[{"data":1,"prerenderedAt":-1},["ShallowReactive",2],{"detail-sidebar-cat-0-en-105":3,"doc-seo-450026-105":59,"doc-detail-450026-en":130},{"code":4,"msg":5,"data":6},0,"success",[7,13,18,23,28,33,38,43,48,51,55],{"id":8,"doc_module":4,"doc_module_name":9,"category_name":10,"show_sort_weight":11,"slug":12},1,"Document","Story & Novel",90,"story-novel",{"id":14,"doc_module":4,"doc_module_name":9,"category_name":15,"show_sort_weight":16,"slug":17},2,"Literature",80,"literature",{"id":19,"doc_module":4,"doc_module_name":9,"category_name":20,"show_sort_weight":21,"slug":22},4,"Exam",70,"exam",{"id":24,"doc_module":4,"doc_module_name":9,"category_name":25,"show_sort_weight":26,"slug":27},5,"Comic",60,"comic",{"id":29,"doc_module":4,"doc_module_name":9,"category_name":30,"show_sort_weight":31,"slug":32},6,"Technology",50,"technology",{"id":34,"doc_module":4,"doc_module_name":9,"category_name":35,"show_sort_weight":36,"slug":37},7,"Healthcare",40,"healthcare",{"id":39,"doc_module":4,"doc_module_name":9,"category_name":40,"show_sort_weight":41,"slug":42},8,"Research & Report",30,"research-report",{"id":44,"doc_module":4,"doc_module_name":9,"category_name":45,"show_sort_weight":46,"slug":47},9,"Religion & Spirituality",20,"religion-spirituality",{"id":46,"doc_module":4,"doc_module_name":9,"category_name":49,"show_sort_weight":46,"slug":50},"World Cup","world-cup",{"id":52,"doc_module":4,"doc_module_name":9,"category_name":53,"show_sort_weight":52,"slug":54},10,"Lifestyle","lifestyle",{"id":56,"doc_module":4,"doc_module_name":9,"category_name":57,"show_sort_weight":24,"slug":58},19,"General","general",{"code":4,"msg":60,"data":61},"ok",{"site_id":62,"language":63,"slug":64,"title":65,"keywords":66,"description":67,"schema_data":68,"social_meta":123,"head_meta":125,"extra_data":127,"updated_unix":129},105,"en","tuning-optical-properties-and-local-lone-pair-off-centering-in-hollow-fa1-xenxpbh-ysnybr3-perovskites","Tuning optical properties and local lone-pair off-centering in “hollow” FA1-x{en}xPbh-ySnyBr3 perovskites","","Hollow metal halide perovskites extend tunability within limited compositional spaces, enabling control of optical properties and local structure via lone-pair induced off-centering. The study focuses on mixed-metal FA1−xenxPbh−ySnyBr3 hollow perovskites with optical gaps from 1.9 eV to 2.6 eV, combining Pb/Sn bandgap red-shifting and blue-shifting from organic substitution. Single-crystal X-ray diffraction and total X-ray scattering pair distribution function analyses reveal incoherent off-centering distortions locally correlated with Sn concentration. Ethylenediammonium dications regulate metal off-centering, opening research opportunities.",{"@graph":69,"@context":122},[70,84,105],{"@type":71,"itemListElement":72},"BreadcrumbList",[73,77,79,82],{"item":74,"name":75,"@type":76,"position":8},"https://docshare.wps.com","Home","ListItem",{"item":78,"name":9,"@type":76,"position":14},"https://docshare.wps.com/document/",{"item":80,"name":40,"@type":76,"position":81},"https://docshare.wps.com/document/research-report/",3,{"item":83,"name":65,"@type":76,"position":19},"https://docshare.wps.com/document/tuning-optical-properties-and-local-lone-pair-off-centering-in-hollow-fa1-xenxpbh-ysnybr3-perovskites/450026/",{"url":83,"name":65,"@type":85,"image":86,"author":91,"headline":65,"publisher":94,"fileFormat":97,"inLanguage":63,"description":67,"dateModified":98,"datePublished":99,"encodingFormat":97,"isAccessibleForFree":100,"interactionStatistic":101},"DigitalDocument",{"url":87,"@type":88,"width":89,"height":90},"https://docshare.wps.com/thumbnails/tuning-optical-properties-and-local-lone-pair-off-centering-in-hollow-fa1-xenxpbh-ysnybr3-perovskites/450026.png","ImageObject",300,407,{"name":92,"@type":93},"Logic","Person",{"url":74,"name":95,"@type":96},"DocShare","Organization","application/pdf","2026-10-07","2026-09-30",true,{"@type":102,"interactionType":103,"userInteractionCount":81},"InteractionCounter",{"@type":104},"ViewAction",{"@type":106,"mainEntity":107},"FAQPage",[108,114,118],{"name":109,"@type":110,"acceptedAnswer":111},"What material system is investigated in the study?","Question",{"text":112,"@type":113},"The research examines mixed-metal hollow perovskites of the form FA1−xenxPbh−ySnyBr3, where ethylenediammonium regulates structural behavior and Pb/Sn mixing tunes optical responses.","Answer",{"name":115,"@type":110,"acceptedAnswer":116},"How are optical properties tuned across the studied compounds?",{"text":117,"@type":113},"Optical gaps range from 1.9 eV to 2.6 eV by combining anomalous bandgap red-shifting from Pb/Sn mixing with blue-shifting effects caused by organic substitution.",{"name":119,"@type":110,"acceptedAnswer":120},"What evidence is used to analyze local structure and off-centering?",{"text":121,"@type":113},"Average and local structural studies use single-crystal X-ray diffraction and total X-ray scattering pair distribution function analyses, which indicate strong incoherent off-centering distortions correlated with Sn concentration.","https://schema.org",{"og:url":83,"og:type":124,"og:title":65,"og:site_name":95,"og:description":67},"article",{"robots":126,"canonical":83},"index,follow",{"doc_id":128,"site_id":62},450026,1791030874,{"code":4,"msg":5,"data":131},{"doc_id":128,"user_id":132,"nickname":92,"user_avatar":133,"doc_module":4,"category_id":39,"category_name":40,"doc_title":65,"doc_description":67,"doc_content":134,"file_id":135,"file_url":136,"file_type":137,"file_size":138,"view_count":81,"is_deleted":4,"is_public":8,"is_downloadable":8,"audit_status":8,"page_count":139,"language":140,"language_code":63,"site_id":62,"html_lang":63,"table_of_contents":141,"faqs":142,"seo_title":143,"seo_description":67,"update_tm":144,"read_time":145},1099513958762,"https://ap-avatar.wpscdn.com/avatar/1000023916a998db790?x-image-process=image/resize,m_fixed,w_180,h_180&k=1784791008015729253","Chemical Science  \nEDGE ARTICLE  \nCite this: DOI: 10 .1039/d5sc01841b  \nAll publication charges for this article have been paid for by the Royal Society of Chemistry  \nReceived 7th March 2025 Accepted 20th October 2025 DOI: 10.1039/d5sc01841b  \n[rsc.li/chemical-science](rsc.li/chemical-science)  \nTuning optical properties and local lone-pair offcentering in “hollow” FA1 −x{en}xPbh −ySny Br3 perovskites  \nAdam Balvanz,  a Anastasia Pournara,a Robert P. Reynolds,  a Patricia E. Meza,  b Christos D. Malliakas,  a Jared D. Fletcher,a Ram Seshadri,  c Vinayak P. Dravid  band Mercouri G. Kanatzidis  *ad  \nHollow metal halide perovskites, while a relatively recent discovery, have already been shown to push the boundaries of tuneability within an inherently limited compositional space. Here, we further expand our knowledge of these complex materials demonstrating the ability to control optical properties and local structure, notably lone-pair induced off-centering. We focus on the mixed metal FA1 −xenxPbh −ySnyBr3 hollow perovskites. These compounds have wide ranging optical gaps from 1 . 9 eV (deep red) to 2 . 6 eV (light yellow), combining the anomalous bandgap red-shifting of Pb/Sn mixing with the blue-shifting effects of the organic substitution. Average and local structural studies employing single crystal X-ray diffraction and total X-ray scattering pair distribution function analyses respectively suggest strong incoherent off-centering distortions that are locally correlated with Sn concentration. The inclusion of ethylenediammonium dications appears to regulate metal off-centering, opening new opportunities of research into this phenomenon.  \n1 Introduction  \nMetal halide perovskites (MHPs) are a promising class of optoelectronic materials with wide-ranging applications in devices that employ high-performance semiconductors: photovoltaics (including single1–5 and multijunction6–11 devices), radiation detectors,12–16 and light-emitting diodes (LEDs)17–20 to name a few. These compounds are highly absorbing, direct-gap semiconductors with high charge carrier mobilities21 that can be easily synthesized through low-cost synthetic methods and starting materials.22 Unlike conventional semiconductors such as silicon and gallium arsenide, MHPs display a remarkable resiliency to electronic defect states, making them a focal point for scienti􀀁c research efforts and technological advancements as a cost-effective alternative.23–25 In addition, compositions can be engineered to match a desired optical band gap (Eg), with few exceptions, through simple chemical substitutions, accessing semiconductors with Eg ∼1.2–2.4 eV.26–29 With regard to photovoltaic applications, despite their rapid accent in power  \naNorthwestern University Department of Chemistry, Evanston, IL 60208, USA. E-mail: [m-kanatzidis@northwestern.edu](m-kanatzidis@northwestern.edu)  \nbNorthwestern University Department of Materials Science and Engineering, Evanston IL, 20208, USA  \ncMaterials Department and Materials Research Laboratory, University of California, Santa Barbara, CA 93106, USA  \ndMaterials Science Division, Argonne National Laboratory, Lemont, IL 60439, USA  \nconversion efficiency, MHPs fundamentally suffer from two endemic pitfalls to their commercial viability.  \nA limiting feature of the MHP family, speci􀀁cally the highestperforming three-dimensional (3D) variety, is the constrained compositional space. De􀀁ned as an AMX3 composition (where A and M are mono and divalent cations respectively and X is a monovalent anion) there are only three A-site cations (formamidinium (FA+), methylammonium (MA+), and Cs+) and limited M-site cations (Ge2+, Sn2+, Pb2+) and three X-site anions (Cl − , Br − , I −) that can form a perovskite framework (with some exceptions).30,31 These limitations are re􀀃ective of the geometric requirements to stabilize the 3D perovskite structure.32,33 If only considering compositions with potential applications, the Msite possibilities are narrowed furthe","cbCairEFuehMGR2U","https://ap.wps.com/l/cbCairEFuehMGR2U","pdf",3796582,18,"English","# Introduction\n## Metal halide perovskites as optoelectronic semiconductors\n## Limits from constrained compositional space\n## Limits from ambient stability and degradation\n## Motivation for “hollow” metal halide perovskites (hMHP)","[{\"question\":\"What material system is investigated in the study?\",\"answer\":\"The research examines mixed-metal hollow perovskites of the form FA1−xenxPbh−ySnyBr3, where ethylenediammonium regulates structural behavior and Pb/Sn mixing tunes optical responses.\"},{\"question\":\"How are optical properties tuned across the studied compounds?\",\"answer\":\"Optical gaps range from 1.9 eV to 2.6 eV by combining anomalous bandgap red-shifting from Pb/Sn mixing with blue-shifting effects caused by organic substitution.\"},{\"question\":\"What evidence is used to analyze local structure and off-centering?\",\"answer\":\"Average and local structural studies use single-crystal X-ray diffraction and total X-ray scattering pair distribution function analyses, which indicate strong incoherent off-centering distortions correlated with Sn concentration.\"}]","Tuning optical properties and local lone-pair off-centering in “hollow” FA1-x{en}xPbh-ySnyBr3 perovskites | PDF",1790731855,45]