pattern of preparation is than more uniform, high-sequential, line footpath 70-300nm, height
About 70-80 μm, Pt nanoparticle is plated in the side wall of silicon nanowires by electrochemistry electro-plating method by uniform sink.Platinum grain
Diameter range is between tens to hundreds of nanometers, and 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, and moderate length, line footpath is uniform, and platinum grain uniform deposition is in silicon
Nanowire surface, good dispersion, specific surface area is big, high catalytic efficiency.
2) preparation method and traditional integrated circuit process compatible of platinum of the invention modification silicon nanowires nano structure electrode,
Electrochemical process mainly is used, cost is low, 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-
Deposited metal Argent grain mask and H2O2+HF mixed solutions prepare uniform silicon nanowire array, while silver nitrate is recyclable
It is used for multiple times.This method process conditions are gentle, easy to operate, be can popularization and application a kind of low-cost silicon micro-processing technology.
4) plating solution of electroplatinizing is prepared simply in the preparation method of platinum of the invention modification silicon nanowires nanostructured, used
Reagent is common, cheap, and cost is low, and the platinum film of deposition is evenly distributed, through quick thermal annealing process, the contact of platinum silicon nanowires
Layer physical and chemical properties are stable.
5) platinum/silicon nanowires has more catalytic activity than plane platinum film, and its higher catalytic activity is from not only homogeneous
The platinum nanoclusters structure of branch, the micro-nano spacing effect of silicon nanowire array substrate is relevant, also with platinum after rapid thermal annealing-
The Schottky Electric Field Distribution of silicon nanowires contact layer is relevant with the electrons transport property of the contact layer.Based on platinum/silicon nanowires pair
The dye-sensitized cell of electrode can obtain up to 8.30% energy conversion efficiency, and it is than by sputtering Pt/ silicon planar counter electrode structures
Into dye-sensitized cell in the energy conversion efficiency that obtains it is taller.
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 is cut：Using single-sided polishing, n-type<100>Crystal orientation silicon chip, cut into 1cm × 1cm prints.
2nd, print cleans：Acetone soln is cleaned by ultrasonic 10-20min first, removes organic flaws such as surface dirt, greasy dirt and wax
Dirty particle；Then ethylene glycol solution is cleaned by ultrasonic 10-20min, removes the residual of surface organic matter；Afterwards by going to rush from water
Wash, remove surface organic solvent；10-20min is boiled by being heated up in H2SO4: H2O2=3: 1 (volume ratio) solution afterwards,
To remove metallic and to generate hydrophilic thin oxide layer in silicon chip surface；Last print is cleaned by ultrasonic in a large amount of deionized waters
The drying of taking-up nitrogen is standby after removing removal of residue.
3rd, prepared by high-sequential silicon nanowires (SiNWs) array：Print polish upwardly, be immersed in AgNO3+HF+ go from
In sub- water mixed solution, wherein AgNO3 concentration is 0.5-1.0mM, and HF concentration is 1-2M, ultrasonic reaction time 30-40min, is made
Argent 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, high-sequential silicon nanowires (SiNWs) array substrate is prepared, unnecessary Ag particles are dilute with 20-30%
Salpeter solution clean and reuse.
Second step, silicon nanowire array substrate pre-treatment：Silicon nanowires substrate print immerses the TritonX- of concentration 3%
30-60s in 100 solution, with the wellability for reducing internal pressure stress and improving SiNWs, rinsed well after taking-up with deionized water.
3rd step, plating prepare platinum-silicon nanowires to electrode：KCL solution is electrolyte, concentration 0.1-0.2M；
H2PtCl6 is as platinum source, concentration 2-4mM, and ethylenediamine tetra-acetic acid (EDTA) is complexing agent, concentration 10-15mg L-1；Magnetic force stirs
Mix 55-85 DEG C of water-bath；PH value is adjusted by adding ammoniacal liquor and is maintained at 8.0-9.0；Two electrode systems, working electrode are received for silicon
Nanowire arrays substrate, is platinum plate electrode to electrode, and working pulse voltage waveform is 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 of rapid thermal annealing 400-600s.
Through above-mentioned technical process, the silicon nanowires pattern of preparation is than more uniform, high-sequential, line footpath 70-300nm, height
About 70-80 μm, Pt nanoparticle is plated in the side wall of silicon nanowires by electrochemistry electro-plating method by uniform sink.Platinum grain
Diameter range is between tens to hundreds of nanometers, and platinum particles uniform deposition is in whole silicon nanowires side wall and bottom.
Claims (3)
1. a kind of high-sequential platinum silicon nanowires is to the preparation method of electrode, it is characterised in that：Its preparation method following steps：
1) print is cut：Using single-sided polishing, n-type<100>Crystal orientation silicon chip, cut into 1cm × 1cm prints；
2) print cleans：Acetone soln is cleaned by ultrasonic 10-20min, removes organic stained particles such as surface dirt, greasy dirt and wax；
Then ethylene glycol solution is cleaned by ultrasonic 10-20min, removes the residual of surface organic matter；Afterwards by deionized water rinsing, remove
Surface organic solvent；10-20min is boiled by being heated up in H2SO4: H2O2=3: 1 (volume ratio) solution afterwards, removes metal
Particle simultaneously generates hydrophilic thin oxide layer in silicon chip surface；Last print is cleaned by ultrasonic in a large amount of deionized waters remove removal of residue after
Taking-up is dried up standby with nitrogen；
3) prepared by metal inducement selective wet chemical etching silicon nanowire array substrate：Print polishes upwardly, is immersed in AgNO3+HF+
In deionized water mixed solution, wherein AgNO3 concentration is 0.5-1.0mM, and HF concentration is 1-2M, ultrasonic reaction time 30-
40min, make Argent grain uniform deposition to silicon chip surface；Print is taken out, polishing upwardly, is immersed in HF: H2O2=1: 1 (volume
Than) in solution, room temperature etching 40-60min, high-sequential silicon nanowires (SiNWs) array substrate is prepared, unnecessary Ag particles are used
20-30% dilute nitric acid solution clean and reuses；
4) platinum-silicon nanowires is prepared to electrode：30-60s in the Triton X-100 solution of substrate print immersion concentration 3%, with
Reduce internal pressure stress and improve SiNWs wellability, rinsed well after taking-up with deionized water；KCL solution is electrolyte, concentration
For 0.1-0.2M；H2PtCl6 is as platinum source, concentration 2-4mM, and 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 adjusted by adding ammoniacal liquor and is maintained at 8.0-9.0；Two electrode systems, work
Electrode is silicon nanowire array substrate, is platinum plate electrode to electrode, and working pulse voltage waveform is 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.
2. a kind of high-sequential platinum silicon nanowires according to claim 1 is to the preparation method of electrode, it is characterised in that：Institute
The metal inducement selective wet chemical etching silicon nanowire array substrate fabrication method stated：
1) metal inducement mask pre-processes：Print polishes upwardly, is immersed in AgNO3+HF+ deionized water mixed solutions, its
Middle AgNO3 concentration is 0.5-1.0mM, and HF concentration is 1-2M, ultrasonic reaction time 30-40min, makes Argent grain uniform deposition to silicon
Piece surface；
2) prepared by metal inducement selective wet chemical etching silicon nanowires：Print polishes upwardly, is immersed in HF: H2O2=1: 1 (volume
Than) in solution, room temperature etching 40-60min, high-sequential silicon nanowires (SiNWs) array substrate is prepared, unnecessary Ag particles are used
20-30% dilute nitric acid solution clean and reuses.
3. a kind of high-sequential platinum silicon nanowires according to claim 1 is to the preparation method of electrode, it is characterised in that：Institute
Platinum-the silicon nanowires stated 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 the wellability for improving SiNWs；
2) electrolyte forms：KCL solution is electrolyte, concentration 0.1-0.2M；H2PtCl6 is as platinum source, concentration 2-4mM,
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, which is adjusted, is maintained at 8.0-9.0；Two electrode systems, working electrode are silicon nanowire array substrate, to electrode platinum plate electrode,
Working pulse voltage waveform is triangular wave, high level 0.5V, low level -0.4V, sweep speed 100mVs-1, continues 100-200
Circulation；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。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610852108.2A CN107871613A (en) | 2016-09-26 | 2016-09-26 | A kind of preparation method of high-sequential platinum silicon nanowires to electrode |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610852108.2A CN107871613A (en) | 2016-09-26 | 2016-09-26 | A kind of preparation method of high-sequential platinum silicon nanowires to electrode |
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| Publication Number | Publication Date |
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| CN107871613A true CN107871613A (en) | 2018-04-03 |
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| CN201610852108.2A Pending CN107871613A (en) | 2016-09-26 | 2016-09-26 | A kind of preparation method of high-sequential platinum silicon nanowires to electrode |
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2016
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Application publication date: 20180403 |