CN102903538B - The electrochemical method of the quantum dot sensitized wide bandgap semiconductor electrode of a kind of controlled synthesis - Google Patents

The electrochemical method of the quantum dot sensitized wide bandgap semiconductor electrode of a kind of controlled synthesis Download PDF

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CN102903538B
CN102903538B CN201210396512.5A CN201210396512A CN102903538B CN 102903538 B CN102903538 B CN 102903538B CN 201210396512 A CN201210396512 A CN 201210396512A CN 102903538 B CN102903538 B CN 102903538B
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quantum dot
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CN102903538A (en
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汪敏强
宋孝辉
邓建平
姚熹
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Xian Jiaotong University
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Abstract

The invention discloses a kind of preparation method of the quantum dot sensitized wide bandgap semiconductor electrode for solar cell, the method comprises the following steps: on FTO electro-conductive glass, first prepare wide bandgap semiconductor electrode (as TiO 2, ZnO, SnO 2deng); Then with this electrode for negative electrode, take inert electrode as anode, negative electrode and anode be placed in the electrolyte configured, and apply a constant current to negative electrode, by redox reaction separate out quantum dot be adsorbed on wide bandgap semiconductor electrode surface; Finally by successively ionic adsorption and reaction method (SILAR) coated one deck ZnS passivation layer on the quantum dot sensitized electrode prepared.The invention has the advantages that simple to operate, preparation time is short, and controllability is strong; By the homoepitaxial of quantum dot on semi-conducting electrode surface can be realized to the optimization of electrochemical parameter; The existence of ZnS passivation layer simultaneously inhibits the compound of light induced electron, effectively improves battery performance.

Description

The electrochemical method of the quantum dot sensitized wide bandgap semiconductor electrode of a kind of controlled synthesis
Technical field:
The invention belongs to Solar use and field of nanometer material technology, be specifically related to the electrochemical method of the quantum dot sensitized wide bandgap semiconductor electrode of a kind of controlled synthesis.
Background technology
Quantum dot sensitized solar cell (writing a Chinese character in simplified form into QDSSC) is a kind of third generation solar cell occurred the nineties in last century, its structure is similar with traditional DSSC (writing a Chinese character in simplified form into DSSC), primarily of the wide bandgap semiconductor electrode of bigger serface, quantum dot sensitising agent, redox electrolytes matter, to a few part composition such as electrode and conductive substrates, just instead of the sensitising agent of dyestuff as absorption sunlight with the inorganic semiconductor quantum dot (QD) of low energy gap.Compared with dyestuff, semiconductor-quantum-point is because having higher molar extinction coefficient (W.W.Yu etc., Chem.Mater., 2003,15,2854-2860 page) and regulatable band structure (E.H.Sargent, Adv.Mater., 2008,20,3958-3964 page) and be considered to a kind of desirable light absorbent that can be used for sensitization solar cell; In addition, QDSSC obtains the quantum yield (J.B.Sambur etc. higher than 100% by the distinctive impact ionization of quantum dot, Science, 2010,330,63-66 page), if these light induced electrons successfully can be utilized, the theoretical electricity conversion of QDSSC can reach 44%; By the control to quantum point grain diameter, or the quanta point material of mixed different light absorption range, full spectral absorption (the P.V.Kamat to sunlight can be realized, J.Phys.Chem.C, 2008,112,18737th – 18753 pages), therefore QDSSC has considerable investigation and application prospect.
But because the research of the aspects such as the preparation method to quantum dot sensitized electrode, the selection to electrode, the optimization of battery structure system is not yet ripe, and the transmission of charge carrier in battery system and recombination process comparatively complicated, the QDSSC peak efficiency reported in current document is only 4-5%.The preparation method of quantum dot sensitized electrode probably can be divided in situ synthesis and dystopy absorption method, and in-situ method puts into quantum dot precursor liquid wide bandgap semiconductor electrode exactly, at semiconductor surface direct growth quantum dot.In-situ method is mainly divided into SILAR method (SILAR) and chemical bath deposition method (CBD), and this method also exists quantum dot at wide bandgap semiconductor electrode surface skewness, the shortcomings such as preparation time is long, process is loaded down with trivial details.Dystopy absorption method is that synthetic quantum dot solution is put in wide bandgap semiconductor substrate, by a linker molecule with difunctional, quantum dot is adsorbed onto semiconductor substrate surface.This method also exists quantum dot in the too low shortcoming of semi-conducting electrode surface coverage, and the surface ligand of quantum dot hinders the transmission of light induced electron between quantum dot/semi-conducting electrode simultaneously, and the standby QDSSC efficiency of dystopy legal system is usually all lower than 2%.Therefore study the preparation method of new quantum dot sensitized electrode, the coverage rate and the electric transmission efficiency that improve quantum dot improve an effective way of QDSSC performance.
Summary of the invention
The object of the invention is to the defect overcoming above-mentioned quantum dot sensitized electrode preparation method, propose a kind of simple to operate, preparation time is short, the electrochemical method of the quantum dot sensitized wide bandgap semiconductor electrode of the controlled synthesis that controllability is strong.Namely by the homoepitaxial of quantum dot on semi-conducting electrode surface can be realized to the optimization of electrochemical parameter; The existence of ZnS passivation layer simultaneously inhibits the compound of light induced electron, effectively improves battery performance.
For achieving the above object, the technical solution used in the present invention is:
1) preparation of porous nanocrystalline electrode:
By TiO 2, SnO 2or ZnO slurry is coated in the FTO conductive glass surface cleaned up by silk screen print method, then puts into Muffle furnace and sinter 30min at 500 DEG C, form at FTO conductive glass surface the porous TiO that thickness is 8 ~ 12 μm 2, porous SnO 2or the nanocrystalline electrode of porous ZnO;
2) preparation of electric depositing solution:
The preparation of front body liquid: by the Na of the Se powder of 2mmol or Te powder, 8mmol 2sO 3at 70-100 DEG C, add hot reflux after even with 50ml deionized water and stirring and form water white solution, be cooled to the Na that room temperature forms 0.04mol/L 2seSO 3or Na 2teSO 3solution;
The preparation of cadmium precursor liquid: by the Cd (CH of 0.8mmol 3cOO) 2be dissolved in the deionized water of 20ml with 1.6mmol disodium ethylene diamine tetraacetate, formed after stirring 0.04mol/L cadmium precursor liquid;
The preparation of electric depositing solution: the Na getting 20ml 2seSO 3or Na 2teSO 3solution joins in cadmium precursor liquid, after uniform stirring 10min, is that namely 7.5-8 forms CdSe or CdTe electric depositing solution by the NaOH aqueous solution adjust ph of 1mol/L;
3) electrochemical process deposition CdSe or CdTe quantum:
At room temperature, two electrode systems are adopted to carry out galvanostatic method electrochemical deposition CdSe or CdTe, to be coated with porous TiO 2, porous SnO 2or the nanocrystalline FTO of porous ZnO is work electrode, inert electrode is to electrode, two interelectrode distances are 0.5-2cm, and electrode is placed in electric depositing solution and applies constant current to work electrode, the charged particle in electrodeposit liquid moves to porous TiO under the effect of electric field 2, porous SnO 2or porous ZnO nanocrystal surface, be adsorbed on TiO by redox reaction formation CdSe or CdTe quantum 2, SnO 2or on ZnO, after question response terminates, electrode is taken out, clean with deionized water rinsing, be placed on N 2under dry up and obtain quantum dot sensitized wide bandgap semiconductor electrode.
The quantum dot sensitized wide bandgap semiconductor electrode being also included in preparation deposits ZnS passivation layer, and its step is as follows:
Standby quantum dot sensitized wide bandgap semiconductor electrode step 3) prepared first immerses the Zn (NO of 0.1mol/L 3) 21min in the aqueous solution, removes absorption Zn loosely with deionized water rinsing after taking-up 2+, and then be placed on the Na of 0.1mol/L 21min, Zn in the S aqueous solution 2+with S 2-ion reacts and forms ZnS, take out rear deionized water rinsing, above process is a SILAR circulation, after 3 SILAR circulations, form one deck ZnS passivation layer at quantum dot sensitized wide bandgap semiconductor electrode surface, finally fall unreacted Zn with deionized water rinsing 2+and S 2-ion, is placed on N 2under dry up.
Described inert electrode employing itself does not participate in the graphite electrode, gold electrode or the platinum electrode that react.
The current density of described constant current is 0.2-0.6mA/cm 2, sedimentation time is 5-30min.
The method is respectively using wide bandgap semiconductor electrode and inert electrode as work electrode with to electrode, then a constant current is applied to work electrode, charged particle in electrodeposit liquid moves on wide bandgap semiconductor electrode under the effect of electric field, in electrode surface generation redox reaction, separate out quantum dot and be adsorbed on electrode surface.By controlling the deposition process of quantum dot at electrode surface to the size of constant current and the optimization of electrolyte intermediate ion concentration, thus coverage rate and the uniformity of quantum dot can be improved.
Useful achievement of the present invention is: compared with prior art, and the electrochemical method of the quantum dot sensitized wide bandgap semiconductor electrode of a kind of controlled synthesis, has the following advantages:
(1) electrodeposition technology flow process is simple, with low cost, preparation time is short, efficiency is high.
(2) in the process of electro-deposition quantum dot, quantum dot moved to wide bandgap semiconductor surface with the form of ion before this, and then was adsorbed onto electrode surface by chemical reaction formation quantum dot, was so just conducive to quantum dot and penetrated into porous TiO 2electrode interior, improves the coverage rate of quantum dot to semi-conducting electrode and the uniformity of distribution.
(3) by controlling the composition of electrolyte, temperature, deposition current and sedimentation time, the control of the size to quantum dot, distribution and sensitization electrode pattern can be realized.
Accompanying drawing illustrates:
Fig. 1 is the sensitized porous TiO of CdSe quantum dot that the embodiment of the present invention 1 prepares 2the surperficial FESEM figure of nanocrystalline electrode;
Fig. 2 is the sensitized porous TiO of CdSe quantum dot that the embodiment of the present invention 2 prepares 2the surperficial FESEM figure of nanocrystalline electrode;
Fig. 3 is the sensitized porous TiO of CdSe quantum dot that the embodiment of the present invention 3 prepares 2the surperficial FESEM figure of nanocrystalline electrode;
Fig. 4 is the sensitized porous TiO of CdSe quantum dot prepared by embodiment of the present invention 1-4 2the J-V curve of the solar cell of nanocrystalline electrode assembling.
Embodiment
Referring to instantiation, the present invention is described in detail, but content of the present invention is not limited thereto.
Embodiment 1:
1) preparation of porous nanocrystalline electrode:
By Dyesol18NR-TTiO 2(Australian Dyesol company produces) slurry is coated in the FTO conductive glass surface cleaned up by silk screen print method, then put into Muffle furnace and sinter 30min at 500 DEG C, forms at FTO conductive glass surface the porous TiO that thickness is 10 μm 2nanocrystalline electrode;
2) preparation of electric depositing solution:
The preparation of front body liquid: by the Se powder of 2mmol, the Na of 8mmol 2sO 3at 90 DEG C, add hot reflux after even with 50ml deionized water and stirring and form water white solution, be cooled to the Na that room temperature forms 0.04mol/L 2seSO 3solution;
The preparation of cadmium precursor liquid: by the Cd (CH of 0.8mmol 3cOO) 2be dissolved in the deionized water of 20ml with 1.6mmol disodium ethylene diamine tetraacetate, after stirring 10min, form the cadmium precursor liquid of 0.04mol/L;
The preparation of electric depositing solution: the Na getting 20ml 2seSO 3solution joins in cadmium precursor liquid, after uniform stirring 10min, is 7.8 namely form CdSe electric depositing solution by the NaOH aqueous solution adjust ph of 1mol/L;
3) electrochemical process deposition CdSe quantum dot:
At room temperature, two electrode systems are adopted to carry out galvanostatic method electrochemical deposition CdSe, to be coated with porous TiO 2nanocrystalline FTO is work electrode, and the platinum electrode itself not participating in reacting is that two interelectrode distances are 1cm to electrode, electrode is placed in electric depositing solution and applies 0.6mA/cm to work electrode 2constant current, the charged particle in electrodeposit liquid moves to porous TiO under the effect of electric field 2nanocrystal surface, forms CdSe quantum dot by redox reaction and is adsorbed on TiO 2on, after deposition 8min question response terminates, electrode is taken out, clean with deionized water rinsing, be placed on N 2under dry up and obtain quantum dot sensitized wide bandgap semiconductor electrode.
Fig. 1 is 0.6mA/cm 2the sensitized porous TiO of the CdSe quantum dot prepared under current density 2field emission scanning electron microscope (FESEM) figure of electrode surface, as can be seen from the figure CdSe quantum dot is completely by TiO 2hole blocks, and face checking, causes TiO 2film is easy to come off.This is that deposition velocity is too fast, Se because depositing current density is comparatively large 2-and Cd 2+ion does not also move to TiO 2hole inside just reacts formation CdSe quantum dot, thus plugs TiO 2cavity entrance.Because quantum dot deposition is uneven, TiO 2inside creates stress, causes TiO 2cracking.
Embodiment 2:
1) preparation of porous nanocrystalline electrode:
By Dyesol18NR-TTiO 2(Australian Dyesol company produces) slurry is coated in the FTO conductive glass surface cleaned up by silk screen print method, then put into Muffle furnace and sinter 30min at 500 DEG C, forms at FTO conductive glass surface the porous TiO that thickness is 10 μm 2nanocrystalline electrode;
2) preparation of electric depositing solution:
The preparation of front body liquid: by the Se powder of 2mmol, the Na of 8mmol 2sO 3at 90 DEG C, add hot reflux after even with 50ml deionized water and stirring and form water white solution, be cooled to the Na that room temperature forms 0.04mol/L 2seSO 3solution;
The preparation of cadmium precursor liquid: by the Cd (CH of 0.8mmol 3cOO) 2be dissolved in the deionized water of 20ml with 1.6mmol disodium ethylene diamine tetraacetate, after stirring 10min, form the cadmium precursor liquid of 0.04mol/L;
The preparation of electric depositing solution: the Na getting 20ml 2seSO 3solution joins in cadmium precursor liquid, after uniform stirring 10min, is 7.8 namely form CdSe electric depositing solution by the NaOH aqueous solution adjust ph of 1mol/L;
3) electrochemical process deposition CdSe quantum dot:
At room temperature, two electrode systems are adopted to carry out galvanostatic method electrochemical deposition CdSe, to be coated with porous TiO 2nanocrystalline FTO is work electrode, and the platinum electrode itself not participating in reacting is that two interelectrode distances are 1cm to electrode, electrode is placed in electric depositing solution and applies 0.4mA/cm to work electrode 2constant current, the charged particle in electrodeposit liquid moves to porous TiO under the effect of electric field 2nanocrystal surface, forms CdSe quantum dot by redox reaction and is adsorbed on TiO 2on, after deposition 12min question response terminates, electrode is taken out, clean with deionized water rinsing, be placed on N 2under dry up and obtain quantum dot sensitized wide bandgap semiconductor electrode.
Fig. 2 is 0.4mA/cm 2the sensitized porous TiO of the CdSe quantum dot prepared under current density 2the surperficial FESEM figure of nanocrystalline electrode.After depositing current density reduces as we can see from the figure, CdSe sensitization TiO 2the pattern of electrode is improved, TiO 2hole be not completely plugged, simultaneously crackle also disappears.But the CdSe quantum dot that electro-deposition is formed is reunited, formation is about the Cluster deposition of 80nm at TiO 2surface, and infiltrate TiO 2the CdSe quantum dot of hole is little.This remains because current density is excessive, causes quantum dot deposition velocity very fast, thus have impact on CdSe quantum dot at porous TiO 2the uniformity distributed in electrode.
Embodiment 3:
1) preparation of porous nanocrystalline electrode:
By Dyesol18NR-TTiO 2(Australian Dyesol company produces) slurry is coated in the FTO conductive glass surface cleaned up by silk screen print method, then put into Muffle furnace and sinter 30min at 500 DEG C, forms at FTO conductive glass surface the porous TiO that thickness is 10 μm 2nanocrystalline electrode;
2) preparation of electric depositing solution:
The preparation of front body liquid: by the Se powder of 2mmol, the Na of 8mmol 2sO 3at 90 DEG C, add hot reflux after even with 50ml deionized water and stirring and form water white solution, be cooled to the Na that room temperature forms 0.04mol/L 2seSO 3solution;
The preparation of cadmium precursor liquid: by the Cd (CH of 0.8mmol 3cOO) 2be dissolved in the deionized water of 20ml with 1.6mmol disodium ethylene diamine tetraacetate, after stirring 10min, form the cadmium precursor liquid of 0.04mol/L;
The preparation of electric depositing solution: the Na getting 20ml 2seSO 3solution joins in cadmium precursor liquid, after uniform stirring 10min, is 7.8 namely form CdSe electric depositing solution by the NaOH aqueous solution adjust ph of 1mol/L;
3) electrochemical process deposition CdSe quantum dot:
At room temperature, two electrode systems are adopted to carry out galvanostatic method electrochemical deposition CdSe, to be coated with porous TiO 2nanocrystalline FTO is work electrode, and the platinum electrode itself not participating in reacting is that two interelectrode distances are 1cm to electrode, electrode is placed in electric depositing solution and applies 0.2mA/cm to work electrode 2constant current, the charged particle in electrodeposit liquid moves to porous TiO under the effect of electric field 2nanocrystal surface, forms CdSe quantum dot by redox reaction and is adsorbed on TiO 2on, after deposition 24min question response terminates, electrode is taken out, clean with deionized water rinsing, be placed on N 2under dry up and obtain quantum dot sensitized wide bandgap semiconductor electrode.
Fig. 3 is 0.2mA/cm 2the sensitized porous TiO of the CdSe quantum dot prepared under current density 2the surperficial FESEM figure of electrode.Deposit the TiO of CdSe quantum dot as we can see from the figure 2electrode remains its original loose structure, but space diminishes, and particle diameter increases, and illustrates that CdSe quantum dot has successfully been deposited on TiO 2nanocrystal surface, CdSe quantum dot is at TiO as can also be seen from Figure 2electrode surface covers evenly, and do not have the generation of agglomeration, these are all conducive to the raising of battery performance.
In order to improve the performance of QDSSC further, the present invention also carries out ZnS modification to the sensitization electrode prepared, namely obtain sensitization electrode surface by SILAR method in electro-deposition and cover one deck ZnS passivation layer, because ZnS is a kind of semiconductor material with wide forbidden band, position at the bottom of its conduction band is higher than at the bottom of the conduction band of some conventional semiconductor-quantum-points, such as CdSe, CdS, CdTe etc., make the heterostructure forming Type I between quantum dot and ZnS, thus effectively can stop the compound of redox couple in the light induced electron produced in quantum dot or the electronics be transferred in semi-conducting electrode and electrolyte, improve the opto-electronic conversion performance of QDSSC.The existence of ZnS passivation layer decreases the blemish of quantum dot, inhibits the compound of redox couple in light induced electron and electrolyte, thus improves the performance of QDSSC.
Embodiment 4:
1) preparation of porous nanocrystalline electrode:
By Dyesol18NR-TTiO 2(Australian Dyesol company produces) slurry is coated in the FTO conductive glass surface cleaned up by silk screen print method, then put into Muffle furnace and sinter 30min at 500 DEG C, forms at FTO conductive glass surface the porous TiO that thickness is 10 μm 2nanocrystalline electrode;
2) preparation of electric depositing solution
The preparation of front body liquid: by the Se powder of 2mmol, the Na of 8mmol 2sO 3at 90 DEG C, add hot reflux after even with 50ml deionized water and stirring and form water white solution, be cooled to the Na that room temperature forms 0.04mol/L 2seSO 3solution;
The preparation of cadmium precursor liquid: by the Cd (CH of 0.8mmol 3cOO) 2be dissolved in the deionized water of 20ml with 1.6mmol disodium ethylene diamine tetraacetate, after stirring 10min, form the cadmium precursor liquid of 0.04mol/L;
The preparation of electric depositing solution: the Na getting 20ml 2seSO 3solution joins in cadmium precursor liquid, after uniform stirring 10min, is 7.8 namely form CdSe electric depositing solution by the NaOH aqueous solution adjust ph of 1mol/L;
3) electrochemical process deposition CdSe quantum dot:
At room temperature, two electrode systems are adopted to carry out galvanostatic method electrochemical deposition CdSe, to be coated with porous TiO 2nanocrystalline FTO is work electrode, and the platinum electrode itself not participating in reacting is that two interelectrode distances are 1cm to electrode, electrode is placed in electric depositing solution and applies 0.2mA/cm to work electrode 2constant current, the charged particle in electrodeposit liquid moves to porous TiO under the effect of electric field 2nanocrystal surface, forms CdSe quantum dot by redox reaction and is adsorbed on TiO 2on, after deposition 24min question response terminates, electrode is taken out, clean with deionized water rinsing, be placed on N 2under dry up and obtain quantum dot sensitized wide bandgap semiconductor electrode;
4) SILAR method deposition ZnS passivation layer:
Standby quantum dot sensitized wide bandgap semiconductor electrode step 3) prepared first immerses the Zn (NO of 0.1mol/L 3) 21min in the aqueous solution, removes absorption Zn loosely with deionized water rinsing after taking-up 2+, and then be placed on the Na of 0.1mol/L 21min, Zn in the S aqueous solution 2+with S 2-ion reacts and forms ZnS, take out rear deionized water rinsing, above process is a SILAR circulation, after 3 SILAR circulations, form one deck ZnS passivation layer at quantum dot sensitized wide bandgap semiconductor electrode surface, finally fall unreacted Zn with deionized water rinsing 2+and S 2-ion, is placed on N 2under dry up.
Fig. 4 is by TiO 2/ CdSe and TiO 2the J-V curve of two quantum dot sensitized batteries that/CdSe/ZnS electrode assembling becomes, deposit the short circuit current of the battery of ZnS passivation layer and open circuit voltage as we can see from the figure and have raising in various degree, thus the photoelectric conversion efficiency of QDSSC obtains and increases substantially.Because ZnS passivation layer is very little to the contribution of visible absorption, so the lifting of battery efficiency is mainly because ZnS passivation layer decreases the blemish of CdSe quantum dot, and inhibit quantum dot and TiO 2in light induced electron and electrolyte in the compound of redox couple, instead of extend the absorption region of visible ray.
Embodiment 5:
1) preparation of porous nanocrystalline electrode:
By SnO 2slurry is coated in the FTO conductive glass surface cleaned up by silk screen print method, then put into Muffle furnace and sinter 30min at 500 DEG C, forms at FTO conductive glass surface the porous SnO that thickness is 8 μm 2nanocrystalline electrode;
2) preparation of electric depositing solution:
The preparation of front body liquid: by the Te powder of 2mmol, the Na of 8mmol 2sO 3at 70,100 DEG C, add hot reflux after even with 50ml deionized water and stirring and form water white solution, be cooled to the Na that room temperature forms 0.04mol/L 2teSO 3solution;
The preparation of cadmium precursor liquid: by the Cd (CH of 0.8mmol 3cOO) 2be dissolved in the deionized water of 20ml with 1.6mmol disodium ethylene diamine tetraacetate, formed after stirring 0.04mol/L cadmium precursor liquid;
The preparation of electric depositing solution: the Na getting 20ml 2teSO 3solution joins in cadmium precursor liquid, after uniform stirring 10min, is 7.5 namely form CdTe electric depositing solution by the NaOH aqueous solution adjust ph of 1mol/L;
3) electrochemical process deposition CdTe quantum:
At room temperature, two electrode systems are adopted to carry out galvanostatic method electrochemical deposition CdTe, to be coated with porous SnO 2nanocrystalline FTO is work electrode, and the graphite electrode itself not participating in reacting is that two interelectrode distances are 0.5cm to electrode, electrode is placed in electric depositing solution and applies 0.3mA/cm to work electrode 2constant current, the charged particle in electrodeposit liquid moves to porous SnO under the effect of electric field 2nanocrystal surface, forms CdTe quantum by redox reaction and is adsorbed on SnO 2on, after deposition 5min question response terminates, electrode is taken out, clean with deionized water rinsing, be placed on N 2under dry up and obtain quantum dot sensitized wide bandgap semiconductor electrode;
4) SILAR method deposition ZnS passivation layer:
Standby quantum dot sensitized wide bandgap semiconductor electrode step 3) prepared first immerses the Zn (NO of 0.1mol/L 3) 21min in the aqueous solution, removes absorption Zn loosely with deionized water rinsing after taking-up 2+, and then be placed on the Na of 0.1mol/L 21min, Zn in the S aqueous solution 2+with S 2-ion reacts and forms ZnS, take out rear deionized water rinsing, above process is a SILAR circulation, after 3 SILAR circulations, form one deck ZnS passivation layer at quantum dot sensitized wide bandgap semiconductor electrode surface, finally fall unreacted Zn with deionized water rinsing 2+and S 2-ion, is placed on N 2under dry up.
Embodiment 6:
1) preparation of porous nanocrystalline electrode:
ZnO slurry is coated in the FTO conductive glass surface cleaned up by silk screen print method, then puts into Muffle furnace and sinter 30min at 500 DEG C, form at FTO conductive glass surface the nanocrystalline electrode of porous ZnO that thickness is 12 μm;
2) preparation of electric depositing solution:
The preparation of front body liquid: by the Te powder of 2mmol, the Na of 8mmol 2sO 3at 100 DEG C, add hot reflux after even with 50ml deionized water and stirring and form water white solution, be cooled to the Na that room temperature forms 0.04mol/L 2teSO 3solution;
The preparation of cadmium precursor liquid: by the Cd (CH of 0.8mmol 3cOO) 2be dissolved in the deionized water of 20ml with 1.6mmol disodium ethylene diamine tetraacetate, formed after stirring 0.04mol/L cadmium precursor liquid;
The preparation of electric depositing solution: the Na getting 20ml 2teSO 3solution joins in cadmium precursor liquid, after uniform stirring 10min, is 8 namely form CdTe electric depositing solution by the NaOH aqueous solution adjust ph of 1mol/L;
3) electrochemical process deposition CdTe quantum:
At room temperature, two electrode systems are adopted to carry out galvanostatic method electrochemical deposition CdTe, to be coated with the nanocrystalline FTO of porous ZnO for work electrode, the gold electrode itself not participating in reacting is to electrode, two interelectrode distances are 2cm, electrode are placed in electric depositing solution and apply 0.5mA/cm to work electrode 2constant current, charged particle in electrodeposit liquid moves to porous ZnO nanocrystal surface under the effect of electric field, forms CdTe quantum be adsorbed on ZnO by redox reaction, is taken out by electrode after deposition 30min question response terminates, clean with deionized water rinsing, be placed on N 2under dry up and obtain quantum dot sensitized wide bandgap semiconductor electrode;
4) SILAR method deposition ZnS passivation layer:
Standby quantum dot sensitized wide bandgap semiconductor electrode step 3) prepared first immerses the Zn (NO of 0.1mol/L 3) 21min in the aqueous solution, removes absorption Zn loosely with deionized water rinsing after taking-up 2+, and then be placed on the Na of 0.1mol/L 21min, Zn in the S aqueous solution 2+with S 2-ion reacts and forms ZnS, take out rear deionized water rinsing, above process is a SILAR circulation, after 3 SILAR circulations, form one deck ZnS passivation layer at quantum dot sensitized wide bandgap semiconductor electrode surface, finally fall unreacted Zn with deionized water rinsing 2+and S 2-ion, is placed on N 2under dry up.

Claims (3)

1. an electrochemical method for the quantum dot sensitized wide bandgap semiconductor electrode of controlled synthesis, is characterized in that comprising the following steps:
1) preparation of porous nanocrystalline electrode:
By TiO 2, SnO 2or ZnO slurry is coated in the FTO conductive glass surface cleaned up by silk screen print method, then puts into Muffle furnace and sinter 30min at 500 DEG C, form at FTO conductive glass surface the porous TiO that thickness is 8 ~ 12 μm 2, porous SnO 2or the nanocrystalline electrode of porous ZnO;
2) preparation of electric depositing solution:
The preparation of front body liquid: by the Na of the Se powder of 2mmol or Te powder, 8mmol 2sO 3at 70-100 DEG C, add hot reflux after even with 50ml deionized water and stirring and form water white solution, be cooled to the Na that room temperature forms 0.04mol/L 2seSO 3or Na 2teSO 3solution;
The preparation of cadmium precursor liquid: by the Cd (CH of 0.8mmol 3cOO) 2be dissolved in the deionized water of 20ml with 1.6mmol disodium ethylene diamine tetraacetate, formed after stirring 0.04mol/L cadmium precursor liquid;
The preparation of electric depositing solution: the Na getting 20ml 2seSO 3or Na 2teSO 3solution joins in cadmium precursor liquid, after uniform stirring 10min, is that namely 7.5-8 forms CdSe or CdTe electric depositing solution by the NaOH aqueous solution adjust ph of 1mol/L;
3) electrochemical process deposition CdSe or CdTe quantum:
At room temperature, two electrode systems are adopted to carry out galvanostatic method electrochemical deposition CdSe or CdTe, to be coated with porous TiO 2, porous SnO 2or the nanocrystalline FTO of porous ZnO is work electrode, inert electrode is to electrode, two interelectrode distances are 0.5-2cm, and electrode is placed in electric depositing solution and applies constant current to work electrode, the charged particle in electrodeposit liquid moves to porous TiO under the effect of electric field 2, porous SnO 2or porous ZnO nanocrystal surface, be adsorbed on TiO by redox reaction formation CdSe or CdTe quantum 2, SnO 2or on ZnO, after question response terminates, electrode is taken out, clean with deionized water rinsing, be placed on N 2under dry up and obtain quantum dot sensitized wide bandgap semiconductor electrode;
The current density of described constant current is 0.2-0.6mA/cm 2, sedimentation time is 5-30min.
2. the electrochemical method of the quantum dot sensitized wide bandgap semiconductor electrode of controlled synthesis according to claim 1, is characterized in that: the quantum dot sensitized wide bandgap semiconductor electrode being also included in preparation deposits ZnS passivation layer, and its step is as follows:
By step 3) the standby quantum dot sensitized wide bandgap semiconductor electrode prepared first immerses the Zn (NO of 0.1mol/L 3) 21min in the aqueous solution, removes absorption Zn loosely with deionized water rinsing after taking-up 2+, and then be placed on the Na of 0.1mol/L 21min, Zn in the S aqueous solution 2+with S 2-ion reacts and forms ZnS, take out rear deionized water rinsing, above process is a SILAR circulation, after 3 SILAR circulations, form one deck ZnS passivation layer at quantum dot sensitized wide bandgap semiconductor electrode surface, finally fall unreacted Zn with deionized water rinsing 2+and S 2-ion, is placed on N 2under dry up.
3. the electrochemical method of the quantum dot sensitized wide bandgap semiconductor electrode of controlled synthesis according to claim 1, is characterized in that: inert electrode employing itself does not participate in the graphite electrode, gold electrode or the platinum electrode that react.
CN201210396512.5A 2012-10-17 2012-10-17 The electrochemical method of the quantum dot sensitized wide bandgap semiconductor electrode of a kind of controlled synthesis Expired - Fee Related CN102903538B (en)

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