CN107123693A - A kind of efficient CdTe nanometer crystalline solar cell with high transparency window layer material processed based on solwution method and preparation method thereof - Google Patents

A kind of efficient CdTe nanometer crystalline solar cell with high transparency window layer material processed based on solwution method and preparation method thereof Download PDF

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CN107123693A
CN107123693A CN201710242991.8A CN201710242991A CN107123693A CN 107123693 A CN107123693 A CN 107123693A CN 201710242991 A CN201710242991 A CN 201710242991A CN 107123693 A CN107123693 A CN 107123693A
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solar cell
window layer
cdte
high transparency
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CN107123693B (en
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覃东欢
温诗雅
李妙姿
刘鑫妍
刘松炜
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South China University of Technology SCUT
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    • H01L31/1828Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof the active layers comprising only AIIBVI compounds, e.g. CdS, ZnS, CdTe
    • H01L31/1836Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof the active layers comprising only AIIBVI compounds, e.g. CdS, ZnS, CdTe comprising a growth substrate not being an AIIBVI compound
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Abstract

The invention discloses a kind of efficient CdTe nanometer crystalline solar cell with high transparency window layer material processed based on solwution method and preparation method thereof.The solar cell is stacked gradually and constituted by glass substrate, negative electrode, cathode interface layer, Window layer, photoactive layer, anode.Cathode interface layer refers to ZnO, and Window layer is the TiO doped with Mg, Sb, In, Al, Bi, Zr, Pb, Nb2Or ZnS films, photoactive layer by one or more layers CdTe nanometer crystalline layer constitute;Negative electrode refers at least one of indium tin oxide conductive film, doping stannic oxide, metal film and metal-oxide film;Anode is Au;The solar cell of the present invention uses solution processing technology, realizes the ultrathin of solar cell, and excellent performance, energy conversion efficiency is up to 3.53%.The present invention is simple, and main process solution can be machined in common fume hood, and be heat-treated using lower temperature, greatly reduce cost of manufacture.

Description

A kind of efficient CdTe with high transparency window layer material processed based on solwution method is received Brilliant solar cell of rice and preparation method thereof
Technical field
The invention belongs to field of photoelectric devices, and in particular to a kind of to have high transparency Window layer material based on what solwution method was processed Efficient CdTe nanometer crystalline solar cell of material and preparation method thereof.
Background technology
Since 21st century, large scale mining of the fossil energy through many decades is used, and has been on the brink of exhaustion.The industrial revolution is extremely The present, greenhouse effects cause the mean temperature of the earth to rise 0.3~0.6 DEG C, sea level rise 10~25cm.Greenhouse effects gas The main component of body is carbon dioxide, and wherein 80% is produced by the consumption of fossil fuel.It can be seen that, the mankind just meet with the energy Shortage and the Double jeopardy of environmental degradation.Develop a kind of energy of high-efficiency cleaning, be the problem of mankind nowadays letter is to be solved.Exploitation Solar energy, is the inexorable trend of current energy extraction, because solar energy exactly meets the green energy resource of above-mentioned condition.Solar energy Volt generates electricity, compared with traditional electricity generating principle, with without other media, no-rotary part, modular construction, operation maintenance Simply, the advantages of construction period is short and utilizes desert soil and building roof resource, is to large-scale develop and utilize solar energy Only way.
Traditional crystal silicon battery, because it is larger to raw material and energy demand, cost remain high, and energy recovery term compared with Long, cost performance has much room for improvement.In recent years, hull cell is a dark horse with its absolute predominance with low cost, mainly including silicon substrate Thin film solar cell, inorganic compound thin film battery (CIGS (CIGS) hull cell, cadmium telluride (CdTe) solar cell) With organic polymer thin film battery.Wherein, inorganic compound thin film solar cell advantage be can be matched well with solar spectrum, Absorption coefficient is larger, energy conversion efficiency is high.In the recent period, the energy of the cadmium telluride film solar cells of the making in laboratory in the U.S. turns Change efficiency and reached 20.4%, with the highest transformation efficiency of polycrystalline silicon solar cell closely.But, its main preparation side Method is close spaced sublimation method, vacuum vapour deposition, electrochemical deposition method, magnetron sputtering method etc., vacuum or hot environment restrict its into This further reduction.The inorganic nano-crystal solar cell processed based on solwution method, can be processed by introducing volume to volume solution Method, realizes industrial low cost, large area, light weight, the preparation of bendable film solar cell, and can keep inorganic semiconductor The advantage of the good solar spectrum response of material, carrier transmission performance and good stability.Nano crystal solar cell is One focus of current research.Moreover, nanocrystalline material can carry out band gap tune by adjusting the size of crystal grain Control, realizes a variety of band gap of homogenous material, this is the incomparable advantage of polymeric material.
2005, Alivisatos (I.Gur, N.A.Fromer, M.L.Geier, A.P.Alivisatos, Science, 2005,310,462.) research group has carried out the research that inorganic nano-crystal solar cell is prepared based on spin coating method.Mainly borrow The method for organic polymer soln film forming of having reflected, is prepared with nanocrystalline respectively as donor and acceptor material using solvent-thermal method Material, using the method for spin coating, to be successfully prepared structure nanocrystalline for ITO/CdTe (100nm)/CdSe (100nm)/Al full-inorganic Solar cell.The electron hole pair of solar energy generation is wherein mainly absorbed as donor layer, as receptive layers, for transmitting electricity Son, forms typical diode device structure.They improve crystal face by sintering processes, defect state density are reduced, so as to subtract Small series resistance, increases open-circuit voltage.Under standard AM1.5 simulated solar light irradiations, its short circuit current flow is 13.2mA/cm2, open Road voltage is 0.45V, and fill factor, curve factor is 49%, and transformation efficiency is 2.9%.In fact, can also by reduce sum mismatch ratio come Open-circuit voltage is further improved, so as to improve electricity conversion.So far, solwution method processing full-inorganic nano crystal solar cell quilt Extensive concern.
2010, Anderson (J.D.Olson, Y.W.Rodriguez, L.D.Yang, G.B.Alers, S.A.Carter, Appl.Phys.Lett., 2010,96,242103.) research group develops non-aluminum metal electrode, and study CdTe, influence of the CdSe thickness degree to device performance, discovery by increasing the thickness of CdTe layer can obtain preferable energy Transformation efficiency, but the transformation efficiency of best device is also only 2.6%.Main cause is that the flatness of film is undesirable and still suffer from Substantial amounts of crystal boundary and defect state, in addition the size of crystal grain be not also well controlled.The same year, Olson (J.D.0l son, Y.W.Rodriguez, L.D.Yang, G.B.Alers, S.A.Carter, Appl.Phys.Lett., 2010,96,242103.) Research group is prepared for CdTe/Al Schottky solar cells, and its efficiency reaches 5%.They point out CdCl2Heat treatment causes CdTe Crystal grain is grown up, and is eliminated quantum confined effect by optimizing heat treatment condition, is enhanced the absorption to sunshine.But this Xiao Te There is some raisings for limiting its efficiency in the structure of base solar cell in itself.I.e. just from anode (transparency electrode ITO) What one end was injected, and schottky junction occurs to be combined in cathode terminal, electronic transmission process, diffusion length is limited, it is impossible to whole quilts Absorb.
2011, Jasieniak (J.Jasieniak, B. work .MacDonald, S.E.Watkins, P.Mulvaney, Nano Lett., 2011,11,2856.) research group employs the method that whole soln is layering, and prepare CdTe/ZnO and receive The brilliant solar cell of rice, energy conversion efficiency is up to 6.9%.Because larger stress occurs in heat treatment process, destruction film is brilliant The periodicity of body, the destruction of stress can be reduced using layer-by-layer methods by reducing each layer of thickness, this Outside, the defect produced for last layer, next layer can play good compensating action, so as to generally improve crystal layer Quality.
2013, Donghuan Qin (Donghuan Qin, Yiyao Tian, Yi j ie Zhang, Yizhao Lin, Kuo Gao, J Nanopart Re s, (2013) 15:2053) research group sinters processing method using spin coating layer by layer, succeeds first The inorganic nano-crystal solar cell of ITO/ZnO-In/CdS/CdTe/MoOx/Ag inverted structures is prepared, its efficiency reaches 3.73%, it is the highest level of similar device in current report.They use the design of inverted structure battery, reduce light in device The distance propagated in part, makes incident light from p-n junction closer to being conducive to the collection of carrier, improve the absorption efficiency to light.By ZnO-In prepared by sol method, spin-coated sintering forms fine and close smooth boundary layer, it is ensured that it is smooth homogeneous that CdS layer is sprawled, So as to effectively prevent CdTe layer and ITO direct contact causes larger leakage current, the performance of device is improved.But, device Part is not good in the response of short wavelength range, and this is due to that photoresponses of the Window layer CdS to short wavelength is poor, reduces active layer pair The utilization of short wavelength, so as to constrain the raising of transformation efficiency.
, Troy K.Townsend (Troy K.Townsend, Edward in 2014 E.Foos.Phys.Chem.Chem.Phys, 2014,16,16458) structure is successfully prepared with solwution method is ITO/ for research group CdSe/CdTe/Au whole soln inorganic nano-crystal solar cell, wherein the electricity of the ITO and Au electrodes using the processing of whole soln method Pond transformation efficiency is 1.7%, and the ITO electrode transformation efficiency for changing ITO electrode prepared by solwution method into business is 2.0%, will be molten It is 1.3% that liquid method, which prepares Au electrodes and changes vapour deposition method Au electrodes transformation efficiency into, while using business ITO electrode and vapour deposition method Au electricity Pole transformation efficiency has reached 3.8%.It is nanocrystalline generally to have relatively low fusing point for faced blocks material, thus phase can be used To low heat treatment temperature, make it possible the electrode that battery is made using ITO.Although low workfunction metal can be with n-layer shape Into Ohmic contact, but it is oxidized easily, influences the life-span of device, thus common high-efficiency battery uses inverted structure, with Strengthen the stability of device.The efficiency of the structure devices is not too much preferable, and mainly CdSe is deposited directly on ITO, defect meeting It is more, easily cause the short circuit of device, thus device open-circuit voltage and fill factor, curve factor all than relatively low, have impact on the energy of device Conversion efficiency.
For the nanocrystalline heterojunction solar battery of formal dress cadmium telluride, its device architecture by glass substrate, anode and its Cushion, photoactive layer and negative electrode stack gradually composition.This active layer is on ITO substrates, and n-layer has one in outermost layer The problem of determining:Active layer CdTe is directly spin-coated on ITO, and just incident from ITO side, therefore p-n junction is in away from entering The opposite side of light is penetrated, the separation and transmission for carrier are totally unfavorable, and photo-generated carrier needs to pass through thicker active layer Interface is got to, just inevitable produce is combined in transmitting procedure, so as to reduce efficiency of light absorption;On the other hand, it is cloudy Extremely main using low workfunction metals such as Al, this metal is easily aoxidized, and usually requires 400 DEG C of temperature heat treatments, and ITO exists Performance can decline under 400 DEG C of high temperature, and the stability of device is just difficult to be guaranteed.It is when business to find a kind of Low Temperature Heat Treatment mode It is anxious.
The content of the invention
For problem above, the present invention provides a kind of based on the efficient with high transparency window layer material of solwution method processing CdTe nanometer crystalline solar cell.
It is a further object to provide a kind of method that solwution method prepares above-mentioned solar cell.
The purpose of the present invention is realized by following proposal.
A kind of efficient CdTe nanometer crystalline solar cell with high transparency window layer material processed based on solwution method, it is described Solar cell is formed by glass substrate, negative electrode, cathode interface layer, Window layer, photoactive layer and anode lamination successively from down to up; The thickness of the Window layer is 10~100nm, by one or more layers TiO doped with Mg, Sb, In, Al, Bi, Zr, Pb, Nb2It is thin Film or ZnS films composition;The photoactive layer is CdTe nanometer crystalline layer.
It is made up of compared to traditional solar cell glass substrate, anode and its cushion, photoactive layer, anode, this hair Bright solar cell is inverted structure, also add high transparency Window layer.The inverted structure ensure that heterojunction regions are close Incident light beam strikes face, it is ensured that the efficient collection and separation of carrier.The high transparency Window layer can be realized to the effective of electronics Absorb and increase utilization of the photoactive layer to sunshine.
Further optimize, the negative electrode refers to indium tin oxide conductive film (FTO), fluorine-doped tin dioxide conducting film (ITO), gold Belong at least one of film and metal-oxide film, preferably use FTO, FTO transparent conductive glass surface resistance used 15ohm/sq, light transmittance 83%, thickness 1.6mm.The thickness of the negative electrode is 80~200nm.
Further optimize, the cathode interface layer refers to ZnO film, thickness is 20~100nm.
Further optimize, described high transparency Window layer refers to TiO2Or ZnS films.TiO2It is transparent n to be with ZnS Molded breadth bandgap semiconductor material, TiO2HOMO, lumo energy is respectively 7.1eV and 3.81eV, TiO2With CdTe nanometer crystalline film Hetero-junctions is formed, promotes exciton dissociation, TiO2HOMO energy levels it is relatively deep have barrier effect to hole, can prevent hole from entering cloudy Pole, and promote electronics to cathode motion;Due to TiO2Wellability of the presoma on FTO surfaces it is bad, it is difficult to form high-quality The film of amount, so in TiO2Layer of ZnO is introduced between FTO and improves TiO2The quality of film;ZnO can function as resistance simultaneously Barrier, is prevented due to TiO2The defect of layer causes CdTe and FTO directly to contact.
Further optimize, the preparation of the Window layer comprises the following steps:Butyl titanate is dissolved in organic solvent, Titania gel is obtained, then obtains titania-doped solidifying by volatilization is sufficiently stirred in dopant addition titania gel Glue, by titania-doped gel is spin-coated, brushing, spraying, dip-coating, roller coat, printing (being preferably silk-screen printing) or ink-jet beat India side formula is deposited on cathode interface layer, obtains Window layer;Described organic solvent refers in triethanolamine, acetic acid and absolute ethyl alcohol It is one or more of.Formed Window layer described in doping medicine include magnesium acetate, ethoxyquin antimony, indium acetate, aluminum acetate, bismuth acetate, Ethoxyquin zirconium, lead acetate, acetic acid niobium.
Further optimize, described Window layer is deposited after film forming every time using sintering treatment method layer by layer, be required for pair Film is heat-treated, and is heat-treated the film of gained heating 30~60min in 400~500 DEG C on warm table;Further preferred window The thickness of mouth layer is 40nm.
Further optimize, the preparation of the photoactive layer comprises the following steps:CdTe is prepared using solvent-thermal method It is nanocrystalline, be re-dissolved in organic solvent obtaining dark solution, i.e. nanocrystal solution, by nanocrystal solution it is spin-coated, brush, spray Apply, printing (being preferably silk-screen printing) or inkjet printing mode are deposited in Window layer, immerse afterwards at the methanol solution of saturation Reason, 350 DEG C of high-temperature process for a period of time, obtain nanocrystalline individual layer, then be made and can be had by the mode solution processing being layering Reduce boundary defect and internal stress, the photoactive layer of even compact in effect ground;The photoactive layer is by one or more layers cadmium telluride It is nanocrystalline to be formed by stacking.
Further optimize, dissolving CdTe nanometer crystalline organic solvent refers to polar organic solvent, such as normal propyl alcohol, pyridine, first Yl pyridines, phenmethylol one or more combination are formed.
CdTe nanometer crystalline reference literature (S.Sun, H.M.Liu, Y.P.Gao, D.H.Qin, J.Materials.Chemistry., 6856.) 2012,517,6,853 1 prepare.
Further optimize, the photoactive layer thickness can be by adjusting nanocrystalline concentration, spin coating rotating speed and rotation The number of plies is applied to obtain.
Further optimize, the thickness of the photoactive layer is 100~700nm, and preferred thickness is 500~600nm, by many Layer is nanocrystalline to be formed by stacking.
The anode is Au or Al, and thickness is 80~200nm.Au is a kind of high work function metal, work function 5.1eV, can be with Match with CdTe HOMO energy levels, form Ohmic contact.Further optimizing, the anode refers to Au, thickness is 20~ 100nm。
Prepare a kind of above-described efficient CdTe nanometers with high transparency window layer material processed based on solwution method The method of brilliant solar cell, comprises the following steps:
(1) glass substrate for being attached with negative electrode is cleaned, dried;
(2) in cathode surface deposition cathode interface layer by the way of solution processing;
(3) Window layer is prepared on cathode interface layer using solution processing method;
(4) photoactive layer is prepared in Window layer using solution processing method;
(5) anode is deposited on photoactive layer using vapour deposition method, obtains the efficient CdTe with high transparency window layer material and receive The brilliant solar cell of rice.
Cathode interface layer, the TiO being sequentially prepared on cathode substrate2Film, CdTe thin film are in conventional chemistry ventilation Carried out in kitchen, it is not necessary to any gas shield or especially clean measure.
The present invention mechanism be:
Solar cell of the present invention uses inverted structure, it is ensured that interface is close to incident light beam strikes face, it is ensured that the height of carrier Effect is collected and separated;Anode is used as hole-collecting electrode using high work function Au, it is ensured that the stability of anode;Processed using solution Technology, prepares CdTe ultrathins layer etc., simplifies preparation technology.ZnO boundary layers are introduced, make TiO2Film is uniform, fine and close, nothing Pin hole, prevents the TiO on upper strata2Directly contacted with FTO, reduce the generation of leakage current, the final performance for improving device.Introduce TiO2 High transparency Window layer effectively improves the collection to electronics, and realization is more effectively matched with CdTe lattices, and improves opening for battery device Road voltage.
The present invention has the following advantages and beneficial effect relative to prior art:
(1) solar cell of the present invention uses inverted structure, it is ensured that interface is close to incident light beam strikes face, it is ensured that carrier Efficiently collect and separate, the performance of the nanocrystalline heterojunction solar battery of cadmium telluride of inverted structure, energy conversion can be greatly improved Efficiency reaches 3.53%.
(2) anode is used as hole-collecting electrode using Au, it is therefore prevented that low workfunction metal is directly contacted with active layer, is protected The stability of anode is demonstrate,proved, extends the life-span of nano crystal solar cell.
(3) TiO is used2Gel prepares high transparency Window layer and effectively improves carrier collection efficiency, improves device performance.
(4) using the film conduct of the transmissivity to solar spectrum (wavelength is in 250~2400nm) with more than 10% The anode and cathode electrode at two ends, realize transparent or translucent solar cell.
(5) solar cell of the invention uses solution processing technology, prepares ultrathin layer, realizes the super of solar cell Thinning.
(6) preparation technology of solar cell of the present invention is simple, save raw material, easily realizes large-scale production.
Brief description of the drawings
Fig. 1 has the structure chart of the efficient CdTe nanometer crystalline solar cell of high transparency window layer material for the present invention.
Embodiment
The solar cell of the present invention is by glass substrate, negative electrode, cathode interface layer, high transparency Window layer, photoactive layer, anode Lamination forms (as shown in Figure 1) successively.Cathode interface layer is added between negative electrode and high transparency Window layer and is employed layer by layer Sintering process prepares CdTe nanometer crystalline photoactive layer, and the cathode interface layer refers to ZnO layer.Cathode interface layer serves not only as electricity Sub- transport layer, also enhances the electric property of device, and CdTe thin film, which is grown in cellular high transparency Window layer, improves electronics receipts Collect area, improve the battery performance of the hetero-junctions.Due to the presence of ZnO layer, the FTO that hole is collected originally is changed into collecting electronics, The light path that incident light enters p-n junction shortens, and is conducive to improving the separative efficiency of carrier.In addition, solar cell inverted structure by The performance for causing device in the metal (gold) using high work function is more stablized.Cathode interface layer ZnO is by by presoma material Material is dissolved in organic solvent, colloidal sol is made, then spin-coated, brushing, spraying, dip-coating, roller coat, printing (silk-screen printing) or ink-jet are beaten India side formula, which is deposited on FTO, forms cathode interface layer;Described high transparency Window layer is prepared by sol-gel methods, by the fourth of metatitanic acid four Ester is dissolved in organic solvent, obtains titania gel, then the medicine addition titania gel that will adulterate is sufficiently stirred for volatilization and obtained Titania-doped gel, by the gel spin coating, brushing, spraying, dip-coating, roller coat, printing (silk-screen printing) or inkjet printing Mode is deposited on cathode interface layer, obtains high transparency Window layer;CdTe nanometer crystalline is dissolved in organic solvent, obtains nanocrystalline scattered Liquid, then spin-coated, brushing, spraying, dip-coating, roller coat, printing (silk-screen printing) or inkjet printing mode are deposited on CdTe thin film On, and pass through CdCl layer by layer2The method of sintering, obtains photoactive layer;Finally anode material is deposited on by evaporation mode In CdTe thin film, anode is formed.
With reference to embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited In this.
Embodiment 1
First, the system for the efficient CdTe nanometer crystalline solar cell with high transparency window layer material processed based on solwution method It is standby:
(1) cleaning of FTO Conducting Glass:(specification is 15 millimeters × 15 millimeters, and FTO thickness is 130nm, its side Block resistance is 20 ohms/squares, from Zhuhai Kaivo Electronic Components Co., Ltd.'s purchase) by substrate successively in toluene, acetone, half Ultrasonically treated l0min in conductor special purpose detergent, deionized water, isopropanol, cleans FTO substrate surface, then puts FTO pieces Enter and stand 2h drying in constant temperature oven at 80 DEG C.
(2) ZnO colloidal sols are configured:By Zinc diacetate dihydrate (3.2925g), monoethanolamine (0.905m1), ethylene glycol monomethyl ether (30m1) is fitted into there-necked flask, sealing.80 DEG C of holding oil bath heating 2 hours.(it is the pure medicine of analysis above, from Guangzhou lush luxuriant growth Chemical glass Co., Ltd buys), filtered with 0.45 μm of filter, load vial and be filled with nitrogen, that is, obtain ZnO molten Glue.
(3) preparation of cathode interface layer:FTO pieces after drying are placed in sol evenning machine and (in (KW-4A types), step (2) are added dropwise The ZnO colloidal sols prepared, through high speed spin coating (3000rpm, time 20s), wipe the ZnO layer of cathode site off, are put in warm table On, l0min, then 400 DEG C of heating l0min are heat-treated at 200 DEG C of elder generation, room temperature is cooled to, is respectively placed in acetone and isopropanol and surpasses Sound l0min (ultrasonic power is 1000W), nitrogen gun drying obtains the cathode interface layer that thickness is 40nm.
(4) preparation of high transparency Window layer:
①TiO2The preparation of gel:25ml absolute methanols are measured with graduated cylinder, 4.25ml metatitanic acids four are extracted with syringe respectively Butyl ester and 3.75ml triethanolamines are added in 50ml beakers, stir 2h, and 5ml acetic acid is added with plastic dropper, 5ml deionized waters, Add appropriate ethoxyquin antimony to be doped, continue to stir 24h, record temperature, humidity evaporate into gel state in fume hood, obtained TiO2Gel.(being the pure medicine of analysis above, from the purchase of Guangzhou Qian Hui chemical glasses Co., Ltd)
2. the substrate of step (3) processing is placed in sol evenning machine and (in (KW-4A types), above-mentioned TiO is added dropwise2Gel, high speed spin coating (speed is 2500rpm, time 15s), wipes the Window layer of cathode site off, is placed on 500 DEG C of heating 1h on warm table, is placed in isopropyl Ultrasound 8min in alcohol, nitrogen gun drying is placed on warm table with 150 DEG C of processing l5min, obtains the high transparency window that thickness is 40nm Mouth layer.
(5) preparation of photoactive layer:
1. the preparation of CdTe nanometer crystalline:Reference literature (S.Sun, H.M.Liu, Y.P.Gao, D.H.Qin, J.Materials.Chemistry., 2012,517,6853-6856.), specific preparation process is as follows:Weigh tetradecylic acid cadmium (l.6mmo1,906mg), aoxidizes trioctylphosphine phosphorus 2.35g tetradecylic acid (myristic acid, C13H26COOH, 92mg) add the three of 50m1 In mouth bottle (bottleneck is respectively provided with thermometer, condenser pipe, airway tube), 240 DEG C are heated under nitrogen protection, now tetradecylic acid cadmium (decomposition temperature is 228 DEG C) has been decomposed, yellow solution is presented.Keep 5min at this temperature, by the tellurium of trioctylphosphine phosphorus one (tellurium Concentration is 0.8mmo1/mL, takes lml) being injected into reaction system rapidly, (wherein trioctylphosphine phosphorus, oxidation trioctylphosphine phosphorus are purchased from me Fourth chemical reagents corporation, remaining is purchased from Qian Hui chemical glasses Co., Ltd), entirely react and continue 30min at 240 DEG C;Then Cleaned 3 times by methanol, centrifuge product;By product add 20mL pyridines in, at 100 DEG C, nitrogen protection, flow back l0h, return Stream adds 60ml n-hexane solvents after terminating, and centrifuges, and final product is dried up with nitrogen gun, obtains CdTe nanometer crystalline.
2. it is 1 the above-mentioned CdTe nanometer crystalline prepared to be dissolved in into volume ratio:The mixed solvent of 1 normal propyl alcohol/pyridine In, concentration is 0.04g/mL, ultrasonic 2h (ultrasonic power is 1000W), is filtered, obtained by 0.45m (organic system) filter CdTe nanometer crystalline solution.
The substrate of step (4) processing is placed in sol evenning machine and (in (KW-4A types), above-mentioned CdTe nanometer crystalline solution is added dropwise, at a high speed Spin coating (speed is 1100rpm, time 20s), is placed on 150 DEG C of heating 3min on warm table and removes organic solvent, wipe Window layer off Nano-crystalline layers, 150 DEG C of CdCl of immersion2Saturation methanol solution in l0s, then immerse in 120 DEG C of normal propyl alcohol, it is many to remove Remaining CdCl2, dried up, be placed on 350 DEG C of warm tables with nitrogen, be heat-treated 40s, then be placed on 150 DEG C of warm table processing 2min, leaching Enter and 4s is rinsed in 120 DEG C of methanol, nitrogen gun drying, with 400 DEG C of processing l5min, obtains the CdTe nanometer crystalline that thickness is 100nm Layer.5 layers of spin coating is repeated, multi-layer C dTe is obtained nanocrystalline.
(6) evaporation of anode:Substrate obtained by step (5) is put into Vacuum Deposition chamber, 3 × 10-4Under Pa high vacuum, evaporation Au (80nm), obtains anode.
Obtained device is packaged processing, structure is obtained for FTO/ZnO/TiO2/ CdTe/Au inverted structure is inorganic CdTe nanometer crystalline heterojunction solar battery (structural representation is shown in Fig. 1).
2nd, the performance measurement of CdTe nanometer crystalline heterojunction solar battery:
The measure of solar cell device parameter performance will be using sunshine as testing standard.Measured in laboratory with AM 1.5G The radiant illumination of standard is 1000W/m2.When carrying out nano crystal solar cell performance test with solar simulation light, first have to use Normal cell judges whether light source meets AM1.5G irradiation level.Standard silicon solar cell is by calibration:In AM 1.5G standard light Under spectrum, i.e. 1000W/m2Radiant illumination light irradiation under, obtained short circuit current flow be 125mA.Determine after irradiation intensity, you can Device is tested.Solar cell performance test is carried out with solar simulation light, the energy conversion efficiency of solar cell is:
Wherein PMAXFor peak power output (unit:MW), Pin is radiant illumination (unit:mW/cm2), S has for device Imitate area (unit:cm2).The apparatus for measuring polymer body heterojunction solar cell performance is as shown in table 1.
Table 1
Embodiment 1
Influence of the various concentrations ethoxyquin Sb doped to CdTe nanometer crystalline solar cell:
Respectively from the TiO undoped, ethoxyquin antimony concentration of adulterating is 3wt%, 5wt%, 8wt%2Film is used as window Layer, TiO2Heat treatment temperature is 500 DEG C, and ZnO is set to 40nm, and cadmium-telluride layer is set to 500nm, CdCl2Sintering temperature is set to 400 DEG C, Sintering time is 15min, and other parameters condition is implemented according to embodiment 1.
Table 2
Table 2 compares the efficiency of cadmium-Te solar battery under different ethoxyquin Sb doped concentration, it can be seen that doping 3wt% When efficiency reached maximum, afterwards continue increase doping concentration efficiency change it is little.
Embodiment 2
Different CdCl2Influence of the sintering temperature to CdTe nanometer crystalline solar cell
It is respectively CdCl from 370 DEG C, 380 DEG C, 390 DEG C, 400 DEG C2Sintering temperature, TiO2Heat treatment temperature is 500 DEG C, ZnO is set to 40nm, and cadmium-telluride layer is set to 500nm, the TiO for being 3wt% from doping ethoxyquin antimony concentration2Film is used as window Layer, sintering time is 15min, and other parameters condition is implemented according to embodiment 1.
Table 2
Table 2 compares different CdCl2The open-circuit voltage of cadmium-Te solar battery, short circuit current flow, efficiency etc. under sintering temperature The change of aspect, it can be seen that as heating-up temperature is in 370 DEG C to 400 DEG C change procedures, efficiency of solar cell is stepped up, Higher heat treatment temperature is conducive to growing and effectively reducing the finer and close lattice of defect generation for CdTe nanometer crystalline.
Embodiment 3
Different CdCl2Influence of the sintering time to CdTe nanometer crystalline solar cell
It is respectively CdCl from 10min, 15min, 20min, 30min2Sintering time, TiO2Heat treatment temperature is 500 DEG C, ZnO is set to 40nm, and cadmium-telluride layer is set to 500nm, the TiO for being 3wt% from doping ethoxyquin antimony concentration2Film is used as window Layer, sintering temperature is 400 DEG C, and other parameters condition is implemented according to embodiment 1.
Table 3
Table 3 compares different CdCl2The open-circuit voltage of cadmium-Te solar battery, short circuit current flow, efficiency etc. under sintering time The change of aspect, from data it can be found that when efficiency of solar cell is substantially better than other processing under 15min heat treatment time Between, it is shorter than nano-crystalline granule in 15min sintering times and is in the stage not grown completely, device efficiency is limited, more than 15min Sintering time after water oxygen in CdTe layer material and air produce the further lifting that reaction have impact on battery efficiency.
Embodiment 4
Influence of the different dopants to CdTe nanometer crystalline solar cell:
Respectively from doping ethoxyquin antimony, indium acetate, aluminum acetate, the TiO of ethoxyquin zirconium2Film is used as Window layer, doping Concentration is 3wt%, and heat treatment temperature is 500 DEG C, and ZnO is set to 40nm, and cadmium-telluride layer is set to 500nm, and sintering temperature is 400 DEG C, 15min, other parameters condition is implemented according to embodiment 1.
Table 4
Table 4 compares influence of the doping different material to CdTe solar cells, wherein the Window layer material of doping ethoxyquin antimony Material has measured most outstanding battery device.Different dopants change TiO2The film forming characteristics of Window layer, structural change Cause Window layer change corresponding to charge collection efficiency.
Embodiment 5
Influence of the different windows layer to CdTe nanometer crystalline solar cell
TiO is selected respectively2Film, ZnS films are as Window layer, and doping concentration is 3wt% ethoxyquin antimony, heat treatment temperature Spend for 500 DEG C, ZnO is set to 40nm, cadmium-telluride layer is set to 500nm, and sintering temperature is 400 DEG C, and 15min, other parameters condition is pressed Implement according to embodiment 1.
Table 5
Table 5 compares two kinds of different materials as influence during Window layer to battery device, and different materials are after treatment Film Morphology difference and device performance is have impact on ZnO film with the Lattice Matching of CdTe photoactive layers.
Embodiment 6
Influence of the different windows thickness degree to CdTe nanometer crystalline solar cell
Respectively from the TiO that thickness is 20nm, 40nm, 60nm, 80nm, 100nm2Film is used as Window layer, TiO2Film is mixed Miscellaneous concentration is 3wt% ethoxyquin antimony, and heat treatment temperature is 500 DEG C, and heat treatment time is 1h, and ZnO is set to 40nm cadmium-telluride layers It is set to 500nm, CdCl2Sintering temperature is set to 400 DEG C, and sintering time is 15min, and other parameters condition is implemented according to embodiment 1.
Table 6
Table 6 compares influence of the different windows thickness degree to battery device, different window layer thickness influence TiO2Film Interface shape so as to influenceing the collection to electronics.Relatively thin Window layer is low to Electron absorption efficiency, produces leakage current;Thicker Window layer influences the utilization to sunshine, is unfavorable for improving efficiency.
Embodiment 7
Influence of the Window layer treatment temperature to CdTe nanometer crystalline solar cell
Respectively TiO is used as from 400 DEG C, 450 DEG C, 500 DEG C2The heat treatment temperature of film, TiO2Film doping concentration is 3wt% ethoxyquin antimony, thickness 40nm, heat treatment temperature is 500 DEG C, and the time is 60min.ZnO is set to 40nm, and cadmium-telluride layer is fixed For 500nm, sintering temperature is 400 DEG C, and 15min, other parameters condition is implemented according to embodiment 1.
Table 7
Table 7 compares influence of the Window layer to battery device under different heat treatment, because FTO electro-conductive glass thickness is larger, needs Will higher heat treatment temperature make TiO2Forming thin film is finer and close, thus improves battery device efficiency.
Embodiment 8
Influence of the Window layer heat treatment time to CdTe nanometer crystalline solar cell
Respectively TiO is used as from 30min, 40min, 45min, 55min, 60min2Film heat treatment time, TiO2Film is mixed Miscellaneous concentration is 3wt% ethoxyquin antimony, and thickness 40nm, heat treatment temperature is 500 DEG C, and ZnO is set to 40nm, and cadmium-telluride layer is set to 500nm, sintering temperature is 400 DEG C, and 15min, other parameters condition is implemented according to embodiment 1.
Table 8
Table 8 compares influence of the different windows layer heat treatment time to battery device, with the increasing of heat treatment time length Plus, battery efficiency is effectively changed, reaches that the heat treatment time of certain length is conducive to the film forming of film to improve Window layer Absorption to electronics, reduces the generation of leakage current.
Above-described embodiment is preferably embodiment, but embodiments of the present invention are not by above-described embodiment of the invention Limitation, other any Spirit Essences without departing from the present invention and the change made under principle, modification, replacement, combine, simplification, Equivalent substitute mode is should be, is included within protection scope of the present invention.

Claims (10)

1. a kind of efficient CdTe nanometer crystalline solar cell with high transparency window layer material processed based on solwution method, its feature It is, the solar cell is from down to up successively by glass substrate, negative electrode, cathode interface layer, Window layer, photoactive layer and anode Lamination is formed;The thickness of the Window layer is 10~100nm, by one or more layers doped with Mg, Sb, In, Al, Bi, Zr, Pb or Nb'sFilm or ZnS films composition;The photoactive layer is CdTe nanometer crystalline layer.
2. a kind of efficient CdTe with high transparency window layer material processed based on solwution method according to claim 1 is received The brilliant solar cell of rice, it is characterised in that the negative electrode refers in indium tin oxide conductive film and fluorine-doped tin dioxide conducting film at least One kind, the thickness of the negative electrode is 80~200nm.
3. a kind of efficient CdTe with high transparency window layer material processed based on solwution method according to claim 1 is received The brilliant solar cell of rice, it is characterised in that the cathode interface layer refers to ZnO film, thickness is 20~100nm.
4. a kind of efficient CdTe with high transparency window layer material processed based on solwution method according to claim 1 is received The brilliant solar cell of rice, it is characterised in that the preparation of the Window layer comprises the following steps:Butyl titanate is dissolved in organic solvent In, titania gel is obtained, then titanium dioxide of adulterating is obtained by volatilization is sufficiently stirred in dopant addition titania gel Titanium gel, by titania-doped gel is spin-coated, brushing, spraying, dip-coating, roller coat, printing or inkjet printing mode deposit to On cathode interface layer, Window layer is obtained.
5. a kind of efficient CdTe with high transparency window layer material processed based on solwution method according to claim 4 is received The brilliant solar cell of rice, it is characterised in that described organic solvent refer to one kind in triethanolamine, acetic acid and absolute ethyl alcohol or with On;The dopant is magnesium acetate, ethoxyquin antimony, indium acetate, aluminum acetate, bismuth acetate, ethoxyquin zirconium, lead acetate or acetic acid Niobium.
6. require that a kind of described efficient CdTe with high transparency window layer material processed based on solwution method is received according to right 4 The brilliant solar cell of rice, it is characterised in that described Window layer is all needed after deposition film forming every time using sintering treatment method layer by layer Film is heat-treated, be heat-treated the film of gained heating 30~60min in 400~500 DEG C on warm table.
7. a kind of efficient CdTe with high transparency window layer material processed based on solwution method according to claim 1 is received The brilliant solar cell of rice, it is characterised in that the preparation of the photoactive layer comprises the following steps:Prepared using solvent-thermal method CdTe nanometer crystalline, is re-dissolved in organic solvent obtaining dark solution, i.e. nanocrystal solution, by nanocrystal solution it is spin-coated, brush Apply, spray, printing or inkjet printing mode are deposited in Window layer, obtain CdTe nanometer crystalline layer;The photoactive layer is by multilayer tellurium Cadmium is nanocrystalline to be formed by stacking.
8. a kind of efficient CdTe with high transparency window layer material processed based on solwution method according to claim 1 is received The brilliant solar cell of rice, it is characterised in that the thickness of the photoactive layer is 100~700nm.
9. a kind of efficient CdTe with high transparency window layer material processed based on solwution method according to claim 1 is received The brilliant solar cell of rice, it is characterised in that the anode is Au or Al, thickness is 80~200nm.
10. prepare described in any one of claim 1~9 a kind of has high transparency window layer material based on what solwution method was processed The method of efficient CdTe nanometer crystalline solar cell, it is characterised in that comprise the following steps:
(1)The glass substrate for being attached with negative electrode is cleaned, dried;
(2)In cathode surface deposition cathode interface layer by the way of solution is processed;
(3)Window layer is prepared on cathode interface layer using solution processing method;
(4)Photoactive layer is prepared in Window layer using solution processing method;
(5)Anode is deposited on photoactive layer using vapour deposition method, the efficient CdTe nanometer crystalline with high transparency window layer material is obtained Solar cell.
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