Negligible Electronic Interaction between Photoexcited Electron–Hole Pairs and Free Electrons in Phosphorus–Boron Co-Doped Silicon Nanocrystals

Limpens, Rens; Fujii, Minoru; Neale, Nathan R.; Gregorkiewicz, Tom

doi:10.1021/acs.jpcc.7b12313

Title: Negligible Electronic Interaction between Photoexcited Electron–Hole Pairs and Free Electrons in Phosphorus–Boron Co-Doped Silicon Nanocrystals

Journal Article · Mon Mar 05 00:00:00 EST 2018 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.7b12313· OSTI ID:1427876

^[1];

^[2];

^[1];

^[3]

National Renewable Energy Laboratory, 15013 Denver West Parkway, Golden, Colorado 80401, United States
Department of Electrical and Electronic Engineering, Kobe University, Rokkodai, Nada, Kobe 657-8501, Japan
Van der Waals-Zeeman, University of Amsterdam, Science Park 904, 1098 XH Amsterdam, The Netherlands

Phosphorus (P) and boron (B) co-doped Si nanocrystals (NCs) have raised interest in the optoelectronic industry due to their electronic tunability, optimal carrier multiplication properties, and straightforward dispersibility in polar solvents. Yet a basic understanding of the interaction of photoexcited electron-hole (e-h) pairs with new physical features that are introduced by the co-doping process (free carriers, defect states, and surface chemistry) is missing. Here, we present the first study of the ultrafast carrier dynamics in SiO2-embedded P-B co-doped Si NC ensembles using induced absorption spectroscopy through a two-step approach. First, the induced absorption data show that the large fraction of the dopants residing on the NC surface slows down carrier relaxation dynamics within the first 20 ps relative to intrinsic (undoped) Si NCs, which we interpret as enhanced surface passivation. On longer time-scales (picosecond to nanosecond regime), we observe a speeding up of the carrier relaxation dynamics and ascribe it to doping-induced trap states. This argument is deduced from the second part of the study, where we investigate multiexciton interactions. From a stochastic modeling approach we show that localized carriers, which are introduced by the P or B dopants, have minor electronic interactions with the photoexcited e-h pairs. This is understood in light of the strong localization of the introduced carriers on their original P- or B-dopant atoms, due to the strong quantum confinement regime in these relatively small NCs (<6 nm).

View Journal Article

Cite

Export

Save

Research Organization:: National Renewable Energy Laboratory (NREL), Golden, CO (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division

Grant/Contract Number:: AC36- 08GO28308; AC36-08GO28308

OSTI ID:: 1427876

Alternate ID(s):: OSTI ID: 1435709; OSTI ID: 1508756

Report Number(s):: NREL/JA-5900-70658

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Vol. 122 Journal Issue: 11; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 13 works

Citation information provided by
Web of Science

References (43)

Trapping time of excitons in Si nanocrystals embedded in a ${SiO}_{2}$ matrix de Jong, E. M. L. D.; de Boer, W. D. A. M.; Yassievich, I. N. Physical Review B, Vol. 95, Issue 19 https://doi.org/10.1103/PhysRevB.95.195312	journal	May 2017
High-Throughput Study of Compositions and Optical Properties in Heavily Co-Doped Silicon Nanoparticles Somogyi, Bálint; Derian, René; Štich, Ivan The Journal of Physical Chemistry C, Vol. 121, Issue 49 https://doi.org/10.1021/acs.jpcc.7b09501	journal	November 2017
Doped and codoped silicon nanocrystals: The role of surfaces and interfaces Marri, Ivan; Degoli, Elena; Ossicini, Stefano Progress in Surface Science, Vol. 92, Issue 4 https://doi.org/10.1016/j.progsurf.2017.07.003	journal	December 2017
Preferential Positioning of Dopants and Co-Dopants in Embedded and Freestanding Si Nanocrystals Guerra, Roberto; Ossicini, Stefano Journal of the American Chemical Society, Vol. 136, Issue 11 https://doi.org/10.1021/ja5002357	journal	March 2014
Room-temperature below bulk-Si band gap photoluminescence from P and B co-doped and compensated Si nanocrystals with narrow size distributions Fukuda, Masatoshi; Fujii, Minoru; Hayashi, Shinji Journal of Luminescence, Vol. 131, Issue 5 https://doi.org/10.1016/j.jlumin.2011.01.023	journal	May 2011
Phosphorus Doping in Si Nanocrystals/SiO2 Multilayers and Light Emission with Wavelength Compatible for Optical Telecommunication Lu, Peng; Mu, Weiwei; Xu, Jun Scientific Reports, Vol. 6, Issue 1 https://doi.org/10.1038/srep22888	journal	March 2016
Donor—acceptor pairs in semiconductors Williams, F. Physica Status Solidi (b), Vol. 25, Issue 2 https://doi.org/10.1002/pssb.19680250202	journal	January 1968
Universal Size-Dependent Trend in Auger Recombination in Direct-Gap and Indirect-Gap Semiconductor Nanocrystals Robel, István; Gresback, Ryan; Kortshagen, Uwe Physical Review Letters, Vol. 102, Issue 17, Article No. 177404 https://doi.org/10.1103/PhysRevLett.102.177404	journal	May 2009
Engineering silicon nanocrystals: Theoretical study of the effect of codoping with boron and phosphorus Iori, Federico; Degoli, Elena; Magri, Rita Physical Review B, Vol. 76, Issue 8 https://doi.org/10.1103/PhysRevB.76.085302	journal	August 2007
Formation and evolution of luminescent Si nanoclusters produced by thermal annealing of SiOx films Iacona, Fabio; Bongiorno, Corrado; Spinella, Corrado Journal of Applied Physics, Vol. 95, Issue 7 https://doi.org/10.1063/1.1664026	journal	April 2004
Synthesis of boron and phosphorus codoped all-inorganic colloidal silicon nanocrystals from hydrogen silsesquioxane Sugimoto, Hiroshi; Fujii, Minoru; Imakita, Kenji Nanoscale, Vol. 6, Issue 21 https://doi.org/10.1039/C4NR03857F	journal	January 2014
All-inorganic water-dispersible silicon quantum dots: highly efficient near-infrared luminescence in a wide pH range Sugimoto, Hiroshi; Fujii, Minoru; Fukuda, Yuki Nanoscale, Vol. 6, Issue 1 https://doi.org/10.1039/C3NR03863G	journal	January 2014
Multiple Exciton Generation in Colloidal Silicon Nanocrystals Beard, Matthew C.; Knutsen, Kelly P.; Yu, Pingrong Nano Letters, Vol. 7, Issue 8 https://doi.org/10.1021/nl071486l	journal	August 2007
Experimental Investigations and Modeling of Auger Recombination in Silicon Nanocrystals Trinh, M. Tuan; Limpens, Rens; Gregorkiewicz, Tom The Journal of Physical Chemistry C, Vol. 117, Issue 11 https://doi.org/10.1021/jp311124c	journal	March 2013
Spectroscopic investigations of dark Si nanocrystals in SiO ₂ and their role in external quantum efficiency quenching Limpens, Rens; Gregorkiewicz, Tom Journal of Applied Physics, Vol. 114, Issue 7 https://doi.org/10.1063/1.4818580	journal	August 2013
Size-Dependent Exciton Formation Dynamics in Colloidal Silicon Quantum Dots Bergren, Matthew R.; Palomaki, Peter K. B.; Neale, Nathan R. ACS Nano, Vol. 10, Issue 2 https://doi.org/10.1021/acsnano.5b07073	journal	January 2016
Modulation of surface states by phosphorus to improve the optical properties of ultra-small Si nanocrystals Li, Dongke; Jiang, Yicheng; Liu, Jingjing Nanotechnology, Vol. 28, Issue 47 https://doi.org/10.1088/1361-6528/aa852e	journal	October 2017
Optical generation of electron-hole pairs in phosphor and boron co-doped Si nanocrystals in SiO ₂: Optical generation of e-h pairs in PB co-doped Si NCs in SiO ₂ Chung, Nguyen Xuan; Limpens, Rens; Lesage, Arnon physica status solidi (a), Vol. 213, Issue 11 https://doi.org/10.1002/pssa.201600381	journal	November 2016
Single-dot spectroscopy of boron and phosphorus codoped silicon quantum dots Kanno, Takashi; Sugimoto, Hiroshi; Fucikova, Anna Journal of Applied Physics, Vol. 120, Issue 16 https://doi.org/10.1063/1.4965986	journal	October 2016
Phosphorus Concentration Limitation in Czochralski Silicon Crystals Chiou, Herng-Der Journal of The Electrochemical Society, Vol. 147, Issue 1 https://doi.org/10.1149/1.1393198	journal	January 2000
Atom Probe Tomography Analysis of Boron and/or Phosphorus Distribution in Doped Silicon Nanocrystals Nomoto, Keita; Sugimoto, Hiroshi; Breen, Andrew The Journal of Physical Chemistry C, Vol. 120, Issue 31 https://doi.org/10.1021/acs.jpcc.6b06197	journal	July 2016
Chemical trends of defect formation in Si quantum dots: The case of group-III and group-V dopants Xu, Qiang; Luo, Jun-Wei; Li, Shu-Shen Physical Review B, Vol. 75, Issue 23 https://doi.org/10.1103/PhysRevB.75.235304	journal	June 2007
Emission efficiency limit of Si nanocrystals Limpens, Rens; Luxembourg, Stefan L.; Weeber, Arthur W. Scientific Reports, Vol. 6, Issue 1 https://doi.org/10.1038/srep19566	journal	January 2016
Codoping n- and p-Type Impurities in Colloidal Silicon Nanocrystals: Controlling Luminescence Energy from below Bulk Band Gap to Visible Range Sugimoto, Hiroshi; Fujii, Minoru; Imakita, Kenji The Journal of Physical Chemistry C, Vol. 117, Issue 22 https://doi.org/10.1021/jp4027767	journal	May 2013
Passivation effects in B doped self-assembled Si nanocrystals Puthen Veettil, B.; Wu, Lingfeng; Jia, Xuguang Applied Physics Letters, Vol. 105, Issue 22 https://doi.org/10.1063/1.4903776	journal	December 2014
Spectral and Dynamical Properties of Multiexcitons in Semiconductor Nanocrystals Klimov, Victor I. Annual Review of Physical Chemistry, Vol. 58, Issue 1 https://doi.org/10.1146/annurev.physchem.58.032806.104537	journal	May 2007
Localized surface plasmon resonances arising from free carriers in doped quantum dots Luther, Joseph M.; Jain, Prashant K.; Ewers, Trevor Nature Materials, Vol. 10, Issue 5, p. 361-366 https://doi.org/10.1038/nmat3004	journal	April 2011
Highly Colloidally Stable Hyperbranched Polyglycerol Grafted Red Fluorescent Silicon Nanoparticle as Bioimaging Probe Das, Pradip; Jana, Nikhil R. ACS Applied Materials & Interfaces, Vol. 6, Issue 6 https://doi.org/10.1021/am406061x	journal	March 2014
Doping efficiency in freestanding silicon nanocrystals from the gas phase: Phosphorus incorporation and defect-induced compensation Stegner, A. R.; Pereira, R. N.; Lechner, R. Physical Review B, Vol. 80, Issue 16 https://doi.org/10.1103/PhysRevB.80.165326	journal	October 2009
Self-trapped exciton state in Si nanocrystals revealed by induced absorption de Boer, W. D. A. M.; Timmerman, D.; Gregorkiewicz, T. Physical Review B, Vol. 85, Issue 16 https://doi.org/10.1103/PhysRevB.85.161409	journal	April 2012
Kinetics of $H_{2}$ passivation of Si nanocrystals in ${SiO}_{2}$ Wilkinson, A. R.; Elliman, R. G. Physical Review B, Vol. 68, Issue 15 https://doi.org/10.1103/PhysRevB.68.155302	journal	October 2003
Defect-Induced Luminescence Quenching vs. Charge Carrier Generation of Phosphorus Incorporated in Silicon Nanocrystals as Function of Size Hiller, Daniel; López-Vidrier, Julian; Gutsch, Sebastian Scientific Reports, Vol. 7, Issue 1 https://doi.org/10.1038/s41598-017-01001-1	journal	April 2017
Spectroscopy of carrier multiplication in nanocrystals Bruhn, Benjamin; Limpens, Rens; Chung, Nguyen Xuan Scientific Reports, Vol. 6, Issue 1 https://doi.org/10.1038/srep20538	journal	February 2016
Size confinement of Si nanocrystals in multinanolayer structures Limpens, Rens; Lesage, Arnon; Fujii, Minoru Scientific Reports, Vol. 5, Issue 1 https://doi.org/10.1038/srep17289	journal	November 2015
Control of photoluminescence properties of Si nanocrystals by simultaneously doping n- and p-type impurities Fujii, Minoru; Yamaguchi, Yasuhiro; Takase, Yuji Applied Physics Letters, Vol. 85, Issue 7 https://doi.org/10.1063/1.1779955	journal	August 2004
Auger Recombination of Biexcitons and Negative and Positive Trions in Individual Quantum Dots Park, Young-Shin; Bae, Wan Ki; Pietryga, Jeffrey M. ACS Nano, Vol. 8, Issue 7 https://doi.org/10.1021/nn5023473	journal	June 2014
High-Efficiency Carrier Multiplication and Ultrafast Charge Separation in Semiconductor Nanocrystals Studied via Time-Resolved Photoluminescence ^† Schaller, Richard D.; Sykora, Milan; Jeong, Sohee The Journal of Physical Chemistry B, Vol. 110, Issue 50 https://doi.org/10.1021/jp065282p	journal	December 2006
Size-dependent photoluminescence from surface-oxidized Si nanocrystals in a weak confinement regime Takeoka, Shinji; Fujii, Minoru; Hayashi, Shinji Physical Review B, Vol. 62, Issue 24 https://doi.org/10.1103/PhysRevB.62.16820	journal	December 2000
Optical characterizations of doped silicon nanocrystals grown by co-implantation of Si and dopants in SiO ₂ Frégnaux, M.; Khelifi, R.; Muller, D. Journal of Applied Physics, Vol. 116, Issue 14 https://doi.org/10.1063/1.4898038	journal	October 2014
Thermodynamic efficiency limits for semiconductor solar cells with carrier multiplication Brendel, R.; Werner, J.; Queisser, H. Solar Energy Materials and Solar Cells, Vol. 41-42 https://doi.org/10.1016/0927-0248(95)00125-5	journal	June 1996
Kinetics of $H_{2}$ passivation of $P_{b}$ centers at the (111) Si- ${SiO}_{2}$ interface Brower, K. L. Physical Review B, Vol. 38, Issue 14 https://doi.org/10.1103/PhysRevB.38.9657	journal	November 1988
Doping efficiency, dopant location, and oxidation of Si nanocrystals Pi, X. D.; Gresback, R.; Liptak, R. W. Applied Physics Letters, Vol. 92, Issue 12 https://doi.org/10.1063/1.2897291	journal	March 2008
Photoluminescence and free-electron absorption in heavily phosphorus-doped Si nanocrystals Mimura, Atsushi; Fujii, Minoru; Hayashi, Shinji Physical Review B, Vol. 62, Issue 19 https://doi.org/10.1103/PhysRevB.62.12625	journal	November 2000