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In these systems, the operational band profile can depend on interdiffusion, secondary phases, charged defects, interface dipoles, Fermi-level pinning, and the thermal or chemical history of the junction. This Topical Review uses the term reactive heterophase region (RHR) as an explicit synthesis of established interface-layer and transition-layer descriptions, extended to reactive chalcogenides by coupling composition and phase, defect charge, electrostatic potential, and process or operating history. RHR is not proposed as a universal new phase: the framework includes the abrupt and weakly coupled limits and is invoked only when evidence or a physically justified process model supports a finite reactive interval. We first define natural, near-interface, and operational band offsets and consolidate the roles of pinning, dipoles, trap-assisted tunnelling, and ultrathin de-pinning layers. We then apply a concept-to-evidence-to-design-rule sequence to absorber\/buffer junctions, back contacts, passivating contacts, van der Waals interfaces, chalcogenide\u2013silicon tandems, and photodetectors. A claim-driven metrology section replaces a technique catalogue with an evidence architecture linking chemistry, ensemble and local energetics, device function, and stability. It also systematically distinguishes reactive-interface effects from alternative causes of discrepant offsets, including surface preparation, charging and referencing, valence-band fitting, facet dependence, lateral heterogeneity, sample damage, and model dependence. Case studies on Cu\n                    <jats:sub>2<\/jats:sub>\n                    ZnSn(S,Se)\n                    <jats:sub>4<\/jats:sub>\n                    (CZTSSe), SnS, Sb\n                    <jats:sub>2<\/jats:sub>\n                    Se\n                    <jats:sub>3<\/jats:sub>\n                    \/Sb\n                    <jats:sub>2<\/jats:sub>\n                    (S,Se)\n                    <jats:sub>3<\/jats:sub>\n                    , and selenium illustrate transferable and material-specific limits. The review closes with compact reporting and reliability standards intended to improve causal attribution, reproducibility, and cross-study comparison.\n                  <\/jats:p>","DOI":"10.1088\/1361-6528\/ae9d26","type":"journal-article","created":{"date-parts":[[2026,8,23]],"date-time":"2026-08-23T22:47:57Z","timestamp":1787525277000},"page":"362002","update-policy":"https:\/\/doi.org\/10.1088\/crossmark-policy","source":"Crossref","is-referenced-by-count":0,"title":["Interface nanochemistry and band alignment control in emerging metal chalcogenide nanostructures"],"prefix":"10.1088","volume":"37","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-0802-6681","authenticated-orcid":true,"given":"Cheng-Ying","family":"Chen","sequence":"first","affiliation":[{"name":"National Taiwan Ocean University"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"266","published-online":{"date-parts":[[2026,9,8]]},"reference":[{"key":"nanoae9d26bib1","doi-asserted-by":"publisher","first-page":"510","DOI":"10.1063\/1.1736034","type":"journal-article","article-title":"Detailed balance limit of efficiency of p\u2013n junction solar cells","volume":"32","author":"Shockley","year":"1961","journal-title":"J. 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