The application of polymers to replace oleylamine(OLA)and oleic acid(OA)as ligands for perovskite nanocrystals is an effective strategy to improve their stability and durability especially for the solution-based proce...The application of polymers to replace oleylamine(OLA)and oleic acid(OA)as ligands for perovskite nanocrystals is an effective strategy to improve their stability and durability especially for the solution-based processing.Herein,we report a mechanosynthesis of lead bromide perovskite nanoparticles(NPs)stabilized by partially hydrolyzed poly(methyl methacrylate)(h-PMMA)and highmolecular-weight highly-branched poly(ethylenimine)(PEI-25K).The as-synthesized NP solutions exhibited green emission centered at 516 nm,possessing a narrow full-width at half-maximum of 17 nm and as high photoluminescence quantum yield(PL QY)as 85%,while showing excellent durability and resistance to polar solvents,e.g.,methanol.The colloids of polymer-stabilized NPs were directly processable toform stable and strongly-emitting thin films and solids,making them attractive as gain media.Furthermore,the roles of h-PMMA and PEI-25K in the grinding process were studied in depth.The h-PMMA can form micelles in the grinding solvent of dichloromethane to act as size-regulating templates for the growth of NPs.The PEI-25K with large amounts of amino groups induced significant enrichment of PbBr_(2)in the reaction mixture,which in turn caused the formation of CsPb_(2)Br_(5)-mPbBr_(2)and CsPbBr_(3)-Cs_(4)PbBr_(6)-nCsBr NPs.The presence of CsPbBr_(3)-Cs_(4)PbBr_(6)-nCsBr NPs was responsible for the high PL QY,as the Cs_(4)PbBr_(6)phase with a wide energy bandgap can passivate the surface defects of the CsPbBr_(3)phase.This work describes a direct and facile mechanosynthesis of polymer-coordinated perovskite NPs and promotes in-depth understanding of the formation and phase conversion for perovskite NPs in the grinding process.展开更多
A nanofabrication method for the production of ultra-dense planar metallic nanowire arrays scalable to wafer-size is presented. The method is based on an efficient template deposition process to grow diverse metallic ...A nanofabrication method for the production of ultra-dense planar metallic nanowire arrays scalable to wafer-size is presented. The method is based on an efficient template deposition process to grow diverse metallic nanowire arrays with extreme regularity in only two steps. First, Ⅲ-Ⅴ semiconductor substrates are irradiated by a low-energy ion beam at an elevated temperature, forming a highly ordered nanogroove pattern by a ＂reverse epitaxy＂ process due to self-assembly of surface vacancies. Second, diverse metallic nanowire arrays （Au, Fe, Ni, Co, FeAl alloy） are fabricated on these Ⅲ-Ⅴ templates by deposition at a glancing incidence angle. This method allows for the fabrication of metallic nanowire arrays with periodicities down to 45 nm scaled up to wafer-size fabrication. As typical noble and magnetic metals, the Au and Fe nanowire arrays produced here exhibited large anisotropic optical and magnetic properties, respectively. The excitation of localized surface plasmon resonances （LSPRs） of the Au nanowire arrays resulted in a high electric field enhancement, which was used to detect phthalocyanine （CoPc） in surface-enhanced Raman scattering （SERS）. Furthermore, the Fe nanowire arrays showed a very high in-plane magnetic anisotropy of approximately 412 mT, which may be the largest in-plane magnetic anisotropy field yet reported that is solely induced via shape anisotropy within the plane of a thin film.展开更多
基金G.J.acknow ledges the China Scholarship Council(No.201706740088).This work was partly supported by the bilateral IB-BMBF-TOBITAK Project ColMiBack(01DL20002)and DFG project EY 16/14-3.O.E.acknowledges TOBITAK for the financial support through BIDEB-2211 program.H.V.D.gratefully acknowledges support from TUBA.The use of the HZDR Ion Beam Center TEM facilities and the funding of TEM Talos by the German Federal Ministry of Education of Research(BMBF),Grant No.03SF0451,in the framework o f HEMCP are acknowledged.M.G.acknowledges the Swiss National Science Foundation(SNF)and the German Research Foundation(DFG EY 16/18-2)for financial support.W.W.received supports from Jiangsu Overseas Visiting Scholar Program for University Prom inent Young&Middle-aged Teachers and Presidents.X.F.acknowledges the China Scholarship Council(No.201606340161).J.W.received supports from the National Natural Science Foundation of China(No.21701143).We are very grateful to Prof.A lexander Eychmuller,Dr.Vladim ir Lesnyak and Dr.Alexey Shavel for the valuable discussions.We are grateful to Susanne Goldberg for TEM imaging,Franziska Eichler for the instruction to the PL decay measurements.We appreciate Linlin Wang and Dr.Juliane Simmchen for their help with DLS measurements.We thank Dr.Andre Wolf for his corrections to the draft.
文摘The application of polymers to replace oleylamine(OLA)and oleic acid(OA)as ligands for perovskite nanocrystals is an effective strategy to improve their stability and durability especially for the solution-based processing.Herein,we report a mechanosynthesis of lead bromide perovskite nanoparticles(NPs)stabilized by partially hydrolyzed poly(methyl methacrylate)(h-PMMA)and highmolecular-weight highly-branched poly(ethylenimine)(PEI-25K).The as-synthesized NP solutions exhibited green emission centered at 516 nm,possessing a narrow full-width at half-maximum of 17 nm and as high photoluminescence quantum yield(PL QY)as 85%,while showing excellent durability and resistance to polar solvents,e.g.,methanol.The colloids of polymer-stabilized NPs were directly processable toform stable and strongly-emitting thin films and solids,making them attractive as gain media.Furthermore,the roles of h-PMMA and PEI-25K in the grinding process were studied in depth.The h-PMMA can form micelles in the grinding solvent of dichloromethane to act as size-regulating templates for the growth of NPs.The PEI-25K with large amounts of amino groups induced significant enrichment of PbBr_(2)in the reaction mixture,which in turn caused the formation of CsPb_(2)Br_(5)-mPbBr_(2)and CsPbBr_(3)-Cs_(4)PbBr_(6)-nCsBr NPs.The presence of CsPbBr_(3)-Cs_(4)PbBr_(6)-nCsBr NPs was responsible for the high PL QY,as the Cs_(4)PbBr_(6)phase with a wide energy bandgap can passivate the surface defects of the CsPbBr_(3)phase.This work describes a direct and facile mechanosynthesis of polymer-coordinated perovskite NPs and promotes in-depth understanding of the formation and phase conversion for perovskite NPs in the grinding process.
基金This work was supported by the National Natural Science Foundation of China （Nos. 11622545 and U1732268）, One Hundred Talent Program of CAS and the Deutsche Forschungsgemeinschaft （No. LE2443/5-1）.
文摘A nanofabrication method for the production of ultra-dense planar metallic nanowire arrays scalable to wafer-size is presented. The method is based on an efficient template deposition process to grow diverse metallic nanowire arrays with extreme regularity in only two steps. First, Ⅲ-Ⅴ semiconductor substrates are irradiated by a low-energy ion beam at an elevated temperature, forming a highly ordered nanogroove pattern by a ＂reverse epitaxy＂ process due to self-assembly of surface vacancies. Second, diverse metallic nanowire arrays （Au, Fe, Ni, Co, FeAl alloy） are fabricated on these Ⅲ-Ⅴ templates by deposition at a glancing incidence angle. This method allows for the fabrication of metallic nanowire arrays with periodicities down to 45 nm scaled up to wafer-size fabrication. As typical noble and magnetic metals, the Au and Fe nanowire arrays produced here exhibited large anisotropic optical and magnetic properties, respectively. The excitation of localized surface plasmon resonances （LSPRs） of the Au nanowire arrays resulted in a high electric field enhancement, which was used to detect phthalocyanine （CoPc） in surface-enhanced Raman scattering （SERS）. Furthermore, the Fe nanowire arrays showed a very high in-plane magnetic anisotropy of approximately 412 mT, which may be the largest in-plane magnetic anisotropy field yet reported that is solely induced via shape anisotropy within the plane of a thin film.
