Abstract
Previously unwelcome, defects are emerging as a new frontier of research, providing a molecular focal point to study the coupling of electrons, excitons, phonons and spin in low-dimensional materials. This opportunity is particularly intriguing in semiconducting single-walled carbon nanotubes, in which covalently bonding organic functional groups to the sp2 carbon lattice can produce tunable sp3 quantum defects that fluoresce brightly in the shortwave IR, emitting pure single photons at room temperature. These novel physical properties have made such synthetic defects, or ‘organic colour centres’, exciting new systems for chemistry, physics, materials science, engineering and quantum technologies. This Review examines progress in this emerging field and presents a unified description of this new family of quantum emitters, as well as providing an outlook of the rapidly expanding research and applications of synthetic defects.
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References
Saito, R., Dresselhaus, G. & Dresselhaus, M. S. Physical Properties of Carbon Nanotubes (Imperial College Press, 1998).
De Volder, M. F. L., Tawfick, S. H., Baughman, R. H. & Hart, A. J. Carbon nanotubes: present and future commercial applications. Science 339, 535–539 (2013).
Castro Neto, A. H., Guinea, F., Peres, N. M. R., Novoselov, K. S. & Geim, A. K. The electronic properties of graphene. Rev. Mod. Phys. 81, 109–162 (2009).
Zhu, Y. et al. Graphene and graphene oxide: synthesis, properties, and applications. Adv. Mater. 22, 3906–3924 (2010).
Wang, Q. H., Kalantar-Zadeh, K., Kis, A., Coleman, J. N. & Strano, M. S. Electronics and optoelectronics of two-dimensional transition metal dichalcogenides. Nat. Nanotechnol. 7, 699–712 (2012).
Chhowalla, M. et al. The chemistry of two-dimensional layered transition metal dichalcogenide nanosheets. Nat. Chem. 5, 263–275 (2013).
Piao, Y. et al. Brightening of carbon nanotube photoluminescence through the incorporation of sp3 defects. Nat. Chem. 5, 840–845 (2013).
Kwon, H. et al. Molecularly tunable fluorescent quantum defects. J. Am. Chem. Soc. 138, 6878–6885 (2016).
He, X. et al. Tunable room-temperature single-photon emission at telecom wavelengths from sp3 defects in carbon nanotubes. Nat. Photon. 11, 577–582 (2017).
Wang, Q. H. & Strano, M. S. Carbon nanotubes: a bright future for defects. Nat. Chem. 5, 812–813 (2013).
Brozena, A. H., Leeds, J. D., Zhang, Y., Fourkas, J. T. & Wang, Y. Controlled defects in semiconducting carbon nanotubes promote efficient generation and luminescence of trions. ACS Nano 8, 4239–4247 (2014).
Kwon, H. et al. Optical probing of local pH and temperature in complex fluids with covalently functionalized, semiconducting carbon nanotubes. J. Phys. Chem. C 119, 3733–3739 (2015).
Kim, M. et al. Fluorescent carbon nanotube defects manifest substantial vibrational reorganization. J. Phys. Chem. C 120, 11268–11276 (2016).
Hartmann, N. F. et al. Photoluminescence dynamics of aryl sp3 defect states in single-walled carbon nanotubes. ACS Nano 10, 8355–8365 (2016).
He, X. et al. Low-temperature single carbon nanotube spectroscopy of sp3 quantum defects. ACS Nano 11, 10785–10796 (2017).
Danné, N. et al. Ultrashort carbon nanotubes that fluoresce brightly in the near-infrared. ACS Nano 12, 6059–6065 (2018).
Wu, X., Kim, M., Kwon, H. & Wang, Y. Photochemical creation of fluorescent quantum defects in semiconducting carbon nanotube hosts. Angew. Chem. Int. Ed. 57, 648–653 (2018).
Srinivasan, K. & Zheng, M. Nanotube chemistry tunes light. Nat. Photon. 11, 535–537 (2017).
Schrödinger, E. Versuch zur modellmässigen deutung des terms der scharfen nebenserien. Z. Phys. 4, 347–354 (1921).
Voiry, D. et al. Covalent functionalization of monolayered transition metal dichalcogenides by phase engineering. Nat. Chem. 7, 45–49 (2014).
Maeda, Y., Takehana, Y., Yamada, M., Suzuki, M. & Murakami, T. Control of the photoluminescence properties of single-walled carbon nanotubes by alkylation and subsequent thermal treatment. Chem. Commun. 51, 13462–13465 (2015).
Jiang, S. et al. Tailoring the electronic structure of covalently functionalized germanane via the interplay of ligand strain and electronegativity. Chem. Mater. 28, 8071–8077 (2016).
Shiraki, T. et al. Emergence of new red-shifted carbon nanotube photoluminescence based on proximal doped-site design. Sci. Rep. 6, 28393 (2016).
Shiraki, T., Onitsuka, H., Shiraishi, T. & Nakashima, N. Near infrared photoluminescence modulation of single-walled carbon nanotubes based on a molecular recognition approach. Chem. Commun. 52, 12972–12975 (2016).
Shiraishi, T., Shiraki, T. & Nakashima, N. Substituent effects on the redox states of locally functionalized single-walled carbon nanotubes revealed by in situ photoluminescence spectroelectrochemistry. Nanoscale 9, 16900–16907 (2017).
Onitsuka, H., Fujigaya, T., Nakashima, N. & Shiraki, T. Control of the near infrared photoluminescence of locally functionalized single-walled carbon nanotubes via doping by azacrown-ether modification. Chem. Eur. J. 24, 9393–9398 (2018).
Chu, X. S. et al. Direct covalent chemical functionalization of unmodified two-dimensional molybdenum disulfide. Chem. Mater. 30, 2112–2128 (2018).
Kim, M. et al. Mapping structure–property relationships of organic color centers. Chem 4, 1–12 (2018).
Aota, S., Akizuki, N., Mouri, S., Matsuda, K. & Miyauchi, Y. Upconversion photoluminescence imaging and spectroscopy of individual single-walled carbon nanotubes. Appl. Phys. Express 9, 045103 (2016).
Akizuki, N., Aota, S., Mouri, S., Matsuda, K. & Miyauchi, Y. Efficient near-infrared up-conversion photoluminescence in carbon nanotubes. Nat. Commun. 6, 8920 (2015).
Saha, A. et al. Narrow-band single-photon emission through selective aryl functionalization of zigzag carbon nanotubes. Nat. Chem. 10, 1089–1095 (2018).
Goldsmith, B. R. et al. Conductance-controlled point functionalization of single-walled carbon nanotubes. Science 315, 77–81 (2007).
Wilson, H. et al. Electrical monitoring of sp3 defect formation in individual carbon nanotubes. J. Phys. Chem. C 120, 1971–1976 (2016).
Maciel, I. O. et al. Electron and phonon renormalization near charged defects in carbon nanotubes. Nat. Mater. 7, 878–883 (2008).
Ma, X., Hartmann, N. F., Baldwin, J. K. S., Doorn, S. K. & Htoon, H. Room-temperature single-photon generation from solitary dopants of carbon nanotubes. Nat. Nanotechnol. 10, 671–675 (2015).
Hartmann, N. F. et al. Photoluminescence imaging of solitary dopant sites in covalently doped single-wall carbon nanotubes. Nanoscale 7, 20521–20530 (2015).
Harutyunyan, H. et al. Defect-induced photoluminescence from dark excitonic states in individual single-walled carbon nanotubes. Nano Lett. 9, 2010–2014 (2009).
Ghosh, S., Bachilo, S. M., Simonette, R. A., Beckingham, K. M. & Weisman, R. B. Oxygen doping modifies near-infrared band gaps in fluorescent single-walled carbon nanotubes. Science 330, 1656–1659 (2010).
Kilina, S., Ramirez, J. & Tretiak, S. Brightening of the lowest exciton in carbon nanotubes via chemical functionalization. Nano Lett. 12, 2306–2312 (2012).
Gifford, B. J., Kilina, S., Htoon, H., Doorn, S. K. & Tretiak, S. Exciton localization and optical emission in aryl-functionalized carbon nanotubes. J. Phys. Chem. C 122, 1828–1838 (2018).
Gifford, B. J. et al. Correction scheme for comparison of computed and experimental optical transition energies in functionalized single-walled carbon nanotubes. J. Phys. Chem. Lett. 9, 2460–2468 (2018).
Glückert, J. T. et al. Dipolar and charged localized excitons in carbon nanotubes. Phys. Rev. B 98, 195413 (2018).
Nan, H. et al. Strong photoluminescence enhancement of MoS2 through defect engineering and oxygen bonding. ACS Nano 8, 5738–5745 (2014).
Tongay, S. et al. Defects activated photoluminescence in two-dimensional semiconductors: interplay between bound, charged, and free excitons. Sci. Rep. 3, 2657 (2013).
Chow, P. K. et al. Defect-induced photoluminescence in monolayer semiconducting transition metal dichalcogenides. ACS Nano 9, 1520–1527 (2015).
Yore, A. E. et al. Visualization of defect-induced excitonic properties of the edges and grain boundaries in synthesized monolayer molybdenum disulfide. J. Phys. Chem. C 120, 24080–24087 (2016).
Galland, C. & Imamoglu, A. All-optical manipulation of electron spins in carbon-nanotube quantum dots. Phys. Rev. Lett. 101, 157404 (2008).
Fan, Y., Goldsmith, B. R. & Collins, P. G. Identifying and counting point defects in carbon nanotubes. Nat. Mater. 4, 906–911 (2005).
Beveratos, A. et al. Single photon quantum cryptography. Phys. Rev. Lett. 89, 187901 (2002).
Inam, F. A. et al. Emission and nonradiative decay of nanodiamond NV centers in a low refractive index environment. ACS Nano 7, 3833–3843 (2013).
Kurtsiefer, C., Mayer, S., Zarda, P. & Weinfurter, H. Stable solid-state source of single photons. Phys. Rev. Lett. 85, 290–293 (2000).
Resch-Genger, U., Grabolle, M., Cavaliere-Jaricot, S., Nitschke, R. & Nann, T. Quantum dots versus organic dyes as fluorescent labels. Nat. Methods 5, 763–775 (2008).
Zhang, M. et al. Bright quantum dots emitting at ~1,600 nm in the NIR-IIb window for deep tissue fluorescence imaging. Proc. Natl Acad. Sci. USA 115, 6590–6595 (2018).
Senellart, P., Solomon, G. & White, A. High-performance semiconductor quantum-dot single-photon sources. Nat. Nanotechnol. 12, 1026–1039 (2017).
Castelletto, S. et al. A silicon carbide room-temperature single-photon source. Nat. Mater. 13, 151–156 (2013).
Knirsch, K. C. et al. Basal-plane functionalization of chemically exfoliated molybdenum disulfide by diazonium salts. ACS Nano 9, 6018–6030 (2015).
Powell, L. R., Piao, Y. & Wang, Y. Optical excitation of carbon nanotubes drives localized diazonium reactions. J. Phys. Chem. Lett. 7, 3690–3694 (2016).
Powell, L. R., Kim, M. & Wang, Y. Chirality-selective functionalization of semiconducting carbon nanotubes with a reactivity-switchable molecule. J. Am. Chem. Soc. 139, 12533–12540 (2017).
Shiraki, T., Uchimura, S., Shiraishi, T., Onitsuka, H. & Nakashima, N. Near infrared photoluminescence modulation by defect site design using aryl isomers in locally functionalized single-walled carbon nanotubes. Chem. Commun. 53, 12544–12547 (2017).
Maultzsch, J. et al. Exciton binding energies in carbon nanotubes from two-photon photoluminescence. Phys. Rev. B 72, 241402 (2005).
Berber, S., Kwon, Y.-K. & Tománek, D. Unusually high thermal conductivity of carbon nanotubes. Phys. Rev. Lett. 84, 4613–4616 (2000).
Dürkop, T., Getty, S. A., Cobas, E. & Fuhrer, M. S. Extraordinary mobility in semiconducting carbon nanotubes. Nano Lett. 4, 35–39 (2004).
Du, X., Skachko, I., Barker, A. & Andrei, E. Y. Approaching ballistic transport in suspended graphene Nat. Nanotechol. 3, 491–495 (2008).
Fujii, M. et al. Measuring the thermal conductivity of a single carbon nanotube. Phys. Rev. Lett. 95, 065502 (2005).
Balandin, A. A. et al. Superior thermal conductivity of single-layer graphene. Nano Lett. 8, 902–907 (2008).
Crochet, J. J., Duque, J. G., Werner, J. H. & Doorn, S. K. Photoluminescence imaging of electronic-impurity-induced exciton quenching in single-walled carbon nanotubes. Nat. Nanotechol. 7, 126–132 (2012).
Manzoni, C. et al. Intersubband exciton relaxation dynamics in single-walled carbon nanotubes. Phys. Rev. Lett. 94, 207401 (2005).
Wang, F., Dukovic, G., Brus, L. E. & Heinz, T. F. The optical resonances in carbon nanotubes arise from excitons. Science 308, 838–841 (2005).
Zhao, H. & Mazumdar, S. Electron–electron interaction effects on the optical excitations of semiconducting single-walled carbon nanotubes. Phys. Rev. Lett. 93, 157402 (2004).
Ando, T. Effects of valley mixing and exchange on excitons in carbon nanotubes with Aharonov–Bohm flux. J. Phys. Soc. Jpn 75, 024707 (2006).
Spataru, C. D., Ismail-Beigi, S., Capaz, R. B. & Louie, S. G. Theory and ab initio calculation of radiative lifetime of excitons in semiconducting carbon nanotubes. Phys. Rev. Lett. 95, 247402 (2005).
Berciaud, S., Cognet, L. & Lounis, B. Luminescence decay and the absorption cross section of individual single-walled carbon nanotubes. Phys. Rev. Lett. 101, 077402 (2008).
Srivastava, A., Htoon, H., Klimov, V. I. & Kono, J. Direct observation of dark excitons in individual carbon nanotubes: inhomogeneity in the exchange splitting. Phys. Rev. Lett. 101, 087402 (2008).
Lee, A. J. et al. Bright fluorescence from individual single-walled carbon nanotubes. Nano Lett. 11, 1636–1640 (2011).
Cognet, L. et al. Stepwise quenching of exciton fluorescence in carbon nanotubes by single-molecule reactions. Science 316, 1465–1468 (2007).
Kelly, A. & Knowles, K. M. Crystallography and Crystal Defects (John Wiley & Sons, 2012).
Charlier, J. C. Defects in carbon nanotubes. Acc. Chem. Res. 35, 1063–1069 (2002).
Hersam, M. C. Progress towards monodisperse single-walled carbon nanotubes. Nat. Nanotechol. 3, 387–394 (2008).
Wang, P. et al. Superacid-surfactant exchange: enabling nondestructive dispersion of full-length carbon nanotubes in water. ACS Nano 11, 9231–9238 (2017).
Dukovic, G. et al. Reversible surface oxidation and efficient luminescence quenching in semiconductor single-wall carbon nanotubes. J. Am. Chem. Soc. 126, 15269–15276 (2004).
Hertel, T., Himmelein, S., Ackermann, T., Stich, D. & Crochet, J. Diffusion limited photoluminescence quantum yields in 1D semiconductors: single-wall carbon nanotubes. ACS Nano 4, 7161–7168 (2010).
Harrah, D. M. & Swan, A. K. The role of length and defects on optical quantum efficiency and exciton decay dynamics in single-walled carbon nanotubes. ACS Nano 5, 647–655 (2011).
Collins, P. G. in Oxford Handbook of Nanoscience & Technology (eds Narlikar, A. V. & Fu, Y. Y.) 31–93 (Oxford Univ. Press, 2010).
Queisser, H. J. & Haller, E. E. Defects in semiconductors: some fatal, some vital. Science 281, 945–950 (1998).
Banhart, F., Kotakoski, J. & Krasheninnikov, A. V. Structural defects in graphene. ACS Nano 5, 26–41 (2011).
Mandel, L. Sub-Poissonian photon statistics in resonance fluorescence. Opt. Lett. 4, 205–207 (1979).
Powell, L. R., Piao, Y., Ng, A. L. & Wang, Y. Channeling excitons to emissive defect sites in carbon nanotube semiconductors beyond the dilute regime. J. Phys. Chem. Lett. 9, 2803–2807 (2018).
Ramirez, J., Mayo, M. L., Kilina, S. & Tretiak, S. Electronic structure and optical spectra of semiconducting carbon nanotubes functionalized by diazonium salts. Chem. Phys. 413, 89–101 (2013).
Takagahara, T. & Hanamura, E. Giant-oscillator-strength effect on excitonic optical nonlinearities due to localization. Phys. Rev. Lett. 56, 2533–2536 (1986).
Miyauchi, Y. et al. Brightening of excitons in carbon nanotubes on dimensionality modification. Nat. Photon. 7, 715–719 (2013).
Citrin, D. S. Long intrinsic radiative lifetimes of excitons in quantum wires. Phys. Rev. Lett. 69, 3393–3396 (1992).
Mouri, S., Miyauchi, Y., Iwamura, M. & Matsuda, K. Temperature dependence of photoluminescence spectra in hole-doped single-walled carbon nanotubes: Implications of trion localization. Phys. Rev. B 87, 045408 (2013).
Iwamura, M. et al. Nonlinear photoluminescence spectroscopy of carbon nanotubes with localized exciton states. ACS Nano 8, 11254–11260 (2014).
Shaver, J. et al. Magnetic brightening of carbon nanotube photoluminescence through symmetry breaking. Nano Lett. 7, 1851–1855 (2007).
Hansch, C., Leo, A. & Taft, R. W. A survey of Hammett substituent constants and resonance and field parameters. Chem. Rev. 91, 165–195 (1991).
Iakoubovskii, K. et al. Midgap luminescence centers in single-wall carbon nanotubes created by ultraviolet illumination. Appl. Phys. Lett. 89, 173108 (2006).
McDonald, T. J., Blackburn, J. L., Metzger, W. K., Rumbles, G. & Heben, M. J. Chiral-selective protection of single-walled carbon nanotube photoluminescence by surfactant selection. J. Phys. Chem. C 111, 17894–17900 (2007).
Deng, S. et al. Confined propagation of covalent chemical reactions on single-walled carbon nanotubes. Nat. Commun. 2, 382 (2011).
Zhang, Y. et al. Propagative sidewall alkylcarboxylation that induces red-shifted near-IR photoluminescence in single-walled carbon nanotubes. J. Phys. Chem. Lett. 4, 826–830 (2013).
Strano, M. S. et al. Electronic structure control of single-walled carbon nanotube functionalization. Science 301, 1519–1522 (2003).
An, L., Fu, Q., Lu, C. & Liu, J. A simple chemical route to selectively eliminate metallic carbon nanotubes in nanotube network devices. J. Am. Chem. Soc. 126, 10520–10521 (2004).
Kaplan, A. et al. Current and future directions in electron transfer chemistry of graphene. Chem. Soc. Rev. 46, 4530–4571 (2017).
Ryder, C. R. et al. Covalent functionalization and passivation of exfoliated black phosphorus via aryl diazonium chemistry. Nat. Chem. 8, 597–602 (2016).
Schmidt, G., Gallon, S., Esnouf, S., Bourgoin, J. P. & Chenevier, P. Mechanism of the coupling of diazonium to single-walled carbon nanotubes and its consequences. Chem. Eur. J. 15, 2101–2110 (2009).
Usrey, M. L., Lippmann, E. S. & Strano, M. S. Evidence for a two-step mechanism in electronically selective single-walled carbon nanotube reactions. J. Am. Chem. Soc. 127, 16129–16135 (2005).
Qin, S. et al. Solubilization and purification of single-wall carbon nanotubes in water by in situ radical polymerization of sodium 4-styrenesulfonate. Macromolecules 37, 3965–3967 (2004).
Crochet, J. J. et al. Disorder limited exciton transport in colloidal single-wall carbon nanotubes. Nano Lett. 12, 5091–5096 (2012).
He, X. et al. Carbon nanotubes as emerging quantum-light sources. Nat. Mater. 17, 663–670 (2018).
Robinson, J. A., Snow, E. S., Badescu, S. C., Reinecke, T. L. & Perkins, F. K. Role of defects in single-walled carbon nanotube chemical sensors. Nano Lett. 6, 1747–1751 (2006).
Barone, P. W., Baik, S., Heller, D. A. & Strano, M. S. Near-infrared optical sensors based on single-walled carbon nanotubes. Nat. Mater. 4, 86–92 (2004).
Heller, D. A. et al. Optical detection of DNA conformational polymorphism on single-walled carbon nanotubes. Science 311, 508–511 (2006).
Harvey, J. D., Baker, H. A., Mercer, E., Budhathoki-Uprety, J. & Heller, D. A. Control of carbon nanotube solvatochromic response to chemotherapeutic agents. ACS Appl. Mater. Interfaces 9, 37947–37953 (2017).
Williams, R. M., Lee, C. & Heller, D. A. A fluorescent carbon nanotube sensor detects the metastatic prostate cancer biomarker uPA. ACS Sens. 3, 1838–1845 (2018).
Hong, G., Diao, S., Antaris, A. L. & Dai, H. Carbon nanomaterials for biological imaging and nanomedicinal therapy. Chem. Rev. 115, 10816–10906 (2015).
Scholes, G. D. et al. Low-lying exciton states determine the photophysics of semiconducting single wall carbon nanotubes. J. Phys. Chem. C 111, 11139–11149 (2007).
Högele, A., Galland, C., Winger, M. & Imamoglu, A. Photon antibunching in the photoluminescence spectra of a single carbon nanotube. Phys. Rev. Lett. 100, 217401 (2008).
Kako, S. et al. A gallium nitride single-photon source operating at 200 K. Nat. Mater. 5, 887–892 (2006).
Gisin, N., Ribordy, G., Tittel, W. & Zbinden, H. Quantum cryptography. Rev. Mod. Phys. 74, 145–195 (2002).
Gisin, N. & Thew, R. Quantum communication. Nat. Photon. 1, 165–171 (2007).
Ishii, A., Uda, T. & Kato, Y. K. Room-temperature single-photon emission from micrometer-long air-suspended carbon nanotubes. Phys. Rev. Appl. 8, 054039 (2017).
Ma, X., Baldwin, J. K. S., Hartmann, N. F., Doorn, S. K. & Htoon, H. Solid-state approach for fabrication of photostable, oxygen-doped carbon nanotubes. Adv. Func. Mater. 25, 6157–6164 (2015).
Cao, Q. & Han, S.-J. Single-walled carbon nanotubes for high-performance electronics. Nanoscale 5, 8852–8863 (2013).
Cao, Q., Tersoff, J., Farmer, D. B., Zhu, Y. & Han, S.-J. Carbon nanotube transistors scaled to a 40-nanometer footprint. Science 356, 1369–1372 (2017).
Salaita, K., Wang, Y. & Mirkin, C. A. Applications of dip-pen nanolithography. Nat. Nanotechnol. 2, 145–155 (2007).
Huang, Z. et al. Photoactuated pens for molecular printing. Adv. Mater. 30, 1705303 (2018).
Dyke, C. A. & Tour, J. M. Covalent functionalization of single-walled carbon nanotubes for materials applications. J. Phys. Chem. A 108, 11151–11159 (2004).
Tasis, D., Tagmatarchis, N., Bianco, A. & Prato, M. Chemistry of carbon nanotubes. Chem. Rev. 106, 1105–1136 (2006).
Quintana, M., Vazquez, E. & Prato, M. Organic functionalization of graphene in dispersions. Acc. Chem. Res. 46, 138–148 (2013).
Peng, F., Zhang, L., Wang, H., Lv, P. & Yu, H. Sulfonated carbon nanotubes as a strong protonic acid catalyst. Carbon 43, 2405–2408 (2005).
Ma, X. et al. Electronic structure and chemical nature of oxygen dopant states in carbon nanotubes. ACS Nano 8, 10782–10789 (2014).
Park, H., Zhao, J. & Lu, J. P. Effects of sidewall functionalization on conducting properties of single wall carbon nanotubes. Nano Lett. 6, 916–919 (2006).
Ao, G. & Zheng, M. Preparation and separation of DNA-wrapped carbon nanotubes. Curr. Protoc. Chem. Biol. 7, 43–51 (2017).
Zhu, S. et al. Graphene quantum dots with controllable surface oxidation, tunable fluorescence and up-conversion emission. RSC Adv. 2, 2717–2720 (2012).
Wang, L. et al. Common origin of green luminescence in carbon nanodots and graphene quantum dots. ACS Nano 8, 2541–2547 (2014).
Zhu, S. et al. Surface chemistry routes to modulate the photoluminescence of graphene quantum dots: from fluorescence mechanism to up-conversion bioimaging applications. Adv. Func. Mater. 22, 4732–4740 (2012).
Feng, L. et al. Propagative exfoliation of high quality graphene. Chem. Mater. 25, 4487–4496 (2013).
Tisler, J. et al. Fluorescence and spin properties of defects in single digit nanodiamonds. ACS Nano 3, 1959–1965 (2009).
Sivakov, V. A., Voigt, F., Berger, A., Bauer, G. & Christiansen, S. H. Roughness of silicon nanowire sidewalls and room temperature photoluminescence. Phys. Rev. B 82, 125446 (2010).
Mannix, A. J., Kiraly, B., Hersam, M. C. & Guisinger, N. P. Synthesis and chemistry of elemental 2D materials. Nat. Rev. Chem. 1, 0014 (2017).
Chakraborty, C., Kinnischtzke, L., Goodfellow, K. M., Beams, R. & Vamivakas, A. N. Voltage-controlled quantum light from an atomically thin semiconductor. Nat. Nanotechnol. 10, 507–511 (2015).
Museur, L., Feldbach, E. & Kanaev, A. Defect-related photoluminescence of hexagonal boron nitride. Phys. Rev. B 78, 155204 (2008).
Tran, T. T., Bray, K., Ford, M. J., Toth, M. & Aharonovich, I. Quantum emission from hexagonal boron nitride monolayers. Nat. Nanotechnol. 11, 37–41 (2015).
Grosso, G. et al. Tunable and high-purity room temperature single-photon emission from atomic defects in hexagonal boron nitride. Nat. Commun. 8, 705 (2017).
Wang, X. et al. Highly anisotropic and robust excitons in monolayer black phosphorus. Nat. Nanotechol. 10, 517 (2015).
Martínez, L. J. et al. Efficient single photon emission from a high-purity hexagonal boron nitride crystal. Phys. Rev. B 94, 121405 (2016).
Benson, E. E. et al. Balancing the hydrogen evolution reaction, surface energetics, and stability of metallic MoS2 nanosheets via covalent functionalization. J. Am. Chem. Soc. 140, 441–450 (2018).
Welsher, K. et al. A route to brightly fluorescent carbon nanotubes for near-infrared imaging in mice. Nat. Nanotechnol. 4, 773–780 (2009).
Bachilo, S. M. et al. Structure-assigned optical spectra of single-walled carbon nanotubes. Science 298, 2361–2366 (2002).
Heller, D. A., Baik, S., Eurell, T. E. & Strano, M. S. Single-walled carbon nanotube spectroscopy in live cells: towards long-term labels and optical sensors. Adv. Mater. 17, 2793–2799 (2005).
Godin, A. G. et al. Single-nanotube tracking reveals the nanoscale organization of the extracellular space in the live brain. Nat. Nanotechol. 12, 238–243 (2016).
Gross, L. Recent advances in submolecular resolution with scanning probe microscopy. Nat. Chem. 3, 273–278 (2011).
Mohn, F., Schuler, B., Gross, L. & Meyer, G. Different tips for high-resolution atomic force microscopy and scanning tunneling microscopy of single molecules. Appl. Phys. Lett. 102, 073109 (2013).
Wong, D. et al. Characterization and manipulation of individual defects in insulating hexagonal boron nitride using scanning tunnelling microscopy. Nat. Nanotechnol. 10, 949–953 (2015).
Rossel, F., Pivetta, M. & Schneider, W.-D. Luminescence experiments on supported molecules with the scanning tunneling microscope. Surf. Sci. Rep. 65, 129–144 (2010).
Zhang, C. et al. Fabrication of silver tips for scanning tunneling microscope induced luminescence. Rev. Sci. Instrum. 82, 083101 (2011).
Bahr, J. L. & Tour, J. M. Covalent chemistry of single-wall carbon nanotubes. J. Mater. Chem. 12, 1952–1958 (2002).
Liang, S. et al. Solid state carbon nanotube device for controllable trion electroluminescence emission. Nanoscale 8, 6761–6769 (2016).
Igumenshchev, K. I., Tretiak, S. & Chernyak, V. Y. Excitonic effects in a time-dependent density functional theory. J. Chem. Phys. 127, 114902 (2007).
Yang, Z.-h, Li, Y. & Ullrich, C. A. A minimal model for excitons within time-dependent density-functional theory. J. Chem. Phys. 137, 014513 (2012).
Mewes, S. A., Plasser, F., Krylov, A. & Dreuw, A. Benchmarking excited-state calculations using exciton properties. J. Chem. Theory Comput. 14, 710–725 (2018).
Turkowski, V., Din, U. N. & Rahman, S. T. Time-dependent density-functional theory and excitons in bulk and two-dimensional semiconductors. Computation 5, 39 (2017).
Acknowledgements
This work was supported partially by the National Science Foundation (NSF) through grant PHY1839165. The authors are also grateful to the NSF (CHE1507974, which is continued as CHE1904488), the Air Force Office of Scientific Research (AFOSR; FA9550-16-1-0150) and the US National Institutes of Health (NIH)/National Institute of General Medical Sciences (NIGMS) (R01GM114167) for providing financial support to students and postdoctoral researchers who have participated in various aspects of the works cited in this Review.
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Nature Reviews Chemistry thanks Haitao Liu, Tomohiro Shiraki and the other anonymous reviewer(s) for their contribution to the peer review of this work.
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Y.H.W. conceptualized the work. A.H.B., M.K., L.R.P. and Y.H.W. jointly wrote the manuscript.
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Glossary
- Single photon
-
Photons that exhibit photon antibunching, such that it can be considered as emitting one at a time.
- Quantum defects
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Chemical defects that exhibit well-defined quantum mechanical characteristics, such as single-photon emission, and that may be described as a two-level system.
- Organic colour centres
-
(OCC). Photon-emitting centres induced by covalently bonding organic molecules onto a host crystal.
- Dark exciton
-
An exciton forms when an electron and a hole are bound together by the Coulomb interaction. Dark excitons are not optically allowed as they recombine non-radiatively.
- Van Hove singularities
-
Singularities in the density of states of a crystal, named after the Belgian physicist Léon Van Hove.
- Chirality
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A general structural identifier of single-walled carbon nanotubes, referencing the nanotube’s chiral roll-up vector and indicative of the material’s diameter and electronic structure. Each chirality can be indexed by a pair of integers (n,m) and may include an additional label, if required, to differentiate its left-handed or right-handed helicity.
- Taft constant
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An empirical constant that describes the relative steric, inductive and resonance effects of substituents.
- Photon antibunching
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The lack of simultaneous emission of more than two photons at a time.
- Hammett constant
-
An empirical constant that describes the relative inductive effect of a substituent of benzene derivatives.
- Mulliken population analysis
-
A computational method used to estimate the partial charges on atoms in a molecule or material system.
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Brozena, A.H., Kim, M., Powell, L.R. et al. Controlling the optical properties of carbon nanotubes with organic colour-centre quantum defects. Nat Rev Chem 3, 375–392 (2019). https://doi.org/10.1038/s41570-019-0103-5
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DOI: https://doi.org/10.1038/s41570-019-0103-5
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