Defects of perovskite semiconductor CsPbBr3 investigated via photoluminescence and thermally stimulated current spectroscopies
Halide perovskites are essential materials for hard radiation detectors at ambient temperature. To improve detector performance, charge transport must be investigated and optimized. Using photoluminescence (PL) and thermally stimulated current (TSC) spectroscopies, we investigate photogenerated char...
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description | Halide perovskites are essential materials for hard radiation detectors at ambient temperature. To improve detector performance, charge transport must be investigated and optimized. Using photoluminescence (PL) and thermally stimulated current (TSC) spectroscopies, we investigate photogenerated charge carriers in Bridgman-grown CsPbBr3 single crystals to understand the nature of charge transport. PL spectroscopy of these halide perovskites revealed the presence of strong emission bands at the band edge, which were attributed to free or bound excitons. It is shown that a wide broadening of the excitonic linewidth in these halide perovskites arises from strong exciton–phonon coupling, which is substantially dominated by longitudinal optical phonons via Fröhlich interaction. An additional contribution due to the presence of ionized impurities was also observed. Crystals with a detectable sensitivity to high-energy gamma radiation are characterized by a higher intensity and a narrower linewidth of the principal PL peak at 2.326 eV. Defect states beyond 2.214 eV have a negative impact on detector sensitivity to high-energy gamma radiation. TSC spectroscopy reveals an array of trap levels spanning 0.15–0.70 eV, attributed to intrinsic point defects and multiple extrinsic defects involving dopants or impurities. Defects identified included Cs and Br vacancies, as well as Pb interstitials with concentrations in the 1011–1016 cm−3 range. Understanding how the synthesis process impacts the types and concentrations of the defects present is currently under investigation. Elimination or suppression of the defect/trap states should result in halide perovskite materials with longer carrier diffusion lengths and improved detector characteristics. |
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To improve detector performance, charge transport must be investigated and optimized. Using photoluminescence (PL) and thermally stimulated current (TSC) spectroscopies, we investigate photogenerated charge carriers in Bridgman-grown CsPbBr3 single crystals to understand the nature of charge transport. PL spectroscopy of these halide perovskites revealed the presence of strong emission bands at the band edge, which were attributed to free or bound excitons. It is shown that a wide broadening of the excitonic linewidth in these halide perovskites arises from strong exciton–phonon coupling, which is substantially dominated by longitudinal optical phonons via Fröhlich interaction. An additional contribution due to the presence of ionized impurities was also observed. Crystals with a detectable sensitivity to high-energy gamma radiation are characterized by a higher intensity and a narrower linewidth of the principal PL peak at 2.326 eV. Defect states beyond 2.214 eV have a negative impact on detector sensitivity to high-energy gamma radiation. TSC spectroscopy reveals an array of trap levels spanning 0.15–0.70 eV, attributed to intrinsic point defects and multiple extrinsic defects involving dopants or impurities. Defects identified included Cs and Br vacancies, as well as Pb interstitials with concentrations in the 1011–1016 cm−3 range. Understanding how the synthesis process impacts the types and concentrations of the defects present is currently under investigation. Elimination or suppression of the defect/trap states should result in halide perovskite materials with longer carrier diffusion lengths and improved detector characteristics.</description><identifier>ISSN: 0021-8979</identifier><identifier>EISSN: 1089-7550</identifier><identifier>DOI: 10.1063/5.0177809</identifier><identifier>CODEN: JAPIAU</identifier><language>eng</language><publisher>Melville: American Institute of Physics</publisher><subject>Ambient temperature ; Bridgman method ; Charge transport ; Crystal defects ; Crystal growth ; Current carriers ; Excitons ; Gamma rays ; Impurities ; Interstitials ; Investigations ; Ionizing radiation ; Perovskites ; Phonons ; Photoluminescence ; Point defects ; Radiation ; Radiation detectors ; Sensitivity ; Sensors ; Single crystals ; Spectroscopy ; Spectrum analysis ; Thermally stimulated current</subject><ispartof>Journal of applied physics, 2023-12, Vol.134 (24)</ispartof><rights>Author(s)</rights><rights>2023 Author(s). Published under an exclusive license by AIP Publishing.</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><cites>FETCH-LOGICAL-c287t-1172338bbbae0ee6b6f3ccf2a9ece01f59f68e38ac1e6862d68c6523938aee993</cites><orcidid>0000-0001-5955-4815 ; 0000-0003-2357-1909 ; 0009-0008-7588-533X ; 0000-0002-2039-2457 ; 0000-0003-2037-4168 ; 0000-0002-8957-7097 ; 0000-0001-9087-1114</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktohtml>$$Uhttps://pubs.aip.org/jap/article-lookup/doi/10.1063/5.0177809$$EHTML$$P50$$Gscitation$$H</linktohtml><link.rule.ids>314,776,780,790,4498,27901,27902,76126</link.rule.ids></links><search><creatorcontrib>Liu, Zhifu</creatorcontrib><creatorcontrib>Peters, John A.</creatorcontrib><creatorcontrib>Bayikadi, Khasim Saheb</creatorcontrib><creatorcontrib>Klepov, Vladislav</creatorcontrib><creatorcontrib>Pan, Lei</creatorcontrib><creatorcontrib>Pandey, Indra Raj</creatorcontrib><creatorcontrib>Kanatzidis, Mercouri G.</creatorcontrib><creatorcontrib>Wessels, Bruce W.</creatorcontrib><title>Defects of perovskite semiconductor CsPbBr3 investigated via photoluminescence and thermally stimulated current spectroscopies</title><title>Journal of applied physics</title><description>Halide perovskites are essential materials for hard radiation detectors at ambient temperature. To improve detector performance, charge transport must be investigated and optimized. Using photoluminescence (PL) and thermally stimulated current (TSC) spectroscopies, we investigate photogenerated charge carriers in Bridgman-grown CsPbBr3 single crystals to understand the nature of charge transport. PL spectroscopy of these halide perovskites revealed the presence of strong emission bands at the band edge, which were attributed to free or bound excitons. It is shown that a wide broadening of the excitonic linewidth in these halide perovskites arises from strong exciton–phonon coupling, which is substantially dominated by longitudinal optical phonons via Fröhlich interaction. An additional contribution due to the presence of ionized impurities was also observed. Crystals with a detectable sensitivity to high-energy gamma radiation are characterized by a higher intensity and a narrower linewidth of the principal PL peak at 2.326 eV. Defect states beyond 2.214 eV have a negative impact on detector sensitivity to high-energy gamma radiation. TSC spectroscopy reveals an array of trap levels spanning 0.15–0.70 eV, attributed to intrinsic point defects and multiple extrinsic defects involving dopants or impurities. Defects identified included Cs and Br vacancies, as well as Pb interstitials with concentrations in the 1011–1016 cm−3 range. Understanding how the synthesis process impacts the types and concentrations of the defects present is currently under investigation. Elimination or suppression of the defect/trap states should result in halide perovskite materials with longer carrier diffusion lengths and improved detector characteristics.</description><subject>Ambient temperature</subject><subject>Bridgman method</subject><subject>Charge transport</subject><subject>Crystal defects</subject><subject>Crystal growth</subject><subject>Current carriers</subject><subject>Excitons</subject><subject>Gamma rays</subject><subject>Impurities</subject><subject>Interstitials</subject><subject>Investigations</subject><subject>Ionizing radiation</subject><subject>Perovskites</subject><subject>Phonons</subject><subject>Photoluminescence</subject><subject>Point defects</subject><subject>Radiation</subject><subject>Radiation detectors</subject><subject>Sensitivity</subject><subject>Sensors</subject><subject>Single crystals</subject><subject>Spectroscopy</subject><subject>Spectrum analysis</subject><subject>Thermally stimulated current</subject><issn>0021-8979</issn><issn>1089-7550</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2023</creationdate><recordtype>article</recordtype><recordid>eNp90E1LAzEQBuAgCtbqwX8Q8KSwmg82mxy1fkJBD3pesunEpu4ma5It9OJvd2t79jQwPMw7MwidU3JNieA35TWhVSWJOkATSqQqqrIkh2hCCKOFVJU6RicprQihVHI1QT_3YMHkhIPFPcSwTl8uA07QORP8YjA5RDxLb81d5Nj5NaTsPnWGBV47jftlyKEdOuchGfAGsPYLnJcQO922Gzzibmj_uBliBJ9x6se4GJIJvYN0io6sbhOc7esUfTw-vM-ei_nr08vsdl4YJqtcUFoxzmXTNBoIgGiE5cZYphUYINSWygoJXGpDQUjBFkIaUTKuxhaAUnyKLnZz-xi-h_GIehWG6MfImikiCOOk3KrLnTLjgimCrfvoOh03NSX19r11We_fO9qrnU3GZZ1d8P_gXzZEfd0</recordid><startdate>20231228</startdate><enddate>20231228</enddate><creator>Liu, Zhifu</creator><creator>Peters, John A.</creator><creator>Bayikadi, Khasim Saheb</creator><creator>Klepov, Vladislav</creator><creator>Pan, Lei</creator><creator>Pandey, Indra Raj</creator><creator>Kanatzidis, Mercouri G.</creator><creator>Wessels, Bruce W.</creator><general>American Institute of Physics</general><scope>AAYXX</scope><scope>CITATION</scope><scope>8FD</scope><scope>H8D</scope><scope>L7M</scope><orcidid>https://orcid.org/0000-0001-5955-4815</orcidid><orcidid>https://orcid.org/0000-0003-2357-1909</orcidid><orcidid>https://orcid.org/0009-0008-7588-533X</orcidid><orcidid>https://orcid.org/0000-0002-2039-2457</orcidid><orcidid>https://orcid.org/0000-0003-2037-4168</orcidid><orcidid>https://orcid.org/0000-0002-8957-7097</orcidid><orcidid>https://orcid.org/0000-0001-9087-1114</orcidid></search><sort><creationdate>20231228</creationdate><title>Defects of perovskite semiconductor CsPbBr3 investigated via photoluminescence and thermally stimulated current spectroscopies</title><author>Liu, Zhifu ; Peters, John A. ; Bayikadi, Khasim Saheb ; Klepov, Vladislav ; Pan, Lei ; Pandey, Indra Raj ; Kanatzidis, Mercouri G. ; Wessels, Bruce W.</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c287t-1172338bbbae0ee6b6f3ccf2a9ece01f59f68e38ac1e6862d68c6523938aee993</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2023</creationdate><topic>Ambient temperature</topic><topic>Bridgman method</topic><topic>Charge transport</topic><topic>Crystal defects</topic><topic>Crystal growth</topic><topic>Current carriers</topic><topic>Excitons</topic><topic>Gamma rays</topic><topic>Impurities</topic><topic>Interstitials</topic><topic>Investigations</topic><topic>Ionizing radiation</topic><topic>Perovskites</topic><topic>Phonons</topic><topic>Photoluminescence</topic><topic>Point defects</topic><topic>Radiation</topic><topic>Radiation detectors</topic><topic>Sensitivity</topic><topic>Sensors</topic><topic>Single crystals</topic><topic>Spectroscopy</topic><topic>Spectrum analysis</topic><topic>Thermally stimulated current</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Liu, Zhifu</creatorcontrib><creatorcontrib>Peters, John A.</creatorcontrib><creatorcontrib>Bayikadi, Khasim Saheb</creatorcontrib><creatorcontrib>Klepov, Vladislav</creatorcontrib><creatorcontrib>Pan, Lei</creatorcontrib><creatorcontrib>Pandey, Indra Raj</creatorcontrib><creatorcontrib>Kanatzidis, Mercouri G.</creatorcontrib><creatorcontrib>Wessels, Bruce W.</creatorcontrib><collection>CrossRef</collection><collection>Technology Research Database</collection><collection>Aerospace Database</collection><collection>Advanced Technologies Database with Aerospace</collection><jtitle>Journal of applied physics</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Liu, Zhifu</au><au>Peters, John A.</au><au>Bayikadi, Khasim Saheb</au><au>Klepov, Vladislav</au><au>Pan, Lei</au><au>Pandey, Indra Raj</au><au>Kanatzidis, Mercouri G.</au><au>Wessels, Bruce W.</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Defects of perovskite semiconductor CsPbBr3 investigated via photoluminescence and thermally stimulated current spectroscopies</atitle><jtitle>Journal of applied physics</jtitle><date>2023-12-28</date><risdate>2023</risdate><volume>134</volume><issue>24</issue><issn>0021-8979</issn><eissn>1089-7550</eissn><coden>JAPIAU</coden><abstract>Halide perovskites are essential materials for hard radiation detectors at ambient temperature. To improve detector performance, charge transport must be investigated and optimized. Using photoluminescence (PL) and thermally stimulated current (TSC) spectroscopies, we investigate photogenerated charge carriers in Bridgman-grown CsPbBr3 single crystals to understand the nature of charge transport. PL spectroscopy of these halide perovskites revealed the presence of strong emission bands at the band edge, which were attributed to free or bound excitons. It is shown that a wide broadening of the excitonic linewidth in these halide perovskites arises from strong exciton–phonon coupling, which is substantially dominated by longitudinal optical phonons via Fröhlich interaction. An additional contribution due to the presence of ionized impurities was also observed. Crystals with a detectable sensitivity to high-energy gamma radiation are characterized by a higher intensity and a narrower linewidth of the principal PL peak at 2.326 eV. Defect states beyond 2.214 eV have a negative impact on detector sensitivity to high-energy gamma radiation. TSC spectroscopy reveals an array of trap levels spanning 0.15–0.70 eV, attributed to intrinsic point defects and multiple extrinsic defects involving dopants or impurities. Defects identified included Cs and Br vacancies, as well as Pb interstitials with concentrations in the 1011–1016 cm−3 range. Understanding how the synthesis process impacts the types and concentrations of the defects present is currently under investigation. Elimination or suppression of the defect/trap states should result in halide perovskite materials with longer carrier diffusion lengths and improved detector characteristics.</abstract><cop>Melville</cop><pub>American Institute of Physics</pub><doi>10.1063/5.0177809</doi><tpages>9</tpages><orcidid>https://orcid.org/0000-0001-5955-4815</orcidid><orcidid>https://orcid.org/0000-0003-2357-1909</orcidid><orcidid>https://orcid.org/0009-0008-7588-533X</orcidid><orcidid>https://orcid.org/0000-0002-2039-2457</orcidid><orcidid>https://orcid.org/0000-0003-2037-4168</orcidid><orcidid>https://orcid.org/0000-0002-8957-7097</orcidid><orcidid>https://orcid.org/0000-0001-9087-1114</orcidid><oa>free_for_read</oa></addata></record> |
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subjects | Ambient temperature Bridgman method Charge transport Crystal defects Crystal growth Current carriers Excitons Gamma rays Impurities Interstitials Investigations Ionizing radiation Perovskites Phonons Photoluminescence Point defects Radiation Radiation detectors Sensitivity Sensors Single crystals Spectroscopy Spectrum analysis Thermally stimulated current |
title | Defects of perovskite semiconductor CsPbBr3 investigated via photoluminescence and thermally stimulated current spectroscopies |
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