skip to main content


Title: Mid‐ to Far‐Infrared Anisotropic Dielectric Function of HfS 2 and HfSe 2
Abstract

The far‐infrared (far‐IR) remains a relatively underexplored region of the electromagnetic spectrum extending roughly from 20 to 100 µm in free‐space wavelength. Research within this range has been restricted due to a lack of optical materials that can be optimized to reduce losses and increase sensitivity, as well as by the long free‐space wavelengths associated with this spectral region. Here the exceptionally broad Reststrahlen bands of two Hf‐based transition metal dichalcogenides (TMDs) that can support surface phonon polaritons (SPhPs) within the mid‐infrared (mid‐IR) into the terahertz (THz) are reported. In this vein, the IR transmission and reflectance spectra of hafnium disulfide (HfS2) and hafnium diselenide (HfSe2) flakes are measured and their corresponding dielectric functions are extracted. These exceptionally broad Reststrahlen bands (HfS2: 165 cm−1; HfSe2: 95 cm−1) dramatically exceed that of the more commonly explored molybdenum‐ (Mo) and tungsten‐ (W) based TMDs (≈5–10 cm−1), which results from the over sevenfold increase in the Born effective charge of the Hf‐containing compounds. This work therefore identifies a class of materials for nanophotonic and sensing applications in the mid‐ to far‐IR, such as deeply sub‐diffractional hyperbolic and polaritonic optical antennas, as is predicted via electromagnetic simulations using the extracted dielectric function.

 
more » « less
Award ID(s):
1904793 2128240 1904760 1852157
NSF-PAR ID:
10371089
Author(s) / Creator(s):
 ;  ;  ;  ;  ;  ;  ;  ;  ;  
Publisher / Repository:
Wiley Blackwell (John Wiley & Sons)
Date Published:
Journal Name:
Advanced Optical Materials
Volume:
10
Issue:
23
ISSN:
2195-1071
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Abstract

    In recent years, the excitation of surface phonon polaritons (SPhPs) in van der Waals materials received wide attention from the nanophotonics community. Alpha-phase Molybdenum trioxide (α-MoO3), a naturally occurring biaxial hyperbolic crystal, emerged as a promising polaritonic material due to its ability to support SPhPs for three orthogonal directions at different wavelength bands (range 10–20μm). Here, we report on the fabrication, structural, morphological, and optical IR characterization of large-area (over 1 cm2size)α-MoO3polycrystalline film deposited on fused silica substrates by pulsed laser deposition. Due to the random grain distribution, the thin film does not display any optical anisotropy at normal incidence. However, the proposed fabrication method allows us to achieve a singleα-phase, preserving the typical strong dispersion related to the phononic response ofα-MoO3flakes. Remarkable spectral properties of interest for IR photonics applications are reported. For instance, a polarization-tunable reflection peak at 1006 cm−1with a dynamic range of ΔR= 0.3 and a resonanceQ-factor as high as 53 is observed at 45° angle of incidence. Additionally, we report the fulfillment of an impedance matching condition with the SiO2substrate leading to a polarization-independent almost perfect absorption condition (R< 0.01) at 972 cm−1which is maintained for a broad angle of incidence. In this framework our findings appear extremely promising for the further development of mid-IR lithography-free, scalable films, for efficient and large-scale sensors, filters, thermal emitters, and label-free biochemical sensing devices operating in the free space, using far-field detection setups.

     
    more » « less
  2. We present mid-IR spectroscopic characterization of the low-phonon chalcogenide glass, Ga2Ge5S13(GGS) doped with Er3+ions. Under the excitation at ∼800 nm, Er3+:GGS exhibited broad mid-IR emission bands centered at ∼2.7, ∼3.5, and ∼4.5 µm at room temperature. The emission lifetime of the4I9/2level of Er3+ions in GGS glass was found to be millisecond-long at room temperature. The measured fluorescence lifetimes were nearly independent of temperature, indicating negligibly small nonradiative decay rate for the4I9/2state, as can be expected for a low-maximum-phonon energy host. The transition line-strengths, radiative lifetimes, fluorescence branching ratios were calculated by using the Judd-Ofelt method. The peak stimulated emission cross-section of the4I9/24I11/2transition of Er3+ion was determined to be ∼0.10×10−20cm2at room temperature.

     
    more » « less
  3. Abstract

    Atomically thin transition metal dichalcogenides (TMDs) in their excited states can serve as exceptionally small building blocks for active optical platforms. In this scheme, optical excitation provides a practical approach to control light‐TMD interactions via the photocarrier generation, in an ultrafast manner. Here, it is demonstrated that via a controlled generation of photocarriers the second‐harmonic generation (SHG) from a monolayer MoS2crystal can be substantially modulated up to ≈55% within a timeframe of ≈250 fs, a set of performance characteristics that showcases the promise of low‐dimensional materials for all‐optical nonlinear data processing. The combined experimental and theoretical study suggests that the large SHG modulation stems from the correlation between the second‐order dielectric susceptibility χ(2)and the density of photoexcited carriers in MoS2. Indeed, the depopulation of the conduction band electrons, at the vicinity of the high‐symmetryK/K′points of MoS2, suppresses the contribution of interband electronic transitions in the effective χ(2)of the monolayer crystal, enabling the all‐optical modulation of the SHG signal. The strong dependence of the second‐order optical response on the density of photocarriers reveals the promise of time‐resolved nonlinear characterization as an alternative route to monitoring carrier dynamics in excited states of TMDs.

     
    more » « less
  4. Abstract

    The structures of glasses in the lithium–bismuth orthoborate composition range deviate significantly from the short‐range order structure of the two crystalline end‐members. Although binary Li3BO3and BiBO3are solely of comprised trigonal orthoborate anions, all glasses formed by their combination contain four‐coordinated borate tetrahedra. We analyze the structure of (75−1.5x)Li2O–xBi2O3–(25+0.5x)B2O3glasses in increments ofx = 5, with11B magic‐angle spinning nuclear magnetic resonance (NMR), infrared (IR), and Raman spectroscopy. For the full series, the oxygen‐to‐boron ratio remains constant at O/B = 3:1. NMR quantifies an increase in the fraction of tetrahedral boron with increasing bismuth oxide content. Evolution of the mid‐IR profile suggests multiple types of tetrahedral boron sites. Raman spectroscopy reveals that Bi2O3tends to cluster within the lithium borate matrix when initially introduced and that this behavior transforms into a bismuthate network with increasing bismuth oxide content. In all cases, mixed Bi–O–B linkages are observed. The dual role of bismuth as network modifier and network former is likewise observed in the far IR. The glass transition temperature continuously increases with bismuth oxide content; however, the glass stability displays a maximum in the multicomponent glass ofx = 40.

     
    more » « less
  5. Abstract

    Reconfiguration of chiral ceramic nanostructures after ion intercalation should favor specific nanoscale twists leading to strong chiroptical effects.  In this work, V2O3nanoparticles are shown to have “built‐in” chiral distortions caused by binding of tartaric acid enantiomers to the nanoparticle surface. As evidenced by spectroscopy/microscopy techniques and calculations of nanoscale chirality measures, the intercalation of Zn2+ions into the V2O3lattice results in particle expansion, untwist deformations, and chirality reduction. Coherent deformations in the particle ensemble manifest as changes in sign and positions of circular polarization bands at ultraviolet, visible, mid‐infrared (IR), near‐IR (NIR), and IR wavelengths. Theg‐factors observed for IR and NIR spectral diapasons are ≈100–400 times higher than those for previously reported dielectric, semiconductor, and plasmonic nanoparticles. Nanocomposite films layer‐by‐layer assembled (LBL) from V2O3nanoparticles reveal cyclic‐voltage‐driven modulation of optical activity. Device prototypes for IR and NIR range problematic for liquid crystals and other organic materials are demonstrated. High optical activity, synthetic simplicity, sustainable processability, and environmental robustness of the chiral LBL nanocomposites provide a versatile platform for photonic devices. Similar reconfigurations of particle shapes are expected for multiple chiral ceramic nanostructures, leading to unique optical, electrical, and magnetic properties.

     
    more » « less