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Title: Very High Refractive Index Transition Metal Dichalcogenide Photonic Conformal Coatings by Conversion of ALD Metal Oxides

Abstract

Materials for nanophotonic devices ideally combine ease of deposition, very high refractive index, and facile pattern formation through lithographic templating and/or etching. In this work, we present a scalable method for producing high refractive index WS2 layers by chemical conversion of WO3 synthesized via atomic layer deposition (ALD). These conformal nanocrystalline thin films demonstrate a surprisingly high index of refraction (n > 3.9), and structural fidelity compatible with lithographically defined features down to ~10 nm. Although this process yields highly polycrystalline films, the optical constants are in agreement with those reported for single crystal bulk WS2. Subsequently, we demonstrate three photonic structures - first, a two-dimensional hole array made possible by patterning and etching an ALD WO3 thin film before conversion, second, an analogue of the 2D hole array first patterned into fused silica before conformal coating and conversion, and third, a three-dimensional inverse opal photonic crystal made by conformal coating of a self-assembled polystyrene bead template. Furthermore these results can be trivially extended to other transition metal dichalcogenides, thus opening new opportunities for photonic devices based on high refractive index materials.

Authors:
ORCiD logo [1];  [2];  [1];  [1];  [1];  [1];  [1];  [1]; ORCiD logo [1];  [1];  [1]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  2. Univ. degli Studi di Milano-Bicocca, Milano (Italy)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division
OSTI Identifier:
1503660
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Scientific Reports
Additional Journal Information:
Journal Volume: 9; Journal Issue: 1; Journal ID: ISSN 2045-2322
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Chen, Christopher T., Pedrini, Jacopo, Gaulding, E. Ashley, Kastl, Christoph, Calafiore, Giuseppe, Dhuey, Scott, Kuykendall, Tevye R., Cabrini, Stefano, Toma, Francesca M., Aloni, Shaul, and Schwartzberg, Adam M. Very High Refractive Index Transition Metal Dichalcogenide Photonic Conformal Coatings by Conversion of ALD Metal Oxides. United States: N. p., 2019. Web. doi:10.1038/s41598-019-39115-3.
Chen, Christopher T., Pedrini, Jacopo, Gaulding, E. Ashley, Kastl, Christoph, Calafiore, Giuseppe, Dhuey, Scott, Kuykendall, Tevye R., Cabrini, Stefano, Toma, Francesca M., Aloni, Shaul, & Schwartzberg, Adam M. Very High Refractive Index Transition Metal Dichalcogenide Photonic Conformal Coatings by Conversion of ALD Metal Oxides. United States. https://doi.org/10.1038/s41598-019-39115-3
Chen, Christopher T., Pedrini, Jacopo, Gaulding, E. Ashley, Kastl, Christoph, Calafiore, Giuseppe, Dhuey, Scott, Kuykendall, Tevye R., Cabrini, Stefano, Toma, Francesca M., Aloni, Shaul, and Schwartzberg, Adam M. Tue . "Very High Refractive Index Transition Metal Dichalcogenide Photonic Conformal Coatings by Conversion of ALD Metal Oxides". United States. https://doi.org/10.1038/s41598-019-39115-3. https://www.osti.gov/servlets/purl/1503660.
@article{osti_1503660,
title = {Very High Refractive Index Transition Metal Dichalcogenide Photonic Conformal Coatings by Conversion of ALD Metal Oxides},
author = {Chen, Christopher T. and Pedrini, Jacopo and Gaulding, E. Ashley and Kastl, Christoph and Calafiore, Giuseppe and Dhuey, Scott and Kuykendall, Tevye R. and Cabrini, Stefano and Toma, Francesca M. and Aloni, Shaul and Schwartzberg, Adam M.},
abstractNote = {Materials for nanophotonic devices ideally combine ease of deposition, very high refractive index, and facile pattern formation through lithographic templating and/or etching. In this work, we present a scalable method for producing high refractive index WS2 layers by chemical conversion of WO3 synthesized via atomic layer deposition (ALD). These conformal nanocrystalline thin films demonstrate a surprisingly high index of refraction (n > 3.9), and structural fidelity compatible with lithographically defined features down to ~10 nm. Although this process yields highly polycrystalline films, the optical constants are in agreement with those reported for single crystal bulk WS2. Subsequently, we demonstrate three photonic structures - first, a two-dimensional hole array made possible by patterning and etching an ALD WO3 thin film before conversion, second, an analogue of the 2D hole array first patterned into fused silica before conformal coating and conversion, and third, a three-dimensional inverse opal photonic crystal made by conformal coating of a self-assembled polystyrene bead template. Furthermore these results can be trivially extended to other transition metal dichalcogenides, thus opening new opportunities for photonic devices based on high refractive index materials.},
doi = {10.1038/s41598-019-39115-3},
journal = {Scientific Reports},
number = 1,
volume = 9,
place = {United States},
year = {2019},
month = {2}
}

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Cited by: 9 works
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Figures / Tables:

Figure 1 Figure 1: Synthesis, optical properties, and comparison of refractive indices of converted WS2 thin films. (a) Thin films of ALD metal oxides are heated in a chalcogen-containing gas environment at high temperatures to yield TMD thin films. (b) Representative thin film Raman spectrum. (c) Refractive index values of WS2 convertedmore » at 650 °C and 850 °C compared to literature values for bulk WS215, Si21, and GaP (Woollam, J.A. GaP tabulated from UNL. Unpublished, CompleteEASE Materials Library.). Extracted refractive index values for thin film have features from the expected excitonic contributions and n > 4 for much of the visible into the IR. (d) Comparison of thin film absorption coefficient to literature values for bulk 3R-WS2, Si, and GaP. The absorption coefficient falls off near the expected indirect gap value of ~1.2 eV for both conversion temperatures.« less

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Works referenced in this record:

Imaging spectroscopic ellipsometry of MoS 2
journal, July 2016


Photonic band tuning in two-dimensional photonic crystal slab waveguides by atomic layer deposition
journal, October 2006

  • Graugnard, E.; Gaillot, D. P.; Dunham, S. N.
  • Applied Physics Letters, Vol. 89, Issue 18
  • DOI: 10.1063/1.2360236

Epitaxial Growth of High Dielectric Contrast Three-Dimensional Photonic Crystals
journal, May 2001


Crystal structures of tungsten disulfide and diselenide
journal, October 1987


Solar Cell Light Trapping beyond the Ray Optic Limit
journal, December 2011

  • Callahan, Dennis M.; Munday, Jeremy N.; Atwater, Harry A.
  • Nano Letters, Vol. 12, Issue 1
  • DOI: 10.1021/nl203351k

Optical Properties of Inverse Opal Photonic Crystals
journal, August 2002

  • Schroden, Rick C.; Al-Daous, Mohammed; Blanford, Christopher F.
  • Chemistry of Materials, Vol. 14, Issue 8
  • DOI: 10.1021/cm020100z

Mixing Behavior in Small Molecule:Fullerene Organic Photovoltaics
journal, March 2017


Fabrication of Single Crystal Gallium Phosphide Thin Films on Glass
journal, July 2017


Wafer-scale MoS2 thin layers prepared by MoO3 sulfurization
journal, January 2012

  • Lin, Yu-Chuan; Zhang, Wenjing; Huang, Jing-Kai
  • Nanoscale, Vol. 4, Issue 20
  • DOI: 10.1039/c2nr31833d

Gallium phosphide photonic crystal nanocavities in the visible
journal, August 2008

  • Rivoire, Kelley; Faraon, Andrei; Vuckovic, Jelena
  • Applied Physics Letters, Vol. 93, Issue 6
  • DOI: 10.1063/1.2971200

Kramers-Kronig analysis of the reflectivity spectra of 2H-MoS 2 , 2H-MoSe 2 and 2H-MoTe 2
journal, March 1979


Polyhedral and cylindrical structures of tungsten disulphide
journal, December 1992

  • Tenne, R.; Margulis, L.; Genut, M.
  • Nature, Vol. 360, Issue 6403
  • DOI: 10.1038/360444a0

Smallest possible electromagnetic mode volume in a dielectric cavity
journal, December 1998

  • Boroditsky, M.; Coccioli, R.; Yablonovitch, E.
  • IEE Proceedings - Optoelectronics, Vol. 145, Issue 6
  • DOI: 10.1049/ip-opt:19982468

Optical properties of monolayer transition metal dichalcogenides probed by spectroscopic ellipsometry
journal, November 2014

  • Liu, Hsiang-Lin; Shen, Chih-Chiang; Su, Sheng-Han
  • Applied Physics Letters, Vol. 105, Issue 20
  • DOI: 10.1063/1.4901836

Large-scale synthesis of a silicon photonic crystal with a complete three-dimensional bandgap near 1.5 micrometres
journal, May 2000

  • Blanco, Alvaro; Chomski, Emmanuel; Grabtchak, Serguei
  • Nature, Vol. 405, Issue 6785
  • DOI: 10.1038/35013024

Atomically Thin MoS2 A New Direct-Gap Semiconductor
journal, September 2010


Optical Microresonators for Sensing and Transduction: A Materials Perspective
journal, June 2017

  • Heylman, Kevin D.; Knapper, Kassandra A.; Horak, Erik H.
  • Advanced Materials, Vol. 29, Issue 30
  • DOI: 10.1002/adma.201700037

Control of two-dimensional excitonic light emission via photonic crystal
journal, April 2014


Fabrication of Three-Dimensional Photonic Crystals Using Multibeam Interference Lithography and Electrodeposition
journal, August 2009

  • Miyake, Masao; Chen, Ying-Chieh; Braun, Paul V.
  • Advanced Materials, Vol. 21, Issue 29
  • DOI: 10.1002/adma.200802085

The important role of water in growth of monolayer transition metal dichalcogenides
journal, March 2017


Scherrer grain-size analysis adapted to grazing-incidence scattering with area detectors
journal, October 2009


Photonic band-gap structures
journal, January 1993

  • Yablonovitch, E.
  • Journal of the Optical Society of America B, Vol. 10, Issue 2, p. 283-295
  • DOI: 10.1364/JOSAB.10.000283

Excitons in 2H-WSe 2 and 3R-WS 2
journal, June 1976


Low-loss, submicron chalcogenide integrated photonics with chlorine plasma etching
journal, March 2015

  • Chiles, Jeff; Malinowski, Marcin; Rao, Ashutosh
  • Applied Physics Letters, Vol. 106, Issue 11
  • DOI: 10.1063/1.4916207

Highly Conformal Thin Films of Tungsten Nitride Prepared by Atomic Layer Deposition from a Novel Precursor
journal, July 2003

  • Becker, Jill S.; Suh, Seigi; Wang, Shenglong
  • Chemistry of Materials, Vol. 15, Issue 15
  • DOI: 10.1021/cm021772s

Photonic crystals: putting a new twist on light
journal, March 1997

  • Joannopoulos, J. D.; Villeneuve, Pierre R.; Fan, Shanhui
  • Nature, Vol. 386, Issue 6621
  • DOI: 10.1038/386143a0

Kramers-Kronig analysis of the reflectivity spectra of 3R-WS 2 and 2H-WSe 2
journal, June 1976

  • Beal, A. R.; Liang, W. Y.; Hughes, H. P.
  • Journal of Physics C: Solid State Physics, Vol. 9, Issue 12
  • DOI: 10.1088/0022-3719/9/12/027

The Past, Present, and Future of Silicon Photonics
journal, January 2006


Epitaxial growth of three-dimensionally architectured optoelectronic devices
journal, July 2011

  • Nelson, Erik C.; Dias, Neville L.; Bassett, Kevin P.
  • Nature Materials, Vol. 10, Issue 9
  • DOI: 10.1038/nmat3071

Three-Dimensional Single Gyroid Photonic Crystals with a Mid-Infrared Bandgap
journal, April 2016


Photonic Crystal Films with High Refractive Index Contrast
journal, October 2000


Three-dimensional single gyroid photonic crystals with a mid-infrared bandgap
preprint, January 2016


Works referencing / citing this record:

Lithographically defined synthesis of transition metal dichalcogenides
journal, September 2019


Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.