Understanding the Impact of Bismuth Heterovalent Doping on the Structural and Photophysical Properties of CH3NH3PbBr3 Halide Perovskite Crystals with Near‐IR Photoluminescence
A comprehensive study unveiling the impact of heterovalent doping with Bi3+ on the structural, semiconductive, and photoluminescent properties of a single crystal of lead halide perovskites (CH3NH3PbBr3) is presented. As indicated by single‐crystal XRD, a perfect cubic structure in Bi3+‐doped CH3NH3...
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| Veröffentlicht in: | Chemistry : a European journal 2019-04, Vol.25 (21), p.5480-5488 |
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| creator | Meng, Rui Wu, Guangbao Zhou, Jiyu Zhou, Huiqiong Fang, Honghua Loi, Maria A. Zhang, Yuan |
| description | A comprehensive study unveiling the impact of heterovalent doping with Bi3+ on the structural, semiconductive, and photoluminescent properties of a single crystal of lead halide perovskites (CH3NH3PbBr3) is presented. As indicated by single‐crystal XRD, a perfect cubic structure in Bi3+‐doped CH3NH3PbBr3 crystals is maintained in association with a slight lattice contraction. Time‐resolved and power‐dependent photoluminescence (PL) spectroscopy illustrates a progressively quenched PL of visible emission, alongside the appearance of a new PL signal in the near‐infrared (NIR) regime, which is likely to be due to energy transfer to the Bi sites. These optical characteristics indicate the role of Bi3+ dopants as nonradiative recombination centers, which explains the observed transition from bimolecular recombination in pristine CH3NH3PbBr3 to a dominant trap‐assisted monomolecular recombination with Bi3+ doping. Electrically, it is found that the mobility in pristine perovskite crystals can be boosted with a low Bi3+ concentration, which may be related to a trap‐filling mechanism. Aided by temperature (T)‐dependent measurements, two temperature regimes are observed in association with different activation energies (Ea) for electrical conductivity. The reduction of Ea at lower T may be ascribed to suppression of ionic conduction induced by doping. The modified electrical properties and NIR emission with the control of Bi3+ concentration shed light on the opportunity to apply heterovalent doping of perovskite single crystals for NIR optoelectronic applications.
Infiltrating single crystals: Heterovalent doping with Bi3+ (see figure) leads to modulation of the charge carrier mobility and thermal activation energy of electrical conductivity in CH3NH3PbBr3 single crystals. Upon doping, a new photoluminescent emission appears in the near‐infrared region of the spectrum. |
| doi_str_mv | 10.1002/chem.201805370 |
| format | Article |
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Infiltrating single crystals: Heterovalent doping with Bi3+ (see figure) leads to modulation of the charge carrier mobility and thermal activation energy of electrical conductivity in CH3NH3PbBr3 single crystals. Upon doping, a new photoluminescent emission appears in the near‐infrared region of the spectrum.</description><identifier>ISSN: 0947-6539</identifier><identifier>EISSN: 1521-3765</identifier><identifier>DOI: 10.1002/chem.201805370</identifier><language>eng</language><publisher>Weinheim: Wiley Subscription Services, Inc</publisher><subject>Bismuth ; Chemistry ; Conduction ; Contraction ; Crystal lattices ; Crystal structure ; Crystals ; Doping ; Electrical conductivity ; Electrical properties ; Electrical resistivity ; Emissions control ; Energy transfer ; Lead ; Luminescence ; Metal halides ; Optical properties ; Optoelectronics ; perovskite phases ; Perovskites ; photochemistry ; Photoluminescence ; Photons ; Recombination ; Single crystals ; Spectroscopy ; Temperature dependence ; Time dependence</subject><ispartof>Chemistry : a European journal, 2019-04, Vol.25 (21), p.5480-5488</ispartof><rights>2019 Wiley‐VCH Verlag GmbH & Co. KGaA, Weinheim</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><orcidid>0000-0003-0670-2428</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://onlinelibrary.wiley.com/doi/pdf/10.1002%2Fchem.201805370$$EPDF$$P50$$Gwiley$$H</linktopdf><linktohtml>$$Uhttps://onlinelibrary.wiley.com/doi/full/10.1002%2Fchem.201805370$$EHTML$$P50$$Gwiley$$H</linktohtml><link.rule.ids>315,781,785,1418,27929,27930,45579,45580</link.rule.ids></links><search><creatorcontrib>Meng, Rui</creatorcontrib><creatorcontrib>Wu, Guangbao</creatorcontrib><creatorcontrib>Zhou, Jiyu</creatorcontrib><creatorcontrib>Zhou, Huiqiong</creatorcontrib><creatorcontrib>Fang, Honghua</creatorcontrib><creatorcontrib>Loi, Maria A.</creatorcontrib><creatorcontrib>Zhang, Yuan</creatorcontrib><title>Understanding the Impact of Bismuth Heterovalent Doping on the Structural and Photophysical Properties of CH3NH3PbBr3 Halide Perovskite Crystals with Near‐IR Photoluminescence</title><title>Chemistry : a European journal</title><description>A comprehensive study unveiling the impact of heterovalent doping with Bi3+ on the structural, semiconductive, and photoluminescent properties of a single crystal of lead halide perovskites (CH3NH3PbBr3) is presented. As indicated by single‐crystal XRD, a perfect cubic structure in Bi3+‐doped CH3NH3PbBr3 crystals is maintained in association with a slight lattice contraction. Time‐resolved and power‐dependent photoluminescence (PL) spectroscopy illustrates a progressively quenched PL of visible emission, alongside the appearance of a new PL signal in the near‐infrared (NIR) regime, which is likely to be due to energy transfer to the Bi sites. These optical characteristics indicate the role of Bi3+ dopants as nonradiative recombination centers, which explains the observed transition from bimolecular recombination in pristine CH3NH3PbBr3 to a dominant trap‐assisted monomolecular recombination with Bi3+ doping. Electrically, it is found that the mobility in pristine perovskite crystals can be boosted with a low Bi3+ concentration, which may be related to a trap‐filling mechanism. Aided by temperature (T)‐dependent measurements, two temperature regimes are observed in association with different activation energies (Ea) for electrical conductivity. The reduction of Ea at lower T may be ascribed to suppression of ionic conduction induced by doping. The modified electrical properties and NIR emission with the control of Bi3+ concentration shed light on the opportunity to apply heterovalent doping of perovskite single crystals for NIR optoelectronic applications.
Infiltrating single crystals: Heterovalent doping with Bi3+ (see figure) leads to modulation of the charge carrier mobility and thermal activation energy of electrical conductivity in CH3NH3PbBr3 single crystals. Upon doping, a new photoluminescent emission appears in the near‐infrared region of the spectrum.</description><subject>Bismuth</subject><subject>Chemistry</subject><subject>Conduction</subject><subject>Contraction</subject><subject>Crystal lattices</subject><subject>Crystal structure</subject><subject>Crystals</subject><subject>Doping</subject><subject>Electrical conductivity</subject><subject>Electrical properties</subject><subject>Electrical resistivity</subject><subject>Emissions control</subject><subject>Energy transfer</subject><subject>Lead</subject><subject>Luminescence</subject><subject>Metal halides</subject><subject>Optical properties</subject><subject>Optoelectronics</subject><subject>perovskite phases</subject><subject>Perovskites</subject><subject>photochemistry</subject><subject>Photoluminescence</subject><subject>Photons</subject><subject>Recombination</subject><subject>Single crystals</subject><subject>Spectroscopy</subject><subject>Temperature dependence</subject><subject>Time dependence</subject><issn>0947-6539</issn><issn>1521-3765</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2019</creationdate><recordtype>article</recordtype><recordid>eNo9kc9O3DAQhy0EUpc_154tcQ4d24mzOUIKzUp0uwL2HHmdCTEkcWo7RXvrI_RV-kp9kibditNoRp--30g_Qj4yuGIA_JNusLviwJaQiBSOyIIlnEUilckxWUAWp5FMRPaBnHr_AgCZFGJBfm_7Cp0Pqq9M_0xDg3TVDUoHamt6Y3w3hoYWGNDZH6rFPtDPdphJ2_-DH4MbdRidaumkoJvGBjs0e2_0dNk4O6ALBv1sywuxLsRmd-MELVRrKqSbWetfTUCau_30Revpm5kS16jcn5-_Vg8HYzt2pkevsdd4Tk7qicOL__OMbO9un_Iiuv_2ZZVf30fPPAaIdF3FKaAWWR3LZcZ3cglqpyoW7xgwrbJ6KRXjyCWfsFrVqJM6kVqjlqzKuDgjlwfv4Oz3EX0oX-zo-imy5BxSnvIkTScqO1BvpsV9OTjTKbcvGZRzJ-XcSfneSZkXt1_fN_EXKliHfA</recordid><startdate>20190411</startdate><enddate>20190411</enddate><creator>Meng, Rui</creator><creator>Wu, Guangbao</creator><creator>Zhou, Jiyu</creator><creator>Zhou, Huiqiong</creator><creator>Fang, Honghua</creator><creator>Loi, Maria A.</creator><creator>Zhang, Yuan</creator><general>Wiley Subscription Services, Inc</general><scope>7SR</scope><scope>8BQ</scope><scope>8FD</scope><scope>JG9</scope><scope>K9.</scope><orcidid>https://orcid.org/0000-0003-0670-2428</orcidid></search><sort><creationdate>20190411</creationdate><title>Understanding the Impact of Bismuth Heterovalent Doping on the Structural and Photophysical Properties of CH3NH3PbBr3 Halide Perovskite Crystals with Near‐IR Photoluminescence</title><author>Meng, Rui ; Wu, Guangbao ; Zhou, Jiyu ; Zhou, Huiqiong ; Fang, Honghua ; Loi, Maria A. ; Zhang, Yuan</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-g2400-cfd470ec39f46892b680abad14b101ca9f86a12e26270efafec5f56ccec61d923</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2019</creationdate><topic>Bismuth</topic><topic>Chemistry</topic><topic>Conduction</topic><topic>Contraction</topic><topic>Crystal lattices</topic><topic>Crystal structure</topic><topic>Crystals</topic><topic>Doping</topic><topic>Electrical conductivity</topic><topic>Electrical properties</topic><topic>Electrical resistivity</topic><topic>Emissions control</topic><topic>Energy transfer</topic><topic>Lead</topic><topic>Luminescence</topic><topic>Metal halides</topic><topic>Optical properties</topic><topic>Optoelectronics</topic><topic>perovskite phases</topic><topic>Perovskites</topic><topic>photochemistry</topic><topic>Photoluminescence</topic><topic>Photons</topic><topic>Recombination</topic><topic>Single crystals</topic><topic>Spectroscopy</topic><topic>Temperature dependence</topic><topic>Time dependence</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Meng, Rui</creatorcontrib><creatorcontrib>Wu, Guangbao</creatorcontrib><creatorcontrib>Zhou, Jiyu</creatorcontrib><creatorcontrib>Zhou, Huiqiong</creatorcontrib><creatorcontrib>Fang, Honghua</creatorcontrib><creatorcontrib>Loi, Maria A.</creatorcontrib><creatorcontrib>Zhang, Yuan</creatorcontrib><collection>Engineered Materials Abstracts</collection><collection>METADEX</collection><collection>Technology Research Database</collection><collection>Materials Research Database</collection><collection>ProQuest Health & Medical Complete (Alumni)</collection><jtitle>Chemistry : a European journal</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Meng, Rui</au><au>Wu, Guangbao</au><au>Zhou, Jiyu</au><au>Zhou, Huiqiong</au><au>Fang, Honghua</au><au>Loi, Maria A.</au><au>Zhang, Yuan</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Understanding the Impact of Bismuth Heterovalent Doping on the Structural and Photophysical Properties of CH3NH3PbBr3 Halide Perovskite Crystals with Near‐IR Photoluminescence</atitle><jtitle>Chemistry : a European journal</jtitle><date>2019-04-11</date><risdate>2019</risdate><volume>25</volume><issue>21</issue><spage>5480</spage><epage>5488</epage><pages>5480-5488</pages><issn>0947-6539</issn><eissn>1521-3765</eissn><abstract>A comprehensive study unveiling the impact of heterovalent doping with Bi3+ on the structural, semiconductive, and photoluminescent properties of a single crystal of lead halide perovskites (CH3NH3PbBr3) is presented. As indicated by single‐crystal XRD, a perfect cubic structure in Bi3+‐doped CH3NH3PbBr3 crystals is maintained in association with a slight lattice contraction. Time‐resolved and power‐dependent photoluminescence (PL) spectroscopy illustrates a progressively quenched PL of visible emission, alongside the appearance of a new PL signal in the near‐infrared (NIR) regime, which is likely to be due to energy transfer to the Bi sites. These optical characteristics indicate the role of Bi3+ dopants as nonradiative recombination centers, which explains the observed transition from bimolecular recombination in pristine CH3NH3PbBr3 to a dominant trap‐assisted monomolecular recombination with Bi3+ doping. Electrically, it is found that the mobility in pristine perovskite crystals can be boosted with a low Bi3+ concentration, which may be related to a trap‐filling mechanism. Aided by temperature (T)‐dependent measurements, two temperature regimes are observed in association with different activation energies (Ea) for electrical conductivity. The reduction of Ea at lower T may be ascribed to suppression of ionic conduction induced by doping. The modified electrical properties and NIR emission with the control of Bi3+ concentration shed light on the opportunity to apply heterovalent doping of perovskite single crystals for NIR optoelectronic applications.
Infiltrating single crystals: Heterovalent doping with Bi3+ (see figure) leads to modulation of the charge carrier mobility and thermal activation energy of electrical conductivity in CH3NH3PbBr3 single crystals. Upon doping, a new photoluminescent emission appears in the near‐infrared region of the spectrum.</abstract><cop>Weinheim</cop><pub>Wiley Subscription Services, Inc</pub><doi>10.1002/chem.201805370</doi><tpages>9</tpages><orcidid>https://orcid.org/0000-0003-0670-2428</orcidid><oa>free_for_read</oa></addata></record> |
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| subjects | Bismuth Chemistry Conduction Contraction Crystal lattices Crystal structure Crystals Doping Electrical conductivity Electrical properties Electrical resistivity Emissions control Energy transfer Lead Luminescence Metal halides Optical properties Optoelectronics perovskite phases Perovskites photochemistry Photoluminescence Photons Recombination Single crystals Spectroscopy Temperature dependence Time dependence |
| title | Understanding the Impact of Bismuth Heterovalent Doping on the Structural and Photophysical Properties of CH3NH3PbBr3 Halide Perovskite Crystals with Near‐IR Photoluminescence |
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