CN103137868A - 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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CN103137868A
CN103137868A CN2013100198592A CN201310019859A CN103137868A CN 103137868 A CN103137868 A CN 103137868A CN 2013100198592 A CN2013100198592 A CN 2013100198592A CN 201310019859 A CN201310019859 A CN 201310019859A CN 103137868 A CN103137868 A CN 103137868A
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CN103137868B (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 the 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 the ternary nano array and preparation method thereof.
Background technology:
The polymer solar cells that is comprised of conjugatd polymers and inorganic semiconductor nanostructure is a kind of novel hybrid solar cell.Due to its advantage that has polymer (lightweight, pliability good, easy large tracts of land film forming etc. at a low price) and inorganic semiconductor material (carrier mobility is high, stable in properties, easy control of structure system etc.) concurrently, become in recent years the important research object in the low price solar cell.Usually, the inorganic semiconductor nano particle is mixed in organic solvent with organic polymer, realize simple blend, then by appropriate ways, these simple blend are made unordered hybrid battery; For example, 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, the solar cell that forms of inorganic semiconductor nano particle such as 12784-12791).Yet this type of battery efficiency is lower, and wherein not having desirable electron propagation ducts to reach comparatively serious interface charge compound is important influencing factor.
The composite construction that replaces nano particle and organic polymer formation with one-dimensional inorganic nanometer rods (or line) array 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; Energy Environ. Sci. 2011,4,2700-2720).At first, nano-structure array can provide direct electron propagation ducts, and light induced electron directly is transported on passive electrode along the nano-array of oriented growth, can reduce the compound of electric charge; Secondly, in this composite construction, both can obtain larger separation of charge interfacial area, can overcome again the shortcoming of exciton active diffusion length short (5-20 nm) in polymer, improve the utilization ratio of exciton in the polymer; Moreover, be grown in advance the array on the lining base, can keep organic/inorganic interface and electric charge transmission channel in three-dimensional stable distribution.ZnO nanorod or linear array (are called for short, ZnO-NA) have many advantages, for example, stable in properties, environmental friendliness, high the reaching of electron mobility are easily realized large tracts of land preparation etc. by simple method, to use maximum a kind of material (Energy Environ. Sci. 2009 in this type of orientation texture hydridization solar cell at present, 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 that ZnO-NA and polymer form (being called for short polymer/ZnO-NA battery) 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 in 0.1-0.4 V left and right).
At present, people are mostly by improving the contact performance at polymer/ZnO interface with a kind of organic molecule, having obtained the J that significantly improves sc, also improved to a certain extent the V of battery oc(J. Mater. Chem. 2006,16,2088-2096; J. Phys. Chem. B 2006,110,7635-7639; J. Phys. Chem. C 2011,115,3745-3752); After organic decoration, the J of battery scAlso undesirable (generally at 5 mA/cm 2About), and V ocStill not high (mostly below 0.5 V).Except organic decoration, people have also attempted modifying ZnO-NA with inorganic matter, 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 is 15778-15782) by ald (ALD) technology TiO 2Modify ZnO-NA, formed take ZnO as core TiO 2ZnO-TiO for shell 2Heterogeneous nuclear shell structure nano rod array (is called for short ZnO-TiO 2-NA), although compare polymer/ZnO-TiO with polymer/ZnO-NA battery 2The J of-NA battery scGet improvement to a certain extent, but the V of battery ocStill less than 0.5 V.Lee etc. (IEEE J. Selected Topics in Quantum Electronics 2010,16,1587 – 1594) are by ALD technology TiO xModify ZnO-NA, formed with TiO xZnO-TiO for shell xHeterogeneous nuclear shell structure nano rod array (is called for short ZnO-TiO x-NA), compare polymer/ZnO-TiO with polymer/ZnO-NA battery xThe V of-NA battery ocSignificantly improve and can reach 0.8 V, but the J of battery scBut be exponential form and decay to very little numerical value.(the J. Electrochem. Soc. 2011 such as Wang, 158, H804 – H807) by chemical bath deposition (CBD) the technology quantum dot sensitized ZnO-NA of CdS, obtaining the quantum dot sensitized ZnO nano-rod array of CdS (is called for short, CdS-ZnO-NA), compare the V of polymer/CdS-ZnO-NA battery with polymer/ZnO-NA battery ocHad and improved significantly (can reach 0.85 V), but J scStill not high.Inventor seminar, by the absorption of sheath successively and reaction (successive ion layer adsorption and reaction, SILAR) technology is modified ZnO-NA with the CdS quantum dot, obtain take the single crystal ZnO nanometer rods as core and polycrystalline film that the CdS quantum dot forms (is called for short as the heterogeneous nuclear shell structure nano rod array of shell, ZnO-CdS-NA), compare the V of polymer/ZnO-CdS-NA battery with polymer/ZnO-NA battery ocAnd J scAll be greatly improved, V ocReached about 0.9 V, but J scStill undesirable (less than 3 mA/cm 2) [Chinese invention patent (application) number: 201110310230.4].Recently, inventor seminar, modify ZnO-NA by the hydro-thermal reaction technology in autoclave with ZnO quantum dot, obtain take the single crystal ZnO nanometer rods as core and polycrystalline film that ZnO quantum dot forms (is called for short as the homogeneity nuclear shell structure nano rod array of shell, ZnO-ZnO-NA), compare the V of polymer/ZnO-ZnO-NA battery with polymer/ZnO-NA battery ocSignificantly increased, reached 0.71V; Further with a kind of organic substance, ZnO-ZnO-NA is modified, obtained the ZnO homogeneity nuclear shell structure nano rod array (abbreviation that organic substance N719 modifies, ZnO-ZnO-N719-NA), compare the J of polymer/ZnO-ZnO-N719-NA battery with polymer/ZnO-ZnO-NA battery ocSignificantly increased, reached nearly 4 mA/cm 2Left and right, but V ocReally some reduces [Chinese invention patent (application) number: 201110387893.6] because of organic introducing.This shows, for improving the performance of polymer/ZnO-NA battery, people are mainly with organic substance, inorganic matter or use all both at present, ZnO-NA are modified the two component nanometer stick arrays that are comprised of ZnO and another inorganic matter or ZnO and an organic substance of acquisition; Wherein, inorganic modification mainly can improve V ocBut less to the electric current raising, and organic decoration is to improving J scLarger effect is arranged but to V ocRaising not remarkable or unfavorable.
In the present invention, we first deposit the CdS quantum dot by the SILAR technology on ZnO-NA, obtain take the single crystal ZnO nanometer rods as core and polycrystalline film that the CdS quantum dot forms as the heterogeneous nuclear shell structure nano rod array of shell (namely, ZnO-CdS-NA), then deposit Sb with the amorphous deposition with the thermal crystalline multiple techniques on ZnO-CdS-NA 2S 3Nano particle obtains by ZnO, CdS and Sb 2S 3The three inorganic component nanometer stick arrays that form (are called for short ZnO-CdS-Sb 2S 3-NA), and with ZnO-CdS-Sb 2S 3Compound novel hydridization solar cell (abbreviation, the polymer/ZnO-CdS-Sb of having made of-NA and polymer 2S 3-NA battery); Compare 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 objective of the invention is in order to make up the defective of prior art, provide a kind of efficient, cost is lower, technique is simple, be convenient to hybrid solar cell of large-area manufacturing and preparation method thereof.
To achieve these goals, the present invention adopts following technical scheme:
A kind of hybrid solar cell based on the ternary nano array is characterized in that: include the glass lined base, as ITO layer, the ZnO-CdS-Sb of anode 2S 3Three component nanometer stick arrays, MEH-PPV rete, PEDOT:PSS hole transmission layer and as the Au rete of the negative electrode of battery; Described ITO layer is plated on the glass lined base anode as battery, with the ZnO-CdS-Sb of vertical-growth on the ITO layer 2S 3Three component nanometer stick arrays are the electron propagation ducts of battery, and light absorbing material MEH-PPV is filled into ZnO-CdS-Sb 2S 3Among the gap of three component nanometer rods, simultaneously at ZnO-CdS-Sb 2S 3Three component nanometer stick array top formation MEH-PPV retes, deposition PEDOT:PSS is as hole transmission layer on the MEH-PPV rete, and deposition Au film is as the negative electrode of battery on hole transmission layer; Described ZnO-CdS-Sb 2S 3Three component nanometer rods are 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 the ternary nano array, it is characterized in that: the thickness of ITO layer is 50-200 nm, ZnO-CdS-Sb 2S 3The length of three component nanometer stick arrays is that 150-700 nm, diameter are that 20-90 nm, excellent number density are 3-6 * 10 2Individual/μ m 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 component nanometer stick arrays is 30-200 nm, and the PEDOT:PSS thickness of hole transport layer is 40-80 nm, and the Au film thickness is 60-120 nm.
Described a kind of hybrid solar cell based on the ternary nano array, it is characterized in that: the mixed liquor that described hole transmission layer preferably is comprised of deposition PEDOT:PSS and isopropyl alcohol on the MEH-PPV rete and getting, the volume ratio of described PEDOT:PSS and isopropyl alcohol is 1:0.5-1.5.
The preparation method of described hybrid solar cell based on the ternary nano array is characterized in that comprising the following steps:
A, the hydrochloric acid and the Zn powder that are 5.5-6.5 mol/L with the ITO layer concentration on the ITO electro-conductive glass are etched into slice, cleaner through acetone, isopropyl alcohol, ultra-pure water ultrasonic cleaning, after drying treated ITO electro-conductive glass is standby;
0.12-0.20 gram zinc acetate is dissolved in 0.8-1.2 gram water, add until completely dissolved 3-5 milliliter absolute ethyl alcohol, drip again 80-120 microlitre glacial acetic acid, the mixture that obtains was at room temperature stirred 1.8-2.2 hour, achromaticity and clarification clear solution with gained is spun on treated ITO electro-conductive glass again, obtain uniform zinc acetate film, then calcined 18-22 minute under 320-380 ℃ in Muffle furnace, obtain covering the ZnO dense film on the ITO conductive substrate, be placed on the zinc nitrate [ZnO (NO of 0.02-0.06 mol/L 3) 26H 2O] and the aqueous solution that forms of the hexa of 0.02-0.06 mol/L in, after sealing, reaction 1-3 hour in 85-95 ℃ of baking oven, obtain ZnO nano-rod array;
B, configuration concentration is 0.5-1.5 * 10 respectively -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 respectively 20-40 second in the S aqueous solution, 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 1:0.9-1.1, after repeated several times SILAR process, obtains the ZnO-CdS nuclear shell structure nano rod array of vertical-growth on the ITO layer take CdS as shell, and the CdS shell thickness is controlled to be 5-7 nm by SILAR process number of times;
C, configuration concentration is the Na of 0.1-0.5 mol/L respectively 2S 2O 3The aqueous solution and concentration are the SbCl of 0.1-0.5 mol/L 3Acetone soln; With Na 2S 2O 3The aqueous solution be cooled to 8-12 ℃, with SbCl 3Acetone soln slowly be added dropwise to Na 2S 2O 3The aqueous solution in, reacted 60-120 minute, obtain depositing Sb 2S 3Precursor solution, described Na 2S 2O 3And SbCl 3Mol ratio be 1:0.5-1.5; With the ZnO-CdS nuclear shell structure nano rod array face down that obtains in step B, be suspended in deposition Sb 2S 3Precursor solution in 5-20 minute; Take out substrate, after drip washing and drying, with substrate under inert gas shielding in 250-350 ℃ of lower heat treatment 5-15 minute, obtain ZnO-CdS-Sb 2S 3Three component nanometer stick arrays;
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 component nanometer stick arrays, and under inert gas shielding in 120-180 ℃ of heat treatment 5-30 minute, make MEH-PPV be filled into ZnO-CdS-Sb 2S 3Among the gap of three component nanometer rods and at ZnO-CdS-Sb 2S 3Three component nanometer stick array top formation MEH-PPV retes;
E, spin coating one deck volume ratio is the mixed liquor that the PEDOT:PSS of 1:0.5-1.5 and isopropyl alcohol form on the MEH-PPV rete of step D gained, under inert gas shielding in 80-120 ℃ of lower heat treatment 5-30 minute, obtain the PEDOT:PSS rete as hole transmission layer, by thermal evaporation method evaporation Au film, obtain the hydridization solar cell on the PEDOT:PSS rete;
F, the hydridization solar cell is encapsulated under inert gas shielding namely get product.
Described hybrid solar cell preparation method based on the ternary nano array is characterized in that: the glass lined base of the described ITO electro-conductive glass of steps A can replace with other transparency materials.
Described hybrid solar cell preparation method based on the ternary nano array is characterized in that: the solvent of the described MEH-PPV solution of step D is a kind of in chlorobenzene, oxolane, chloroform, benzene.
Described hybrid solar cell preparation method based on the ternary nano array is characterized in that: step D adopt a kind of in spin-coating method, silk screen print method, scraping blade method or ink-jet printing process with MEH-PPV in the ZnO-CdS-Sb of room temperature deposit to step C gained 2S 3On three component nanometer stick arrays.
Described hybrid solar cell preparation method based on the ternary nano array is characterized in that: step C, D, the described inert gas preferred nitrogen of E, F.
Principle of the present invention is:
The present invention by the ZnO nano-rod array of preparation vertical-growth on the ITO layer (namely, ZnO-NA) as template, by the shell that the CdS quantum dot forms, obtain the heterogeneous nuclear shell structure nano rod array of ZnO-CdS (that is, ZnO-CdS-NA) by deposition on ZnO nanorod; With 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 component nanometer stick array (that is, ZnO-CdS-Sb 2S 3-NA).In 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 3Be 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 by twice array mould plate method, in conjunction with amorphous deposition and thermal crystalline multiple techniques, has prepared ZnO-CdS-Sb 2S 3Three component nanometer stick arrays are with ZnO-CdS-Sb 2S 3Three component nanometer stick arrays are applied to the hydridization solar cell, take conjugatd polymers as main light absorbing material and Sb 2S 3Be auxiliary light absorbent with CdS, the complementation by organic substance and inorganic matter absorbing properties has realized in 300-800 nm wide spectral range the absorption to solar photon; The present invention has set up a kind of based on ZnO-CdS-Sb 2S 3Three component nanometer stick arrays also have the preparation method of the hydridization solar cell of wide spectral absorption.ZnO-CdS-Sb in the present invention 2S 3The preparation method of-NA and battery device is easy, and is low for equipment requirements, is fit 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 controlling Sb 2S 3Reactant concentration during deposition and sedimentation time, having overcome ZnO can be by acid (alkali) property solution heavy corrosion (ACS Nano 2010,4, technological difficulties 3302-3308); Use by three components has made up the technological deficiency of two component nanometer stick arrays (usually by organic substance, inorganic matter or both all use ZnO-NA is modified make), and (that is, inorganic modification mainly can improve V ocBut less to the electric current raising, and organic decoration is to improving J scLarger effect is arranged but to the V of battery ocImprove not remarkable or unfavorable), the photoresponse spectral limit of hybrid battery is widened, and V oc, J scAnd conversion efficiency all is 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% is compared with polymer/ZnO-NA battery, has improved respectively 1244%, 121% and 2667%.
Description of drawings:
Fig. 1 is ZnO-CdS-Sb of the present invention 2S 3The structural representation of the hybrid solar cell of three component nanometer stick arrays; 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 3The XRD of three component nanometer stick arrays and UV-vis absorption spectrum characterization result; 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 component nanometer stick arrays; Wherein, (a) t=5 minute, (b) t=10 minutes, (c) t=15 minutes;
Fig. 6 is ZnO-CdS-Sb of the present invention 2S 3The TEM(a of three component nanometer stick arrays, c, 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 is corresponding to square frame part 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 conditions; 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:
First (ITO thickness is 100-120 nm, and the ITO layer concentration on≤15 Ω/) is that hydrochloric acid and the Zn powder of 6 mol/L is etched into 12 * 4 mm with the ITO electro-conductive glass 2Slice; Clean through acetone, isopropyl alcohol, ultra-pure water ultrasonic cleaning, dry up rear standby with dry nitrogen.
With 0.16 gram zinc acetate [Zn (CH 3COO) 22H 2O] be dissolved in 1 gram water, add until completely dissolved 4 milliliters of absolute ethyl alcohols, then drip 100 microlitre glacial acetic acid; Mixture at room temperature stirred 2 hours, obtained the achromaticity and clarification clear solution.Mentioned solution is spun on (2000 rev/mins, 60 seconds) on ito glass, repeats four times, obtain uniform film.Then, with the zinc acetate film under relative humidity 52%(room temperature) container in ageing 24 hours, then in Muffle furnace under 350 ℃ calcining obtained the ZnO dense film in 20 minutes.
(1-2) preparation of ZnO nano-rod array:
Unsettled zinc nitrate [ZnO (the NO that is placed in of ito glass face down that the ZnO dense film covers 3) 26H 2O] in the aqueous solution that forms of (0.04 mol/L) and hexa (0.04 mol/L), after sealing, reaction 2 hours in 90 ℃ of baking ovens, obtain ZnO nano-rod array (that is, ZnO-NA).
(1-3) sign of product:
The characterization result of ZnO-NA is seen accompanying drawing 2.X-ray diffraction (XRD) is tested and is shown, ZnO nanorod is wurtzite structure, and nanometer rods is grown along [001] direction; Scanning electron microscopy (SEM) photo shows, the ZnO nanorod of gained is perpendicular to the ITO substrate grown, and length is 360-400 nm, and diameter is 20-60 nm, and the number density of rod is 4-5 * 10 2Individual/μ m 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 with ZnO nano-rod array in concentration -3Cd (the NO of mol/L 3) 2Soak in the aqueous solution after 30 seconds, with water wash 30 seconds to remove the surperficial a large amount of Cd (NO of ZnO nanorod 3) 2Solution; Then, with this ZnO nano-rod array immediately 10 * 10 -3The Na of mol/L 2Soaked in the S aqueous solution 30 seconds, and with water wash 30 seconds to remove unreacted Na 2S solution; So far complete a SILAR process.Circulate 30 times, the thickness that namely obtains the CdS layer be 6 nm the ZnO-CdS nuclear shell structure nano rod array (that is, ZnO-CdS-NA).
(2-3) sign of product:
The characterization result of ZnO-CdS-NA is seen accompanying drawing 3 and 4a.The XRD result shows, the ZnO nanorod surface has formed CdS(JCPDS #80-0019); SEM shows, after the CdS deposition, nanorod surfaces becomes coarse, but the pattern of nanometer stick array is uninfluenced; TEM shows, CdS is wrapped in equably the ZnO nanorod surface and has formed core-shell structure, and the thickness of CdS shell is 6 nm left and right.
Embodiment 3:ZnO-CdS-Sb 2S 3The preparation of three component nanometer stick arrays:
(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 component nanometer stick arrays:
Under room temperature, with 18.61 gram Na 2S 2O 35H 2O is dissolved in 270 ml deionized water, obtains Na 2S 2O 3The aqueous solution; With 1.95 gram SbCl 3Be dissolved in 30 milliliters of acetone, obtain SbCl 3Acetone soln.With Na 2S 2O 3The aqueous solution be cooled to 10 ℃, after temperature stabilization, with SbCl 3Acetone soln join Na with the speed of 2 drops/secs 2S 2O 3The aqueous solution in, and follow and continue to stir, continue to allow Na after all dripping off 2S 2O 3With SbCl 3Reacted 90 minutes, and formed orange red suspension;
With ZnO-CdS nuclear shell structure nano rod array face down, be suspended in the orange red suspension that obtains and deposit Sb 2S 3, deposit respectively 5,10 or 15 minutes; After deposition finishes, take out substrate, dry up with water wash, nitrogen; With sample under nitrogen gas protection in 300 ℃ of lower heat treatments 5 minutes, obtain ZnO-CdS-Sb 2S 3Three component 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 seen accompanying drawing 4,5 and 6.The XRD result shows, ZnO-CdS core-shell nanometer rod surface has formed Sb 2S 3Crystal (JCPDS #42-1393).Ultraviolet-visible (UV-vis) absorption spectrum shows, ZnO-CdS-NA presents the absorption of ZnO at 388 nm places and have the absorption of CdS between 400-550 nm; ZnO-CdS-Sb 2S 3There is Sb in-NA between 300-850 nm except the Absorption Characteristics of ZnO and CdS 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 3The nano particle size is 5-10 nm; When t=5 minute, Sb 2S 3Nano particle also mainly is dispersed on ZnO-CdS-NA with discontinuous form; When t 〉=10 minute, Sb 2S 3Nano particle has formed continuous polycrystalline film outer shell, Sb outside the CdS layer 2S 3The thickness of outer shell thickens with the increase of sedimentation time t, when sedimentation time 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 component nanometer stick array solar cells.
(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 component nanometer stick arrays: with embodiment 3.
(4-4) MEH-PPV/ZnO-CdS-Sb 2S 3The preparation of-NA solar cell:
Take new steaming chlorobenzene as solvent, compound concentration is the MEH-PPV solution of 10 mg/mL, and stirs 24 hours under room temperature.The MEH-PPV solution of 100 microlitres is dispersed in ZnO-CdS-Sb 2S 3On-NA layer, then carry out spin coating (1500 rev/mins, 60 seconds) and make polymer deposition to ZnO-CdS-Sb 2S 3On-NA; With after removing the solvent chlorobenzene, in 150 ℃ of heat treatments 10 minutes, so that polymer fully is penetrated between nanometer rods, the thickness of nanometer rods top polymeric layer was 30-80 nm in the glove box of nitrogen protection in 60 ℃ of lower vacuumizes 12 hours.
Then, the mixed liquor (volume ratio is 1:1) (2000 rev/mins, 60 seconds) that spin coating PEDOT:PSS and isopropyl alcohol form on the MEH-PPV layer; In the glove box of nitrogen protection in 100 ℃ of lower heat treatments 15 minutes; to remove the moisture in PEDOT:PSS; then PEDOT:PSS hole transmission layer (thickness 40 nm) upper by vacuum thermal evaporation method 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 50 nm) 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 (seeing 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:
For the use of the verifying three components improvement effect to battery performance, prepared the polymer that pure ZnO nanorod forms/ZnO-NA solar cell as reference cell.Except there is no CdS and Sb on the 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:
The current-voltage of solar cell (J-V) performance characterization the results are shown in accompanying drawing 7.The J-V test is at AM 1.5 simulated solar irradiation (light intensity P in=100 mW/cm 2) under complete in laboratory environment; Result shows deposition 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 3Nano particle mainly was dispersed in ZnO-CdS-NA when upper (, t=5 minute) with discontinuous form, and the electric current of battery is still undesirable.Work as Sb 2S 3Nano particle form the thick continuous polycrystalline film of 5 nm as outer shell after (that is, t=10 minute), the performance of battery is best, conversion efficiency reaches 3.32%; Compare MEH-PPV/ZnO-CdS-Sb with the MEH-PPV/ZnO-NA battery 2S 3The V of-NA (t=10 minute) battery oc, J scImproved respectively 121%, 1244% and 2667% with efficiency eta.Too thick Sb 2S 3The formation of rete (as, t=15 minute) can make electric current significantly reduce.In detail relatively see Table 1.
Table 1.
Figure BDA0000275330981
Annotate: the J-V performance test is completed in laboratory environment, and the effective area of battery is 4 mm 2V oc, J sc, FF and η be respectively open circuit voltage, short circuit current, fill factor, curve factor and the conversion efficiency of battery, η=J scV ocFF/P in1 expression MEH-PPV/ZnO-NA, 2-4 represents 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 (8)

1. hybrid solar cell based on the ternary nano array is characterized in that: include the glass lined base, as ITO layer, the ZnO-CdS-Sb of anode 2S 3Three component nanometer stick arrays, MEH-PPV rete, PEDOT:PSS hole transmission layer and as the Au rete of the negative electrode of battery; Described ITO layer is plated on the glass lined base anode as battery, with the ZnO-CdS-Sb of vertical-growth on the ITO layer 2S 3Three component nanometer stick arrays are the electron propagation ducts of battery, and light absorbing material MEH-PPV is filled into ZnO-CdS-Sb 2S 3Among the gap of three component nanometer rods, simultaneously at ZnO-CdS-Sb 2S 3Three component nanometer stick array top formation MEH-PPV retes, deposition PEDOT:PSS is as hole transmission layer on the MEH-PPV rete, and deposition Au film is as the negative electrode of battery on hole transmission layer; Described ZnO-CdS-Sb 2S 3Three component nanometer rods are 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 the ternary nano array according to claim 1, it is characterized in that: the thickness of ITO layer is 50-200 nm, ZnO-CdS-Sb 2S 3The length of three component nanometer stick arrays is that 150-700 nm, diameter are that 20-90 nm, excellent number density are 3-6 * 10 2Individual/μ m 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 component nanometer stick arrays is 30-200 nm, and the PEDOT:PSS thickness of hole transport layer is 40-80 nm, and the Au film thickness is 60-120 nm.
3. a kind of hybrid solar cell based on the ternary nano array according to claim 1, it is characterized in that: the mixed liquor that described hole transmission layer preferably is comprised of deposition PEDOT:PSS and isopropyl alcohol on the MEH-PPV rete and getting, the volume ratio of described PEDOT:PSS and isopropyl alcohol is 1:0.5-1.5.
4. the preparation method of the hybrid solar cell based on the ternary nano array claimed in claim 1 is characterized in that comprising the following steps:
A, the hydrochloric acid and the Zn powder that are 5.5-6.5 mol/L with the ITO layer concentration on the ITO electro-conductive glass are etched into slice, cleaner through acetone, isopropyl alcohol, ultra-pure water ultrasonic cleaning, after drying treated ITO electro-conductive glass is standby;
0.12-0.20 gram zinc acetate is dissolved in 0.8-1.2 gram water, add until completely dissolved 3-5 milliliter absolute ethyl alcohol, drip again 80-120 microlitre glacial acetic acid, the mixture that obtains was at room temperature stirred 1.8-2.2 hour, achromaticity and clarification clear solution with gained is spun on treated ITO electro-conductive glass again, obtain uniform zinc acetate film, then calcined 18-22 minute under 320-380 ℃ in Muffle furnace, obtain covering the ZnO dense film on the ITO conductive substrate, be placed in the aqueous solution that the hexa of the zinc nitrate of 0.02-0.06 mol/L and 0.02-0.06 mol/L forms, reacted 1-3 hour in 85-95 ℃ of baking oven after sealing, obtain ZnO nano-rod array,
B, configuration concentration is 0.5-1.5 * 10 respectively -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 respectively 20-40 second in the S aqueous solution, 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 1:0.9-1.1, after repeated several times SILAR process, obtains the ZnO-CdS nuclear shell structure nano rod array of vertical-growth on the ITO layer take CdS as shell, and the CdS shell thickness is controlled to be 5-7 nm by SILAR process number of times;
C, configuration concentration is the Na of 0.1-0.5 mol/L respectively 2S 2O 3The aqueous solution and concentration are the SbCl of 0.1-0.5 mol/L 3Acetone soln; With Na 2S 2O 3The aqueous solution be cooled to 8-12 ℃, with SbCl 3Acetone soln slowly be added dropwise to Na 2S 2O 3The aqueous solution in, reacted 60-120 minute, obtain depositing Sb 2S 3Precursor solution, described Na 2S 2O 3And SbCl 3Mol ratio be 1:0.5-1.5; With the ZnO-CdS nuclear shell structure nano rod array face down that obtains in step B, be suspended in deposition Sb 2S 3Precursor solution in 5-20 minute; Take out substrate, after drip washing and drying, with substrate under inert gas shielding in 250-350 ℃ of lower heat treatment 5-15 minute, obtain ZnO-CdS-Sb 2S 3Three component nanometer stick arrays; ;
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 component nanometer stick arrays, and under inert gas shielding in 120-180 ℃ of heat treatment 5-30 minute, make MEH-PPV be filled into ZnO-CdS-Sb 2S 3Among the gap of three component nanometer rods and at ZnO-CdS-Sb 2S 3Three component nanometer stick array top formation MEH-PPV retes;
E, spin coating one deck volume ratio is the mixed liquor that the PEDOT:PSS of 1:0.5-1.5 and isopropyl alcohol form on the MEH-PPV rete of step D gained, under inert gas shielding in 80-120 ℃ of lower heat treatment 5-30 minute, obtain the PEDOT:PSS rete as hole transmission layer, by thermal evaporation method evaporation Au film, obtain the hydridization solar cell on the PEDOT:PSS rete;
F, the hydridization solar cell is encapsulated under inert gas shielding namely get product.
5. the hybrid solar cell preparation method based on the ternary nano array according to claim 4 is characterized in that: the glass lined base of the described ITO electro-conductive glass of steps A can replace with other transparency materials.
6. the hybrid solar cell preparation method based on the ternary nano array according to claim 4 is characterized in that: the solvent of the described MEH-PPV solution of step D is a kind of in chlorobenzene, oxolane, chloroform, benzene.
7. the hybrid solar cell preparation method based on the ternary nano array according to claim 4 is characterized in that: step D adopt a kind of in spin-coating method, silk screen print method, scraping blade method or ink-jet printing process with MEH-PPV in the ZnO-CdS-Sb of room temperature deposit to step C gained 2S 3On three component nanometer stick arrays.
8. the hybrid solar cell preparation method based on the ternary nano array according to claim 4, is characterized in that: step C, D, the described inert gas preferred nitrogen of E, F.
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103904217A (en) * 2014-01-10 2014-07-02 中国科学院等离子体物理研究所 Multi-element organic/ inorganic hybridization solar cell and preparation method thereof
CN105498802A (en) * 2015-12-04 2016-04-20 福州大学 ZnO-Au-CdS ternary composite photocatalyst
CN105645462A (en) * 2016-01-06 2016-06-08 浙江大学城市学院 Preparation method of CdS/ZnO core-shell-structure nanowires
CN107732014A (en) * 2017-10-23 2018-02-23 中国科学院合肥物质科学研究院 A kind of solar cell based on the inorganic build hetero-junction thin-film of ternary and preparation method thereof
CN109534285A (en) * 2018-11-06 2019-03-29 浙江海洋大学 A kind of ZnO nano column and preparation method based on photon structure seed layer
CN110970579A (en) * 2018-09-30 2020-04-07 纳晶科技股份有限公司 Zinc oxide nanocrystalline electron transport layer, preparation method thereof and electronic device

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101066019B1 (en) * 2009-02-19 2011-09-20 국민대학교산학협력단 Transparent Electrode Film or Activated Layer of Organic Solar Cell Composing Conductive Polymer and Composite Thin Film and, Manufacturing Method Thereof
CN102412369A (en) * 2011-10-14 2012-04-11 中国科学院等离子体物理研究所 Organic/inorganic hybrid solar cell and preparation method thereof
CN102834929A (en) * 2010-02-18 2012-12-19 韩国化学研究院 Method for manufacturing a nanostructured inorganic/organic heterojunction solar cell
CN102842676A (en) * 2012-06-25 2012-12-26 中国科学院等离子体物理研究所 TiO2-CuInS2 core-shell nanorod array-based organic/inorganic hybrid solar battery and manufacturing method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101066019B1 (en) * 2009-02-19 2011-09-20 국민대학교산학협력단 Transparent Electrode Film or Activated Layer of Organic Solar Cell Composing Conductive Polymer and Composite Thin Film and, Manufacturing Method Thereof
CN102834929A (en) * 2010-02-18 2012-12-19 韩国化学研究院 Method for manufacturing a nanostructured inorganic/organic heterojunction solar cell
CN102412369A (en) * 2011-10-14 2012-04-11 中国科学院等离子体物理研究所 Organic/inorganic hybrid solar cell and preparation method thereof
CN102842676A (en) * 2012-06-25 2012-12-26 中国科学院等离子体物理研究所 TiO2-CuInS2 core-shell nanorod array-based organic/inorganic hybrid solar battery and manufacturing method thereof

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103904217A (en) * 2014-01-10 2014-07-02 中国科学院等离子体物理研究所 Multi-element organic/ inorganic hybridization solar cell and preparation method thereof
CN103904217B (en) * 2014-01-10 2017-04-12 中国科学院等离子体物理研究所 Multi-element organic/ inorganic hybridization solar cell and preparation method thereof
CN105498802A (en) * 2015-12-04 2016-04-20 福州大学 ZnO-Au-CdS ternary composite photocatalyst
CN105498802B (en) * 2015-12-04 2017-12-08 福州大学 A kind of zinc oxide gold cadmium sulfide ternary composite type photochemical catalyst
CN105645462A (en) * 2016-01-06 2016-06-08 浙江大学城市学院 Preparation method of CdS/ZnO core-shell-structure nanowires
CN107732014A (en) * 2017-10-23 2018-02-23 中国科学院合肥物质科学研究院 A kind of solar cell based on the inorganic build hetero-junction thin-film of ternary and preparation method thereof
CN110970579A (en) * 2018-09-30 2020-04-07 纳晶科技股份有限公司 Zinc oxide nanocrystalline electron transport layer, preparation method thereof and electronic device
CN110970579B (en) * 2018-09-30 2022-12-02 纳晶科技股份有限公司 Zinc oxide nanocrystalline electron transport layer, preparation method thereof and electronic device
CN109534285A (en) * 2018-11-06 2019-03-29 浙江海洋大学 A kind of ZnO nano column and preparation method based on photon structure seed layer
CN109534285B (en) * 2018-11-06 2020-03-27 浙江海洋大学 ZnO nano column based on photonic structure seed layer and preparation method

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