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Cs3Bi2\u2013xSbxI9 exemplifies this behavior, exhibiting 0D (\u03b1) and 2D (\u03b2) polymorphs whose synthetic accessibility varies strongly with composition, temperature, and sealed-ampule conditions. Here, we establish a protocol-dependent accessibility map (i.e., the \u03b1\/\u03b2 (or mixed-phase) and CsI outcome as a function of composition, thermal protocol, and the sealed-ampule environment that governs SbI3-mediated transport\/concomitant CsI formation) for the Cs3Bi2\u2013xSbxI9 polymorphs. We show that the \u03b1-polymorph is accessible across the full Bi\/Sb range, whereas the production of predominantly the \u03b2-polymorph is restricted to Sb-rich compositions at room temperature (x \u2265 1.42) and is favored under lower-temperature conditions consistent with minimized SbI3 vapor\/CsI production. Density functional theory indicates both polymorphs are locally stable, with the \u03b1-phase lower in energy but with a diminishing \u03b1\u2013\u03b2 energy gap as Sb content increases, supporting the increased energetic accessibility of the corner-sharing \u03b2-phase structures in the Sb-rich regime. Variable-temperature powder X-ray diffraction directly captures high-temperature \u03b1 \u2194 \u03b2 interconversion in Bi-rich samples. Optoelectronic measurements reveal band gap bowing across the \u03b1-series (Eg = 1.89\u20132.08 eV; b = 0.11 \u00b1 0.02 eV) and a Bi-dependent reduction of Eg in the \u03b2-series (1.79\u20131.95 eV), consistent with calculated band-edge orbital character. The results highlight that vapor-phase halide chemistry and polymorph\/phase identity can be decisive hidden variables in composition\u2013property relationships for lead-free perovskite-related semiconductors.<\/jats:p>","DOI":"10.1021\/jacs.6c08526","type":"journal-article","created":{"date-parts":[[2026,9,2]],"date-time":"2026-09-02T06:36:23Z","timestamp":1788330983000},"page":"37909-37929","source":"Crossref","is-referenced-by-count":1,"title":["Mapping and Controlling\nDimensional Polymorphism and\nBandgap Bowing in Cs3Bi2\u2013\n                    <i>x<\/i>\n                    Sb\n                    <i>x<\/i>\n                    I9"],"prefix":"10.1021","volume":"148","author":[{"ORCID":"https:\/\/orcid.org\/0009-0009-0107-0055","authenticated-orcid":true,"suffix":"II","given":"Alann P.","family":"Au","sequence":"first","affiliation":[{"name":"Northwestern University , , , ,","place":["Evanston, Illinois, United States, 60208"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-5378-7327","authenticated-orcid":true,"given":"Adam","family":"Balvanz","sequence":"additional","affiliation":[{"name":"Northwestern University , , , ,","place":["Evanston, Illinois, United States, 60208"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-1882-2072","authenticated-orcid":true,"given":"Haowen","family":"Tian","sequence":"additional","affiliation":[{"name":"University of California , , , ,","place":["Santa Barbara, California, United States, 93106"]},{"name":"University of California , , , ,","place":["Santa Barbara, California, United States, 93106"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0009-0000-1129-6685","authenticated-orcid":true,"given":"Gabriel","family":"Joalland","sequence":"additional","affiliation":[{"name":"Univ Rennes, ENSCR, INSA Rennes, CNRS, ISCR (Institut des Sciences Chimiques de Rennes), UMR 6226 , ,","place":["Rennes, France, 35042"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jerry G.","family":"Hu","sequence":"additional","affiliation":[{"name":"University of California , , , ,","place":["Santa Barbara, California, United States, 93106"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-1518-4845","authenticated-orcid":true,"given":"Anthony K.","family":"Cheetham","sequence":"additional","affiliation":[{"name":"University of California , , , ,","place":["Santa Barbara, California, United States, 93106"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-3047-2298","authenticated-orcid":true,"given":"George","family":"Volonakis","sequence":"additional","affiliation":[{"name":"Univ Rennes, ENSCR, INSA Rennes, CNRS, ISCR (Institut des Sciences Chimiques de Rennes), UMR 6226 , ,","place":["Rennes, France, 35042"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-5858-4027","authenticated-orcid":true,"given":"Ram","family":"Seshadri","sequence":"additional","affiliation":[{"name":"University of California , , , ,","place":["Santa Barbara, California, United States, 93106"]},{"name":"University of California , , , ,","place":["Santa Barbara, California, United States, 93106"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-2037-4168","authenticated-orcid":true,"given":"Mercouri G.","family":"Kanatzidis","sequence":"additional","affiliation":[{"name":"Northwestern University , , , ,","place":["Evanston, Illinois, United States, 60208"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,8,28]]},"reference":[{"issue":"6","key":"2026090910082179700_cit1","doi-asserted-by":"publisher","first-page":"1233","DOI":"10.1021\/acsenergylett.6b00499","article-title":"Toward Lead-Free Perovskite Solar Cells","volume":"1","author":"Giustino","year":"2016","journal-title":"ACS Energy Lett."},{"key":"2026090910082179700_cit2","doi-asserted-by":"publisher","DOI":"10.1016\/j.apsadv.2023.100495","article-title":"Prospective and challenges for lead-free\npure inorganic\nperovskite semiconductor materials in photovoltaic application: A\ncomprehensive review","volume":"18","author":"Kumar","year":"2023","journal-title":"Appl. Surf. Sci. Adv."},{"issue":"37","key":"2026090910082179700_cit3","doi-asserted-by":"publisher","first-page":"6691","DOI":"10.1039\/D4CC06835A","article-title":"Lead-free\nperovskites for solar cell\napplications: recent progress, ongoing challenges, and strategic approaches","volume":"61","author":"Ahmed","year":"2025","journal-title":"Chem. Commun."},{"issue":"16","key":"2026090910082179700_cit4","doi-asserted-by":"publisher","first-page":"5622","DOI":"10.1021\/acs.chemmater.5b01989","article-title":"Thin-Film\nPreparation and Characterization of Cs3Sb2I9: A Lead-Free Layered Perovskite Semiconductor","volume":"27","author":"Saparov","year":"2015","journal-title":"Chem. Mater."},{"issue":"1","key":"2026090910082179700_cit5","doi-asserted-by":"publisher","DOI":"10.1038\/s41427-024-00552-w","article-title":"Inorganic\nCs3Bi2I9 lead-free halide perovskite\nfilm for large-area X-ray detector via low-cost ambient spray coating","volume":"16","author":"Chen","year":"2024","journal-title":"NPG Asia Mater."},{"key":"2026090910082179700_cit6","doi-asserted-by":"publisher","DOI":"10.1016\/j.omx.2024.100397","article-title":"Evaluation\nof the optical, structural, morphological and electronic properties\nof Rb3Bi2I9 Perovskites films prepared\nby Sequential Evaporation","volume":"25","author":"Gordillo","year":"2025","journal-title":"Opt. Mater.: X"},{"issue":"20","key":"2026090910082179700_cit7","doi-asserted-by":"publisher","first-page":"7137","DOI":"10.1021\/acs.chemmater.5b03147","article-title":"Crystal and Electronic\nStructures\nof Complex Bismuth Iodides A3Bi2I9 (A = K, Rb, Cs) Related to Perovskite: Aiding the Rational Design\nof Photovoltaics","volume":"27","author":"Lehner","year":"2015","journal-title":"Chem. Mater."},{"issue":"21","key":"2026090910082179700_cit8","doi-asserted-by":"publisher","first-page":"11756","DOI":"10.1021\/acs.jpcc.1c02870","article-title":"Why are Double Perovskite Iodides\nso Rare?","volume":"125","author":"Vishnoi","year":"2021","journal-title":"J. Phys. Chem. C"},{"issue":"8","key":"2026090910082179700_cit9","doi-asserted-by":"publisher","DOI":"10.1002\/chem.202404009","article-title":"Iodide Double\nPerovskites and the Limits of their Structural Stability","volume":"31","author":"Mulligan","year":"2025","journal-title":"Chem. \u2013 Eur. 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Rev."},{"issue":"7","key":"2026090910082179700_cit16","doi-asserted-by":"publisher","first-page":"3646","DOI":"10.1021\/acs.jpcc.1c08815","article-title":"Centimeter-Sized Stable\nZero-Dimensional Cs3Bi2I9 Single\nCrystal for Mid-Infrared Lead-Free Perovskite Photodetector","volume":"126","author":"Li","year":"2022","journal-title":"J. Phys. Chem. C"},{"issue":"27","key":"2026090910082179700_cit17","doi-asserted-by":"publisher","DOI":"10.1002\/adom.202501263","article-title":"High-Anisotropic\nFlexible Photodetector Based on Centimeter-Sized\nCs3Bi2I9 Single-Crystal Sheet","volume":"13","author":"Zhang","year":"2025","journal-title":"Adv. Opt. Mater."},{"issue":"1","key":"2026090910082179700_cit18","doi-asserted-by":"publisher","DOI":"10.1038\/s41467-020-16034-w","article-title":"Nucleation-controlled\ngrowth of superior lead-free perovskite Cs3Bi2I9 single-crystals for high-performance X-ray detection","volume":"11","author":"Zhang","year":"2020","journal-title":"Nat. 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Growth Des."},{"issue":"39","key":"2026090910082179700_cit26","doi-asserted-by":"publisher","DOI":"10.1002\/adma.202001344","article-title":"Lead-Free Halide Perovskite Cs3Bi2xSb2\u20132xI9 (x \u2248\n0.3) Possessing the Photocatalytic Activity for Hydrogen Evolution\nComparable to that of (CH3NH3)PbI3","volume":"32","author":"Chen","year":"2020","journal-title":"Adv. Mater."},{"issue":"6","key":"2026090910082179700_cit27","doi-asserted-by":"publisher","first-page":"6952","DOI":"10.1021\/acsaem.2c00591","article-title":"Understanding\nof the Band Gap Transition\nin Cs3Sb2Cl9\u2013xBrx: Anion Site Preference-Induced Structural\nDistortion","volume":"5","author":"Pradhan","year":"2022","journal-title":"ACS Appl. Energy Mater."},{"issue":"3B","key":"2026090910082179700_cit28","doi-asserted-by":"publisher","first-page":"B864","DOI":"10.1103\/PhysRev.136.B864","article-title":"Inhomogeneous Electron\nGas","volume":"136","author":"Hohenberg","year":"1964","journal-title":"Phys. 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