CN101692481B - Solar cell having integrated structure of plane-bulk heterojunction and preparation method thereof - Google Patents
Solar cell having integrated structure of plane-bulk heterojunction and preparation method thereof Download PDFInfo
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- CN101692481B CN101692481B CN 200910093531 CN200910093531A CN101692481B CN 101692481 B CN101692481 B CN 101692481B CN 200910093531 CN200910093531 CN 200910093531 CN 200910093531 A CN200910093531 A CN 200910093531A CN 101692481 B CN101692481 B CN 101692481B
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Abstract
The invention discloses a solar cell having an integrated structure of plane-bulk heterojunction and a preparation method thereof, belonging to the technical field of solar cells. The solar cell of the invention comprises a glass substrate, an anode, an anode decoration layer, a photoelectric activation layer and a cathode which are sequentially stacked; and the solar cell is characterized in that a conjugated polymer electron donor material layer with the thickness thereof being 2nm to 30nm is arranged between the anode decoration layer and the photoelectric activation layer; and the conjugated polymer electron donor material coating and the photoelectric activation layer formed by mixing the conjugated polymer electron donor material and the semi-conductor nano-crystalline electron donor material are prepared by using the spin-coating method or the ink-jet printing method. The invention has the advantages of cells with both the planer structure and the bulk heterojunction structure, and further has various advantages of simple preparation process, easy control, good reproducibility, solution processability, etc.; and meanwhile, compared with that with the common bulk heterojunction structure, the solar cell with the structure of the invention can remarkably improve the energy conversion efficiency.
Description
Technical field
The invention belongs to technical field of solar batteries, particularly a kind of plane-body heterojunction solar cell having integrated structure and preparation method thereof.
Background technology
In order to utilize the overall optical spectral limit of sunlight to greatest extent, the structure that the semiconductor nano quantum dot (like CdSe, PbS, PbSe) with narrow band gap comes the hybrid solar cell of sensitization conjugated polymer has been proposed recently, show the absorbing properties (1:S.A.Mcdonald of enhancing in this structure in long wavelength's direction greater than 650nm; G.Konstantatos, S.Zhang, P.W.Cyr; E.J.D.Klem; L.Levina, and E.H.Sargent, Nature Mater.2005; 4,138; 2:D.Cui, J.Xu, T.Zhu, G.Paradee, and S.Ashok, Appl.Phys.Lett.2006,88,183111).Simultaneously, the hybrid solar cell have preparation technology simple, in light weight, cheap, prepare advantages such as large area flexible device easily and paid close attention to (1:W.U.Huynh, J.J.Dittmer widely; And A.P.Alivisotos; Science 2002,295, and 2425; 2:X.Jiang, R.D.Schaller, S.B.Lee, J.M.Pietryga, V.I.Klimov, and A.A.Zakhidov, J.Mater.Res.2007,22,2204; 3:D.Qi, M.Fischbein, M.Drndic, and S.Selmic, Appl.Phys.Lett.2005,86,093103; 4:S.Kumar and G.D.Scholes, Microchim.Acta 2008,160,315; 5:G.Konstantatos, I.Howard, A.Fischer, S.Hoogland, J.Clifford, E.Klem, L.Levina, and E.H.Sargent, Nature 2006,442, and 180).What nearly all hybrid solar battery structure was used all is the body heterojunction structure; This is owing to the photoproduction exciton in the conjugated polymer in the body heterojunction structure can have very high photo-generated carrier efficient effectively giving the acceptor interfacial separation.Yet research is illustrated in the body heterojunction that conjugated polymer/the semiconductor nano blend forms, and hole and the electronics migration distance before compound is less than the distance (1:W.U.Huynh in straight polymer; J.J.Dittmer, N.Teclemariam, D.J.Milliron; A.P.Alivisatos, and K.W.J.Bamham, Phys.Rev.B 2003; 67,115326).If can planar heterojunction and body heterojunction be integrated, not only can improve the transmission and the collection efficiency of charge carrier, and can further make full use of the full spectrum of sunlight with the method for solution processing.
Summary of the invention
The purpose of this invention is to provide a kind of plane-body heterojunction solar cell having integrated structure and preparation method thereof.
A kind of plane-body heterojunction solar cell having integrated structure; Comprise the glass substrate 1, anode 2, anode modification layer 3, photoelectricity active layer 4, the negative electrode 5 that stack gradually; It is characterized in that between anode modification layer 3 and photoelectricity active layer 4, being provided with conjugated polymer electron donor material layer 6, said conjugated polymer electron donor material layer thickness is 2-30nm.
Said conjugated polymer electron donor material is selected from: the inferior vinyl of polyparaphenylene, polyarylene vinylene class, poly base class, Polyarylene-based, polythiophene class, poly quinoline class.
Said photoelectricity active layer 4 is the photoelectricity active layer that conjugated polymer electron donor material and semiconductor nano electron acceptor material mix; Wherein, Said conjugated polymer electron donor material is selected from: gather (to the inferior ethene of phenylene) class, gather (arlydene ethenylidene) class, gather (to phenylene) class, gather (arlydene) class, polythiophene class, poly quinoline class, said semiconductor nano electron acceptor material is from the group of III-V family, II-VI family and IV-VI compound semiconductor, to choose.
Said negative electrode comprises the alloy that alkali metal, alkaline-earth metal, aluminium, silver, copper, perhaps above-mentioned metal are formed.
The preparation method of a kind of plane-body heterojunction solar cell having integrated structure is characterized in that this method step is following:
(1) the ultrasonic cleaning sputter has the transparent conducting glass of ito anode, uses the ozone treatment substrate surface then;
(2) again the rotation coat 30 nanometer thickness PEDOT:PSS as anode modification film, drying;
(3) the conjugated polymer electron donor material is dissolved in the solvent; Method with spin-coating or inkjet printing is coated in it above-mentioned on the substrate of anode modification; Dry 10-48min under 80-250 ℃ naturally cools to room temperature, and forming thickness is the conjugated polymer electron donor material layer of 2-30nm;
(4) with conjugated polymer electron donor material and semiconductor nano electron acceptor material and solvent; The method of the mixed solution that forms with spin-coating or inkjet printing directly is coated on the conjugated polymer electron donor material layer; Naturally cool to room temperature after the drying, form the photoelectricity active layer;
(5) pass through directly vacuum evaporation metal formation negative electrode on the photoelectricity active layer of mask plate, obtain conjugated polymer/semiconductor nano plane-body heterojunction solar cell having integrated structure.
In the said step (3) during spin-coating rotating speed be that 1000-3000 changes per minute.
Beneficial effect of the present invention is:
1. this method can directly apply through the method for spin-coating or inkjet printing conjugated polymer/semiconductor nano photoelectric active layer directly is coated on lower floor's conjugated polymer;
2. when spin coating or inkjet printing upper strata conjugated polymer/semiconductor nano photoelectric active layer, lower floor's conjugated polymer had no destruction;
3. this method technology is simple, with low cost, and thickness is controlled easily, is suitable for large-scale industrial production;
4. the conjugated polymer layer in this method needs higher temperature dry, and baking temperature can from 80 to 250 degrees centigrade, and drying time can be from 10 minutes to 48 hours;
5. conjugated polymer/semiconductor nano the solar cell with this integrated morphology preparation has the photovoltaic energy conversion efficient that is superior to traditional body heterojunction structure devices.
Description of drawings
Fig. 1 is the device architecture of solar cell, wherein, (a) is the body heterojunction solar cell, (b) is plane of the present invention-body heterojunction integrated morphology conjugated polymer/semiconductor nano solar cell;
Fig. 2 is the profile scanning Electronic Speculum figure of solar cell, wherein, (a) is the body heterojunction solar cell, (b) is plane of the present invention-body heterojunction integrated morphology conjugated polymer/semiconductor nano solar cell;
Fig. 3 is that body heterojunction and plane-body heterojunction integrated morphology (1000rpm the prepares P3HT) solar cell of embodiment 1 preparation and body heterojunction structure solar cell that Comparative Examples prepares are at 100mW/cm
2532nm illumination under the I-V curve;
Fig. 4 is that body heterojunction and plane-body heterojunction integrated morphology (1000rpm the prepares P3HT) solar cell of embodiment 1 preparation and body heterojunction structure solar cell that Comparative Examples prepares are at 100mW/cm
2808nm illumination under the I-V curve;
Fig. 5 is that body heterojunction and plane-body heterojunction integrated morphology (2000rpm the prepares P3HT) solar cell of embodiment 2 preparation and body heterojunction structure solar cell that Comparative Examples prepares are at 100mW/cm
2532nm illumination under the I-V curve;
Fig. 6 is that body heterojunction and plane-body heterojunction integrated morphology (2000rpm the prepares P3HT) solar cell of embodiment 2 preparation and body heterojunction structure solar cell that Comparative Examples prepares are at 100mW/cm
2808nm illumination under the I-V curve;
Fig. 7 is that body heterojunction and plane-body heterojunction integrated morphology (3000rpm the prepares P3HT) solar cell of embodiment 3 preparation and body heterojunction structure solar cell that Comparative Examples prepares are at 100mW/cm
2532nm illumination under the I-V curve;
Fig. 8 is that body heterojunction and plane-body heterojunction integrated morphology (3000rpm the prepares P3HT) solar cell of embodiment 3 preparation and body heterojunction structure solar cell that Comparative Examples prepares are at 100mW/cm
2808nm illumination under the I-V curve;
Label among the figure: 1-glass substrate; The 2-anode; 3-anode modification layer; 4-photoelectricity active layer; The 5-negative electrode; 6 conjugated polymer electron donor material layers.
Embodiment
Below in conjunction with accompanying drawing the present invention is described further:
Body heterojunction structure solar cell is shown in Fig. 1 (a); Comprise the glass substrate 1, anode 2, anode modification layer 3, photoelectricity active layer 4, the negative electrode 5 that stack gradually; Plane of the present invention-body heterojunction solar cell having integrated structure; Shown in Fig. 1 (b); Comprise the glass substrate 1, anode 2, anode modification layer 3, photoelectricity active layer 4, the negative electrode 5 that stack gradually, and between anode modification layer 3 and photoelectricity active layer 4, be provided with conjugated polymer electron donor material layer 6, said conjugated polymer electron donor material layer thickness is 2-30nm.
Comparative Examples tradition body heterojunction structure solar cell
There is the transparent conducting glass of ITO (anode) to use liquid detergent, deionized water, acetone, isopropyl alcohol ultrasonic cleaning successively sputter; Use the ozone treatment substrate surface then; Again rotation coat 30 nanometer thickness PEDOT:PSS as the anode modification film, 150 ℃ of dryings 10 minutes are dissolved in the mixed solution that chlorobenzene solution obtains with P3HT and PbSe and (contain 10 milligrams of P3HT in every milliliter of chlorobenzene solution; Contain 50 milligrams of PbSe) 1000 change directly be spun under the rotating speed of per minutes (rpm) above-mentioned on the substrate of anode modification; 80 ℃ of dryings are 30 minutes then, naturally cool to room temperature, and forming thickness is the photoelectric active layer of 50nm; At last, through mask plate 5 * 10
-5The aluminium of vacuum evaporation 150 nanometers is made negative electrode under the handkerchief, obtains body heterojunction structure solar cell, and device architecture is shown in Fig. 1 (a).
The body heterojunction structure solar cell of doing contrast in following examples is the solar cell for preparing in this Comparative Examples; As can be seen from the figure, traditional body heterojunction structure solar cell open circuit voltage under the 532nm of every square centimeter of 100 milliwatt rayed is 0.28 volt, and short circuit current is 0.9 milliampere every square centimeter; Fill factor, curve factor is 0.39; Conversion efficiency is 0.1%, and open circuit voltage is 0.25 volt under the 808nm of every square centimeter of 100 milliwatt rayed, and short circuit current is 1.1 milliamperes every square centimeter; Fill factor, curve factor is 0.36, and conversion efficiency is 0.1%.
There is the transparent conducting glass of ITO (anode) to use liquid detergent, deionized water, acetone, isopropyl alcohol ultrasonic cleaning successively sputter; Use the ozone treatment substrate surface then; Again rotation coat 30 nanometer thickness PEDOT:PSS as the anode modification film, 150 ℃ of dryings 10 minutes, with 10 milligrams every milliliter P3HT chlorobenzene solution (containing 10 milligrams of P3HT in every milliliter of chlorobenzene solution) 1000 change directly be spun under the rotating speed of per minutes (rpm) above-mentioned on the substrate of anode modification; 150 ℃ of dryings are 30 minutes then; Naturally cool to room temperature, forming thickness is the conjugated polymer electron donor material layer of 20nm, P3HT and PbSe is dissolved in the mixed solution that chlorobenzene solution obtains (contains 10 milligrams of P3HT in every milliliter of chlorobenzene solution; Contain 50 milligrams of PbSe) under the rotating speed of 1000 commentaries on classics per minutes (rpm), directly be spun on the P3HT film; 80 ℃ of dryings are 30 minutes then, naturally cool to room temperature, and forming thickness is the photoelectric active layer of 50nm; At last, through mask plate 5 * 10
-5The aluminium of vacuum evaporation 150 nanometers obtains conjugated polymer/semiconductor nano plane-body heterojunction solar cell having integrated structure as negative electrode under the handkerchief, and device architecture is shown in Fig. 1 (b).
Profile scanning electromicroscopic photograph shown in Fig. 2 reflects that clearly the P3HT:PbSe hybrid films on upper strata does not cause any destruction to the P3HT of lower floor.
Fig. 3, Fig. 4 have expressed the plane that present embodiment makes-body heterojunction solar cell having integrated structure through the 532nm of every square centimeter of 100 milliwatt and the current-voltage curve under the 808nm irradiation; As can be seen from the figure; The plane that present embodiment makes-body heterojunction solar cell having integrated structure open circuit voltage under the 532nm of every square centimeter of 100 milliwatt rayed is 0.39 volt; Short circuit current is 0.94 milliampere every square centimeter; Fill factor, curve factor is 0.35, and conversion efficiency is 0.13%, and device performance has improved 33% than traditional body heterojunction Structure Conversion efficient; Open circuit voltage is 0.36 volt under the 808nm of every square centimeter of 100 milliwatt rayed; Short circuit current is 1.36 milliamperes every square centimeter; Fill factor, curve factor is 0.33, and conversion efficiency is 0.16%, and device performance has improved 60% than traditional body heterojunction Structure Conversion efficient.
There is the transparent conducting glass of ITO (anode) to use liquid detergent, deionized water, acetone, isopropyl alcohol ultrasonic cleaning successively sputter; Use the ozone treatment substrate surface then; Again rotation coat 30 nanometer thickness PEDOT:PSS as the anode modification film, 150 ℃ of dryings 10 minutes, with 10 milligrams every milliliter P3HT chlorobenzene solution (containing 10 milligrams of P3HT in every milliliter of chlorobenzene solution) 2000 change directly be spun under the rotating speed of per minutes (rpm) above-mentioned on the substrate of anode modification; 150 ℃ of dryings are 30 minutes then; Naturally cool to room temperature, forming thickness is the conjugated polymer electron donor material layer of 15nm, P3HT and PbSe is dissolved in the mixed solution that chlorobenzene solution obtains (contains 10 milligrams of P3HT in every milliliter of chlorobenzene solution; Contain 50 milligrams of PbSe) under the rotating speed of 1000 commentaries on classics per minutes (rpm), directly be spun on the P3HT film; 80 ℃ of dryings are 30 minutes then, naturally cool to room temperature, and forming thickness is the photoelectric active layer of 50nm; At last, through mask plate 5 * 10
-5The aluminium of vacuum evaporation 150 nanometers obtains conjugated polymer/semiconductor nano plane-body heterojunction solar cell having integrated structure as negative electrode under the handkerchief, and device architecture is shown in Fig. 1 (b).
Fig. 5, Fig. 6 have expressed the plane that present embodiment makes-body heterojunction solar cell having integrated structure through the 532nm of every square centimeter of 100 milliwatt and the current-voltage curve under the 808nm irradiation; As can be seen from the figure; The plane that present embodiment makes-body heterojunction solar cell having integrated structure open circuit voltage under the 532nm of every square centimeter of 100 milliwatt rayed is 0.35 volt; Short circuit current is 1.35 milliamperes every square centimeter; Fill factor, curve factor is 0.44, and conversion efficiency is 0.21%, and device performance has improved 110% than traditional body heterojunction Structure Conversion efficient; Open circuit voltage is 0.38 volt under the 808nm of every square centimeter of 100 milliwatt rayed; Short circuit current is 1.73 milliamperes every square centimeter; Fill factor, curve factor is 0.40, and conversion efficiency is 0.26%, and device performance has improved 160% than traditional body heterojunction Structure Conversion efficient.
There is the transparent conducting glass of ITO (anode) to use liquid detergent, deionized water, acetone, isopropyl alcohol ultrasonic cleaning successively sputter; Use the ozone treatment substrate surface then; Again rotation coat 30 nanometer thickness PEDOT:PSS as the anode modification film, 150 ℃ of dryings 10 minutes, with 10 milligrams every milliliter P3HT chlorobenzene solution (containing 10 milligrams of P3HT in every milliliter of chlorobenzene solution) 3000 change directly be spun under the rotating speed of per minutes (rpm) above-mentioned on the substrate of anode modification; 150 ℃ of dryings are 30 minutes then; Naturally cool to room temperature, forming thickness is the conjugated polymer electron donor material layer of 10nm, P3HT and PbSe is dissolved in the mixed solution that chlorobenzene solution obtains (contains 10 milligrams of P3HT in every milliliter of chlorobenzene solution; Contain 50 milligrams of PbSe) under the rotating speed of 1000 commentaries on classics per minutes (rpm), directly be spun on the P3HT film; 80 ℃ of dryings are 30 minutes then, naturally cool to room temperature, and forming thickness is the photoelectric active layer of 50nm; At last, through mask plate 5 * 10
-5The aluminium of vacuum evaporation 150 nanometers obtains conjugated polymer/semiconductor nano plane-body heterojunction solar cell having integrated structure as negative electrode under the handkerchief, and device architecture is shown in Fig. 1 (b).
Fig. 7, Fig. 8 have expressed the plane that present embodiment makes-body heterojunction solar cell having integrated structure through the 532nm of every square centimeter of 100 milliwatt and the current-voltage curve under the 808nm irradiation; As can be seen from the figure; The plane that present embodiment makes-body heterojunction solar cell having integrated structure open circuit voltage under the 532nm of every square centimeter of 100 milliwatt rayed is 0.38 volt; Short circuit current is 1.12 milliamperes every square centimeter; Fill factor, curve factor is 0.38, and conversion efficiency is 0.16%, and device performance has improved 60% than traditional body heterojunction Structure Conversion efficient; Open circuit voltage is 0.36 volt under the 808nm of every square centimeter of 100 milliwatt rayed; Short circuit current is 1.57 milliamperes every square centimeter; Fill factor, curve factor is 0.36, and conversion efficiency is 0.20%, and device performance has improved 100% than traditional body heterojunction Structure Conversion efficient.
Above embodiment shows that plane-body heterojunction integrated morphology can effectively improve the performance of device.This structure not only improves open circuit voltage, increases short circuit current, has also improved fill factor, curve factor simultaneously, and then has increased the photoelectric conversion efficiency of solar cell.Its cheap cost, simple technology and its remarkable performance have great application prospect it in industry.
Claims (5)
1. plane-body heterojunction solar cell having integrated structure; Comprise the glass substrate (1), anode (2), anode modification layer (3), photoelectricity active layer (4), the negative electrode (5) that stack gradually; It is characterized in that between anode modification layer (3) and photoelectricity active layer (4), being provided with conjugated polymer electron donor material layer (6); Said conjugated polymer electron donor material layer thickness is 2-30nm, and said conjugated polymer electron donor material is selected from: gather (to the inferior ethene of phenylene) class, gather (arlydene ethenylidene) class, gather (to phenylene) class, gather (arlydene) class, polythiophene class, poly quinoline class.
2. a kind of plane according to claim 1-body heterojunction solar cell having integrated structure; It is characterized in that said photoelectricity active layer (4) is the photoelectricity active layer that conjugated polymer electron donor material and semiconductor nano electron acceptor material mix; Wherein, Said conjugated polymer electron donor material is selected from: gather (to the inferior ethene of phenylene) class, gather (arlydene ethenylidene) class, gather (to phenylene) class, gather (arlydene) class, polythiophene class, poly quinoline class, said semiconductor nano electron acceptor material is from the group of III-V family, II-VI family and IV-VI compound semiconductor, to choose.
3. a kind of plane according to claim 1-body heterojunction solar cell having integrated structure is characterized in that said negative electrode comprises the alloy that alkali metal, alkaline-earth metal, aluminium, silver, copper, perhaps above-mentioned metal are formed.
4. the preparation method of plane-body heterojunction solar cell having integrated structure is characterized in that this method step is following:
(1) the ultrasonic cleaning sputter has the transparent conducting glass of ito anode, uses the ozone treatment substrate surface then;
(2) again the rotation coat 30 nanometer thickness PEDOT:PSS as anode modification film, drying;
(3) the conjugated polymer electron donor material is dissolved in the solvent; Method with spin-coating or inkjet printing is coated in it above-mentioned on the substrate of anode modification; Dry 10-48min under 80-250 ℃; Naturally cool to room temperature; Forming thickness is the conjugated polymer electron donor material layer of 2-30nm, and wherein the conjugated polymer electron donor material is selected from: gather (to the inferior ethene of phenylene) class, gather (arlydene ethenylidene) class, gather (to phenylene) class, gather (arlydene) class, polythiophene class, poly quinoline class;
(4) with conjugated polymer electron donor material and semiconductor nano electron acceptor material and solvent; The method of the mixed solution that forms with spin-coating or inkjet printing directly is coated on the conjugated polymer electron donor material layer; Naturally cool to room temperature after the drying, form the photoelectricity active layer;
(5) pass through directly vacuum evaporation metal formation negative electrode on the photoelectricity active layer of mask plate, obtain conjugated polymer/semiconductor nano plane-body heterojunction solar cell having integrated structure.
5. the preparation method of a kind of plane according to claim 4-body heterojunction solar cell having integrated structure, rotating speed is that 1000-3000 changes per minute when it is characterized in that in the said step (3) spin-coating.
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