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Raman laser from an optical resonator with a grafted single-molecule monolayer

Nature Photonics volume 14, pages 95–101 (2020)Cite this article

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Abstract

Raman-based technologies have enabled many ground-breaking scientific discoveries related to surface science, single-molecule chemistry and biology. For example, researchers have identified surface-bound molecules by their Raman vibrational modes and demonstrated polarization-dependent Raman gain. However, a surface-constrained Raman laser has yet to be demonstrated because of the challenges associated with achieving a sufficiently high photon population located at a surface to transition from spontaneous to stimulated Raman scattering. Here, advances in surface chemistry and in integrated photonics are combined to demonstrate lasing based on surface stimulated Raman scattering (SSRS). By creating an oriented, constrained Si–O–Si monolayer on the surface of integrated silica optical microresonators, the requisite conditions for SSRS are achieved with low threshold powers (200 μW). The expected polarization dependence of SSRS due to the orientation of the Si–O–Si bond is observed. Owing to the ordered monolayer, the Raman lasing efficiency is improved from ~5% to over 40%.

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Fig. 1: Excitation of SSRS using an integrated optical microcavity.
Fig. 2: Surface chemistry on silica resonator devices.
Fig. 3: Device characterization method and optical device performance.
Fig. 4: Characterization of Raman emission.
Fig. 5: Raman lasing behaviours.
Fig. 6: Comparison of Raman lasing performance from OH, MS and DMS devices with two different diameters (~53 μm and ~83 μm) excited at two different polarizations.

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Data availability

The data that support the plots with this paper and other findings of this study are available from the corresponding authors upon reasonable request.

References

  1. Minck, R. W., Terhune, R. W. & Rado, W. G. Laser-stimulated Raman effect and resonant four-photon interactions in gases H2, D2, and CH4. Appl. Phys. Lett. 3, 181–184 (1963).

    Article  ADS  Google Scholar 

  2. Stolen, R. Polarization effects in fiber Raman and Brillouin lasers. IEEE J. Quant. Electron. 15, 1157–1160 (1979).

    Article  ADS  Google Scholar 

  3. Karpov, V. I. et al. Laser-diode-pumped phosphosilicate-fiber Raman laser with an output power of 1 W at 1.48 µm. Opt. Lett. 24, 887–889 (1999).

    Article  ADS  Google Scholar 

  4. Benabid, F., Knight, J., Antonopoulos, G. & Russell, P. Stimulated Raman scattering in hydrogen-filled hollow-core photonic crystal fiber. Science 298, 399–402 (2002).

    Article  ADS  Google Scholar 

  5. Rong, H. et al. An all-silicon Raman laser. Nature 433, 292–294 (2005).

    Article  ADS  Google Scholar 

  6. Feve, J.-P. M., Shortoff, K. E., Bohn, M. J. & Brasseur, J. K. High average power diamond Raman laser. Opt. Express 19, 913–922 (2011).

    Article  ADS  Google Scholar 

  7. Liu, X. et al. Integrated continuous-wave aluminum nitride Raman laser. Optica 4, 893–896 (2017).

    Article  ADS  Google Scholar 

  8. Eckhardt, G., Bortfeld, D. & Geller, M. Stimulated emission of Stokes and anti-Stokes Raman lines from diamond, calcite, and α-sulfur single crystals. Appl. Phys. Lett. 3, 137–138 (1963).

    Article  ADS  Google Scholar 

  9. Pan, A. et al. Stimulated emissions in aligned CdS nanowires at room temperature. J. Phys. Chem. B 109, 24268–24272 (2005).

    Article  Google Scholar 

  10. Hokr, B. H. et al. Bright emission from a random Raman laser. Nat. Commun. 5, 4356 (2014).

    Article  ADS  Google Scholar 

  11. Basiev, T. New crystals for Raman lasers. Phys. Solid State 47, 1400–1405 (2005).

    Article  ADS  Google Scholar 

  12. Latawiec, P. et al. On-chip diamond Raman laser. Optica 2, 924–928 (2015).

    Article  ADS  Google Scholar 

  13. Raymer, M. G., Mostowski, J. & Carlsten, J. L. Theory of stimulated Raman scattering with broad-band lasers. Phys. Rev. A 19, 2304–2316 (1979).

    Article  ADS  Google Scholar 

  14. Raman, C. & Krishnan, K. A new type of secondary radiation. Nature 121, 501–502 (1928).

    Article  ADS  Google Scholar 

  15. Heritage, J. P. in Picosecond Phenomena II (eds Shank, C. V. et al.) 343–347 (Springer Berlin Heidelberg, 1980).

  16. Cazzanelli, M. & Schilling, J. Second order optical nonlinearity in silicon by symmetry breaking. Appl. Phys. Rev. 3, 011104 (2016).

    Article  ADS  Google Scholar 

  17. Zhang, X. et al. Symmetry-breaking-induced nonlinear optics at a microcavity surface. Nat. Photon. 13, 21–24 (2019).

    Article  ADS  Google Scholar 

  18. Jalali, B., Raghunathan, V., Dimitropoulos, D. & Boyraz, O. Raman-based silicon photonics. IEEE J. Sel. Top. Quant. Electron. 12, 412–421 (2006).

    Article  ADS  Google Scholar 

  19. Wei, H. et al. Polarization dependence of surface-enhanced Raman scattering in gold nanoparticle-nanowire systems. Nano Lett. 8, 2497–2502 (2008).

    Article  ADS  Google Scholar 

  20. Presser, V. et al. Raman polarization studies of highly oriented organic thin films. J. Raman Spectrosc. 40, 2015–2022 (2009).

    Article  ADS  Google Scholar 

  21. Shen, Y. R. Nonlinear optical studies of surfaces. Appl. Phys. A 59, 541–543 (1994).

    Article  ADS  Google Scholar 

  22. Vahala, K. Optical microcavities. Nature 424, 839–846 (2003).

    Article  ADS  Google Scholar 

  23. Shi, C., Soltani, S. & Armani, A. M. Gold nanorod plasmonic upconversion microlaser. Nano Lett. 13, 5827–5831 (2013).

    Article  ADS  Google Scholar 

  24. Maker, A. J. & Armani, A. M. Nanowatt threshold, alumina sensitized neodymium laser integrated on silicon. Opt. Express 21, 27238–27245 (2013).

    Article  ADS  Google Scholar 

  25. Castro-Beltrán, R., Diep, V. M., Soltani, S., Gungor, E. & Armani, A. M. Plasmonically enhanced Kerr frequency combs. ACS Photon. 4, 2828–2834 (2017).

    Article  Google Scholar 

  26. Choi, H. & Armani, A. M. Raman–Kerr frequency combs in Zr-doped silica hybrid microresonators. Opt. Lett. 43, 2949–2952 (2018).

    Article  ADS  Google Scholar 

  27. Ma, J., Jiang, X. & Xiao, M. Kerr frequency combs in large-size, ultra-high-Q toroid microcavities with low repetition rates. Photon. Res. 5, B54–B58 (2017).

    Article  Google Scholar 

  28. Ilchenko, V. & Matsko, A. Optical resonators with whispering-gallery modes—part II: applications. IEEE J. Sel. Top. Quant. Electron. 12, 15–32 (2006).

    Article  ADS  Google Scholar 

  29. Spillane, S. M., Kippenberg, T. J. & Vahala, K. J. Ultralow-threshold Raman laser using a spherical dielectric microcavity. Nature 415, 621–623 (2002).

    Article  ADS  Google Scholar 

  30. Choi, H. & Armani, A. M. High efficiency Raman lasers based on Zr-doped silica hybrid microcavities. ACS Photon. 3, 2383–2388 (2016).

    Article  Google Scholar 

  31. Dimitropoulos, D., Houshmand, B., Claps, R. & Jalali, B. Coupled-mode theory of the Raman effect in silicon-on-insulator waveguides. Opt. Lett. 28, 1954–1956 (2003).

    Article  ADS  Google Scholar 

  32. Sabella, A., Piper, J. A. & Mildren, R. P. 1240 nm diamond Raman laser operating near the quantum limit. Opt. Lett. 35, 3874–3876 (2010).

    Article  ADS  Google Scholar 

  33. Chen, C.-Y. et al. Understanding the interplay between molecule orientation and graphene using polarized Raman spectroscopy. ACS Photon. 3, 985–991 (2016).

    Article  Google Scholar 

  34. Armani, D., Kippenberg, T., Spillane, S. & Vahala, K. Ultra-high-Q toroid microcavity on a chip. Nature 421, 925–928 (2003).

    Article  ADS  Google Scholar 

  35. Facchetti, A. et al. Strategies for electrooptic film fabrication. Influence of pyrrole-pyridine-based dibranched chromophore architecture on covalent self-assembly, thin-film microstructure, and nonlinear optical response. J. Am. Chem. Soc. 128, 2142–2153 (2006).

    Article  Google Scholar 

  36. Schlecht, C. A. & Maurer, J. A. Functionalization of glass substrates: mechanistic insights into the surface reaction of trialkoxysilanes. RSC Adv. 1, 1446–1448 (2011).

    Article  Google Scholar 

  37. Newton, M. D. & Gibbs, G. V. Ab initio calculated geometries and charge distributions for H4SiO4 and H6Si2O7 compared with experimental values for silicates and siloxanes. Phys. Chem. Miner. 6, 221–246 (1980).

    Article  ADS  Google Scholar 

  38. Tyaginov, S., Sverdlov, V., Starkov, I., Goes, W. & Grasser, T. Impact of O-Si-O bond angle fluctuations on the Si-O bond-breakage rate. Microelectron. Reliab. 49, 998–1002 (2009).

    Article  Google Scholar 

  39. Hunt, H. K., Soteropulos, C. & Armani, A. M. Bioconjugation strategies for microtoroidal optical resonators. Sensors 10, 9317–9336 (2010).

    Article  Google Scholar 

  40. Zhao, W., He, A. & Xu, Y. Raman second hyperpolarizability determination using computational Raman activities and a comparison with experiments. J. Phys. Chem. A 117, 6217–6223 (2013).

    Article  Google Scholar 

  41. Goda, K., Mahjoubfar, A. & Jalali, B. Demonstration of Raman gain at 800 nm in single-mode fiber and its potential application to biological sensing and imaging. Appl. Phys. Lett. 95, 251101 (2009).

    Article  ADS  Google Scholar 

  42. Mookherjea, S. & Yariv, A. Coupled resonator optical waveguides. IEEE J. Sel. Top. Quant. Electron. 8, 448–456 (2002).

    Article  ADS  Google Scholar 

  43. Deka, N., Maker, A. J. & Armani, A. M. Titanium-enhanced Raman microcavity laser. Opt. Lett. 39, 1354–1357 (2014).

    Article  ADS  Google Scholar 

  44. Hollenbeck, D. & Cantrell, C. D. Multiple-vibrational-mode model for fiber-optic Raman gain spectrum and response function. J. Opt. Soc. Am. B 19, 2886–2892 (2002).

    Article  ADS  Google Scholar 

  45. Yu, Y. et al. New C-H stretching vibrational spectral features in the Raman spectra of gaseous and liquid ethanol. J. Phys. Chem. C 111, 8971–8978 (2007).

    Article  Google Scholar 

  46. Shen, X., Castro Beltran, R., Diep, V. M., Soltani, S. & Armani, A. M. Low-threshold parametric oscillation in organically modified microcavities. Sci. Adv. 4, eaao4507 (2018).

    Article  ADS  Google Scholar 

  47. Ye, Y. et al. Monolayer excitonic laser. Nat. Photon. 9, 733–737 (2015).

    Article  ADS  Google Scholar 

  48. Longhi, S. & Feng, L. Unidirectional lasing in semiconductor microring lasers at an exceptional point. Photon. Res. 5, B1–B6 (2017).

    Article  Google Scholar 

  49. Yao, B. et al. Gate-tunable frequency combs in graphene–nitride microresonators. Nature 558, 410–414 (2018).

    Article  ADS  Google Scholar 

  50. Reeves, L., Wang, Y. & Krauss, T. F. 2D material microcavity light emitters: to lase or not to lase? Adv. Opt. Mater. 6, 1800272 (2018).

    Article  Google Scholar 

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Acknowledgements

We thank Y. Xiao and J. Chen for helpful discussions and M. Veksler for scientific visualization. We would like to acknowledge IARPA (2016-16070100002) and the Office of Naval Research (N00014-17-2270).

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Author notes

  1. Xiaoqin Shen

    Present address: School of Physical Science and Technology, ShanghaiTech University, Shanghai, China

  2. These authors contributed equally: Xiaoqin Shen, Hyungwoo Choi.

Authors and Affiliations

  1. Mork Family Department of Chemical Engineering and Material Science, University of Southern California, Los Angeles, CA, USA

    Xiaoqin Shen, Hyungwoo Choi & Andrea M. Armani

  2. Ming Hsieh Department of Electrical Engineering-Electrophysics, University of Southern California, Los Angeles, CA, USA

    Dongyu Chen & Andrea M. Armani

  3. Department of Chemistry, University of Arkansas at Little Rock, Little Rock, AR, USA

    Wei Zhao

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Contributions

X.S. and H.C. conceived the project. X.S., H.C. and A.M.A. designed the experiments. H.C. fabricated the devices. X.S. functionalized the devices. X.S. and H.C. conducted testing and data analysis. W.Z. conducted DFT simulations of the model molecules. D.C. performed the finite-element method simulations. X.S., H.C. and A.M.A. wrote the manuscript. All authors revised and commented on the manuscript. All authors have given approval to the final version of the manuscript and Supplementary Information.

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Correspondence to Xiaoqin Shen or Andrea M. Armani.

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Supplementary Information

Supplementary details, Figs. 1–6, refs. 1–10 and Tables 1–3.

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Shen, X., Choi, H., Chen, D. et al. Raman laser from an optical resonator with a grafted single-molecule monolayer. Nat. Photonics 14, 95–101 (2020). https://doi.org/10.1038/s41566-019-0563-7

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