Origin of Broad Emission Spectra in InP Quantum Dots: Contributions from Structural and Electronic Disorder

Janke, Eric M.; Williams, Nicholas E.; She, Chunxing; Zherebetskyy, Danylo; Hudson, Margaret H.; Wang, Lili; Gosztola, David J.; Schaller, Richard D.; Lee, Byeongdu; Sun, Chengjun; Engel, Gregory S.; Talapin, Dmitri V.

doi:10.1021/jacs.8b08753

Title: Origin of Broad Emission Spectra in InP Quantum Dots: Contributions from Structural and Electronic Disorder

Journal Article · Thu Oct 04 00:00:00 EDT 2018 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.8b08753· OSTI ID:1505169

Janke, Eric M. ^[1]; Williams, Nicholas E. ^[1];

^[1]; Zherebetskyy, Danylo ^[2];

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^[5]; Sun, Chengjun ^[5];

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Univ. of Chicago, IL (United States). James Franck Inst., Dept. of Chemistry
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division
Argonne National Lab. (ANL), Argonne, IL (United States). Center for Nanoscale Materials
Argonne National Lab. (ANL), Argonne, IL (United States). Center for Nanoscale Materials; Northwestern Univ., Evanston, IL (United States). Dept. of Chemistry
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Univ. of Chicago, IL (United States). James Franck Inst., Dept. of Chemistry; Argonne National Lab. (ANL), Argonne, IL (United States). Center for Nanoscale Materials

The ensemble emission spectra of colloidal InP quantum dots are broader than achievable spectra of cadmium- and lead-based quantum dots, despite similar single-particle line widths and significant efforts invested in the improvement of synthetic protocols. Here, we seek to explain the origin of persistently broad ensemble emission spectra of colloidal InP quantum dots by investigating the nature of the electronic states responsible for luminescence. We identify a correlation between red-shifted emission spectra and anomalous broadening of the excitation spectra of luminescent InP colloids, suggesting a trap-associated emission pathway in highly emissive core shell quantum dots. Time-resolved pump probe experiments find that s are largely untrapped on photoluminescence relevant time scales pointing to emission from recombination of localized holes with free electrons. Two-dimensional electronic spectroscopy on InP quantum dots reveals multiple emissive states and increased electron phonon coupling associated with hole localization. These localized hole states near the valence band edge are hypothesized to arise from incomplete surface passivation and structural disorder associated with lattice defects. We confirm the presence and effect of lattice disorder by X-ray absorption spectroscopy and Raman scattering measurements. Participation of localized electronic states that are associated with various classes of lattice defects gives rise to phonon-coupled defect related emission. These findings explain the origins of the persistently broad emission spectra of colloidal InP quantum dots and suggest future strategies to narrow ensemble emission lines comparable to what is observed for cadmium-based materials.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: National Science Foundation (NSF); Air Force Research Laboratory (AFRL) - Air Force Office of Scientific Research (AFOSR); USDOE Office of Science (SC)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1505169

Journal Information:: Journal of the American Chemical Society, Vol. 140, Issue 46; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 94 works

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