skip to main content

Title: Small energy gap revealed in CrBr 3 by scanning tunneling spectroscopy
CrBr 3 is a layered van der Waals material with magnetic ordering down to the 2D limit. For decades, based on optical measurements, it is believed that the energy gap of CrBr 3 is in the range of 1.68–2.1 eV. However, controversial results have indicated that the band gap of CrBr 3 is possibly smaller than that. An unambiguous determination of the energy gap is critical to the correct interpretations of the experimental results of CrBr 3 . Here, we present the scanning tunneling microscopy and spectroscopy (STM/S) results of CrBr 3 thin and thick flakes exfoliated onto highly ordered pyrolytic graphite (HOPG) surfaces and density functional theory (DFT) calculations to reveal the small energy gap (peak-to-peak energy gap to be 0.57 ± 0.04 eV; or the onset signal energy gap to be 0.29 ± 0.05 eV from d I /d V spectra). Atomic resolution topography images show the defect-free crystal structure and the d I /d V spectra exhibit multiple peak features measured at 77 K. The conduction band – valence band peak pairs in the multi-peak d I /d V spectrum agree very well with all reported optical transitions. STM topography images of mono- and bi-layer CrBr 3 more » flakes exhibit edge degradation due to short air exposure (∼15 min) during sample transfer. The unambiguously determined small energy gap settles the controversy and is the key in better understanding CrBr 3 and similar materials. « less
Authors:
; ; ; ; ; ; ; ; ; ;
Award ID(s):
1710512
Publication Date:
NSF-PAR ID:
10275865
Journal Name:
Physical Chemistry Chemical Physics
Volume:
23
Issue:
5
Page Range or eLocation-ID:
3225 to 3232
ISSN:
1463-9076
Sponsoring Org:
National Science Foundation
More Like this
  1. Resonant tunneling diodes (RTDs) have come full-circle in the past 10 years after their demonstration in the early 1990s as the fastest room-temperature semiconductor oscillator, displaying experimental results up to 712 GHz and fmax values exceeding 1.0 THz [1]. Now the RTD is once again the preeminent electronic oscillator above 1.0 THz and is being implemented as a coherent source [2] and a self-oscillating mixer [3], amongst other applications. This paper concerns RTD electroluminescence – an effect that has been studied very little in the past 30+ years of RTD development, and not at room temperature. We present experiments and modeling of an n-type In0.53Ga0.47As/AlAs double-barrier RTD operating as a cross-gap light emitter at ~300K. The MBE-growth stack is shown in Fig. 1(a). A 15-μm-diam-mesa device was defined by standard planar processing including a top annular ohmic contact with a 5-μm-diam pinhole in the center to couple out enough of the internal emission for accurate free-space power measurements [4]. The emission spectra have the behavior displayed in Fig. 1(b), parameterized by bias voltage (VB). The long wavelength emission edge is at  = 1684 nm - close to the In0.53Ga0.47As bandgap energy of Ug ≈ 0.75 eV at 300 K.more »The spectral peaks for VB = 2.8 and 3.0 V both occur around  = 1550 nm (h = 0.75 eV), so blue-shifted relative to the peak of the “ideal”, bulk InGaAs emission spectrum shown in Fig. 1(b) [5]. These results are consistent with the model displayed in Fig. 1(c), whereby the broad emission peak is attributed to the radiative recombination between electrons accumulated on the emitter side, and holes generated on the emitter side by interband tunneling with current density Jinter. The blue-shifted main peak is attributed to the quantum-size effect on the emitter side, which creates a radiative recombination rate RN,2 comparable to the band-edge cross-gap rate RN,1. Further support for this model is provided by the shorter wavelength and weaker emission peak shown in Fig. 1(b) around = 1148 nm. Our quantum mechanical calculations attribute this to radiative recombination RR,3 in the RTD quantum well between the electron ground-state level E1,e, and the hole level E1,h. To further test the model and estimate quantum efficiencies, we conducted optical power measurements using a large-area Ge photodiode located ≈3 mm away from the RTD pinhole, and having spectral response between 800 and 1800 nm with a peak responsivity of ≈0.85 A/W at  =1550 nm. Simultaneous I-V and L-V plots were obtained and are plotted in Fig. 2(a) with positive bias on the top contact (emitter on the bottom). The I-V curve displays a pronounced NDR region having a current peak-to-valley current ratio of 10.7 (typical for In0.53Ga0.47As RTDs). The external quantum efficiency (EQE) was calculated from EQE = e∙IP/(∙IE∙h) where IP is the photodiode dc current and IE the RTD current. The plot of EQE is shown in Fig. 2(b) where we see a very rapid rise with VB, but a maximum value (at VB= 3.0 V) of only ≈2×10-5. To extract the internal quantum efficiency (IQE), we use the expression EQE= c ∙i ∙r ≡ c∙IQE where ci, and r are the optical-coupling, electrical-injection, and radiative recombination efficiencies, respectively [6]. Our separate optical calculations yield c≈3.4×10-4 (limited primarily by the small pinhole) from which we obtain the curve of IQE plotted in Fig. 2(b) (right-hand scale). The maximum value of IQE (again at VB = 3.0 V) is 6.0%. From the implicit definition of IQE in terms of i and r given above, and the fact that the recombination efficiency in In0.53Ga0.47As is likely limited by Auger scattering, this result for IQE suggests that i might be significantly high. To estimate i, we have used the experimental total current of Fig. 2(a), the Kane two-band model of interband tunneling [7] computed in conjunction with a solution to Poisson’s equation across the entire structure, and a rate-equation model of Auger recombination on the emitter side [6] assuming a free-electron density of 2×1018 cm3. We focus on the high-bias regime above VB = 2.5 V of Fig. 2(a) where most of the interband tunneling should occur in the depletion region on the collector side [Jinter,2 in Fig. 1(c)]. And because of the high-quality of the InGaAs/AlAs heterostructure (very few traps or deep levels), most of the holes should reach the emitter side by some combination of drift, diffusion, and tunneling through the valence-band double barriers (Type-I offset) between InGaAs and AlAs. The computed interband current density Jinter is shown in Fig. 3(a) along with the total current density Jtot. At the maximum Jinter (at VB=3.0 V) of 7.4×102 A/cm2, we get i = Jinter/Jtot = 0.18, which is surprisingly high considering there is no p-type doping in the device. When combined with the Auger-limited r of 0.41 and c ≈ 3.4×10-4, we find a model value of IQE = 7.4% in good agreement with experiment. This leads to the model values for EQE plotted in Fig. 2(b) - also in good agreement with experiment. Finally, we address the high Jinter and consider a possible universal nature of the light-emission mechanism. Fig. 3(b) shows the tunneling probability T according to the Kane two-band model in the three materials, In0.53Ga0.47As, GaAs, and GaN, following our observation of a similar electroluminescence mechanism in GaN/AlN RTDs (due to strong polarization field of wurtzite structures) [8]. The expression is Tinter = (2/9)∙exp[(-2 ∙Ug 2 ∙me)/(2h∙P∙E)], where Ug is the bandgap energy, P is the valence-to-conduction-band momentum matrix element, and E is the electric field. Values for the highest calculated internal E fields for the InGaAs and GaN are also shown, indicating that Tinter in those structures approaches values of ~10-5. As shown, a GaAs RTD would require an internal field of ~6×105 V/cm, which is rarely realized in standard GaAs RTDs, perhaps explaining why there have been few if any reports of room-temperature electroluminescence in the GaAs devices. [1] E.R. Brown,et al., Appl. Phys. Lett., vol. 58, 2291, 1991. [5] S. Sze, Physics of Semiconductor Devices, 2nd Ed. 12.2.1 (Wiley, 1981). [2] M. Feiginov et al., Appl. Phys. Lett., 99, 233506, 2011. [6] L. Coldren, Diode Lasers and Photonic Integrated Circuits, (Wiley, 1995). [3] Y. Nishida et al., Nature Sci. Reports, 9, 18125, 2019. [7] E.O. Kane, J. of Appl. Phy 32, 83 (1961). [4] P. Fakhimi, et al., 2019 DRC Conference Digest. [8] T. Growden, et al., Nature Light: Science & Applications 7, 17150 (2018). [5] S. Sze, Physics of Semiconductor Devices, 2nd Ed. 12.2.1 (Wiley, 1981). [6] L. Coldren, Diode Lasers and Photonic Integrated Circuits, (Wiley, 1995). [7] E.O. Kane, J. of Appl. Phy 32, 83 (1961). [8] T. Growden, et al., Nature Light: Science & Applications 7, 17150 (2018).« less
  2. The absorption spectra of molecular organic chromophores in aqueous media are of considerable importance in environmental chemistry. In this work, the UV-vis spectra of benzoic acid (BA), the simplest aromatic carboxylic acid, in aqueous solutions at varying pH and in the presence of salts are measured experimentally. The solutions of different pH provide insights into the contributions from both the non-dissociated acid molecule and the deprotonated anionic species. The microscopic interpretation of these spectra is then provided by quantum chemical calculations for small cluster models of benzoic species (benzoic acid and benzoate anion) with water molecules. Calculations of the UV-vis absorbance spectra are then carried out for different clusters such as C 6 H 5 COOH·(H 2 O) n and C 6 H 5 COO − ·(H 2 O) n , where n = 0–8. The following main conclusions from these calculations and the comparison to experimental results can be made: (i) the small water cluster yields good quantitative agreement with observed solution experiments; (ii) the main peak position is found to be very similar at different levels of theory and is in excellent agreement with the experimental value, however, a weaker feature about 1 eV to lower energy (redmore »shift) of the main peak is correctly reproduced only by using high level of theory, such as Algebraic Diagrammatic Construction (ADC); (iii) dissociation of the BA into ions is found to occur with a minimum of water molecules of n = 8; (iv) the deprotonation of BA has an influence on the computed spectrum and the energetics of the lowest energy electronic transitions; (v) the effect of the water on the spectra is much larger for the deprotonated species than for the non-dissociated acid. It was found that to reproduce experimental spectrum at pH 8.0, additional continuum representation for the extended solvent environment must be included in combination with explicit solvent molecules ( n ≥ 3); (vi) salts (NaCl and CaCl 2 ) have minimal effect on the absorption spectrum and; (vii) experimental results showed that B-band of neutral BA is not sensitive to the solvent effects whereas the effect of the water on the C-band is significant. The water effects blue-shift this band up to ∼0.2 eV. Overall, the results demonstrate the ability to further our understanding of the microscopic interpretation of the electronic structure and absorption spectra of BA in aqueous media through calculations restricted to small cluster models.« less
  3. We conducted a tip-enhanced Raman scattering spectroscopy (TERS) and photoluminescence (PL) study of quasi-1D TaSe 3− δ nanoribbons exfoliated onto gold substrates. At a selenium deficiency of δ ∼ 0.25 (Se/Ta = 2.75), the nanoribbons exhibit a strong, broad PL peak centered around ∼920 nm (1.35 eV), suggesting their semiconducting behavior. Such nanoribbons revealed a strong TERS response under 785 nm (1.58 eV) laser excitation, allowing for their nanoscale spectroscopic imaging. Nanoribbons with a smaller selenium deficiency (Se/Ta = 2.85, δ ∼ 0.15) did not show any PL or TERS response. The confocal Raman spectra of these samples agree with the previously-reported spectra of metallic TaSe 3 . The differences in the optical response of the nanoribbons examined in this study suggest that even small variations in Se content can induce changes in electronic band structure, causing samples to exhibit either metallic or semiconducting character. The temperature-dependent electrical measurements of devices fabricated with both types of materials corroborate these observations. The density-functional-theory calculations revealed that substitution of an oxygen atom in a Se vacancy can result in band gap opening and thus enable the transition from a metal to a semiconductor. However, the predicted band gap is substantially smaller thanmore »that derived from the PL data. These results indicate that the properties of van der Waals materials can vary significantly depending on stoichiometry, defect types and concentration, and possibly environmental and substrate effects. In view of this finding, local probing of nanoribbon properties with TERS becomes essential to understanding such low-dimensional systems.« less
  4. We report on growth and electrical properties of α-Ga2O3films prepared by halide vapor phase epitaxy (HVPE) at 500 °C on α-Cr2O3buffers predeposited on sapphire by magnetron sputtering. The α-Cr2O3buffers showed a wide microcathodoluminescence (MCL) peak near 350 nm corresponding to the α-Cr2O3bandgap and a sharp MCL line near 700 nm due to the Cr+intracenter transition. Ohmic contacts to Cr2O3were made with both Ti/Au or Ni, producing linear current–voltage ( I– V) characteristics over a wide temperature range with an activation energy of conductivity of ∼75 meV. The sign of thermoelectric power indicated p-type conductivity of the buffers. Sn-doped, 2- μm-thick α-Ga2O3films prepared on this buffer by HVPE showed donor ionization energies of 0.2–0.25 eV, while undoped films were resistive with the Fermi level pinned at ECof 0.3 eV. The I– V and capacitance–voltage ( C– V) characteristics of Ni Schottky diodes on Sn-doped samples using a Cr2O3buffer indicated the presence of two face-to-face junctions, one between n-Ga2O3and p-Cr2O3, the other due to the Ni Schottky diode with n-Ga2O3. The spectral dependence of the photocurrent measured on the structure showed the presence of three major deep traps with optical ionization thresholds near 1.3, 2, and 2.8 eV. Photoinduced current transient spectroscopy spectra of the structures were dominated bymore »deep traps with an ionization energy of 0.95 eV. These experiments suggest another pathway to obtain p–n heterojunctions in the α-Ga2O3system.

    « less
  5. Delafossite structured ternary nitrides, ABN 2 , have been of recent experimental investigation for applications such as tandem solar and photoelectrochemical cells. We present a thorough first principles computational investigation of their stability, electronic structure, and optical properties. Nine compounds, where A = Cu, Ag, Au and B = V, Nb, Ta, were studied. For three of these compounds, CuTaN 2 , CuNbN 2 , and AgTaN 2 , our computations agree well with experimental results. Optimized lattice parameters, formation energies, and mechanical properties have been computed using the generalized gradient approximation (GGA). Phonon density of states computed at zero-temperature shows that all compounds are dynamically unstable at low temperatures. Including finite-temperature anharmonic effects stabilizes all compounds at 300 K, with the exception of AgVN 2 . Analysis of Crystal Orbital Hamiltonian Populations (COHP) provides insight into the bonding and antibonding characters of A–N and B–N pairs. Instability at low temperatures can be attributed to strong A–N antibonding character near the Fermi energy. B–N bonding is found to be crucial in maintaining stability of the structure. AgVN 2 is the only compound to display significant B–N antibonding below the Fermi energy, as well as the strongest degree of A–N antibonding,more »both of which provide explanation for the sustained instability of this compound up to 900 K. Hybrid functional calculations of electronic and optical properties show that real static dielectric constants in the semiconductors are related to corresponding band gaps through the Moss relation. CuTaN 2 , CuNbN 2 , AgTaN 2 , AgNbN 2 , AgVN 2 , AuTaN 2 , and AuNbN 2 exhibit indirect electronic band gaps while CuVN 2 and AuVN 2 are metallic. Imaginary parts of the dielectric function are characterized by d–d interband transitions in the semiconductors and d–d intraband transitions in the metals. Four compounds, CuTaN 2 , CuNbN 2 , AgTaN 2 , and AgNbN 2 , are predicted to exhibit large light absorption in the range of 1.0 to 1.7 eV, therefore making these materials good candidates for solar-energy conversion applications. Two compounds, AuTaN 2 and AuNbN 2 , have band gaps and absorption onsets near the ideal range for obtaining high solar-cell conversion efficiency, suggesting that these compounds could become potential candidates as absorber materials in tandem solar cells or for band-gap engineering by alloying.« less