- Open Access
Ultrafast large third-order optical nonlinearity in titanium carbide MXene- hybrids
APS Open Sci. 1, 000004 – Published 29 April, 2026
DOI: https://doi.org/10.1103/4by2-78fx
Abstract
The ultrafast nonlinear optical responses of materials are not just theoretical concepts, but they play a significant role in developing modern photonic and optoelectronic devices, including optical time crystals. However, conventional materials often display either weak optical nonlinearities or slow response in the nanosecond timescale, rendering them ineffective for single-shot femtosecond pulse. This limitation can be overcome by leveraging the ultrafast charge transfer that is less than or equal to the pulse width of the laser in a donor-acceptor material pair. However, the low charge-transfer rates limit their effectiveness in high-speed applications. Here, we synthesized titanium carbide MXene- hybrids characterized by strong electronic coupling, resulting in a remarkable enhancement in the ultrafast third-order nonlinear optical responses, enabled by charge transfer in less than the pulse width. For instance, we obtained a third-order nonlinear optical absorption coefficient of cm/GW and a self-focusing (positive) nonlinear refractive index of at 800 nm in the femtosecond domain, both exceeding control samples by more than an order of magnitude. These enhancements are attributed to efficient charge transfer within the hybrid structure, supported by first-principles calculations and Bader charge analysis. Our findings have led to the development of an ultrafast optical limiter, featuring an onset threshold as low as , with a differential limiting transmittance of . These parameters are better than or comparable to the known benchmarks for high-speed nonlinear optical applications, demonstrating the potential for advanced photonic and optoelectronic devices.
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References (66)
- R. W. Boyd, Nonlinear Optics, 3rd ed. (Academic Press, Amsterdam, 2008).
- D. N. Christodoulides, I. C. Khoo, G. J. Salamo, G. I. Stegeman, and E. W. V. Stryland, Nonlinear refraction and absorption: Mechanisms and magnitudes, Adv. Opt. Photonics 2, 60 (2010).
- R. K. Yadav, J. Aneesh, R. Sharma, P. Abhiramnath, T. K. Maji, G. J. Omar, A. K. Mishra, D. Karmakar, and K. V. Adarsh, Designing hybrids of graphene oxide and gold nanoparticles for nonlinear optical response, Phys. Rev. Appl. 9, 044043 (2018).
- L. Tutt and A. Kost, Optical limiting performance of and solutions, Nature (London) 356, 225 (1992).
- O. Y. Long, K. Wang, A. Dutt, and S. Fan, Time reflection and refraction in synthetic frequency dimension, Phys. Rev. Res. 5, L012046 (2023).
- Y. Zhou, M. Z. Alam, M. Karimi, J. Upham, O. Reshef, C. Liu, A. E. Willner, and R. W. Boyd, Broadband frequency translation through time refraction in an epsilon-near-zero material, Nat. Commun. 11, 2180 (2020).
- Y. Li, C. Wang, Y. Tang, and Y. C. Liu, Time crystal in a single-mode nonlinear cavity, Phys. Rev. Lett. 132, 183803 (2024).
- H. Wang, Z. Hu, J. Deng, X. Zhang, J. Chen, K. Li, and G. Li, All-optical ultrafast polarization switching with nonlinear plasmonic metasurfaces, Sci. Adv. 10, eadk3882 (2024).
- W. Yang, N. Xu, and H. Zhang, Nonlinear absorption properties of indium selenide and its application for demonstrating pulsed Er-doped fiber laser, Laser Phys. Lett. 15, 105101 (2018).
- M. Bapna, R. Sharma, A. R. Barik, P. Khan, R. R. Kumar, and K. V. Adarsh, Light induced diffusion driven self-assembly of Ag nanoparticles in a-Se/Ag bi-layer thin film with ultrafast optical response, Appl. Phys. Lett. 102, 213110 (2013).
- C. Cui, K. P. Seshadreesan, S. Guha, and L. Fan, High-dimensional frequency-encoded quantum information processing with passive photonics and time-resolving detection, Phys. Rev. Lett. 124, 190502 (2020).
- P. Adhikari, M. Hafezi, and J. M. Taylor, Nonlinear optics quantum computing with circuit QED, Phys. Rev. Lett. 110, 060503 (2013).
- J. Peng, M. Sorokina, S. Sugavanam, N. Tarasov, D. V. Churkin, S. K. Turitsyn, and H. Zeng, Real-time observation of dissipative soliton formation in nonlinear polarization rotation mode-locked fibre lasers, Commun. Phys. 1, 20 (2018).
- D. L. Silva, L. Misoguti, and C. R. Mendonca, Control of two-photon absorption in organic compounds by pulse shaping: Spectral dependence, J. Phys. Chem. A 113, 5594 (2009).
- D. Strickland, Nobel lecture: Generating high-intensity ultrashort optical pulses, Rev. Mod. Phys. 91, 030502 (2019).
- N. Alifu, A. Zebibula, H. Q. Zhang, H. W. Ni, L. Zhu, W. Xi, Y. L. Wang, X. L. Zhang, C. F. Wu, and J. Qian, NIR-IIb excitable bright polymer dots with deep-red emission for in vivo through-skull three-photon fluorescence bioimaging, Nano Res. 13, 2632 (2020).
- H. Qian, S. Li, C. F. Chen, S. W. Hsu, S. E. Bopp, Q. Ma, A. R. Tao, and Z. Liu, Large optical nonlinearity enabled by coupled metallic quantum wells, Light: Sci. Appl. 8, 13 (2019).
- M. Kauranen and A. V. Zayats, Nonlinear plasmonics, Nat. Photonics 6, 737 (2012).
- M. Z. Alam, I. De Leon, and R. W. Boyd, Large optical nonlinearity of indium tin oxide in its epsilon-near-zero region, Science 352, 795 (2016).
- L. Caspani, R. P. M. Kaipurath, M. Clerici, M. Ferrera, T. Roger, J. Kim, N. Kinsey, M. Pietrzyk, A. Di Falco, V. M. Shalaev, A. Boltasseva, and D. Faccio, Enhanced nonlinear refractive index in -near-zero materials, Phys. Rev. Lett. 116, 233901 (2016).
- F. Hipolito and T. G. Pedersen, Optical third harmonic generation in black phosphorus, Phys. Rev. B 97, 035431 (2018).
- S. R. Flom, R. G. S. Pong, F. J. Bartoli, and Z. H. Kafafi, Resonant nonlinear optical response of the fullerenes and , Phys. Rev. B 46, 15598(R) (1992).
- H. Chu, Y. Li, C. Wang, H. Zhang, and D. Li, Recent investigations on nonlinear absorption properties of carbon nanotubes, Nanophotonics 9, 761 (2020).
- P. N. Immanuel, S. J. Huang, P. Taank, A. Goldreich, J. Prilusky, A. Byregowda, R. Carmieli, H. Shalom, A. Leybovich, A. Zak, N. Aggarwal, K. V. Adarsh, and L. Yadgarov, Enhanced photocatalytic activity of hybrid nanocomposite, Adv. Energy Sustainability Res. 5, 2300193 (2024).
- J. Yu, X. Kuang, J. Li, J. Zhong, C. Zeng, L. Cao, Z. Liu, Z. Zeng, Z. Luo, T. He, A. Pan, and Y. Liu, Giant nonlinear optical activity in two-dimensional palladium diselenide, Nat. Commun. 12, 1083 (2021).
- A. Sharma, M. Pathak, R. K. Trivedi, A. Das, R. Sharma, D. Sharma, B. Chakraborty, R. S. Singh, C. S. Rout, and K. V. Adarsh. Overcoming the pulse-width limitation of third-order optical nonlinearity for above bandgap excitation in nanoparticles, Phys. Rev. Mater. 9, 055201 (2025).
- A. Sharma, P. Khan, D. Mandal, M. Pathak, C. S. Rout, and K. V. Adarsh, Unveiling and engineering of third-order optical nonlinearities in nanoflowers, Opt. Lett. 46, 5930 (2021).
- N. Aggarwal, P. V. Shinde, C. S. Rout, and K. V. Adarsh, Unravelling excited-state absorption in nanoparticles, in Optica Advanced Photonics Congress 2022, Technical Digest Series (Optica Publishing Group, Washington, D.C., 2022), paper JW3A.43.
- V. Kumar, R. Sharma, A. Bhatt, I. Csarnovics, P. Nemec, H. Jain, and K. V. Adarsh, Ultrafast third-order nonlinear optical response of charge coupled gold nanoparticle- heterostructure, J. Non-Cryst. Solids: X 19, 100196 (2023).
- A. Sazhin, V. N. Gladilin, A. Erglis, G. Hellmann, F. Vewinger, M. Weitz, M. Wouters, and J. Schmitt, Observation of nonlinear response and Onsager regression in a photon Bose-Einstein condensate, Nat. Commun. 15, 4730 (2024).
- V. Kumar, Afreen, S. R. Ka, P. Mane, B. Chakraborty, C. S. Rout, and K. V. Adarsh, Enhancing the ultrafast third-order nonlinear optical response by charge transfer in -reduced graphene oxide hybrid, J. Phys. Chem. C 127, 18485 (2023).
- V. Kumar, D. Mandal, K. A. Sree Raj, B. Chakraborty, A. Agarwal, C. S. Rout, and K. V. Adarsh, Single-wall-carbon-nanotube- nanohybrid for ultrafast visible-to-near-infrared third-order nonlinear optical limiters, Phys. Rev. Appl. 19, 044081 (2023).
- R. Sharma, J. Aneesh, R. K. Yadav, S. Sanda, A. R. Barik, A. K. Mishra, T. K. Maji, D. Karmakar, and K. V. Adarsh, Strong interlayer coupling mediated giant two-photon absorption in /graphene oxide heterostructure: Quenching of exciton bands, Phys. Rev. B 93, 155433 (2016).
- V. Sreeramulu, K. K. Haldar, A. Patra, and D. Narayana Rao, Nonlinear optical switching and enhanced nonlinear optical response of Au-CdSe heteronanostructures, J. Phys. Chem. C 118, 30333 (2014).
- T. Abhijith, S. Edappadikkunnummal, R. Suthar, S. Thomas, and S. Karak, Au- nanohybrids with enhanced optical nonlinearity for optical limiting applications, ACS Appl. Nano Mater. 6, 2327 (2023).
- X. Sun, B. Zhang, Y. Li, X. Luo, G. Li, Y. Chen, C. Zhang, and J. He, Tunable ultrafast nonlinear optical properties of graphene/ van der Waals heterostructures and their application in solid-state bulk lasers, ACS Nano 12, 11376 (2018).
- A. Sharma, P. Mane, B. Chakraborty, and C. S. Rout, 1T-/MXene hybrid as a superior electrode material for asymmetric supercapacitors: Experimental and theoretical investigations, ACS Appl. Energy Mater. 4, 14198 (2021).
- T. Schultz, P. Bärmann, E. Longhi, R. Meena, Y. Geerts, Y. Gogotsi, S. Barlow, S. R. Marder, T. Petit, and N. Koch, Work function and energy level alignment tuning at MXene surfaces and interfaces using (metal)organic donor/acceptor molecules, Phys. Rev. Mater. 7, 045002 (2023).
- Y. Gogotsi and Q. Huang, Two-dimensional building blocks for future materials and devices, ACS Nano 15, 5775 (2021).
- J. Feng, X. Sun, C. Wu, L. Peng, C. Lin, S. Hu, J. Yang, and Y. Xie, Metallic few-layered ultrathin nanosheets: High two-dimensional conductivity for in-plane supercapacitors, J. Am. Chem. Soc. 133, 17832 (2011).
- M. Nadafan, M. Parishani, and R. Malekfar, -scan investigation to evaluate the third-order nonlinear optical properties of cauliflower-like structures, J. Opt. Soc. Am. B 38, 1586 (2021).
- W. Fang, H. Zhao, Y. Xie, J. Fang, J. Xu, and Z. Chen, Facile hydrothermal synthesis of /graphene nanocomposites with superior high-rate capability as lithium-ion battery cathodes, ACS Appl. Mater. Interfaces 7, 13044 (2015).
- L. Liu, et al., Grain-boundary-rich polycrystalline monolayer film for attomolar-level sensors, Nat. Commun. 12, 3870 (2021).
- Q. Jiang, N. Kurra, K. Maleski, Y. Lei, H. Liang, Y. Zhang, Y. Gogotsi, and H. N. Alshareef, On-chip MXene microsupercapacitors for AC-line filtering applications, Adv. Energy Mater. 9, 1901061 (2019).
- See Supplemental Material at http://link.aps.org/supplemental/10.1103/4by2-78fx for the details on synthesis, PXRD analysis, -scan theory, five-level rate equation, computational details, fitting parameters, and optical limiting performance parameter measurement.
- A. Feng, T. Hou, Z. Jia, Y. Zhang, F. Zhang, and G. Wu, Preparation and characterization of epoxy resin filled with MXene nanosheets with excellent electric conductivity, Nanomaterials 10, 162 (2020).
- S. Elumalai, J. R. Lombardi, and M. Yoshimura, The surface-enhanced resonance Raman scattering of dye molecules adsorbed on two-dimensional titanium carbide (MXene) film, Mater. Adv. 1, 146 (2020).
- M. Sheik-Bahae, A. A. Said, T. H. Wei, D. J. Hagan, and E. W. Van Stryland, Sensitive measurement of optical nonlinearities using a single beam, IEEE J. Quantum Electron. 26, 760 (1990).
- R. Karmakar, D. Mandal, M. Shrivastava, and K. V. Adarsh, Defect-mediated carrier dynamics and third-order nonlinear optical response of quantum dots, Opt. Lett. 47, 5196 (2022).
- R. L. Sutherland, Handbook of Nonlinear Optics, 2nd ed. (Dekker, New York, 2003).
- Y. Dong, S. Chertopalov, K. Maleski, B. Anasori, L. Hu, S. Bhattacharya, A. M. Rao, Y. Gogotsi, V. N. Mochalin, and R. Podila, Saturable absorption in 2D MXene thin films for passive photonic diodes, Adv. Mater. 30, 1705714 (2018).
- Z. Burshtein, P. Blau, Y. Kalisky, Y. Shimony, and M. R. Kikta, Excited-state absorption studies of ions in several garnet host crystals, IEEE J. Quantum Electron. 34, 292 (1998).
- M. Sheik-Bahae, D. J. Hagan, and E. W. Van Stryland, Dispersion and band-gap scaling of the electronic Kerr effect in solids associated with two-photon absorption, Phys. Rev. Lett. 65, 96 (1990).
- B. S. Kalanoor, L. Gouda, R. Gottesman, S. Tirosh, E. Haltzi, A. Zaban, and Y. R. Tischler, Third-order optical nonlinearities in organometallic methylammonium lead iodide perovskite thin films, ACS Photonics 3, 361 (2016).
- Y. Feng, N. Dong, G. Wang, Y. Li, S. Zhang, K. Wang, L. Zhang, W. J. Blau, and J. Wang, Saturable absorption behavior of free-standing graphene polymer composite films over broad wavelength and time ranges, Opt. Express 23, 559 (2015).
- B. Gu, W. Ji, and X. Q. Huang, Analytical expression for femtosecond-pulsed scans on instantaneous nonlinearity, Appl. Opt. 47, 1187 (2008).
- A. Mushtaq, B. Pradhan, D. Kushavah, Y. Zhang, M. Wolf, N. Schrenker, E. Fron, S. Bals, J. Hofkens, E. Debroye, and S. K. Pal, Third-order nonlinear optical properties and saturation of two-photon absorption in lead-free double perovskite nanocrystals under femtosecond excitation, ACS Photonics 8, 3365 (2021).
- M. Daimon and A. Masumura, Measurement of the refractive index of distilled water from the near-infrared region to the ultraviolet region, Appl. Opt. 46, 3811 (2007).
- G. Kresse and D. Joubert, From ultrasoft pseudopotentials to the projector augmented-wave method, Phys. Rev. B 59, 1758 (1999).
- G. Kresse and J. Furthmüller, Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set, Comput. Mater. Sci. 6, 15 (1996).
- G. Kresse and J. Furthmüller, Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set, Phys. Rev. B 54, 11169 (1996).
- J. P. Perdew, K. Burke, and M. Ernzerhof, Generalized gradient approximation made simple, Phys. Rev. Lett. 77, 3865 (1996).
- S. Grimme, Semiempirical GGA-type density functional constructed with a long-range dispersion correction, J. Comput. Chem. 27, 1787 (2006).
- H. J. Monkhorst and J. D. Pack, Special points for Brillouin-zone integrations, Phys. Rev. B 13, 5188 (1976).
- W. Tang, E. Sanville, and G. Henkelman, A grid-based Bader analysis algorithm without lattice bias, J. Phys.: Condens. Matter 21, 084204 (2009).
- K. A. Ann Mary, N. V. Unnikrishnan, and R. Philip, Cubic to amorphous transformation of Se in silica with improved ultrafast optical nonlinearity, RSC Adv. 5, 14034 (2015).