CN108206093A - A kind of high-sequential platinum silicon nanowires is to the preparation method of electrode - Google Patents
A kind of high-sequential platinum silicon nanowires is to the preparation method of electrode Download PDFInfo
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- CN108206093A CN108206093A CN201611188381.6A CN201611188381A CN108206093A CN 108206093 A CN108206093 A CN 108206093A CN 201611188381 A CN201611188381 A CN 201611188381A CN 108206093 A CN108206093 A CN 108206093A
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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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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/18—Electroplating using modulated, pulsed or reversing current
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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
The invention discloses a kind of high-sequential platinum/silicon nanowires to the preparation method of electrode, belong to dye-sensitized solar cells technical field, the present invention be using high-sequential silicon nanowires substrate and pass through 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, convenient for preparing 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 3 ions of I in electrolyte is greatly improved, dye-sensitized solar cells 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
Battery technology field.
Background technology
Since 1991And O ' Regan propose about dye-sensitized solar cells (DSSC) report, DSSC because
There is potential low cost, abundant raw materials are easy to large-scale production, energy flexible manufacturing and higher photoelectric efficiency,
It is 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 in electronics to 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
I3- receives electron reduction as I- on to electrode.In platinum DSSC batteries to electrode common catalyst.Platinum base is usually 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,
The features such as controllable thickness and large-scale production.Silicon-based nano cable architecture can provide more bigger serface to support effective catalysis
The good dispersion of agent, at the same silicon-based substrate material also allow for traditional integrated circuit process compatible, for integrable miniature dye it is quick too
Positive energy battery lays the foundation.
Invention content
The present invention provides a kind of high-sequential platinum/silicon nanowires to the preparation method of electrode, using the high-sequential platinum
Silicon nanowires improves electrode the opto-electronic conversion performance of dye-sensitized solar cells.
The technical solution adopted by the present invention to solve the technical problems is：A kind of high-sequential platinum/silicon nanowires is to electrode
Preparation method, include the following steps：
The first step prepares silicon nanowires using metal inducement selective wet chemical etching
1st, print is cut：Using single-sided polishing, N-shaped<100>Crystal orientation silicon chip cuts into 1cm × 1cm prints.
2nd, print cleans：Acetone soln is cleaned by ultrasonic 10-20min, organic flaws such as removal surface dirt, greasy dirt and wax first
Dirty particle；Then ethylene glycol solution is cleaned by ultrasonic 10-20min, removes the residual of surface organic matter；Later by going to rush from water
It washes, removes surface organic solvent；10-20min is boiled by heating up in H2SO4: H2O2=3: 1 (volume ratio) solution later,
Metallic and generate hydrophilic thin oxide layer in silicon chip surface to remove；Last print is cleaned by ultrasonic in a large amount of deionized waters
The drying of taking-up nitrogen is spare after removing removal of residue.
3rd, prepared by high-sequential silicon nanowires (SiNWs) array：Print polishing face upward, be immersed in AgNO3+HF+ go from
In sub- water mixed solution, wherein AgNO3 a concentration of 0.5-1.0mM, HF a concentration of 1-2M, ultrasonic reaction time 30-40min make
Argent grain uniform deposition is to silicon chip surface；Print is taken out, polishing faces upward, and is immersed in HF: H2O2=1: 1 (volume ratio) solution
In, room temperature etching 40-60min prepares high-sequential silicon nanowires (SiNWs) array substrate, extra 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, is rinsed well after taking-up with deionized water.
Third walks, and plating prepares platinum-silicon nanowires to electrode：KCL solution be electrolyte, a concentration of 0.1-0.2M；
H2PtCl6 is as platinum source, a concentration of 2-4mM, and ethylenediamine tetra-acetic acid (EDTA) is complexing agent, concentration 10-15mgL-1；Magnetic force stirs
Mix 55-85 DEG C of water-bath；PH value is adjusted by adding in ammonium hydroxide and is maintained at 8.0-9.0；Two electrode systems, working electrode are received for silicon
Nanowire arrays 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 cycles.
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 by uniform sink on the side wall of silicon nanowires by electrochemistry electro-plating method.Platinum grain
Diameter range is between tens to hundreds of nanometers, and platinum particles uniform deposition is in entire 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, large specific surface area, high catalytic efficiency.
2) preparation method of platinum of the invention modification silicon nanowires nano structure electrode and traditional integrated circuit process compatible,
Mainly using electrochemical process, at low cost, easy to operate, process conditions are mild, and it is easy to realize.
3) silicon nanowire array substrate fabrication method of the invention is using 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 mild, easy to operate, are a kind of low-cost silicon micro-processing technologies that can be promoted and applied.
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, at low cost, 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 stablized.
5) platinum/silicon nanowires has more catalytic activity than plane platinum film, its higher catalytic activity is from not only uniform
The platinum nanoclusters structure of branch, the micro-nano spacing effect of silicon nanowire array substrate is related, also with platinum after rapid thermal annealing-
The Schottky electric field distribution of silicon nanowires contact layer is related 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, 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.
Specific embodiment
A kind of high-sequential platinum/silicon nanowires includes the following steps the preparation method of electrode：
The first step prepares silicon nanowires using metal inducement selective wet chemical etching
1st, print is cut：Using single-sided polishing, N-shaped<100>Crystal orientation silicon chip cuts into 1cm × 1cm prints.
2nd, print cleans：Acetone soln is cleaned by ultrasonic 10-20min, organic flaws such as removal surface dirt, greasy dirt and wax first
Dirty particle；Then ethylene glycol solution is cleaned by ultrasonic 10-20min, removes the residual of surface organic matter；Later by going to rush from water
It washes, removes surface organic solvent；10-20min is boiled by heating up in H2SO4: H2O2=3: 1 (volume ratio) solution later,
Metallic and generate hydrophilic thin oxide layer in silicon chip surface to remove；Last print is cleaned by ultrasonic in a large amount of deionized waters
The drying of taking-up nitrogen is spare after removing removal of residue.
3rd, prepared by high-sequential silicon nanowires (SiNWs) array：Print polishing face upward, be immersed in AgNO3+HF+ go from
In sub- water mixed solution, wherein AgNO3 a concentration of 0.5-1.0mM, HF a concentration of 1-2M, ultrasonic reaction time 30-40min make
Argent grain uniform deposition is to silicon chip surface；Print is taken out, polishing faces upward, and is immersed in HF: H2O2=1: 1 (volume ratio) solution
In, room temperature etching 40-60min prepares high-sequential silicon nanowires (SiNWs) array substrate, extra 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, is rinsed well after taking-up with deionized water.
Third walks, and plating prepares platinum-silicon nanowires to electrode：KCL solution be electrolyte, a concentration of 0.1-0.2M；
H2PtCl6 is as platinum source, a concentration of 2-4mM, and ethylenediamine tetra-acetic acid (EDTA) is complexing agent, concentration 10-15mgL-1；Magnetic force stirs
Mix 55-85 DEG C of water-bath；PH value is adjusted by adding in ammonium hydroxide and is maintained at 8.0-9.0；Two electrode systems, working electrode are received for silicon
Nanowire arrays 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 cycles.
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 by uniform sink on the side wall of silicon nanowires by electrochemistry electro-plating method.Platinum grain
Diameter range is between tens to hundreds of nanometers, and platinum particles uniform deposition is in entire 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：Preparation method following steps：
1) print is cut：Using single-sided polishing, N-shaped<100>Crystal orientation silicon chip cuts into 1cm × 1cm prints；
2) print cleans：Acetone soln is cleaned by ultrasonic 10-20min, organic stained particles such as removal surface dirt, greasy dirt and wax；
Then ethylene glycol solution is cleaned by ultrasonic 10-20min, removes the residual of surface organic matter；It is rinsed, removed by deionized water later
Surface organic solvent；10-20min is boiled by heating up in H2 SO 4: H2 O 2=3: 1 (volume ratio) solution later, is removed
Metallic simultaneously generates hydrophilic thin oxide layer in silicon chip surface；Last print is cleaned by ultrasonic removal residual in a large amount of deionized waters
Taking-up nitrogen dries up spare after object；
3) prepared by metal inducement selective wet chemical etching silicon nanowire array substrate：Print polishing faces upward, and is immersed in AgNO 3+HF
In+deionized water mixed solution, wherein 3 a concentration of 0.5-1.0mM of AgNO, a concentration of 1-2M of HF, ultrasonic reaction time 30-
40min makes Argent grain uniform deposition to silicon chip surface；Print is taken out, polishing faces upward, and is immersed in HF: H 2O2=1: 1 (volume
Than) in solution, room temperature etching 40-60min prepares high-sequential silicon nanowires (SiNWs) array substrate, and extra Ag particles are used
20-30% dilute nitric acid solution clean and reuses；
4) platinum-silicon nanowires prepares electrode：30-60s in the Triton X-100 solution of substrate print immersion concentration 3%, with
It reduces internal pressure stress and improves the wellability of SiNWs, rinsed well after taking-up with deionized water；KCL solution be electrolyte, concentration
For 0.1-0.2 M；H2 PtCl 6 are as platinum source, a concentration of 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 in ammonium hydroxide and is maintained at 8.0-9.0；Two electrode bodies
System, working electrode are silicon nanowire array substrate, are platinum plate electrode to electrode, and working pulse voltage waveform is triangular wave, high electricity
Flat 0.5V, low level -0.4V, sweep speed 100mVs-1 continue 100-200 cycles；Platinum-silicon nanowires protects electrode nitrogen atmosphere
Shield, 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 polishing faces upward, and is immersed in AgNO 3+HF+ deionized water mixed solutions,
Middle 3 a concentration of 0.5-1.0mM of AgNO, a concentration of 1-2M of HF, ultrasonic reaction time 30-40min arrive Argent grain uniform deposition
Silicon chip surface；
2) prepared by metal inducement selective wet chemical etching silicon nanowires：Print polishing faces upward, and is immersed in HF: H2O 2=1: 1 (body
Product ratio) in solution, room temperature etching 40-60min prepares high-sequential silicon nanowires (SiNWs) array substrate, and extra 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 electrode electrochemistry pulsed deposition, 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 be electrolyte, a concentration of 0.1-0.2M；H2 PtCl 6 are as platinum source, a concentration of 2-
4mM, ethylenediamine tetra-acetic acid (EDTA) be complexing agent, concentration 10-15mg L-1；55-85 DEG C of water-bath of magnetic agitation；PH value is by adding
Enter ammonium hydroxide and be adjusted to be maintained at 8.0-9.0；Two electrode systems, working electrode is silicon nanowire array substrate, to electrode platinized platinum
Electrode, working pulse voltage waveform be triangular wave, high level 0.5V, low level -0.4V, sweep speed 100mVs-1, continue
100-200 is recycled；Platinum-silicon nanowires moves back electrode nitrogen atmosphere protection, nitrogen flow 1-1.5Lmin-1,400-500 DEG C of fast speed heat
Fiery 400-600s.
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| CN201611188381.6A CN108206093A (en) | 2016-12-20 | 2016-12-20 | A kind of high-sequential platinum silicon nanowires is to the preparation method of electrode |
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| CN201611188381.6A CN108206093A (en) | 2016-12-20 | 2016-12-20 | A kind of high-sequential platinum silicon nanowires is to the preparation method of electrode |
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Application publication date: 20180626 |