CN102903538A - Electrochemical method for controlled preparing quantum dot sensitizing wide bandgap semiconductor electrode - Google Patents

Electrochemical method for controlled preparing quantum dot sensitizing wide bandgap semiconductor electrode Download PDF

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CN102903538A
CN102903538A CN2012103965125A CN201210396512A CN102903538A CN 102903538 A CN102903538 A CN 102903538A CN 2012103965125 A CN2012103965125 A CN 2012103965125A CN 201210396512 A CN201210396512 A CN 201210396512A CN 102903538 A CN102903538 A CN 102903538A
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electrode
quantum dot
preparation
wide bandgap
bandgap semiconductor
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CN102903538B (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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Xian Jiaotong University
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Abstract

The invention discloses a preparation method of a quantum dot sensitizing wide bandgap semiconductor electrode for a solar cell. The method comprises the following steps of: firstly, preparing the wide bandgap semiconductor electrode (such as TiO2, ZnO, SnO2 and the like) on an FTO (Fluorinedoped Tin Oxide) conductive glass; secondly, taking the electrode as a negative electrode and a noble electrode as a positive electrode, putting the negative electrode and the positive electrode in prepared electrolyte, applying a constant current to the negative electrode, separating quantum dots out through redox reaction, and adsorbing the quantum dots onto a surface of the wide bandgap semiconductor electrode; and finally, cladding a layer of ZnS passivation layer onto the prepared quantum dot sensitizing electrode through successive ionic layer adsorption and reaction (SILAR). The preparation method has the advantages that the operation is simple, the preparation time is short, and the controllability is strong; through optimizing electrochemistry parameters, the uniform growth of the quantum dots on the surface of the semiconductor electrode can be realized; and simultaneously, due to the ZnS passivation layer, the composition of photoinduced electrons is suppressed, and the battery performance is effectively improved.

Description

The electrochemical method of the quantum dot sensitized wide bandgap semiconductor electrode of a kind of controlled preparation
Technical field:
The invention belongs to solar energy utilization 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 preparation.
Background technology
Quantum dot sensitized solar cell (writing a Chinese character in simplified form into QDSSC) is a kind of third generation solar cell that occurs the nineties in last century, its structure is similar with traditional DSSC (writing a Chinese character in simplified form into DSSC), mainly by photosensitive dose of wide bandgap semiconductor electrode, quantum dot, the redox electrolytes matter of bigger serface, several parts such as electrode and conductive substrates are formed, just the inorganic semiconductor quantum dot (QD) with low energy gap has replaced the sensitising agent of dyestuff as the absorption sunlight.Compare with dyestuff, semiconductor-quantum-point is because having higher molar extinction coefficient (W.W.Yu etc., Chem.Mater., 2003,15, the 2854-2860 page or leaf) and regulatable band structure (E.H.Sargent, Adv.Mater., the 2008,20, the 3958-3964 page or leaf) is considered to a kind of desirable light absorbent that can be used for the sensitization solar cell; In addition, QDSSC can obtain being higher than 100% quantum yield (J.B.Sambur etc., Science by the distinctive impact ionization of quantum dot, 2010,330, the 63-66 page or leaf), 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 use the quanta point material of different extinction scopes with, can realize the full spectral absorption (P.V.Kamat to sunlight, J.Phys.Chem.C, 2008, so QDSSC has considerable research and application prospect 18753 pages of 112, the 18737 –).
But because to the preparation method of quantum dot sensitized electrode, not yet ripe to the research of the aspects such as the selection of electrode, the optimization of battery structure system, and the transmission of the charge carrier in the battery system and recombination process are comparatively complicated, and the QDSSC peak efficiency of reporting in the document at present only is 4-5%.The preparation method of quantum dot sensitized electrode can probably be divided in situ synthesis and dystopy absorption method, and in-situ method is put into the quantum dot precursor liquid to the wide bandgap semiconductor electrode exactly, at semiconductor surface direct growth quantum dot.The shortcomings such as in-situ method mainly is divided into continuous ionic layer adsorption reaction method (SILAR) and chemical bath deposition method (CBD), and this method exists quantum dot at wide bandgap semiconductor electrode surface skewness, and preparation time is long, process is loaded down with trivial details.The dystopy absorption method is that synthetic quantum dot solution is put in the wide bandgap semiconductor substrate, by a linker molecule with difunctional quantum dot is adsorbed onto semiconductor-based basal surface.This method exists quantum dot in the excessively low shortcoming of semi-conducting electrode surface coverage, and the surface ligand of quantum dot has hindered the transmission of light induced electron between quantum dot/semi-conducting electrode simultaneously, and the standby QDSSC efficient of dystopy legal system all is lower than 2% usually.Therefore study the preparation method of new quantum dot sensitized electrode, the coverage rate and the electric transmission efficient that improve quantum dot are to improve an effective way of QDSSC performance.
Summary of the invention
The object of the invention is to overcome the defective of above-mentioned quantum dot sensitized electrode preparation method, proposed a kind of simple to operately, preparation time is short, the electrochemical method of the quantum dot sensitized wide bandgap semiconductor electrode of controlled preparation that controllability is strong.Namely can realize that by the optimization to electrochemical parameter quantum dot is in the even growth on semi-conducting electrode surface; The simultaneously existence of ZnS passivation layer has suppressed the compound of light induced electron, Effective Raise battery performance.
For achieving the above object, the technical solution used in the present invention is:
1) preparation of porous nanocrystalline electrode:
With TiO 2, SnO 2Or the ZnO slurry is coated in the FTO conductive glass surface that cleans up by silk screen print method, then puts into Muffle furnace in 500 ℃ of lower sintering 30min, and forming thickness at the FTO conductive glass surface is the porous TiO of 8～12 μ m 2, porous SnO 2Or the nanocrystalline electrode of porous ZnO;
2) preparation of electric depositing solution:
The preparation of front body liquid: with the Na of the Se powder of 2mmol or Te powder, 8mmol 2SO 3Add hot reflux at 70-100 ℃ lower with the 50ml deionized water and stirring after evenly 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: with the Cd (CH of 0.8mmol 3COO) 2Be dissolved in the deionized water of 20ml with the 1.6mmol disodium ethylene diamine tetraacetate, the rear formation 0.04mol/L that stirs the cadmium precursor liquid;
The preparation of electric depositing solution: the Na that gets 20ml 2SeSO 3Or Na 2TeSO 3Solution joins in the cadmium precursor liquid, and behind the uniform stirring 10min, regulating the pH value with the NaOH aqueous solution of 1mol/L is that 7.5-8 namely forms CdSe or CdTe electric depositing solution;
3) electrochemical process deposition CdSe or CdTe quantum dot:
At room temperature, adopt two electrode systems 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, place electric depositing solution to apply constant current to work electrode at electrode, and the charged particle in the electrodeposit liquid moves to porous TiO under the effect of electric field 2, porous SnO 2Or the porous ZnO nanocrystal surface, be adsorbed on TiO by redox reaction formation CdSe or CdTe quantum dot 2, SnO 2Or on the ZnO, after question response finishes electrode is taken out, rinse well with deionized water, be placed on N 2Under dry up and obtain quantum dot sensitized wide bandgap semiconductor electrode.
Also be included in deposition ZnS passivation layer on the quantum dot sensitized wide bandgap semiconductor electrode of preparation, its step is as follows:
The standby quantum dot sensitized wide bandgap semiconductor electrode of step 3) preparation is immersed first the Zn (NO of 0.1mol/L 3) 21min in the aqueous solution removes the not firm Zn of absorption with deionized water rinsing after taking out 2+, and then be placed on the Na of 0.1mol/L 21min in the S aqueous solution, Zn 2+With S 2-Ion reacts and forms ZnS, using deionized water rinsing, above process after taking out is a SILAR circulation, after 3 SILAR circulations, form one deck ZnS passivation layer at quantum dot sensitized wide bandgap semiconductor electrode surface, rinse out unreacted Zn with deionized water at last 2+And S 2-Ion is placed on N 2Under dry up and get final product.
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 respectively with wide bandgap semiconductor electrode and inert electrode as work electrode with to electrode, then apply a constant current to work electrode, charged particle in the electrodeposit liquid is moving under the effect of electric field on the wide bandgap semiconductor electrode, in electrode surface generation redox reaction, separate out quantum dot and be adsorbed on electrode surface.Can be by the size of constant current and the optimization of electrolyte intermediate ion concentration be controlled quantum dot in the deposition process of electrode surface, thus coverage rate and the uniformity of quantum dot improved.
Useful achievement of the present invention is: compared with prior art, the electrochemical method of the quantum dot sensitized wide bandgap semiconductor electrode of a kind of controlled preparation has the following advantages:
(1) the electrodeposition technology flow process is simple, with low cost, preparation time is short, efficient is high.
(2) in the process of electro-deposition quantum point, quantum dot moved to the wide bandgap semiconductor surface with the form of ion before this, and then was adsorbed onto electrode surface by chemical reaction formation quantum dot, so just was conducive to quantum dot and penetrated into porous TiO 2Electrode interior improves quantum dot to the coverage rate of semi-conducting electrode and the uniformity of distribution.
(3) by composition, temperature, deposition current and the sedimentation time of control electrolyte, can realize the control of size, distribution and sensitization electrode pattern to quantum dot.
Description of drawings:
Fig. 1 is the quantum dot sensitized porous TiO of CdSe that the embodiment of the invention 1 prepares 2The surperficial FESEM figure of nanocrystalline electrode;
Fig. 2 is the quantum dot sensitized porous TiO of CdSe that the embodiment of the invention 2 prepares 2The surperficial FESEM figure of nanocrystalline electrode;
Fig. 3 is the quantum dot sensitized porous TiO of CdSe that the embodiment of the invention 3 prepares 2The surperficial FESEM figure of nanocrystalline electrode;
Fig. 4 is the quantum dot sensitized porous TiO of CdSe by embodiment of the invention 1-4 preparation 2The J-V curve of the solar cell of nanocrystalline electrode assembling.
Embodiment
The present invention is described in detail below with reference to instantiation, but content of the present invention is not limited to this.
Embodiment 1:
1) preparation of porous nanocrystalline electrode:
With Dyesol18NR-TTiO 2(Australian Dyesol company produce) slurry is coated in the FTO conductive glass surface that cleans up by silk screen print method, then put into Muffle furnace in 500 ℃ of lower sintering 30min, and forming thickness at the FTO conductive glass surface is the porous TiO of 10 μ m 2Nanocrystalline electrode;
2) preparation of electric depositing solution:
The preparation of front body liquid: with the Se powder of 2mmol, the Na of 8mmol 2SO 3Add hot reflux at 90 ℃ lower with the 50ml deionized water and stirring after evenly 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: with the Cd (CH of 0.8mmol 3COO) 2Be dissolved in the deionized water of 20ml with the 1.6mmol disodium ethylene diamine tetraacetate, form the cadmium precursor liquid of 0.04mol/L behind the stirring 10min;
The preparation of electric depositing solution: the Na that gets 20ml 2SeSO 3Solution joins in the cadmium precursor liquid, and behind the uniform stirring 10min, regulating the pH value with the NaOH aqueous solution of 1mol/L is 7.8 namely to form the CdSe electric depositing solution;
3) electrochemical process deposition CdSe quantum dot:
At room temperature, adopt two electrode systems to carry out galvanostatic method electrochemical deposition CdSe, to be coated with porous TiO 2Nanocrystalline FTO is work electrode, and the platinum electrode that itself does not participate in reacting is that two interelectrode distances are 1cm, place electric depositing solution to apply 0.6mA/cm to work electrode at electrode to electrode 2Constant current, the charged particle in the electrodeposit liquid move to porous TiO under the effect of electric field 2Nanocrystal surface forms the CdSe quantum dot by redox reaction and is adsorbed on TiO 2On, after deposition 8min question response finishes electrode is taken out, rinse well with deionized water, be placed on N 2Under dry up and obtain quantum dot sensitized wide bandgap semiconductor electrode.
Fig. 1 is 0.6mA/cm 2The quantum dot sensitized porous TiO of the CdSe for preparing under the current density 2The field emission scanning electron microscope of electrode surface (FESEM) figure, as can be seen from the figure the CdSe quantum dot is fully with TiO 2Hole stops up, 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 larger 2-And Cd 2+Ion does not also move to TiO 2Hole inside just reacts and forms the CdSe quantum dot, thereby has stopped up TiO 2The cavity entrance.Because the quantum dot deposition is inhomogeneous, TiO 2Inside has produced stress, causes TiO 2Cracking.
Embodiment 2:
1) preparation of porous nanocrystalline electrode:
With Dyesol18NR-TTiO 2(Australian Dyesol company produce) slurry is coated in the FTO conductive glass surface that cleans up by silk screen print method, then put into Muffle furnace in 500 ℃ of lower sintering 30min, and forming thickness at the FTO conductive glass surface is the porous TiO of 10 μ m 2Nanocrystalline electrode;
2) preparation of electric depositing solution:
The preparation of front body liquid: with the Se powder of 2mmol, the Na of 8mmol 2SO 3Add hot reflux at 90 ℃ lower with the 50ml deionized water and stirring after evenly 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: with the Cd (CH of 0.8mmol 3COO) 2Be dissolved in the deionized water of 20ml with the 1.6mmol disodium ethylene diamine tetraacetate, form the cadmium precursor liquid of 0.04mol/L behind the stirring 10min;
The preparation of electric depositing solution: the Na that gets 20ml 2SeSO 3Solution joins in the cadmium precursor liquid, and behind the uniform stirring 10min, regulating the pH value with the NaOH aqueous solution of 1mol/L is 7.8 namely to form the CdSe electric depositing solution;
3) electrochemical process deposition CdSe quantum dot:
At room temperature, adopt two electrode systems to carry out galvanostatic method electrochemical deposition CdSe, to be coated with porous TiO 2Nanocrystalline FTO is work electrode, and the platinum electrode that itself does not participate in reacting is that two interelectrode distances are 1cm, place electric depositing solution to apply 0.4mA/cm to work electrode at electrode to electrode 2Constant current, the charged particle in the electrodeposit liquid move to porous TiO under the effect of electric field 2Nanocrystal surface forms the CdSe quantum dot by redox reaction and is adsorbed on TiO 2On, after deposition 12min question response finishes electrode is taken out, rinse well with deionized water, be placed on N 2Under dry up and obtain quantum dot sensitized wide bandgap semiconductor electrode.
Fig. 2 is 0.4mA/cm 2The quantum dot sensitized porous TiO of the CdSe for preparing under the 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 do not stopped up fully, simultaneously crackle has also disappeared.But the CdSe quantum dot that electro-deposition forms is reunited, and forms the cluster that is about 80nm and is deposited on TiO 2The surface, and infiltrate TiO 2The CdSe quantum dot of hole seldom.This remains because current density is excessive, causes the quantum dot deposition velocity very fast, thereby has affected the CdSe quantum dot at porous TiO 2The uniformity that distributes in the electrode.
Embodiment 3:
1) preparation of porous nanocrystalline electrode:
With Dyesol18NR-TTiO 2(Australian Dyesol company produce) slurry is coated in the FTO conductive glass surface that cleans up by silk screen print method, then put into Muffle furnace in 500 ℃ of lower sintering 30min, and forming thickness at the FTO conductive glass surface is the porous TiO of 10 μ m 2Nanocrystalline electrode;
2) preparation of electric depositing solution:
The preparation of front body liquid: with the Se powder of 2mmol, the Na of 8mmol 2SO 3Add hot reflux at 90 ℃ lower with the 50ml deionized water and stirring after evenly 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: with the Cd (CH of 0.8mmol 3COO) 2Be dissolved in the deionized water of 20ml with the 1.6mmol disodium ethylene diamine tetraacetate, form the cadmium precursor liquid of 0.04mol/L behind the stirring 10min;
The preparation of electric depositing solution: the Na that gets 20ml 2SeSO 3Solution joins in the cadmium precursor liquid, and behind the uniform stirring 10min, regulating the pH value with the NaOH aqueous solution of 1mol/L is 7.8 namely to form the CdSe electric depositing solution;
3) electrochemical process deposition CdSe quantum dot:
At room temperature, adopt two electrode systems to carry out galvanostatic method electrochemical deposition CdSe, to be coated with porous TiO 2Nanocrystalline FTO is work electrode, and the platinum electrode that itself does not participate in reacting is that two interelectrode distances are 1cm, place electric depositing solution to apply 0.2mA/cm to work electrode at electrode to electrode 2Constant current, the charged particle in the electrodeposit liquid move to porous TiO under the effect of electric field 2Nanocrystal surface forms the CdSe quantum dot by redox reaction and is adsorbed on TiO 2On, after deposition 24min question response finishes electrode is taken out, rinse well with deionized water, be placed on N 2Under dry up and obtain quantum dot sensitized wide bandgap semiconductor electrode.
Fig. 3 is 0.2mA/cm 2The quantum dot sensitized porous TiO of the CdSe for preparing under the current density 2The surperficial FESEM figure of electrode.Deposit as we can see from the figure the TiO of CdSe quantum dot 2Electrode has kept its original loose structure, but the space diminishes, and particle diameter increases, and illustrates that the CdSe quantum dot successfully has been deposited on TiO 2Nanocrystal surface, the CdSe quantum dot is at TiO as can also be seen from Figure 2Electrode surface covers evenly, does not have the generation of agglomeration, and these all are conducive to the raising of battery performance.
In order further to improve the performance of QDSSC, the present invention also carries out the ZnS modification to the sensitization electrode for preparing, namely obtain the sensitization electrode surface by the 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 will be higher than at the bottom of the conduction band of some semiconductor-quantum-points commonly used, such as CdSe, CdS, CdTe etc., make the heterostructure that forms the Type I between quantum dot and the ZnS, thereby can effectively stop the light induced electron that produces in the quantum dot or be transferred to electronics in the semi-conducting electrode and electrolyte in redox couple compound, improve the opto-electronic conversion performance of QDSSC.The existence of ZnS passivation layer has reduced the blemish of quantum dot, has suppressed the compound of redox couple in light induced electron and the electrolyte, thereby has improved the performance of QDSSC.
Embodiment 4:
1) preparation of porous nanocrystalline electrode:
With Dyesol18NR-TTiO 2(Australian Dyesol company produce) slurry is coated in the FTO conductive glass surface that cleans up by silk screen print method, then put into Muffle furnace in 500 ℃ of lower sintering 30min, and forming thickness at the FTO conductive glass surface is the porous TiO of 10 μ m 2Nanocrystalline electrode;
2) preparation of electric depositing solution
The preparation of front body liquid: with the Se powder of 2mmol, the Na of 8mmol 2SO 3Add hot reflux at 90 ℃ lower with the 50ml deionized water and stirring after evenly 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: with the Cd (CH of 0.8mmol 3COO) 2Be dissolved in the deionized water of 20ml with the 1.6mmol disodium ethylene diamine tetraacetate, form the cadmium precursor liquid of 0.04mol/L behind the stirring 10min;
The preparation of electric depositing solution: the Na that gets 20ml 2SeSO 3Solution joins in the cadmium precursor liquid, and behind the uniform stirring 10min, regulating the pH value with the NaOH aqueous solution of 1mol/L is 7.8 namely to form the CdSe electric depositing solution;
3) electrochemical process deposition CdSe quantum dot:
At room temperature, adopt two electrode systems to carry out galvanostatic method electrochemical deposition CdSe, to be coated with porous TiO 2Nanocrystalline FTO is work electrode, and the platinum electrode that itself does not participate in reacting is that two interelectrode distances are 1cm, place electric depositing solution to apply 0.2mA/cm to work electrode at electrode to electrode 2Constant current, the charged particle in the electrodeposit liquid move to porous TiO under the effect of electric field 2Nanocrystal surface forms the CdSe quantum dot by redox reaction and is adsorbed on TiO 2On, after deposition 24min question response finishes electrode is taken out, rinse well with deionized water, be placed on N 2Under dry up and obtain quantum dot sensitized wide bandgap semiconductor electrode;
4) SILAR method deposition ZnS passivation layer:
The standby quantum dot sensitized wide bandgap semiconductor electrode of step 3) preparation is immersed first the Zn (NO of 0.1mol/L 3) 21min in the aqueous solution removes the not firm Zn of absorption with deionized water rinsing after taking out 2+, and then be placed on the Na of 0.1mol/L 21min in the S aqueous solution, Zn 2+With S 2-Ion reacts and forms ZnS, using deionized water rinsing, above process after taking out is a SILAR circulation, after 3 SILAR circulations, form one deck ZnS passivation layer at quantum dot sensitized wide bandgap semiconductor electrode surface, rinse out unreacted Zn with deionized water at last 2+And S 2-Ion is placed on N 2Under dry up and get final product.
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, depositing as we can see from the figure the short circuit current of battery of ZnS passivation layer and open circuit voltage has in various degree raising, thereby the photoelectric conversion efficiency of QDSSC has obtained increasing substantially.Because the ZnS passivation layer is very little to the contribution of visible absorption, so the lifting of battery efficiency mainly is because the ZnS passivation layer has reduced the blemish of CdSe quantum dot, and quantum dot and TiO have been suppressed 2In light induced electron and electrolyte in redox couple compound, rather than extended the absorption region of visible light.
Embodiment 5:
1) preparation of porous nanocrystalline electrode:
With SnO 2Slurry is coated in the FTO conductive glass surface that cleans up by silk screen print method, then put into Muffle furnace in 500 ℃ of lower sintering 30min, and forming thickness at the FTO conductive glass surface is the porous SnO of 8 μ m 2Nanocrystalline electrode;
2) preparation of electric depositing solution:
The preparation of front body liquid: with the Te powder of 2mmol, the Na of 8mmol 2SO 3Add hot reflux at 70,100 ℃ lower with the 50ml deionized water and stirring after evenly 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: with the Cd (CH of 0.8mmol 3COO) 2Be dissolved in the deionized water of 20ml with the 1.6mmol disodium ethylene diamine tetraacetate, the rear formation 0.04mol/L that stirs the cadmium precursor liquid;
The preparation of electric depositing solution: the Na that gets 20ml 2TeSO 3Solution joins in the cadmium precursor liquid, and behind the uniform stirring 10min, regulating the pH value with the NaOH aqueous solution of 1mol/L is 7.5 namely to form the CdTe electric depositing solution;
3) electrochemical process deposition CdTe quantum dot:
At room temperature, adopt two electrode systems to carry out galvanostatic method electrochemical deposition CdTe, to be coated with porous SnO 2Nanocrystalline FTO is work electrode, and the graphite electrode that itself does not participate in reacting is that two interelectrode distances are 0.5cm, place electric depositing solution to apply 0.3mA/cm to work electrode at electrode to electrode 2Constant current, the charged particle in the electrodeposit liquid moves to porous SnO under the effect of electric field 2Nanocrystal surface forms the CdTe quantum dot by redox reaction and is adsorbed on SnO 2On, after deposition 5min question response finishes electrode is taken out, rinse well with deionized water, be placed on N 2Under dry up and obtain quantum dot sensitized wide bandgap semiconductor electrode;
4) SILAR method deposition ZnS passivation layer:
The standby quantum dot sensitized wide bandgap semiconductor electrode of step 3) preparation is immersed first the Zn (NO of 0.1mol/L 3) 21min in the aqueous solution removes the not firm Zn of absorption with deionized water rinsing after taking out 2+, and then be placed on the Na of 0.1mol/L 21min in the S aqueous solution, Zn 2+With S 2-Ion reacts and forms ZnS, using deionized water rinsing, above process after taking out is a SILAR circulation, after 3 SILAR circulations, form one deck ZnS passivation layer at quantum dot sensitized wide bandgap semiconductor electrode surface, rinse out unreacted Zn with deionized water at last 2+And S 2-Ion is placed on N 2Under dry up and get final product.
Embodiment 6:
1) preparation of porous nanocrystalline electrode:
The ZnO slurry is coated in the FTO conductive glass surface that cleans up by silk screen print method, then puts into Muffle furnace in 500 ℃ of lower sintering 30min, forming thickness at the FTO conductive glass surface is the nanocrystalline electrode of porous ZnO of 12 μ m;
2) preparation of electric depositing solution:
The preparation of front body liquid: with the Te powder of 2mmol, the Na of 8mmol 2SO 3Add hot reflux at 100 ℃ lower with the 50ml deionized water and stirring after evenly 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: with the Cd (CH of 0.8mmol 3COO) 2Be dissolved in the deionized water of 20ml with the 1.6mmol disodium ethylene diamine tetraacetate, the rear formation 0.04mol/L that stirs the cadmium precursor liquid;
The preparation of electric depositing solution: the Na that gets 20ml 2TeSO 3Solution joins in the cadmium precursor liquid, and behind the uniform stirring 10min, regulating the pH value with the NaOH aqueous solution of 1mol/L is 8 namely to form the CdTe electric depositing solution;
3) electrochemical process deposition CdTe quantum dot:
At room temperature, adopt two electrode systems to carry out galvanostatic method electrochemical deposition CdTe, to be coated with the nanocrystalline FTO of porous ZnO as work electrode, the gold electrode that itself does not participate in reacting is to electrode, two interelectrode distances are 2cm, place electric depositing solution to apply 0.5mA/cm to work electrode at electrode 2Constant current, charged particle in the electrodeposit liquid moves to the porous ZnO nanocrystal surface under the effect of electric field, form the CdTe quantum dot by redox reaction and be adsorbed on the ZnO, after deposition 30min question response finishes electrode is taken out, rinse well with deionized water, be placed on N 2Under dry up and obtain quantum dot sensitized wide bandgap semiconductor electrode;
4) SILAR method deposition ZnS passivation layer:
The standby quantum dot sensitized wide bandgap semiconductor electrode of step 3) preparation is immersed first the Zn (NO of 0.1mol/L 3) 21min in the aqueous solution removes the not firm Zn of absorption with deionized water rinsing after taking out 2+, and then be placed on the Na of 0.1mol/L 21min in the S aqueous solution, Zn 2+With S 2-Ion reacts and forms ZnS, using deionized water rinsing, above process after taking out is a SILAR circulation, after 3 SILAR circulations, form one deck ZnS passivation layer at quantum dot sensitized wide bandgap semiconductor electrode surface, rinse out unreacted Zn with deionized water at last 2+And S 2-Ion is placed on N 2Under dry up and get final product.

Claims (4)

1. the electrochemical method of the quantum dot sensitized wide bandgap semiconductor electrode of controlled preparation is characterized in that may further comprise the steps:
1) preparation of porous nanocrystalline electrode:
With TiO 2, SnO 2Or the ZnO slurry is coated in the FTO conductive glass surface that cleans up by silk screen print method, then puts into Muffle furnace in 500 ℃ of lower sintering 30min, and forming thickness at the FTO conductive glass surface is the porous TiO of 8～12 μ m 2, porous SnO 2Or the nanocrystalline electrode of porous ZnO;
2) preparation of electric depositing solution:
The preparation of front body liquid: with the Na of the Se powder of 2mmol or Te powder, 8mmol 2SO 3Add hot reflux at 70-100 ℃ lower with the 50ml deionized water and stirring after evenly 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: with the Cd (CH of 0.8mmol 3COO) 2Be dissolved in the deionized water of 20ml with the 1.6mmol disodium ethylene diamine tetraacetate, the rear formation 0.04mol/L that stirs the cadmium precursor liquid;
The preparation of electric depositing solution: the Na that gets 20ml 2SeSO 3Or Na 2TeSO 3Solution joins in the cadmium precursor liquid, and behind the uniform stirring 10min, regulating the pH value with the NaOH aqueous solution of 1mol/L is that 7.5-8 namely forms CdSe or CdTe electric depositing solution;
3) electrochemical process deposition CdSe or CdTe quantum dot:
At room temperature, adopt two electrode systems 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, place electric depositing solution to apply constant current to work electrode at electrode, and the charged particle in the electrodeposit liquid moves to porous TiO under the effect of electric field 2, porous SnO 2Or the porous ZnO nanocrystal surface, be adsorbed on TiO by redox reaction formation CdSe or CdTe quantum dot 2, SnO 2Or on the ZnO, after question response finishes electrode is taken out, rinse well with deionized water, be placed on N 2Under dry up and obtain quantum dot sensitized wide bandgap semiconductor electrode.
2. the electrochemical method of the quantum dot sensitized wide bandgap semiconductor electrode of controlled preparation according to claim 1 is characterized in that: also be included in deposition ZnS passivation layer on the quantum dot sensitized wide bandgap semiconductor electrode of preparation, its step is as follows:
The standby quantum dot sensitized wide bandgap semiconductor electrode of step 3) preparation is immersed first the Zn (NO of 0.1mol/L 3) 21min in the aqueous solution removes the not firm Zn of absorption with deionized water rinsing after taking out 2+, and then be placed on the Na of 0.1mol/L 21min in the S aqueous solution, Zn 2+With S 2-Ion reacts and forms ZnS, using deionized water rinsing, above process after taking out is a SILAR circulation, after 3 SILAR circulations, form one deck ZnS passivation layer at quantum dot sensitized wide bandgap semiconductor electrode surface, rinse out unreacted Zn with deionized water at last 2+And S 2-Ion is placed on N 2Under dry up and get final product.
3. the electrochemical method of the quantum dot sensitized wide bandgap semiconductor electrode of controlled preparation 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.
4. the electrochemical method of the quantum dot sensitized wide bandgap semiconductor electrode of controlled preparation according to claim 1, it is characterized in that: the current density of described constant current is 0.2-0.6mA/cm 2, sedimentation time is 5-30min.
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