Spin-glass-like freezing of inner and outer surface layers in hollow γ-Fe2O3 nanoparticles
Abstract
Disorder among surface spins largely dominates the magnetic response of ultrafine magnetic particle systems. In this work, we examine time-dependent magnetization in high-quality, monodisperse hollow maghemite nanoparticles (NPs) with a 14.8±0.5 nm outer diameter and enhanced surface-to-volume ratio. The nanoparticle ensemble exhibits spin-glass-like signatures in dc magnetic aging and memory protocols and ac magnetic susceptibility. The dynamics of the system slow near 50 K, and becomes frozen on experimental time scales below 20 K. Remanence curves indicate the development of magnetic irreversibility concurrent with the freezing of the spin dynamics. A strong exchange-bias effect and its training behavior point to highly frustrated surface spins that rearrange much more slowly than interior spins with bulk coordination. Monte Carlo simulations of a hollow particle reproducing the experimental morphology corroborate strongly disordered surface layers with complex energy landscapes that underlie both glass-like dynamics and magnetic irreversibility. Calculated hysteresis loops reveal that magnetic behavior is not identical at the inner and outer surfaces, with spins at the outer surface layer of the 15 nm hollow particles exhibiting a higher degree of frustration. Lastly, our combined experimental and simulated results shed light on the origin of spin-glass-like phenomena and the important role played by themore »
- Authors:
-
- Univ. of South Florida, Tampa, FL (United States)
- Univ. of Barcelona (Spain)
- Univ. of South Florida, Tampa, FL (United States); BCMaterials Edificio No. 500, Derio (Spain)
- Argonne National Lab. (ANL), Argonne, IL (United States)
- BCMaterials Edificio No. 500, Derio (Spain); Univ. Pierre et Marie Curie, Paris (France)
- Publication Date:
- Research Org.:
- Argonne National Laboratory (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1237916
- Grant/Contract Number:
- AC02-06CH11357; FG02-07ER46438
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Scientific Reports
- Additional Journal Information:
- Journal Volume: 5; Journal ID: ISSN 2045-2322
- Publisher:
- Nature Publishing Group
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS; Exchange bias; Hollow nanoparticles; Spin glass; Surface spins
Citation Formats
Khurshid, Hafsa, Lampen-Kelley, Paula, Iglesias, Òscar, Alonso, Javier, Phan, Manh-Huong, Sun, Cheng-Jun, Saboungi, Marie-Louise, and Srikanth, Hariharan. Spin-glass-like freezing of inner and outer surface layers in hollow γ-Fe2O3 nanoparticles. United States: N. p., 2015.
Web. doi:10.1038/srep15054.
Khurshid, Hafsa, Lampen-Kelley, Paula, Iglesias, Òscar, Alonso, Javier, Phan, Manh-Huong, Sun, Cheng-Jun, Saboungi, Marie-Louise, & Srikanth, Hariharan. Spin-glass-like freezing of inner and outer surface layers in hollow γ-Fe2O3 nanoparticles. United States. https://doi.org/10.1038/srep15054
Khurshid, Hafsa, Lampen-Kelley, Paula, Iglesias, Òscar, Alonso, Javier, Phan, Manh-Huong, Sun, Cheng-Jun, Saboungi, Marie-Louise, and Srikanth, Hariharan. Tue .
"Spin-glass-like freezing of inner and outer surface layers in hollow γ-Fe2O3 nanoparticles". United States. https://doi.org/10.1038/srep15054. https://www.osti.gov/servlets/purl/1237916.
@article{osti_1237916,
title = {Spin-glass-like freezing of inner and outer surface layers in hollow γ-Fe2O3 nanoparticles},
author = {Khurshid, Hafsa and Lampen-Kelley, Paula and Iglesias, Òscar and Alonso, Javier and Phan, Manh-Huong and Sun, Cheng-Jun and Saboungi, Marie-Louise and Srikanth, Hariharan},
abstractNote = {Disorder among surface spins largely dominates the magnetic response of ultrafine magnetic particle systems. In this work, we examine time-dependent magnetization in high-quality, monodisperse hollow maghemite nanoparticles (NPs) with a 14.8±0.5 nm outer diameter and enhanced surface-to-volume ratio. The nanoparticle ensemble exhibits spin-glass-like signatures in dc magnetic aging and memory protocols and ac magnetic susceptibility. The dynamics of the system slow near 50 K, and becomes frozen on experimental time scales below 20 K. Remanence curves indicate the development of magnetic irreversibility concurrent with the freezing of the spin dynamics. A strong exchange-bias effect and its training behavior point to highly frustrated surface spins that rearrange much more slowly than interior spins with bulk coordination. Monte Carlo simulations of a hollow particle reproducing the experimental morphology corroborate strongly disordered surface layers with complex energy landscapes that underlie both glass-like dynamics and magnetic irreversibility. Calculated hysteresis loops reveal that magnetic behavior is not identical at the inner and outer surfaces, with spins at the outer surface layer of the 15 nm hollow particles exhibiting a higher degree of frustration. Lastly, our combined experimental and simulated results shed light on the origin of spin-glass-like phenomena and the important role played by the surface spins in magnetic hollow nanostructures.},
doi = {10.1038/srep15054},
journal = {Scientific Reports},
number = ,
volume = 5,
place = {United States},
year = {Tue Oct 27 00:00:00 EDT 2015},
month = {Tue Oct 27 00:00:00 EDT 2015}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Cited by: 82 works
Citation information provided by
Web of Science
Web of Science
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT
journal, June 2005
- Ravel, B.; Newville, M.
- Journal of Synchrotron Radiation, Vol. 12, Issue 4
Magnetic domains and surface effects in hollow maghemite nanoparticles
journal, March 2009
- Cabot, Andreu; Alivisatos, A. Paul; Puntes, Víctor F.
- Physical Review B, Vol. 79, Issue 9
A dynamic study of small interacting particles: superparamagnetic model and spin-glass laws
journal, April 1988
- Dormann, J. L.; Bessais, L.; Fiorani, D.
- Journal of Physics C: Solid State Physics, Vol. 21, Issue 10
Surface effects in the magnetic properties of crystalline 3 nm ferrite nanoparticles chemically synthesized
journal, November 2010
- Lima, E.; De Biasi, E.; Mansilla, M. Vasquez
- Journal of Applied Physics, Vol. 108, Issue 10
Low Temperature Surface Spin-Glass Transition in - Nanoparticles
journal, January 1998
- Martínez, B.; Obradors, X.; Balcells, Ll.
- Physical Review Letters, Vol. 80, Issue 1
Distinguishing magnetic blocking and surface spin-glass freezing in nickel ferrite nanoparticles
journal, January 2011
- Nadeem, K.; Krenn, H.; Traussing, T.
- Journal of Applied Physics, Vol. 109, Issue 1
Spin-glass behavior in a fine particle system
journal, July 1991
- Chantrell, R. W.; El-Hilo, M.; O'Grady, K.
- IEEE Transactions on Magnetics, Vol. 27, Issue 4
Metal Oxide Nanostructures and Their Gas Sensing Properties: A Review
journal, February 2012
- Sun, Yu-Feng; Liu, Shao-Bo; Meng, Fan-Li
- Sensors, Vol. 12, Issue 3
Magnetic interactions between nanoparticles
journal, January 2010
- Mørup, Steen; Hansen, Mikkel Fougt; Frandsen, Cathrine
- Beilstein Journal of Nanotechnology, Vol. 1
Spin glass-like phase below ∼210 K in magnetoelectric gallium ferrite
journal, March 2012
- Mukherjee, Somdutta; Garg, Ashish; Gupta, Rajeev
- Applied Physics Letters, Vol. 100, Issue 11
Aging and memory in a superspin glass
journal, June 2003
- Sahoo, S.; Petracic, O.; Kleemann, W.
- Physical Review B, Vol. 67, Issue 21
Aging phenomena in spin-glass and ferromagnetic phases: Domain growth and wall dynamics
journal, June 2000
- Vincent, E.; Dupuis, V.; Alba, M.
- Europhysics Letters (EPL), Vol. 50, Issue 5
Nonequilibrium dynamics of spin glasses
journal, July 1988
- Fisher, Daniel S.; Huse, David A.
- Physical Review B, Vol. 38, Issue 1
Comment on “Memory Effects in an Interacting Magnetic Nanoparticle System”
journal, September 2004
- Zheng, R. K.; Gu, Hongwei; Zhang, X. X.
- Physical Review Letters, Vol. 93, Issue 13
Applications of magnetic nanoparticles in biomedicine
journal, June 2003
- Pankhurst, Q. A.; Connolly, J.; Jones, S. K.
- Journal of Physics D: Applied Physics, Vol. 36, Issue 13
Supermagnetism
journal, December 2008
- Bedanta, Subhankar; Kleemann, Wolfgang
- Journal of Physics D: Applied Physics, Vol. 42, Issue 1
Aging, rejuvenation, and memory effects in Ising and Heisenberg spin glasses
journal, October 2001
- Dupuis, V.; Vincent, E.; Bouchaud, J. -P.
- Physical Review B, Vol. 64, Issue 17
Observation of superspin glass state in magnetically textured ferrofluid (γ-Fe2O3)
journal, April 2009
- Nakamae, S.; Tahri, Y.; Thibierge, C.
- Journal of Applied Physics, Vol. 105, Issue 7
Hollow Spheres of Iron Carbide Nanoparticles Encased in Graphitic Layers as Oxygen Reduction Catalysts
journal, February 2014
- Hu, Yang; Jensen, Jens Oluf; Zhang, Wei
- Angewandte Chemie International Edition, Vol. 53, Issue 14
Superspin glass originating from dipolar interaction with controlled interparticle distance among -Fe O nanoparticles with silica shells
journal, June 2011
- Hiroi, Kosuke; Komatsu, Katsuyoshi; Sato, Tetsuya
- Physical Review B, Vol. 83, Issue 22
Gold/Iron Oxide Core/Hollow-Shell Nanoparticles
journal, November 2008
- Shevchenko, Elena V.; Bodnarchuk, Maryna I.; Kovalenko, Maksym V.
- Advanced Materials, Vol. 20, Issue 22, p. 4323-4329
Observation of superspin-glass behavior in nanoparticles
journal, January 2009
- Suzuki, Masatsugu; Fullem, Sharbani I.; Suzuki, Itsuko S.
- Physical Review B, Vol. 79, Issue 2
Spin glass to cluster glass transition in geometrically frustrated ferrimagnets
journal, June 2009
- Vijayanandhini, K.; Simon, Ch.; Pralong, V.
- Physical Review B, Vol. 79, Issue 22
Equilibrium behavior of the spin-glass ordered phase
journal, July 1988
- Fisher, Daniel S.; Huse, David A.
- Physical Review B, Vol. 38, Issue 1
Surface spin disorder and exchange-bias in hollow maghemite nanoparticles
journal, July 2012
- Khurshid, Hafsa; Li, Wanfeng; Phan, Manh-Huong
- Applied Physics Letters, Vol. 101, Issue 2
Role of Frozen Spins in the Exchange Anisotropy of Core−Shell Fe@Fe 3 O 4 Nanoparticles
journal, January 2011
- Ong, Quy Khac; Lin, Xiao-Min; Wei, Alexander
- The Journal of Physical Chemistry C, Vol. 115, Issue 6
Collective states of interacting ferromagnetic nanoparticles
journal, May 2006
- Petracic, O.; Chen, X.; Bedanta, S.
- Journal of Magnetism and Magnetic Materials, Vol. 300, Issue 1
Growth of a dynamical correlation length in an aging superspin glass
journal, October 2008
- Wandersman, E.; Dupuis, V.; Dubois, E.
- EPL (Europhysics Letters), Vol. 84, Issue 3
Hollow Iron Oxide Nanoparticles for Application in Lithium Ion Batteries
journal, April 2012
- Koo, Bonil; Xiong, Hui; Slater, Michael D.
- Nano Letters, Vol. 12, Issue 5, p. 2429-2435
Spin dynamics and criteria for onset of exchange bias in superspin glass Fe/ -Fe O core-shell nanoparticles
journal, July 2012
- Chandra, Sayan; Khurshid, H.; Li, Wanfeng
- Physical Review B, Vol. 86, Issue 1
Ageing phenomena in a spin-glass : effect of temperature changes below Tg
journal, January 1987
- Refregier, Ph.; Vincent, E.; Hammann, J.
- Journal de Physique, Vol. 48, Issue 9
Aging and memory effects in superparamagnets and superspin glasses
journal, March 2005
- Sasaki, M.; Jönsson, P. E.; Takayama, H.
- Physical Review B, Vol. 71, Issue 10
Impacts of surface spins and inter-particle interactions on the magnetism of hollow γ-Fe 2 O 3 nanoparticles
journal, May 2014
- Khusrhid, Hafsa; Nemati Porshokouh, Zohreh; Phan, Manh-Huong
- Journal of Applied Physics, Vol. 115, Issue 17
Hierarchically Nanostructured Magnetic Hollow Spheres of Fe3O4 and γ-Fe2O3: Preparation and Potential Application in Drug Delivery
journal, January 2008
- Cao, Shao-Wen; Zhu, Ying-Jie; Ma, Ming-Yan
- The Journal of Physical Chemistry C, Vol. 112, Issue 6
Core-Shell Magnetic Morphology of Structurally Uniform Magnetite Nanoparticles
journal, May 2010
- Krycka, K. L.; Booth, R. A.; Hogg, C. R.
- Physical Review Letters, Vol. 104, Issue 20
Particle blocking and carrier fluid freezing effects on the magnetic properties of Fe3O4-based ferrofluids
journal, April 2009
- Morales, M. B.; Phan, M. H.; Pal, S.
- Journal of Applied Physics, Vol. 105, Issue 7
Surface spin disorder and spin-glass-like behaviour in manganese-substituted cobalt ferrite nanoparticles
journal, September 2012
- Topkaya, R.; Akman, Ö.; Kazan, S.
- Journal of Nanoparticle Research, Vol. 14, Issue 10
Morphology influence on nanoscale magnetism of Co nanoparticles: Experimental and theoretical aspects of exchange bias
journal, October 2011
- Simeonidis, K.; Martinez-Boubeta, C.; Iglesias, O.
- Physical Review B, Vol. 84, Issue 14
Magnetic order in - nanoparticles: a XMCD study
journal, March 2005
- Brice-Profeta, S.; Arrio, M. -A.; Tronc, E.
- Journal of Magnetism and Magnetic Materials, Vol. 288
Dynamics of an Interacting Particle System: Evidence of Critical Slowing Down
journal, December 1997
- Djurberg, C.; Svedlindh, P.; Nordblad, P.
- Physical Review Letters, Vol. 79, Issue 25
Memory and Chaos Effects in Spin Glasses
journal, October 1998
- Jonason, K.; Vincent, E.; Hammann, J.
- Physical Review Letters, Vol. 81, Issue 15
Spin glasses: Experimental facts, theoretical concepts, and open questions
journal, October 1986
- Binder, K.; Young, A. P.
- Reviews of Modern Physics, Vol. 58, Issue 4
Magnetic nanoparticles
journal, October 1999
- Kodama, R. H.
- Journal of Magnetism and Magnetic Materials, Vol. 200, Issue 1-3
Surface and Internal Spin Canting in γ-Fe 2 O 3 Nanoparticles
journal, November 1999
- Morales, M. P.; Veintemillas-Verdaguer, S.; Montero, M. I.
- Chemistry of Materials, Vol. 11, Issue 11
Interacting ferromagnetic nanoparticles in discontinuous multilayers: From superspin glass to reentrant superferromagnetism
journal, March 2001
- Kleemann, W.; Petracic, O.; Binek, Ch.
- Physical Review B, Vol. 63, Issue 13
Chemically synthesized hollow nanostructures in iron oxides
journal, May 2011
- Khurshid, Hafsa; Li, Wanfeng; Tzitzios, Vasillis
- Nanotechnology, Vol. 22, Issue 26
Synthesis of Hollow Nanocubes and Macroporous Monoliths of Silicalite-1 by Alkaline Treatment
journal, October 2013
- Dai, Chengyi; Zhang, Anfeng; Li, Lingling
- Chemistry of Materials, Vol. 25, Issue 21
Surfactant effects in magnetite nanoparticles of controlled size
journal, September 2007
- Guardia, P.; Batlle-Brugal, B.; Roca, A. G.
- Journal of Magnetism and Magnetic Materials, Vol. 316, Issue 2
Memory and superposition in a spin glass
journal, January 2001
- Mathieu, R.; Jönsson, P.; Nam, D. N. H.
- Physical Review B, Vol. 63, Issue 9
Spin glasses: redux: an updated experimental/materials survey
journal, April 2015
- Mydosh, J. A.
- Reports on Progress in Physics, Vol. 78, Issue 5
The effect of surface spin disorder on the magnetism of γ-Fe 2 O 3 nanoparticle dispersions
journal, October 2007
- Shendruk, T. N.; Desautels, R. D.; Southern, B. W.
- Nanotechnology, Vol. 18, Issue 45
Surface spin glass and exchange bias in nanoparticles compacted under high pressure
journal, September 2004
- Wang, H.; Zhu, T.; Zhao, K.
- Physical Review B, Vol. 70, Issue 9
Fingerprinting the magnetic behavior of antiferromagnetic nanostructures using remanent magnetization curves
journal, April 2011
- Benitez, M. J.; Petracic, O.; Tüysüz, H.
- Physical Review B, Vol. 83, Issue 13
Superspin Glass Mediated Giant Spontaneous Exchange Bias in a Nanocomposite of
journal, March 2013
- Maity, Tuhin; Goswami, Sudipta; Bhattacharya, Dipten
- Physical Review Letters, Vol. 110, Issue 10
Exchange Bias Phenomenology and Models of Core/Shell Nanoparticles
journal, June 2008
- Iglesias, Òscar; Labarta, Amílcar; Batlle, Xavier
- Journal of Nanoscience and Nanotechnology, Vol. 8, Issue 6
Core-Shell Magnetic Morphology of Structurally Uniform Magnetite Nanoparticles
text, January 2010
- Kryka, K. L.; Booth, Ryan A.; Hogg, Charles R.
- Carnegie Mellon University
Hollow Spheres of Iron Carbide Nanoparticles Encased in Graphitic Layers as Oxygen Reduction Catalysts
journal, February 2014
- Hu, Yang; Jensen, Jens Oluf; Zhang, Wei
- Angewandte Chemie, Vol. 126, Issue 14
Spin glasses
journal, October 1984
- Korenblit, I. Ya.; Shender, E. F.
- Soviet Physics Journal, Vol. 27, Issue 10
Core-Shell Magnetic Morphology of Structurally Uniform Magnetite Nanoparticles
text, January 2010
- Kryka, K. L.; Booth, Ryan A.; Hogg, Charles R.
- Carnegie Mellon University
Observation of superspin glass state in magnetically textured ferrofluid (gamma-Fe2O3)
text, January 2008
- Nakamae, Sawako; Tahri, Youssef; Thibierge, Caroline
- arXiv
Spin Glass-like Phase below ~ 210 K in Magnetoelectric Gallium Ferrite
text, January 2012
- Mukherjee, Somdutta; Garg, Ashish; Gupta, Rajeev
- arXiv
Collective states of interacting ferromagnetic nanoparticles
text, January 2005
- Petracic, O.; Chen, X.; Bedanta, S.
- arXiv
Surface spin disorder and spin-glass-like behaviour in manganese-substituted cobalt ferrite nanoparticles
journal, September 2012
- Topkaya, R.; Akman, Ö.; Kazan, S.
- Journal of Nanoparticle Research, Vol. 14, Issue 10
Magnetic transitions and spin-glass reentrance in two-dimensional [Mn II (TCNE)(NCMe) 2 ]X (X = PF 6 ,AsF 6 ,SbF 6 ) molecular magnets
journal, June 2013
- Olson, C. S.; Heth, C. L.; Alema, F. L.
- Journal of Physics: Condensed Matter, Vol. 25, Issue 25
Magnetic entropy change in core/shell and hollow nanoparticles
journal, September 2013
- Chandra, Sayan; Biswas, Anis; Khurshid, Hafsa
- Journal of Physics: Condensed Matter, Vol. 25, Issue 42
Remanent magnetization in spin-glasses
journal, May 1979
- Kinzel, Wolfgang
- Physical Review B, Vol. 19, Issue 9
Dynamics of an Ising Spin-Glass in the Vicinity of the Spin-Glass Temperature
journal, August 1988
- Gunnarsson, K.; Svedlindh, P.; Nordblad, P.
- Physical Review Letters, Vol. 61, Issue 6
Metal Oxide Nanostructures and Their Gas Sensing Properties: A Review
journal, February 2012
- Sun, Yu-Feng; Liu, Shao-Bo; Meng, Fan-Li
- Sensors, Vol. 12, Issue 3
Growth of a dynamical correlation length in an aging superspin glass
text, January 2008
- Wandersman, Elie; Dupuis, V.; Dubois, Emmanuelle
- arXiv
Works referencing / citing this record:
Enhanced Exchange Bias Effect by Modulating Relative Ratio of Magnetic Ions in Y 2 Co 2− x Mn x O 6 ( x = 1.0–1.9)
journal, March 2019
- Oh, Sang Hyub; Moon, Jae Young; Oh, Dong Gun
- physica status solidi (RRL) – Rapid Research Letters, Vol. 13, Issue 7
Structural and magnetic properties of cobalt iron disulfide (CoxFe1−xS2) nanocrystals
journal, March 2018
- Gabold, Henrik; Luan, Zhongyue; Paul, Neelima
- Scientific Reports, Vol. 8, Issue 1
Core/shell iron/iron oxide nanoparticles: are they promising for magnetic hyperthermia?
journal, January 2016
- Nemati, Z.; Alonso, J.; Khurshid, H.
- RSC Advances, Vol. 6, Issue 45
Site dilution and charge disorder effect on physical properties in SrRu 1− x Ga x O 3
journal, October 2019
- Gupta, Renu; Bhatti, Imtiaz Noor; Pramanik, A. K.
- Journal of Physics: Condensed Matter, Vol. 32, Issue 3
Magnetoelectric memory in reentrant frozen state and considerable ferroelectricity in the multiferroic spin-chain compound
journal, March 2017
- Indra, A.; Dey, K.; Majumdar, S.
- Physical Review B, Vol. 95, Issue 9
Strong Pinned-Spin-Mediated Memory Effect in NiO Nanoparticles
journal, March 2017
- Gandhi, Ashish Chhaganlal; Chan, Ting Shan; Pant, Jayashree
- Nanoscale Research Letters, Vol. 12, Issue 1
Exchange Bias Effects in Iron Oxide-Based Nanoparticle Systems
journal, November 2016
- Phan, Manh-Huong; Alonso, Javier; Khurshid, Hafsa
- Nanomaterials, Vol. 6, Issue 11
Magnetoelectric memory in reentrant frozen state and considerable ferroelectricity in the multiferroic spin-chain compound Sm$_{2}$BaNiO$_{5}$
text, January 2017
- Indra, A.; Dey, K.; Majumdar, S.
- Deutsches Elektronen-Synchrotron, DESY, Hamburg
Exchange Bias Effects in Iron Oxide-Based Nanoparticle Systems
text, January 2016
- Phan, Manh-Huong; Alonso, Javier; Khurshid, Hafsa
- arXiv
Site dilution and charge disorder effect on physical properties in SrRu$_{1-x}$Ga$_x$O$_3$
text, January 2019
- Gupta, Renu; Bhatti, Imtiaz Noor; Pramanik, A. K.
- arXiv
Strong Pinned-Spin-Mediated Memory Effect in NiO Nanoparticles
journal, March 2017
- Gandhi, Ashish Chhaganlal; Chan, Ting Shan; Pant, Jayashree
- Nanoscale Research Letters, Vol. 12, Issue 1
Exchange Bias Effects in Iron Oxide-Based Nanoparticle Systems
text, January 2016
- Phan, Manh-Huong; Alonso, Javier; Khurshid, Hafsa
- arXiv