Abstract
Optical measurements of nanoscale objects offer major insights into fundamental biological, material and photonic properties. In absorption spectroscopy, sensitivity limits applications at the nanoscale. Here, we present a new single-particle double-modulation photothermal absorption spectroscopy method that employs on-chip optical whispering-gallery-mode (WGM) microresonators as ultrasensitive thermometers. Optical excitation of a nanoscale object on the microresonator produces increased local temperatures that are proportional to the absorption cross-section of the object. We resolve photothermal shifts in the resonance frequency of the microresonator that are smaller than 100 Hz, orders of magnitude smaller than previous WGM sensing schemes. The application of our new technique to single gold nanorods reveals a dense array of sharp Fano resonances arising from the coupling between the localized surface plasmon of the gold nanorod and the WGMs of the resonator, allowing for the exploration of plasmonic–photonic hybridization. In terms of the wider applicability, our approach adds label-free spectroscopic identification to microresonator-based detection schemes.
This is a preview of subscription content, access via your institution
Access options
Subscribe to this journal
Receive 12 print issues and online access
$209.00 per year
only $17.42 per issue
Buy this article
- Purchase on SpringerLink
- Instant access to full article PDF
Prices may be subject to local taxes which are calculated during checkout
Similar content being viewed by others
References
Baaske, M. D., Foreman, M. R. & Vollmer, F. Single-molecule nucleic acid interactions monitored on a label-free microcavity biosensor platform. Nat. Nanotech. 9, 933–939 (2014).
Dantham, V. et al. Label-free detection of single protein using a nanoplasmonic-photonic hybrid microcavity. Nano Lett. 13, 3347–3351 (2013).
Yu, W., Jiang, W. C., Lin, Q. & Lu, T. Cavity optomechanical spring sensing of single molecules. Nat. Commun. 7, 12311 (2016).
Zijlstra, P., Paulo, P. M. & Orrit, M. Optical detection of single non-absorbing molecules using the surface plasmon resonance of a gold nanorod. Nat. Nanotech. 7, 379–382 (2012).
Ozdemir, S. et al. Highly sensitive detection of nanoparticles with a self-referenced and self-heterodyned whispering-gallery Raman microlaser. Proc. Natl Acad. Sci. USA 111, 3836–3844 (2014).
Lu, T. et al. High sensitivity nanoparticle detection using optical microcavities. Proc. Natl Acad. Sci. USA 108, 5976–5979 (2011).
Li, B.-B. et al. Single nanoparticle detection using split-mode microcavity Raman lasers. Proc. Natl Acad. Sci. USA 111, 14657–14662 (2014).
Swaim, J., Knittel, J. & Bowen, W. Detection of nanoparticles with a frequency locked whispering gallery mode microresonator. Appl. Phys. Lett. 102, 183106 (2013).
Mader, M., Reichel, J., Hänsch, T. W. & Hunger, D. A scanning cavity microscope. Nat. Commun. 6, 7249 (2015).
Muskens, O. L. et al. Quantitative absorption spectroscopy of a single gold nanorod. J. Phys. Chem. C 112, 8917–8921 (2008).
Li, Z., Mao, W., Devadas, M. S. & Hartland, G. V. Absorption spectroscopy of single optically trapped gold nanorods. Nano Lett. 15, 7731–7735 (2015).
Cognet, L., Berciaud, S., Lasne, D. & Lounis, B. Photothermal methods for single nonluminescent nano-objects. Anal. Chem. 80, 2288–2294 (2008).
Yorulmaz, M. et al. Single-particle absorption spectroscopy by photothermal contrast. Nano Lett. 15, 3041–3047 (2015).
Bailey, R. C. Applications of optical microcavity resonators in analytical chemistry. Annu. Rev. Anal. Chem. 9, 1–25 (2016).
Gaiduk, A., Yorulmaz, M., Ruijgrok, P. & Orrit, M. Room-temperature detection of a single molecule's absorption by photothermal contrast. Science 330, 353–356 (2010).
Celebrano, M., Kukura, P., Renn, A. & Sandoghdar, V. Single-molecule imaging by optical absorption. Nat. Photon. 5, 95–98 (2011).
Chong, S., Min, W. & Xie, X. Ground-state depletion microscopy: detection sensitivity of single-molecule optical absorption at room temperature. J. Phys. Chem. Lett. 1, 3316–3322 (2010).
Piliarik, M. & Sandoghdar, V. Direct optical sensing of single unlabelled proteins and super-resolution imaging of their binding sites. Nat. Commun. 5, 4495 (2014).
Moerner, W. E. & Kador, L. Optical detection and spectroscopy of single molecules in a solid. Phys. Rev. Lett. 62, 2535–2538 (1989).
Kador, L., Latychevskaia, T., Renn, A. & Wild, U. P. Absorption spectroscopy on single molecules in solids. J. Chem. Phys. 111, 8755–8758 (1999).
Gerhardt, I. et al. Strong extinction of a laser beam by a single molecule. Phys. Rev. Lett. 98, 033601 (2007).
Rezus, Y. et al. Single-photon spectroscopy of a single molecule. Phys. Rev. Lett. 108, 093601 (2012).
Armani, D., Kippenberg, T., Spillane, S. & Vahala, K. Ultra-high-Q toroid microcavity on a chip. Nature 421, 925–928 (2003).
Aoki, T. et al. Observation of strong coupling between one atom and a monolithic microresonator. Nature 443, 671–674 (2006).
Xiao, Y.-F. et al. Strongly enhanced light-matter interaction in a hybrid photonic-plasmonic resonator. Phys. Rev. A 85, 031805 (2012).
Link, S. & El-Sayed, M. A. Spectral properties and relaxation dynamics of surface plasmon electronic oscillations in gold and silver nanodots and nanorods. J. Phys. Chem. B 103, 8410–8426 (1999).
Arnold, S., Shopova, S. & Holler, S. Whispering gallery mode bio-sensor for label-free detection of single molecules: thermo-optic vs. reactive mechanism. Opt. Express 18, 281–287 (2010).
Heylman, K. & Goldsmith, R. Photothermal mapping and free-space laser tuning of toroidal optical microcavities. Appl. Phys. Lett. 103, 211116 (2013).
Black, E. An introduction to pound-drever-hall laser frequency stabilization. Am. J. Phys 69, 79–87 (2001).
Carmon, T. et al. Feedback control of ultra-high-Q microcavities: application to micro-Raman lasers and microparametric oscillators. Opt. Express 13, 3558–3566 (2005).
Barnes, J., Gagliardi, G. & Loock, H.-P. Absolute absorption cross-section measurement of a submonolayer film on a silica microresonator. Optica 1, 75–83 (2014).
Weng, W., Anstie, J. D. & Luiten, A. N. Refractometry with ultralow detection limit using anisotropic whispering-gallery-mode resonators. Phys. Rev. Appl. 3, 044015 (2015).
Heylman, K., Knapper, K. & Goldsmith, R. Photothermal microscopy of nonluminescent single particles enabled by optical microresonators. J. Phys. Chem. Lett. 5, 1917–1923 (2014).
Knapper, K. A., Heylman, K. D., Horak, E. H. & Goldsmith, R. H. Chip-scale fabrication of high-Q all-glass toroidal microresonators for single-particle label-free imaging. Adv. Mater. 28, 2945–2950 (2016).
Keng, D., Tan, X. & Arnold, S. Whispering gallery micro-global positioning system for nanoparticle sizing in real time. Appl. Phys. Lett. 105, 071105 (2014).
Schliesser, A., Anetsberger, G., Rivière, R., Arcizet, O. & Kippenberg, T. J. High-sensitivity monitoring of micromechanical vibration using optical whispering gallery mode resonators. New J. Phys. 10, 095015 (2008).
Fano, U. Effects of configuration interaction on intensities and phase shifts. Phys. Rev. 124, 1866–1878 (1961).
Anderson, P. W. Localized magnetic states in metals. Phys. Rev. 124, 41–53 (1961).
Miroshnichenko, A. E., Flach, S. & Kivshar, Y. S. Fano resonances in nanoscale structures. Rev. Mod. Phys. 82, 2257–2298 (2010).
Li, B.-B. et al. Experimental observation of Fano resonance in a single whispering-gallery microresonator. Appl. Phys. Lett. 98, 021116 (2011).
Barclay, P. E., Santori, C., Fu, K.-M., Beausoleil, R. G. & Painter, O. Coherent interference effects in a nano-assembled diamond NV center cavity-QED system. Opt. Express 17, 8081–8197 (2009).
Kroner, M. et al. The nonlinear Fano effect. Nature 451, 311–314 (2008).
Stern, L., Grajower, M. & Levy, U. Fano resonances and all-optical switching in a resonantly coupled plasmonic–atomic system. Nat. Commun. 5, 4865 (2014).
Giannini, V., Francescato, Y., Amrania, H., Phillips, C. C. & Maier, S. A. Fano resonances in nanoscale plasmonic systems: a parameter-free modeling approach. Nano Lett. 11, 2835–2840 (2011).
Foreman, M. R. & Vollmer, F. Level repulsion in hybrid photonic-plasmonic microresonators for enhanced biodetection. Phys. Rev. A 88, 023831 (2013).
Foreman, M. R. & Vollmer, F. Theory of resonance shifts of whispering gallery modes by arbitrary plasmonic nanoparticles. New J. Phys. 15, 083006 (2013).
Gallinet, B. & Martin, O. J. Analytical description of Fano resonances in plasmonic nanostructures. Am. Inst. Phys. Conf. Proc. 1398, 73–75 (2011).
Langbein, D. Non-retarded dispersion energy between macroscopic spheres. J. Phys. Chem. Solids 32, 1657–1667 (1971).
Wiersig, J. Structure of whispering-gallery modes in optical microdisks perturbed by nanoparticles. Phys. Rev. A 84, 063828 (2011).
Zhang, S., Bao, K., Halas, N. J., Xu, H. & Nordlander, P. Substrate-induced Fano resonances of a plasmonic nanocube: a route to increased-sensitivity localized surface plasmon resonance sensors revealed. Nano Lett. 11, 1657–1663 (2011).
Zhang, Y., Wen, F., Zhen, Y.-R., Nordlander, P. & Halas, N. J. Coherent Fano resonances in a plasmonic nanocluster enhance optical four-wave mixing. Proc. Natl Acad. Sci. USA 110, 9215–9219 (2013).
Zhang, Y. et al. Coherent anti-stokes Raman scattering with single-molecule sensitivity using a plasmonic Fano resonance. Nat. Commun. 5 ( 2014).
Jager, J. et al. High-Q silica microcavities on a chip: from microtoroid to microsphere. Appl. Phys. Lett. 99, 181123 (2011).
Link, S., Burda, C., Nikoobakht, B. & El-Sayed, M. Laser-induced shape changes of colloidal gold nanorods using femtosecond and nanosecond laser pulses. J. Phys. Chem. B 104, 6152–6163 (2000).
Leviton, D. & Frey, B. Temperature-dependent absolute refractive index measurements of synthetic fused silica. Proc. SPIE 6273, 62732K (2006).
Rokhsari, H., Spillane, S. M. & Vahala, K. J. Loss characterization in microcavities using the thermal bistability effect. Appl. Phys. Lett. 85, 3029–3031 (2004).
Fernandes, L. A. Birefringence and Bragg Grating Control in Femtosecond Laser Written Optical Circuits PhD thesis, Universidade do Porto (2012).
Acknowledgements
We thank M. Stolt and S. Jin for technical assistance with electron microscopy, A. Sheth for useful references regarding the statistical analysis and N. Eason (nipaeason.com) for graphic design contributions to this work. This work was partially supported by the NSF under award numbers DBI-1556241 and UW-MRSEC DMR-1121288 (R.H.G.), CHE-1253775 (D.J.M.), DGE-1256082 (N.T.), and DGE-1256259 (K.A.K.).
Author information
Authors and Affiliations
Contributions
K.D.H. and E.H.H. built the spectrometer and carried out the measurements and analysis with help from R.H.G. N.T., S.C.Q. and C.C. formulated the theoretical model and performed simulations with help from D.J.M. K.A.K. fabricated the resonators. K.D.H., N.T., R.H.G. and D.J.M. wrote the paper with contributions from all co-authors.
Corresponding authors
Ethics declarations
Competing interests
The authors declare no competing financial interests.
Supplementary information
Supplementary information
Supplementary information (PDF 2473 kb)
Rights and permissions
About this article
Cite this article
Heylman, K., Thakkar, N., Horak, E. et al. Optical microresonators as single-particle absorption spectrometers. Nature Photon 10, 788–795 (2016). https://doi.org/10.1038/nphoton.2016.217
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1038/nphoton.2016.217
This article is cited by
-
A whispering-gallery scanning microprobe for Raman spectroscopy and imaging
Light: Science & Applications (2023)
-
Inverse designed plasmonic metasurface with parts per billion optical hydrogen detection
Nature Communications (2022)
-
RGB WGM lasing woven in fiber braiding cavity
Science China Information Sciences (2022)
-
Nanoscale cooperative adsorption for materials control
Nature Communications (2021)
-
Optical whispering-gallery mode barcodes for high-precision and wide-range temperature measurements
Light: Science & Applications (2021)