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Nanoplasmonic Sensing using Metal Nanoparticles
Linköping University, Department of Physics, Chemistry and Biology, Molecular Physics. Linköping University, The Institute of Technology.
2014 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

In our modern society, we are surrounded by numerous sensors, constantly feeding us information about our physical environment. From small, wearable sensors that monitor our physiological status to large satellites orbiting around the earth, detecting global changes. Although, the performance of these sensors have been significantly improved during the last decades there is still a demand for faster and more reliable sensing systems with improved sensitivity and selectivity. The rapid progress in nanofabrication techniques has made a profound impact for the development of small, novel sensors that enables miniaturization and integration. A specific area where nanostructures are especially attractive is biochemical sensing, where the exceptional properties of nanomaterials can be utilized in order to detect and analyze biomolecular interactions. 

The focus of this thesis is to investigate plasmonic nanoparticles composed of gold or silver and optimize their performance as signal transducers in optical biosensors. Metal nanoparticles exhibit unique optical properties due to excitation of localized surface plasmons, which makes them highly sensitive probes for detecting small, local changes in their surrounding environment, for instance the binding of a biomolecule to the nanoparticle surface. This is the basic principle behind nanoplasmonic sensing based on refractometric detection, a sensing scheme that offers real-time and label-free detection of molecular interactions. 

This thesis shows that the sensitivity for detecting local refractive index changes is highly dependent on the geometry of the metal nanoparticles, their interaction with neighboring particles and their chemical composition and functionalization. An increased knowledge about how these parameters affects the sensitivity is essential when developing nanoplasmonic sensing devices with high performance based on metal nanoparticles. 

Place, publisher, year, edition, pages
Linköping: Linköping University Electronic Press, 2014. , 76 p.
Series
Linköping Studies in Science and Technology. Dissertations, ISSN 0345-7524 ; 1624
Keyword [en]
Nanoparticles, sensing, biosensors, refractive index sensing, plasmonics, nanoplasmonics
National Category
Nano Technology
Identifiers
URN: urn:nbn:se:liu:diva-111841DOI: 10.3384/diss.diva-111841ISBN: 978-91-7519-223-9 (print)OAI: oai:DiVA.org:liu-111841DiVA: diva2:760957
Public defence
2014-11-28, Planck, Fysikhuset, Campus Valla, Linköpings universitet, Linköping, 09:15 (English)
Opponent
Supervisors
Available from: 2014-11-06 Created: 2014-11-05 Last updated: 2017-01-11Bibliographically approved
List of papers
1. Local Refractive Index Sensing Based on Edge Gold-Coated Silver Nanoprisms
Open this publication in new window or tab >>Local Refractive Index Sensing Based on Edge Gold-Coated Silver Nanoprisms
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2013 (English)In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 117, no 44, 23148-23154 p.Article in journal (Refereed) Published
Abstract [en]

Bulk and surface refractive index sensitivity for localized surface plasmon resonance (LSPR) sensing based on edge gold-coated silver nanoprisms (GSNPs) and gold nanospheres was investigated and compared with conventional surface plasmon resonance (SPR) sensing based on propagating surface plasmons. The hybrid GSNPs benefit from an improved stability since the gold frame protecting the unstable silver facets located at the silver nanoprisms (SNPs) edges and tips prevents truncation or rounding of their sharp tips or edges, maintaining a high refractive index sensitivity even under harsh conditions. By using layer-by-layer deposition of polyelectrolytes and protein adsorption, we found that GSNPs exhibit 4-fold higher local refractive index sensitivity in close proximity (andlt;10 nm) to the surface compared to a flat gold film in the conventional SPR setup. Moreover, the sensitivity was 8-fold higher with GSNPs than with gold nanospheres. This shows that relatively simple plasmonic nanostructures for LSPR-based sensing can be engineered to outperform conventional SPR, which is particularly interesting in the context of detecting low molecular weight compounds where a small sensing volume, reducing bulk signals, is desired.

Place, publisher, year, edition, pages
American Chemical Society, 2013
National Category
Engineering and Technology
Identifiers
urn:nbn:se:liu:diva-102498 (URN)10.1021/jp408187e (DOI)000326845400076 ()
Note

Funding Agencies|Swedish Foundation for Strategic Research (SSF)||Knut and Alice Wallenberg Foundation (KAW)||Centre in Nano science and technology (CeNano)||Singapore MOE|RG 44/11M0E2012-T2-2-041ARC 5/13|CRP program from NRF Singapore|NRF-CRP5-2009-04|Science & Engineering Research Council (SERC) of Agency for Science Technology and Research (A*STAR)|102 152 0015|Swedish Research Council (VR)||

Available from: 2013-12-12 Created: 2013-12-12 Last updated: 2017-12-06
2. Optimizing the Refractive Index Sensitivity of Plasmonically Coupled Gold Nanoparticles
Open this publication in new window or tab >>Optimizing the Refractive Index Sensitivity of Plasmonically Coupled Gold Nanoparticles
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2014 (English)In: PLASMONICS, ISSN 1557-1955, Vol. 9, no 4, 773-780 p.Article in journal (Refereed) Published
Abstract [en]

The possibility to enhance the local refractive index sensitivity using plasmonic coupling between spherical gold nanoparticles (Au-NPs) has been investigated. A strong and distinct optical coupling between Au-NPs of various sizes was achieved by controlling the interparticle separation using a layer-by-layer assembly of polyelectrolytes. The frequency of the coupled plasmon peak could be tuned by varying either the particle size or the interparticle separation, shown both experimentally and by theoretical simulations. The bulk refractive index (RI) sensitivity for the plasmonic coupling modes was investigated and compared to the RI sensitivity of monolayers of well-separated Au-NPs, and the results clearly demonstrates that the RI sensitivity can be significantly enhanced in plasmonically coupled Au-NPs. The proposed approach is simple and scalable and improves the rather modest RI sensitivity of spherical gold nanoparticles with a factor of 3, providing a new route for fabrication of inexpensive sensors based on plasmonic nanostructures.

Place, publisher, year, edition, pages
Springer Verlag (Germany), 2014
Keyword
Metal nanoparticles; Localized surface plasmon resonance ( LSPR); Plasmonic coupling; Polyelectrolytes; Layer-by-layer
National Category
Physical Sciences Biological Sciences
Identifiers
urn:nbn:se:liu:diva-111291 (URN)10.1007/s11468-013-9659-y (DOI)000341423800007 ()
Note

Funding Agencies|Link ping University; Swedish Research Council (VR); Swedish Foundation for Strategic Research (SSF); Knut and Alice Wallenberg Foundation (KAW); Center in Nano science and technology (CeNano); MINECO, Explora Project [MAT2011-12645-E]

Available from: 2014-10-14 Created: 2014-10-14 Last updated: 2014-11-06
3. Substrate Effect on the Refractive Index Sensitivity of Silver Nanoparticles
Open this publication in new window or tab >>Substrate Effect on the Refractive Index Sensitivity of Silver Nanoparticles
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2014 (English)In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 118, no 42, 24680-24687 p.Article in journal (Refereed) Published
Abstract [en]

The bulk refractive index (RI) sensitivity of dispersed and immobilized silver nanoparticles of three different shapes (spheres, cubes, and plates) is investigated. We demonstrate, both experimentally and theoretically, that the influence of immobilization on the RI sensitivity is highly dependent on the shape of the nanoparticles. A strong correlation is seen between the fraction of the particle surface area in direct contact with the substrate and the decrease in RI sensitivity when the particles are immobilized on a glass substrate. The largest decrease (−36%) is seen for the most sensitive nanoparticles (plates), drastically reducing their advantage over other nanoparticle shapes. The shape-dependent substrate effect is thus an important factor to consider when designing nanoplasmonic sensors based on colloidal noble-metal nanoparticles.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2014
National Category
Nano Technology
Identifiers
urn:nbn:se:liu:diva-111838 (URN)10.1021/jp5084086 (DOI)000343740300051 ()
Funder
Swedish Foundation for Strategic Research Swedish Research Council
Available from: 2014-11-05 Created: 2014-11-05 Last updated: 2017-12-05
4. Influence of Surfactant Bilayers on the Refractive Index Sensitivity and Catalytic Properties of Anisotropic Gold Nanoparticles
Open this publication in new window or tab >>Influence of Surfactant Bilayers on the Refractive Index Sensitivity and Catalytic Properties of Anisotropic Gold Nanoparticles
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2016 (English)In: Small, ISSN 1613-6810, E-ISSN 1613-6829, Vol. 12, no 3, 330-342 p.Article in journal (Refereed) Published
Abstract [en]

Shape-controlled synthesis of gold nanoparticles generally involves the use of surfactants, typically cetyltrimethylammonium (CTAX, X = Cl-, Br-), to regulate the nucleation growth process and to obtain colloidally stable nanoparticles. The surfactants adsorb on the nanoparticle surface making further functionalization difficult and therefore limit their use in many applications. Herein, the influence of CTAX on nanoparticle sensitivity to local dielectric environment changes is reported. It is shown, both experimentally and theoretically, that the CTAX bilayer significantly reduces the refractive index (RI) sensitivity of anisotropic gold nanoparticles such as nanocubes and concave nanocubes, nanorods, and nanoprisms. The RI sensitivity can be increased by up to 40% by removing the surfactant layer from nanoparticles immobilized on a solid substrate using oxygen plasma treatment. This increase compensates for the otherwise problematic decrease in RI sensitivity caused by the substrate effect. Moreover, the removal of the surfactants both facilitates nanoparticle biofunctionalization and significantly improves their catalytic properties. The strategy presented herein is a simple yet effective universal method for enhancing the RI sensitivity of CTAX-stabilized gold nanoparticles and increasing their potential as transducers in nanoplasmonic sensors, as well as in catalytic and biomedical applications.

Place, publisher, year, edition, pages
WILEY-V C H VERLAG GMBH, 2016
National Category
Physical Sciences
Identifiers
urn:nbn:se:liu:diva-125149 (URN)10.1002/smll.201502449 (DOI)000368707800006 ()26583756 (PubMedID)
Note

Funding Agencies|Swedish Research Council (VR); Stockholm Brain Institute (SBI); AFOSR [FA9550-12-1-0280]; NSFs MRSEC program at the Materials Research Center of Northwestern University [DMR-1121262]; Singapore Agency for Science, Technology and Research (A*STAR); Nanyang Technological University Postdoctoral Fellowship by Institute of Nano-System Interface Science & Technology (INSIST).

The previous status of this article was Manuscript.

Available from: 2016-02-15 Created: 2016-02-15 Last updated: 2017-11-30Bibliographically approved

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