Isolating single molecules in the solid state has allowed fundamental experiments in basic and applied sciences. When cooled down to liquid helium temperature, certain molecules show transition lines that are tens of megahertz wide, limited by only the excited-state lifetime. The extreme flexibility in the synthesis of organic materials provides, at low costs, a wide palette of emission wavelengths and supporting matrices for such single chromophores. In the past few decades, their controlled coupling to photonic structures has led to an optimized interaction efficiency with light. Molecules can hence be operated as single-photon sources and as nonlinear elements with competitive performance in terms of coherence, scalability and compatibility with diverse integrated platforms. Moreover, they can be used as transducers for the optical read-out of fields and material properties, with the promise of single-quanta resolution in the sensing of charges and motion. We show that quantum emitters based on single molecules hold promise to play a key role in the development of quantum science and technologies.
This is a preview of subscription content, access via your institution
Open Access articles citing this article.
Photonic-circuited resonance fluorescence of single molecules with an ultrastable lifetime-limited transition
Nature Communications Open Access 09 July 2022
Nature Communications Open Access 26 May 2022
Subscribe to Nature+
Get immediate online access to the entire Nature family of 50+ journals
Subscribe to Journal
Get full journal access for 1 year
only $9.92 per issue
All prices are NET prices.
VAT will be added later in the checkout.
Tax calculation will be finalised during checkout.
Get time limited or full article access on ReadCube.
All prices are NET prices.
Aspuru-Guzik, A. & Walther, P. Photonic quantum simulators. Nat. Phys. 8, 285–291 (2012).
Zhong, H.-S. et al. Quantum computational advantage using photons. Science 370, 1460–1463 (2020).
Knill, E., Laflamme, R. & Milburn, G. A scheme for efficient quantum computation with linear optics. Nature 409, 46–52 (2001).
Sangouard, N. & Zbinden, H. What are single photons good for? J. Mod. Opt. 59, 1458–1464 (2012).
Gatto Monticone, D. et al. Beating the Abbe diffraction limit in confocal microscopy via nonclassical photon statistics. Phys. Rev. Lett. 113, 143602 (2014).
Lombardi, P. et al. A molecule‐based single‐photon source applied in quantum radiometry. Adv. Quantum Technol. 3, 1900083 (2019).
Duan, L.-M. & Kimble, H. J. Scalable photonic quantum computation through cavity-assisted interactions. Phys. Rev. Lett. 92, 127902 (2004).
Basché, T., Moerner, W. E., Orrit, M. & Wild, U. P. Single-Molecule Optical Detection, Imaging and Spectroscopy (VCH, 1997).
Plakhotnik, T., Donley, E. A. & Wild, U. P. Single-molecule spectroscopy. Annu. Rev. Phys. Chem. 48, 181–212 (1997).
Kozankiewicz, B. & Orrit, M. Single-molecule photophysics, from cryogenic to ambient conditions. Chem. Soc. Rev. 43, 1029–1043 (2014).
Orrit, M. & Bernard, J. Single pentacene molecules detected by fluorescence excitation in a p-terphenyl crystal. Phys. Rev. Lett. 65, 2716–2719 (1990).
Weiss, S. Fluorescence spectroscopy of single biomolecules. Science 283, 1676–1683 (1999).
Zürner, A., Kirstein, J., Döblinger, M., Bräuchle, C. & Bein, T. Visualizing single-molecule diffusion in mesoporous materials. Nature 450, 705–708 (2007).
Buchler, B. C., Kalkbrenner, T., Hettich, C. & Sandoghdar, V. Measuring the quantum efficiency of the optical emission of single radiating dipoles using a scanning mirror. Phys. Rev. Lett. 95, 063003 (2005).
Wang, D. et al. Turning a molecule into a coherent two-level quantum system. Nat. Phys. 15, 483–489 (2019).
Basché, T., Moerner, W. E., Orrit, M. & Talon, H. Photon antibunching in the fluorescence of single dye molecule trapped in a solid. Phys. Rev. Lett. 69, 1516–1519 (1992).
Wrigge, G., Gerhardt, I., Hwang, J., Zumofen, G. & Sandoghdar, V. Efficient coupling of photons to a single molecule and the observation of its resonance fluorescence. Nat. Phys. 4, 60–66 (2008).
Gerhardt, I. et al. Coherent state preparation and observation of Rabi oscillations in a single molecule. Phys. Rev. A 79, 011402(R) (2009).
Lettow, R. et al. Quantum interference of tunably indistinguishable photons from remote organic molecules. Phys. Rev. Lett. 104, 123605 (2010).
Trebbia, B., Tamarat, P. & Lounis, B. Indistinguishable near-infrared single photons from an individual organic molecule. Phys. Rev. A 82, 063803 (2010).
Nonn, T. & Plakhotnik, T. Fluorescence excitation spectroscopy of vibronic transitions in single molecules. Chem. Phys. Lett. 336, 97–104 (2001).
Kiefer, W., Rezai, M., Wrachtrup, J. & Gerhardt, I. An atomic spectrum recorded with a single molecule light source. Appl. Phys. B 122, 38 (2016).
De Martini, F., Di Giuseppe, G. & Marrocco, M. Single-mode generation of quantum photon states by excited single molecules in a microcavity trap. Phys. Rev. Lett. 76, 900–903 (1996).
Ambrose, W. P. et al. Fluorescence photon antibunching from single molecules on a surface. Chem. Phys. Lett. 269, 365–370 (1997).
Lounis, B. & Moerner, W. Single photons on demand from a single molecule at room temperature. Nature 407, 491–493 (2000).
Senellart, P., Solomon, G. & White, A. High-performance semiconductor quantum-dot single-photon sources. Nat. Nanotechnol. 12, 1026–1039 (2017).
Lenzini, F., Gruhler, N., Walter, N. & Pernice, W. H. P. Diamond as a platform for integrated quantum photonics. Adv. Quantum Technol. 1, 1800061 (2018).
Chakraborty, C., Vamivakas, N. & Englund, D. Advances in quantum light emission from 2D materials. Nanophotonics 8, 2017–2032 (2019).
Rezai, M., Wrachtrup, J. & Gerhardt, I. Coherence properties of molecular single photons for quantum networks. Phys. Rev. X 8, 031026 (2018).
Nicolet, A. A. L., Hofmann, C., Kol’chenko, M., Kozankiewicz, B. & Orrit, M. Single dibenzoterrylene molecules in an anthracene crystal: spectroscopy and photophysics. ChemPhysChem 8, 1215–1220 (2007).
Toninelli, C. et al. Near-infrared single-photons from aligned molecules in ultrathin crystalline films at room temperature. Opt. Express 18, 6577–6582 (2010).
Polisseni, C. et al. Stable, single-photon emitter in a thin organic crystal for application to quantum-photonic devices. Opt. Express 24, 5615–5627 (2016).
Trebbia, J.-B., Ruf, H., Tamarat, P. & Lounis, B. Efficient generation of near-infrared single photons from the zero-phonon line of a single molecule. Opt. Express 17, 23986 (2009).
Chu, X., Götzinger, S. & Sandoghdar, V. A single molecule as a high-fidelity photon gun for producing intensity-squeezed light. Nat. Photon. 11, 58–62 (2017).
Colautti, M. et al. A 3D polymeric platform for photonic quantum technologies. Adv. Quantum Technol. 3, 2000004 (2020).
Lee, K. et al. A planar dielectric antenna for directional single-photon emission and near-unity collection efficiency. Nat. Photon. 5, 166–169 (2011).
Zirkelbach, J. et al. Partial cloaking of a gold particle by a single molecule. Phys. Rev. Lett. 125, 123603 (2020).
Siyushev, P., Stein, G., Wrachtrup, J. & Gerhardt, I. Molecular photons interfaced with alkali atoms. Nature 509, 66–70 (2014).
Kiraz, A. et al. Indistinguishable photons from a single molecule. Phys. Rev. Lett. 94, 223602 (2005).
Lombardi, P. et al. Indistinguishable photons on demand from an organic dye molecule. Preprint at https://arxiv.org/abs/2102.13055 (2021).
Wild, U. P., Guettler, F., Pirotta, M. & Renn, A. Single molecule spectroscopy: Stark effect of pentacene in p-terphenyl. Chem. Phys. Lett. 193, 451–455 (1992).
Rezai, M., Wrachtrup, J. & Gerhardt, I. Polarization-entangled photon pairs from a single molecule. Optica 6, 34–40 (2019).
Brunel, C., Tamarat, P., Lounis, B., Woehl, J. C. & Orrit, M. Stark effect on single molecules of dibenzanthanthrene in naphthalene crystal and in a n-hexadecane Shpol’skii matrix. J. Phys. Chem. A 103, 2429–2434 (1999).
Moradi, A., Ristanović, Z., Orrit, M., Deperasińska, I. & Kozankiewicz, B. Matrix‐induced linear Stark effect of single dibenzoterrylene molecules in 2,3‐dibromonaphthalene crystal. Chem. Phys. Chem. 20, 55–61 (2019).
Schaedler, K. et al. Electrical control of lifetime-limited quantum emitters using 2D materials. Nano Lett. 19, 3789–3795 (2019).
Colautti, M. et al. Laser-induced frequency tuning of Fourier-limited single-molecule emitters. ACS Nano 14, 13584–13592 (2020).
Lombardi, P. et al. Photostable molecules on chip: integrated sources of nonclassical light. ACS Photon. 5, 126–132 (2018).
Hwang, J. et al. A single-molecule optical transistor. Nature 460, 76–80 (2009).
Mollow, B. R. Stimulated emission and absorption near resonance for driven systems. Phys. Rev. A 5, 2217–2222 (1972).
Lounis, B., Jelezko, F. & Orrit, M. Single molecules driven by strong resonant fields: hyper-Raman and subharmonic resonances. Phys. Rev. Lett. 78, 3673–3676 (1997).
Lezama, A., Zhu, Y., Kanskar, M. & Mossberg, T. W. Radiative emission of driven two-level atoms into the modes of an enclosing optical cavity: the transition from fluorescence to lasing. Phys. Rev. A 41, 1576–1581 (1990).
Maser, A., Gmeiner, B., Utikal, T., Götzinger, S. & Sandoghdar, V. Few-photon coherent nonlinear optics with a single molecule. Nat. Photon. 10, 450–453 (2016).
Leuchs, G. & Sondermann, M. Light–matter interaction in free space. J. Mod. Opt. 60, 36–42 (2013).
Barnes, W. L. et al. Solid-state single photon sources: light collection strategies. Eur. Phys. J. D 18, 197–210 (2002).
Checcucci, S. et al. Beaming light from a quantum emitter with a planar optical antenna. Light. Sci. Appl. 6, e16245 (2017).
Skoff, S. M., Papencordt, D., Schauffert, H., Bayer, B. C. & Rauschenbeutel, A. Optical-nanofiber-based interface for single molecules. Phys. Rev. A 97, 043839 (2018).
Stein, G., Bushmakin, V., Wang, Y., Schell, A. W. & Gerhardt, I. Narrow-band fiber-coupled single-photon source. Phys. Rev. Appl. 13, 054042 (2020).
Faez, S., Türschmann, P., Haakh, H. R., Götzinger, S. & Sandoghdar, V. Coherent interaction of light and single molecules in a dielectric nanoguide. Phys. Rev. Lett. 113, 213601 (2014).
Ferrari, S., Schck, C. & Pernice, W. Waveguide-integrated superconducting nanowire single-photon detectors. Nanophotonics 7, 1725–1728 (2018).
Türschmann, P. et al. Chip-based all-optical control of single molecules coherently coupled to a nanoguide. Nano Lett. 17, 4941–4945 (2017).
Boissier, S. et al. Coherent characterisation of a single molecule in a photonic black box. Nat. Commun. 12, 706 (2021).
Hwang, J. & Hinds, E. A. Dye molecules as single-photon sources and large optical nonlinearities on a chip. New J. Phys. 13, 085009 (2011).
Rivoire, K. et al. Lithographic positioning of fluorescent molecules on high-Q photonic crystal cavities. Appl. Phys. Lett. 95, 123113 (2009).
Ciancico, C. et al. Narrow line width quantum emitters in an electron-beam-shaped polymer. ACS Photon. 6, 3120–3125 (2019).
Shi, Q. et al. Wiring up pre-characterized single-photon emitters by laser lithography. Sci. Rep. 6, 31135 (2016).
Hail, C. U. et al. Nanoprinting organic molecules at the quantum level. Nat. Commun. 10, 1880 (2019).
Kewes, G. et al. A realistic fabrication and design concept for quantum gates based on single emitters integrated in plasmonic-dielectric waveguide structures. Sci. Rep. 6, 28877 (2016).
Grandi, S. et al. Hybrid plasmonic waveguide coupling of photons from a single molecule. APL Photon. 4, 086101 (2019).
Rattenbacher, D. et al. Coherent coupling of single molecules to on-chip ring resonators. New J. Phys. 21, 062002 (2019).
Toninelli, C. et al. A scanning microcavity for in situ control of single-molecule emission. Appl. Phys. Lett. 97, 021107 (2010).
Wang, D. et al. Coherent coupling of a single molecule to a scanning Fabry–Perot microscavity. Phys. Rev. X 7, 021014 (2017).
Lodahl, P., Mahmoodian, S. & Stobbe, S. Interfacing single photons and single quantum dots with photonic nanostructures. Rev. Mod. Phys. 87, 347–400 (2015).
Zhang, J. L. et al. Strongly cavity-enhanced spontaneous emission from silicon-vacancy centers in diamond. Nano Lett. 18, 1360–1365 (2018).
Schwartz, T., Hutchison, J. A., Genet, C. & Ebbesen, T. W. Reversible switching of ultrastrong light-molecule coupling. Phys. Rev. Lett. 106, 196405 (2011).
Haakh, H. R., Faez, S. & Sadoghdar, V. Polaritonic normal-mode splitting and light localization in a one-dimensional nanoguide. Phys. Rev. A 94, 053840 (2016).
Kim, J., Yang, D., Oh, S.-H. & An, K. Coherent single-atom superradiance. Science 359, 662–666 (2018).
Hettich, C. et al. Nanometer resolution and coherent optical dipole coupling of two individual molecules. Science 298, 385–389 (2002).
Gerhardt, I., Wrigge, G., Hwang, J., Zumofen, G. & Sandoghdar, V. Coherent nonlinear single molecule microscopy. Phys. Rev. A 82, 063823 (2010).
Orrit, M., Bernard, J., Zumbusch, A. & Personov, R. Stark effect on single molecules in a polymer matrix. Chem. Phys. Lett. 196, 595–600 (1992).
Brunel, C., Lounis, B., Tamarat, P. & Orrit, M. Rabi resonances of a single molecule driven by rf and laser fields. Phys. Rev. Lett. 81, 2679–2682 (1998).
Caruge, J. M. & Orrit, M. Probing local currents in semiconductors with single molecules. Phys. Rev. B 64, 205202 (2001).
Kador, L., Latychevskaia, T., Renn, A. & Wild, U. P. Radio-frequency Stark effect modulation of single-molecule lines. J. Lumin. 86, 189–194 (2000).
Plakhotnik, T. Sensing single electrons with single molecules. J. Lumin. 127, 235–238 (2007).
Faez, S., van der Molen, S. & Orrit, M. Optical tracing of multiple charges in single-electron devices. Phys. Rev. B 90, 205405 (2014).
Plakhotnik, T. Single-molecule dynamic triangulation. ChemPhysChem 7, 1699–1704 (2006).
Croci, M., Müschenborn, H.-J., Güttler, F., Renn, A. & Wild, U. P. Single molecule spectroscopy: pressure effect on pentacene in p-terphenyl. Chem. Phys. Lett. 212, 71–77 (1993).
Kol’chenko, M. A. et al. Single molecules detect ultra-slow oscillators in a molecular crystal excited by ac voltages. New J. Phys. 11, 023037 (2009).
Tian, Y., Navarro, P. & Orrit, M. Single molecule as a local acoustic detector for mechanical oscillators. Phys. Rev. Lett. 113, 135505 (2014).
Puller, V., Lounis, B. & Pistolesi, F. Single molecule detection of nanomechanical motion. Phys. Rev. Lett. 110, 125501 (2013).
Dutreix, C., Avriller, R., Lounis, B. & Pistolesi, F. Two-level system as topological actuator for nano-mechanical modes. Phys. Rev. Res. 2, 023268 (2020).
Bauer, M. & Kador, L. Zeeman effect of single-molecule lines. Chem. Phys. Lett. 407, 450–453 (2005).
Wrachtrup, J., von Borczyskowski, C., Bernard, J., Orrit, M. & Brown, R. Optical detection of magnetic resonance in a single molecule. Nature 363, 244–245 (1993).
Köhler, J. et al. Magnetic resonance of a single molecular spin. Nature 363, 242–244 (1993).
Brouwer, A. C. J., Groenen, E. J. J. & Schmidt, J. Detecting magnetic resonance through quantum jumps of single molecules. Phys. Rev. Lett. 80, 3944 (1998).
Gaudreau, L. et al. Universal distance-scaling of nonradiative energy transfer to graphene. Nano Lett. 13, 2030–2035 (2013).
Mazzamuto et al. Single-molecule study for a graphene-based nano-position sensor. New J. Phys. 16, 113007 (2014).
Das, S., Elfving, V. E., Faez, S. & Sorensen, A. S. Interfacing superconducting qubits and single optical photons using molecules in waveguides. Phys. Rev. Lett. 118, 140501 (2017).
Muschik, C. A. et al. Harnessing vacuum forces for quantum sensing of graphene motion. Phys. Rev. Lett. 112, 223601 (2014).
Carusotto, J. & Ciuti, C. Quantum fluids of light. Rev. Mod. Phys. 85, 299–366 (2013).
Sandoghdar, V. Nano-optics in 2020 ± 20. Nano Lett. 20, 4721–4723 (2020).
Philippe Roelli, P., Galland, C., Piro, N. & Kippenberg, T. J. Molecular cavity optomechanics as a theory of plasmon-enhanced Raman scattering. Nat. Nanotechnol. 11, 164–169 (2016).
Clear, C. et al. Phonon-induced optical dephasing in single organic molecules. Phys. Rev. Lett. 124, 153602 (2020).
Reitz, M. et al. Molecule–photon interactions in phononic environments. Phys. Rev. Res. 2, 033270 (2020).
Wasielewski, M. R. et al. Exploiting chemistry and molecular systems for quantum information science. Nat. Rev. Chem. 4, 490–504 (2020).
Bonizzoni, C. et al. Storage and retrieval of microwave pulses with molecular spin ensembles. npj Quantum Inf. 6, 68 (2020).
Bayliss, S. L. et al. Optically addressable molecular spins for quantum information processing. Science 370, 1309–1312 (2020).
Pazzagli, S. et al. Self-assembled nanocrystals of polycyclic aromatic hydrocarbons show photostable single-photon emission. ACS Nano 12, 4295–4303 (2018).
Hildner, R., Brinks, D., Nieder, J. B., Cogdell, R. J. & van Hulst, N. F. Quantum coherent energy transfer over varying pathways in single light-harvesting complexes. Science 340, 1448–1451 (2013).
Liebel, M., Toninelli, C. & van Hulst, N. F. Room-temperature ultrafast nonlinear spectroscopy of a single molecule. Nat. Photon. 12, 45–49 (2018).
Zhang, L. et al. Electrically driven single-photon emission from an isolated single molecule. Nat. Commun. 8, 580 (2017).
Nicolet, A., Kol’chenko, M., Kozankiewicz, B. & Orrit, M. Intermolecular intersystem-crossing in single-molecule spectroscopy, terrylene in anthracene crystals. J. Chem. Phys. 124, 164711 (2006).
Ambrose, W. P., Basché, T. & Moerner, W. E. Detection and spectroscopy of single pentacene molecules in a p‐terphenyl crystal by means of fluorescence excitation. J. Chem. Phys. 95, 7150–7163 (1991).
Sola, M. Forty years of Clar’s aromatic π-sextet rule. Front. Chem. https://doi.org/10.3389/fchem.2013.00022 (2013).
Avlasevich, Y. & Müllen, K. Dibenzopentarylenebis(dicarboximide)s: novel near-infrared absorbing dyes. Chem. Commun. 42, 4440–4442 (2006).
Langhals, H., Zgela, D. & Lüling, R. Sexterrylenetetracarboxylic bisimides: NIR dyes. J. Org. Chem. 80, 12146–12150 (2015).
Henry, B. R. & Siebrand, W. in Organic Molecular Photophysics (ed. Birks, J. B.) Ch. 4 (Wiley, 1973).
Sakamoto, Y. et al. Perfluoropentacene and perfluorotetracene: syntheses, crystal structures, and FET characteristics. Mol. Cryst. Liq. Cryst. 444, 225–232 (2006).
Yamada, H. Photochemical synthesis of pentacene and its derivatives. Chem. Eur. J. 11, 6212–6220 (2005).
Watanabe, M. et al. The synthesis, crystal structure and charge transport properties of hexacene. Nat. Chem. 4, 574–578 (2012).
Jancarik, A., levet, G. & Gourdon, A. A practical general method for the preparation of long acenes. Chem. Eur. J. 25, 2366–2374 (2019).
Lounis, B. & Orrit, M. Single-photon sources. Rep. Prog. Phys. 68, 1129–1179 (2005).
Schofield, R. C. et al. Efficient excitation of dye molecules for single photon generation. J. Phys. Commun. 2, 115027 (2018).
Steinberg, A. M., Kwiat, P. G. & Chiao, R. Y. Dispersion cancellation in a measurement of the single-photon propagation velocity in glass. Phys. Rev. Lett. 68, 2421–2424 (1992).
Bennet, C. H. et al. Teleporting an unknown quantum state via dual classical and Einstein–Podolsky–Rosen channels. Phys. Rev. Lett. 70, 1895–1899 (1993).
Bouwmeester, D. et al. Experimental quantum teleportation. Nature 390, 575–579 (1997).
Grandi, S. et al. Quantum dynamics of a driven two-level molecule with variable dephasing. Phys. Rev. A 94, 063839 (2016).
This project has received funding from the EraNET Cofund Initiatives QuantERA within the European Union’s Horizon 2020 research and innovation programme grant agreement no. 731473 (project ORQUID). A.S.C. acknowledges a University Research Fellowship from the Royal Society (UF160475) and funding from the EPSRC (EP/P030130/1, EP/P01058X/1 and EP/R044031/1). W.H.P. and I.G. acknowledge funding from the Deutsche Forschungs gemeinschaft (DFG) - Projektnummer 332724366 and GE2737/5-1, respectively. F.H.L.K. and A.R.-P. acknowledge support from the Government of Spain (FIS2016-81044; Severo Ochoa CEX2019-000910-S), Fundació Cellex, Fundació Mir-Puig, and Generalitat de Catalunya (CERCA, AGAUR, SGR 1656). Furthermore, the research leading to these results has received funding from the European Union’s Horizon 2020 under grant agreement no. 820378 (Quantum Flagship). We thank A. Moradi for discussions and NWO (The Dutch Research Council) for funding of his PhD grant on sensing of single charges. C.T. thanks A. Renn for always useful discussions.
The authors declare no competing interests.
Peer review information Nature Materials thanks the anonymous reviewers for their contribution to the peer review of this work.
Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
About this article
Cite this article
Toninelli, C., Gerhardt, I., Clark, A.S. et al. Single organic molecules for photonic quantum technologies. Nat. Mater. 20, 1615–1628 (2021). https://doi.org/10.1038/s41563-021-00987-4
Nature Communications (2022)
Photonic-circuited resonance fluorescence of single molecules with an ultrastable lifetime-limited transition
Nature Communications (2022)
Nano Research (2022)