CN105448524A - Silver-doped organometallic perovskite material, solar cell and manufacturing method thereof - Google Patents
Silver-doped organometallic perovskite material, solar cell and manufacturing method thereof Download PDFInfo
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- CN105448524A CN105448524A CN201410452093.1A CN201410452093A CN105448524A CN 105448524 A CN105448524 A CN 105448524A CN 201410452093 A CN201410452093 A CN 201410452093A CN 105448524 A CN105448524 A CN 105448524A
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Abstract
The invention discloses a silver-doped organometallic perovskite material, a solar cell and a manufacturing method thereof. The general formula of the silver-doped organometallic perovskite material is shown as AB1-xAgxX3, wherein A is an organic group, B is Pb or Sn, X is one or combination of Cl, Br, I and F, and x is greater than 0 and less than or equal to 0.15. According to the Silver-doped organometallic perovskite material, the solar cell and the manufacturing method thereof, the Ag doping enhances light absorption in the near infrared section, the degree of crystallinity is significantly increases with 5% Ag doped, the photoelectric conversion efficiency under the doped situation reaches 13.3% when the silver-doped organometallic perovskite material is applied to a solar cell device (ITO/PEDOT:PSS/Perovskite/PCBM/Al), and is increased by 30% when compared with the conversion efficiency(10.3%) under the un-doped situation.
Description
Technical field
The application belongs to field of photoelectric devices, particularly relates to a kind of Ag doping organic metal perovskite material, solar cell and preparation method thereof.
Background technology
Organic metal Ca-Ti ore type solar cell is the novel solar battery having prospect occurred recent years.2009, the people such as Miyasaka were with mesoporous TiO 2 (TiO
2) as light anode, with organic metal perovskite (CH
3nH
3pbX
3, X=I, Br) and as light absorbing zone, prepared solar cell, efficiency reaches 3.81%, but to use at that time be liquid electrolyte, the time that organic metal perovskite is survived in liquid electrolyte is very short.2012,
deng people 2,2', 7,7'-tetra-[N, N-bis-(4-methoxyphenyl) is amino]-9,9'-spiral shell two fluorenes (Spiro-OMeTAD) substitute original liquid electrolyte, and the efficiency of the organic metal Ca-Ti ore type solar cell of preparation reaches 9.7%.Recently, the efficiency of this kind of solar cell breaches 19%, has very much the prospect commercially produced.
Till now, the how available general formula ABX of the organic metal perovskite material related in research
3represent, wherein A represents organic group, and as methylamino, ethylamino-, carbonamidine base, B represents Pb or Sn, and X represents Cl, Br, I and combination thereof.The efficiency of Ca-Ti ore type solar cell to be improved further, must optimize and revise further the structure of organic metal perovskite, optics and electrology characteristic.Organic metal perovskite material has stronger absorption to light, but its absorptance in blue green light district ruddiness and near infrared region much better than.If can absorption spectrum be regulated, near infrared absorption district is strengthened to some extent, thus make corresponding photovoltaic device have higher photoelectric current.Though there is report to show that in organic metal perovskite material, charge carrier has longer diffusion length (relative to P3HT, the organic materials such as PCBM), but typical thickness of optimizing is at about 300nm, which imply that and be necessary that a nearly step improves the transfer ability of charge carrier.
Summary of the invention
The object of the present invention is to provide a kind of Ag doping organic metal perovskite material, solar cell and preparation method thereof, to overcome deficiency of the prior art.
For achieving the above object, the invention provides following technical scheme:
The embodiment of the present application discloses a kind of general formula and is expressed as AB
1-xag
xx
3ag doping organic metal perovskite material, wherein, A is organic group, B to be Pb or Sn, X be Cl, Br, I, F or its combination, 0 < x≤0.15.
Above-mentionedly be expressed as AB
1-xag
xx
3ag doping organic metal perovskite material be pure phase organic metal perovskite.
Preferably, in above-mentioned Ag doping organic metal perovskite material, x=0.05.
Preferably, in above-mentioned Ag doping organic metal perovskite material, described organic group is methylamino, ethylamino-or carbonamidine base.
Correspondingly, the embodiment of the present application also discloses a kind of preparation method of Ag doping organic metal perovskite material, comprises step:
(1), a certain amount of first raw material, the second raw material and silver-colored source material is taken respectively, wherein, first raw material is selected from one or more the mixture in methylamine halogen, ethamine halogen or carbonamidine halogen, second raw material is selected from one or more the mixture in lead halide, tin halides, the raw material taken is added the solvent of certain volume, fully obtain precursor solution after mixing;
(2), to precursor solution carry out drying and sintering, obtain perovskite material.
In the preparation method of above-mentioned Ag doping organic metal perovskite material, silver-colored source material is preferably AgCl, AgBr, AgI, AgF or AgNO
3deng salt.
The embodiment of the present application also discloses a kind of solar cell, comprises absorbed layer, the Ag doping organic metal perovskite material described in described absorbed layer adopts.
Correspondingly, the embodiment of the present application also discloses a kind of manufacture method of solar cell, comprising:
(1) Ag doping organic metal perovskite precursor solution, is prepared;
(2), in substrate, the first electrode layer and the first conductive layer is made successively;
(3), by precursor solution be spun on the first conductive layer, after heat treatment, form Ag doping organic metal perovskite thin film;
(4), on the Ag doping organic metal perovskite thin film obtained, the second conductive layer and the second electrode lay is formed successively.
Preferably, in the manufacture method of above-mentioned solar cell, in described step (1), according to the Ag doping concentration of setting, take a certain amount of first raw material, the second raw material and silver-colored source material respectively, wherein, first raw material is selected from one or more the mixture in methylamine halogen, ethamine halogen or carbonamidine halogen, second raw material is selected from one or more the mixture in lead halide, tin halides, the raw material taken is added the solvent of certain volume, fully obtains precursor solution after mixing.
Preferably, in the manufacture method of above-mentioned solar cell, in described step (2), rigidity or flexible substrates are chosen in substrate; Rigid basement comprises glass etc., and flexible substrates comprises PETG (PET), PEN (PEN), polyimides, but is not limited to above several substrate.
Preferably, in the manufacture method of above-mentioned solar cell, the material of described first electrode layer is ITO or FTO, and processing method also can be sputtering, vapour deposition process (CVD), thermal evaporation, sol-gal process etc.; The material of described first conductive layer is poly-(3,4-ethylene dioxythiophene), kayexalate salt (PEDOT:PSS), zinc oxide (ZnO), titanium oxide (TiO
2) or nickel oxide (NiO).
Preferably, in the manufacture method of above-mentioned solar cell, in described step (3), after precursor solution is spun on the first conductive layer, anneal 2-3 hour between 80 DEG C to 90 DEG C.
Preferably, in the manufacture method of above-mentioned solar cell, the material of described second conductive layer is (6,6) phenyl C61-methyl butyrate (PC61BM), (6,6) phenyl C71-methyl butyrate (PC71BM), (6,6) phenyl C61-butyric acid three octyloxy benzene methyl (PCBB-C8) or 2,2', 7,7'-tetra-[N, N-bis-(4-methoxyphenyl) is amino]-9,9'-spiral shell two fluorenes (Spiro-OMeTAD), the second conductive layer adopts the coating methods such as vapour deposition, blade coating, volume to volume; The material of described the second electrode lay is magnesium/silver, calcium/aluminium, silver, aluminium, lithium fluoride/aluminium or gold electrode.Wherein, magnesium/silver, calcium/aluminium, lithium fluoride/aluminium refer to the double membrane structure of two kinds of materials.
Compared with prior art, the invention has the advantages that:
1, Ag doping makes light absorption strengthen in near-infrared section.
2, the lower degree of crystallinity of 5%Ag doping significantly improves.
3, be applied to (ITO/PEDOT:PSS/Perovskite/PCBM/Al) in solar cell device, photoelectric conversion efficiency under doping situation reaches 13.3%, has the lifting of 30% relative to the conversion efficiency (10.3%) under situation of not adulterating.
Accompanying drawing explanation
In order to be illustrated more clearly in the embodiment of the present application or technical scheme of the prior art, be briefly described to the accompanying drawing used required in embodiment or description of the prior art below, apparently, the accompanying drawing that the following describes is only some embodiments recorded in the application, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to these accompanying drawings.
Figure 1 shows that the x-ray diffraction pattern of the ITO/PEDOT:PSS/Perovskite film under different Ag doping;
Figure 2 shows that the optical absorption spectra of the ITO/PEDOT:PSS/Perovskite film under different Ag doping;
Figure 3 shows that the I-V curve chart of Ag doping (5%) and non-doped perovskite type solar cell, battery structure is ITO/PEDOT:PSS/Perovskite/PC
61bM/TiO
2/ Al.
Embodiment
Electronic structure calculates and shows, the s track state of s, p track state and halogen that the valence band of organic metal perovskite material and conduction band mainly contain Pb (Sn) is formed.The present invention Ag replaces part Pb (Sn) and regulates and controls the structure of organic metal perovskite, optics and electrology characteristic, thus realizes the object improving photovoltaic performance.We it will be appreciated that, Ag doping will significantly improve the absorbent properties of material in red light district, and improves degree of crystallinity.Ag is adulterated organic calcium metal titanium ore materials application in photovoltaic device, adopt same device architecture, its efficiency has the lifting of 30%.
Below in conjunction with the accompanying drawing in the embodiment of the present invention, be described in detail the technical scheme in the embodiment of the present invention, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, the every other embodiment that those of ordinary skill in the art obtain under the prerequisite not making creative work, all belongs to the scope of protection of the invention.
Be made as example below with solar cell, but one skilled in the art will appreciate that the perovskite material of the silver-doped in this case can be applied to other photoelectric devices such as fet, light emitting diode, transducer, photo-detector equally.
The manufacture method of Ag doping organic metal Ca-Ti ore type solar cell is as follows:
Embodiment 1
(1) Ag doping organic metal perovskite precursor solution, is prepared.
Take 0.7631 gram of CH
3nH
3i, 0.4227 gram of PbCl
2, 0.0115 gram of AgCl, add 2 milliliters of N, N-2 methylformamide (DMF), 60 DEG C of thermal station stir and within 8 hours, obtains clarifying precursor solution, wherein the doping ratio of Ag is 5%.
(2), on glass, plate one deck ITO, by etching, obtain 6 pieces of ITO regions, with washing agent, ethanol, acetone and isopropyl alcohol ultrasonic cleaning ito glass sheet respectively.Etching ito glass, for the preparation of device, does not etch ITO for film characterization.
(3), spin coating one deck 35nm is thick on ito glass sheet PEDOT:PSS, the precursor solution spin coating thin film of preparation in rear step of annealing (1), then anneals 165 minutes at 84 DEG C.
(4), on perovskite rete spin coating one deck PC61BM, PC61BM concentration is 20mg/ml, and flux is chlorobenzene.Be coated with last layer TiO again
2film, the Al electrode that after annealing, evaporation one deck 100nm is thick.The area of battery is 0.12cm
2.
Embodiment 2
The doping ratio of Ag in embodiment 1 step (1) is adjusted to 2.5%, other conditions making solar cell identical with embodiment 1.
Embodiment 3
The doping ratio of Ag in embodiment 1 step (1) is adjusted to 7.5%, other conditions making solar cell identical with embodiment 1.
Embodiment 4
The doping ratio of Ag in embodiment 1 step (1) is adjusted to 10%, other conditions making solar cell identical with embodiment 1.
Comparative example
The doping ratio of Ag in embodiment 1 step (1) is adjusted to 0%, other conditions making solar cell identical with embodiment 1.
Fig. 1 shows the x-ray diffraction pattern in embodiment 1 to embodiment 4 and comparative example under different levels of doping, wherein under x=0.05 (Ag doping content is 5%) situation, film has stronger diffracted intensity, and this shows that the Ag doping of debita spissitudo has and promotes that perovskite coordinates the effect of phase.
Fig. 2 shows the optical absorption spectra in embodiment 1 to embodiment 4 and comparative example under different levels of doping.Can find out in figure, Ag doping makes the absorption of blue green light place weaken gradually, goes out to strengthen at near-infrared.
Fig. 3 is the I-V curve comparison figure of the Ca-Ti ore type solar cell that embodiment 1 is prepared with comparative example, and as can be seen from the figure, the conversion efficiency of the battery under 5%Ag doping situation has the lifting of 30% relative to situation of not adulterating.
Following table is the performance parameter contrast table of the Ca-Ti ore type solar cell that embodiment 1 is prepared with comparative example, and the performance of the solar cell as can be seen from the table after Ag doping has obvious lifting.
It should be noted that, in this article, the such as relational terms of first and second grades and so on is only used for an entity or operation to separate with another entity or operating space, and not necessarily requires or imply the relation that there is any this reality between these entities or operation or sequentially.And, term " comprises ", " comprising " or its any other variant are intended to contain comprising of nonexcludability, thus make to comprise the process of a series of key element, method, article or equipment and not only comprise those key elements, but also comprise other key elements clearly do not listed, or also comprise by the intrinsic key element of this process, method, article or equipment.When not more restrictions, the key element limited by statement " comprising ... ", and be not precluded within process, method, article or the equipment comprising described key element and also there is other identical element.
The above is only the embodiment of the application; it should be pointed out that for those skilled in the art, under the prerequisite not departing from the application's principle; can also make some improvements and modifications, these improvements and modifications also should be considered as the protection range of the application.
Claims (10)
1. a general formula is expressed as AB
1-xag
xx
3ag doping organic metal perovskite material, wherein, A is organic group, B to be Pb or Sn, X be Cl, Br, I, F or its combination, 0 < x≤0.15.
2. Ag doping organic metal perovskite material according to claim 1, is characterized in that: x=0.05.
3. Ag doping organic metal perovskite material according to claim 1, is characterized in that: described organic group is methylamino, ethylamino-or carbonamidine base.
4. the preparation method of the arbitrary described Ag doping organic metal perovskite material of claims 1 to 3, is characterized in that, comprise step:
(1), a certain amount of first raw material, the second raw material and silver-colored source material is taken respectively; wherein; first raw material is selected from one or more the mixture in methylamine halogen, ethamine halogen or carbonamidine halogen; second raw material is selected from one or more the mixture in lead halide, tin halides; the raw material taken is added the solvent of certain volume, fully obtain precursor solution after mixing;
(2), to precursor solution carry out drying and sintering, obtain perovskite material.
5. a solar cell, comprises absorbed layer, it is characterized in that: described absorbed layer adopts Ag doping organic metal perovskite material according to claim 1.
6. the manufacture method of solar cell according to claim 5, is characterized in that, comprising:
(1) Ag doping organic metal perovskite precursor solution, is prepared;
(2), in substrate, the first electrode layer and the first conductive layer is made successively;
(3), by precursor solution be spun on the first conductive layer, after heat treatment, form Ag doping organic metal perovskite thin film;
(4), on the Ag doping organic metal perovskite thin film obtained, the second conductive layer and the second electrode lay is formed successively.
7. the manufacture method of solar cell according to claim 6, it is characterized in that, in described step (1), according to the Ag doping concentration of setting, take a certain amount of first raw material, the second raw material and silver-colored source material respectively, wherein, first raw material is selected from one or more the mixture in methylamine halogen, ethamine halogen or carbonamidine halogen, second raw material is selected from one or more the mixture in lead halide, tin halides, the raw material taken is added the solvent of certain volume, fully obtain precursor solution after mixing.
8. the manufacture method of solar cell according to claim 6, is characterized in that, the material of described first electrode layer is ITO or FTO; The material of described first conductive layer is poly-(3,4-ethylene dioxythiophene), kayexalate salt (PEDOT:PSS), zinc oxide (ZnO), titanium oxide (TiO
2) or nickel oxide (NiO).
9. the manufacture method of solar cell according to claim 6, is characterized in that, in described step (3), after precursor solution is spun on the first conductive layer, anneal 2-3 hour between 80 DEG C to 90 DEG C.
10. the manufacture method of solar cell according to claim 6, it is characterized in that, the material of described second conductive layer is (6,6) phenyl C61-methyl butyrate (PC61BM), (6,6) phenyl C71-methyl butyrate (PC71BM), (6,6) phenyl C61-butyric acid three octyloxy benzene methyl (PCBB-C8) or 2,2', 7,7'-tetra-[N, N-bis-(4-methoxyphenyl) is amino]-9,9'-spiral shell two fluorenes (Spiro-OMeTAD); The material of described the second electrode lay is magnesium/silver, calcium/aluminium, silver, aluminium, lithium fluoride/aluminium or gold electrode.
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| CN105702865A (en) * | 2016-04-05 | 2016-06-22 | 河北大学 | Metal-ion-doped perovskite thin film, preparation method and application therefor |
| CN105789447A (en) * | 2016-04-05 | 2016-07-20 | 天津市职业大学 | Perovskite solar cell light absorption layer coating liquid and preparation method thereof |
| CN107993848A (en) * | 2017-11-08 | 2018-05-04 | 华中科技大学 | Based on titania-doped perovskite solar cell of nickel and preparation method thereof |
| CN111470528A (en) * | 2020-04-11 | 2020-07-31 | 上海科技大学 | Tin-containing semiconductor material and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105702865A (en) * | 2016-04-05 | 2016-06-22 | 河北大学 | Metal-ion-doped perovskite thin film, preparation method and application therefor |
| CN105789447A (en) * | 2016-04-05 | 2016-07-20 | 天津市职业大学 | Perovskite solar cell light absorption layer coating liquid and preparation method thereof |
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| CN107993848A (en) * | 2017-11-08 | 2018-05-04 | 华中科技大学 | Based on titania-doped perovskite solar cell of nickel and preparation method thereof |
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| CN111470528A (en) * | 2020-04-11 | 2020-07-31 | 上海科技大学 | Tin-containing semiconductor material and preparation method thereof |
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