CN102651281B - Ga doped ZnO nanometer line array dye sensitization solar cell (DSSC) and preparation method of Ga doped ZnO nanometer line array DSSC - Google Patents
Ga doped ZnO nanometer line array dye sensitization solar cell (DSSC) and preparation method of Ga doped ZnO nanometer line array DSSC Download PDFInfo
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Abstract
The invention provides a Ga doped ZnO nanometer line array dye sensitization solar cell (DSSC) and a preparation method of the Ga doped ZnO nanometer line array DSSC. The Ga doped ZnO nanometer line array DSSC consists of a fluorine doped tin oxide (FTO) conducting glass substrate, a ZnO buffer film layer, a Ga doped ZnO nanometer line array layer, ruthenium complex dye N719, I<->/I<3-> electrolyte and a Pt/FTO counter electrode according to sequences from bottom to top. The Ga doping ZnO is carried out by an electric field auxiliary chemical method, so the photoelectric conversion efficiency of the Ga doped ZnO nanometer line array DSSC provided by the invention reaches 1.53 percent. The preparation process provided by the invention is simple, the implementation is easy, the cost is low, the yield is high, and good market application prospects are realized.
Description
Technical field
The invention belongs to the research field of solar cell, be specifically related to the preparation method of the array dye sensilized solar cell of a kind of Ga doped ZnO nano-wire.
Background technology
In recent years, DSSC (be called for short DSSC) has the focus that the advantage such as with low cost, theoretical conversion efficiencies is high, preparation technology is simple becomes regenerative resource research field.One-dimensional nano-array electrode then effectively can reduce electron scattering and electric transmission path, improves electron diffusion length and electron transfer rate.Researcher gradually adopts one-dimensional nano-array as light anode to construct DSSC battery.
Because zinc oxide (ZnO) has higher electron mobility, manageable pattern, lower crystallization temperature, highly beneficial to the photoelectric conversion efficiency improving electron transfer rate and battery.Since the people such as Peidong Yang in 2005 propose ZnO nanowire array DSSC battery, one of assembling One-Dimensional ZnO nano-array DSSC battery focus becoming research, and the photoelectric conversion efficiency of the One-Dimensional ZnO base DSSC battery reported at present is all not bery desirable, mainly due to intrinsic ZnO carrier concentration with conductivity is too low and large area, low cost making ZnO array films difficulty in conductive substrates.
For improving the electric property of N-shaped ZnO, III higher race's element doping of valence state is usually adopted to improve its conductivity.At present, III race element doping ZnO is generally thin-film state, as conductive layer, for DSSC battery.Present stage, making ZnO array films mainly adopts hydro thermal method on conductive substrates.The ZnO nano array uniformity that hydro thermal method obtains is very poor, and thickness is wayward, and adhesive force is bad, generally all will through double annealing, complex process, limits its application in solar cell.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, provide a kind of Ga doping zinc oxide nanometer linear array DSSC battery, the Ga doping zinc oxide nanometer linear array of this DSSC battery adopts the growth of electric field-assisted chemical method.
The present invention is achieved through the following technical solutions.The array dye sensilized solar cell of a kind of Ga doped ZnO nano-wire of the present invention be by according to from top to bottom order FTO Conducting Glass, ZnO buffer, Ga doping zinc oxide nanometer array layers, N719 dyestuff, I
-/ I
3 -electrolyte and Pt/FTO form electrode, and wherein Ga doping zinc oxide nanometer array layers adopts electric field-assisted chemical method, ZnO buffer deposit Ga doping zinc oxide nanometer linear array forms.
The preparation method of Ga doping zinc oxide nanometer linear array DSSC battery of the present invention, comprises following step:
Step 1: with deionized water, acetone and alcohol, ultrasonic cleaning is carried out respectively to FTO conductive glass surface, then dries up, and proceed in magnetron sputtering coater or pulsed laser deposition equipment immediately, in vacuum degree 10
-3-10
-5protect under the condition of Pa;
Step 2: adopt the method for magnetron sputtering or pulsed laser deposition to deposit ZnO buffer on FTO electro-conductive glass; The thickness of ZnO buffer is 50-80nm;
Step 3; Adopt electric field-assisted chemical method, ZnO buffer deposits Ga doping zinc oxide nanometer linear array, is conducive to the linear transmission of light induced electron;
Described Ga doping zinc oxide nanometer linear array adopts electric field-assisted chemical method to prepare, and the zinc source of employing is zinc nitrate, and this zinc nitrate amount is 0.01-0.02M, gallium source is gallium nitrate, and gallium nitrate amount is 0.0005 ~ 0.001M, and pH value is 6.5-8, adopt two electrode assemblies, reaction temperature is 80-85
oc, voltage is 0.5-0.8V, reaction time 1-1.5 hour.The state modulator of Ga doped ZnO nano-wire diameter be 100-200nm, the concentration of length 3-5 m, Ga doping is in the scope of 0.5-1.0%;
Step 4: the FTO electro-conductive glass of deposition Ga doped ZnO nano-wire is soaked 1-2 hour, cleaning in N719 dyestuff, dries; Make Ga doped ZnO nano-wire display absorbing dye N719 molecule, obtain dye sensitization light anode;
The concentration of described N719 dyestuff is 0.3-0.5mM, and solvent is ethanol;
Step 5: separately get one piece of FTO electro-conductive glass through clean, by step 2 sputter cathode Pt target 1 minute, obtains Pt/FTO to electrode;
Step 6: the dye sensitization light anode of step 4 is become sandwich structure with the Pt/FTO of step 5 to electrode assembling, and injects electrolyte.Sealing, 80-90
oc toasts 3-10 minute, Ga doped ZnO nano-wire DSSC battery have been prepared.
Electrolyte solution proportioning is: 0.6M 1-butyl-3-methylpyridinium iodide imidazoles iodine [BMII], 0.03M iodine [I
2], 0.1M guanidinium isothiocyanate [GUSCN], 0.5M4-tert .-butylpyridine [TBP], solvent is acetonitrile/valeronitrile (volume ratio is 85:15) mixed solution;
Ga doped ZnO nano-wire DSSC battery structure of the present invention is shown in accompanying drawing 1.
The Ga doped ZnO nano-wire prepared has carried out scanning electron microscopy (SEM), current-voltage (I-V) characteristic curve and Ga doped ZnO nano-wire DSSC Cell current density and the analysis of voltage (J-V) characteristic curve.These analysis results are listed in accompanying drawing 2-4 respectively.
Beneficial effect of the present invention is:
The present invention utilizes electric field-assisted chemical method in ZnO buffer, grow Ga doping zinc oxide nanometer linear array.Under electric field-assisted effect, be conducive to Ga doping and enter ZnO, and Ga doping ZnO is along c-axis polar growth, electric field-assisted chemical method is due to chilling process, and high production rate, is easy to large area deposition, simple to operate, is conducive to suitability for industrialized production in the future.
Ga doping zinc oxide nanometer linear array DSSC battery prepared by the present invention, preparation technology had both achieved Ga doping ZnO and has improve the electron mobility of semiconductor film thus improve electron transfer rate, overcome again semiconductor film/substrate adhesion difference and cause dye molecule and FTO, the charge recombination at electrolyte and FTO interface and the problem such as semiconductor film/substrate interface resistance is larger, control the load capacity of dyestuff simultaneously flexibly and then improve efficiency of light absorption.
Further, because in the nano wire of one-dimentional structure, the transmission path of electronics shortens, diffusion length is elongated, and make electric transmission in DSSC battery faster to electrode speed, charge recombination reduces.Therefore, it is low that the Ga doped ZnO nano-wire DSSC battery that the present invention proposes can effectively overcome electric transmission speed, substantially improves again efficiency of light absorption and photovoltaic performance.
Accompanying drawing explanation
Fig. 1 is Ga doping zinc oxide nanometer linear array DSSC battery structure figure of the present invention.
Wherein 1----FTO substrate, 2----ZnO buffer, 3----Ga doped ZnO nano-wire, 4----N719 dye molecule, 5----liquid electrolyte, 6----Pt/FTO substrate.
Fig. 2 is the SEM figure of Ga doping zinc oxide nanometer linear array of the present invention.
Fig. 3 is that Ga of the present invention adulterates and non-blended ZnO nano-wire array current-voltage (I-V) relation spectrum; Nano wire/resilient coating/FTO electro-conductive glass structural representation when illustration is I-V test.
Fig. 4 is Current density-voltage (J-V) graph of relation of Ga doping zinc oxide nanometer linear array (2) of the present invention and non-blended ZnO nano-wire array (1) DSSC battery.
Embodiment
Refer to shown in Fig. 1, the invention provides a kind of preparation method of Ga doping zinc oxide nanometer linear array DSSC battery, preparation process is as follows:
Step 1, FTO conductive glass surface cleaning preliminary treatment
FTO conductive glass surface carries out ultrasonic cleaning with deionized water, acetone and alcohol respectively, then dries up, and proceeds in magnetron sputtering coater or pulsed laser deposition equipment immediately, in vacuum degree 10
-3-10
-5protect under the condition of Pa;
Step 2, making ZnO resilient coating
Electro-conductive glass deposits ZnO buffer, and described deposition ZnO buffer is the method adopting magnetron sputtering or pulsed laser deposition, and the thickness of this ZnO buffer is 50-80nm;
Step 3, electric field-assisted chemical method growth Ga doping zinc oxide nanometer linear array
Adopt electric field-assisted chemical method, ZnO buffer grows Ga doping zinc oxide nanometer linear array, the zinc source adopted is zinc nitrate solution, gallium source is gallium nitrate, in this solution, nitric acid zinc concentration is 0.01-0.02M, the concentration of gallium nitrate is 0.0005 ~ 0.001M, by adding hexa, ammoniacal liquor in zinc nitrate and gallium nitrate mixed solution, makes reacting solution pH value be 6.5-8.Adopting two electrode assemblies, using step 2) the FTO electro-conductive glass with ZnO buffer prepared is as negative electrode, and zinc metal sheet, as anode, utilizes thermostat water bath to be heated to 80-85 to reactant liquor
oc, then carries out reaction 1-1.5 hour at 0.5-0.8V, after reaction terminates, takes out the conductive substrate of negative electrode, first with the surface of deionized water flushing membrane repeatedly, then 80
oin C thermostatic drying chamber, drying 2 hours, obtains Ga doping zinc oxide nanometer linear array;
Step 4, absorbing dye N719
Dyestuff adopts N719 dyestuff, and the concentration of this N719 dyestuff is 0.3-0.5mM, and solvent is ethanol;
Then, step 3) the Ga doping zinc oxide nanometer electrode prepared at room temperature is immersed in above-mentioned dyestuff N719 solution, and soak 1-2 hour, make the abundant adsorpting dye molecule of electrode; Wash away the dyestuff of remained on surface after taking-up with ethanol, dry, obtain dye sensitization light anode;
Step 5, to prepare electrode
Clean one piece of FTO electro-conductive glass by step 1, by step 2 sputter cathode Pt target 1 minute, obtain Pt/FTO to electrode;
Step 6, assembling Ga doped ZnO nano-wire DSSC battery
Adopt the Pt/FTO of step 5 as to electrode, with step 4) dye sensitization light anode unit dress up sandwich structure, and inject electrolyte.Sealing, 80-90
oc toasts 3-10 minute, completes the preparation of Ga doped ZnO nano-wire DSSC battery.
To the pattern of the Ga doped ZnO nano-wire of preparation, electrology characteristic carries out testing and testing the photovoltaic property of Ga doped ZnO nano-wire DSSC.
The Ga doped ZnO nano-wire scanning electron microscopy (FE-SEM obtained by step 3, JSM-6700F), observe its surface topography, the diameter of Ga doped ZnO nano-wire is 100-200nm as shown in Figure 2, Ga doped ZnO nano-wire tiles whole visual field substantially, distributes more even.The instrument that current-voltage (I-V) characteristic test of Ga doped ZnO nano-wire uses is Keithley digital sourcemeter, and as shown in Figure 3, compared with non-blended ZnO nano wire, Ga doping makes the conductivity of ZnO nano-wire obviously strengthen.
Under Oriel solar simulator light source irradiation, radiation intensity is 100mW/cm
2, battery light-receiving area 0.16 cm
2.Ga doping zinc oxide nanometer linear array DSSC battery has short circuit current is as shown in Figure 4 6.05 mA cm
2, open circuit voltage is 0.56V, and fill factor, curve factor is 45%, and photoelectric conversion efficiency is 1.53%.The photovoltaic performance short circuit current being obviously better than non-dopen Nano linear array DSSC battery is 2.98 mA cm
2, open circuit voltage is 0.52 V, and fill factor, curve factor is 43%, and photoelectric conversion efficiency is 0.67%.
Claims (4)
1. a preparation method for the array dye sensilized solar cell of Ga doped ZnO nano-wire, is characterized in that, comprise the steps:
Step 1: with deionized water, acetone and alcohol, ultrasonic cleaning is carried out respectively to FTO conductive glass surface, then dries up, and proceed in magnetron sputtering coater or pulsed laser deposition equipment immediately, in vacuum degree 10
-3-10
-5protect under the condition of Pa;
Step 2: adopt the method for magnetron sputtering or pulsed laser deposition to deposit ZnO buffer on FTO electro-conductive glass;
Step 3: adopt electric field-assisted chemical method, ZnO buffer deposits Ga doping zinc oxide nanometer linear array;
Described Ga doping zinc oxide nanometer linear array adopts electric field-assisted chemical method to prepare, the zinc source adopted is zinc nitrate, this zinc nitrate amount is 0.01-0.02M, gallium source is gallium nitrate, and gallium nitrate amount is 0.0005 ~ 0.001M, and pH value is 6.5-8, adopt two electrode assemblies, reaction temperature is 80-85 DEG C, and voltage is 0.5-0.8V, reaction time 1-1.5 hour;
Step 4: the FTO electro-conductive glass of deposition Ga doped ZnO nano-wire is soaked 1-2 hour, cleaning in N719 dyestuff, dries; Make Ga doping zinc oxide nanometer linear array adsorb N719 dye molecule, obtain dye sensitization light anode;
Step 5: separately get one piece of FTO electro-conductive glass through clean, presses step 2 sputter cathode Pt target 1 minute thereon, obtains Pt/FTO to electrode;
Step 6: the dye sensitization light anode of step 4 is become sandwich structure with the Pt/FTO of step 5 to electrode assembling, injects electrolyte; Sealing, prepared by 80-90 DEG C of baking 3-10 minute, Ga doped ZnO nano-wire DSSC.
2. the preparation method of the array dye sensilized solar cell of a kind of Ga doped ZnO nano-wire according to claim 1, is characterized in that the thickness of the ZnO buffer of step 2 is 50-80nm.
3. the preparation method of the array dye sensilized solar cell of a kind of Ga doped ZnO nano-wire according to claim 1, it is characterized in that the dyestuff described in step 4 is N719 dyestuff, the concentration of this dyestuff is 0.3-0.5mM, and solvent is ethanol.
4. the preparation method of the array dye sensilized solar cell of a kind of Ga doped ZnO nano-wire according to claim 1, it is characterized in that the electrolyte solution proportioning described in step 6 is: 0.6M 1-butyl-3-methylpyridinium iodide imidazoles iodine [BMII], 0.03M iodine [I
2], 0.1M guanidinium isothiocyanate [GUSCN], 0.5M4-tert .-butylpyridine [TBP], solvent is acetonitrile/valeronitrile mixed solution, and its volume ratio is 85:15.
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| CN105040107A (en) * | 2015-06-02 | 2015-11-11 | 济南大学 | Additional electrostatic field assisted semiconductor material doping method |
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Citations (2)
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|---|---|---|---|---|
| CN1755948A (en) * | 2004-04-23 | 2006-04-05 | 三星Sdi株式会社 | Module of dye-sensitive solar cell |
| CN101872681A (en) * | 2010-02-09 | 2010-10-27 | 南京大学 | Dye-sensitized solar cell working electrode and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1755948A (en) * | 2004-04-23 | 2006-04-05 | 三星Sdi株式会社 | Module of dye-sensitive solar cell |
| CN101872681A (en) * | 2010-02-09 | 2010-10-27 | 南京大学 | Dye-sensitized solar cell working electrode and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| Low Temperature Synthesis and Optical Properties of ZnO Nanowires;Chang Peng等;《半导体学报》;20071031;第28卷(第10期);1503-1507 * |
| Optical and Electrical Properties of Ga-Doped ZnO Nanowire Arrays on Conducting Substrates;Minjie Zhou等;《J. Phys. Chem. C》;20090422(第113期);8945–8947 * |
| 电场辅助电化学法沉积ZnO纳米线;常鹏等;《人工晶体学报》;20080228;第37卷(第1期);56-59 * |
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