Temperature-dependent Absorption Research Articles

Activationless Charge Transfer Drives Photocurrent Generation in Organic Photovoltaic Blends Independent of Energetic Offset.

Organic photovoltaics (OPVs) have recently shown substantial progress in enhancing device efficiency, driven in particular by advances in the design of nonfullerene acceptors and the reduction of the energy offset driving exciton separation at the donor/acceptor interface. Herein, we employ temperature-dependent transient absorption spectroscopy to investigate the activation energy for charge generation and recombination in a range of bulk heterojunction blends with nonfullerene acceptors. Remarkably, we find that in all cases charge generation is almost activationless, in the range of 11-21 meV, independent of energetic offset. Geminate recombination is also observed to be almost activationless, with only the kinetics of bimolecular charge recombination being strongly temperature-dependent, with an activation energy >400 meV. Our observation of essentially activationless charge generation, independent of energy offset, strongly indicates that charge generation in such blends does not follow Marcus theory but can rather be considered an adiabatic process associated with the motion of thermally unrelaxed carriers.

Molecular Design and Synthetic Approaches for the Realization of Multichannel Radiative Decay Pathways in Gold(III) Complexes and Their Applications in Organic Light-Emitting Devices.

A unique class of tridentate diaryltriazine ligand-containing gold(III) complexes with thermally activated delayed fluorescence (TADF) and/or thermally stimulated delayed phosphorescence (TSDP) properties has been designed and synthesized. With a simple structural modification on the coordination of carbazole moiety in the monodentate ligand, a large spectral shift of ∼160 nm (ca. 4900 cm-1) spanning from sky blue to red emissions has been demonstrated in solid-state thin films. Three-state or four-state models have been employed in fitting the emission lifetimes of the gold(III) complexes at various temperatures. The findings clearly indicate the presence of three emitting states, S1, T1, and T1', suggesting the coexistence of TADF, phosphorescence, and TSDP. Notably, a minor structural change in the donor moiety between phenylcarbazolyl and diphenylaminoaryl has been demonstrated to turn on/off the TSDP, resulting in TADF-TSDP-phosphorescence or TADF-phosphorescence emitters. The TADF and/or TSDP properties have also been supported by temperature-dependent ultrafast transient absorption studies, with the direct observation of reverse intersystem crossing (RISC) and reverse internal conversion (RIC) and the determination of the activation parameters and excited state dynamics. Solution-processed and vacuum-deposited organic light-emitting devices (OLEDs) have been prepared, in which sky blue emitting devices based on 5 exhibit an operational lifetime LT70 ∼ 5 times longer than the previously reported sky blue emitting analogue that shows only TSDP property. These results have provided valuable insights into the manipulation of the excited states via rational molecular design toward the realization of gold(III)-based TSDP and/or TADF materials with multiple radiative decay pathways that show enhanced radiative decay rate constants (kr) for practical OLED applications.

Exploring the denaturations in cancer and non-cancer DNA molecules by optical absorption, thermal, and electric measurements: A case study

In this article, we carried out the temperature dependent UV-Visible (UV-Vis) spectroscopy, differential scanning calorimetry (DSC), and electrical studies for normal and cancerous (glioma) DNA samples of single patient. Based on this method, we were able to monitor the denaturation process and thermal stability in these molecules. From the temperature dependent optical absorption data, we calculated various optical parameters for these two types of samples. The optical band gap of these samples were also estimated and discussed as per the experimental conditions. The various optical parameters calculated indicate that mutated (tumor) DNA is less stable than the normal one. From the DSC data, clear melting peaks were observed for the tumor and normal samples. Also various thermodynamic parameters like change in enthalpy (ΔH), entropy (ΔS), and specific heat (Cp) were estimated. From the thermal study, it seems that the tumor DNA is less stable. Further from the electrical or current-voltage (I-V) characteristics data, the resistance for normal DNA decreases with temperature. But for tumor sample, it show anomalous behavior (like decreasing and then increasing trend) with temperature. For electrical transport, small polaron hopping could be the possible transport mechanism in the current sample. Here from these studies, the tumor sample seems more disordered, and structural fluctuations due to the speculated structure could be the best reason for this behavior. If such kind of molecular (at nano scale range) studied are done more vividly, then these calculated parameters of the molecule could be explored for further confirmation/diagnostics of the diseases in addition to clinical investigations.

Temperature-dependent optical and dielectric properties of polyvinyl chloride and polystyrene blends in terahertz regime

Terahertz time-domain spectroscopy (THz-TDS) has been used to study the temperature-dependent refractive index, absorption coefficient and dielectric constant of polyvinyl chloride/polystyrene (PVC/PS) blends in frequency range of 0.2–1.8 THz. Moreover, the Sellmeier and thermo optic coefficients of PVC/PS blends with different weight ratios have been explored in the temperature range of 25–80 °C. These parameters are used to evaluate the dispersion properties of these blends in the observed frequency range. A clear indication of temperature dependence on the values of refractive index and the real dielectric constant of these blends have been observed. Their values decrease linearly with increasing temperature up to 80 °C. Whereas, no noticeable change has been observed in the imaginary dielectric constant and the absorption coefficient. These results provide a database of temperature-dependent optical and dielectric parameters of PVC/PS polymer blends for their efficient utilization for device fabrication in THz technology.

An imidazole-copper(I) metallacycle complex exhibiting thermochromic fluorescence.

In this paper, we firstly report the synthesis and structural characterization of a discrete coordination metallacycle complex, [CuI (bipy)]2 (1). The x-ray diffraction structure, temperature-dependent electronic absorption, and photoluminescence spectra have been investigated. The solid-state fluorescence at variable temperatures shows that complex 1 exhibits an obvious thermochromic fluorescence. At low temperature, the dual fluorescence with peaks at 590 and 694 nm was observed. The emission color significantly changes from red at 77 K to yellow at 200 K and blue-green at 330 K. The thermochromic fluorescent molecular materials show great potential as temperature sensing.

Optical Study on Temperature-Dependent Absorption Edge of γ-InSe-Layered Semiconductor

We have studied the variations in the temperature-dependent absorption edge of a bulk InSe-layered semiconductor using photoconductivity (PC) measurements. From both the X-ray diffraction (XRD) and Raman experimental results, the structural phase of the as-prepared InSe sample was confirmed to be γ-polytype. Upon heating from 15 K to 300 K, the absorption edge of PC spectra was found to shift significantly toward lower energy, and the absorption edge as a function of temperature was further analyzed by the Varshni’s relationship and Bose–Einstein empirical equation. The Urbach energy as a function of temperature was obtained by fitting the absorption tail below the absorption coefficient of the PC spectrum, and the effective phonon energy can be derived from the temperature-dependent steepness parameter associated with Urbach energy. Our study indicates that the broadening of the absorption edge in the as-synthesized bulk γ-InSe is caused by a combination of electron/exciton–phonon interactions and thermal/structural disorder.

VUV absorption spectra of water and nitrous oxide by a double-duty differentially pumped gas filter.

The differentially pumped rare-gas filter at the end of the VUV beamline of the Swiss Light Source has been adapted to house a windowless absorption cell for gases. Absorption spectra can be recorded from 7 eV to up to 21 eV photon energies routinely, as shown by a new water and nitrous oxide absorption spectrum. By and large, the spectra agree with previously published ones both in terms of resonance energies and absorption cross sections, but that of N2O exhibits a small shift in the {\tilde{\bf D}} band and tentative fine structures that have not yet been fully described. This setup will facilitate the measurement of absorption spectra in the VUV above the absorption edge of LiF and MgF2 windows. It will also allow us to carry out condensed-phase measurements on thin liquid sheets and solid films. Further development options are discussed, including the recording of temperature-dependent absorption spectra, a stationary gas cell for calibration measurements, and the improvement of the photon energy resolution.

Solvatochromism mechanism of perylene diimide radicals stabilized by low barrier hydrogen bond and detection of formaldehyde in real food samples

Formaldehyde (FA) is widely used for food preservation and whitening because of its preservative and bleaching effects. Excessive FA seriously endangers human health, so monitoring FA-treated food is of great significance for food safety. In this paper, perylene diimide radicals with the chirality (BTFPDI) and water-solubility (TFPDI-bPEI) were designed respectively based on our previous studies. Property of solvatochromism induced by these perylene diimide radicals aggregation was demonstrated by the concentration and temperature dependent absorption spectrum and the circular dichroism spectrum. Further the colorimetric monitoring of trace FA in gaseous and liquid was realized by the condensation reaction of FA with amine to induce TFPDI-bPEI aggregation. After the addition of FA, TFPDI-bPEI molecule aggregated in aqueous solution due to the specific reaction of a large number of –NH2 groups with FA, resulting in a blue-shift of the maximum absorption peak from 780 nm to 561 nm, and the detection limit as low as 0.86 μM to FA and the response time of only 20 s. This method could further detect FA in food with good recoveries and detect FA in contaminated food samples.

Application Of Two Dye Two-Color Laser-Induced Fluorescence Spectroscopy On Droplets Of Green Solvent Mixtures Containing Water And Ethanol

In order to reach a higher sustainability, the utilization of green solvents is decisive in many technical applications. Water and ethanol substitute more complex solvents, showing advantages like ecological manufacturing, reusability or biodegradation. Both liquids are found in various industrial areas, ranging from a use as additives in biofuels, coolants or solvents for extraction in pharmaceutical, medical or food industries. Regarding these industrial processes, important variables are the liquid phase temperature and the composition in binary fluids. The focus of this work is two dye two-color laser induced fluorescence (2c-LIF) measurements in ethanol, water and their mixtures. Liquid phase thermometry via 2c LIF requires a selection of suitable fluorescence dyes regarding solubility, temperature sensitivity and the interaction among the dyes themselves. A mixture of a temperature sensitive and a temperature insensitive dye is used in order to reach a large change in signal ratio for thermometry. In this work, two dyes – fluorescein disodium (FL) and sulforhodamine 101 (SRh), as proposed by Chaze et al. (Chaze et al. 2016) – are analyzed regarding their absorption and emission behavior in various ethanol/water mixtures, which are examples of "green solvents". The absorption spectra of the dissolved dye mixture are measured with a spectrophotometer at temperatures from 293 K to 343 K. Information on the temperature dependent absorption of the single dyes and reabsorption effects in ethanol/water mixtures is obtained. Additionally, the fluorescence of the mixtures is analyzed spectrally and by an imaging system. Therefore, a fiber coupled spectrometer and a system with two sCMOS cameras equipped with a long distance (LD) microscope are applied for simultaneous detection of the signal of tempered solutions a monodisperse droplet chain. A study of small droplets with sizes below 50 μm are evaluated and the limit of the spectral detection system is determined and discussed. The application of the measurement technique to several solvent mixtures is investigated. Additionally, an application for composition investigations of binary water/ethanol droplets via 3c-LIF is proposed.

Impact of the spatial structure of alkyl chains on properties of thiophene-substituted diketopyrrolopyrroles: Part II – Spectroscopic study

The study concerns the impact of a difference in geometry of the side alkyl chains of oligothiophene derivatives of diketopyrrolopyrrole (DPP) on their spectroscopic properties and aggregation in solutions, in Langmuir layers, and thin films. Using a combination of theoretical and experimental approaches, this study aims to explain the aggregating behaviour of thiophene-substituted DPP derivatives. Various methods were used to characterise the dyes, including absorption spectroscopy also with polarized light, fluorescence spectroscopy, Langmuir techniques, and time-dependent density functional theory (TD-DFT) calculations. The presented results emphasise a significant impact of side alkyl chains on DPP's molecular behaviour, notably evident in thin-layer structures. Interestingly, the deconvolution of the absorption spectra revealed three bands in the red region. Insightful analysis of temperature-dependent absorption, excitation, and emission fluorescence spectra indicates the co-existence of monomer, dimer, and a higher aggregate forms, most likely a tetrameric structures. Moreover, such a complexity of molecular organisation of dyes appears already in the solution. Differences in spectral properties of the dyes studied are robustly visible in changes in the spectra of the air–water interface, where the dye with the branched side group changes the mutual orientation in dimeric structures, leading to the formation of H-type aggregates, which was observed as an almost 20-nm spectral blue shift during Langmuir layer compression. The results presented highlight the need for care in interpretation of the intensity ratio of DPP spectra and spectral shift as the sole determinants of the aggregation state.

Study on temperature-sensitive factors relevant to thermographic features of Tb3+-doped phosphate glasses

Intensities of the 5D4 luminescence with the 5D3 level populated by GSA and ESA transitions of Tb3+ in ternary phosphate glass were measured at different temperature between 300 K and 675 K. Acquired 5D4 luminescence intensities related to GSA and ESA excitation transitions from thermally coupled 7F6 and 7F5 levels were treated to assess luminescence intensity ratios (LIR) as a function of temperature and resulting values of relative sensitivity SR. To understand origin of marked dissimilarity of SR values observed in some few Tb3+-doped hosts reported thus far an in-depth analysis of the excitation energy flow in systems under study is made. Spectra of absorption cross section and temperature dependent absorption coefficient for ESA transition were evaluated. Rates of temperature dependent cross relaxation process governing energy transfer between 5D3 and 5D4 were calculated. It was supposed that temperature-dependent absorption of colour centres in the blue region may affect adversely relative thermal sensitivity.

Revealing the Singlet Fission Mechanism for a Silane-Bridged Thienotetracene Dimer.

Tetraceno[2,3-b]thiophene is regarded as a strong candidate for singlet fission-based solar cell applications due to its mixed characteristics of tetracene and pentacene that balance exothermicity and triplet energy. An electronically weakly coupled tetraceno[2,3-b]thiophene dimer (Et2Si(TIPSTT)2) with a single silicon atom bridge has been synthesized, providing a new platform to investigate the singlet fission mechanism involving the two acene chromophores. We study the excited state dynamics of Et2Si(TIPSTT)2 by monitoring the evolution of multiexciton coupled triplet states, 1TT to 5TT to 3TT to T1 + S0, upon photoexcitation with transient absorption, temperature-dependent transient absorption, and transient/pulsed electron paramagnetic resonance spectroscopies. We find that the photoexcited singlet lifetime is 107 ps, with 90% evolving to form the TT state, and the complicated evolution between the multiexciton states is unraveled, which can be an important reference for future efforts toward tetraceno[2,3-b]thiophene-based singlet fission solar cells.

Temperature-dependent local structure and lattice dynamics of 1T-TiSe[formula omitted] and 1T-VSe[formula omitted] probed by X-ray absorption spectroscopy

The local atomic structure and lattice dynamics of two isostructural layered transition metal dichalcogenides (TMDs), 1T-TiSe2 and 1T-VSe2, were studied using temperature-dependent X-ray absorption spectroscopy at the Ti, V, and Se K-edges. Analysis of the extended X-ray absorption fine structure (EXAFS) spectra, employing reverse Monte Carlo (RMC) simulations, enabled tracking of the temperature evolution of the local environment in the range of 10–300 K. The atomic coordinates derived from the final atomic configurations obtained using the RMC method were used to calculate the partial radial distribution functions (RDFs) and the mean-square relative displacement (MSRD) factors for the first ten coordination shells around the absorbing atoms. Characteristic Einstein frequencies and effective force constants were determined for TiSe, TiTi, VSe, VV, and SeSe atom pairs from the temperature dependencies of MSRDs. The obtained results reveal differences in the temperature evolution of lattice dynamics and the strengths of intralayer and interlayer interactions in TiSe2 and VSe2.

Wavelength-equilibrium temperature dual-tunable photothermal convertible materials for temperature-controlled therapy of cancer

Mild photothermal therapy (PTT) at temperature window of 42–47 °C has received tremendous attention for its minor heat damage to the normal tissues. As the critical step in mild PTT process, accurate temperature control still suffers from the complex environment of tumor tissue. Here we proposed a wavelength-equilibrium temperature dual-tunable temperature-controlled PTT strategy based on oligonucleotides (OGN) assembled Au nanomaterials. The NIR absorption of the Au nanomaterials enhances with the plasmon coupling caused by the OGN assembly, and rapidly reverts upon the melting temperature (Tm) of the OGN in the PTT process. The temperature-dependent NIR absorption enables the Au assembly geometry to be exempt from the external disturbance and maintain the equilibrium temperature at the Tm of the OGN. In vivo experiments have confirmed that the OGN assembled Au nanomaterials can effectively ablate the tumor with minimal side effects.

Evidence of local structural distortions and subtle thermal disorder in transparent photochromic yttrium oxyhydride

The structural properties of photochromic yttrium oxyhydride powder in its transparent state were examined using x-ray diffraction and temperature-dependent extended x-ray absorption fine structure spectroscopy (EXAFS) combined with reverse Monte Carlo (RMC) simulations. The refinement of the x-ray powder diffraction pattern, employing the Rietveld method, indicates that yttrium oxyhydride crystallizes in the nanocrystalline phase with the cubic space group Fm-3m (225), at room temperature. The lattice parameter was determined as a = 5.404(3) Å, and the nanocrystallite size was estimated at d = 16(2) nm. The partial radial distribution functions (RDFs) g(r) for Y–O, O–O, and Y–Y atom pairs were obtained from the results of the RMC simulations of the Y K-edge EXAFS spectra measured at three temperatures (10, 150, and 300 K). The analysis of the RDFs reveals a subtle impact of the thermal disorder and splitting of the second coordination shell of yttrium atoms (the Y–Y RDF), remaining at all temperatures. This observation, also supported by our density functional theory calculations, suggests the presence of local structural distortions associated with yttrium sites, which do not affect the long-range crystal order.

Temperature-dependent chlorosomal self-aggregation of bacteriochlorophyll-d analogs with a branched alkyl chain in a single 1-chlorooctane solvent

Abstract Recently, the supramolecular polymerization of chlorophyll pigments mimicking a natural light-harvesting apparatus (chlorosome) was demonstrated in low-polar organic solvents or aqueous solutions. To obtain the most aggregation models, a concentrated solution of the pigments in a polar organic solvent was diluted with a large amount of a nonpolar organic solvent or water. Here, bacteriochlorophyll-d analogs possessing branched alkyl chains of different lengths at the peripheral 17-propionate residue on the core chlorin π-system were prepared and their highly soluble chlorosomal supramolecules were produced in single 1-chlorooctane as a low-polar solvent. Temperature-dependent electronic absorption and circular dichroism spectroscopies were employed to analyze their self-aggregation and disaggregation mechanisms. The synthetic analogs were monomeric at high temperatures and self-aggregated during cooling of the hot solution through a non-sigmoidal pathway. The obtained chlorosomal self-aggregates were reversibly monomerized by heating the homogeneous solution. The disaggregation pathway was fitted to an isodesmic model whose melting points depended on the alkyl-chain lengths.

Influence of temperature on bandgap shifts, optical properties and photovoltaic parameters of GaAs/AlAs and GaAs/AlSb p–n heterojunctions: insights from ab-initio DFT + NEGF studies

The III–V group semiconductors are highly promising absorbers for heterojunctions based solar cell devices due to their high conversion efficiency. In this work, we explore the solar cell properties and the role of electron–phonon coupling (EPC) on the solar cell parameters of GaAs/AlSb and GaAs/AlAs p–n heterojunctions using non-equilibrium Green function method (NEGF) in combination of ab-initio density functional theory (DFT). In addition, the band offsets at the heterointerfaces, optical absorption and bandgap shifts (BGSs) due to temperature are estimated using DFT + NEGF approach. The interface band gaps in heterostructures are found to be lower than bulk band gaps leading to a shift in optical absorption coefficient towards lower energy side that results in stronger photocurrent. The temperature dependent electronic BGS is significantly influenced by the phonon density and phonon energy via EPC. The phonon influenced BGS is found to change the optical absorption, photocurrent density and open-circuit voltage. In case of GaAs/AlSb junction, the interface phonons are found to have significantly higher energies as compared to the bulk phonons and thereby may have important implications for photovoltaic (PV) properties. Overall, the present study reveals the influence of EPC on the optical absorption and PV properties of GaAs/AlSb and GaAs/AlSb p–n heterojunctions. Furthermore, the study shows that the DFT + NEGF method can be successfully used to obtain the reasonable quantitative estimates of temperature dependent BGSs, optical absorption and PV properties of p–n heterojunctions.

Temperature-dependent tuning of band gap of Fe3O4 nanoparticles for optoelectronic applications

We have investigated structural, morphological and temperature dependent absorption characteristics of Fe3O4 nanoparticles. X-ray diffraction pattern exhibited six diffraction peaks belonging to the cubic phase structure with lattice parameter of a = 8.1602 Å. Spectral variation of absorption coefficient were utilized to achieve Tauc and spectral derivative analyses providing the band gap of the Fe3O4 at varying temperature. The band gap of Fe3O4 nanoparticles was found around 2.08 eV at 300 K and around 2.14 eV at 10 K. The band gap variation with applied temperatures between 10 and 300 K were also investigated using Varshni relation.

Sensitive Thermochromic Behavior of InSeI, a Highly Anisotropic and Tubular 1D van der Waals Crystal.

Thermochromism, the change in color of a material with temperature, is the fundamental basis of optical thermometry. A longstanding challenge in realizing sensitive optical thermometers for widespread use is identifying materials with pronounced thermometric optical performance in the visible range. Herein, it is demonstrated that single crystals of indium selenium iodide (InSeI), a 1D van der Waals (vdW) solid consisting of weakly bound helical chains, exhibit considerable visible range thermochromism. A strong temperature-dependent optical band edge absorption shift ranging from 450 to 530 nm (2.8 to 2.3 eV) over a 380 K temperature range with an experimental (dEg/dT)max value extracted to be 1.26 × 10-3 eV K-1 is shown. This value lies appreciably above most dense conventional semiconductors in the visible range and is comparable to soft lattice solids. The authors further seek to understand the origin of this unusually sensitive thermochromic behavior and find that it arises from strong electron-phonon interactions and anharmonic phonons that significantly broaden band edges and lower the Eg with increasing temperature. The identification of structural signatures resulting in sensitive thermochromism in 1D vdW crystals opens avenues in discovering low-dimensional solids with strong temperature-dependent optical responses across broad spectral windows, dimensionalities, and size regimes.

Evidence of Temperature-Dependent Interplay between Spin and Orbital Moment in van der Waals Ferromagnet VI3.

van der Waals materials provide a versatile toolbox for the emergence of new quantum phenomena and fabrication of functional heterostructures. Among them, the trihalide VI3 stands out for its unique magnetic and structural landscape. Here we investigate the spin and orbital magnetic degrees of freedom in the layered ferromagnet VI3 by means of temperature-dependent X-ray absorption spectroscopy and X-ray magnetic circular and linear dichroism. We detect localized electronic states and reduced magnetic dimensionality, due to electronic correlations. We furthermore provide experimental evidence of (a) an unquenched orbital magnetic moment (up to 0.66(7) μB/V atom) in the ferromagnetic state and (b) an instability of the orbital moment in the proximity of the spin reorientation transition. Our results support a coherent picture where electronic correlations give rise to a strong magnetic anisotropy and a large orbital moment and establish VI3 as a prime candidate for the study of orbital quantum effects.