CN104851987A - Perovskite structure organic-inorganic ternary alloy heterocomplex film photoanode with adjustable absorption spectrum and preparation method thereof - Google Patents

Perovskite structure organic-inorganic ternary alloy heterocomplex film photoanode with adjustable absorption spectrum and preparation method thereof Download PDF

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CN104851987A
CN104851987A CN201510166025.3A CN201510166025A CN104851987A CN 104851987 A CN104851987 A CN 104851987A CN 201510166025 A CN201510166025 A CN 201510166025A CN 104851987 A CN104851987 A CN 104851987A
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heterocomplex
perovskite structure
ternary alloy
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rnh
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CN104851987B (en
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徐雪青
王军霞
梁柱荣
徐刚
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Guangzhou Institute of Energy Conversion of CAS
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Guangzhou Institute of Energy Conversion of CAS
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Abstract

The invention provides a perovskite structure organic-inorganic ternary alloy heterocomplex film photoanode with adjustable absorption spectrum and a preparation method thereof. The perovskite structure organic-inorganic ternary alloy heterocomplex film photoanode comprises a conductive glass layer, a titanium dioxide layer, a perovskite structure organic-inorganic ternary alloy heterocomplex layer which are successively stacked. The general formula of the perovskite structure organic-inorganic ternary alloy heterocomplex is RNH<3>(Pb<x>Sn<1-x>)<y>Ge<1-y>I<3>, wherein R=CH3, C2H5, or C3H7, 0 < x< 1, and 0 < y < 1. The perovskite structure organic-inorganic ternary alloy heterocomplex is used as a photoanode absorption layer. Compared with a conventional perovskite film photoanode, the perovskite structure organic-inorganic ternary alloy heterocomplex film photoanode uses the perovskite structure organic-inorganic ternary alloy heterocomplex as the photoanode absorption layer so as to reduce the toxicity of absorption material and widen the spectrum absorption of the absorption layer material, and may achieve band gap regulation and control of perovskite absorption material by adjusting a ratio of metal elements.

Description

A kind of absorption spectrum adjustable perovskite structure Organic-inorganic ternary alloy heterocomplex film light anode and preparation method thereof
Technical field
The present invention relates to thin film solar cell technical field, particularly relate to a kind of absorption spectrum adjustable perovskite structure Organic-inorganic ternary alloy heterocomplex film light anode and preparation method thereof.
Background technology
In recent years, organic and inorganic perovskite heterocomplex solar cell becomes the study hotspot of photovoltaic art because of the feature of its low cost, high absorptivity.Wherein, the development of Pb based perovskite solar cell is comparatively quick, through the laboratory cells sample efficiencies of regenerative resource National Laboratory of the U.S. (NREL) certification up to 20%, namely reaches Cu (In, Ga) Se 2the level of thin film solar cell.But conventional P b based perovskite heterocomplex Photoelectrochemical stabilization is poor, film absorption cut-off wavelength is about 800nm, and spectral response range still needs to be widened, and the toxicity of Pb also limit its commercial Application.Therefore, perovskite solar cell of needing that research and development are a kind of stable, low toxicity, absorption spectrum are adjustable badly.
Summary of the invention
For the problem of above-mentioned proposition, the invention provides a kind of absorption spectrum adjustable perovskite structure Organic-inorganic ternary alloy heterocomplex film light anode and preparation method thereof, using perovskite structure Organic-inorganic ternary alloy heterocomplex as light anode absorbed layer, reduce the toxicity of absorbing material, widen the spectral absorption of absorbed layer material, the band gap regulation and control of perovskite absorbing material can have been realized by the ratio adjusting metallic element.
Now by the following technical solutions:
A kind of absorption spectrum adjustable perovskite structure Organic-inorganic ternary alloy heterocomplex film light anode, comprise the conductive glass layer, titanium dioxide layer and the perovskite structure Organic-inorganic ternary alloy heterozygosis nitride layer that stack gradually, the general formula of described perovskite structure Organic-inorganic ternary alloy heterocomplex is RNH 3(Pb xsn 1-x) yge 1-yi 3, wherein R is selected from CH 3, C 2h 5or C 3h 7, 0<x<1,0<y<1.
Further, described electro-conductive glass is selected from FTO, ITO, ATO or AZO, is preferably FTO.
Further, 0.1≤x≤0.9,0.1≤y≤0.9.
Further, the thickness of described conductive glass layer is 250 ~ 350nm, and the thickness of described titanium dioxide layer is 100 ~ 600nm, and the thickness of described perovskite structure Organic-inorganic ternary alloy heterozygosis nitride layer is 300 ~ 700nm.
The present invention also provides the preparation method of above-mentioned absorption spectrum adjustable perovskite structure Organic-inorganic ternary alloy heterocomplex film light anode, and the general formula of described perovskite structure Organic-inorganic ternary alloy heterocomplex is RNH 3(Pb xsn 1-x) yge 1-yi 3, wherein R is selected from CH 3, C 2h 5or C 3h 7(comprising n-pro-pyl and isopropyl), 0<x<1,0<y<1; Comprise the following steps:
(1) RNH 3(Pb xsn 1-x) I 3synthesis: get RNH according to stoichiometric proportion 3i, PbI 2and SnI 2(namely according to the amount ratio of the numerical value determination medicine of x in above-mentioned chemical formula, such as, as x=0.1, RNH 3i, PbI 2and SnI 2mol ratio be 10:1:9), be dissolved in HI and H 3pO 2in mixed solvent, react at 90 ~ 120 DEG C, after reaction terminates, (now solution is glassy yellow) cold filtration obtains RNH 3(Pb xsn 1-x) I 3crystal;
(2) RNH 3geI 3synthesis: by GeO 2be dissolved in HI and H 3pO 2in mixed solvent, react at 80 ~ 100 DEG C, reaction terminates rear cold filtration, adds and GeO in filtrate 2equimolar RNH 3i, after being heated to boiling, cold filtration obtains RNH 3geI 3crystal;
(3) RNH 3(Pb xsn 1-x) yGe 1-yi 3preparation: by RNH 3(Pb xsn 1-x) I 3with RNH 3geI 3according to stoichiometric proportion mix (namely determine both ratios according to the numerical value of y in above-mentioned chemical formula, such as, as y=0.1, RNH 3(Pb xsn 1-x) I 3with RNH 3geI 3mol ratio be 1:9), namely obtain perovskite structure ternary alloy three-partalloy heterocomplex RNH 3(Pb xsn 1-x) yge 1-yi 3;
(4) preparation of light anode: deposition of titanium oxide on electro-conductive glass, obtains electro-conductive glass/titanium dioxide composite bed, on electro-conductive glass, the method for deposition of titanium oxide belongs to prior art, preferably, adopt aerosol spray pyrolysismethod, by the ethanolic solution of isopropyl titanate/acetylacetone,2,4-pentanedione (wherein, isopropyl titanate: acetylacetone,2,4-pentanedione: the mass ratio of ethanol is preferably 2:2:1), by solution spraying on electro-conductive glass, sintering (such as, in nitrogen environment 500 DEG C sintering 1h) after obtain electro-conductive glass/titanium dioxide composite bed, the area of electro-conductive glass, the concentration of solution and consumption are according to thickness, actual needs such as density and regulating, use in certain embodiments on the electro-conductive glass of 15mm × 19mm, by RNH 3(Pb xsn 1-x) yge 1-yi 3be dissolved in DMF and obtain heterocomplex solution, heterocomplex solution is dripped in the one side of electro-conductive glass/titanium dioxide composite bed titanium dioxide, spin coating, spin coating post-drying residual solvent can obtain described absorption spectrum adjustable perovskite structure Organic-inorganic ternary alloy heterocomplex film light anode, the concentration of heterocomplex solution and consumption and spin coating speed etc., regulate according to the actual needs such as thickness, density.
Further, in step (1), HI and H in mixed solvent 3pO 2volume ratio be 2:1 ~ 5:1 (preferred 4:1), PbI 2and SnI 2stoichiometric proportion (i.e. mol ratio) be 1:9 ~ 9:1 (i.e. 0.1≤x≤0.9), after dissolving, the total concentration of solution is 0.10 ~ 0.14mol/L (being preferably 0.12mol/L), reaction time is 3 ~ 5h (preferred 4h), and reaction temperature is preferably 110 DEG C.
Above-mentioned RNH 3i can adopt following methods to synthesize: certain density RNH 2/ ethanolic solution (such as 32wt%) and the certain density HI aqueous solution (such as 57wt%), according to RNH 2mix with HI etc. mole, (reaction time preferred 2h) is reacted at 0 DEG C, air-distillation at 50 DEG C (distillation time is preferably 1h), after cooling, the crystal ether obtained washes several times (preferably 3 times), suction filtration, vacuumize (as, vacuumize 24h at 60 DEG C), obtain RNH 3i powder.
Further, in step (2), HI and H in mixed solvent 3pO 2volume ratio be 1:2 ~ 2:1 (be preferably 1:1), GeO in solution after dissolving 2concentration be 0.4 ~ 0.6mol/L (i.e. GeO 2concentration before reaction, is preferably 0.5mol/L), the reaction time is 4 ~ 6h (being preferably 5h), and reaction temperature is preferably 90 DEG C.
Further, in step (3), RNH 3(Pb xsn 1-x) I 3with RNH 3geI 3stoichiometric proportion be 1:9 ~ 9:1 (i.e. 0.1≤y≤0.9).
Further, in step (4), the mass fraction of heterocomplex solution is 30 ~ 50%, and spin coating speed is 3000 ~ 5000rpm.
Further, the amount of solution of spin coating is 30 ~ 50 μ L (preferably 40 μ L), and spin-coating time is 30 ~ 60s (preferred 40s); Bake out temperature is preferably 100 DEG C, and drying time is preferably 2min.
Compared with existing perovskite thin film light anode, the present invention has the following advantages:
(1) perovskite structure Organic-inorganic ternary alloy heterocomplex is as light anode absorbed layer, reduces the toxicity of absorbing material, has widened the spectral absorption of absorbed layer material;
(2) the band gap regulation and control of perovskite absorbing material can be realized by the ratio of adjustment Sn, Pb, Ge.
Embodiment
Below in conjunction with example, the present invention is further illustrated
The optical absorption characteristics of perovskite structure Organic-inorganic ternary alloy heterocomplex film light anode adopts ultraviolet-visible-near infrared spectrometer to measure; With perovskite structure Organic-inorganic ternary alloy heterocomplex film light anode for work electrode, P3HT is hole transmission layer, gold electrode is to electrode, adopts the J-V curve of solar simulator and electrochemical workstation testing solar battery, calculates photoelectric conversion efficiency of the solar battery.
Embodiment 1
In the present embodiment, perovskite structure Organic-inorganic ternary alloy heterocomplex is CH 3nH 3(Pb 0.1sn 0.9) 0.9ge 0.1i 3., namely R is methyl, x=0.1, y=0.9.Conductive glass layer is FTO, and the thickness of conductive glass layer is 300nm, the thickness of titanium dioxide layer is 400nm, the thickness of perovskite structure Organic-inorganic ternary alloy heterozygosis nitride layer is 500nm.Preparation process is as follows:
(1) CH 3nH 3(Pb 0.1sn 0.9) I 3synthesis: by 5mmol CH 3nH 3i and 0.5mmolPbI 2, 4.5mmolSnI 2be dissolved in HI and the H of volume ratio 4:1 3pO 2in mixed solution, after dissolving, the total concentration of solution is 0.12mol/L, and be heated to 110 DEG C of reaction 4h, solution becomes glassy yellow, obtains CH after cold filtration 3nH 3(Pb 0.1sn 0.9) I 3crystal.
(2) CH 3nH 3geI 3synthesis: by 5mmol GeO 2be dissolved in volume ratio 1:1HI and H 3pO 2in mixed solution, GeO 2concentration be 0.5mol/L, in 90 DEG C reaction 5h, cooled and filtered, adds 5mmol CH in filtrate 3nH 3i, after being heated to boiling, cooling, filters, obtains CH 3nH 3geI 3crystal.
(3) CH 3nH 3(Pb 0.1sn 0.9) 0.9ge 0.1i 3preparation: by CH 3nH 3(Pb 0.1sn 0.9) I 3with CH 3nH 3geI 3according to stoichiometric proportion 9:1 mixing, namely obtain perovskite structure ternary alloy three-partalloy heterocomplex CH 3nH 3(Pb 0.1sn 0.9) 0.9ge 0.1i 3.
(4) preparation of perovskite structure ternary alloy three-partalloy heterocomplex film: by the ethanolic solution of isopropyl titanate/acetylacetone,2,4-pentanedione (wherein, isopropyl titanate: acetylacetone,2,4-pentanedione: the mass ratio of ethanol is 2:2:1), by solution spraying on electro-conductive glass FTO, electro-conductive glass/titanium dioxide composite bed is obtained, by the CH of preparation after 500 DEG C of sintering 1h in nitrogen environment 3nH 3(Pb 0.1sn 0.9) 0.9ge 0.1i 3be dissolved in DMF the heterocomplex solution obtaining mass fraction 40%, dripped by heterocomplex solution in the one side of electro-conductive glass/titanium dioxide composite bed titanium dioxide, 4000rpm rotates 40s, and on heating station, 100 DEG C are dried 2min.
CH 3nH 3the preparation of I: by the CH of 32wt% 3nH 2the HI aqueous solution of/ethanolic solution and 57wt%, according to CH 3nH 2mix with HI etc. mole, at 0 DEG C, react 2h, air-distillation 1h at 50 DEG C, after cooling, the crystal ether obtained is washed 3 times, suction filtration, vacuumize 24h at 60 DEG C, obtains CH 3nH 3i powder.
Finally, obtain perovskite structure Organic-inorganic ternary alloy heterocomplex film light anode, absorption spectrum is close to 1000nm, and photoelectric conversion efficiency is 5.7%.
Embodiment 2
Differently from embodiment 1 to be, x=0.9.
Correspondingly, step (1) is: CH 3nH 3(Pb 0.9sn 0.1) I 3synthesis: by 5mmol CH 3nH 3i and 4.5mmolPbI 2, 0.5mmolSnI 2be dissolved in HI and the H of volume ratio 4:1 3pO 2in mixed solution, be heated to 110 DEG C of reaction 4h, solution becomes glassy yellow, obtains CH after cold filtration 3nH 3(Pb 0.9sn 0.1) I 3crystal.
Finally, obtain perovskite structure Organic-inorganic ternary alloy heterocomplex film light anode, absorption spectrum is close to 800nm, and photoelectric conversion efficiency is 4.9%.
Embodiment 3
Differently from embodiment 1 to be, x=0.5.
Correspondingly, step (1) is: CH 3nH 3(Pb 0.5sn 0.5) I 3synthesis: by 5mmol CH 3nH 3i and 2.5mmolPbI 2, 2.5mmolSnI 2be dissolved in HI and the H3PO of volume ratio 4:1 2in mixed solution, be heated to 110 DEG C of reaction 4h, solution becomes glassy yellow, obtains CH after cold filtration 3nH 3pb 0.5sn 0.5i 3crystal.
Finally, obtain perovskite structure Organic-inorganic ternary alloy heterocomplex film light anode, absorption spectrum is close to 950nm, and photoelectric conversion efficiency is 5.2%.
Embodiment 4
Differently from embodiment 1 to be, y=0.1.
Correspondingly, step (3) is, CH 3nH 3(Pb 0.1sn 0.9) 0.1ge 0.9i 3preparation: by CH 3nH 3(Pb 0.1sn 0.9) I 3with CH 3nH 3geI 3according to stoichiometric proportion 1:9 mixing, namely obtain perovskite structure ternary alloy three-partalloy heterocomplex CH 3nH 3(Pb 0.1sn 0.9) 0.1ge 0.9i 3.
Finally, obtain perovskite structure Organic-inorganic ternary alloy heterocomplex film light anode, absorption spectrum is close to 600nm, and photoelectric conversion efficiency is 2.3%.
Embodiment 5
Differently from embodiment 1 to be, y=0.5.
Correspondingly, step (3) is, CH 3nH 3(Pb 0.1sn 0.9) 0.5ge 0.5i 3preparation: by CH 3nH 3(Pb 0.1sn 0.9) I 3with CH 3nH 3geI 3according to stoichiometric proportion 1:1 mixing, namely obtain perovskite structure ternary alloy three-partalloy heterocomplex CH 3nH 3(Pb 0.1sn 0.9) 0.5ge 0.5i 3.
Finally, obtain perovskite structure Organic-inorganic ternary alloy heterocomplex film light anode, absorption spectrum is close to 750nm, and photoelectric conversion efficiency is 2.9%.
Embodiment 6
Differently from embodiment 1 be, in step (2), reaction temperature is 80 DEG C.
Finally, obtain perovskite structure Organic-inorganic ternary alloy heterocomplex film light anode, absorption spectrum is close to 950nm, and photoelectric conversion efficiency is 5.1%.
Embodiment 7
Differently from embodiment 1 be, in step (2), reaction temperature is 100 DEG C.
Finally, obtain perovskite structure Organic-inorganic ternary alloy heterocomplex film light anode, absorption spectrum is close to 1000nm, and photoelectric conversion efficiency is 5.5%.
Embodiment 8
Differently from embodiment 1 be, in step (4), the mass fraction of heterocomplex solution is 30%.Conductive glass layer is ITO, and the thickness of conductive glass layer is 250nm, the thickness of titanium dioxide layer is 100nm, the thickness of perovskite structure Organic-inorganic ternary alloy heterozygosis nitride layer is 300nm.
Finally, obtain perovskite structure Organic-inorganic ternary alloy heterocomplex film light anode, absorption spectrum is close to 880nm, and photoelectric conversion efficiency is 2.3%.
Embodiment 9
Differently from embodiment 1 be, in step (4), the mass fraction of heterocomplex solution is 50%.Conductive glass layer is AZO, and the thickness of conductive glass layer is 350nm, the thickness of titanium dioxide layer is 100nm, the thickness of perovskite structure Organic-inorganic ternary alloy heterozygosis nitride layer is 700nm.
Finally, obtain perovskite structure Organic-inorganic ternary alloy heterocomplex film light anode, absorption spectrum is close to 1000nm, and photoelectric conversion efficiency is 3.3%.
Embodiment 10
Differently from embodiment 1 be, in step (4), spin coating speed is 3000rpm.。
Finally, obtain perovskite structure Organic-inorganic ternary alloy heterocomplex film light anode, absorption spectrum is close to 880nm, and photoelectric conversion efficiency is 2.7%.
Embodiment 11
Differently from embodiment 1 be, in step (4), spin coating speed is 5000rpm.
Finally, obtain perovskite structure Organic-inorganic ternary alloy heterocomplex film light anode, absorption spectrum is close to 1000nm, and photoelectric conversion efficiency is 3.5%.
Embodiment 12
In the present embodiment, perovskite structure Organic-inorganic ternary alloy heterocomplex is C 2h 5nH 3(Pb 0.9sn 0.1) 0.9ge 0.1i 3, namely R is ethyl, x=0.9, y=0.9.Preparation process is as follows:
(1) C 2h 5nH 3(Pb 0.9sn 0.1) I 3synthesis: by 5mmol C 2h 5nH 3i and 4.5mmolPbI 2, 0.5mmolSnI 2be dissolved in HI and the H of volume ratio 4:1 3pO 2in mixed solution, be heated to 110 DEG C of reaction 4h, solution becomes glassy yellow, obtains C after cold filtration 2h 5nH 3(Pb 0.9sn 0.1) I 3crystal.
(2) C 2h 5nH 3geI 3synthesis: 5mmol GeO2 is dissolved in volume ratio 1:1HI and H 3pO 2in 90 DEG C of reaction 5h in mixed solution, cooled and filtered, adds 5mmol C in filtrate 2h 5nH 3i, after being heated to boiling, cooling, filters, obtains C 2h 5nH 3geI 3crystal.
(3) C 2h 5nH 3(Pb 0.9sn 0.1) 0.9ge 0.1the preparation of I3: by C 2h 5nH 3(Pb 0.9sn 0.1) I 3with C 2h 5nH 3nH 3geI 3according to stoichiometric proportion 9:1 mixing, namely obtain perovskite structure ternary alloy three-partalloy heterocomplex C 2h 5nH 3(Pb 0.9sn 0.1) 0.9ge 0.1i3.
(4) preparation of perovskite structure ternary alloy three-partalloy heterocomplex film: by the ethanolic solution of isopropyl titanate/acetylacetone,2,4-pentanedione (wherein, isopropyl titanate: acetylacetone,2,4-pentanedione: the mass ratio of ethanol is 2:2:1), by solution spraying on 15mm × 19mm electro-conductive glass, electro-conductive glass/titanium dioxide composite bed is obtained, by the C of preparation after 500 DEG C of sintering 1h in nitrogen environment 2h 5nH 3(Pb 0.9sn 0.1) 0.9ge 0.1i3 is dissolved in DMF the heterocomplex solution obtaining mass fraction 40%, and dripped by heterocomplex solution in the one side of electro-conductive glass/titanium dioxide composite bed titanium dioxide, 4000rpm rotates 40s, and on heating station, 100 DEG C are dried 2min.
C 2h 5nH 3the preparation of I: by the C of 32wt% 2h 5nH 2the HI aqueous solution of/ethanolic solution and 57wt%, according to C 2h 5nH 2mix with HI etc. mole, at 0 DEG C, react 2h, air-distillation 1h at 50 DEG C, after cooling, the crystal ether obtained is washed 3 times, suction filtration, vacuumize 24h at 60 DEG C, obtains C 2h 5nH 3i powder.
Finally, obtain perovskite structure Organic-inorganic ternary alloy heterocomplex film light anode, absorption spectrum is close to 870nm, and photoelectric conversion efficiency is 4.0%.
Embodiment 13
In the present embodiment, perovskite structure Organic-inorganic ternary alloy heterocomplex is C 3h 7nH 3(Pb 0.9sn 0.1) 0.9ge 0.1i 3, namely R is n-pro-pyl, x=0.9, y=0.9.Preparation process is as follows:
(1) C 3h 7nH 3(Pb 0.9sn 0.1) I 3synthesis: by 5mmol C 3h 7nH 3i and 4.5mmolPbI 2, 0.5mmolSnI 2be dissolved in HI and the H of volume ratio 4:1 3pO 2in mixed solution, be heated to 110 DEG C of reaction 4h, solution becomes glassy yellow, obtains C after cold filtration 3h 7nH 3(Pb 0.9sn 0.1) I 3crystal.
(2) C 3h 7nH 3geI 3synthesis: by 5mmol GeO 2be dissolved in volume ratio 1:1HI and H 3pO 2in 90 DEG C of reaction 5h in mixed solution, cooled and filtered, adds 5mmol C in filtrate 2h 5nH 3i, after being heated to boiling, cooling, filters, obtains C 3h 7nH 3geI 3crystal.
(3) C 3h 7nH 3(Pb 0.9sn 0.1) 0.9ge 0.1i 3preparation: by C 3h 7nH 3(Pb 0.9sn 0.1) I 3with C 3h 7nH 3geI 3according to stoichiometric proportion 9:1 mixing, namely obtain perovskite structure ternary alloy three-partalloy heterocomplex C 3h 7nH 3(Pb 0.9sn 0.1) 0.9ge 0.1i 3.
(4) preparation of perovskite structure ternary alloy three-partalloy heterocomplex film: by the ethanolic solution of isopropyl titanate/acetylacetone,2,4-pentanedione (wherein, isopropyl titanate: acetylacetone,2,4-pentanedione: the mass ratio of ethanol is 2:2:1), by solution spraying on 15mm × 19mm electro-conductive glass, electro-conductive glass/titanium dioxide composite bed is obtained, by the C of preparation after 500 DEG C of sintering 1h in nitrogen environment 3h 7nH 3(Pb 0.9sn 0.1) 0.9ge 0.1i 3be dissolved in DMF the heterocomplex solution obtaining mass fraction 40%, dripped by heterocomplex solution in the one side of electro-conductive glass/titanium dioxide composite bed titanium dioxide, 4000rpm rotates 40s, and on heating station, 100 DEG C are dried 2min.
C 3h 7nH 3the preparation of I: by the C of 32wt% 3h 7nH 2the HI aqueous solution of/ethanolic solution and 57wt%, according to C 3h 7nH 2mix with HI etc. mole, at 0 DEG C, react 2h, air-distillation 1h at 50 DEG C, after cooling, the crystal ether obtained is washed 3 times, suction filtration, vacuumize 24h at 60 DEG C, obtains C 3h 7nH 3i powder.
Finally, obtain perovskite structure Organic-inorganic ternary alloy heterocomplex film light anode, absorption spectrum is close to 750nm, and photoelectric conversion efficiency is 2.5%.
Embodiment 14
Differently from embodiment 1 be, in step (1), reaction temperature is 90 DEG C.
Finally, obtain perovskite structure Organic-inorganic ternary alloy heterocomplex film light anode, absorption spectrum is close to 680nm, and photoelectric conversion efficiency is 1.1%.
Embodiment 15
Differently from embodiment 1 be, in step (1), reaction temperature is 120 DEG C.
Finally, obtain perovskite structure Organic-inorganic ternary alloy heterocomplex film light anode, absorption spectrum is close to 1000nm, and photoelectric conversion efficiency is 5.5%.
Embodiment 16
Differently from embodiment 1 to be, in step (1), HI and H in mixed solvent 3pO 2volume ratio be 5:1, after dissolving, the total concentration of solution is 0.10mol/L.
Finally, obtain perovskite structure Organic-inorganic ternary alloy heterocomplex film light anode, absorption spectrum is close to 1000nm, and photoelectric conversion efficiency is 4.7%.
Embodiment 17
Differently from embodiment 1 to be, in step (1), HI and H in mixed solvent 3pO 2volume ratio be 2:1, after dissolving, the total concentration of solution is 0.14mol/L.
Finally, obtain perovskite structure Organic-inorganic ternary alloy heterocomplex film light anode, absorption spectrum is close to 1000nm, and photoelectric conversion efficiency is 4.9%.
Embodiment 18
Differently from embodiment 1 be, in step (1), the reaction time is 3h.
Finally, obtain perovskite structure Organic-inorganic ternary alloy heterocomplex film light anode, absorption spectrum is close to 680nm, and photoelectric conversion efficiency is 1.3%.
Embodiment 19
Differently from embodiment 1 be, in step (1), the reaction time is 5h.
Finally, obtain perovskite structure Organic-inorganic ternary alloy heterocomplex film light anode, absorption spectrum is close to 1000nm, and photoelectric conversion efficiency is 4.9%.
Embodiment 20
Differently from embodiment 1 to be, in step (2), HI and H in mixed solvent 3pO 2volume ratio be 1:2, GeO in solution after dissolving 2concentration be 0.6mol/L.
Finally, obtain perovskite structure Organic-inorganic ternary alloy heterocomplex film light anode, absorption spectrum is close to 1000nm, and photoelectric conversion efficiency is 3.5%.
Embodiment 21
Differently from embodiment 1 to be, in step (2), HI and H in mixed solvent 3pO 2volume ratio be 2:1, GeO in solution after dissolving 2concentration be 0.4mol/L.
Finally, obtain perovskite structure Organic-inorganic ternary alloy heterocomplex film light anode, absorption spectrum is close to 1000nm, and photoelectric conversion efficiency is 4.0%.
Embodiment 22
Differently from embodiment 1 be, in step (2), the reaction time is 4h.
Finally, obtain perovskite structure Organic-inorganic ternary alloy heterocomplex film light anode, absorption spectrum is close to 1000nm, and photoelectric conversion efficiency is 4.9%.
Embodiment 23
Differently from embodiment 1 be, in step (2), the reaction time is 6h.
Finally, obtain perovskite structure Organic-inorganic ternary alloy heterocomplex film light anode, absorption spectrum is close to 1000nm, and photoelectric conversion efficiency is 5.3%.
Embodiment 24
Differently from embodiment 1 be, conductive glass layer is ATO, and the thickness of conductive glass layer is 250nm, the thickness of titanium dioxide layer is 600nm, the thickness of perovskite structure Organic-inorganic ternary alloy heterozygosis nitride layer is 300nm.
Finally, obtain perovskite structure Organic-inorganic ternary alloy heterocomplex film light anode, absorption spectrum is close to 880nm, and photoelectric conversion efficiency is 2.3%.
Embodiment 25
Differently from embodiment 1 be, in step (4), spin-coating time is 30s.
Finally, obtain perovskite structure Organic-inorganic ternary alloy heterocomplex film light anode, absorption spectrum is close to 880nm, and photoelectric conversion efficiency is 2.5%.
Embodiment 26
Differently from embodiment 1 be, in step (4), spin-coating time is 60s.
Finally, obtain perovskite structure Organic-inorganic ternary alloy heterocomplex film light anode, absorption spectrum is close to 1000nm, and photoelectric conversion efficiency is 3.5%.
Embodiment 27
Differently from embodiment 13 be, R is isopropyl.
Finally, obtain perovskite structure Organic-inorganic ternary alloy heterocomplex film light anode, absorption spectrum is close to 740nm, and photoelectric conversion efficiency is 3.4%.
By said method, can obtain absorption spectrum adjustable perovskite structure Organic-inorganic ternary alloy heterocomplex film light anode, reduce the toxicity of material, absorption spectrum scope spreads to 1000nm, has the photoelectric conversion efficiency up to 5.7%.Simultaneously, the band gap regulation and control of perovskite absorbing material can be realized by the ratio adjusting Sn, Pb, Ge, obtain the perovskite structure Organic-inorganic ternary alloy heterocomplex film light anode of different spectral response wave band and photoelectric properties, for the development of absorption spectrum adjustable perovskite structure Organic-inorganic ternary alloy heterocomplex thin film solar cell provides condition.
Although the foregoing describe the specific embodiment of the present invention, but be familiar with those skilled in the art to be to be understood that, concrete execution mode described by us is illustrative, without departing from the spirit and scope of the present invention, those skilled in the art still can do equivalence according to spirit of the present invention and modify and change.Therefore, scope of the present invention should be understood and regard as and cover all these other modification or amendments.

Claims (9)

1. an absorption spectrum adjustable perovskite structure Organic-inorganic ternary alloy heterocomplex film light anode, is characterized in that, comprises the conductive glass layer, titanium dioxide layer and the perovskite structure Organic-inorganic ternary alloy heterozygosis nitride layer that stack gradually; The general formula of described perovskite structure Organic-inorganic ternary alloy heterocomplex is RNH 3(Pb xsn 1-x) yge 1-yi 3, wherein R is selected from CH 3, C 2h 5or C 3h 7, 0<x<1,0<y<1.
2. absorption spectrum adjustable perovskite structure Organic-inorganic ternary alloy heterocomplex film light anode as claimed in claim 1, it is characterized in that, described electro-conductive glass is selected from FTO, ITO, ATO or AZO.
3. absorption spectrum adjustable perovskite structure Organic-inorganic ternary alloy heterocomplex film light anode as claimed in claim 1 or 2, is characterized in that, 0.1≤x≤0.9,0.1≤y≤0.9.
4. absorption spectrum adjustable perovskite structure Organic-inorganic ternary alloy heterocomplex film light anode as claimed in claim 1 or 2, it is characterized in that, the thickness of described conductive glass layer is 250 ~ 350nm, the thickness of described titanium dioxide layer is 100 ~ 600nm, and the thickness of described perovskite structure Organic-inorganic ternary alloy heterozygosis nitride layer is 300 ~ 700nm.
5. a preparation method for absorption spectrum as claimed in claim 1 adjustable perovskite structure Organic-inorganic ternary alloy heterocomplex film light anode, is characterized in that, comprise the following steps:
(1) RNH 3(Pb xsn 1-x) I 3synthesis: get RNH according to stoichiometric proportion 3i, PbI 2and SnI 2, be dissolved in HI and H 3pO 2in mixed solvent, react at 90 ~ 120 DEG C, reaction terminates rear cold filtration and obtains RNH 3(Pb xsn 1-x) I 3crystal;
(2) RNH 3geI 3synthesis: by GeO 2be dissolved in HI and H 3pO 2in mixed solvent, react at 80 ~ 100 DEG C, reaction terminates rear cold filtration, adds and GeO in filtrate 2equimolar RNH 3i, after being heated to boiling, cold filtration obtains RNH 3geI 3crystal;
(3) RNH 3(Pb xsn 1-x) yGe 1-yi 3preparation: by RNH 3(Pb xsn 1-x) I 3with RNH 3geI 3mix according to stoichiometric proportion, namely obtain perovskite structure ternary alloy three-partalloy heterocomplex RNH 3(Pb xsn 1-x) yge 1-yi 3;
(4) preparation of light anode: deposition of titanium oxide on electro-conductive glass, obtains electro-conductive glass/titanium dioxide composite bed; By RNH 3(Pb xsn 1-x) yge 1-yi 3be dissolved in DMF and obtain heterocomplex solution, heterocomplex solution is dripped in the one side of electro-conductive glass/titanium dioxide composite bed titanium dioxide, spin coating, spin coating post-drying residual solvent can obtain described absorption spectrum adjustable perovskite structure Organic-inorganic ternary alloy heterocomplex film light anode.
6. the preparation method of absorption spectrum adjustable perovskite structure Organic-inorganic ternary alloy heterocomplex film light anode as claimed in claim 5, is characterized in that, in step (1), and HI and H in mixed solvent 3pO 2volume ratio be 2:1 ~ 5:1, PbI 2and SnI 2stoichiometric proportion be 1:9 ~ 9:1, after dissolving, the total concentration of solution is 0.10 ~ 0.14mol/L, and the reaction time is 3 ~ 5h.
7. the preparation method of absorption spectrum adjustable perovskite structure Organic-inorganic ternary alloy heterocomplex film light anode as claimed in claim 5, is characterized in that, in step (2), and HI and H in mixed solvent 3pO 2volume ratio be 1:2 ~ 2:1, GeO in solution after dissolving 2concentration be 0.4 ~ 0.6mol/L, the reaction time is 4 ~ 6h.
8. the preparation method of absorption spectrum adjustable perovskite structure Organic-inorganic ternary alloy heterocomplex film light anode as claimed in claim 5, is characterized in that, in step (3), and RNH 3(Pb xsn 1-x) I 3with RNH 3geI 3stoichiometric proportion be 1:9 ~ 9:1.
9. the preparation method of absorption spectrum adjustable perovskite structure Organic-inorganic ternary alloy heterocomplex film light anode as claimed in claim 5, it is characterized in that, in step (4), the mass fraction of described heterocomplex solution is 30 ~ 50%, described spin coating speed is 3000 ~ 5000rpm, and spin-coating time is 30 ~ 60s.
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