Wafer-scale epitaxy of TiN nanoarrays on fluorophlogopites for flexible, refractory, and multifunctional plasmonic metamaterials

Shaoqin Peng; Xinwei Wang; Jiachang Bi; Shunda Zhang; Tingting Zhang; Jie Sun; Hongtao Cao; Ruyi Zhang; Yanwei Cao

doi:10.59717/j.xinn-mater.2026.100189

The Innovation Materials > 2026 Vol. 4 > No. 1 > 100189

Next Article Previous Article

ARTICLE Open Access

Cite PDF

Wafer-scale epitaxy of TiN nanoarrays on fluorophlogopites for flexible, refractory, and multifunctional plasmonic metamaterials

1.
Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo 315201, China
2.
Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing 100049, China
3.
These authors contributed equally

More Information

Corresponding authors: zhangruyi@nimte.ac.cn (R.Z.); ywcao@nimte.ac.cn (Y.C.)
Received Date: July 21, 2025

Accepted Date: January 05, 2026

Published Online: January 16, 2026

The Innovation Materials 4(1), https://doi.org/10.59717/j.xinn-mater.2026.100189 | Cite this article

GRAPHICAL ABSTRACT

GRAPHICAL ABSTRACT

DownLoad: Full size image

PUBLIC SUMMARY

PUBLIC SUMMARY
1. To overcome challenge of fabricating flexible and single-crystalline plasmonic nanostructure arrays (PNAs).
  
  A wafer-scale route by epitaxy of TiN nanoarrays on fluorophlogopites was demonstrated.
  
  Flexible TiN nanoarrays show plasmonic hyperbolic dispersion, superhydrophilicity, and solar steam generation.
  
  The excellent thermal stability of flexible TiN nanoarrays far surpasses that of ordinary flexible PNAs.

ABSTRACT

ABSTRACT

Developing strategies for flexible, single-crystalline, but refractory plasmonic nanostructure arrays (PNAs) is important for flexible, high-performance, and reliable plasmonic metamaterials, which have broad applications in refractory plasmonics, nanophotonics, sensors, and photothermal conversion. However, the scalable fabrication of flexible, single-crystalline, but refractory PNAs is extremely challenging due to the incompatibilities of synthesis temperatures, crystal structures, and thermal expansion coefficient between typical plasmonic materials and conventional flexible organic substrates. Here, an easy and scalable route to the flexible single-crystalline PNAs is demonstrated by self-assembled growth of TiN nanopillar arrays on flexible van der Waals fluorophlogopite mica substrates using a reactive magnetron sputtering epitaxy system. Remarkably, the wafer scale flexible TiN nanopillar arrays exhibit several intriguing properties, including tunable plasmonic hyperbolic dispersions, superhydrophilicity, strong light absorption, and efficient solar steam generation. Moreover, these flexible TiN nanoarrays demonstrate excellent thermal stability at 800°C, far exceeding the operating temperature (below ~ 200°C) of current flexible noble-metal PNAs on organic substrates. This work offers an easy and scalable approach for fabricating flexible, wafer-scale, single-crystalline, but refractory PNAs with versatile and tunable properties, which can significantly expand the applications of flexible PNAs in flexible electronics, nanophotonic, and photothermal devices.
- Plasmonic nanostructure arrays /
- titanium nitrides /
- flexible plasmonic metamaterials /
- self-assembly /
- single-crystalline

FullText(HTML)

REFERENCES

[1]	Wang W., Ramezani M., Vakevainen A.I., et al. (2018). The rich photonic world of plasmonic nanoparticle arrays. Mater. Today 21:303−314. DOI:10.1016/j.mattod.2017.09.002 View in Article CrossRef Google Scholar
[2]	Zhang H., Kinnear C., and Mulvaney P. (2020). Fabrication of single-nanocrystal arrays. Adv. Mater. 32:1904551. DOI:10.1002/adma.201904551 View in Article CrossRef Google Scholar
[3]	Feng L., Huo P., Liang Y., et al. (2020). Photonic metamaterial absorbers: Morphology engineering and interdisciplinary applications. Adv. Mater. 32:1903787. DOI:10.1002/adma.201903787 View in Article CrossRef Google Scholar
[4]	Yang K., Yao X., Liu B., et al. (2021). Metallic plasmonic array structures: Principles, fabrications, properties, and applications. Adv. Mater. 33:2007988. DOI:10.1002/adma.202007988 View in Article CrossRef Google Scholar
[5]	Liu Y., Kim M., Cho S.H., et al. (2021). Vertically aligned nanostructures for a reliable and ultrasensitive SERS-active platform: Fabrication and engineering strategies. Nano Today 37:101063. DOI:10.1016/j.nantod.2020.101063 View in Article CrossRef Google Scholar
[6]	Wang P., Krasavin A.V., Liu L., et al. (2022). Molecular plasmonics with metamaterials. Chem. Rev. 122:15031−15081. DOI:10.1021/acs.chemrev.2c00333 View in Article CrossRef Google Scholar
[7]	Yang B., Li C., Wang Z., et al. (2022). Thermoplasmonics in solar energy conversion: Materials, nanostructured designs, and applications. Adv. Mater. 34:2107351. DOI:10.1002/adma.202107351 View in Article CrossRef Google Scholar
[8]	Jia H., Tsoi C.C., Abed A.E., et al. (2023). Metallic plasmonic nanostructure arrays for enhanced solar photocatalysis. Laser Photonics Rev. 17:2200700. DOI:10.1002/lpor.202200700 View in Article CrossRef Google Scholar
[9]	Aksu S., Huang M., Artar A., et al. (2011). Flexible plasmonics on unconventional and nonplanar substrates. Adv. Mater. 23:4422−4430. DOI:10.1002/adma.201102430 View in Article CrossRef Google Scholar
[10]	Kim Y.D., Kim H., Cho Y., et al. (2015). Bright visible light emission from graphene. Nat. Nanotechnol. 10:676−681. DOI:10.1038/NNANO.2015.118 View in Article CrossRef Google Scholar
[11]	Li L., Lin H., Qiao S., et al. (2018). Monolithically integrated stretchable photonics. Light: Sci. Appl. 7:17138−17138. DOI:10.1038/lsa.2017.138 View in Article CrossRef Google Scholar
[12]	Geiger S., Michon J., Liu S., et al. (2020). Flexible and stretchable photonics: The next stretch of opportunities. ACS Photonics 7:2618−2635. DOI:10.1021/acsphotonics.0c00983 View in Article CrossRef Google Scholar
[13]	Fu R., Lu Y.,Cheng W. (2022). Soft plasmonics: Design, fabrication, characterization, and applications. Adv. Opt. Mater. 10:2101436. DOI:10.1002/adom.202101436 View in Article CrossRef Google Scholar
[14]	Simovski C.R., Belov P.A., Atrashchenko A.V., et al. (2012). Wire metamaterials: Physics and applications. Adv. Mater. 24:4229−4248. DOI:10.1002/adma.201200931 View in Article CrossRef Google Scholar
[15]	Vinnacombe-Willson G.A., Conti Y., Stefancu A., et al. (2023). Direct bottom-up in situ growth: A paradigm shift for studies in wet-chemical synthesis of gold nanoparticles. Chem. Rev. 123:8488−8529. DOI:10.1021/acs.chemrev.2c00914 View in Article CrossRef Google Scholar
[16]	Walia S., Shah C.M., Gutruf P., et al. (2015). Flexible metasurfaces and metamaterials: A review of materials and fabrication processes at micro- and nano-scales. Appl. Phys. Rev. 2:011303. DOI:10.1063/1.4913751 View in Article CrossRef Google Scholar
[17]	Guler U., Boltasseva A.,Shalaev V.M. (2014). Refractory plasmonics. Science 344:263−264. DOI:10.1126/science.1252722 View in Article CrossRef Google Scholar
[18]	Naik G.V., Shalaev V.M.,Boltasseva A. (2013). Alternative plasmonic materials: Beyond gold and silver. Adv. Mater. 25:3264−3294. DOI:10.1002/adma.201205076 View in Article CrossRef Google Scholar
[19]	Boltasseva A., Shalaev V.M. (2015). All that glitters need not be gold. Science 347:1308−1310. DOI:10.1126/science.aaa8282 View in Article CrossRef Google Scholar
[20]	Gui L., Bagheri S., Strohfeldt N., et al. (2016). Nonlinear refractory plasmonics with titanium nitride nanoantennas. Nano Lett. 16:5708−5713. DOI:10.1021/acs.nanolett.6b02376 View in Article CrossRef Google Scholar
[21]	Korobenko A., Saha S., Godfrey A.T.K., et al. (2021). High-harmonic generation in metallic titanium nitride. Nat. Commun. 12:4981. DOI:10.1038/s41467-021-25224-z View in Article CrossRef Google Scholar
[22]	Reese T., Reed A.N., Sample A.D., et al. (2021). Ultrafast spectroscopy of plasmonic titanium nitride nanoparticle lattices. ACS Photonics 8:1556−1561. DOI:10.1021/acsphotonics.1c00297 View in Article CrossRef Google Scholar
[23]	Zhang R., Li X., Meng F., et al. (2021). Wafer-scale epitaxy of flexible nitride films with superior plasmonic and superconducting performance. ACS Appl. Mater. Interfaces 13:60182−60191. DOI:10.1021/acsami.1c18278 View in Article CrossRef Google Scholar
[24]	Zhang R., Ma Q.-Y., Liu H., et al. (2021). Crystal orientation-dependent oxidation of epitaxial tin films with tunable plasmonics. ACS Photonics 8:847−856. DOI:10.1021/acsphotonics.0c01827 View in Article CrossRef Google Scholar
[25]	Shah D., Yang M., Kudyshev Z., et al. (2022). Thickness-dependent drude plasma frequency in transdimensional plasmonic TiN. Nano Lett. 22:4622−4629. DOI:10.1021/acs.nanolett.1c04692 View in Article CrossRef Google Scholar
[26]	Bitla Y., Chen C., Lee H.-C., et al. (2016). Oxide heteroepitaxy for flexible optoelectronics. ACS Appl. Mater. Interfaces 8:32401−32407. DOI:10.1021/acsami.6b10631 View in Article CrossRef Google Scholar
[27]	Li C.-I., Lin J.-C., Liu H.-J., et al. (2016). Van der waal epitaxy of flexible and transparent VO₂ film on muscovite. Chem. Mater. 28:3914−3919. DOI:10.1021/acs.chemmater.6b01180 View in Article CrossRef Google Scholar
[28]	Yen M., Lai Y.-H., Kuo C.-Y., et al. (2020). Mechanical modulation of colossal magnetoresistance in flexible epitaxial perovskite manganite. Adv. Funct. Mater. 30:2004597. DOI:10.1002/adfm.202004597 View in Article CrossRef Google Scholar
[29]	Jiang J., Bitla Y., Huang C.W., et al. (2017). Flexible ferroelectric element based on van der waals heteroepitaxy. Sci. Adv. 3:e1700121. DOI:10.1126/sciadv.1700121 View in Article CrossRef Google Scholar
[30]	Zhang R., Lin T., Peng S., et al. (2023). Flexible but refractory single-crystalline hyperbolic metamaterials. Nano Lett. 23:3879−3886. DOI:10.1021/acs.nanolett.3c00512 View in Article CrossRef Google Scholar
[31]	Mukhopadhyay D., Rao D., Rawat R.S., et al. (2024). Flexible near-infrared plasmon-polaritons in epitaxial scandium nitride enabled by van der waals heteroepitaxy. Nano Lett. 24:14493−14499. DOI:10.1021/acs.nanolett.4c04616 View in Article CrossRef Google Scholar
[32]	McCauley J.W., Newnham R.E.,Gibbs G.V. (1973). Crystal-structure analysis of synthetic fluorophlogopite. Am. Mineral. 58:249−254. View in Article Google Scholar
[33]	Balasubramanian K., Khare S.V.,Gall D. (2018). Energetics of point defects in rocksalt structure transition metal nitrides: Thermodynamic reasons for deviations from stoichiometry. Acta Mater. 159:77−88. DOI:10.1016/j.actamat.2018.07.074 View in Article CrossRef Google Scholar
[34]	Judek J., Wróbel P., Michałowski P.P., et al. (2021). Titanium nitride as a plasmonic material from near-ultraviolet to very-long-wavelength infrared range. Materials 14:7095. DOI:10.3390/ma14227095 View in Article CrossRef Google Scholar
[35]	Wu P.-C., Chen P.-F., Thi Hien D., et al. (2016). Heteroepitaxy of Fe₃O₄/muscovite: A new perspective for flexible spintronics. ACS Appl. Mater. Interfaces 8:33794−33801. DOI:10.1021/acsami.6b11610 View in Article CrossRef Google Scholar
[36]	Gupta S., Moatti A., Bhaumik A., et al. (2019). Room-temperature ferromagnetism in epitaxial titanium nitride thin films. Acta Mater. 166:221−230. DOI:10.1016/j.actamat.2018.12.041 View in Article CrossRef Google Scholar
[37]	Poddubny A., Iorsh I., Belov P., et al. (2013). Hyperbolic metamaterials. Nat. Photonics 7:948−957. DOI:10.1038/NPHOTON.2013.243 View in Article CrossRef Google Scholar
[38]	Smalley J.S.T., Vallini F., Zhang X., et al. (2018). Dynamically tunable and active hyperbolic metamaterials. Adv. Opt. Photonics 10:354−408. DOI:10.1364/aop.10.000354 View in Article CrossRef Google Scholar
[39]	Huo P., Zhang S., Liang Y., et al. (2019). Hyperbolic metamaterials and metasurfaces: Fundamentals and applications. Adv. Opt. Mater. 7:1801616. DOI:10.1002/adom.201801616 View in Article CrossRef Google Scholar
[40]	Aigner A., Dawes J.M., Maier S.A., et al. (2022). Nanophotonics shines light on hyperbolic metamaterials. Light: Sci. Appl. 11:9. DOI:10.1038/s41377-021-00688-2 View in Article CrossRef Google Scholar
[41]	Wang B., Nawarat P., Lewis K.M., et al. (2021). Tunable infrared plasmonic properties of epitaxial Ti_1-xMg_xN(001) layers. ACS Appl. Mater. Interfaces 13:22738−22748. DOI:10.1021/acsami.1c03667 View in Article CrossRef Google Scholar
[42]	Peng S., Zhang X., Li G., et al. (2025). One-step epitaxy of transition metal nitride nanopillar arrays with an oxidation-tunable hyperbolic dispersion. ACS Appl. Mater. Interfaces 17:3733−3741. DOI:10.1021/acsami.4c13931 View in Article CrossRef Google Scholar
[43]	Naik G.V., Saha B., Liu J., et al. (2014). Epitaxial superlattices with titanium nitride as a plasmonic component for optical hyperbolic metamaterials. Proc. Natl. Acad. Sci. USA 111:7546. DOI:10.1073/pnas.1319446111 View in Article CrossRef Google Scholar
[44]	Yao Y., Zhou J., Liu Z., et al. (2021). Refractory materials and plasmonics based perfect absorbers. Nanotechnology 32:132002. DOI:10.1088/1361-6528/abd275 View in Article CrossRef Google Scholar
[45]	Yang Y., Ding, Q., Wei, Y., et al., (2025) A flexible plasmonic array with both high q ‐factor and strong near‐field. Adv. Opt. Mater. 13:2402274 DOI:10.1002/adom.202402274 View in Article Google Scholar
[46]	Palermo G., Cataldi, U., Condello, A., et al., (2018) Flexible thermo-plasmonics: an opto-mechanical control of the heat generated at the nanoscale. Nanoscale 10:16556-16561 DOI:10.1039/C8NR04228D View in Article Google Scholar
[47]	Zhang J., Yan, Y., Miao, P., et al., (2017) Fabrication of gold-coated PDMS surfaces with arrayed triangular micro/nanopyramids for use as SERS substrates. Beilstein J. Nanotechnol. 8:2271-2282 DOI:10.3762/bjnano.8.227 View in Article Google Scholar
[48]	Li L., Zhao, J., Wu, S., et al., (2025) Flexible plasmonic nanodisk arrays as SERS and biosensing platforms. Opt. Express 33:12989 DOI:10.1364/OE.551641 View in Article Google Scholar
[49]	Ko J., Park, S.-G., Lee, S., et al., (2018) Culture-free detection of bacterial pathogens on plasmonic nanopillar arrays using rapid Raman mapping. ACS Appl. Mater. Interfaces 10:6831-6840 DOI:10.1021/acsami.7b15085 View in Article Google Scholar
[50]	Lim H., Jeon, C.S., Park, Y.M., et al., (2022) Controllable fabrication of silver-deposited polyurethane acrylate nanopillar array film as a flexible surface-enhanced Raman scattering (SERS) substrate with high sensitivity and reproducibility. Microchim. Acta 189:288 DOI:10.1007/s00604-022-05391-6 View in Article Google Scholar
[51]	Li K., Zhang, N., Zhang, T., et al., (2018) Formation of ultra-flexible, conformal, and nano-patterned photonic surfaces via polymer cold-drawing. J. Mater. Chem. C 6:4649-4657 DOI:10.1039/C8TC00884A View in Article Google Scholar
[52]	Che W., Wu, J., Cheng, M., et al., (2021) Polymer-nanoimprinting route for the construction of large-area Au@Ag plasmonic arrays using as highly-uniform SERS platforms. Opt. Mater. 121:111532 DOI:10.1016/j.optmat.2021.111532 View in Article Google Scholar
[53]	Cai J., Zhang, C., Liang, C., et al., (2019) Solution-processed large-area gold nanocheckerboard metasurfaces on flexible plastics for plasmonic biomolecular sensing. Adv. Opt. Mater. 7:1900516 DOI:10.1002/adom.201900516 View in Article Google Scholar
[54]	Wang T.-J., Barveen, N.R., Liu, Z.-Y., et al., (2021) Transparent, flexible plasmonic Ag NP/PMMA substrates using chemically patterned ferroelectric crystals for detecting pesticides on curved surfaces. ACS Appl. Mater. Interfaces 13:34910-34922 DOI:10.1021/acsami.1c08233 View in Article Google Scholar
[55]	Zhang Y., Wang Y., Yu B., et al. (2022). Hierarchically structured black gold film with ultrahigh porosity for solar steam generation. Adv. Mater. 34:e2200108. DOI:10.1002/adma.202200108 View in Article CrossRef Google Scholar
[56]	Zhu C., Xu L., Liu Y., et al. (2024). Polyoxometalate-based plasmonic electron sponge membrane for nanofluidic osmotic energy conversion. Nat. Commun. 15:4213. DOI:10.1038/s41467-024-48613-6 View in Article CrossRef Google Scholar
[57]	Xu B., Ganesan M., Devi R.K., et al. (2025). Hierarchically promoted light harvesting and management in photothermal solar steam generation. Adv. Mater. 37:2406666. DOI:10.1002/adma.202406666 View in Article CrossRef Google Scholar
[58]	Liu L., Gao X., Zheng S., et al. (2025). Recent progress on liquid superspreading and its applications. Adv. Mater. early view:2501734. DOI:10.1002/adma.202501734 View in Article Google Scholar
[59]	Huang Q., Liang X., Yan C., et al. (2021). Review of interface solar-driven steam generation systems: High-efficiency strategies, applications and challenges. Appl. Energy 283:116361. DOI:10.1016/j.apenergy.2020.116361 View in Article CrossRef Google Scholar
[60]	Yu B., Zhang Y., Wang Y., et al. (2023). Recent advances and challenges of metal-based materials for solar steam generation. Adv. Funct. Mater. 33:2307533. DOI:10.1002/adfm.202307533 View in Article CrossRef Google Scholar
[61]	Wu X., Lu Y., Ren X., et al. (2024). Interfacial solar evaporation: From fundamental research to applications. Adv. Mater. 36:2313090. DOI:10.1002/adma.202313090 View in Article CrossRef Google Scholar
[62]	Mascaretti L., Schirato A., Zboril R., et al. (2021). Solar steam generation on scalable ultrathin thermoplasmonic TiN nanocavity arrays. Nano Energy 83:105828. DOI:10.1016/j.nanoen.2021.105828 View in Article CrossRef Google Scholar
[63]	Ghasemi H., Ni, G., Marconnet, A.M., et al., (2014) Solar steam generation by heat localization. Nat. Commun. 5:4449 DOI:10.1038/ncomms5449 View in Article Google Scholar
[64]	Tao P., Ni, G., Song, C., et al., (2018) Solar-driven interfacial evaporation. Nat. Energy 3:1031-1041 DOI:10.1038/s41560-018-0260-7 View in Article Google Scholar
[65]	Wagner W., Pruß, A., (2002) The IAPWS formulation 1995 for the thermodynamic properties of ordinary water substance for general and scientific use. J. Phys. Chem. Ref. Data 31:387-535 DOI:10.1063/1.1461829 View in Article Google Scholar
[66]	Zhang P., Wang H., Wang J., et al. (2024). Boosting the viable water harvesting in solar vapor generation: From interfacial engineering to devices design. Adv. Mater. 36:2303976. DOI:10.1002/adma.202303976 View in Article CrossRef Google Scholar

Cited by

ABOUT THIS ARTICLE

Cite this article:

Peng S., Wang X., Bi J., et al. (2026). Wafer-scale epitaxy of TiN nanoarrays on fluorophlogopites for flexible, refractory, and multifunctional plasmonic metamaterials. The Innovation Materials 4:100189. https://doi.org/10.59717/j.xinn-mater.2026.100189

Peng S., Wang X., Bi J., et al. (2026). Wafer-scale epitaxy of TiN nanoarrays on fluorophlogopites for flexible, refractory, and multifunctional plasmonic metamaterials. The Innovation Materials 4:100189. https://doi.org/10.59717/j.xinn-mater.2026.100189

Welcome!

To request copyright permission to republish or share portions of our works, please visit Copyright Clearance Center's (CCC) Marketplace website at marketplace.copyright.com.

Standard PDF

Extended PDF

Figures(6) Tables(1)

Article Metrics

Article views(2460) PDF downloads(564)

Wafer-scale epitaxy of TiN nanoarrays on fluorophlogopites for flexible, refractory, and multifunctional plasmonic metamaterials

GRAPHICAL ABSTRACT

PUBLIC SUMMARY

ABSTRACT

REFERENCES

ABOUT THIS ARTICLE

Cite this article:

Welcome!

Share

Article Metrics

Relative Articles

Cited by

Catalog

{{newsColumn.name}}

Official Account

{{newsColumn.name}}

Stay connected

{{newsColumn.name}}

Wafer-scale epitaxy of TiN nanoarrays on fluorophlogopites for flexible, refractory, and multifunctional plasmonic metamaterials

GRAPHICAL ABSTRACT

PUBLIC SUMMARY

ABSTRACT

REFERENCES

ABOUT THIS ARTICLE

Cite this article:

Welcome!

Share

Article Metrics

Relative Articles

Cited by

Catalog

Export File

Citation

Format

Content

{{newsColumn.name}}

Official Account

{{newsColumn.name}}

Stay connected

{{newsColumn.name}}