CN105448524B - Ag doping organic metal perovskite material, solar cell and preparation method thereof - Google Patents
Ag doping organic metal perovskite material, solar cell and preparation method thereof Download PDFInfo
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- CN105448524B CN105448524B CN201410452093.1A CN201410452093A CN105448524B CN 105448524 B CN105448524 B CN 105448524B CN 201410452093 A CN201410452093 A CN 201410452093A CN 105448524 B CN105448524 B CN 105448524B
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Abstract
This application discloses a kind of Ag doping organic metal perovskite material, solar cell and preparation method thereof, Ag doping organic metal perovskite material formula is expressed as AB1‑xAgxX3, wherein, A is organic group, and B is Pb or Sn, X Cl, Br, I, F or it is combined, 0 ＜ x≤0.15.In the present invention, Ag, which is adulterated, causes light absorbs to strengthen in near-infrared section, and the lower crystallinity of 5%Ag doping significantly improves, and is applied in solar cell device（ITO/PEDOT:PSS/Perovskite/PCBM/Al）, the photoelectric transformation efficiency under situation is adulterated up to 13.3%, relative to undoped with the conversion efficiency under situation（10.3%）There is 30% lifting.
Description
Technical field
The application belongs to field of photoelectric devices, more particularly to a kind of Ag doping organic metal perovskite material, solar energy
Battery and preparation method thereof.
Background technology
Organic metal Ca-Ti ore type solar cell is the novel solar battery of the great prospect occurred recent years.
2009, Miyasaka et al. mesoporous TiO 2 (TiO2) light anode is used as, with organic metal perovskite (CH3NH3PbX3,
X=I, Br) light absorbing layer is used as, solar cell is prepared for, efficiency reaches 3.81%, but it is liquid electricity to use at that time
Xie Zhi, the time that organic metal perovskite is survived in liquid electrolyte are very short.2012,Et al. 2,2', 7,
The fluorenes (Spiro-OMeTAD) of 7'- tetra- [N, N- bis- (4- methoxyphenyls) amino] -9,9'- spiral shells two substitutes original liquid electrolyte
Matter, the efficiency of the organic metal Ca-Ti ore type solar cell of preparation reach 9.7%.Recently, the efficiency of this kind of solar cell
19% is breached, there is very much the prospect commercially produced.
Till now, the organic metal perovskite material being related in research can use formula ABX more3Represent, wherein A generations
Table organic group, such as methylamino, ethylamino-, carbonamidine base, B represents Pb or Sn, X represent Cl, Br, I and combinations thereof.Further to carry
The efficiency of high Ca-Ti ore type solar cell, one must be entered to the structure of organic metal perovskite, optics and electrology characteristic
Step is optimized and revised.Organic metal perovskite material has stronger absorption to light, but its blue green light area absorptance feux rouges with
And near infrared region is much better than.If absorption spectrum can be adjusted so that near infrared absorption area has strengthened, so that corresponding
Photovoltaic device has higher photoelectric current.Show that carrier has longer diffusion length in organic metal perovskite material though having been reported that
(relative to organic materials such as P3HT, PCBM), but typically optimization thickness is in 300nm or so, which imply that being necessary further
Improve the transfer ability of carrier.
The content of the invention
It is an object of the invention to provide a kind of Ag doping organic metal perovskite material, solar cell and its making side
Method, to overcome deficiency of the prior art.
To achieve the above object, the present invention provides following technical scheme：
The embodiment of the present application discloses a kind of formula and is expressed as AB1-xAgxX3Ag doping organic metal perovskite material, its
In, A is organic group, and B is Pb or Sn, X Cl, Br, I, F or it is combined, 0 ＜ x≤0.15.
It is above-mentioned to be expressed as AB1-xAgxX3Ag 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, the organic group is methylamino, ethamine
Base or carbonamidine base.
Correspondingly, the embodiment of the present application also discloses a kind of preparation method of Ag doping organic metal perovskite material, bag
Include step：
(1) a certain amount of first raw material, the second raw material and silver-colored source material, are weighed respectively, wherein, the first raw material is selected from methylamine
One or more mixtures in halogen, ethamine halogen or carbonamidine halogen, one kind in lead halide, tin halides of the second raw material or
A variety of mixtures, the raw material weighed is added to the solvent of certain volume, precursor solution is obtained after being sufficiently mixed；
(2), precursor solution is dried and sintered, obtains perovskite material.
In the preparation method of above-mentioned Ag doping organic metal perovskite material, silver-colored source material be preferably AgCl, AgBr,
AgI, AgF or AgNO3Deng salt.
The embodiment of the present application also discloses a kind of solar cell, including absorbed layer, and the absorbed layer uses described silver
Adulterate organic calcium metal titanium ore material.
Correspondingly, the embodiment of the present application also discloses a kind of preparation method of solar cell, including：
(1) Ag doping organic metal perovskite precursor solution, is prepared；
(2) first electrode layer and the first conductive layer, are made successively in substrate；
(3), precursor solution is spun on the first conductive layer, it is thin that Ag doping organic metal perovskite is formed after heat treatment
Film；
(4) the second conductive layer and the second electrode lay, are sequentially formed on obtained Ag doping organic metal perovskite thin film.
Preferably, in the preparation method of above-mentioned solar cell, in the step (1), according to the Ag doping of setting
Concentration, a certain amount of first raw material, the second raw material and silver-colored source material are weighed respectively, wherein, the first raw material is selected from methylamine halogen, ethamine
One or more mixtures in halogen or carbonamidine halogen, the second raw material are one or more mixed in lead halide, tin halides
Compound, the raw material weighed is added to the solvent of certain volume, precursor solution is obtained after being sufficiently mixed.
Preferably, in the preparation method of above-mentioned solar cell, in the step (2), substrate is chosen rigid or soft
Property substrate；For rigid basement including glass etc., flexible substrates include polyethylene terephthalate (PET), poly- naphthalenedicarboxylic acid second
Diol ester (PEN), polyimides, but it is not limited to several substrates of the above.
Preferably, in the preparation method of above-mentioned solar cell, the material of the first electrode layer for ITO or
FTO, processing method can also be sputtering, vapour deposition process (CVD), thermal evaporation, sol-gal process etc.；First conductive layer
Material be poly- (3,4-ethylene dioxythiophene), kayexalate salt (PEDOT:PSS), zinc oxide (ZnO), titanium oxide
(TiO2) or nickel oxide (NiO).
Preferably, in the preparation method of above-mentioned solar cell, in the step (3), precursor solution is spun on
After first conductive layer, annealed between 80 DEG C to 90 DEG C 2-3 hours.
Preferably, in the preparation method of above-mentioned solar cell, the material of second conductive layer is (6,6) phenyl
C61- methyl butyrates (PC61BM), (6,6) phenyl C71- methyl butyrates (PC71BM), the octyloxy of (6,6) phenyl C61- butyric acid three
Benzene methyl (PCBB-C8) or the fluorenes (Spiro- of 2,2', 7,7'- tetra- [N, N- bis- (4- methoxyphenyls) amino] -9,9'- spiral shells two
OMeTAD), the second conductive layer is using the coating method such as vapour deposition, blade coating, volume to volume；The material of 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 two kinds of materials
Double membrane structure.
Compared with prior art, the advantage of the invention is that：
1st, Ag, which is adulterated, causes light absorbs to strengthen in near-infrared section.
2nd, the lower crystallinity of 5%Ag doping significantly improves.
3rd, (ITO/PEDOT is applied in solar cell device:), PSS/Perovskite/PCBM/Al adulterate under situation
Photoelectric transformation efficiency up to 13.3%, relative to the lifting for having 30% undoped with the conversion efficiency (10.3%) under situation.
Brief description of the drawings
, below will be to embodiment or existing in order to illustrate more clearly of the embodiment of the present application or technical scheme of the prior art
There is the required accompanying drawing used in technology description to be briefly described, it should be apparent that, drawings in the following description are only this
Some embodiments described in application, for those of ordinary skill in the art, on the premise of not paying creative work,
Other accompanying drawings can also be obtained according to these accompanying drawings.
Fig. 1 show the ITO/PEDOT under different Ag doping:The X-ray diffraction pattern of PSS/Perovskite films；
Fig. 2 show the ITO/PEDOT under different Ag doping:The optical absorption spectra of PSS/Perovskite films；
Fig. 3 show Ag doping (5%) and the I-V curve figure undoped with Ca-Ti ore type solar cell, and battery structure is
ITO/PEDOT:PSS/Perovskite/PC61BM/TiO2/Al。
Embodiment
Electronic structure, which calculates, to be shown, the valence band and conduction band of organic metal perovskite material mainly have Pb (Sn) s, p track
State and the s tracks state of halogen are formed.The present invention substitutes part Pb (Sn) to regulate and control the structure of organic metal perovskite, optics with Ag
And electrology characteristic, so as to realize the purpose for improving photovoltaic performance.We will be appreciated that Ag doping will significantly improve material and exist
The absorbent properties of red light district, and improve crystallinity.Ag is adulterated into organic calcium metal titanium ore materials application into photovoltaic device,
Using same device architecture, its efficiency has 30% lifting.
Below in conjunction with the accompanying drawing in the embodiment of the present invention, detailed retouch is carried out to the technical scheme in the embodiment of the present invention
State, it is clear that described embodiment is only part of the embodiment of the present invention, rather than whole embodiments.Based on the present invention
In embodiment, the every other implementation that those of ordinary skill in the art are obtained on the premise of creative work is not made
Example, belongs to the scope of protection of the invention.
Below by taking the making of solar cell as an example, it will be understood by those skilled in the art that the doping in this case
The perovskite material of silver can be applied equally to other light such as fet, light emitting diode, sensor, photo-detector
Electrical part.
The preparation 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.
Weigh 0.7631 gram of CH3NH3I, 0.4227 gram of PbCl2, 0.0115 gram of AgCl, add 2 milliliters of N, N-2 methyl formyls
Amine (DMF), stirred in 60 DEG C of thermal station and obtain within 8 hours clarifying precursor solution, wherein Ag doping ratio is 5%.
(2), on glass plate last layer ITO, by etching, obtain 6 pieces of ITO regions, with detergent, ethanol, acetone and
Isopropanol is cleaned by ultrasonic ito glass piece respectively.Etching ito glass is used to prepare device, does not etch ITO and is used for film characterization.
(3), PEDOT thick one layer of 35nm of spin coating on ito glass piece:PSS, with before preparation in step (1) after annealing
Liquid solution spin coating thin film is driven, is then annealed 165 minutes at 84 DEG C.
(4), one layer of PC61BM of spin coating in perovskite film layer, PC61BM concentration are 20mg/ml, and flux is chlorobenzene.Apply again
Last layer TiO2Film, the thick Al electrodes of one layer of 100nm are deposited after annealing.The area of battery is 0.12cm2。
Embodiment 2
The doping ratio of Ag in the step of embodiment 1 (1) is adjusted to 2.5%, other conditions making same as Example 1 is too
Positive energy battery.
Embodiment 3
The doping ratio of Ag in the step of embodiment 1 (1) is adjusted to 7.5%, other conditions making same as Example 1 is too
Positive energy battery.
Embodiment 4
The doping ratio of Ag in the step of embodiment 1 (1) is adjusted to 10%, other conditions making same as Example 1 is too
Positive energy battery.
Comparative example
The doping ratio of Ag in the step of embodiment 1 (1) is adjusted to 0%, the other conditions making sun same as Example 1
Can battery.
Fig. 1 shows X-ray diffraction pattern of the embodiment 1 into embodiment 4 and comparative example under different levels of doping, wherein x
Film has stronger diffracted intensity under=0.05 (Ag doping concentrations are 5%) situation, and this shows that the Ag doping of debita spissitudo has rush
Enter effect of the Perovskite Phase into phase.
Fig. 2 shows optical absorption spectra of the embodiment 1 into embodiment 4 and comparative example under different levels of doping.Can in figure
To find out, Ag, which adulterates to absorb at blue green light, gradually to be weakened, and goes out to strengthen in near-infrared.
Fig. 3 is the I-V curve comparison diagram for the Ca-Ti ore type solar cell that embodiment 1 is prepared with comparative example, can from figure
To find out, the conversion efficiency of the battery under 5%Ag doping situations is relative to the lifting for having 30% undoped with situation.
Following table is the performance parameter contrast table for the Ca-Ti ore type solar cell that embodiment 1 is prepared with comparative example, from table
It can be seen that the performance of the solar cell after Ag doping is obviously improved.
It should be noted that herein, such as first and second or the like relational terms are used merely to a reality
Body or operation make a distinction with another entity or operation, and not necessarily require or imply and deposited between these entities or operation
In any this actual relation or order.Moreover, term " comprising ", "comprising" or its any other variant are intended to
Nonexcludability includes, so that process, method, article or equipment including a series of elements not only will including those
Element, but also the other element including being not expressly set out, or it is this process, method, article or equipment also to include
Intrinsic key element.In the absence of more restrictions, the key element limited by sentence "including a ...", it is not excluded that
Other identical element also be present in process, method, article or equipment including the key element.
Described above is only the embodiment of the application, it is noted that for the ordinary skill people of the art
For member, on the premise of the application principle is not departed from, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as the protection domain of the application.
Claims (10)
1. a kind of formula is expressed as AB1-xAgxX3Ag doping organic metal perovskite material, wherein, A is organic group, B Pb
Or Sn, X Cl, Br, I, F or its combination, 0 ＜ x≤0.15.
2. Ag doping organic metal perovskite material according to claim 1, it is characterised in that：x=0.05.
3. Ag doping organic metal perovskite material according to claim 1, it is characterised in that：The organic group is first
Amido, ethylamino- or carbonamidine base.
4. the preparation method of any Ag doping organic metal perovskite material of claims 1 to 3, it is characterised in that including
Step：
（1）, weigh a certain amount of first raw material, the second raw material and silver-colored source material respectively, wherein, the first raw material be selected from methylamine halogen,
One or more mixtures in ethamine halogen or carbonamidine halogen, one or more of second raw material in lead halide, tin halides
Mixture, by the raw material weighed add certain volume solvent, obtain precursor solution after being sufficiently mixed;
（2）, precursor solution is dried and sintered, obtain perovskite material.
5. a kind of solar cell, including absorbed layer, it is characterised in that：The absorbed layer is mixed using the silver described in claim 1
Miscellaneous organic metal perovskite material.
6. the preparation method of the solar cell described in claim 5, it is characterised in that including：
（1）, prepare Ag doping organic metal perovskite precursor solution；
（2）, make first electrode layer and the first conductive layer successively in substrate；
（3）, precursor solution is spun on the first conductive layer, Ag doping organic metal perovskite thin film is formed after heat treatment；
（4）, on obtained Ag doping organic metal perovskite thin film sequentially form the second conductive layer and the second electrode lay.
7. the preparation method of solar cell according to claim 6, it is characterised in that the step（1）In, according to setting
Fixed Ag doping concentration, a certain amount of first raw material, the second raw material and silver-colored source material are weighed respectively, wherein, the first raw material is selected from
One or more mixtures in methylamine halogen, ethamine halogen or carbonamidine halogen, the second raw material in lead halide, tin halides one
Kind or a variety of mixtures, the raw material weighed is added to the solvent of certain volume, precursor solution is obtained after being sufficiently mixed.
8. the preparation method of solar cell according to claim 6, it is characterised in that the material of the first electrode layer
For ITO or FTO；The material of first conductive layer is poly-（3,4-ethylene dioxythiophene）, kayexalate salt
（PEDOT:PSS）, zinc oxide（ZnO）, titanium oxide（TiO2）Or nickel oxide（NiO）.
9. the preparation method of solar cell according to claim 6, it is characterised in that the step（3）In, forerunner
After liquid solution is spun on the first conductive layer, annealed between 80 DEG C to 90 DEG C 2-3 hours.
10. the preparation method of solar cell according to claim 6, it is characterised in that the material of second conductive layer
Matter is (6,6) phenyl C61- methyl butyrates（PC61BM）, (6,6) phenyl C71- methyl butyrates（PC71BM）, (6,6) phenyl C61-
The octyloxy benzene methyl of butyric acid three（PCBB-C8）Or 2,2', 7,7'- tetra- [N, N- bis- (4- methoxyphenyls) amino] -9,9'- spiral shells two
Fluorenes（Spiro-OMeTAD）；The material of the second electrode lay is magnesium/silver, calcium/aluminium, silver, aluminium, lithium fluoride/aluminium or gold electrode.
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| 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 |
| CN105702865B (en) * | 2016-04-05 | 2018-08-21 | 河北大学 | A kind of metal-doped perovskite thin film, preparation method and application |
| CN107993848B (en) * | 2017-11-08 | 2019-04-23 | 华中科技大学 | Based on the titania-doped perovskite solar battery and preparation method thereof of nickel |
| 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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| CN103346018A (en) * | 2013-06-26 | 2013-10-09 | 中国科学院青岛生物能源与过程研究所 | Iodide solar cell prepared through solid-liquid reactions and provided with perovskite structures |
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| GB201208793D0 (en) * | 2012-05-18 | 2012-07-04 | Isis Innovation | Optoelectronic device |
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| CA2895654A1 (en) * | 2012-12-20 | 2014-06-26 | Yissum Research Development Company Of The Hebrew University Of Jerusalem Ltd. | Perovskite schottky type solar cell |
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| CN103400697A (en) * | 2013-08-15 | 2013-11-20 | 厦门大学 | All-solid-state flexible sensitized solar cell and preparation method thereof |
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