The Preparation And Photoelectric Properties Of Layered Organic-inorganic Hybrids （C₆H₅CH₂NH₃）₂（CH₃NH₃）₂Pb₃I₁₀ Film

Layered organic-inorganic perovskite materials show good crystallization,film-forming properties and excellent humidity stability owe to its unique organic-inorganic laminated structure,providing a new way to solve the problems about large size preparation and humidity stability.In this paper,organic amine cation C₆H₅CH₂NH₃⁺（BZA）was introduced into CH₃NH₃PbI₃（MAPbI₃）to prepare layered organic-inorganic perovskite material（BZA）₂（MA）₂Pb₃I₁₀,and explored the best preparation process of（BZA）₂（MA）₂Pb₃I₁₀ thin films.In addition,the organic diamine cation[NH₃（CH₂）₆NH₃]²⁺（HDA）was introduced into MAPbI₃ for the first time to prepare the（HDA）（MA）₂Pb₃I₁₀ thin films,and the morphology,structure,photoelectric properties and humidity stability of the films were studied.When added（HDA）（MA）₂Pb₃I₁₀ into（BZA）₂（MA）₂Pb₃I₁₀ thin films,the effects of（HDA）（MA）₂Pb₃I₁₀0 doping concentration on the morphology,structure,photoelectric properties and humidity stability of（BZA）_2-2x（HDA）_x（MA）₂Pb₃I₁₀（n=0.025,0.050,0.075,0.100）thin films were studied.The main research results are as follows:（1）The（BZA）₂（MA）₂Pb₃I₁₀ thin films were prepared by one-step spin coating,and the effects of perovskite precursor solution concentration,anti solvent technology,annealing temperature and time on the morphology,structure and photoelectric properties of the films were investigated.The results showed that the concentration of precursor solution,anti solvent technology,annealing temperature and time have a significant effect on the morphology of（BZA）₂（MA）₂Pb₃I₁₀ films and the photoelectric conversion properties of perovskite solar cells,but have no obvious effect on the composition,structure and forbidden band width of the films.The（BZA）₂（MA）₂Pb₃I₁₀ thin films are composed of（BZA）₂（MA）₂Pb₃I₁₀ and a small number of secondary products（BZA）₂（MA）Pb₂I₇ and（BZA）₂PbI₄,and their forbidden band widths are respectively 1.95eV,2.10eV and 2.25eV.When the precursor solution concentration is 0.4M,the best quality（BZA）₂（MA）₂Pb₃I₁₀ film can be prepared by utilizing the anti solvent（CBZ）process,then annealing at 60℃for 30min and the photoelectric conversion efficiency of the battery device is 1.59%.（2）When the organic diamine cation HDA was introduced into MAPbI₃,double amine layered organic-inorganic perovskite material（HDA）（MA）₂Pb₃I₁₀ was obtained,and investigated the morphology,structure and photoelectric properties of（HDA）（MA）₂Pb₃I₁₀ thin film,obtaining its perovskite solar cell with photoelectric conversion efficiency of 3.24%.Compared with（BZA）₂（MA）₂Pb₃I₁₀ thin film,（HDA）（MA）₂Pb₃I₁₀ thin film has better crystallization,film formation and photoelectric properties,but its humidity stability is relatively poor,easy to decompose in wet environment.（3）The incorporation of（HDA）（MA）₂Pb₃I₁₀ into（BZA）₂（MA）₂Pb₃I₁₀ film can effectively improve the conductivity of（BZA）_2-2x（HDA）_x（MA）₂Pb₃I₁₀0 thin films and the photoelectric conversion efficiency of their battery devices.The incorporation of（HDA）（MA）₂Pb₃I₁₀ affects the crystalline state and morphology of（BZA）_2-2x（HDA）_x（MA）₂Pb₃I₁₀ thin films,but does not affect the structure,visible light absorption capacity and forbidden band width of the films.When the compositionoflayeredorganic-inorganicperovskitethinfilmsis（BZA）_1.90（HDA）_0.05（MA）₂Pb₃I₁₀,the conductivity and the photoelectric conversion efficiency of perovskite solar cells reach the highest（3.33%）and showed good humidity stability.