Abstract
Lithium niobate (LiNbO3) is viewed as a promising material for optical communications and quantum photonic chips1,2. Recent breakthroughs in LiNbO3 nanophotonics have considerably boosted the development of high-speed electro-optic modulators3,4,5, frequency combs6,7 and broadband spectrometers8. However, the traditional method of electrical poling for ferroelectric domain engineering in optic9,10,11,12,13, acoustic14,15,16,17 and electronic applications18,19 is limited to two-dimensional space and micrometre-scale resolution. Here we demonstrate a non-reciprocal near-infrared laser-writing technique for reconfigurable three-dimensional ferroelectric domain engineering in LiNbO3 with nanoscale resolution. The proposed method is based on a laser-induced electric field that can either write or erase domain structures in the crystal, depending on the laser-writing direction. This approach offers a pathway for controllable nanoscale domain engineering in LiNbO3 and other transparent ferroelectric crystals, which has potential applications in high-efficiency frequency mixing20,21, high-frequency acoustic resonators14,15,16,17 and high-capacity non-volatile ferroelectric memory19,22.
This is a preview of subscription content, access via your institution
Access options
Access Nature and 54 other Nature Portfolio journals
Get Nature+, our best-value online-access subscription
$29.99 / 30 days
cancel any time
Subscribe to this journal
Receive 51 print issues and online access
$199.00 per year
only $3.90 per issue
Buy this article
- Purchase on SpringerLink
- Instant access to full article PDF
Prices may be subject to local taxes which are calculated during checkout
Similar content being viewed by others
Data availability
Source data for Extended Data Figs. 4b and 6b are provided with the paper. The data supporting the findings of this study are available within the article.
References
Zhu, D. et al. Integrated photonics on thin-film lithium niobate. Adv. Opt. Photon. 13, 242–352 (2021).
Sun, D. H. et al. Microstructure and domain engineering of lithium niobate crystal films for integrated photonic applications. Light Sci. Appl. 9, 197 (2020).
Wang, C. et al. Integrated lithium niobate electro-optic modulators operating at CMOS-compatible voltages. Nature 562, 101–104 (2018).
He, M. B. et al. High-performance hybrid silicon and lithium niobate Mach-Zehnder modulators for 100 Gbit s−1 and beyond. Nat. Photon. 13, 359–365 (2019).
Li, M. X. et al. Lithium niobate photonic-crystal electro-optic modulator. Nat. Commun. 11, 4123 (2020).
Zhang, M. et al. Broadband electro-optic frequency comb generation in a lithium niobate microring resonator. Nature 568, 373–377 (2019).
He, Y. et al. Self-starting bi-chromatic LiNbO3 soliton microcomb. Optica 6, 1138–1144 (2019).
Pohl, D. et al. An integrated broadband spectrometer on thin-film lithium niobate. Nat. Photon. 14, 24–29 (2019).
Bartnick, M. et al. Cryogenic second-harmonic generation in periodically poled lithium niobate waveguides. Phys. Rev. Appl. 15, 024028 (2021).
Jankowski, M. et al. Ultrabroadband nonlinear optics in nanophotonic periodically poled lithium niobate waveguides. Optica 7, 40–46 (2020).
Zhu, S. N., Zhu, Y. Y. & Ming, N. B. Quasi–phase-matched third-harmonic generation in a quasi-periodic optical superlattice. Science 278, 843–846 (1997).
Ellenbogen, T., Noa, V. B., Ayelet, G. P. & Arie, A. Nonlinear generation and manipulation of Airy beams. Nat. Photon. 3, 395–398 (2009).
Yuan, S. et al. Strongly enhanced second harmonic generation in a thin film lithium niobate heterostructure cavity. Phys. Rev. Lett. 127, 153901 (2021).
Yudistira, D., Benchabane, S., Janner, D. & Pruneri, V. Diffraction less and strongly confined surface acoustic waves in domain inverted LiNbO3 superlattices. Appl. Phys. Lett. 98, 233504 (2011).
Yin, R. C., Yu, S. Y., He, C., Lu, M. H. & Chen, Y. F. Bulk acoustic wave delay line in acoustic superlattice. Appl. Phys. Lett. 97, 092905 (2010).
Yudistira, D., Benchabane, S., Janner, D. & Pruneri, V. Surface acoustic wave generation in zx-cut LiNbO3 superlattices using coplanar electrodes. Appl. Phys. Lett. 95, 052901 (2009).
Lu, Y. Q. et al. Optical properties of an ionic-type phononic crystal. Science 284, 1822–1824 (1999).
Chai, X. et al. Nonvolatile ferroelectric field-effect transistors. Nat. Commun. 11, 2811 (2020).
Meier, D. & Selbach, S. M. Ferroelectric domain walls for nanotechnology. Nat. Rev. Mater. 7, 157–173 (2021).
Canalias, C. & Pasiskevicius, V. Mirrorless optical parametric oscillator. Nat. Photon. 1, 459–462 (2007).
Jia, K. P. et al. Midinfrared tunable laser with noncritical frequency matching in box resonator geometry. Phys. Rev. Lett. 127, 213902 (2021).
Sharma, P. et al. Nonvolatile ferroelectric domain wall memory. Sci. Adv. 3, 1700512 (2017).
Marpaung, D., Yao, J. P. & Capmany, J. Integrated microwave photonics. Nat. Photon. 13, 80–90 (2019).
Jin, H. et al. On-chip generation and manipulation of entangled photons based on reconfigurable lithium-niobate waveguide circuits. Phys. Rev. Lett. 113, 103601 (2014).
Solntsev, A. S. et al. Generation of nonclassical biphoton states through cascaded quantum walks on a nonlinear chip. Phys. Rev. X 4, 031007 (2014).
Saravi, S., Pertsch, T. & Setzpfandt, F. Lithium niobate on insulator: An emerging platform for integrated quantum photonics. Adv. Opt. Mater. 9, 2100789 (2021).
Zhao, J., Ma, C., Rusing, M. & Mookherjea, S. High quality entangled photon pair generation in periodically poled thin-film lithium niobate waveguides. Phys. Rev. Lett. 124, 163603 (2020).
Lehr, D. et al. Enhancing second harmonic generation in gold nanoring resonators filled with lithium niobate. Nano Lett. 15, 1025–1030 (2015).
Wang, J. et al. High-Q lithium niobate microdisk resonators on a chip for efficient electro-optic modulation. Opt. Express 23, 23072–23078 (2015).
Shur, V. Y., Akhmatkhanov, A. R. & Baturin, I. S. Micro- and nano-domain engineering in lithium niobate. Appl. Phys. Lett. 2, 040604 (2015).
Ying, C. Y. J. et al. Light-mediated ferroelectric domain engineering and micro-structuring of lithium niobate crystals. Laser Photonics Rev. 6, 526–548 (2012).
Sun, J., Hao, Y. X., Zhang, L., Xu, J. J. & Zhu, S. N. Brief review of lithium niobate crystal and its applications. J. Synth. Cryst. 49, 947–964 (2020).
Armstrong, J. A., Bloembergen, N., Ducuing, J. & Pershan, P. S. Interactions between light waves in a nonlinear dielectric. Phys. Rev. 127, 1918–1939 (1962).
Cao, B. et al. Efficient generation of ultra-broadband parametric fluorescence using chirped quasi-phase-matched waveguide devices. Opt. Express 29, 21615–21628 (2021).
Yudistira, D., Janner, D., Benchabane, S. & Pruneri, V. Low power consumption integrated acoustooptic filter in domain inverted LiNbO3 superlattice. Opt. Express 18, 27181–27190 (2010).
Rosenman, G., Urenski, P., Agronin, A., Rosenwaks, Y. & Molotskii, M. Submicron ferroelectric domain structures tailored by high-voltage scanning probe microscopy. Appl. Phys. Lett. 82, 103–105 (2003).
Yamada, M. & Kishima, K. Fabrication of periodically reversed domain structure for SHG in LiNbO3 by direct electron beam lithography at room temperature. Electron. Lett. 27, 828–829 (1991).
Shur, V. Y. Domain nanotechnology in ferroelectrics: nano-domain engineering in lithium niobate crystals. Ferroelectrics 373, 1–10 (2010).
Shur, V. Y. et al. Self-assembled shape evolution of the domain wall and formation of nanodomain wall traces induced by multiple IR laser pulse irradiation in lithium niobate. J. Appl. Phys. 127, 094103 (2020).
Shur, V. Y. et al. Dimensionality increase of ferroelectric domain shape by pulse laser irradiation. Acta Mater. 219, 117270 (2021).
Rodenas, A. et al. Three-dimensional femtosecond laser nanolithography of crystals. Nat. Photon. 13, 105–109 (2018).
Gattass, R. R. & Mazur, E. Femtosecond laser micromachining in transparent materials. Nat. Photon. 2, 219–225 (2008).
Huang, X. J. et al. Reversible 3D laser printing of perovskite quantum dots inside a transparent medium. Nat. Photon. 14, 82–88 (2019).
Yang, W., Kazansky, P. G. & Svirko, Y. P. Non-reciprocal ultrafast laser writing. Nat. Photon. 2, 99–104 (2008).
Wei, D. Z. et al. Experimental demonstration of a three-dimensional lithium niobate nonlinear photonic crystal. Nat. Photon. 12, 596–601 (2018).
Xu, T. X. et al. Three-dimensional nonlinear photonic crystal in ferroelectric barium calcium titanate. Nat. Photon. 12, 591–595 (2018).
Chen, X. et al. Ferroelectric domain engineering by focused infrared femtosecond pulses. Appl. Phys. Lett. 107, 141102 (2015).
Imbrock, J., Hanafi, H., Ayoub, M. & Denz, C. Local domain inversion in MgO-doped lithium niobate by pyroelectric field-assisted femtosecond laser lithography. Appl. Phys. Lett. 113, 252901 (2018).
Zhang, Y., Sheng, Y., Zhu, S. N., Xiao, M. & Krolikowski, W. Nonlinear photonic crystals: from 2D to 3D. Optica 8, 372–381 (2021).
Zhu, B., Liu, H., Chen, Y. & Chen, X. High conversion efficiency second-harmonic beam shaping via amplitude-type nonlinear photonic crystals. Opt. Lett. 45, 220–223 (2019).
Steigerwald, H., Cube, F. V., Luedtke, F., Dierolf, V. & Buse, K. Influence of heat and UV light on the coercive field of lithium niobate crystals. Appl. Phys. B 101, 535–539 (2010).
Saltiel, S. M. et al. Nonlinear diffraction from a virtual beam. Phys. Rev. Lett. 104, 083902 (2010).
Bhatt, R. et al. Studies on nonlinear optical properties of ferroelectric MgO-LiNbO3 single crystals. Ferroelectrics 323, 165–169 (2005).
Reddy, J. N. B., Elizabeth, S., Bhat, H. L., Venkatram, N. & Rao, D. N. Influence of non-stoichiometric defects on nonlinear absorption and refraction in Nd:Zn co-doped lithium niobate. Opt. Mater. 31, 1022–1026 (2009).
Maekawa, S. et al. in Physics of Transition Metal Oxides (eds Cardona, M. et al.) 323–331 (Springer, 2004).
Ashcroft, N. W. & Mermin, N. D. in Solid State Physics (ed. Crane, D. G.) 253–258 (Harcourt College, 1976).
Kosorotov, V. F., Kremenchugskij, L. S., Levash, L. V. & Shchedrina, L. V. Tertiary pyroelectric effect in lithium niobate and lithium tantalate crystals. Ferroelectrics 70, 27–37 (1986).
Bo, H. F. et al. Temperature-dependent ferroelectric properties of near stoichiometric lithium niobate single crystal. Appl. Phys. A 124, 691 (2018).
Fridkin, V. M. & Ducharme, S. General features of the intrinsic ferroelectric coercive field. Phys. Solid State 43, 1320–1324 (2001).
Ishizuki, H., Shoji, I. & Taira, T. Periodical poling characteristics of congruent MgO:LiNbO3 crystals at elevated temperature. Appl. Phys. Lett. 82, 4062–4064 (2003).
Lee, W. H. Binary computer-generated holograms. Appl. Opt. 18, 3661–3669 (1979).
Shapira, A., Shiloh, R., Juwiler, I. & Arie, A. Two-dimensional nonlinear beam shaping. Opt. Lett. 37, 2136–2138 (2012).
Kogelnik, H. & Li, T. Laser beams and resonators. Appl. Opt. 5, 1550–1567 (1966).
Soergel, E. Piezoresponse force microscopy (PFM). J. Phys. D 44, 464003 (2011).
Sheng, Y. et al. Three-dimensional ferroelectric domain visualization by Čerenkov-type second harmonic generation. Opt. Express 18, 16539–16545 (2010).
Huang, X. Y. et al. Second-harmonic interference imaging of ferroelectric domains through a scanning microscope. J. Phys. D 50, 485105 (2017).
Zhu, Y. Y., Chen, Y. F., Zhu, S. N., Qin, Y. Q. & Ming, N. B. Acoustic superlattices and ultrasonic waves excited by crossed-field scheme. Mater. Lett. 28, 503–505 (1996).
Anhorn, M., Engan, H. E. & Ronnekleiv, A. New saw velocity measurements on y-cut LiNbO3. In IEEE 1987 Ultrasonics Symposium (ed. McAvoy, B. R.) 279–284 (IEEE, 1987).
Acknowledgements
This work was supported by the National Key R&D Programme of China (grant nos. 2021YFA1400803 and 2017YFA0303703), the National Natural Science Foundation of China (NSFC) (grant nos. 91950206, 92163216, 11874213, 51725203, U1932115, 51721001 and 62005164), the Science and Technology Commission of Shanghai Municipality (grant no. 21DZ1100500), the Shanghai Municipal Science and Technology Major Project, the Shanghai Frontiers Science Centre Programme (grant no. 2021-2025 No. 20), the Zhangjiang National Innovation Demonstration Zone (grant no. ZJ2019-ZD-005), the Shanghai Rising-Star Program (grant no. 20QA1404100), the National Key Scientific Instrument and Equipment Development Project (grant no. 61927814) and the Fundamental Research Funds for the Central Universities (grant no. 021314380191).
Author information
Authors and Affiliations
Contributions
Y.Z. conceived the idea and supervised the project with M.X. X.X., T.W., P.C., C.Z, J.M., D. Wei, H.W., B.N. and X.F. performed the experiments and numerical simulations under the guidance of Y.Z., S.Z., D. Wu, M.G. and M.X. All authors contributed to the discussion of experimental results.
Corresponding author
Ethics declarations
Competing interests
The authors declare no competing interests.
Peer review
Peer review information
Nature thanks Airán Ródenas Seguí and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.
Additional information
Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Extended data figures and tables
Extended Data Fig. 1 Femtosecond laser writing system for LiNbO3 nanodomain engineering.
The z-polarized laser beam is focused into the sample along the x direction.
Extended Data Fig. 2 The theoretical simulation of temperature (a), temperature gradient (b), the z-component of the thermoelectric field (c), and the pyroelectric field (d).
The marked area in c indicates the electric field above the threshold value. In d, the black arrow shows the laser writing direction (v = 10 μm/s) and the white arrows indicate the direction of pyroelectric field. The input laser propagates along the x direction with its polarization along the z direction.
Extended Data Fig. 3 The procedures to fabricate nanodomains along the x, y, and z directions, through laser poling-erasing strategy.
a, The laser writing process to fabricate LiNbO3 nanodomains along the y direction. First, we move the laser beam along the –z direction to write a domain line. Then, we shift the LiNbO3 sample by a designed distance d along the +y (or -y) direction. Finally, we remove part of the created domain by moving the laser beam back along the +z direction. The remaining domain width along the y direction is d (a). By shifting the LiNbO3 sample along the x direction, similar laser writing strategy is applied to reduce the domain linewidth along the x direction (c). b, The procedure to produce nanosized domain along the z direction, we first move the laser beam along the y direction to write a domain line. Then, we apply the laser eraser point by point to reduce the domain width along the z direction. d, The fabrication process of a nanodomain array.
Extended Data Fig. 4 The dependence of domain width on the writing direction.
a, Schematic diagram of laser writing along an angle of θ relative to the -z direction. a and b define the effective thermoelectric field. The achieved domain linewidth satisfies \({d}^{{\prime} }=\sqrt{{a}^{2}{{\rm{c}}{\rm{o}}{\rm{s}}}^{2}\theta +{b}^{2}{{\rm{s}}{\rm{i}}{\rm{n}}}^{2}\theta }\). b, The calculated and measured domain widths at different θ.
Extended Data Fig. 5 SH generations in 2D and 3D periodic domain structures.
a, The typical QPM configuration45. b, c, The QPM SH patterns in 2D and 3D LiNbO3 domain structures, respectively. The intensities of the SH spots depend on whether the QPM condition is fully satisfied. At input fundamental wavelengths of 755 nm, 742 nm, and 726 nm, the non-collinear QPM SH generations from 2D domain array are realized by involving \({{\boldsymbol{G}}}_{0,1,-1}{/{\boldsymbol{G}}}_{0,1,1}\), \({{\boldsymbol{G}}}_{0,1,-2}{/\overrightarrow{G}}_{0,1,2}\), and \({{\boldsymbol{G}}}_{0,1,-3}{/{\boldsymbol{G}}}_{0,1,3}\), respectively. The corresponding SH pattern presents two symmetric bright spots (b). In comparison to 2D case, the number of the SH spots from 3D domain structure clearly increases because the QPM condition is simultaneously satisfied by more reciprocal vectors (c). Notably, the central SH spot is bright because it is produced through a collinear SH generation process that has a much longer interaction length than those under non-collinear SH generation configurations. d, e, The measured and calculated emitting angles of the output SH beams.
Extended Data Fig. 6 SH HG-mode generation in a 3D nonlinear grating.
a, A 3D χ(2)-grating structure for SH \({{\rm{H}}{\rm{G}}}_{11}\) beam generation under 3D QPM condition66. b, The measured dependence of the SH power at the \({1}^{{st}}\) order on the fundamental wavelength. The 3D QPM condition is satisfied at 768 nm. The deviation in b can be attributed to the broad bandwidth of the input femtosecond laser and the limited period number of the domain structure.
Extended Data Fig. 7 Stability test of LiNbO3 domain structures.
a, The PFM image of a LiNbO3 domain structure prepared by laser writing in Oct. 2019. After being kept at room temperature for over two years, one can clearly observe the domain structure (c). We also put the ruler-shaped nanodomain structure (b) in a tube furnace for an annealing treatment. The sample temperature is increased to 300 °C at a heating rate of about 10 °C/min. After 2-h heat treatment at 300 °C, the sample is naturally cooled down to room temperature. The domain structure successfully survives after such annealing process (d). The domain structures have no significant changes after a two-year storage or an annealing treatment.
Extended Data Fig. 8 Surface acoustic waves (SAW) generation in LiNbO3 nanodomain arrays.
a, The diagram of SAW device based on LiNbO3 nanodomain array. In such LiNbO3 domain structure (also called acoustic superlattice), the sign of the piezoelectric coefficients is periodically switched, which can produce SAW by using uniform electrodes. The SAW resonant frequency is given by67 \(f=\frac{v}{\lambda }\), where \(v\) is the SAW velocity, and \(\lambda \) is the acoustic wavelength that is equal to the period of the LiNbO3 domain structure. b, The calculated dependence of SAW resonant frequency on the domain period. The SAW velocity is 3718 m/s68. For the nanodomain structures with periods of 100 nm and 50 nm, the SAW frequencies reach \(37.2\,{\rm{G}}{\rm{H}}{\rm{z}}\) and \(74.4\,{\rm{G}}{\rm{H}}{\rm{z}}\), respectively.
Extended Data Fig. 9 Comparison of laser writing with/without the use of a drain line.
The solid white line indicates the drain line. When laser writing starts from the drain line, one can produce a LiNbO3 domain line (left). In contrast, under the same laser writing parameters, one cannot write LiNbO3 domains without the use of drain line. The laser writing track is marked by the dashed white line (right). In experiment, we use conductive atomic force microscopy to measure the electric conductivity of drain line, which is several orders of magnitude higher than the value of LiNbO3 crystal.
Extended Data Fig. 10 The linear diffraction patterns from the gratings in Fig. 4a–c at an input wavelength of 690 nm.
The non-zero diffraction order can be barely observed, which indicates no significant change in the refractive index.
Rights and permissions
About this article
Cite this article
Xu, X., Wang, T., Chen, P. et al. Femtosecond laser writing of lithium niobate ferroelectric nanodomains. Nature 609, 496–501 (2022). https://doi.org/10.1038/s41586-022-05042-z
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1038/s41586-022-05042-z
This article is cited by
-
Vectorial adaptive optics: expanding the frontiers of optical correction
Light: Science & Applications (2024)
-
Femtosecond laser direct nanolithography of perovskite hydration for temporally programmable holograms
Nature Communications (2024)
-
Laser nanofabrication inside silicon with spatial beam modulation and anisotropic seeding
Nature Communications (2024)
-
All-optical polarization switching in ferroelectrics
Nature Photonics (2024)
-
Epsilon-near-zero regime enables permanent ultrafast all-optical reversal of ferroelectric polarization
Nature Photonics (2024)
Comments
By submitting a comment you agree to abide by our Terms and Community Guidelines. If you find something abusive or that does not comply with our terms or guidelines please flag it as inappropriate.
