Abstract

The enhancement of light-matter coupling when light is confined to wavelength scale volumes is useful both for studying small sample volumes and increasing the overall sensing ability. At these length scales, nonradiative interactions are of key interest to which near-field optical techniques may reveal new phenomena facilitating next-generation material functionalities and applications. Efforts to develop novel chemical or biological sensors using metamaterials have yielded innovative ideas in the optical and terahertz frequency range whereby the spatially integrated response over a resonator structure is monitored via the re-radiated or leaked light. But although terahertz waves generally exhibit distinctive response in chemical molecules or biological tissue, there is little absorption for subwavelength size sample and therefore poor image contrast. Here, we introduce a method that spatially resolves the differential near-field phase response of the entire resonator as a spectral fingerprint. By simultaneously probing two metallic ring resonators, where one loaded with the sample of interest, the differential phase response is able to resolve the presence of guest molecules (e.g. methanol) as they are adsorbed or released within the pores of a prototypical porous coordination polymer.

© 2014 Optical Society of America

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References

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  6. J. A. Schuller, E. S. Barnard, W. Cai, Y. C. Jun, J. S. White, and M. L. Brongersma, “Plasmonics for extreme light concentration and manipulation,” Nat. Mater. 9(3), 193–204 (2010).
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  8. N. Liu, T. Weiss, M. Mesch, L. Langguth, U. Eigenthaler, M. Hirscher, C. Sönnichsen, and H. Giessen, “Planar metamaterial analogue of electromagnetically induced transparency for plasmonic sensing,” Nano Lett. 10(4), 1103–1107 (2010).
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  9. D. Brinks, M. Castro-Lopez, R. Hildner, and N. F. van Hulst, “Plasmonic antennas as design elements for coherent ultrafast nanophotonics,” Proc. Natl. Acad. Sci. U.S.A. 110(46), 18386–18390 (2013).
    [Crossref] [PubMed]
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    [Crossref]
  11. P. H. Bolivar, M. Nagel, F. Richter, M. Brucherseifer, H. Kurz, A. Bosserhoff, and R. Büttner, “Label-free THz sensing of genetic sequences: towards ‘THz biochips’,” Philos. T. Roy. Soc. A 362(1815), 323–335 (2004).
    [Crossref]
  12. N. I. Landy, C. M. Bingham, T. Tyler, N. Jokerst, D. R. Smith, and W. J. Padilla, “Design, theory, and measurement of a polarization-insensitive absorber for terahertz imaging,” Phys. Rev. B 79(12), 125104 (2009).
    [Crossref]
  13. J. R. Knab, A. J. L. Adam, R. Chakkittakandy, and P. C. M. Planken, “Terahertz near-field microspectroscopy,” Appl. Phys. Lett. 97(3), 031115 (2010).
    [Crossref]
  14. H. Tao, W. J. Padilla, X. Zhang, and R. D. Averitt, “Recent Progress in Electromagnetic Metamaterial Devices for Terahertz Applications,” IEEE J. Sel. Top. Quantum Electron. 17(1), 92–101 (2011).
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    [Crossref]
  19. P. C. M. Planken, A. J. L. Adam, and D. Kim, “Terahertz Near-Field Imaging,” Spr. Ser. Opt. Sci. 171, 389–413 (2013).
    [Crossref]
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    [Crossref]
  21. H. Hirori, A. Doi, F. Blanchard, and K. Tanaka, “Single-cycle terahertz pulses with amplitudes exceeding 1 MV/cm generated by optical rectification in LiNbO3,” Appl. Phys. Lett. 98(9), 091106 (2011).
    [Crossref]
  22. M. Liu, H. Y. Hwang, H. Tao, A. C. Strikwerda, K. Fan, G. R. Keiser, A. J. Sternbach, K. G. West, S. Kittiwatanakul, J. Lu, S. A. Wolf, F. G. Omenetto, X. Zhang, K. A. Nelson, and R. D. Averitt, “Terahertz-field-induced insulator-to-metal transition in vanadium dioxide metamaterial,” Nature 487(7407), 345–348 (2012).
    [Crossref] [PubMed]
  23. O. M. Yaghi, M. O’Keeffe, N. W. Ockwig, H. K. Chae, M. Eddaoudi, and J. Kim, “Reticular synthesis and the design of new materials,” Nature 423(6941), 705–714 (2003).
    [Crossref] [PubMed]
  24. H. Uehara, S. Diring, S. Furukawa, Z. Kalay, M. Tsotsalas, M. Nakahama, K. Hirai, M. Kondo, O. Sakata, and S. Kitagawa, “Porous Coordination Polymer Hybrid Device with Quartz Oscillator: Effect of Crystal Size on Sorption Kinetics,” J. Am. Chem. Soc. 133(31), 11932–11935 (2011).
    [Crossref] [PubMed]
  25. M. Tsotsalas, P. Hejcik, K. Sumida, Z. Kalay, S. Furukawa, and S. Kitagawa, “Impact of Molecular Clustering inside Nanopores on Desorption Processes,” J. Am. Chem. Soc. 135(12), 4608–4611 (2013).
    [Crossref] [PubMed]
  26. K. Schröck, F. Schröder, M. Heyden, R. A. Fischer, and M. Havenith, “Characterization of interfacial water in MOF-5 (Zn4(O)(BDC)3)-a combined spectroscopic and theoretical study,” Phys. Chem. Chem. Phys. 10(32), 4732–4739 (2008).
    [Crossref] [PubMed]
  27. L. Novotny and B. Hecht, Principles of Nano-Optics Second edition, (Cambridge University Press, 2012).
  28. C. R. Williams, S. R. Andrews, S. A. Maier, A. I. Fernández-Domínguez, L. Martín-Moreno, and F. J. García-Vidal, “Highly confined guiding of terahertz surface plasmon polaritons on structured metal surfaces,” Nat. Photonics 2(3), 175–179 (2008).
    [Crossref]
  29. A. Doi, F. Blanchard, H. Hirori, and K. Tanaka, “Near-field THz imaging of free induction decay from a tyrosine crystal,” Opt. Express 18(17), 18419–18424 (2010).
    [Crossref] [PubMed]
  30. C. D. Abeyrathne, M. N. Halgamuge, P. M. Farrell, and E. Skafidas, “An ab-initio Computational method to determine dielectric properties of biological materials,” Nature Sci. Rep. 3, 1796 (2013).
    [Crossref] [PubMed]

2013 (6)

D. Brinks, M. Castro-Lopez, R. Hildner, and N. F. van Hulst, “Plasmonic antennas as design elements for coherent ultrafast nanophotonics,” Proc. Natl. Acad. Sci. U.S.A. 110(46), 18386–18390 (2013).
[Crossref] [PubMed]

P. C. M. Planken, A. J. L. Adam, and D. Kim, “Terahertz Near-Field Imaging,” Spr. Ser. Opt. Sci. 171, 389–413 (2013).
[Crossref]

F. Blanchard, A. Doi, T. Tanaka, and K. Tanaka, “Real-Time, Subwavelength Terahertz Imaging,” Annu. Rev. Mater. Res. 43(1), 237–259 (2013).
[Crossref]

M. Tsotsalas, P. Hejcik, K. Sumida, Z. Kalay, S. Furukawa, and S. Kitagawa, “Impact of Molecular Clustering inside Nanopores on Desorption Processes,” J. Am. Chem. Soc. 135(12), 4608–4611 (2013).
[Crossref] [PubMed]

C. D. Abeyrathne, M. N. Halgamuge, P. M. Farrell, and E. Skafidas, “An ab-initio Computational method to determine dielectric properties of biological materials,” Nature Sci. Rep. 3, 1796 (2013).
[Crossref] [PubMed]

J. R. Knab, A. J. L. Adam, E. Shaner, H. J. A. J. Starmans, and P. C. M. Planken, “Terahertz near-field spectroscopy of filled subwavelength sized apertures in thin metal films,” Opt. Express 21(1), 1101–1112 (2013).
[Crossref] [PubMed]

2012 (1)

M. Liu, H. Y. Hwang, H. Tao, A. C. Strikwerda, K. Fan, G. R. Keiser, A. J. Sternbach, K. G. West, S. Kittiwatanakul, J. Lu, S. A. Wolf, F. G. Omenetto, X. Zhang, K. A. Nelson, and R. D. Averitt, “Terahertz-field-induced insulator-to-metal transition in vanadium dioxide metamaterial,” Nature 487(7407), 345–348 (2012).
[Crossref] [PubMed]

2011 (5)

H. Hirori, A. Doi, F. Blanchard, and K. Tanaka, “Single-cycle terahertz pulses with amplitudes exceeding 1 MV/cm generated by optical rectification in LiNbO3,” Appl. Phys. Lett. 98(9), 091106 (2011).
[Crossref]

H. Tao, W. J. Padilla, X. Zhang, and R. D. Averitt, “Recent Progress in Electromagnetic Metamaterial Devices for Terahertz Applications,” IEEE J. Sel. Top. Quantum Electron. 17(1), 92–101 (2011).
[Crossref]

A. J. L. Adam, “Review of Near-Field Terahertz Measurement Methods and Their Applications,” Int. J. Infrared Millim. Waves 32(8-9), 976–1019 (2011).
[Crossref]

L. Novotny and H. van Hulst, “Antennas for light,” Nat. Photonics 5(2), 83–90 (2011).
[Crossref]

H. Uehara, S. Diring, S. Furukawa, Z. Kalay, M. Tsotsalas, M. Nakahama, K. Hirai, M. Kondo, O. Sakata, and S. Kitagawa, “Porous Coordination Polymer Hybrid Device with Quartz Oscillator: Effect of Crystal Size on Sorption Kinetics,” J. Am. Chem. Soc. 133(31), 11932–11935 (2011).
[Crossref] [PubMed]

2010 (5)

J. R. Knab, A. J. L. Adam, R. Chakkittakandy, and P. C. M. Planken, “Terahertz near-field microspectroscopy,” Appl. Phys. Lett. 97(3), 031115 (2010).
[Crossref]

A. Doi, F. Blanchard, H. Hirori, and K. Tanaka, “Near-field THz imaging of free induction decay from a tyrosine crystal,” Opt. Express 18(17), 18419–18424 (2010).
[Crossref] [PubMed]

N. Liu, T. Weiss, M. Mesch, L. Langguth, U. Eigenthaler, M. Hirscher, C. Sönnichsen, and H. Giessen, “Planar metamaterial analogue of electromagnetically induced transparency for plasmonic sensing,” Nano Lett. 10(4), 1103–1107 (2010).
[Crossref] [PubMed]

M. Walther, B. M. Fischer, A. Ortner, A. Bitzer, A. Thoman, and H. Helm, “Chemical sensing and imaging with pulsed terahertz radiation,” Anal. Bioanal. Chem. 397(3), 1009–1017 (2010).
[Crossref] [PubMed]

J. A. Schuller, E. S. Barnard, W. Cai, Y. C. Jun, J. S. White, and M. L. Brongersma, “Plasmonics for extreme light concentration and manipulation,” Nat. Mater. 9(3), 193–204 (2010).
[Crossref] [PubMed]

2009 (1)

N. I. Landy, C. M. Bingham, T. Tyler, N. Jokerst, D. R. Smith, and W. J. Padilla, “Design, theory, and measurement of a polarization-insensitive absorber for terahertz imaging,” Phys. Rev. B 79(12), 125104 (2009).
[Crossref]

2008 (2)

K. Schröck, F. Schröder, M. Heyden, R. A. Fischer, and M. Havenith, “Characterization of interfacial water in MOF-5 (Zn4(O)(BDC)3)-a combined spectroscopic and theoretical study,” Phys. Chem. Chem. Phys. 10(32), 4732–4739 (2008).
[Crossref] [PubMed]

C. R. Williams, S. R. Andrews, S. A. Maier, A. I. Fernández-Domínguez, L. Martín-Moreno, and F. J. García-Vidal, “Highly confined guiding of terahertz surface plasmon polaritons on structured metal surfaces,” Nat. Photonics 2(3), 175–179 (2008).
[Crossref]

2007 (1)

M. Tonouchi, “Cutting-edge terahertz technology,” Nat. Photonics 1(2), 97–105 (2007).
[Crossref]

2005 (1)

P. Mühlschlegel, H.-J. Eisler, O. J. F. Martin, B. Hecht, and D. W. Pohl, “Resonant optical antennas,” Science 308(5728), 1607–1609 (2005).
[Crossref] [PubMed]

2004 (3)

P. H. Bolivar, M. Nagel, F. Richter, M. Brucherseifer, H. Kurz, A. Bosserhoff, and R. Büttner, “Label-free THz sensing of genetic sequences: towards ‘THz biochips’,” Philos. T. Roy. Soc. A 362(1815), 323–335 (2004).
[Crossref]

K. L. Wang and D. M. Mittleman, “Metal wires for terahertz wave guiding,” Nature 432(7015), 376–379 (2004).
[Crossref] [PubMed]

J. Zhang and D. Grischkowsky, “Waveguide terahertz time-domain spectroscopy of nanometer water layers,” Opt. Lett. 29(14), 1617–1619 (2004).
[Crossref] [PubMed]

2003 (1)

O. M. Yaghi, M. O’Keeffe, N. W. Ockwig, H. K. Chae, M. Eddaoudi, and J. Kim, “Reticular synthesis and the design of new materials,” Nature 423(6941), 705–714 (2003).
[Crossref] [PubMed]

1998 (1)

T. W. Ebbesen, H. J. Lezec, H. F. Ghaemi, T. Thio, and P. A. Wolff, “Extraordinary optical transmission through sub-wavelength hole arrays,” Nature 391(6668), 667–669 (1998).
[Crossref]

Abeyrathne, C. D.

C. D. Abeyrathne, M. N. Halgamuge, P. M. Farrell, and E. Skafidas, “An ab-initio Computational method to determine dielectric properties of biological materials,” Nature Sci. Rep. 3, 1796 (2013).
[Crossref] [PubMed]

Adam, A. J. L.

P. C. M. Planken, A. J. L. Adam, and D. Kim, “Terahertz Near-Field Imaging,” Spr. Ser. Opt. Sci. 171, 389–413 (2013).
[Crossref]

J. R. Knab, A. J. L. Adam, E. Shaner, H. J. A. J. Starmans, and P. C. M. Planken, “Terahertz near-field spectroscopy of filled subwavelength sized apertures in thin metal films,” Opt. Express 21(1), 1101–1112 (2013).
[Crossref] [PubMed]

A. J. L. Adam, “Review of Near-Field Terahertz Measurement Methods and Their Applications,” Int. J. Infrared Millim. Waves 32(8-9), 976–1019 (2011).
[Crossref]

J. R. Knab, A. J. L. Adam, R. Chakkittakandy, and P. C. M. Planken, “Terahertz near-field microspectroscopy,” Appl. Phys. Lett. 97(3), 031115 (2010).
[Crossref]

Andrews, S. R.

C. R. Williams, S. R. Andrews, S. A. Maier, A. I. Fernández-Domínguez, L. Martín-Moreno, and F. J. García-Vidal, “Highly confined guiding of terahertz surface plasmon polaritons on structured metal surfaces,” Nat. Photonics 2(3), 175–179 (2008).
[Crossref]

Averitt, R. D.

M. Liu, H. Y. Hwang, H. Tao, A. C. Strikwerda, K. Fan, G. R. Keiser, A. J. Sternbach, K. G. West, S. Kittiwatanakul, J. Lu, S. A. Wolf, F. G. Omenetto, X. Zhang, K. A. Nelson, and R. D. Averitt, “Terahertz-field-induced insulator-to-metal transition in vanadium dioxide metamaterial,” Nature 487(7407), 345–348 (2012).
[Crossref] [PubMed]

H. Tao, W. J. Padilla, X. Zhang, and R. D. Averitt, “Recent Progress in Electromagnetic Metamaterial Devices for Terahertz Applications,” IEEE J. Sel. Top. Quantum Electron. 17(1), 92–101 (2011).
[Crossref]

Barnard, E. S.

J. A. Schuller, E. S. Barnard, W. Cai, Y. C. Jun, J. S. White, and M. L. Brongersma, “Plasmonics for extreme light concentration and manipulation,” Nat. Mater. 9(3), 193–204 (2010).
[Crossref] [PubMed]

Bingham, C. M.

N. I. Landy, C. M. Bingham, T. Tyler, N. Jokerst, D. R. Smith, and W. J. Padilla, “Design, theory, and measurement of a polarization-insensitive absorber for terahertz imaging,” Phys. Rev. B 79(12), 125104 (2009).
[Crossref]

Bitzer, A.

M. Walther, B. M. Fischer, A. Ortner, A. Bitzer, A. Thoman, and H. Helm, “Chemical sensing and imaging with pulsed terahertz radiation,” Anal. Bioanal. Chem. 397(3), 1009–1017 (2010).
[Crossref] [PubMed]

Blanchard, F.

F. Blanchard, A. Doi, T. Tanaka, and K. Tanaka, “Real-Time, Subwavelength Terahertz Imaging,” Annu. Rev. Mater. Res. 43(1), 237–259 (2013).
[Crossref]

H. Hirori, A. Doi, F. Blanchard, and K. Tanaka, “Single-cycle terahertz pulses with amplitudes exceeding 1 MV/cm generated by optical rectification in LiNbO3,” Appl. Phys. Lett. 98(9), 091106 (2011).
[Crossref]

A. Doi, F. Blanchard, H. Hirori, and K. Tanaka, “Near-field THz imaging of free induction decay from a tyrosine crystal,” Opt. Express 18(17), 18419–18424 (2010).
[Crossref] [PubMed]

Bolivar, P. H.

P. H. Bolivar, M. Nagel, F. Richter, M. Brucherseifer, H. Kurz, A. Bosserhoff, and R. Büttner, “Label-free THz sensing of genetic sequences: towards ‘THz biochips’,” Philos. T. Roy. Soc. A 362(1815), 323–335 (2004).
[Crossref]

Bosserhoff, A.

P. H. Bolivar, M. Nagel, F. Richter, M. Brucherseifer, H. Kurz, A. Bosserhoff, and R. Büttner, “Label-free THz sensing of genetic sequences: towards ‘THz biochips’,” Philos. T. Roy. Soc. A 362(1815), 323–335 (2004).
[Crossref]

Brinks, D.

D. Brinks, M. Castro-Lopez, R. Hildner, and N. F. van Hulst, “Plasmonic antennas as design elements for coherent ultrafast nanophotonics,” Proc. Natl. Acad. Sci. U.S.A. 110(46), 18386–18390 (2013).
[Crossref] [PubMed]

Brongersma, M. L.

J. A. Schuller, E. S. Barnard, W. Cai, Y. C. Jun, J. S. White, and M. L. Brongersma, “Plasmonics for extreme light concentration and manipulation,” Nat. Mater. 9(3), 193–204 (2010).
[Crossref] [PubMed]

Brucherseifer, M.

P. H. Bolivar, M. Nagel, F. Richter, M. Brucherseifer, H. Kurz, A. Bosserhoff, and R. Büttner, “Label-free THz sensing of genetic sequences: towards ‘THz biochips’,” Philos. T. Roy. Soc. A 362(1815), 323–335 (2004).
[Crossref]

Büttner, R.

P. H. Bolivar, M. Nagel, F. Richter, M. Brucherseifer, H. Kurz, A. Bosserhoff, and R. Büttner, “Label-free THz sensing of genetic sequences: towards ‘THz biochips’,” Philos. T. Roy. Soc. A 362(1815), 323–335 (2004).
[Crossref]

Cai, W.

J. A. Schuller, E. S. Barnard, W. Cai, Y. C. Jun, J. S. White, and M. L. Brongersma, “Plasmonics for extreme light concentration and manipulation,” Nat. Mater. 9(3), 193–204 (2010).
[Crossref] [PubMed]

Castro-Lopez, M.

D. Brinks, M. Castro-Lopez, R. Hildner, and N. F. van Hulst, “Plasmonic antennas as design elements for coherent ultrafast nanophotonics,” Proc. Natl. Acad. Sci. U.S.A. 110(46), 18386–18390 (2013).
[Crossref] [PubMed]

Chae, H. K.

O. M. Yaghi, M. O’Keeffe, N. W. Ockwig, H. K. Chae, M. Eddaoudi, and J. Kim, “Reticular synthesis and the design of new materials,” Nature 423(6941), 705–714 (2003).
[Crossref] [PubMed]

Chakkittakandy, R.

J. R. Knab, A. J. L. Adam, R. Chakkittakandy, and P. C. M. Planken, “Terahertz near-field microspectroscopy,” Appl. Phys. Lett. 97(3), 031115 (2010).
[Crossref]

Diring, S.

H. Uehara, S. Diring, S. Furukawa, Z. Kalay, M. Tsotsalas, M. Nakahama, K. Hirai, M. Kondo, O. Sakata, and S. Kitagawa, “Porous Coordination Polymer Hybrid Device with Quartz Oscillator: Effect of Crystal Size on Sorption Kinetics,” J. Am. Chem. Soc. 133(31), 11932–11935 (2011).
[Crossref] [PubMed]

Doi, A.

F. Blanchard, A. Doi, T. Tanaka, and K. Tanaka, “Real-Time, Subwavelength Terahertz Imaging,” Annu. Rev. Mater. Res. 43(1), 237–259 (2013).
[Crossref]

H. Hirori, A. Doi, F. Blanchard, and K. Tanaka, “Single-cycle terahertz pulses with amplitudes exceeding 1 MV/cm generated by optical rectification in LiNbO3,” Appl. Phys. Lett. 98(9), 091106 (2011).
[Crossref]

A. Doi, F. Blanchard, H. Hirori, and K. Tanaka, “Near-field THz imaging of free induction decay from a tyrosine crystal,” Opt. Express 18(17), 18419–18424 (2010).
[Crossref] [PubMed]

Ebbesen, T. W.

T. W. Ebbesen, H. J. Lezec, H. F. Ghaemi, T. Thio, and P. A. Wolff, “Extraordinary optical transmission through sub-wavelength hole arrays,” Nature 391(6668), 667–669 (1998).
[Crossref]

Eddaoudi, M.

O. M. Yaghi, M. O’Keeffe, N. W. Ockwig, H. K. Chae, M. Eddaoudi, and J. Kim, “Reticular synthesis and the design of new materials,” Nature 423(6941), 705–714 (2003).
[Crossref] [PubMed]

Eigenthaler, U.

N. Liu, T. Weiss, M. Mesch, L. Langguth, U. Eigenthaler, M. Hirscher, C. Sönnichsen, and H. Giessen, “Planar metamaterial analogue of electromagnetically induced transparency for plasmonic sensing,” Nano Lett. 10(4), 1103–1107 (2010).
[Crossref] [PubMed]

Eisler, H.-J.

P. Mühlschlegel, H.-J. Eisler, O. J. F. Martin, B. Hecht, and D. W. Pohl, “Resonant optical antennas,” Science 308(5728), 1607–1609 (2005).
[Crossref] [PubMed]

Fan, K.

M. Liu, H. Y. Hwang, H. Tao, A. C. Strikwerda, K. Fan, G. R. Keiser, A. J. Sternbach, K. G. West, S. Kittiwatanakul, J. Lu, S. A. Wolf, F. G. Omenetto, X. Zhang, K. A. Nelson, and R. D. Averitt, “Terahertz-field-induced insulator-to-metal transition in vanadium dioxide metamaterial,” Nature 487(7407), 345–348 (2012).
[Crossref] [PubMed]

Farrell, P. M.

C. D. Abeyrathne, M. N. Halgamuge, P. M. Farrell, and E. Skafidas, “An ab-initio Computational method to determine dielectric properties of biological materials,” Nature Sci. Rep. 3, 1796 (2013).
[Crossref] [PubMed]

Fernández-Domínguez, A. I.

C. R. Williams, S. R. Andrews, S. A. Maier, A. I. Fernández-Domínguez, L. Martín-Moreno, and F. J. García-Vidal, “Highly confined guiding of terahertz surface plasmon polaritons on structured metal surfaces,” Nat. Photonics 2(3), 175–179 (2008).
[Crossref]

Fischer, B. M.

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T. W. Ebbesen, H. J. Lezec, H. F. Ghaemi, T. Thio, and P. A. Wolff, “Extraordinary optical transmission through sub-wavelength hole arrays,” Nature 391(6668), 667–669 (1998).
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P. Mühlschlegel, H.-J. Eisler, O. J. F. Martin, B. Hecht, and D. W. Pohl, “Resonant optical antennas,” Science 308(5728), 1607–1609 (2005).
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M. Walther, B. M. Fischer, A. Ortner, A. Bitzer, A. Thoman, and H. Helm, “Chemical sensing and imaging with pulsed terahertz radiation,” Anal. Bioanal. Chem. 397(3), 1009–1017 (2010).
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K. Schröck, F. Schröder, M. Heyden, R. A. Fischer, and M. Havenith, “Characterization of interfacial water in MOF-5 (Zn4(O)(BDC)3)-a combined spectroscopic and theoretical study,” Phys. Chem. Chem. Phys. 10(32), 4732–4739 (2008).
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D. Brinks, M. Castro-Lopez, R. Hildner, and N. F. van Hulst, “Plasmonic antennas as design elements for coherent ultrafast nanophotonics,” Proc. Natl. Acad. Sci. U.S.A. 110(46), 18386–18390 (2013).
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H. Hirori, A. Doi, F. Blanchard, and K. Tanaka, “Single-cycle terahertz pulses with amplitudes exceeding 1 MV/cm generated by optical rectification in LiNbO3,” Appl. Phys. Lett. 98(9), 091106 (2011).
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A. Doi, F. Blanchard, H. Hirori, and K. Tanaka, “Near-field THz imaging of free induction decay from a tyrosine crystal,” Opt. Express 18(17), 18419–18424 (2010).
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J. A. Schuller, E. S. Barnard, W. Cai, Y. C. Jun, J. S. White, and M. L. Brongersma, “Plasmonics for extreme light concentration and manipulation,” Nat. Mater. 9(3), 193–204 (2010).
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M. Tsotsalas, P. Hejcik, K. Sumida, Z. Kalay, S. Furukawa, and S. Kitagawa, “Impact of Molecular Clustering inside Nanopores on Desorption Processes,” J. Am. Chem. Soc. 135(12), 4608–4611 (2013).
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H. Uehara, S. Diring, S. Furukawa, Z. Kalay, M. Tsotsalas, M. Nakahama, K. Hirai, M. Kondo, O. Sakata, and S. Kitagawa, “Porous Coordination Polymer Hybrid Device with Quartz Oscillator: Effect of Crystal Size on Sorption Kinetics,” J. Am. Chem. Soc. 133(31), 11932–11935 (2011).
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M. Liu, H. Y. Hwang, H. Tao, A. C. Strikwerda, K. Fan, G. R. Keiser, A. J. Sternbach, K. G. West, S. Kittiwatanakul, J. Lu, S. A. Wolf, F. G. Omenetto, X. Zhang, K. A. Nelson, and R. D. Averitt, “Terahertz-field-induced insulator-to-metal transition in vanadium dioxide metamaterial,” Nature 487(7407), 345–348 (2012).
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O. M. Yaghi, M. O’Keeffe, N. W. Ockwig, H. K. Chae, M. Eddaoudi, and J. Kim, “Reticular synthesis and the design of new materials,” Nature 423(6941), 705–714 (2003).
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M. Liu, H. Y. Hwang, H. Tao, A. C. Strikwerda, K. Fan, G. R. Keiser, A. J. Sternbach, K. G. West, S. Kittiwatanakul, J. Lu, S. A. Wolf, F. G. Omenetto, X. Zhang, K. A. Nelson, and R. D. Averitt, “Terahertz-field-induced insulator-to-metal transition in vanadium dioxide metamaterial,” Nature 487(7407), 345–348 (2012).
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Kondo, M.

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T. W. Ebbesen, H. J. Lezec, H. F. Ghaemi, T. Thio, and P. A. Wolff, “Extraordinary optical transmission through sub-wavelength hole arrays,” Nature 391(6668), 667–669 (1998).
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M. Liu, H. Y. Hwang, H. Tao, A. C. Strikwerda, K. Fan, G. R. Keiser, A. J. Sternbach, K. G. West, S. Kittiwatanakul, J. Lu, S. A. Wolf, F. G. Omenetto, X. Zhang, K. A. Nelson, and R. D. Averitt, “Terahertz-field-induced insulator-to-metal transition in vanadium dioxide metamaterial,” Nature 487(7407), 345–348 (2012).
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M. Liu, H. Y. Hwang, H. Tao, A. C. Strikwerda, K. Fan, G. R. Keiser, A. J. Sternbach, K. G. West, S. Kittiwatanakul, J. Lu, S. A. Wolf, F. G. Omenetto, X. Zhang, K. A. Nelson, and R. D. Averitt, “Terahertz-field-induced insulator-to-metal transition in vanadium dioxide metamaterial,” Nature 487(7407), 345–348 (2012).
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C. R. Williams, S. R. Andrews, S. A. Maier, A. I. Fernández-Domínguez, L. Martín-Moreno, and F. J. García-Vidal, “Highly confined guiding of terahertz surface plasmon polaritons on structured metal surfaces,” Nat. Photonics 2(3), 175–179 (2008).
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P. Mühlschlegel, H.-J. Eisler, O. J. F. Martin, B. Hecht, and D. W. Pohl, “Resonant optical antennas,” Science 308(5728), 1607–1609 (2005).
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N. Liu, T. Weiss, M. Mesch, L. Langguth, U. Eigenthaler, M. Hirscher, C. Sönnichsen, and H. Giessen, “Planar metamaterial analogue of electromagnetically induced transparency for plasmonic sensing,” Nano Lett. 10(4), 1103–1107 (2010).
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P. Mühlschlegel, H.-J. Eisler, O. J. F. Martin, B. Hecht, and D. W. Pohl, “Resonant optical antennas,” Science 308(5728), 1607–1609 (2005).
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P. H. Bolivar, M. Nagel, F. Richter, M. Brucherseifer, H. Kurz, A. Bosserhoff, and R. Büttner, “Label-free THz sensing of genetic sequences: towards ‘THz biochips’,” Philos. T. Roy. Soc. A 362(1815), 323–335 (2004).
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M. Liu, H. Y. Hwang, H. Tao, A. C. Strikwerda, K. Fan, G. R. Keiser, A. J. Sternbach, K. G. West, S. Kittiwatanakul, J. Lu, S. A. Wolf, F. G. Omenetto, X. Zhang, K. A. Nelson, and R. D. Averitt, “Terahertz-field-induced insulator-to-metal transition in vanadium dioxide metamaterial,” Nature 487(7407), 345–348 (2012).
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O. M. Yaghi, M. O’Keeffe, N. W. Ockwig, H. K. Chae, M. Eddaoudi, and J. Kim, “Reticular synthesis and the design of new materials,” Nature 423(6941), 705–714 (2003).
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M. Liu, H. Y. Hwang, H. Tao, A. C. Strikwerda, K. Fan, G. R. Keiser, A. J. Sternbach, K. G. West, S. Kittiwatanakul, J. Lu, S. A. Wolf, F. G. Omenetto, X. Zhang, K. A. Nelson, and R. D. Averitt, “Terahertz-field-induced insulator-to-metal transition in vanadium dioxide metamaterial,” Nature 487(7407), 345–348 (2012).
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M. Walther, B. M. Fischer, A. Ortner, A. Bitzer, A. Thoman, and H. Helm, “Chemical sensing and imaging with pulsed terahertz radiation,” Anal. Bioanal. Chem. 397(3), 1009–1017 (2010).
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H. Tao, W. J. Padilla, X. Zhang, and R. D. Averitt, “Recent Progress in Electromagnetic Metamaterial Devices for Terahertz Applications,” IEEE J. Sel. Top. Quantum Electron. 17(1), 92–101 (2011).
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N. I. Landy, C. M. Bingham, T. Tyler, N. Jokerst, D. R. Smith, and W. J. Padilla, “Design, theory, and measurement of a polarization-insensitive absorber for terahertz imaging,” Phys. Rev. B 79(12), 125104 (2009).
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P. Mühlschlegel, H.-J. Eisler, O. J. F. Martin, B. Hecht, and D. W. Pohl, “Resonant optical antennas,” Science 308(5728), 1607–1609 (2005).
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P. H. Bolivar, M. Nagel, F. Richter, M. Brucherseifer, H. Kurz, A. Bosserhoff, and R. Büttner, “Label-free THz sensing of genetic sequences: towards ‘THz biochips’,” Philos. T. Roy. Soc. A 362(1815), 323–335 (2004).
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K. Schröck, F. Schröder, M. Heyden, R. A. Fischer, and M. Havenith, “Characterization of interfacial water in MOF-5 (Zn4(O)(BDC)3)-a combined spectroscopic and theoretical study,” Phys. Chem. Chem. Phys. 10(32), 4732–4739 (2008).
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K. Schröck, F. Schröder, M. Heyden, R. A. Fischer, and M. Havenith, “Characterization of interfacial water in MOF-5 (Zn4(O)(BDC)3)-a combined spectroscopic and theoretical study,” Phys. Chem. Chem. Phys. 10(32), 4732–4739 (2008).
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Schuller, J. A.

J. A. Schuller, E. S. Barnard, W. Cai, Y. C. Jun, J. S. White, and M. L. Brongersma, “Plasmonics for extreme light concentration and manipulation,” Nat. Mater. 9(3), 193–204 (2010).
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Skafidas, E.

C. D. Abeyrathne, M. N. Halgamuge, P. M. Farrell, and E. Skafidas, “An ab-initio Computational method to determine dielectric properties of biological materials,” Nature Sci. Rep. 3, 1796 (2013).
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N. I. Landy, C. M. Bingham, T. Tyler, N. Jokerst, D. R. Smith, and W. J. Padilla, “Design, theory, and measurement of a polarization-insensitive absorber for terahertz imaging,” Phys. Rev. B 79(12), 125104 (2009).
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N. Liu, T. Weiss, M. Mesch, L. Langguth, U. Eigenthaler, M. Hirscher, C. Sönnichsen, and H. Giessen, “Planar metamaterial analogue of electromagnetically induced transparency for plasmonic sensing,” Nano Lett. 10(4), 1103–1107 (2010).
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Sternbach, A. J.

M. Liu, H. Y. Hwang, H. Tao, A. C. Strikwerda, K. Fan, G. R. Keiser, A. J. Sternbach, K. G. West, S. Kittiwatanakul, J. Lu, S. A. Wolf, F. G. Omenetto, X. Zhang, K. A. Nelson, and R. D. Averitt, “Terahertz-field-induced insulator-to-metal transition in vanadium dioxide metamaterial,” Nature 487(7407), 345–348 (2012).
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H. Hirori, A. Doi, F. Blanchard, and K. Tanaka, “Single-cycle terahertz pulses with amplitudes exceeding 1 MV/cm generated by optical rectification in LiNbO3,” Appl. Phys. Lett. 98(9), 091106 (2011).
[Crossref]

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[Crossref] [PubMed]

H. Tao, W. J. Padilla, X. Zhang, and R. D. Averitt, “Recent Progress in Electromagnetic Metamaterial Devices for Terahertz Applications,” IEEE J. Sel. Top. Quantum Electron. 17(1), 92–101 (2011).
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T. W. Ebbesen, H. J. Lezec, H. F. Ghaemi, T. Thio, and P. A. Wolff, “Extraordinary optical transmission through sub-wavelength hole arrays,” Nature 391(6668), 667–669 (1998).
[Crossref]

Thoman, A.

M. Walther, B. M. Fischer, A. Ortner, A. Bitzer, A. Thoman, and H. Helm, “Chemical sensing and imaging with pulsed terahertz radiation,” Anal. Bioanal. Chem. 397(3), 1009–1017 (2010).
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[Crossref] [PubMed]

H. Uehara, S. Diring, S. Furukawa, Z. Kalay, M. Tsotsalas, M. Nakahama, K. Hirai, M. Kondo, O. Sakata, and S. Kitagawa, “Porous Coordination Polymer Hybrid Device with Quartz Oscillator: Effect of Crystal Size on Sorption Kinetics,” J. Am. Chem. Soc. 133(31), 11932–11935 (2011).
[Crossref] [PubMed]

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N. I. Landy, C. M. Bingham, T. Tyler, N. Jokerst, D. R. Smith, and W. J. Padilla, “Design, theory, and measurement of a polarization-insensitive absorber for terahertz imaging,” Phys. Rev. B 79(12), 125104 (2009).
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L. Novotny and H. van Hulst, “Antennas for light,” Nat. Photonics 5(2), 83–90 (2011).
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D. Brinks, M. Castro-Lopez, R. Hildner, and N. F. van Hulst, “Plasmonic antennas as design elements for coherent ultrafast nanophotonics,” Proc. Natl. Acad. Sci. U.S.A. 110(46), 18386–18390 (2013).
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N. Liu, T. Weiss, M. Mesch, L. Langguth, U. Eigenthaler, M. Hirscher, C. Sönnichsen, and H. Giessen, “Planar metamaterial analogue of electromagnetically induced transparency for plasmonic sensing,” Nano Lett. 10(4), 1103–1107 (2010).
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J. A. Schuller, E. S. Barnard, W. Cai, Y. C. Jun, J. S. White, and M. L. Brongersma, “Plasmonics for extreme light concentration and manipulation,” Nat. Mater. 9(3), 193–204 (2010).
[Crossref] [PubMed]

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C. R. Williams, S. R. Andrews, S. A. Maier, A. I. Fernández-Domínguez, L. Martín-Moreno, and F. J. García-Vidal, “Highly confined guiding of terahertz surface plasmon polaritons on structured metal surfaces,” Nat. Photonics 2(3), 175–179 (2008).
[Crossref]

Wolf, S. A.

M. Liu, H. Y. Hwang, H. Tao, A. C. Strikwerda, K. Fan, G. R. Keiser, A. J. Sternbach, K. G. West, S. Kittiwatanakul, J. Lu, S. A. Wolf, F. G. Omenetto, X. Zhang, K. A. Nelson, and R. D. Averitt, “Terahertz-field-induced insulator-to-metal transition in vanadium dioxide metamaterial,” Nature 487(7407), 345–348 (2012).
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M. Liu, H. Y. Hwang, H. Tao, A. C. Strikwerda, K. Fan, G. R. Keiser, A. J. Sternbach, K. G. West, S. Kittiwatanakul, J. Lu, S. A. Wolf, F. G. Omenetto, X. Zhang, K. A. Nelson, and R. D. Averitt, “Terahertz-field-induced insulator-to-metal transition in vanadium dioxide metamaterial,” Nature 487(7407), 345–348 (2012).
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Anal. Bioanal. Chem. (1)

M. Walther, B. M. Fischer, A. Ortner, A. Bitzer, A. Thoman, and H. Helm, “Chemical sensing and imaging with pulsed terahertz radiation,” Anal. Bioanal. Chem. 397(3), 1009–1017 (2010).
[Crossref] [PubMed]

Annu. Rev. Mater. Res. (1)

F. Blanchard, A. Doi, T. Tanaka, and K. Tanaka, “Real-Time, Subwavelength Terahertz Imaging,” Annu. Rev. Mater. Res. 43(1), 237–259 (2013).
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Appl. Phys. Lett. (2)

H. Hirori, A. Doi, F. Blanchard, and K. Tanaka, “Single-cycle terahertz pulses with amplitudes exceeding 1 MV/cm generated by optical rectification in LiNbO3,” Appl. Phys. Lett. 98(9), 091106 (2011).
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IEEE J. Sel. Top. Quantum Electron. (1)

H. Tao, W. J. Padilla, X. Zhang, and R. D. Averitt, “Recent Progress in Electromagnetic Metamaterial Devices for Terahertz Applications,” IEEE J. Sel. Top. Quantum Electron. 17(1), 92–101 (2011).
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A. J. L. Adam, “Review of Near-Field Terahertz Measurement Methods and Their Applications,” Int. J. Infrared Millim. Waves 32(8-9), 976–1019 (2011).
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Nano Lett. (1)

N. Liu, T. Weiss, M. Mesch, L. Langguth, U. Eigenthaler, M. Hirscher, C. Sönnichsen, and H. Giessen, “Planar metamaterial analogue of electromagnetically induced transparency for plasmonic sensing,” Nano Lett. 10(4), 1103–1107 (2010).
[Crossref] [PubMed]

Nat. Mater. (1)

J. A. Schuller, E. S. Barnard, W. Cai, Y. C. Jun, J. S. White, and M. L. Brongersma, “Plasmonics for extreme light concentration and manipulation,” Nat. Mater. 9(3), 193–204 (2010).
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L. Novotny and H. van Hulst, “Antennas for light,” Nat. Photonics 5(2), 83–90 (2011).
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C. R. Williams, S. R. Andrews, S. A. Maier, A. I. Fernández-Domínguez, L. Martín-Moreno, and F. J. García-Vidal, “Highly confined guiding of terahertz surface plasmon polaritons on structured metal surfaces,” Nat. Photonics 2(3), 175–179 (2008).
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M. Tonouchi, “Cutting-edge terahertz technology,” Nat. Photonics 1(2), 97–105 (2007).
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[Crossref]

K. L. Wang and D. M. Mittleman, “Metal wires for terahertz wave guiding,” Nature 432(7015), 376–379 (2004).
[Crossref] [PubMed]

M. Liu, H. Y. Hwang, H. Tao, A. C. Strikwerda, K. Fan, G. R. Keiser, A. J. Sternbach, K. G. West, S. Kittiwatanakul, J. Lu, S. A. Wolf, F. G. Omenetto, X. Zhang, K. A. Nelson, and R. D. Averitt, “Terahertz-field-induced insulator-to-metal transition in vanadium dioxide metamaterial,” Nature 487(7407), 345–348 (2012).
[Crossref] [PubMed]

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Supplementary Material (3)

» Media 1: AVI (2269 KB)     
» Media 2: AVI (2216 KB)     
» Media 3: AVI (2175 KB)     

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Figures (4)

Fig. 1
Fig. 1 The basic principle of our THz sensing scheme. (a) An electro-optic crystal for near-field detection, with two metallic ring patterns on top (therefore called sensor), is enclosed in a miniature controlled gas cell in which the Cu3(btc)2 sample (visible inset) fully covers one metallic ring. The upper inset shows the experimental near-field Fourier transforms of the THz pulse located at the center position of the metallic ring (blue curve) and without metallic ring pattern (black curve). (b) Schematic illustration of a PCP nanocrystal loaded with methanol molecules irradiated by THz waves.

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Fig. 2
Fig. 2 Visible images showing the metallic ring structure with (i) and without (iv) sample. THz images at a fixed time delay of 3.25 ps for exposure to He: with (ii) and without sample (v) (i.e. extracted from Media 1 and Media 2, respectively). THz images at a fixed time delay of 3.25 ps for exposure to methanol: with (iii) and without sample (vi) (i.e. extracted from Media 3).

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Fig. 3
Fig. 3 Simulation approach. (a) Reference (black curve) and Cu3(btc)2 THz pulses measured by THz-TDS. The inset shows the Fourier transforms of the corresponding reference and signal THz pulses. (b) Measured refractive index of the Cu3(btc)2 sample derived from the data presented in (a). (c) Illustration of the simulation conditions. The lower inset shows the simulated near-field Fourier transforms of the THz pulse located at the center and off center of one metallic ring (the blue and red curves, respectively) and without metallic ring pattern (black curve). (d) Simulated near-field THz electric field maps of the two metallic ring patterns at the corresponding time delay of Fig. 2 (i.e., 3.25 ps). Empty sensor (i), material with constant n = 1.2 on top of the lower ring (ii), material with n = 1.2 along with 60% (Vol) methanol over the lower ring (iii).

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Fig. 4
Fig. 4 Phase difference plots. (a) Visible image of the sensor loaded with Cu3(btc)2 on the left hand side. Near-field experimental phase map at 0.72 THz of the sample under the initial He purge. The subtracted areas are identified in the THz phase map image by the dotted lines. (b) Near-field simulation of the phase map at 0.73 THz of the sample with refractive index of 1.2. (c) Experimental measurement of the phase differences between the upper and lower rings (Δθ) for an empty sample under He (black curve), Δθ of Cu3(btc)2 under 80% methanol vapor (full blue circle), Δθ of Cu3(btc)2 after 5 minutes of purging with He upon methanol loading (half blue circle), and Δθ of Cu3(btc)2 after 12 hours of purging with He upon methanol loading (void blue circle). (d) Simulations of Δθ for an unloaded/pristine PCP represented by a material with n = 1.2 (black curve). The red curves are the Δθ for 60%, 50%, 30%, and 10% volume ratios of nMeOH (i.e., compared with the remaining volume of n = 1.2), respectively.

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