Novel high-temperature phase and crystal structure evolution of CsCuBr3 halide identified by neutron powder diffraction
- Autores
- Abia, Carmen; Lopez, Carlos Alberto; Gainza, Javier; Rodrigues, João Elias F. S.; Fernández Díaz, María Teresa; Céspedes, Eva; Martínez, José Luis; Alonso, José Antonio
- Año de publicación
- 2023
- Idioma
- inglés
- Tipo de recurso
- artículo
- Estado
- versión publicada
- Descripción
- The search for novel lead-free materials with potential optoelectronic applications is a main research topic nowadays for an environment-friendly energy transition. Based on promising all-inorganic CsPbBr3 perovskite, we tested here the substitution of toxic Pb2+ with Cu2+ and explored the understudied CsCuBr3 halide. We present a mechanically-synthesized CsCuBr3 specimen obtained by ball milling, consisting of a well-crystallized and pure sample. Calorimetric measurements revealed a thermal event suggesting a structural phase transition around 422 K, immediately below the decomposition of the sample due to Br loss. A detailed structural analysis was carried out using neutron powder diffraction data from 20 to 420 K, focusing on the evolution of the orthorhombic phase (space-group: C2221) up to 400 K; this crystal arrangement consists of dimer units of face-sharing [CuBr6] octahedra containing Cu–Cu dimers with conspicuously short distances that account for the magnetic coupling between Cu2+ spins described before. Additionally, at 420 K, we identified a novel high-temperature phase as described in the hexagonal P6522 space group, where infinite chains of [CuBr4] square-planar units were observed. An additional study considering the Debye model was carried out, providing information on the relative Cs–Br and Cu–Br chemical bonds. From diffuse reflectance UV-Vis measurements, an optical gap of ∼1.8 eV was estimated for the orthorhombic phase at room temperature. Magnetic measurements indicate that the effective magnetization behavior versus temperature appears close to linear and seems to extrapolate to zero (smaller than 10−5 μB/Cu atom) at temperatures above 420 K, coinciding with onset of phase transition.
Fil: Abia, Carmen. Instituto de Ciencia de Materiales de Madrid; España
Fil: Lopez, Carlos Alberto. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Área Química General e Inorgánica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto de Investigaciones en Tecnología Química. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Instituto de Investigaciones en Tecnología Química; Argentina. Instituto de Ciencia de Materiales de Madrid; España
Fil: Gainza, Javier. Instituto de Ciencia de Materiales de Madrid; España
Fil: Rodrigues, João Elias F. S.. European Synchrotron Radiation Facility; Francia
Fil: Fernández Díaz, María Teresa. Institut Laue Langevin; Francia
Fil: Céspedes, Eva. Instituto de Ciencia de Materiales de Madrid; España
Fil: Martínez, José Luis. Instituto de Ciencia de Materiales de Madrid; España
Fil: Alonso, José Antonio. Instituto de Ciencia de Materiales de Madrid; España - Materia
- High-temperature
- Nivel de accesibilidad
- acceso abierto
- Condiciones de uso
- https://creativecommons.org/licenses/by-nc/2.5/ar/
- Repositorio
.jpg)
- Institución
- Consejo Nacional de Investigaciones Científicas y Técnicas
- OAI Identificador
- oai:ri.conicet.gov.ar:11336/232192
Ver los metadatos del registro completo
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Novel high-temperature phase and crystal structure evolution of CsCuBr3 halide identified by neutron powder diffractionAbia, CarmenLopez, Carlos AlbertoGainza, JavierRodrigues, João Elias F. S.Fernández Díaz, María TeresaCéspedes, EvaMartínez, José LuisAlonso, José AntonioHigh-temperaturehttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The search for novel lead-free materials with potential optoelectronic applications is a main research topic nowadays for an environment-friendly energy transition. Based on promising all-inorganic CsPbBr3 perovskite, we tested here the substitution of toxic Pb2+ with Cu2+ and explored the understudied CsCuBr3 halide. We present a mechanically-synthesized CsCuBr3 specimen obtained by ball milling, consisting of a well-crystallized and pure sample. Calorimetric measurements revealed a thermal event suggesting a structural phase transition around 422 K, immediately below the decomposition of the sample due to Br loss. A detailed structural analysis was carried out using neutron powder diffraction data from 20 to 420 K, focusing on the evolution of the orthorhombic phase (space-group: C2221) up to 400 K; this crystal arrangement consists of dimer units of face-sharing [CuBr6] octahedra containing Cu–Cu dimers with conspicuously short distances that account for the magnetic coupling between Cu2+ spins described before. Additionally, at 420 K, we identified a novel high-temperature phase as described in the hexagonal P6522 space group, where infinite chains of [CuBr4] square-planar units were observed. An additional study considering the Debye model was carried out, providing information on the relative Cs–Br and Cu–Br chemical bonds. From diffuse reflectance UV-Vis measurements, an optical gap of ∼1.8 eV was estimated for the orthorhombic phase at room temperature. Magnetic measurements indicate that the effective magnetization behavior versus temperature appears close to linear and seems to extrapolate to zero (smaller than 10−5 μB/Cu atom) at temperatures above 420 K, coinciding with onset of phase transition.Fil: Abia, Carmen. Instituto de Ciencia de Materiales de Madrid; EspañaFil: Lopez, Carlos Alberto. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Área Química General e Inorgánica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto de Investigaciones en Tecnología Química. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Instituto de Investigaciones en Tecnología Química; Argentina. Instituto de Ciencia de Materiales de Madrid; EspañaFil: Gainza, Javier. Instituto de Ciencia de Materiales de Madrid; EspañaFil: Rodrigues, João Elias F. S.. European Synchrotron Radiation Facility; FranciaFil: Fernández Díaz, María Teresa. Institut Laue Langevin; FranciaFil: Céspedes, Eva. Instituto de Ciencia de Materiales de Madrid; EspañaFil: Martínez, José Luis. Instituto de Ciencia de Materiales de Madrid; EspañaFil: Alonso, José Antonio. Instituto de Ciencia de Materiales de Madrid; EspañaRoyal Society of Chemistry2023-05info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/232192Abia, Carmen; Lopez, Carlos Alberto; Gainza, Javier; Rodrigues, João Elias F. S.; Fernández Díaz, María Teresa; et al.; Novel high-temperature phase and crystal structure evolution of CsCuBr3 halide identified by neutron powder diffraction; Royal Society of Chemistry; CrystEngComm; 25; 31; 5-2023; 4417-44261466-8033CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1039/d3ce00432einfo:eu-repo/semantics/altIdentifier/url/https://pubs.rsc.org/en/content/articlelanding/2023/ce/d3ce00432einfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-22T11:40:41Zoai:ri.conicet.gov.ar:11336/232192instacron:CONICETInstitucionalhttp://ri.conicet.gov.ar/Organismo científico-tecnológicoNo correspondehttp://ri.conicet.gov.ar/oai/requestdasensio@conicet.gov.ar; lcarlino@conicet.gov.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:34982025-10-22 11:40:42.059CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse |
| dc.title.none.fl_str_mv |
Novel high-temperature phase and crystal structure evolution of CsCuBr3 halide identified by neutron powder diffraction |
| title |
Novel high-temperature phase and crystal structure evolution of CsCuBr3 halide identified by neutron powder diffraction |
| spellingShingle |
Novel high-temperature phase and crystal structure evolution of CsCuBr3 halide identified by neutron powder diffraction Abia, Carmen High-temperature |
| title_short |
Novel high-temperature phase and crystal structure evolution of CsCuBr3 halide identified by neutron powder diffraction |
| title_full |
Novel high-temperature phase and crystal structure evolution of CsCuBr3 halide identified by neutron powder diffraction |
| title_fullStr |
Novel high-temperature phase and crystal structure evolution of CsCuBr3 halide identified by neutron powder diffraction |
| title_full_unstemmed |
Novel high-temperature phase and crystal structure evolution of CsCuBr3 halide identified by neutron powder diffraction |
| title_sort |
Novel high-temperature phase and crystal structure evolution of CsCuBr3 halide identified by neutron powder diffraction |
| dc.creator.none.fl_str_mv |
Abia, Carmen Lopez, Carlos Alberto Gainza, Javier Rodrigues, João Elias F. S. Fernández Díaz, María Teresa Céspedes, Eva Martínez, José Luis Alonso, José Antonio |
| author |
Abia, Carmen |
| author_facet |
Abia, Carmen Lopez, Carlos Alberto Gainza, Javier Rodrigues, João Elias F. S. Fernández Díaz, María Teresa Céspedes, Eva Martínez, José Luis Alonso, José Antonio |
| author_role |
author |
| author2 |
Lopez, Carlos Alberto Gainza, Javier Rodrigues, João Elias F. S. Fernández Díaz, María Teresa Céspedes, Eva Martínez, José Luis Alonso, José Antonio |
| author2_role |
author author author author author author author |
| dc.subject.none.fl_str_mv |
High-temperature |
| topic |
High-temperature |
| purl_subject.fl_str_mv |
https://purl.org/becyt/ford/1.4 https://purl.org/becyt/ford/1 |
| dc.description.none.fl_txt_mv |
The search for novel lead-free materials with potential optoelectronic applications is a main research topic nowadays for an environment-friendly energy transition. Based on promising all-inorganic CsPbBr3 perovskite, we tested here the substitution of toxic Pb2+ with Cu2+ and explored the understudied CsCuBr3 halide. We present a mechanically-synthesized CsCuBr3 specimen obtained by ball milling, consisting of a well-crystallized and pure sample. Calorimetric measurements revealed a thermal event suggesting a structural phase transition around 422 K, immediately below the decomposition of the sample due to Br loss. A detailed structural analysis was carried out using neutron powder diffraction data from 20 to 420 K, focusing on the evolution of the orthorhombic phase (space-group: C2221) up to 400 K; this crystal arrangement consists of dimer units of face-sharing [CuBr6] octahedra containing Cu–Cu dimers with conspicuously short distances that account for the magnetic coupling between Cu2+ spins described before. Additionally, at 420 K, we identified a novel high-temperature phase as described in the hexagonal P6522 space group, where infinite chains of [CuBr4] square-planar units were observed. An additional study considering the Debye model was carried out, providing information on the relative Cs–Br and Cu–Br chemical bonds. From diffuse reflectance UV-Vis measurements, an optical gap of ∼1.8 eV was estimated for the orthorhombic phase at room temperature. Magnetic measurements indicate that the effective magnetization behavior versus temperature appears close to linear and seems to extrapolate to zero (smaller than 10−5 μB/Cu atom) at temperatures above 420 K, coinciding with onset of phase transition. Fil: Abia, Carmen. Instituto de Ciencia de Materiales de Madrid; España Fil: Lopez, Carlos Alberto. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Área Química General e Inorgánica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto de Investigaciones en Tecnología Química. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Instituto de Investigaciones en Tecnología Química; Argentina. Instituto de Ciencia de Materiales de Madrid; España Fil: Gainza, Javier. Instituto de Ciencia de Materiales de Madrid; España Fil: Rodrigues, João Elias F. S.. European Synchrotron Radiation Facility; Francia Fil: Fernández Díaz, María Teresa. Institut Laue Langevin; Francia Fil: Céspedes, Eva. Instituto de Ciencia de Materiales de Madrid; España Fil: Martínez, José Luis. Instituto de Ciencia de Materiales de Madrid; España Fil: Alonso, José Antonio. Instituto de Ciencia de Materiales de Madrid; España |
| description |
The search for novel lead-free materials with potential optoelectronic applications is a main research topic nowadays for an environment-friendly energy transition. Based on promising all-inorganic CsPbBr3 perovskite, we tested here the substitution of toxic Pb2+ with Cu2+ and explored the understudied CsCuBr3 halide. We present a mechanically-synthesized CsCuBr3 specimen obtained by ball milling, consisting of a well-crystallized and pure sample. Calorimetric measurements revealed a thermal event suggesting a structural phase transition around 422 K, immediately below the decomposition of the sample due to Br loss. A detailed structural analysis was carried out using neutron powder diffraction data from 20 to 420 K, focusing on the evolution of the orthorhombic phase (space-group: C2221) up to 400 K; this crystal arrangement consists of dimer units of face-sharing [CuBr6] octahedra containing Cu–Cu dimers with conspicuously short distances that account for the magnetic coupling between Cu2+ spins described before. Additionally, at 420 K, we identified a novel high-temperature phase as described in the hexagonal P6522 space group, where infinite chains of [CuBr4] square-planar units were observed. An additional study considering the Debye model was carried out, providing information on the relative Cs–Br and Cu–Br chemical bonds. From diffuse reflectance UV-Vis measurements, an optical gap of ∼1.8 eV was estimated for the orthorhombic phase at room temperature. Magnetic measurements indicate that the effective magnetization behavior versus temperature appears close to linear and seems to extrapolate to zero (smaller than 10−5 μB/Cu atom) at temperatures above 420 K, coinciding with onset of phase transition. |
| publishDate |
2023 |
| dc.date.none.fl_str_mv |
2023-05 |
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info:eu-repo/semantics/article info:eu-repo/semantics/publishedVersion http://purl.org/coar/resource_type/c_6501 info:ar-repo/semantics/articulo |
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article |
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publishedVersion |
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http://hdl.handle.net/11336/232192 Abia, Carmen; Lopez, Carlos Alberto; Gainza, Javier; Rodrigues, João Elias F. S.; Fernández Díaz, María Teresa; et al.; Novel high-temperature phase and crystal structure evolution of CsCuBr3 halide identified by neutron powder diffraction; Royal Society of Chemistry; CrystEngComm; 25; 31; 5-2023; 4417-4426 1466-8033 CONICET Digital CONICET |
| url |
http://hdl.handle.net/11336/232192 |
| identifier_str_mv |
Abia, Carmen; Lopez, Carlos Alberto; Gainza, Javier; Rodrigues, João Elias F. S.; Fernández Díaz, María Teresa; et al.; Novel high-temperature phase and crystal structure evolution of CsCuBr3 halide identified by neutron powder diffraction; Royal Society of Chemistry; CrystEngComm; 25; 31; 5-2023; 4417-4426 1466-8033 CONICET Digital CONICET |
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eng |
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eng |
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Royal Society of Chemistry |
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Royal Society of Chemistry |
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CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicas |
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