CN103137868B - Organic/ inorganic hybridization solar battery based on ternary nanometer array and preparation method thereof - Google Patents

Organic/ inorganic hybridization solar battery based on ternary nanometer array and preparation method thereof Download PDF

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CN103137868B
CN103137868B CN201310019859.2A CN201310019859A CN103137868B CN 103137868 B CN103137868 B CN 103137868B CN 201310019859 A CN201310019859 A CN 201310019859A CN 103137868 B CN103137868 B CN 103137868B
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cds
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ppv
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CN103137868A (en
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刘长文
王命泰
邱泽亮
张慧
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Institute of Plasma Physics of CAS
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Abstract

The invention discloses an organic/ inorganic hybridization solar battery based on a ternary nanometer array and a preparation method of the organic/ inorganic hybridization solar battery. Components of the battery comprise a glass substrate, an information technology outsourcing (ITO) layer serving as a positive pole, ZnO-CdS-Sb2S3 three-component nanorod array, a microsomal epoxide hydrolase (MEH)-positive predictive value (PPV) film layer, a poly ethylenedioxythiophene (PEDOT): packet switching service (PSS) hole transporting layer and an atom unit ( Au) film layer serving as a battery negative pole. The organic/ inorganic hybridization solar battery based on the ternary nanometer array and the preparation method of the organic/ inorganic hybridization solar battery is simple in preparation method, and the thickness of an Sb2S3 layer is easy to control.

Description

A kind of hybrid solar cell based on ternary nano array and preparation method thereof
Technical field:
The present invention relates to nano material and energy field, is exactly a kind of hybrid solar cell based on ternary nano array and preparation method thereof.
Background technology:
The polymer solar cells be made up of conjugatd polymers and inorganic semiconductor nanostructure is a kind of novel hybrid solar cell.Due to the advantage that it has polymer (lightweight, pliability good, easy large area at a low price film forming etc.) and inorganic semiconductor material (carrier mobility high, stable in properties, easy control of structure etc.) concurrently, become the important research object in low price solar cell in recent years.Usually, inorganic semiconductor nano particle is mixed in organic solvent with organic polymer, realizes simple blend, then by appropriate ways, these simple blend are made unordered hybrid battery; Such as, organic polymer and ZnO(Adv. Funct. Mater.2006,16,1112-1116), TiO 2(Appl. Phys. Lett. 2007,90,183513), PbS(Nanotechnology 2009,20,095202), PbSe(ACS Nano 2009,3,1345-1352) or CdSe(J. Phys. Chem. C 2010,114,12784-12791) etc. inorganic semiconductor nano particle composition solar cell.But this type of battery efficiency is lower, desirable electron propagation ducts and comparatively serious interface charge compound is not wherein had to be important influencing factors.
Replacing with one-dimensional inorganic nanometer rods (or line) array the composite construction that nano particle and organic polymer formed is a kind of desirable hybrid solar battery structure form (Chem. Rev.2007,107,1324-1338; Energy Environ. Sci. 2010,3,1851-1864; Adv. Mater. 2011,23,1810-1828; EnergyEnviron. Sci. 2011,4,2700-2720).First, nano-structure array can provide direct electron propagation ducts, light induced electron is directly transported on passive electrode along the nano-array of oriented growth, can reduces the compound of electric charge; Secondly, in this composite construction, both can obtain larger separation of charge interfacial area, and the shortcoming of exciton active diffusion length in polymer short (5-20 nm) can have been overcome again, improve the utilization ratio of exciton in polymer; Moreover, grow the array on lining base in advance, organic/inorganic interface and transferring charge passage can be kept at three-dimensional Stable distritation.ZnO nanorod or linear array (are called for short, ZnO-NA) there is many advantages, such as, stable in properties, environmental friendliness, electron mobility are high and easily realize large area by simple method and prepare, use maximum a kind of material (Energy Environ. Sci. 2009 in this type of orientation texture hydridization solar cell current, 2,19-34; Adv. Mater. 2011,23,1810-1828; Energy Environ. Sci. 2011,4,2700-2720).Usually, the open circuit voltage (V of the hydridization solar cell (being called for short, polymer/ZnO-NA battery) that ZnO-NA and polymer form oc) and short circuit current (J sc) not ideal, cause the conversion efficiency of battery lower (mostly at 0.2%-0.5%), especially V oclower (mostly at about 0.1-0.4V).
At present, people are mostly the contact performancies by improving polymer/ZnO interface with a kind of organic molecule, obtain the J significantly improved sc, also improve the V of battery to a certain extent oc(J.Mater. Chem. 2006,16,2088-2096; J. Phys. Chem. B2006,110,7635-7639; J. Phys. Chem. C 2011,115,3745-3752); After organic decoration, the J of battery scalso undesirable (generally at 5 mA/cm 2left and right), and V ocstill not high (mostly at 0.5 below V).Except organic decoration, people also trial inorganic matter modify ZnO-NA, to improve the performance of battery.Greene etc. (J. Phys. Chem. C 2007,111,18451-18456) and Lee etc. (J. Phys.Chem. C 2009,113,15778-15782) are by ald (ALD) technology TiO 2modify ZnO-NA, defining with ZnO is core TiO 2for the ZnO-TiO of shell 2heterogeneous nuclear shell structure nano rod array (is called for short, ZnO-TiO 2-NA), although compared with polymer/ZnO-NA battery, polymer/ZnO-TiO 2the J of-NA battery scobtain improvement to a certain extent, but the V of battery ocstill 0.5 V is less than.Lee etc. (IEEE J. Selected Topics in Quantum Electronics 2010,16,1587 – 1594) are by ALD technology TiO xmodify ZnO-NA, define with TiO xfor the ZnO-TiO of shell xheterogeneous nuclear shell structure nano rod array (is called for short, ZnO-TiO x-NA), compared with polymer/ZnO-NA battery, polymer/ZnO-TiO xthe V of-NA battery ocsignificantly improve and 0.8 V can be reached, but the J of battery scbut exponentially form decays to very little numerical value.(the J. Electrochem. Soc. 2011 such as Wang, 158, H804 – H807) by chemical bath deposition (CBD) technology CdS quantum dot sensitization ZnO-NA, the ZnO nano-rod array obtaining CdS quantum dot sensitization (is called for short, CdS-ZnO-NA), compared with polymer/ZnO-NA battery, the V of polymer/CdS-ZnO-NA battery ochave and improved (0.85 V can be reached) significantly, but J scstill not high.The present inventor seminar, by successively ion layer adsorption and reaction (successive ion layer adsorption and reaction, SILAR) technology CdS quantum dot modifies ZnO-NA, to obtain with the single crystal ZnO nanometer rods polycrystalline film that is core and CdS quantum dot composition be shell, and heterogeneous nuclear shell structure nano rod array (is called for short, ZnO-CdS-NA), compared with polymer/ZnO-NA battery, the V of polymer/ZnO-CdS-NA battery ocand J scall be greatly improved, V ocreach about 0.9 V, but J scstill undesirablely (be less than 3 mA/cm 2) [Chinese invention patent (application) number: 201110310230.4].Recently, the present inventor seminar, ZnO-NA is modified by the hydro-thermal reaction technology ZnO quantum dot in autoclave, to obtain with the single crystal ZnO nanometer rods polycrystalline film that is core and ZnO quantum dot composition be shell, and homogeneity nuclear shell structure nano rod array (is called for short, ZnO-ZnO-NA), compared with polymer/ZnO-NA battery, the V of polymer/ZnO-ZnO-NA battery ocsignificantly increased, reached 0.71V; With a kind of organic substance, ZnO-ZnO-NA is modified further, obtain the ZnO homogeneity nuclear shell structure nano rod array (abbreviation that organic substance N719 modifies, ZnO-ZnO-N719-NA), compared with polymer/ZnO-ZnO-NA battery, the J of polymer/ZnO-ZnO-N719-NA battery ocsignificantly increased, reached nearly 4 mA/cm 2left and right, but V ocreally because of organic introducing, some reduces [Chinese invention patent (application) number: 201110387893.6].As can be seen here, for improving the performance of polymer/ZnO-NA battery, people mainly use organic substance, inorganic matter or the two all use at present, modify ZnO-NA, the two component nanometer stick arrays be made up of ZnO and another inorganic matter or ZnO and an organic substance of acquisition; Wherein, inorganic modification mainly can improve V ocbut improve less to electric current, and organic decoration is to raising J scthere is larger effect but to V ocraising not remarkable or unfavorable.
In the present invention, we first deposit CdS quantum dot by SILAR technology on ZnO-NA, obtain with the single crystal ZnO nanometer rods polycrystalline film that is core and CdS quantum dot composition the heterogeneous nuclear shell structure nano rod array that is shell (namely, ZnO-CdS-NA), then on ZnO-CdS-NA, Sb is deposited by amorphous deposition and thermal crystalline multiple techniques 2s 3nano particle, obtains by ZnO, CdS and Sb 2s 3three inorganic component nanometer stick arrays of composition (are called for short, ZnO-CdS-Sb 2s 3-NA), and by ZnO-CdS-Sb 2s 3-NA and polymer compound have been made novel hydridization solar cell and (have been called for short, polymer/ZnO-CdS-Sb 2s 3-NA battery); Compared with corresponding polymer/ZnO-NA battery, polymer/ZnO-CdS-Sb 2s 3the V of-NA battery ocand J scbe significantly improved simultaneously.
Summary of the invention:
The object of the invention is the defect in order to make up prior art, provide a kind of efficient, cost is lower, technique is simple, the hybrid solar cell being convenient to large-area manufacturing and preparation method thereof.
To achieve these goals, the present invention adopts following technical scheme:
Based on a hybrid solar cell for ternary nano array, it is characterized in that: include glass lined base, the ITO layer as anode, ZnO-CdS-Sb 2s 3the Au rete of three components nanometer stick array, MEH-PPV rete, PEDOT:PSS hole transmission layer and the negative electrode as battery; Described ITO layer is plated in the anode as battery on glass lined base, with the ZnO-CdS-Sb of vertical-growth on ITO layer 2s 3three components nanometer stick array is the electron propagation ducts of battery, and light absorbing material MEH-PPV is filled into ZnO-CdS-Sb 2s 3among the gap of three components nanometer rods, simultaneously at ZnO-CdS-Sb 2s 3form MEH-PPV rete above three components nanometer stick array, MEH-PPV rete deposits PEDOT:PSS as hole transmission layer, hole transmission layer deposits the negative electrode of Au film as battery; Described ZnO-CdS-Sb 2s 3three components nanometer rods is by Sb 2s 3shell, CdS subshell, ZnO nanorod form, and described CdS subshell outer cladding Sb 2s 3shell.
Described a kind of hybrid solar cell based on ternary nano array, is characterized in that: the thickness of ITO layer is 50-200 nm, ZnO-CdS-Sb 2s 3the length of three components nanometer stick array is 150-700 nm, diameter is 20-90 nm, the number density of rod is 3-6 × 10 2individual/μm 2, the thickness of CdS subshell is 5-7 nm, Sb 2s 3the thickness of outer shell is 5-10 nm, is positioned at ZnO-CdS-Sb 2s 3mEH-PPV thicknesses of layers above three components nanometer stick array is 30-200 nm, PEDOT:PSS thickness of hole transport layer be 40-80 nm, Au film thickness is 60-120nm.
Described a kind of hybrid solar cell based on ternary nano array, it is characterized in that: described hole transmission layer preferably by depositing mixed liquor that PEDOT:PSS and isopropyl alcohol form and obtaining on MEH-PPV rete, and described PEDOT:PSS and the volume ratio of isopropyl alcohol are 1:0.5-1.5.
The preparation method of the described hybrid solar cell based on ternary nano array, is characterized in that comprising the following steps:
A, be that the hydrochloric acid of 5.5-6.5 mol/L and Zn powder are etched into slice by the ITO layer concentration on ITO electro-conductive glass, cleaner through acetone, isopropyl alcohol, ultra-pure water ultrasonic cleaning, after drying treated ITO electro-conductive glass is for subsequent use;
0.12-0.20 gram of zinc acetate is dissolved in 0.8-1.2 gram of water, add 3-5 milliliter absolute ethyl alcohol until completely dissolved, drip 80-120 microlitre glacial acetic acid again, the mixture obtained at room temperature is stirred 1.8-2.2 hour, again the achromaticity and clarification clear solution of gained is spun on treated ITO electro-conductive glass, obtain uniform zinc acetate film, then in Muffle furnace, at 320-380 DEG C, 18-22 minute is calcined, obtain the ZnO dense film covered on ITO conductive substrate, be placed on the zinc nitrate [ZnO (NO of 0.02-0.06 mol/L 3) 26H 2o] and 0.02-0.06 mol/L hexa composition the aqueous solution in, in 85-95 DEG C of baking oven, react 1-3 hour after sealing, obtain ZnO nano-rod array;
B, respectively configuration concentration are 0.5-1.5 × 10 -2cd (the NO of mol/L 3) 2the aqueous solution and concentration are 0.5-1.5 × 10 -2the Na of mol/L 2the S aqueous solution, at room temperature replaces steps A gained ZnO nano-rod array at Cd (NO 3) 2the aqueous solution and Na 2soak 20-40 second in the S aqueous solution respectively, often complete continuously once at Cd (NO 3) 2the aqueous solution and Na 2the process of soaking respectively in the S aqueous solution is a SILAR process, Cd (NO 3) 2and Na 2the reaction mol ratio of S is after 1:0.9-1.1, repeated several times SILAR process, and obtaining take CdS as the ZnO-CdS nuclear shell structure nano rod array of vertical-growth on ITO layer of shell, and CdS shell thickness is controlled to be 5-7 nm by SILAR process number of times;
C, respectively configuration concentration are the Na of 0.1-0.5 mol/L 2s 2o 3the aqueous solution and concentration are the SbCl of 0.1-0.5 mol/L 3acetone soln; By Na 2s 2o 3the aqueous solution be cooled to 8-12 DEG C, by SbCl 3acetone soln be slowly added dropwise to Na 2s 2o 3the aqueous solution in, reaction 60-120 minute, obtain deposit Sb 2s 3precursor solution, described Na 2s 2o 3and SbCl 3mol ratio be 1:0.5-1.5; By the ZnO-CdS nuclear shell structure nano rod array face down obtained in step B, be suspended in deposition Sb 2s 3precursor solution in 5-20 minute; Take out substrate, after drip washing and drying, by substrate under inert gas shielding at 250-350 DEG C heat treatment 5-15 minute, obtain ZnO-CdS-Sb 2s 3three components nanometer stick array;
D, working concentration are the MEH-PPV solution of 5-15 mg/mL, MEH-PPV are deposited to the ZnO-CdS-Sb of step C gained under room temperature 2s 3on three components nanometer stick array, and in 120-180 DEG C of heat treatment 5-30 minute under inert gas shielding, MEH-PPV is made to be filled into ZnO-CdS-Sb 2s 3among the gap of three components nanometer rods and at ZnO-CdS-Sb 2s 3mEH-PPV rete is formed above three components nanometer stick array;
E, on the MEH-PPV rete of step D gained, spin coating one deck volume ratio is the mixed liquor of the PEDOT:PSS of 1:0.5-1.5 and isopropyl alcohol composition, under inert gas shielding at 80-120 DEG C heat treatment 5-30 minute, obtain PEDOT:PSS rete as hole transmission layer, by thermal evaporation method evaporation Au film on PEDOT:PSS rete, obtain hydridization solar cell;
F, hydridization solar cell is carried out encapsulating and obtaining product under inert gas shielding.
The described hybrid solar cell preparation method based on ternary nano array, is characterized in that: the glass lined base of the ITO electro-conductive glass described in steps A can replace with other transparency materials.
The described hybrid solar cell preparation method based on ternary nano array, is characterized in that: the solvent of the MEH-PPV solution described in step D is the one in chlorobenzene, oxolane, chloroform, benzene.
The described hybrid solar cell preparation method based on ternary nano array, is characterized in that: step D adopts a kind of ZnO-CdS-Sb MEH-PPV being deposited under room temperature step C gained in spin-coating method, silk screen print method, scraping blade method or ink-jet printing process 2s 3on three components nanometer stick array.
The described hybrid solar cell preparation method based on ternary nano array, is characterized in that: the inert gas preferred nitrogen described in step C, D, E, F.
Principle of the present invention is:
(namely the present invention by preparing the ZnO nano-rod array of vertical-growth on ITO layer, ZnO-NA) as template, by depositing the shell be made up of CdS quantum dot on ZnO nanorod, obtain the heterogeneous nuclear shell structure nano rod array of ZnO-CdS (that is, ZnO-CdS-NA); Using ZnO-CdS-NA as template, by method deposited amorphous Sb on ZnO-CdS nucleocapsid composite nanorod of chemical bath 2s 3, then make Sb by the method for thermal crystalline 2s 3crystallization becomes outer shell, obtains ZnO-CdS-Sb 2s 3three components nanometer stick array (that is, ZnO-CdS-Sb 2s 3-NA).In the battery, ZnO-CdS-Sb 2s 3-NA is as electron propagation ducts, and MEH-PPV is main light absorbing material, and CdS and Sb 2s 3for auxiliary light absorbent.Three kinds of materials with different photoelectric properties combine, and the photoresponse spectral limit of hybrid battery is widened, and V ocand J scall be greatly improved.
Beneficial effect of the present invention is:
1. the present invention is by twice array mould plate method, in conjunction with amorphous deposition and thermal crystalline multiple techniques, has prepared ZnO-CdS-Sb 2s 3three components nanometer stick array, by ZnO-CdS-Sb 2s 3three components nanometer stick array is applied to hydridization solar cell, is main light absorbing material and Sb with conjugatd polymers 2s 3be auxiliary light absorbent with CdS, achieve the absorption to solar photon in 300-800 nm wide spectral range by the complementation of organic substance and inorganic matter absorbing properties; The present invention establishes a kind of based on ZnO-CdS-Sb 2s 3three components nanometer stick array also has the preparation method of hydridization solar cell that wide spectral absorbs.ZnO-CdS-Sb in the present invention 2s 3the preparation method of-NA and battery device is easy, low for equipment requirements, is applicable to large-scale application, has very large using value in fields such as photovoltaic material and low price solar cell devices.
2. the present invention is by control Sb 2s 3reactant concentration during deposition and sedimentation time, overcoming ZnO can by the technological difficulties of acid (alkali) property solution heavy corrosion (ACS Nano 2010,4,3302-3308); By the use of three components compensate for two component nanometer stick arrays (usually by organic substance, inorganic matter or the two all obtain with modifying ZnO-NA) technological deficiency (that is, inorganic modification mainly can improve V ocbut improve less to electric current, and organic decoration is to raising J scthere is larger effect but V to battery ocimprove not remarkable or unfavorable), the photoresponse spectral limit of hybrid battery is widened, and V oc, J scand conversion efficiency is all greatly improved.
3. polymer/ZnO-CdS-Sb 2s 3the top performance of-NA battery reaches following index: J sc=15.5 mA/cm 2, V oc=0.73 V and η=3.32%, compared with polymer/ZnO-NA battery, improves 1244%, 121% and 2667% respectively.
Accompanying drawing illustrates:
Fig. 1 is ZnO-CdS-Sb of the present invention 2s 3the structural representation of the hybrid solar cell of three components nanometer stick array; In figure, numerical reference is described as follows: (1) Au film is as negative electrode, (2) PEDOT:PSS hole transmission layer, (3) polymer MEH-PPV, (4) Sb of battery 2s 3shell, (5) CdS subshell, (6) ZnO nanorod, (7) ito anode, (8) glass lined base;
Fig. 2 is XRD and the SEM characterization result of ZnO nano-rod array of the present invention; Wherein, (a) XRD, (b) SEM;
Fig. 3 is SEM and the TEM characterization result of ZnO-CdS nuclear shell structure nano rod array of the present invention, wherein, and (a) SEM, (b) TEM;
Fig. 4 is ZnO-CdS-Sb of the present invention 2s 3xRD and the UV-vis absorption spectrum characterization result of three components nanometer stick array; Wherein, (a) XRD, (b) UV-vis absorption spectrum;
Fig. 5 is ZnO-CdS-Sb of the present invention 2s 3the SEM characterization result of three components nanometer stick array; Wherein, (a) t=5 minute, (b) t=10 minute, (c) t=15 minute;
Fig. 6 is ZnO-CdS-Sb of the present invention 2s 3tEM(a, the c of three components nanometer stick array, e) and HRTEM(b, d, f) characterization result; Wherein, (a, b) t=5 minute; (c, d) t=10 minute; (e, f) t=15 minute; HRTEM corresponds to Blocked portion in TEM;
Fig. 7 is the J-V performance characterization result of hydridization solar cell of the present invention under AM 1.5 simulated solar illumination condition; Wherein, the reference cell that curve 1 forms for ZnO-NA, curve 2 is ZnO-CdS-Sb 2s 3-NA(t=5 minute) battery that forms, curve 3 is ZnO-CdS-Sb 2s 3-NA(t=10 minute) battery that forms, curve 4 is ZnO-CdS-Sb 2s 3-NA(t=15 minute) battery that forms.
Embodiment
Embodiment 1:
The preparation of ZnO nano-rod array.
(1-1) preparation of ZnO dense film:
Be first that hydrochloric acid and the Zn powder of 6 mol/L is etched into 12 × 4 mm by the ITO layer concentration on ITO electro-conductive glass (ITO thickness is 100-120 nm ,≤15 Ω/) 2slice; Through acetone, isopropyl alcohol, ultra-pure water ultrasonic cleaning totally, dry up rear for subsequent use with the nitrogen of drying.
By 0.16 gram of zinc acetate [Zn (CH 3cOO) 22H 2o] be dissolved in 1 gram of water, add 4 milliliters of absolute ethyl alcohols until completely dissolved, then drip 100 microlitre glacial acetic acid; Mixture at room temperature stirs 2 hours, obtains achromaticity and clarification clear solution.Above-mentioned solution is spun on (2000 revs/min, 60 seconds) on ito glass, repeats four times, obtain uniform film.Then, by zinc acetate film under relative humidity 52%(room temperature) container in ageing 24 hours, then in Muffle furnace, at 350 DEG C, calcining obtains ZnO dense film in 20 minutes.
(1-2) preparation of ZnO nano-rod array:
The ito glass face down that ZnO dense film covers is unsettled is placed in zinc nitrate [ZnO (NO 3) 26H 2o] in the aqueous solution that forms of (0.04 mol/L) and hexa (0.04 mol/L), react 2 hours in 90 DEG C of baking ovens after sealing, obtain ZnO nano-rod array (that is, ZnO-NA).
(1-3) sign of product:
The characterization result of ZnO-NA is shown in accompanying drawing 2.X-ray diffraction (XRD) test shows, ZnO nanorod is wurtzite structure, and nanometer rods grows along [001] direction; Scanning electron microscopy (SEM) photo shows, the ZnO nanorod of gained grows perpendicular to ITO substrate, and length is 360-400 nm, and diameter is 20-60 nm, and the number density of rod is 4-5 × 10 2individual/μm 2.
The preparation of embodiment 2:ZnO-CdS nuclear shell structure nano rod array.
(2-1) preparation of ZnO nano-rod array: with embodiment 1.
(2-2) preparation of ZnO-CdS nuclear shell structure nano rod array:
Under room temperature, be 10 × 10 by ZnO nano-rod array in concentration -3cd (the NO of mol/L 3) 2soak after 30 seconds in the aqueous solution, with water wash 30 seconds remove the surperficial a large amount of Cd (NO of ZnO nanorod 3) 2solution; Then, by this ZnO nano-rod array immediately 10 × 10 -3the Na of mol/L 2soak 30 seconds in the S aqueous solution, and with water wash 30 seconds to remove unreacted Na 2s solution; So far a SILAR process is completed.Circulate 30 times, the thickness namely obtaining CdS layer is the ZnO-CdS nuclear shell structure nano rod array (that is, ZnO-CdS-NA) of 6 nm.
(2-3) sign of product:
The characterization result of ZnO-CdS-NA is shown in accompanying drawing 3 and 4a.XRD result shows, ZnO nanorod surface defines CdS(JCPDS #80-0019); SEM shows, after CdS deposition, nanorod surfaces becomes coarse, but the pattern of nanometer stick array is uninfluenced; TEM shows, CdS is wrapped in ZnO nanorod surface equably and defines core-shell structure, and the thickness of CdS shell is about 6 nm.
Embodiment 3:ZnO-CdS-Sb 2s 3the preparation of three components nanometer stick array:
(3-1) preparation of ZnO nano-rod array: with embodiment 1.
(3-2) preparation of ZnO-CdS nuclear shell structure nano rod array: with embodiment 2.
(3-3) ZnO-CdS-Sb 2s 3the preparation of three components nanometer stick array:
Under room temperature, by 18.61 grams of Na 2s 2o 35H 2o is dissolved in 270 ml deionized water, obtains Na 2s 2o 3the aqueous solution; By 1.95 grams of SbCl 3be dissolved in 30 milliliters of acetone, obtain SbCl 3acetone soln.By Na 2s 2o 3the aqueous solution be cooled to 10 DEG C, after temperature stabilization, by SbCl 3acetone soln join Na with the speed of 2 drops/sec 2s 2o 3the aqueous solution in, and with Keep agitation, after all dripping off, continue to allow Na 2s 2o 3with SbCl 3react 90 minutes, form orange red suspension;
By ZnO-CdS nuclear shell structure nano rod array face down, be suspended in obtained orange red suspension and deposit Sb 2s 3, deposit 5,10 or 15 minutes respectively; After deposition terminates, take out substrate, dry up with water wash, nitrogen; By sample heat treatment 5 minutes at 300 DEG C under nitrogen gas protection, obtain ZnO-CdS-Sb 2s 3three components nanometer stick array (that is, ZnO-CdS-Sb 2s 3-NA).
(3-4) sign of product:
ZnO-CdS-Sb 2s 3the characterization result of-NA is shown in accompanying drawing 4,5 and 6.XRD result shows, ZnO-CdS core-shell nanometer rod surface defines Sb 2s 3crystal (JCPDS #42-1393).Ultraviolet-visible (UV-vis) absorption spectrum shows, ZnO-CdS-NA presents the absorption of ZnO and between 400-550 nm, there is the absorption of CdS at 388 nm places; ZnO-CdS-Sb 2s 3except the Absorption Characteristics of ZnO and CdS, between 300-850 nm, there is Sb in-NA 2s 3absorption, and Sb 2s 3absorption intensity strengthens with the increase of its sedimentation time (t), and the Sb on ZnO-CdS core-shell nanometer rod surface is described 2s 3deposition can be controlled by t.SEM shows, Sb 2s 3after deposition, nanorod surfaces becomes more coarse, but the pattern of nanometer stick array is uninfluenced; TEM shows, Sb 2s 3nano particle size is 5-10 nm; When t=5 minute, Sb 2s 3nano particle is also main to be dispersed on ZnO-CdS-NA with discontinuous form; When t>=10 minute, Sb 2s 3nano particle defines continuous print polycrystalline film outer shell outside CdS layer, Sb 2s 3the thickness of outer shell thickens with the increase of sedimentation time t, when when deposited, t is 10 or 15 minutes, and Sb 2s 3outer shell thickness is respectively 5 nm or 8 nm.
Embodiment 4: polymer/ZnO-CdS-Sb 2s 3the preparation of three components nanometer stick array solar cell.
(4-1) preparation of ZnO nano-rod array: with embodiment 1.
(4-2) preparation of ZnO-CdS nuclear shell structure nano rod array: with embodiment 2.
(4-3) ZnO-CdS-Sb 2s 3the preparation of three components nanometer stick array: with embodiment 3.
(4-4) MEH-PPV/ZnO-CdS-Sb 2s 3the preparation of-NA solar cell:
Newly to steam chlorobenzene for solvent, compound concentration is the MEH-PPV solution of 10 mg/mL, and in stirred at ambient temperature 24 hours.The MEH-PPV dissolution homogeneity of 100 microlitres is dispersed in ZnO-CdS-Sb 2s 3on-NA layer, then carry out spin coating (1500 revs/min, 60 seconds) and make polymer deposition to ZnO-CdS-Sb 2s 3on-NA; At 60 DEG C, vacuumize 12 hours is with after removing solvent chlorobenzene, and in 150 DEG C of heat treatments 10 minutes in the glove box of nitrogen protection, to make polymer fully penetrate between nanometer rods, above nanometer rods, the thickness of polymeric layer is 30-80 nm.
Then, on MEH-PPV layer, spin coating PEDOT:PSS and isopropyl alcohol form mixed liquor (volume ratio is 1:1) (2000 revs/min, 60 seconds); Heat treatment 15 minutes at 100 DEG C in the glove box of nitrogen protection; to remove the moisture in PEDOT:PSS; then on PEDOT:PSS hole transmission layer (thickness 40 nm) by vacuum thermal evaporation methods evaporation thickness be the Au film of 100 nm as negative electrode, pressure is 5 × 10 -4pa, evaporation rate is 0.1 dust/second (front 50nm) and 1 dust/second (rear 50 nm).Encapsulate in the glove box of nitrogen protection, obtain MEH-PPV/ZnO-CdS-Sb 2s 3-NA solar cell (see accompanying drawing 1).The size of Au electrode is 1 × 4 mm by template contral 2, and as the effective area of battery.
(4-5) preparation of MEH-PPV/ZnO-NA hydridization solar cell:
In order to verify the improvement result of use to battery performance of three components, prepare the polymer/ZnO-NA solar cell of pure ZnO nanorod composition as reference cell.Except there is no CdS and Sb on ZnO nanorod surface 2s 3outward, MEH-PPV/ZnO-NA hydridization solar cell and MEH-PPV/ZnO-CdS-Sb 2s 3the preparation method of-NA battery is identical.
(4-6) sign of battery:
Current-voltage (J-V) performance characterization of solar cell the results are shown in accompanying drawing 7.J-V test is at AM1.5 simulated solar irradiation (light intensity P in=100 mW/cm 2) under to complete in laboratory environment; Result shows to deposit CdS and Sb 2s 3after, fill factor, curve factor FF changes little, but V ocand J scall far above the battery of pure ZnO-NA.Work as Sb 2s 3when nano particle is mainly dispersed on ZnO-CdS-NA with discontinuous form (that is, t=5 minute), the electric current of battery is still undesirable.Work as Sb 2s 3nano particle forms the thick continuous polycrystalline film of 5 nm as (that is, t=10 minute) after outer shell, and the performance of battery is best, and conversion efficiency reaches 3.32%; Compared with MEH-PPV/ZnO-NA battery, MEH-PPV/ZnO-CdS-Sb 2s 3the V of-NA (t=10 minute) battery oc, J sc121%, 1244% and 2667% is improve respectively with efficiency eta.Too thick Sb 2s 3the formation (e.g., t=15 minutes) of rete can make electric current significantly reduce.Compare in detail in table 1.
Table 1.
Note: J-V performance test completes in laboratory environment, the effective area of battery is 4 mm 2; V oc, J sc, FF and η be respectively the open circuit voltage of battery, short circuit current, fill factor, curve factor and conversion efficiency, η=J scv ocfF/P in.1 represents that MEH-PPV/ZnO-NA, 2-4 represent MEH-PPV/ZnO-CdS-Sb 2s 3-NA battery, wherein Sb 2s 3sedimentation time be respectively 5 minutes (2), 10 minutes (3) and 15 minutes (4).

Claims (7)

1. based on a hybrid solar cell for ternary nano array, it is characterized in that: include glass lined base, the ITO layer as anode, ZnO-CdS-Sb 2s 3the Au rete of three components nanometer stick array, MEH-PPV rete, PEDOT:PSS hole transmission layer and the negative electrode as battery; Described ITO layer is plated in the anode as battery on glass lined base, with the ZnO-CdS-Sb of vertical-growth on ITO layer 2s 3three components nanometer stick array is the electron propagation ducts of battery, and light absorbing material MEH-PPV is filled into ZnO-CdS-Sb 2s 3among the gap of three components nanometer rods, simultaneously at ZnO-CdS-Sb 2s 3form MEH-PPV rete above three components nanometer stick array, MEH-PPV rete deposits PEDOT:PSS as hole transmission layer, hole transmission layer deposits the negative electrode of Au film as battery; Described ZnO-CdS-Sb 2s 3three components nanometer rods is by Sb 2s 3shell, CdS subshell, ZnO nanorod form, and described CdS subshell outer cladding Sb 2s 3shell.
2. a kind of hybrid solar cell based on ternary nano array according to claim 1, is characterized in that: the thickness of ITO layer is 50-200 nm, ZnO-CdS-Sb 2s 3the length of three components nanometer stick array is 150-700 nm, diameter is 20-90 nm, the number density of rod is 3-6 × 10 2individual/ μm 2, the thickness of CdS subshell is 5-7 nm, Sb 2s 3the thickness of outer shell is 5-10 nm, is positioned at ZnO-CdS-Sb 2s 3mEH-PPV thicknesses of layers above three components nanometer stick array is 30-200 nm, PEDOT:PSS thickness of hole transport layer be 40-80 nm, Au film thickness is 60-120 nm.
3. a kind of hybrid solar cell based on ternary nano array according to claim 1, it is characterized in that: described hole transmission layer preferably by depositing mixed liquor that PEDOT:PSS and isopropyl alcohol form and obtaining on MEH-PPV rete, and described PEDOT:PSS and the volume ratio of isopropyl alcohol are 1:0.5-1.5.
4. a preparation method for the hybrid solar cell based on ternary nano array according to claim 1, is characterized in that comprising the following steps:
A, be that the hydrochloric acid of 5.5-6.5 mol/L and Zn powder are etched into slice by the ITO layer concentration on ITO electro-conductive glass, cleaner through acetone, isopropyl alcohol, ultra-pure water ultrasonic cleaning, after drying treated ITO electro-conductive glass is for subsequent use;
0.12-0.20 gram of zinc acetate is dissolved in 0.8-1.2 gram of water, add 3-5 milliliter absolute ethyl alcohol until completely dissolved, drip 80-120 microlitre glacial acetic acid again, the mixture obtained at room temperature is stirred 1.8-2.2 hour, again the achromaticity and clarification clear solution of gained is spun on treated ITO electro-conductive glass, obtain uniform zinc acetate film, then in Muffle furnace, at 320-380 DEG C, 18-22 minute is calcined, obtain the ZnO dense film covered on ITO conductive substrate, be placed in the aqueous solution of the zinc nitrate of 0.02-0.06 mol/L and the hexa composition of 0.02-0.06 mol/L, in 85-95 DEG C of baking oven, 1-3 hour is reacted after sealing, obtain ZnO nano-rod array,
B, respectively configuration concentration are 0.5-1.5 × 10 -2cd (the NO of mol/L 3) 2the aqueous solution and concentration are 0.5-1.5 × 10 -2the Na of mol/L 2the S aqueous solution, at room temperature replaces steps A gained ZnO nano-rod array at Cd (NO 3) 2the aqueous solution and Na 2soak 20-40 second in the S aqueous solution respectively, often complete continuously once at Cd (NO 3) 2the aqueous solution and Na 2the process of soaking respectively in the S aqueous solution is a SILAR process, Cd (NO 3) 2and Na 2the reaction mol ratio of S is after 1:0.9-1.1, repeated several times SILAR process, and obtaining take CdS as the ZnO-CdS nuclear shell structure nano rod array of vertical-growth on ITO layer of shell, and CdS shell thickness is controlled to be 5-7 nm by SILAR process number of times;
C, respectively configuration concentration are the Na of 0.1-0.5 mol/L 2s 2o 3the aqueous solution and concentration are the SbCl of 0.1-0.5 mol/L 3acetone soln; By Na 2s 2o 3the aqueous solution be cooled to 8-12 DEG C, by SbCl 3acetone soln be slowly added dropwise to Na 2s 2o 3the aqueous solution in, reaction 60-120 minute, obtain deposit Sb 2s 3precursor solution, described Na 2s 2o 3and SbCl 3mol ratio be 1:0.5-1.5; By the ZnO-CdS nuclear shell structure nano rod array face down obtained in step B, be suspended in deposition Sb 2s 3precursor solution in 5-20 minute; Take out substrate, after drip washing and drying, by substrate under inert gas shielding at 250-350 DEG C heat treatment 5-15 minute, obtain ZnO-CdS-Sb 2s 3three components nanometer stick array; ;
D, working concentration are the MEH-PPV solution of 5-15 mg/mL, MEH-PPV are deposited to the ZnO-CdS-Sb of step C gained under room temperature 2s 3on three components nanometer stick array, and in 120-180 DEG C of heat treatment 5-30 minute under inert gas shielding, MEH-PPV is made to be filled into ZnO-CdS-Sb 2s 3among the gap of three components nanometer rods and at ZnO-CdS-Sb 2s 3mEH-PPV rete is formed above three components nanometer stick array;
E, on the MEH-PPV rete of step D gained, spin coating one deck volume ratio is the mixed liquor of the PEDOT:PSS of 1:0.5-1.5 and isopropyl alcohol composition, under inert gas shielding at 80-120 DEG C heat treatment 5-30 minute, obtain PEDOT:PSS rete as hole transmission layer, by thermal evaporation method evaporation Au film on PEDOT:PSS rete, obtain hydridization solar cell;
F, hydridization solar cell is carried out encapsulating and obtaining product under inert gas shielding.
5. the hybrid solar cell preparation method based on ternary nano array according to claim 4, is characterized in that: the solvent of the MEH-PPV solution described in step D is the one in chlorobenzene, oxolane, chloroform, benzene.
6. the hybrid solar cell preparation method based on ternary nano array according to claim 4, is characterized in that: step D adopts a kind of ZnO-CdS-Sb MEH-PPV being deposited under room temperature step C gained in spin-coating method, silk screen print method, scraping blade method or ink-jet printing process 2s 3on three components nanometer stick array.
7. the hybrid solar cell preparation method based on ternary nano array according to claim 4, is characterized in that: the inert gas preferred nitrogen described in step C, D, E, F.
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