Temperature-dependent Optical Absorption Spectra Research Articles

Phonon-assisted optical absorption of SiC polytypes from first principles

Silicon carbide (SiC) is an indirect-gap semiconductor material widely used in electronic and optoelectronic applications. While experimental measurements of the phonon-assisted absorption coefficient of SiC across its indirect gap have existed for more than 50 years, theoretical investigations of phonon-assisted absorption have been hampered by their excessive computational cost. In this work, we calculate the phonon-assisted temperature-dependent optical absorption spectra of the commonly occurring SiC polytypes (3C, 2H, 4H, 6H, and 15R), using first-principles approaches based on density functional theory and related techniques. We show that our results agree with experimentally determined absorption coefficients in the spectral region between the direct and indirect band gaps. The temperature dependence of the spectra can be well predicted with taking the temperature dependence of the band gaps into account. Lastly, we compare the spectra obtained with second-order perturbation theory to those determined by the special displacement method and we show that the full consideration of the electronic energy renormalization due to temperature is important to further improve the prediction of the phonon-assisted absorption in SiC. Our insights can be applied to predict the optical spectra of the less common SiC polytypes and other indirect-gap semiconductors in general.

Size-Dependent Thermal Shifts to MOF Nanocrystal Optical Gaps Induced by Dynamic Bonding

Conventional semiconductor nanocrystals exhibit wide-ranging optical behavior, whereas the size-dependent photophysical properties of metal-organic framework (MOF) nanocrystals remain an open research frontier. Here, we present size- and temperature-dependent optical absorption spectra of common MOFs with particle sizes ranging from tens of nanometers to several micrometers. All materials exhibit optical gaps that decrease at elevated temperatures, which we attribute to the dynamic nature of MOF metal-linker bonds. Accordingly, whereas the labile titanium-carboxylate bonds of MIL-125 give rise to bandgaps that red-shift by ∼600 meV over 300 K, the more rigid zinc-imidazolate bonds of ZIF-8 produce a red-shift of only ∼10 meV. Furthermore, smaller particles induce far larger decreases to optical gaps. Taken together, these results suggest MOF bonding becomes more flexible with smaller nanocrystal sizes, offering a powerful tool for manipulating optical behavior through composition, temperature, and dimensionality.

Solvent Induced Helix Folding of Defined Indolenine Squaraine Oligomers.

A protecting group strategy was employed to synthesise a series of indolenine squaraine dye oligomers up to the nonamer. The longer oligomers show a distinct solvent dependence of the absorption spectra, that is, either a strong blue shift or a strong red shift of the lowest energy bands in the near infrared spectral region. This behaviour is explained by exciton coupling theory as being due to H‐ or J‐type coupling of transition moments. The H‐type coupling is a consequence of a helix folding in solvents with a small Hansen dispersity index. DOSY NMR, small angle neutron scattering (SANS), quantum chemical and force field calculations agree upon a helix structure with an unusually large pitch and open voids that are filled with solvent molecules, thereby forming a kind of clathrate. The thermodynamic parameters of the folding process were determined by temperature dependent optical absorption spectra.

Analytical fitting of temperature-dependent spin-flip transitions in absorption spectra of Cr3+-doped silicate glasses

Temperature-dependent optical absorption spectra have been recorded for Cr3+ doped silicate glasses between 10 K and 773 K. Due to the intermediate ligand field strength of the Cr3+ coordination environment, overlap of the lowest-energy spin-allowed 4A2 → 4T2 band and the two spin-forbidden transitions to the 2E and 2T1 states at approximately 650 nm results in interference dips. An analytical model equation is fitted to the spectra and electronic structure parameters extracted. This represents the first time that variations of these parameters with temperature are obtained over a large temperature range, revealing characteristics of all three overlapping d-d transitions.

Enhanced Charge Carrier Transport and Device Performance Through Dual-Cesium Doping in Mixed-Cation Perovskite Solar Cells with Near Unity Free Carrier Ratios.

PbI2-enriched mixed perovskite film [FA0.81MA0.15Pb(I0.836Br0.15)3] has been widely studied due to its great potential in perovskite solar cell (PSC) applications. Herein, a FA0.81MA0.15Pb(I0.836Br0.15)3 film has been fabricated with the temperature-dependent optical absorption spectra utilized to determine its exciton binding energy. A ∼13 meV exciton binding energy is estimated, and a near-unity fraction of free carriers out of the total photoexcitons has been obtained in the solar cell operating regime at equilibrium state. PSCs are fabricated with this mixed perovskite film, but a significant electron transport barrier at the TiO2-perovskite interface limited their performance. Cs2CO3 and CsI are then utilized as functional enhancers with which to substantially balance the electron and hole transport and increase the carriers (both electrons and holes) mobilities in PSCs, resulting in much-improved solar-cell performance. The modified PSCs exhibit reproducible power conversion efficiency (PCE) values with little hysteresis effect in the J-V curves, achieving PCEs up to 19.5% for the Cs2CO3-modified PSC and 20.6% when subsequently further doped with CsI.

Lowest energy Frenkel and charge transfer exciton intermixing in one-dimensional copper phthalocyanine molecular lattice

We report the results of the combined experimental and theoretical studies of the low-lying exciton states in crystalline copper phthalocyanine. We derive the eigen energy spectrum for the two lowest intramolecular Frenkel excitons coupled to the intermolecular charge transfer exciton state and compare it with temperature dependent optical absorption spectra measured experimentally, to obtain the parameters of the Frenkel-charge-transfer exciton intermixing. The two Frenkel exciton states are spaced apart by 0.26 eV, and the charge transfer exciton state is 50 meV above the lowest Frenkel exciton. Both Frenkel excitons are strongly mixed with the charge transfer exciton, showing the coupling constant 0.17 eV which agrees with earlier experimental measurements. These results can be used for the proper interpretation of the physical properties of crystalline phthalocyanines.

One-shot calculation of temperature-dependent optical spectra and phonon-induced band-gap renormalization

Recently, Zacharias et al [Phys. Rev. Lett. 115, 177401 (2015)] developed a new ab initio theory of temperature-dependent optical absorption spectra and band gaps in semiconductors and insulators. In that work the zero-point renormalization and the temperature dependence were obtained by sampling the nuclear wavefunctions using a stochastic approach. In the present work, we show that the stochastic sampling can be replaced by fully deterministic supercell calculations based on a single optimal configuration of the atomic positions. We demonstrate that a single calculation is able to capture the temperature-dependent band gap renormalization including quantum nuclear effects in direct and indirect-gap semiconductors, as well as phonon-assisted optical absorption in indirect-gap semiconductors. In order to demonstrate this methodology we calculate from first principles the temperature-dependent optical absorption spectra and the renormalization of direct and indirect band gaps in Si, C, and GaAs, and we obtain good agreement with experiment and with previous calculations. In this work we also establish the formal connection between the Williams-Lax theory of optical transitions and the related theories of indirect absorption by Hall, Bardeen, and Blatt, and of temperature-dependent band structures by Allen and Heine. Furthermore, we identify an additional band gap renormalization that arises in the case of degenerate band extrema, and which has not been considered in previous work. The present methodology enables systematic ab initio calculations of optical absorption spectra at finite temperature, including both direct and indirect transitions. This feature will be useful for high-throughput calculations of optical properties at finite temperature, and for calculating temperature-dependent optical properties using high-level theories such as GW and Bethe-Salpeter approaches.

Thermodynamic factors impacting the peptide-driven self-assembly of perylene diimide nanofibers.

Synthetic peptides offer enormous potential to encode the assembly of molecular electronic components, provided that the complex range of interactions is distilled into simple design rules. Here, we report a spectroscopic investigation of aggregation in an extensive series of peptide-perylene diiimide conjugates designed to interrogate the effect of structural variations. By fitting different contributions to temperature dependent optical absorption spectra, we quantify both the thermodynamics and the nature of aggregation for peptides by incrementally varying hydrophobicity, charge density, length, as well as asymmetric substitution with a hexyl chain, and stereocenter inversion. We find that coarse effects like hydrophobicity and hexyl substitution have the greatest impact on aggregation thermodynamics, which are separated into enthalpic and entropic contributions. Moreover, significant peptide packing effects are resolved via stereocenter inversion studies, particularly when examining the nature of aggregates formed and the coupling between π electronic orbitals. Our results develop a quantitative framework for establishing structure-function relationships that will underpin the design of self-assembling peptide electronic materials.

Temperature dependence of the optical response of perovskite-type SrIrO3 thin film

We report on the temperature-dependent optical absorption spectra of an orthorhombic SrIrO3 thin film in the energy region between 0.08 and 6 eV. The optical absorption spectra show the characteristic spectral features associated with spin-orbit coupling-induced effective total angular momentum Jeff states. A Drude-like response from the electrons in the Jeff = 1/2 bands is observed in the energy region below about 0.5 eV followed by an interband transition from the Jeff = 3/2 to the Jeff = 1/2 bands at 0.7 eV. The electron excitations between the Jeff bands exhibit a strong temperature dependence that is different from the behavior of conventional metals. The spectral weight analysis of the absorption data suggests an anomalous low-frequency electrodynamic behavior for of SrIrO3.

Synthesis and luminescence properties of lead-halide based organic–inorganic layered perovskite compounds (C nH 2 n+1 NH 3) 2PbI 4 ( n=4, 5, 7, 8 and 9)

This paper describes the synthesis and characterization of organic–inorganic layered perovskite compounds, (C n H 2 n+1 NH 3) 2PbI 4 ( n=4, 5, 7, 8 and 9). The effect of the number of carbon atoms on luminescence properties has been examined. Thin films of microcrystalline (C n H 2 n+1 NH 3) 2PbI 4 fabricated by spin-coating are highly oriented, with the c-axis perpendicular to the substrate surface. Temperature-dependent optical absorption spectra reveal that (C n H 2 n+1 NH 3) 2PbI 4 films ( n=4, 7, 8 and 9) show the structural phase transitions. The excitonic structures of (C n H 2 n+1 NH 3) 2PbI 4 vary with the number of carbon atoms of the alkyl chain length. At low temperatures below 100 K, the lowest-energy free-exciton band of (C n H 2 n+1 NH 3) 2PbI 4 ( n=7, 8 and 9) split into three fine-structure levels. In contrast to (C n H 2 n+1 NH 3) 2PbBr 4 films, (C n H 2 n+1 NH 3) 2PbI 4 ( n=7, 8 and 9) shows no triplet exciton emission, but it shows the Stokes-shifted emission from bound excitons.

Origin of the 2 eV peak in optical absorption spectra of LaMnO3: an explanation based on the orbitally degenerate Hubbard model

We investigated the temperature-dependent optical absorption spectra of LaMnO3 and NdMnO3 epitaxial thin films. We found that both spectra have strong absorption features around 2 eV, and that the 2 eV peak of LaMnO3 has a weak temperature dependence. As the La ions are replaced with Nd ions, the spectral weight of the peak becomes suppressed. From careful comparisons with the orbitally degenerate Hubbard model, we could explain most of the spectral features of the 2 eV peak observed in the absorption spectra. We also found a fine structure of three sub-peaks in the 2 eV peak, whose origin was considered based on currently available ideas.

Temperature dependence of excitonic absorption spectra in ZnO/Zn0.88Mg0.12O multiquantum wells grown on lattice-matched substrates

The excitonic properties of high-quality ZnO/Zn0.88Mg0.12O multiquantum wells grown by laser-molecular-beam epitaxy were investigated using temperature-dependent optical absorption spectra from 5 K to room temperature. The strength of exciton-longitudinal-optical (LO) -phonon coupling was deduced from the temperature dependence of the linewidth of the fundamental excitonic peak. Effective reduction of the exciton-LO-phonon coupling with decreasing the well width was observed, which is consistent with the confinement-induced enhancement of the exciton binding energy. The thermal shift of the lowest excitonic energy is independent of well width, indicating that the strain effect is negligible for this material.