CN103378293B - A kind of solaode and preparation method thereof - Google Patents
A kind of solaode and preparation method thereof Download PDFInfo
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Abstract
The invention provides a kind of solaode and preparation method thereof.Described solaode includes the substrate, anode layer, anode modification layer, photoelectric active layer, cathodic modification layer and the cathode layer that stack gradually, and wherein, described photoelectric active layer contains two kinds of p-type polymer that n-type fullerene derivate is different with absorbing wavelength.The two kinds of p-type polymer contained in solaode provided by the invention have different absorbing wavelength, the absorption spectrum enabling to photoelectric active layer matches with solar spectrum to a greater extent, thus significantly improving the utilization rate to sunlight and the electricity conversion of described solaode.Additionally, solaode provided by the invention to only include monolayer photoelectric active layer, preparation method simple, with low cost, great prospects for commercial application.
Description
Technical field
The present invention relates to a kind of solaode and preparation method thereof.
Background technology
In recent years, organic solar batteries, is mainly based upon the research of the thin-film solar cells of polymer and causes and pay close attention to widely, and such battery has the advantage that inorganic solar cell is incomparable, such as, cost is low, lightweight, preparation technology simple, can prepare into flexible device etc..Although the energy conversion efficiency of polymer solar cell device is significantly improved at present, but compared with inorganic solar cell, also differs greatly, and performance is also unstable.Therefore, polymer thin-film solar cell will being allowed to obtain practical application, what first have to solution is the problem of the photoelectric transformation efficiency improving such battery.
One of approach of photoelectric transformation efficiency improving polymer thin-film solar cell is to improve the active layer material utilization rate to sunlight.The active layer of traditional solaode is made up of a kind of polymer and a kind of fullerene derivate, and wherein, polymer is main extinction component.It is known that sunlight spectrum covers whole visible region and part ultraviolet region, and polymer is typically only capable to absorb a part of visible ray, so that most sunlight is not obtained by.In the past few years, increasing work concentrates on to synthesize and has on the polymer of relatively wide absorption spectrum.Research shows, utilizes the polymer that the polymer with conjugation side chain or Donor acceptor copolymerization obtain can widen the absorption spectrum of polymer to a certain extent, but the absorption region of homogenous material is still wide not.Another method solving the problem that light absorbs existing is to adopt lamination solar cell, two layer solar cells are respectively adopted two kinds of polymer in ultraviolet-visible district with different absorbing wavelength scope, make the absorption spectrum of entirety widen so that the photoelectric transformation efficiency of solaode increases.But in lamination solar cell, due to the reflection etc. to light of the battery on upper strata, the sunlight intensity arriving lower floor's battery weakens, and this battery preparation technique is more complicated compared with monolayer solaode, and therefore, its application has been also affected by restriction.
Summary of the invention
The invention aims to overcome the defect adopting solar cell photoelectric transformation efficiency that existing method prepares relatively low, and the preparation method that solaode that a kind of electricity conversion is higher and this solaode are provided.
The invention provides a kind of solaode, described solaode includes the substrate, anode layer, anode modification layer, photoelectric active layer, cathodic modification layer and the cathode layer that stack gradually, wherein, described photoelectric active layer contains two kinds of p-type polymer that n-type fullerene derivate is different with absorbing wavelength.
The preparation method that present invention also offers described solaode, the method includes sequentially forming anode modification layer, photoelectric active layer, cathodic modification layer and cathode layer on the substrate with anode layer, wherein, the method forming described photoelectric active layer includes the solution of the two kind p-type polymer different with absorbing wavelength containing n-type fullerene derivate is coated on anode modification layer and is dried.
Two kinds of p-type polymer in solaode provided by the invention are present in same photoelectric active layer, it is possible to absorb respectively and convert the sunlight of different wave length, not interfereing with each other.What is more important, both p-type polymer have different absorbing wavelength, the absorption spectrum enabling to photoelectric active layer matches with solar spectrum to a greater extent, thus significantly improving the utilization rate to sunlight and the electricity conversion of described solaode.Additionally, solaode provided by the invention only includes monolayer photoelectric active layer, preparation method is simple, with low cost, great prospects for commercial application.
The present inventor finds through further investigation, a preferred embodiment of the invention, when the compound method of the solution of the two kind p-type polymer different with absorbing wavelength containing n-type fullerene derivate includes at 40-120 DEG C, by two kinds of different for absorbing wavelength p-type polymer and organic solvent exposure 20 minutes-48 hours, obtain mixed liquor, and this mixed liquor is cooled the temperature to 25-60 DEG C of standing 0.5-48 hour with the speed of 10-30 DEG C/h, when then described mixed liquor being mixed homogeneously with n-type fullerene derivate, two kinds of p-type polymer can form nano wire, it is more beneficial in described photoelectric active layer the formation of p-n junction, it is thus possible to more significantly increase the electricity conversion of solaode.
Other features and advantages of the present invention will be described in detail in detailed description of the invention part subsequently.
Accompanying drawing explanation
Fig. 1 is poly-3-hexyl thiophene, poly-[2,6-(4,4-couple-(2-ethylhexyl) two thiophene-[3,2-b:2 ', 3 '-d] thiophene coughs up)-alternately-4,7-(2,1,3-diazosulfide)] and the ultraviolet-visible absorption spectroscopy figure of mixture；
Fig. 2 is the voltage-current curve of the solaode prepared by embodiment 1 and embodiment 2；
Fig. 3 is the voltage-current curve of the solaode prepared by embodiment 3 and embodiment 4；
Fig. 4 is the voltage-current curve of the solaode prepared by embodiment 5；
Fig. 5 is the voltage-current curve of the solaode prepared by embodiment 6；
Fig. 6 is the voltage-current curve of the solaode prepared by comparative example 1, comparative example 2, comparative example 3.
Detailed description of the invention
Hereinafter the specific embodiment of the present invention is described in detail.It should be appreciated that detailed description of the invention described herein is merely to illustrate and explains the present invention, it is not limited to the present invention.
Solaode provided by the invention includes the substrate, anode layer, anode modification layer, photoelectric active layer, cathodic modification layer and the cathode layer that stack gradually, wherein, described photoelectric active layer contains two kinds of p-type polymer that n-type fullerene derivate is different with absorbing wavelength.
According to the present invention, as long as although described photoelectric active layer can improve the electricity conversion of described solaode containing two kinds of p-type polymer that n-type fullerene derivate is different with absorbing wavelength, and the content of described n-type fullerene derivate and two kinds of p-type polymer is not particularly limited, but so that in photoelectric conversion process, P type polymer and n-type fullerene derivate can mate better, it is more beneficial for the formation of p-n junction, under preferable case, with the n-type fullerene derivate of 100 weight portions for benchmark, the total content of two kinds of p-type polymer is 30-300 weight portion；It is highly preferred that the weight ratio of two kinds of p-type polymer is 0.05-20:1.
According to the present invention, the selectable range of the absorbing wavelength of two kinds of p-type polymer is wider, and in order to improve the utilization rate to sunlight, thus improving optoelectronic transformation efficiency, the difference of the maximum absorption wavelength of two kinds of p-type polymer is preferably 50-500 nanometer.Specifically, the absorbing wavelength of two kinds of p-type polymer can respectively 350-650 nanometer and 600-850 nanometer.
According to the present invention, described p-type polymer can also be existing various can as the polymer of the p-type material of photoelectric active layer, such as, two kinds of p-type polymer can be each independently selected from poly-3-hexyl thiophene (to be called for short: P3HT), gather [2,6-(4,4-pair-(2-ethylhexyl) two thiophene-[3,2-b:2 ', 3 '-d] thiophene coughs up)-alternately-4,7-(2,1,3-diazosulfide)] (be called for short: PSBTBT) and gather [2,6-(4,4-couples-(2-ethylhexyl)-4H-ring penta [2,1-b；3,4-b '] double; two thiophene)-alternately-4,7-(2,1,3-diazosulfide)] (it is called for short: one or more in PCPDTBT).Wherein, the number-average molecular weight of described P3HT can be 20000-30000；The number-average molecular weight of described PSBTBT can be 25000-35000；The number-average molecular weight of described PCPDTBT can be 5000-15000.
According to the present invention, described n-type fullerene derivate can be existing various can as the fullerene derivate of the n-type material of photoelectric active layer, for instance, described n-type fullerene derivate can be connected to the material of organic group outside the cage of fullerene.Described organic group can be aromatic radical, the alkyl of C1-C12, the total number of carbon atoms be 2-12 ester group in one or more.More specifically, described n-type fullerene derivate can be selected from (6, IC61BA) and indenes and C70 double adduct (abbreviation: one or more in IC71BA) 6)-phenyl-C61-methyl butyrate (is called for short: PC61BM), (6,6)-phenyl-C71-methyl butyrate (is called for short: PC71BM), indenes and C60 double adduct (be called for short:.
Above-mentioned p-type polymer and n-type fullerene derivate all can be commercially available.
According to the present invention, the thickness of described photoelectric active layer can carry out selecting and changing in wider scope, as a rule, the thickness increasing described photoelectric active layer can utilize sunlight more fully, but when its thickness is too big, sunlight not only can not be irradiated to the bottom of photoelectric active layer, the manufacturing cost that also can increase solaode and weight, therefore, combined factors from every side considers, it is preferable that in situation, the thickness of described photoelectric active layer is 40-250 nanometer.
The present invention thes improvement is that the photoelectric active layer that have employed the two kind p-type polymer different with absorbing wavelength containing n-type fullerene derivate, and the composition of substrate, anode layer, anode modification layer, cathodic modification layer and cathode layer and thickness all reasonably can select according to existing solaode.Such as, described substrate can be glass or laminated polyester film, and the thickness of described substrate can be 0.2-3.5 millimeter；Described anode layer can be that indium tin oxide (is called for short: ITO) layer, the thickness of described anode layer can be 10-200 nanometer；Described anode modification layer can be that poly-(3,4-rthylene dioxythiophene)-polystyrolsulfon acid (is called for short: PEDOT:PSS) layer, the thickness of described anode modification layer can be 20-60 nanometer；Described cathodic modification layer can be calcium metal layer, and the thickness of described cathodic modification layer can be 5-25 nanometer；Described cathode layer can be metallic aluminum, and the thickness of described cathode layer can be 50-200 nanometer.
The preparation method of solaode provided by the invention includes sequentially forming anode modification layer, photoelectric active layer, cathodic modification layer and cathode layer on the substrate with anode layer, wherein, the method forming described photoelectric active layer includes the solution of the two kind p-type polymer different with absorbing wavelength containing n-type fullerene derivate is coated on anode modification layer and is dried.
According to the present invention, as mentioned above, at the compound method of the solution containing n-type fullerene derivate two kinds of p-type polymer different with absorbing wavelength is preferably included in 40-120 DEG C, by two kinds of different for absorbing wavelength p-type polymer and organic solvent exposure 20 minutes-48 hours, obtain mixed liquor, and this mixed liquor is cooled the temperature to 25-60 DEG C of standing 0.5-48 hour with the speed of 10-30 DEG C/h, then described mixed liquor is mixed homogeneously with n-type fullerene derivate, so can more significantly increase the electricity conversion of solaode.
According to the present invention, described organic solvent can be the existing various organic solvent that can be dissolved by two kinds of p-type polymer.Usually, described organic solvent can be selected from one or more in aromatic hydrocarbons, halogenated alkane；Specifically, can be selected from benzene, toluene, ethylbenzene, dimethylbenzene (including o-Dimethylbenzene, meta-xylene and xylol), chlorobenzene, dichloro-benzenes (including o-dichlorohenzene, m-dichlorobenzene and paracide), trichloro-benzenes (include 1,2,4-trichloro-benzenes, 1,3,5-trichloro-benzenes), one or more in chloroform；Preferably one or more in toluene, xylol, chlorobenzene and o-dichlorohenzene.The consumption of described organic solvent can be the conventional selection of this area, it does not have limit especially.In general, the consumption of described organic solvent so that the total concentration of n-type fullerene derivate and p-type polymer is 15-200 mg/ml, can so can ensure that the solution of the two kind p-type polymer different with absorbing wavelength containing n-type fullerene derivate can be easier to, be uniformly coated on anode modification layer.
According to the present invention, the method that the solution of the two kind p-type polymer different with absorbing wavelength containing n-type fullerene derivate is coated on anode modification layer is known to the skilled person, such as, the methods such as spraying, spin coating, showering, brushing, dipping, inkjet printing, roller bearing printing can be adopted to be coated on anode modification layer by described solution, being preferably spin coating, more preferably the rotating speed of spin coating is 800-3000rpm.Additionally, the temperature that described dry condition includes drying can be 25-150 DEG C, the time can be 5 minutes-48 hours.
In accordance with the present invention it is preferred that, the content of two kinds of p-type polymer that described n-type fullerene derivate is different with absorbing wavelength makes the thickness of the described photoelectric active layer formed be 40-250 nanometer；With the n-type fullerene derivate of 100 weight portions for benchmark, the total content of two kinds of p-type polymer is preferably 30-300 weight portion；It is highly preferred that the weight ratio of two kinds of p-type polymer is 0.05-20:1.
According to the present invention, the selection of described n-type fullerene derivate and p-type type of polymer has been described above, and here will not be described in great detail.
Kind and the thickness of described substrate and anode layer are not particularly limited by the present invention, for instance, described substrate can be glass or laminated polyester film, and the thickness of described substrate can be 0.2-3.5 millimeter；Described anode layer can be indium tin oxide layer, and the thickness of described anode layer can be 10-200 nanometer.
According to the present invention, the method forming described anode modification layer includes to contain on the solution coated anode layer gathering (3,4-rthylene dioxythiophene)-polystyrolsulfon acid and drying；The consumption of described poly-(3,4-ethene dioxythiophene)-polystyrolsulfon acid makes the thickness of anode modification layer be 20-60 nanometer.Wherein, the solid content of the solution containing poly-(3,4-rthylene dioxythiophene)-polystyrolsulfon acid can be generally 1.2-1.4%；Coating and dry method reasonably can select according to the coating and dry method forming photoelectric active layer.
According to the present invention, the method forming described cathodic modification layer can include in calcium metal vacuum evaporation to photoelectric active layer, and the consumption of described calcium metal makes the thickness of cathodic modification layer be 5-25 nanometer.The method forming described cathode layer includes in metallic aluminium vacuum evaporation to cathodic modification layer, and the consumption of described metallic aluminium makes the thickness of cathode layer be 50-200 nanometer.The method of described vacuum evaporation is known to the skilled person, and will not be described in great detail at this.
According to the present invention, the preparation method of solaode provided by the invention preferably also includes the substrate with anode layer successively with water, acetone and each ultrasonic cleaning of isopropanol 15 minutes, then with the ozonization surface with anode layer, with the pollutant removal by anode layer surface.It is known to the skilled person by the condition of ozonization, will not be described in great detail at this.
The preferred embodiment of the present invention described in detail above; but, the present invention is not limited to the detail in above-mentioned embodiment, in the technology concept of the present invention; technical scheme can being carried out multiple simple variant, these simple variant belong to protection scope of the present invention.
It is further to note that each the concrete technical characteristic described in above-mentioned detailed description of the invention, in reconcilable situation, it is possible to be combined by any suitable mode.In order to avoid unnecessary repetition, various possible compound modes are no longer illustrated by the present invention separately.
Additionally, can also carry out combination in any between the various different embodiment of the present invention, as long as it is without prejudice to the thought of the present invention, it should be considered as content disclosed in this invention equally.
Hereinafter will be described the present invention by embodiment.
In following example and comparative example:
P3HT purchased from American Sigma-Aldrich, number-average molecular weight is 25000；
PSBTBT is purchased from Jiguang Technology Corporation, and number-average molecular weight is 30000；
PCPDTBT is purchased from Jiguang Technology Corporation, and number-average molecular weight is 10000；
PEDOT:PSS aqueous solution is purchased from Bayer A.G, and density is 1 gram per centimeter3, solid content is 1.4%, and electrical conductivity is 10 Siemens/cm；
PC61BM purchased from American Sigma-Aldrich；
PC71BM purchased from American Sigma-Aldrich.
In following example and comparative example, the voltage that the open-circuit voltage of solaode records when being battery two ends open circuit；The electric current that the short circuit current of solaode records when being battery plus-negative plate short circuit；Current-voltage curve according to measured solaode, it is possible to calculate voltage and the amp product of each point, can obtain peak power output, and thus can calculate the fill factor, curve factor and photoelectric transformation efficiency that obtain solaode further.
Embodiment 1
This embodiment is used for solaode provided by the invention and preparation method thereof is described.
(1) preparation of the solution containing n-type fullerene derivate two kind p-type polymer different with absorbing wavelength:
10 milligrams of P3HT and 10 milligrams of PSBTBT are joined in 1 milliliter of xylol, and the mixed liquor obtained is heated to 80 DEG C of maintenances 0.5 hour, then slowly cool to 40 DEG C with the speed of 20 DEG C/h and stand 36 hours；In this mixed liquor, add 20 milligrams of PC61BM, stir 20 minutes mix homogeneously；
(2) preparation of solaode:
By the transparent conducting glass with indium tin oxide (ITO) layer (100 nanometers), (upper and lower surface area is 0.04cm2, thickness is 2 millimeters) successively with deionized water, acetone, each ultrasonic cleaning of isopropanol 15 minutes, then use ozonization substrate surface；Being spin-coated on indium tin oxide layer by PEDOT:PSS aqueous solution, the rotating speed of spin coating is 800rpm, and dries 15 minutes at 150 DEG C, obtains the anode modification layer that thickness is 40 nanometers.The solution of the two kind p-type polymer different with absorbing wavelength containing n-type fullerene derivate step (1) obtained is spin-coated on anode modification layer, the rotating speed of spin coating is 800rpm, then keep 30 minutes at 150 DEG C, natural cooling, obtain the photoelectric active layer that thickness is 40 nanometers.Last 2 × 10-6In calcium metal vacuum evaporation to photoelectric active layer, the cathodic modification layer that thickness is 10 nanometers will be formed under handkerchief；And 2 × 10-6In metallic aluminium vacuum evaporation to negative electrode decorative layer, the cathode layer that thickness is 100 nanometers will be formed, obtain solaode T1 under handkerchief.
The ultraviolet-visible absorption spectroscopy figure of P3HT, PSBTBT and mixture thereof is as shown in Figure 1, as can be seen from the figure, the absorbing wavelength that the absorbing wavelength of P3HT is the mixture that absorbing wavelength is 600-850nm, P3HT and PSBTBT of 350-650nm, PSBTBT is 350-850nm.
Solaode T1 100 milliwatts/centimetre2Simulated solar irradiation irradiate under voltage-current curve as in figure 2 it is shown, can draw from figure, open-circuit voltage is 0.65 volt, and short circuit current is 7.2 milliamperes/centimetre2, fill factor, curve factor is 43%, and photoelectric transformation efficiency is 2.4%.
Embodiment 2
This embodiment is used for solaode provided by the invention and preparation method thereof is described.
(1) preparation of the solution containing n-type fullerene derivate two kind p-type polymer different with absorbing wavelength:
1 milligram of P3HT and 19 milligrams of PSBTBT is joined in 1 milliliter of xylol, and the mixed liquor obtained is heated to 40 DEG C of maintenances 20 minutes, then slowly cool to 25 DEG C with the speed of 10 DEG C/h and stand 48 hours；In this mixed liquor, add 7 milligrams of PC71BM, stir 20 minutes mix homogeneously；
(2) preparation of solaode:
By the transparent conducting glass with indium tin oxide (ITO) layer (10 nanometers), (upper and lower surface area is 0.04cm2, thickness is 3.5 millimeters) successively with deionized water, acetone, each ultrasonic cleaning of isopropanol 15 minutes, then use ozonization substrate surface；Being spin-coated on indium tin oxide layer by PEDOT:PSS aqueous solution, the rotating speed of spin coating is 800rpm, and dries 15 minutes at 150 DEG C, obtains the anode modification layer that thickness is 60 nanometers.The solution of the two kind p-type polymer different with absorbing wavelength containing n-type fullerene derivate step (1) obtained is spin-coated on anode modification layer, the rotating speed of spin coating is 800rpm, then keep 15 minutes at 150 DEG C, natural cooling, obtain the photoelectric active layer that thickness is 250 nanometers.Last 2 × 10-6In calcium metal vacuum evaporation to photoelectric active layer, the cathodic modification layer that thickness is 5 nanometers will be formed under handkerchief；And 2 × 10-6In metallic aluminium vacuum evaporation to negative electrode decorative layer, the cathode layer that thickness is 50 nanometers will be formed, obtain solaode T2 under handkerchief.
Solaode T2 100 milliwatts/centimetre2Simulated solar irradiation irradiate under voltage-current curve as in figure 2 it is shown, can draw from figure, open-circuit voltage is 0.65 volt, and short circuit current is 6.1 milliamperes/centimetre2, fill factor, curve factor is 41%, and photoelectric transformation efficiency is 1.9%.
Embodiment 3
This embodiment is used for solaode provided by the invention and preparation method thereof is described.
(1) preparation of the solution containing n-type fullerene derivate two kind p-type polymer different with absorbing wavelength:
19 milligrams of P3HT and 1 milligram of PCPDTBT (absorbing wavelength is 600-800 nanometer) are joined in 1 milliliter of xylol, and the mixed liquor obtained is heated to 120 DEG C of maintenances 48 hours, then slowly cool to 60 DEG C with the speed of 30 DEG C/h and stand 0.5 hour；In this mixed liquor, add 65 milligrams of PC61BM, stir 20 minutes mix homogeneously；
(2) preparation of solaode:
By the transparent conducting glass with indium tin oxide (ITO) layer (200 nanometers), (upper and lower surface area is 0.04cm2, thickness is 0.2 millimeter) successively with deionized water, acetone, each ultrasonic cleaning of isopropanol 15 minutes, then use ozonization substrate surface；Being spin-coated on indium tin oxide layer by PEDOT:PSS aqueous solution, the rotating speed of spin coating is 800rpm, and dries 15 minutes at 150 DEG C, obtains the anode modification layer that thickness is 20 nanometers.The solution of the two kind p-type polymer different with absorbing wavelength containing n-type fullerene derivate step (1) obtained is spin-coated on anode modification layer, the rotating speed of spin coating is 800rpm, then keep 60 minutes at 110 DEG C, natural cooling, obtain the photoelectric active layer that thickness is 100 nanometers.Last 2 × 10-6In calcium metal vacuum evaporation to photoelectric active layer, the cathodic modification layer that thickness is 25 nanometers will be formed under handkerchief；And 2 × 10-6In metallic aluminium vacuum evaporation to negative electrode decorative layer, the cathode layer that thickness is 200 nanometers will be formed, obtain solaode T3 under handkerchief.
Solaode T3 100 milliwatts/centimetre2Simulated solar irradiation irradiate under voltage-current curve as it is shown on figure 3, can draw from figure, open-circuit voltage is 0.65 volt, and short circuit current is 6.6 milliamperes/centimetre2, fill factor, curve factor is 43%, and photoelectric transformation efficiency is 2.2%.
Embodiment 4
This embodiment is used for solaode provided by the invention and preparation method thereof is described.
Solaode is prepared according to the method for embodiment 1, the difference is that, in step (1), when preparation contains the solution of the n-type fullerene derivate two kind p-type polymer different with absorbing wavelength, the addition of PC61BM is 70 milligrams, obtains solaode T4.
Solaode T4 100 milliwatts/centimetre2Simulated solar irradiation irradiate under voltage-current curve as it is shown on figure 3, can draw from figure, open-circuit voltage is 0.65 volt, and short circuit current is 6.0 milliamperes/centimetre2, fill factor, curve factor is 41%, and photoelectric transformation efficiency is 1.8%.
Embodiment 5
This embodiment is used for solaode provided by the invention and preparation method thereof is described.
Solaode is prepared according to the method for embodiment 1, the difference is that, the solution containing n-type fullerene derivate two kind p-type polymer different with absorbing wavelength is prepared as follows:
At 100 DEG C, 10 milligrams of P3HT, 10 milligrams of PSBTBT and 20 milligrams of PC61BM are joined in 1 milliliter of xylol and are uniformly mixed, and stands 1 hour, obtain solaode T5.
Solaode T5 100 milliwatts/centimetre2Simulated solar irradiation irradiate under voltage-current curve as shown in Figure 4, can draw from figure, open-circuit voltage is 0.66 volt, and short circuit current is 5.1 milliamperes/centimetre2, fill factor, curve factor is 41%, and photoelectric transformation efficiency is 1.7%.
Embodiment 6
This embodiment is used for solaode provided by the invention and preparation method thereof is described.
Solaode is prepared according to the method for embodiment 1, the difference is that, in step (1), when preparation contains the solution of the n-type fullerene derivate two kind p-type polymer different with absorbing wavelength, the PC61BM IC61BA of identical weight part (purchased from American solarmer company) substitutes, and obtains solaode T6.
Solaode T6 100 milliwatts/centimetre2Simulated solar irradiation irradiate under voltage-current curve as it is shown in figure 5, can draw from figure, open-circuit voltage is 0.59 volt, and short circuit current is 6.4 milliamperes/centimetre2, fill factor, curve factor is 35%, and photoelectric transformation efficiency is 1.6%.
Comparative example 1
This comparative example is used for reference solaode and preparation method thereof is described.
Solaode is prepared according to the method for embodiment 1, the difference is that, in step (1), the PSBTBT P3HT of identical weight part substitutes, and obtains solaode DT1.
Solaode DT1 100 milliwatts/centimetre2Simulated solar irradiation irradiate under voltage-current curve as shown in Figure 6, can draw from figure, open-circuit voltage is 0.59 volt, and short circuit current is 4.0 milliamperes/centimetre2, fill factor, curve factor is 41%, and photoelectric transformation efficiency is 1.2%.
Comparative example 2
This comparative example is used for reference solaode and preparation method thereof is described.
Solaode is prepared according to the method for embodiment 1, the difference is that, in step (1), the P3HT PSBTBT of identical weight part substitutes, and obtains solaode DT2.
Solaode DT2 100 milliwatts/centimetre2Simulated solar irradiation irradiate under voltage-current curve as shown in Figure 6, can draw from figure, open-circuit voltage is 0.66 volt, and short circuit current is 4.1 milliamperes/centimetre2, fill factor, curve factor is 34%, and photoelectric transformation efficiency is 1.1%.
Comparative example 3
This comparative example is used for reference solaode and preparation method thereof is described.
Solaode is prepared according to the method for embodiment 1, the difference is that, in step (1), P3HT and the PSBTBT PCPDTBT of identical weight part substitutes, and obtains solaode DT3.
Solaode DT3 100 milliwatts/centimetre2Simulated solar irradiation irradiate under voltage-current curve as shown in Figure 6, can draw from figure, open-circuit voltage is 0.47 volt, and short circuit current is 6.1 milliamperes/centimetre2, fill factor, curve factor is 33%, and photoelectric transformation efficiency is 1.1%.
As can be seen from the above results, owing to the photoelectric active layer of embodiment 1-6 containing two kinds of p-type polymer that absorbing wavelength is different, the absorbing wavelength scope enabling to photoelectric active layer is wider, match with solar spectrum to a greater extent, and the electricity conversion of the solaode obtained is higher than comparative example 1-3.From contrast with embodiment 4 and embodiment 6 of embodiment 1 it can be seen that when the content of p-type polymer or the kind of n-type fullerene derivate are in the preferable range of the present invention, it is possible to obtain the solaode that electricity conversion is higher.From the contrast of embodiment 1 and embodiment 5 it can be seen that adopt the currently preferred method preparation solution containing the different two kinds of p-type polymer of n-type fullerene derivate and absorbing wavelength, the combination property of the solaode obtained is better.Additionally, solaode provided by the invention to only include monolayer photoelectric active layer, preparation method simple, with low cost.
Claims (11)
1. the preparation method of a solaode, the method includes sequentially forming anode modification layer, photoelectric active layer, cathodic modification layer and cathode layer on the substrate with anode layer, it is characterized in that, the method forming described photoelectric active layer includes the solution of the two kind p-type polymer different with absorbing wavelength containing n-type fullerene derivate is coated on anode modification layer and is dried；The compound method of the solution of the described two kind p-type polymer different with absorbing wavelength containing n-type fullerene derivate includes at 40-120 DEG C, by two kinds of different for absorbing wavelength p-type polymer and organic solvent exposure 20 minutes-48 hours, obtain mixed liquor, and this mixed liquor is cooled the temperature to 25-60 DEG C of standing 0.5-48 hour with the speed of 10-30 DEG C/h, then described mixed liquor is mixed homogeneously with n-type fullerene derivate.
2. the preparation method of solaode according to claim 1, wherein, with the n-type fullerene derivate of 100 weight portions for benchmark, total consumption of two kinds of p-type polymer is 30-300 weight portion.
3. the preparation method of solaode according to claim 2, wherein, the weight ratio of two kinds of p-type polymer is 0.05-20:1.
4. the preparation method of the solaode according to claim 1,2 or 3, wherein, the difference of the maximum absorption wavelength of two kinds of p-type polymer is 50-500 nanometer.
5. the preparation method of solaode according to claim 4, wherein, the absorbing wavelength of two kinds of p-type polymer respectively 350-650 nanometer and 600-850 nanometer.
6. the preparation method of solaode according to claim 5, wherein, two kinds of p-type polymer are each independently selected from poly-3-hexyl thiophene, gather [2,6-(4,4-is double; two-and (2-ethylhexyl) two thiophene-[3,2-b:2 ', 3 '-d] thiophene coughs up)-alternately-4,7-(2,1,3-diazosulfide)] and poly-[2,6-(4,4-pair-(2-ethylhexyl)-4H-ring penta [2,1-b；3,4-b '] double; two thiophene)-alternately-4,7-(2,1,3-diazosulfide)] and in one or more.
7. the preparation method of solaode according to claim 1 and 2, wherein, described n-type fullerene derivate is selected from (6,6) one or more in-phenyl-C61-methyl butyrate, (6,6)-phenyl-C71-methyl butyrate, indenes and C60 double adduct and indenes and C70 double adduct.
8. the preparation method of solaode according to claim 7, wherein, described n-type fullerene derivate is (6,6)-phenyl-C61-methyl butyrate and/or (6,6)-phenyl-C71-methyl butyrate.
9. the preparation method of solaode according to claim 1 and 2, wherein, the thickness of described photoelectric active layer is 40-250 nanometer.
10. the preparation method of solaode according to claim 1 and 2, wherein, described substrate is glass or laminated polyester film, and the thickness of described substrate is 0.2-3.5 millimeter；Described anode layer is indium tin oxide layer, and the thickness of described anode layer is 10-200 nanometer；Described anode modification layer is poly-(3,4-rthylene dioxythiophene)-polystyrolsulfon acid layer, and the thickness of described anode modification layer is 20-60 nanometer；Described cathodic modification layer is metal calcium layer, and the thickness of described cathodic modification layer is 5-25 nanometer；Described cathode layer is metallic aluminum, and the thickness of described cathode layer is 50-200 nanometer.
11. the preparation method of solaode according to claim 1, wherein, the method forming described cathodic modification layer includes in calcium metal vacuum evaporation to photoelectric active layer, and the consumption of described calcium metal makes the thickness of cathodic modification layer be 5-25 nanometer；The method forming described cathode layer includes in metallic aluminium vacuum evaporation to cathodic modification layer, and the consumption of described metallic aluminium makes the thickness of cathode layer be 50-200 nanometer.
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