skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Excitonic pathway to photoinduced magnetism in colloidal nanocrystals with nonmagnetic dopants

Abstract

Electronic doping of colloidal semiconductor nanostructures holds promise for future device concepts in optoelectronic and spin-based technologies. Ag+ is an emerging electronic dopant in III–V and II–VI nanostructures, introducing intragap electronic states optically coupled to the host conduction band. With its full 4d shell Ag+ is nonmagnetic, and the dopant-related luminescence is ascribed to decay of the conduction-band electron following transfer of the photoexcited hole to Ag+. This optical activation process and the associated modification of the electronic configuration of Ag+ remain unclear. Here in this paper, we trace a comprehensive picture of the excitonic process in Ag-doped CdSe nanocrystals and demonstrate that, in contrast to expectations, capture of the photohole leads to conversion of Ag+ to paramagnetic Ag2+. The process of exciton recombination is thus inextricably tied to photoinduced magnetism. Accordingly, we observe strong optically activated magnetism and diluted magnetic semiconductor behaviour, demonstrating that optically switchable magnetic nanomaterials can be obtained by exploiting excitonic processes involving nonmagnetic impurities.

Authors:
ORCiD logo [1];  [2];  [1];  [3];  [1];  [4];  [1];  [2]; ORCiD logo [5]; ORCiD logo [1]
  1. Univ. degli Studi di Milano-Bicocca, Milano (Italy). Dipartimento di Scienza dei Materiali
  2. Beijing Inst. of Technology, Beijing (China). Beijing Key Lab. of Construction Tailorable Advanced Functional Materials and Green Applications, School of Materials Science and Engineering
  3. Politecnico di Milano, Milano (Italy). Dipartimento di Fisica
  4. Politecnico and IFN-CNR, Milano (Italy). Dipartimento di Energia
  5. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Publication Date:
Research Org.:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
National Science Foundation (NSF); USDOE
OSTI Identifier:
1471349
Report Number(s):
LA-UR-17-25541
Journal ID: ISSN 1748-3387
Grant/Contract Number:  
AC52-06NA25396
Resource Type:
Accepted Manuscript
Journal Name:
Nature Nanotechnology
Additional Journal Information:
Journal Volume: 13; Journal Issue: 2; Journal ID: ISSN 1748-3387
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
High Magnetic Field Science

Citation Formats

Pinchetti, Valerio, Di, Qiumei, Lorenzon, Monica, Camellini, Andrea, Fasoli, Mauro, Zavelani-Rossi, Margherita, Meinardi, Francesco, Zhang, Jiatao, Crooker, Scott A., and Brovelli, Sergio. Excitonic pathway to photoinduced magnetism in colloidal nanocrystals with nonmagnetic dopants. United States: N. p., 2017. Web. doi:10.1038/s41565-017-0024-8.
Pinchetti, Valerio, Di, Qiumei, Lorenzon, Monica, Camellini, Andrea, Fasoli, Mauro, Zavelani-Rossi, Margherita, Meinardi, Francesco, Zhang, Jiatao, Crooker, Scott A., & Brovelli, Sergio. Excitonic pathway to photoinduced magnetism in colloidal nanocrystals with nonmagnetic dopants. United States. doi:10.1038/s41565-017-0024-8.
Pinchetti, Valerio, Di, Qiumei, Lorenzon, Monica, Camellini, Andrea, Fasoli, Mauro, Zavelani-Rossi, Margherita, Meinardi, Francesco, Zhang, Jiatao, Crooker, Scott A., and Brovelli, Sergio. Mon . "Excitonic pathway to photoinduced magnetism in colloidal nanocrystals with nonmagnetic dopants". United States. doi:10.1038/s41565-017-0024-8. https://www.osti.gov/servlets/purl/1471349.
@article{osti_1471349,
title = {Excitonic pathway to photoinduced magnetism in colloidal nanocrystals with nonmagnetic dopants},
author = {Pinchetti, Valerio and Di, Qiumei and Lorenzon, Monica and Camellini, Andrea and Fasoli, Mauro and Zavelani-Rossi, Margherita and Meinardi, Francesco and Zhang, Jiatao and Crooker, Scott A. and Brovelli, Sergio},
abstractNote = {Electronic doping of colloidal semiconductor nanostructures holds promise for future device concepts in optoelectronic and spin-based technologies. Ag+ is an emerging electronic dopant in III–V and II–VI nanostructures, introducing intragap electronic states optically coupled to the host conduction band. With its full 4d shell Ag+ is nonmagnetic, and the dopant-related luminescence is ascribed to decay of the conduction-band electron following transfer of the photoexcited hole to Ag+. This optical activation process and the associated modification of the electronic configuration of Ag+ remain unclear. Here in this paper, we trace a comprehensive picture of the excitonic process in Ag-doped CdSe nanocrystals and demonstrate that, in contrast to expectations, capture of the photohole leads to conversion of Ag+ to paramagnetic Ag2+. The process of exciton recombination is thus inextricably tied to photoinduced magnetism. Accordingly, we observe strong optically activated magnetism and diluted magnetic semiconductor behaviour, demonstrating that optically switchable magnetic nanomaterials can be obtained by exploiting excitonic processes involving nonmagnetic impurities.},
doi = {10.1038/s41565-017-0024-8},
journal = {Nature Nanotechnology},
number = 2,
volume = 13,
place = {United States},
year = {2017},
month = {12}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 10 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Spectro-electrochemical Probing of Intrinsic and Extrinsic Processes in Exciton Recombination in I–III–VI 2 Nanocrystals
journal, June 2017


Photoelectronic Properties of ZnSe Crystals
journal, July 1968


Mid-Gap States and Normal vs Inverted Bonding in Luminescent Cu + - and Ag + -Doped CdSe Nanocrystals
journal, May 2017

  • Nelson, Heidi D.; Hinterding, Stijn O. M.; Fainblat, Rachel
  • Journal of the American Chemical Society, Vol. 139, Issue 18
  • DOI: 10.1021/jacs.7b01924

An ODMR investigation of silver doped ZnSe
journal, July 1985


Direct Measurements of Magnetic Polarons in Cd 1– x Mn x Se Nanocrystals from Resonant Photoluminescence
journal, April 2017


Revealing giant internal magnetic fields due to spin fluctuations in magnetically doped colloidal nanocrystals
journal, November 2015

  • Rice, William D.; Liu, Wenyong; Baker, Thomas A.
  • Nature Nanotechnology, Vol. 11, Issue 2
  • DOI: 10.1038/nnano.2015.258

Optical properties of Ag-related centers in bulk ZnSe
journal, July 1985


Highly efficient large-area colourless luminescent solar concentrators using heavy-metal-free colloidal quantum dots
journal, August 2015

  • Meinardi, Francesco; McDaniel, Hunter; Carulli, Francesco
  • Nature Nanotechnology, Vol. 10, Issue 10
  • DOI: 10.1038/nnano.2015.178

The nature of recombination centres in silver- and chlorine-doped CdS phosphors
journal, January 1990


Highly efficient luminescent solar concentrators based on earth-abundant indirect-bandgap silicon quantum dots
journal, February 2017

  • Meinardi, Francesco; Ehrenberg, Samantha; Dhamo, Lorena
  • Nature Photonics, Vol. 11, Issue 3
  • DOI: 10.1038/nphoton.2017.5

Charge-controlled magnetism in colloidal doped semiconductor nanocrystals
journal, August 2009

  • Ochsenbein, Stefan T.; Feng, Yong; Whitaker, Kelly M.
  • Nature Nanotechnology, Vol. 4, Issue 10
  • DOI: 10.1038/nnano.2009.221

Tuning Radiative Recombination in Cu-Doped Nanocrystals via Electrochemical Control of Surface Trapping
journal, July 2012

  • Brovelli, Sergio; Galland, Christophe; Viswanatha, Ranjani
  • Nano Letters, Vol. 12, Issue 8
  • DOI: 10.1021/nl302182u

Empirical one-electron model of optical transitions in Cu-doped ZnS and CdS
journal, January 1994


Reversed oxygen sensing using colloidal quantum wells towards highly emissive photoresponsive varnishes
journal, March 2015

  • Lorenzon, Monica; Christodoulou, Sotirios; Vaccaro, Gianfranco
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms7434

Long-lived photoinduced magnetization in copper-doped ZnSe–CdSe core–shell nanocrystals
journal, December 2012

  • Pandey, A.; Brovelli, S.; Viswanatha, R.
  • Nature Nanotechnology, Vol. 7, Issue 12
  • DOI: 10.1038/nnano.2012.210

Spectroscopic and Device Aspects of Nanocrystal Quantum Dots
journal, September 2016


Ultrafast Electron−Hole Dynamics in Core/Shell CdSe/CdS Dot/Rod Nanocrystals
journal, December 2008

  • Lupo, Maria Grazia; Della Sala, Fabio; Carbone, Luigi
  • Nano Letters, Vol. 8, Issue 12
  • DOI: 10.1021/nl8028366

Colloidal quantum dot solar cells
journal, February 2012


Electron configuration and charge state of electrically active Cu, Ag and Au ions in ZnSe
journal, August 2006

  • Nedeoglo, N. D.; Sirkeli, V. P.; Nedeoglo, D. D.
  • Journal of Physics: Condensed Matter, Vol. 18, Issue 34
  • DOI: 10.1088/0953-8984/18/34/020

Heavily Doped Semiconductor Nanocrystal Quantum Dots
journal, March 2011


Localization of Ag Dopant Atoms in CdSe Nanocrystals by Reverse Monte Carlo Analysis of EXAFS Spectra
journal, August 2015

  • Kompch, Alexander; Sahu, Ayaskanta; Notthoff, Christian
  • The Journal of Physical Chemistry C, Vol. 119, Issue 32
  • DOI: 10.1021/acs.jpcc.5b04399

Magnetic circular dichroism study of CdSe quantum dots
journal, March 1998

  • Kuno, M.; Nirmal, M.; Bawendi, M. G.
  • The Journal of Chemical Physics, Vol. 108, Issue 10
  • DOI: 10.1063/1.475823

Higher Oxidation States of Silver.
journal, February 1962


Diluted magnetic semiconductors
journal, August 1988

  • Furdyna, J. K.
  • Journal of Applied Physics, Vol. 64, Issue 4
  • DOI: 10.1063/1.341700

Quantum dot bioconjugates for imaging, labelling and sensing
journal, June 2005

  • Medintz, Igor L.; Uyeda, H. Tetsuo; Goldman, Ellen R.
  • Nature Materials, Vol. 4, Issue 6, p. 435-446
  • DOI: 10.1038/nmat1390

Doped Nanocrystals
journal, March 2008


Tunable magnetic exchange interactions in manganese-doped inverted core–shell ZnSe–CdSe nanocrystals
journal, December 2008

  • Bussian, David A.; Crooker, Scott A.; Yin, Ming
  • Nature Materials, Vol. 8, Issue 1
  • DOI: 10.1038/nmat2342

Current-Induced Magnetic Polarons in a Colloidal Quantum-Dot Device
journal, July 2017


Role of Nonradiative Defects and Environmental Oxygen on Exciton Recombination Processes in CsPbBr 3 Perovskite Nanocrystals
journal, May 2017


From three- to four-coordination in copper(I) and silver(I)
journal, May 1992

  • Burdett, Jeremy K.; Eisenstein, Odile
  • Inorganic Chemistry, Vol. 31, Issue 10
  • DOI: 10.1021/ic00036a007

Optical properties of ZnSe doped with Ag and Au
journal, August 1982


Spectral Dependence of Nanocrystal Photoionization Probability: The Role of Hot-Carrier Transfer
journal, May 2011

  • Padilha, Lazaro A.; Robel, István; Lee, Doh C.
  • ACS Nano, Vol. 5, Issue 6
  • DOI: 10.1021/nn201135k

Direct Observation of sp−d Exchange Interactions in Colloidal Mn 2+ - and Co 2+ -Doped CdSe Quantum Dots
journal, April 2007

  • Archer, Paul I.; Santangelo, Steven A.; Gamelin, Daniel R.
  • Nano Letters, Vol. 7, Issue 4
  • DOI: 10.1021/nl0702362

Tuning the Emission Colors of Semiconductor Nanocrystals Beyond their Bandgap Tunability: All in the Dope
journal, June 2013


Influence of Silver Doping on Electron Transport in Thin Films of PbSe Nanocrystals
journal, November 2012

  • Kang, Moon Sung; Sahu, Ayaskanta; Frisbie, C. Daniel
  • Advanced Materials, Vol. 25, Issue 5
  • DOI: 10.1002/adma.201203114

The defect structure of silver-doped CdS
journal, June 1975


Copper-Doped Inverted Core/Shell Nanocrystals with “Permanent” Optically Active Holes
journal, November 2011

  • Viswanatha, Ranjani; Brovelli, Sergio; Pandey, Anshu
  • Nano Letters, Vol. 11, Issue 11
  • DOI: 10.1021/nl202572c

Orange luminescence of donor-acceptor pairs in CdS:Ag:Cl
journal, August 1992


Doping semiconductor nanocrystals
journal, July 2005

  • Erwin, Steven C.; Zu, Lijun; Haftel, Michael I.
  • Nature, Vol. 436, Issue 7047
  • DOI: 10.1038/nature03832

Spin dynamics in electrochemically charged CdSe quantum dots
journal, October 2005


Optical properties of 3d transition metals in II–VI compounds
journal, September 1982


Metal ion redox potential plays an important role in high-yield synthesis of monodisperse silver nanoparticles
journal, January 2012

  • Li, Lun; Hu, Feng; Xu, Dongying
  • Chemical Communications, Vol. 48, Issue 39
  • DOI: 10.1039/c2cc18152e

High-Quality Manganese-Doped ZnSe Nanocrystals
journal, January 2001

  • Norris, D. J.; Yao, Nan; Charnock, F. T.
  • Nano Letters, Vol. 1, Issue 1
  • DOI: 10.1021/nl005503h

Doping Cu in Semiconductor Nanocrystals: Some Old and Some New Physical Insights
journal, February 2011

  • Srivastava, Bhupendra B.; Jana, Santanu; Pradhan, Narayan
  • Journal of the American Chemical Society, Vol. 133, Issue 4
  • DOI: 10.1021/ja1089809

Electronic Impurity Doping in CdSe Nanocrystals
journal, April 2012

  • Sahu, Ayaskanta; Kang, Moon Sung; Kompch, Alexander
  • Nano Letters, Vol. 12, Issue 5
  • DOI: 10.1021/nl300880g

Real and Hypothetical Intermediate-Valence AgII/AgIII and AgII/AgI Fluoride Systems as Potential Superconductors
journal, August 2001


Transition metal impurities in compound semiconductors: Experimental situation
journal, March 1987


Spin spectroscopy of dark excitons in CdSe quantum dots to 60 T
journal, April 2001


    Works referencing / citing this record:

    Evidence for the Band‐Edge Exciton of CuInS 2 Nanocrystals Enables Record Efficient Large‐Area Luminescent Solar Concentrators
    journal, November 2019

    • Anand, Abhinav; Zaffalon, Matteo L.; Gariano, Graziella
    • Advanced Functional Materials, Vol. 30, Issue 4
    • DOI: 10.1002/adfm.201906629

    Near‐Infrared‐Emitting Five‐Monolayer Thick Copper‐Doped CdSe Nanoplatelets
    journal, August 2019

    • Sharma, Ashma; Sharma, Manoj; Gungor, Kivanc
    • Advanced Optical Materials, Vol. 7, Issue 22
    • DOI: 10.1002/adom.201900831

    Blue Light Emitting Defective Nanocrystals Composed of Earth‐Abundant Elements
    journal, December 2019


    Semiconductor Nanocrystal Engineering by Applying Thiol‐ and Solvent‐Coordinated Cation Exchange Kinetics
    journal, April 2019

    • Bai, Bing; Xu, Meng; Li, Nan
    • Angewandte Chemie International Edition, Vol. 58, Issue 15
    • DOI: 10.1002/anie.201807695

    Blue Light Emitting Defective Nanocrystals Composed of Earth‐Abundant Elements
    journal, January 2020

    • Hansen, Eric C.; Liu, Yun; Utzat, Hendrik
    • Angewandte Chemie International Edition, Vol. 59, Issue 2
    • DOI: 10.1002/anie.201911436

    Detecting electronic structure evolution of semiconductor nanocrystals by magnetic circular dichroism spectroscopy
    journal, January 2019

    • Gao, Xiaoqing; Zhang, Xiuwen; Yang, Xuekang
    • Nanoscale, Vol. 11, Issue 41
    • DOI: 10.1039/c9nr03630j

    Two-dimensional CdX (X = Se, Te) nanosheets: controlled synthesis and their photoluminescence properties
    journal, January 2019

    • Haleem, Yasir A.; Di, Qiumei; Bai, Bing
    • Journal of Materials Chemistry C, Vol. 7, Issue 44
    • DOI: 10.1039/c9tc04997e