CN106384785A - Tin-doped CH3NH3SnxPb1-xI3 perovskite solar cell - Google Patents

Tin-doped CH3NH3SnxPb1-xI3 perovskite solar cell Download PDF

Info

Publication number
CN106384785A
CN106384785A CN201611006451.1A CN201611006451A CN106384785A CN 106384785 A CN106384785 A CN 106384785A CN 201611006451 A CN201611006451 A CN 201611006451A CN 106384785 A CN106384785 A CN 106384785A
Authority
CN
China
Prior art keywords
thin film
layer
tin
spin
spin coating
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201611006451.1A
Other languages
Chinese (zh)
Other versions
CN106384785B (en
Inventor
郝玉英
李林钢
房晓红
张帆
张青兰
孙钦军
李战峰
崔艳霞
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Taiyuan University of Technology
Original Assignee
Taiyuan University of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Taiyuan University of Technology filed Critical Taiyuan University of Technology
Priority to CN201611006451.1A priority Critical patent/CN106384785B/en
Publication of CN106384785A publication Critical patent/CN106384785A/en
Application granted granted Critical
Publication of CN106384785B publication Critical patent/CN106384785B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H10K71/15—Deposition of organic active material using liquid deposition, e.g. spin coating characterised by the solvent used
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/40—Thermal treatment, e.g. annealing in the presence of a solvent vapour
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Abstract

The invention relates to the field of a solar cell, and particularly to an organic-inorganic hybrid perovskite solar cell. The invention provides a tin-doped CH3NH3SnxPb1-xI3 perovskite solar cell, wherein an active layer is a tin-doped CH3NH3SnxPb1-xI3 perovskite film. The tin-doped CH3NH3SnxPb1-xI3 perovskite film has a planar heterojunction structure. The invention provides a method for preparing the tin-doped CH3NH3SnxPb1-xI3 perovskite solar cell according to a one-step method in which multiple solvent processing procedures are utilized. A high-quality perovskite film is obtained, and high photoelectric conversion efficiency is realized.

Description

A kind of tin dope methyl ammonium lead iodide perovskite solaode
Technical field
The present invention relates to area of solar cell, specifically a kind of hybrid inorganic-organic Ca-Ti ore type solaode.
Background technology
Perovskite solar cell light absorption layer is a kind of hybrid inorganic-organic perovskite-type material, and chemical formula is AMX3 （A：CH3NH3+； M：IVA race Pb, Sn blending element；X：Halogen）, cell configuration MX6Constitute octahedra and contact with each other, Constitute three dimensional structure, NH3CH3+It is embedded.The research and development of perovskite solaode are honest and clean to being provided that using the sun on a large scale Valency electric energy tool is of great significance.At present, the maximum that tin dope methyl ammonium lead iodide perovskite solaode exists Problem is that photoelectric transformation efficiency is low, and stability is poor, is unsatisfactory for the demand of commercial applications.Improve such cell photoelectric conversion effect One crucial solution of rate is exactly to improve the quality of forming film of cell light absorption layer.Battery be can ensure that using thick active layer Light absorbs, but quality of forming film is difficult to ensure that, is unfavorable for the transmission of carrier and effective collects.Prepare active layer using two-step method Thin film can efficiently solve this problem, that is, utilize two step spin-coating methods, by regulating and controlling annealing temperature and annealing time, same to time control Solution concentration processed, to improve crystal growth quality, promotes transmission and the collection of carrier, improves the light absorbs of active layer simultaneously, from And realize efficient tin dope methyl ammonium lead iodide perovskite solaode.For example, 2014, Feng Hao et al. designed With mesoporous TiO2For electrode, spiro-OMeTAD is the tin dope methyl ammonium lead iodide perovskite electricity of hole mobile material Pond, making to mix stannum ratio is 25%（I.e. CH3NH3Sn0.25Pb0.75I3）Cell photoelectric transformation efficiency reached 7.37%, mix stannum ratio For 50%（I.e. CH3NH3Sn0.5Pb0.5I3）Battery reached 7.27%【J. Am. Chem. Soc. 2014, 136, 8094− 8099】；2016, Leize Zhu, et al. employ two-step method and DMSO annealing auxiliary make to mix the cell light of stannum ratio 10% Electric transformation efficiency has reached 10.25%【Nanoscale, 2016,8, 7621-7630】；In July, 2016, Yunlong Li et al. Same make to mix the tin-lead perovskite cell photoelectric transformation efficiency that stannum ratio is 50% using two-step method reached 13.6%【Adv. Energy Mater. 2016, 1601353】, make the efficiency of tin-lead perovskite solaode reach a new high degree.With Upper document all makes tin dope methyl ammonium lead iodide perovskite solaode using two step method, and these reports are pointed out only to adopt Make the quality of guarantee battery thin film of two-step method, smooth including the crystallinity of thin film, consistency and film surface Degree etc., and one-step method preparation is impossible to obtain a high-quality battery thin film.Although obtained higher using two-step method Electricity conversion, but experiment Making programme is excessively loaded down with trivial details, not only wastes the plenty of time but also also consumes substantial amounts of money Source, causes cost of manufacture high, and not environmentally.The present invention proposes to process using one-step method and by means of more solvent, makes stannum and mixes Miscellaneous methyl ammonium lead iodide perovskite battery, makes to mix the battery peak efficiency that stannum ratio is 25% and has reached 12.08%, and this invention is Fast and low-cost is prepared such battery and is provided a kind of effective scheme, and the commercial applications for promoting such battery have important meaning Justice.
Content of the invention
The technical problem to be solved is：How tin dope methyl ammonium lead iodide calcium titanium is made using one-step method Ore deposit battery.
The technical solution adopted in the present invention is：A kind of tin dope methyl ammonium lead iodide perovskite solaode, sinks The long-pending anode as battery for the substrate of glass having one layer of uniform indium tin oxide ITO, in the substrate of glass of indium tin oxide ITO A upper redeposited strata (3,4- ethene dioxythiophene)-polystyrolsulfon acid PEDOT:PSS thin film as hole transmission layer, Poly- (3,4- ethene dioxythiophene)-polystyrolsulfon acid PEDOT:Redeposited one layer of active layer on PSS thin film, then in activity Layer one layer of [6,6]-phenyl C60- methyl butyrate PC of spin coating more above60BM, as electron transfer layer, is finally steamed by Vacuum Heat again Plate one layer of continuous aluminium film or silverskin as the negative electrode of battery, active layer is the methyl ammonium lead iodide perovskite of tin dope CH3NH3SnxPb1-xI3Thin film, x is the positive number less than 1.Tin dope methyl ammonium lead iodide perovskite solaode of the present invention There is planar heterojunction structure.
As a kind of optimal way：Deposition one layer of active layer process be：By methylpyridinium iodide amine CH3NH3I, lead iodide PbI2 With Tin tetraiodide. SnI2It is 1.08 according to mol ratio:(1-x):xIt is dissolved in DMF DMF and dimethyl sulfoxide DMSO Form precursor liquid, in precursor liquid, methylpyridinium iodide amine CH in mixed solvent3NH3The molar concentration of I is 1.62 mol/L, N, N- diformazan The volume ratio of base Methanamide DMF and dimethyl sulfoxide DMSO is 10:1, using solution spin-coating method in poly- (3,4- ethylene dioxy thiophenes Fen)-polystyrolsulfon acid PEDOT:Spin coating precursor liquid on PSS thin film, spin coating speed is 6000-6500 rpm, and spin-coating time is 30-40s, during this spin coating, Deca sec-butyl alcohol cleans, that is, requires under keeping substrate of glass rotation status, and Deca is secondary Butanol cleans, and the time starting to clean is carried out after spin coating starts 5-15s, and scavenging period is 1-1.5s, and said process is tied In N after bundle2In atmosphere, 100 °C of annealing 25 s of keeping temperature, then soak 5-10 s, glass base during immersion using sec-butyl alcohol Bottom remains static, and soaks rotary glass substrate again after terminating, speed of rotation 6000-6500 rpm, rotational time 25-35 S, then in N2100 °C of annealing 25 min of keeping temperature in atmosphere, finally anneal under DMF vapourss 25 min, annealing temperature Remain at 100 °C, finally produce the methyl ammonium lead iodide perovskite of the tin dope that thickness is 290 nm -310 nm CH3NH3SnxPb1-xI3Thin film.
The present invention prepares CH in one-step method3NH3SnxPb1-xI3During perovskite thin film, processed by means of more solvent Process, including the cleaning of organic reagent sec-butyl alcohol and immersion process, and N2DMF solvent annealing process under atmosphere.In spin coating CH3NH3SnxPb1-xI3Make use of during perovskite thin film that sec-butyl alcohol instead of traditional toluene, chlorobenzene is carried out to active layer Cleaning, accelerates the transformation by liquid phase to solid phase for the active layer, improves the crystallization rate of active layer；Recycle secondary after preannealing Butanol soaks the planarization that active layer has been also greatly facilitate active layer film, is favorably improved the current intensity of battery, is living Property layer solution configuration process in employ excessive methylpyridinium iodide amine, with sec-butyl alcohol soak also contribute to remove unnecessary methyl Iodate amine；Sec-butyl alcohol used in the present invention compared with conventionally used toluene, chlorobenzene, low cost, small toxicity；N2Under atmosphere DMF solvent annealing process contribute to forming big crystal grain, fine and close CH3NH3SnxPb1-xI3Perovskite thin film.With an existing step Method prepares CH3NH3SnxPb1-xI3Perovskite thin film technology is compared, the CH of present invention preparation3NH3SnxPb1-xI3Perovskite thin film is brilliant Bigger, the finer and close, degree of crystallinity of grain and flatness are higher, thus the CH of preparation3NH3SnxPb1-xI3Perovskite solar cell photoelectric Transformation efficiency is significantly larger than prior art【See Adv. Energy Mater. 2016,1601353】.With existing two-step method system Standby CH3NH3SnxPb1-xI3Perovskite thin film technology【See Nanoscale, 2016,8,7621-7630】Compare, simplify making Flow process, saves Production Time, reduces cost of manufacture.And the CH prepared by the present invention3NH3SnxPb1-xI3The perovskite sun Energy battery is compared with prior art【See Adv. Energy Mater. 2016,1601353, Nanoscale, 2016,8, 7621-7630】, there is simpler structure, be mainly omitted cathode buffer layer.In a word, the present invention is better than now from performance The CH of some one-step method preparations3NH3SnxPb1-xI3Perovskite solaode, is better than existing two-step method system from preparation technology Standby CH3NH3SnxPb1-xI3Perovskite solaode.
As a kind of optimal way：The substrate of glass thickness of indium tin oxide ITO is 100 nm, hole transport strata (3, 4- ethene dioxythiophene)-polystyrolsulfon acid PEDOT:The thickness of PSS is 30 nm-40 nm, deposition process spin coating speed 3000 Rpm, spin-coating time 30-40 s, after the completion of deposition, 120 °C of annealing temperature of holding in atmosphere, annealing time 10-15 min, Electron transfer layer thickness is 40 nm- 50 nm, spin coating speed 2800 rpm, spin-coating time 30-40 s, and cathode electrode layer thickness is 150 Nm, evaporation rate is 0.5 nm/s.
The invention has the beneficial effects as follows：The present invention proposes the one-step method preparation that a kind of employing more solvent processes auxiliary CH3NH3SnxPb1-xI3The method of perovskite solaode, obtains high-quality perovskite thin film it is achieved that high photoelectricity Transformation efficiency.This invention simplifies the operating process of existing two-step method preparation using one-step method, saves Production Time, reduces Cost of manufacture；This invention sec-butyl alcohol instead of traditional toluene, chlorobenzene as cleaning and soaks solvent, not only with low cost, And low toxic and environment-friendly.
Brief description
Fig. 1 is solar battery structure schematic diagram of the present invention；
Fig. 2 is sec-butyl alcohol cleaning and the CH not cleaned3NH3Sn0.25Pb0.75I3Thin film and its scanning electron microscopy of transverse section （SEM）, wherein a is the CH after being cleaned with sec-butyl alcohol3NH3Sn0.25Pb0.75I3The SEM figure of thin film, c is to be cleaned with sec-butyl alcohol CH afterwards3NH3Sn0.25Pb0.75I3The SEM figure of thin cross-sections, b is the CH not cleaned with sec-butyl alcohol3NH3Sn0.25Pb0.75I3 The SEM figure of thin film, d is the CH not cleaned with sec-butyl alcohol3NH3Sn0.25Pb0.75I3The SEM figure of thin cross-sections；
Fig. 3 sec-butyl alcohol cleans and the CH not cleaned3NH3Sn0.25Pb0.75I3The x-ray diffraction spectrum of thin film（XRD）, a represents unclear The CH washing3NH3Sn0.25Pb0.75I3The XRD spectrum of thin film, b represents the CH after sec-butyl alcohol cleaning3NH3Sn0.25Pb0.75I3Thin film XRD spectrum；
Fig. 4 is CH under different annealing conditions3NH3Sn0.25Pb0.75I3The SEM picture of thin film, a represents CH3NH3Sn0.25Pb0.75I3 Perovskite thin film is in N2In atmosphere, 100 °C of temperature lower thermal annealing 25 min, then under DMF vapourss, at 100 °C of temperature The CH that 25 min that anneal are formed3NH3Sn0.25Pb0.75I3The SEM figure of thin film；B represents CH3NH3Sn0.25Pb0.75I3Perovskite is thin Film in atmosphere, 100 °C of temperature lower thermal annealing 25 min, 25 min shapes of then annealing at 100 °C of temperature under DMF vapourss The CH becoming3NH3Sn0.25Pb0.75I3The SEM figure of thin film；C represents CH3NH3Sn0.25Pb0.75I3Perovskite thin film is in N2In atmosphere, The CH that 100 °C of temperature lower thermal annealing 25 min is formed3NH3Sn0.25Pb0.75I3The SEM figure of thin film；
Fig. 5 is CH under different annealing conditions3NH3Sn0.25Pb0.75I3The X-ray diffraction spectrum of thin film（XRD）, a represents will CH3NH3Sn0.25Pb0.75I3Perovskite thin film is in N2In atmosphere, 100 °C of temperature lower thermal annealing 25 min, then in DMF vapourss The CH that 25 min that anneal at 100 °C of lower temperature are formed3NH3Sn0.25Pb0.75I3The XRD spectrum of thin film；B represents will CH3NH3Sn0.25Pb0.75I3Perovskite thin film is in N2In atmosphere, 100 °C of temperature lower thermal annealing 25 min formed CH3NH3Sn0.25Pb0.75I3The XRD spectrum of thin film.C represents CH3NH3Sn0.25Pb0.75I3Perovskite thin film in atmosphere, temperature 100 °C of lower thermal annealing 25 min, then anneal what 25 min were formed at 100 °C of temperature under DMF vapourss CH3NH3Sn0.25Pb0.75I3The XRD spectrum of thin film；
Fig. 6 is CH3NH3Sn0.25Pb0.75I3The current -voltage curve of perovskite solaode, the open-circuit voltage of this battery 0.77 V, short-circuit current density 24 mA/cm2, fill factor, curve factor 66%, electricity conversion 12.08%；
Fig. 7 is CH3NH3Sn0.25Pb0.75I3The external quantum efficiency curve of perovskite solaode；
Wherein, 1, the substrate of glass of indium tin oxide ITO, 2, poly- (3,4-rthylene dioxythiophene)-polystyrolsulfon acid （PEDOT:PSS）Thin film, 3, the methyl ammonium lead iodide perovskite of tin dope（CH3NH3SnxPb1-xI3）Thin film, 4, [6,6]- Phenyl C60- methyl butyrate（PC60BM）Layer, 5, aluminium film or silverskin.
Specific embodiment
As shown in figure 1, tin dope methyl ammonium lead iodide perovskite solaode has planar heterojunction structure：This reality Applying solar battery structure in example is：ITO/PEDOT:PSS/ CH3NH3SnxPb1-xI3/PC60BM/Al.
In battery structure, the thickness of ito anode is 100 nm, square resistance 10 Ω.
In battery structure, hole transmission layer PEDOT:The thickness of PSS is 30 nm, using solution spin-coating method film forming, Ran Houkong Anneal in gas and be obtained, spin coating speed 3000 rpm, spin-coating time 30 s, 120 °C of annealing temperature, annealing time 10 min,
In battery structure, active layer is CH3NH3Sn0.25Pb0.75I3Perovskite thin film, by methylpyridinium iodide amine（CH3NH3I）, iodate Lead（PbI2）And Tin tetraiodide.（SnI2）According to 1.08:0.25:0.75 mol ratio is dissolved in DMF（DMF）With two Methyl sulfoxide（DMSO）In mixed solvent, then make by spin coating proceeding and with reference to more solvent handling process.
In battery structure, electron transport material is fullerene derivate [6,6]-phenyl C60- methyl butyrate（PC60BM）Structure Become, be obtained using solution spin-coating method, spin coating speed 2800 rpm, spin-coating time 30 s, thickness thickness is 40 nm,
In battery structure, negative electrode is by Al film, is prepared using vacuum thermal evaporation method, film thickness 150 nm, evaporation rate is 0.5 nm/s,
Using solution spin-coating method in ITO/PEDOT:Spin coating CH in PSS substrate3NH3Sn0.25Pb0.75I3Precursor liquid, one-step method system The standby uniform CH of a layer thickness3NH3Sn0.25Pb0.75I3Perovskite thin film, spin coating speed 6300 rpm, spin-coating time 35 s, here During rotation Deca sec-butyl alcohol clean once, sec-butyl alcohol consumption 300 l, place it in after rotary sample terminates in thermal station N2In atmosphere, 100 °C of temperature lower preannealing 25 s, then again Deca sec-butyl alcohol soak 8 s, sec-butyl alcohol consumption 300 l, subsequently Spin coating 30 s under 6300 rpm speed, then be placed in thermal station in N2In atmosphere, 100 °C of temperature lower thermal annealing 25 min, immediately 25 min that anneal under DMF vapourss, annealing temperature remains at 100 °C, the thickness finally produced is 300 nm,
Described CH3NH3Sn0.25Pb0.75I3Perovskite precursor liquid is by methylpyridinium iodide amine（CH3NH3I）, lead iodide（PbI2）And iodine Change stannum（SnI2）According to 1.08:0.25:0.75 mol ratio is dissolved in DMF（DMF）And dimethyl sulfoxide （DMSO）A kind of flavous solution being formed in mixed solvent.
Described DMF（DMF）And dimethyl sulfoxide（DMSO）The volume ratio of mixed solvent is 10:1,
Described CH3NH3Molar concentration 1.62 mol/L of I, described Tin tetraiodide.（SnI2）Molar concentration be 0.375 Mol/L, described lead iodide（PbI2）Molar concentration be 1.125 mol/L,
Described sec-butyl alcohol cleaning process, is in spin coating CH3NH3Sn0.25Pb0.75I3Carry out during perovskite thin film, Start spin coating CH3NH3Sn0.25Pb0.75I3Perovskite thin film starts timing, and the 13rd s starts sec-butyl alcohol cleaning, and cleaning process is in 1 s Inside complete, butanol cleans and the CH not cleaned3NH3Sn0.25Pb0.75I3Thin film compares figure is as shown in Figures 2 and 3.
Described sec-butyl alcohol immersion process, is in spin coating CH3NH3Sn0.25Pb0.75I3Perovskite thin film terminates and in N2Atmosphere In, carry out after 100 °C of temperature lower preannealing 25 s, CH in immersion process3NH3Sn0.25Pb0.75I3Perovskite thin film is static not Dynamic, soak time 8 s.
Described annealing process, is made up of successively three annealing processes, be for the first time sec-butyl alcohol is cleaned after CH3NH3Sn0.25Pb0.75I3Perovskite thin film, in N2In atmosphere, at 100 °C of temperature, carry out preannealing 25 s, second annealed Journey is the CH after soaking sec-butyl alcohol3NH3Sn0.25Pb0.75I3Perovskite thin film after spin coating, in N2In atmosphere, 100 ° of temperature Thermal annealing 25 min under C, anneals followed by third time, is in N2Annealing 25 in atmosphere and DMF vapourss, at 100 °C of temperature Min, CH under different annealing conditions3NH3Sn0.25Pb0.75I3Thin film is as shown in Figure 4 and Figure 5.
The present invention preparation tin dope methyl ammonium lead iodide perovskite solar cell properties figure as shown in Figure 6 and Figure 7, It can be seen that present invention obtains high-quality perovskite thin film is it is achieved that high electricity conversion.

Claims (3)

1. a kind of tin dope methyl ammonium lead iodide perovskite solaode it is characterised in that：Deposition has one layer of uniform indium The substrate of glass of tin-oxide ITO as the anode of battery, a redeposited strata in the substrate of glass of indium tin oxide ITO (3,4- ethene dioxythiophene)-polystyrolsulfon acid PEDOT:PSS thin film as hole transmission layer, in poly- (3,4- ethylene two Oxygen thiophene)-polystyrolsulfon acid PEDOT:Redeposited one layer of active layer on PSS thin film, then in active layer spin coating one again Layer [6,6]-phenyl C60- methyl butyrate PC60BM, as electron transfer layer, finally passes through the continuous aluminum of one layer of vacuum thermal evaporation again , as the negative electrode of battery, active layer is the methyl ammonium lead iodide perovskite CH of tin dope for film or silverskin3NH3SnxPb1-xI3Thin Film, x is the positive number less than 1.
2. a kind of tin dope methyl ammonium lead iodide perovskite solaode according to claim it is characterised in that： Deposition one layer of active layer process be：By methylpyridinium iodide amine CH3NH3I, lead iodide PbI2With Tin tetraiodide. SnI2According to mol ratio it is 1.08:(1-x):xIt is dissolved in formation precursor liquid in DMF DMF and dimethyl sulfoxide DMSO mixed solvent, front Drive in liquid, methylpyridinium iodide amine CH3NH3The molar concentration of I is 1.62 mol/L, DMF DMF and dimethyl sulfoxide The volume ratio of DMSO is 10:1, using solution spin-coating method in poly- (3,4-rthylene dioxythiophene)-polystyrolsulfon acid PEDOT: Spin coating precursor liquid on PSS thin film, spin coating speed is 6000-6500 rpm, and spin-coating time is 30-40s, starts 5-15s in spin coating In the case of keeping spin coating precursor liquid afterwards, Deca sec-butyl alcohol cleans, and scavenging period is 1-1.5s, before continuing spin coating after the completion of cleaning Drive liquid until stopping spin coating after completing precursor liquid spin-coating time, in N2In atmosphere, 100 °C of annealing 25 s of keeping temperature, then make Soak 5-10 s with sec-butyl alcohol, remain static during immersion, soak and terminate rear rotary glass substrate, speed of rotation 6000- 6500 rpm, rotational time 25-35 s, then in N2In atmosphere, 100 °C of annealing 25 min of keeping temperature, finally steam in DMF heat Anneal under vapour 25 min, and annealing temperature remains at 100 °C, finally produces the tin dope that thickness is 290 nm -310 nm Methyl ammonium lead iodide perovskite CH3NH3SnxPb1-xI3Thin film.
3. a kind of tin dope methyl ammonium lead iodide perovskite solaode according to claim 1 it is characterised in that： The substrate of glass thickness of indium tin oxide ITO is 100 nm, hole transport strata (3,4-rthylene dioxythiophene)-polystyrene Sulfonic acid PEDOT:The thickness of PSS is 30 nm-40 nm, and deposition process spin coating speed 3000 rpm, spin-coating time 30-40 s sink After the completion of long-pending, keep 120 °C of annealing temperature, annealing time 10-15 min in atmosphere, electron transfer layer thickness is 40 nm- 50 nm, spin coating speed 2800 rpm, spin-coating time 30-40 s, cathode electrode layer thickness is 150 nm, and evaporation rate is 0.5 nm/s.
CN201611006451.1A 2016-11-16 2016-11-16 A kind of tin dope methyl ammonium lead iodide perovskite solar cell Active CN106384785B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201611006451.1A CN106384785B (en) 2016-11-16 2016-11-16 A kind of tin dope methyl ammonium lead iodide perovskite solar cell

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201611006451.1A CN106384785B (en) 2016-11-16 2016-11-16 A kind of tin dope methyl ammonium lead iodide perovskite solar cell

Publications (2)

Publication Number Publication Date
CN106384785A true CN106384785A (en) 2017-02-08
CN106384785B CN106384785B (en) 2018-10-23

Family

ID=57958680

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201611006451.1A Active CN106384785B (en) 2016-11-16 2016-11-16 A kind of tin dope methyl ammonium lead iodide perovskite solar cell

Country Status (1)

Country Link
CN (1) CN106384785B (en)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107359246A (en) * 2017-06-20 2017-11-17 太原理工大学 A kind of preparation method of methylamine lead iodine perovskite solar cell
CN107887512A (en) * 2017-12-02 2018-04-06 浙江师范大学 A kind of structure, preparation method and the application of perovskite solar cell
CN108183171A (en) * 2018-01-17 2018-06-19 浙江师范大学 A kind of adjustable perovskite solar cell of absorption spectrum
CN109065738A (en) * 2018-08-13 2018-12-21 许昌学院 Method based on Pot metal in-situ one-step synthesis high-crystallinity Copper-cladding Aluminum Bar perovskite thin film
CN110323337A (en) * 2019-06-26 2019-10-11 广西大学 A kind of slicker solder binary perovskite photodetector and preparation method thereof
CN110379924A (en) * 2019-06-11 2019-10-25 北京大学深圳研究生院 A kind of perovskite infrared electro transistor and preparation method thereof
CN113437222A (en) * 2021-06-16 2021-09-24 西北工业大学 Lead-free tin-based perovskite thin film, lead-free tin-based perovskite solar cell and preparation method of lead-free tin-based perovskite solar cell
CN113584594A (en) * 2020-04-30 2021-11-02 南京理工大学 Methylamine lead-iodine monocrystal film doped at lead position and preparation method thereof
WO2022127186A1 (en) * 2020-12-15 2022-06-23 中国华能集团清洁能源技术研究院有限公司 High-stability tin-containing perovskite precursor solution, photoactive layer and battery, and preparation methods therefor

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104300083A (en) * 2014-09-29 2015-01-21 中国科学院广州能源研究所 Method for preparing organic-inorganic perovskite structure heterocomplex thin film solar cell
WO2016105537A1 (en) * 2014-12-23 2016-06-30 Los Alamos National Security, Llc Crystalline perovskite thin films and devices that include the films
CN105870337A (en) * 2016-04-01 2016-08-17 北京化工大学 Preparation and application of highly smooth and compact perovskite thin film material
US20160254472A1 (en) * 2015-02-26 2016-09-01 Nanyang Technological University Perovskite thin films having large crystalline grains
CN106033796A (en) * 2016-07-29 2016-10-19 陕西师范大学 Perovskite thin film battery and absorbing layer thereof and preparation method of absorbing layer

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104300083A (en) * 2014-09-29 2015-01-21 中国科学院广州能源研究所 Method for preparing organic-inorganic perovskite structure heterocomplex thin film solar cell
WO2016105537A1 (en) * 2014-12-23 2016-06-30 Los Alamos National Security, Llc Crystalline perovskite thin films and devices that include the films
US20160254472A1 (en) * 2015-02-26 2016-09-01 Nanyang Technological University Perovskite thin films having large crystalline grains
CN105870337A (en) * 2016-04-01 2016-08-17 北京化工大学 Preparation and application of highly smooth and compact perovskite thin film material
CN106033796A (en) * 2016-07-29 2016-10-19 陕西师范大学 Perovskite thin film battery and absorbing layer thereof and preparation method of absorbing layer

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
YUNLONG LI等: "50% Sn‐Based Planar Perovskite Solar Cell with Power Conversion Efficiency up to 13.6%", 《ADVANCED ENERGY MATERIALS》 *
ZHANG F等: "Sec-Butyl alcohol assisted pinhole-free perovskite film growth for high-performance solar cells", 《JOURNAL OF MATERIALS CHEMISTRY A 》 *

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107359246B (en) * 2017-06-20 2020-04-28 太原理工大学 Manufacturing method of methylamine lead iodoperovskite solar cell
CN107359246A (en) * 2017-06-20 2017-11-17 太原理工大学 A kind of preparation method of methylamine lead iodine perovskite solar cell
CN107887512A (en) * 2017-12-02 2018-04-06 浙江师范大学 A kind of structure, preparation method and the application of perovskite solar cell
CN108183171A (en) * 2018-01-17 2018-06-19 浙江师范大学 A kind of adjustable perovskite solar cell of absorption spectrum
CN109065738A (en) * 2018-08-13 2018-12-21 许昌学院 Method based on Pot metal in-situ one-step synthesis high-crystallinity Copper-cladding Aluminum Bar perovskite thin film
CN109065738B (en) * 2018-08-13 2022-05-06 许昌学院 Method for in-situ synthesis of high-crystallinity copper-doped perovskite thin film
CN110379924A (en) * 2019-06-11 2019-10-25 北京大学深圳研究生院 A kind of perovskite infrared electro transistor and preparation method thereof
CN110323337A (en) * 2019-06-26 2019-10-11 广西大学 A kind of slicker solder binary perovskite photodetector and preparation method thereof
CN113584594A (en) * 2020-04-30 2021-11-02 南京理工大学 Methylamine lead-iodine monocrystal film doped at lead position and preparation method thereof
CN113584594B (en) * 2020-04-30 2022-05-13 南京理工大学 Methylamine lead-iodine monocrystal film doped at lead position and preparation method thereof
WO2022127186A1 (en) * 2020-12-15 2022-06-23 中国华能集团清洁能源技术研究院有限公司 High-stability tin-containing perovskite precursor solution, photoactive layer and battery, and preparation methods therefor
CN113437222A (en) * 2021-06-16 2021-09-24 西北工业大学 Lead-free tin-based perovskite thin film, lead-free tin-based perovskite solar cell and preparation method of lead-free tin-based perovskite solar cell
CN113437222B (en) * 2021-06-16 2023-09-08 西北工业大学 Lead-free tin-based perovskite thin film, lead-free tin-based perovskite solar cell and preparation method thereof

Also Published As

Publication number Publication date
CN106384785B (en) 2018-10-23

Similar Documents

Publication Publication Date Title
CN106384785A (en) Tin-doped CH3NH3SnxPb1-xI3 perovskite solar cell
CN105070841B (en) A kind of preparation method of perovskite solar cell
CN107240643B (en) Bromo element adulterates methylamine lead iodine perovskite solar battery and preparation method thereof
CN106887520B (en) A kind of perovskite solar battery and preparation method thereof of additive auxiliary
CN108598268B (en) Method for preparing planar heterojunction perovskite solar cell by printing under environmental condition
CN107611190A (en) A kind of perovskite solar cell resistant to bending and preparation method
CN109904318B (en) Perovskite thin film preparation method based on anti-solution bath and solar cell
CN110246967B (en) Method for preparing flexible perovskite solar cell at low temperature
CN104993058B (en) A kind of laminated perovskite structure material and the application in methylamine lead iodine perovskite thin film solar cell
Guo et al. A strategy toward air-stable and high-performance ZnO-based perovskite solar cells fabricated under ambient conditions
CN108899420A (en) The preparation method and perovskite solar cell device of perovskite thin film
CN104393177B (en) Solar cell based on Perovskite Phase organic metal halide and preparation method thereof
CN105870341A (en) Method for improving growth quality of perovskite crystal and solar cell device
CN108878661A (en) A kind of preparation method of the perovskite solar battery of carbon quantum dot modification
CN107887510A (en) A kind of two-dimensional layer perovskite thin film, solar cell and preparation method thereof
CN106340587A (en) Perovskite film preparation method and perovskite solar cell
Han et al. A functional sulfonic additive for high efficiency and low hysteresis perovskite solar cells
CN105810831A (en) Lead-tin hybrid perovskite thin film, and preparation method and application therefor
CN110112301A (en) It is a kind of regulate and control calcium titanium ore bed crystal growth method and its application in solar cells
Xi et al. Highly efficient inverted perovskite solar cells mediated by electrodeposition-processed NiO NPs hole-selective contact with different energy structure and surface property
CN115332454A (en) Perovskite solar cell and preparation method thereof
CN106450007A (en) Solar cell based on cuprous iodide/calcium titanium ore bulk heterojunction and preparation method thereof
CN111192964B (en) Perovskite quantum dot solar cell and preparation method thereof
CN108832001A (en) A kind of unleaded perovskite solar cell device and preparation method thereof
CN105070838B (en) A kind of Ca-Ti ore type solar cell of multiple orientation ordered crystalline and preparation method thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant