Blue Shift In Absorption Spectra Research Articles

First-principles study on structural, electronic, and optical properties of mixed alloys of Cs2Ag(SbxBi1−x)Br6 double perovskites for optoelectronic applications

Halide perovskites have attracted promising capabilities of solar cells and light-emitting diode applications due to their high stability and optoelectronics performance. In this work, the effect of chemical substitution on the structural, electronics, and optical properties of mixed alloy Cs2Ag(SbxBi1-x)Br6 perovskites (when x is a mixing ratio varying from 0.0 to 1.0) was explored by using the virtual crystal approximation within the first-principle framework based on DFT-GGA, GGA-TB09, RPA, and BSE. Calculation results reveal that the lattice constant increases linearly as a function of the mixing ratio of a(x) = 11.246–0.0012x Å. These results satisfied the Vegard’s law as well as the reliability of virtual crystal approximation. The band structure calculated with and without the spin–orbit coupling was compared. Band gap of the mixed alloys are lower than that of pure Sb or pure Bi compounds. The band gap increases as a quadratic function of Eg = 2.07 – 0.279x – 0.121x2 eV. The smaller band gap of the mixed alloy results from the energy mismatch between Sb and Bb s and p orbitals. Calculations from DFT-TB09 are in good agreement with experimental results. Blue-shifted absorption spectra to the ultraviolet region were found when the Sb content increased. A linear increase of the static dielectric constant was found when the Sb content increased as a function of εs(x) = 2.849 + 0.266x. BSE@PBEsol calculations are consistent with experimental profiles. Calculation results indicate that the mixed alloy Cs2Ag(SbxBi1-x)Br6 can be tuned regarding its electronic and optical properties.

Exploring the synergistic influence of Cu and Co co-doping on the optical properties of ZnO nanoparticles

In this study, we synthesized Cu and Co co-doped ZnO nanoparticles, denoted as Zn1-2xCuxCoxO (x = 0.01, 0.02, 0.03), using the sol-gel auto-combustion method. Successful integration of Cu and Co elements into the ZnO host lattice was confirmed through a comprehensive array of spectroscopic techniques. Structural analysis revealed the persistence of a hexagonal wurtzite crystal structure with some distinct microstructural variations across all samples. Alteration in lattice parameters and dislocation density strongly suggests the successful incorporation of Cu2+ and Co2+ ions within the ZnO lattice. A prominent increase in crystallite size from 27.19 nm to 33.46 nm was observed with the increase in doping concentration. Field emission scanning electron microscopy showed a combination of uniformly distributed spherical and hexagon-like structures. Furthermore, UV–Visible absorption spectra demonstrated a proportional enhancement in energy band gap from 2.14 eV for Zn0.98Cu0.01Co0.01O to 2.40 eV for Zn0.94Cu0.03Co0.03O. The Burstein−Moss effect was invoked to elucidate the observed blue shift in absorption spectra and energy band gaps, further solidifying our findings. The systematic and substantial correlation between dopant concentration and energy band gap signifies that the co-doping of Cu and Co is a viable strategy for engineering the band gap of ZnO. This collective investigation unveils the substantial potential of Cu and Co co-doping in ZnO nanoparticles for advanced optoelectronic applications, paving the way for tailored optical and photonic functionalities.

Di-chlorinated benzothiadiazole unit: a new strong electron-withdrawing ability acceptor toward fast-switching green low band gap D-A electrochromic polymers

Di-halogenated benzothiadiazole (BT) is one of the potential acceptor units in constructing low band gap d-A polymers, but it has not attracted widespread attention, especially for the di-chlorinated BT unit. Herein, in this work, two kinds of d-π-A-π-D electrochromic conjugated precursors with di-halogenated BT (5,6-dichlorobenzo[c][1,2,5]thiadiazole and 5‑chloro-6-fluorobenzo[c][1,2,5]thiadiazole) as the acceptor unit, 3-dodecyl thiophene as the π bridge, and 3,4-ethylenedioxythiophene (EDOT) as the donor unit, were designed and synthesized, and their corresponding d-A polymers were successfully obtained by electrochemical deposition method. The photophysical study proves that introducing more chlorine atoms among the precursors will lead to stronger steric hindrance, lower HOMO energy level, blue-shifted absorption spectra, lower quantum yield, but larger Stokes shift. Both of them show very low oxidation potential, which is beneficial for them to obtain high-quality d-A polymers. The introduction of di-chlorinated BT unit obviously improved the polymers’ electroactivity and redox stability, and the remained activity of P(ClCl) was above 74.79 after 1000 cycles. The optical band gap of P(ClCl) is further reduced to 1.28 eV, and the reversible transition from the neutral dark green to the oxidized dark blue can be realized in the redox process. As a result, various favorable electrochromic parameters for P(ClCl) were achieved, such as the optical contrast in the near-infrared region is 27.23 %, the response time is as low as 0.4 s, and the coloration efficiency is as high as 151.3 cm2 C−1, as well as the good optical stability and satisfied memory effect. Overall, the subtle change of halogen atoms in BT units is a very efficient method to modulate the photophysical properties of d-π-A-π-D precursors, also providing good guidelines in designing highly efficient d-A electrochromic polymers.

Defect-induced Sr1−xPrxTiO3 crystallites by burial sintering and its optoelectronic applications

The band structure of SrTiO3 was altered by introducing Pr3+ in the Sr2+ site and subsequent graphite burial sintering. The asymmetric nature of the (310) peak in XRD and the emergence of Eg and B1g modes in the Raman spectrum suggest the transformation from cubic to tetragonal phase for the Sr1-xPrxTiO3 system with x ≥ 0.1. The development of the forbidden first-order Raman peaks and novel spectral properties are attributed to the local vibrational modes linked to oxygen vacancies. Structural variations in terms of lattice strain were investigated using a W–H plot, and morphological changes were analyzed by high-resolution FE-SEM. High infrared absorption in UV–Vis–NIR spectra and a significant reduction in band gap from 2.8 eV to 1.8 eV were accomplished through increased disorder in the lattice and the reduction of Ti4+. The blue shift in absorption spectra with Pr concentration can be used to tune the absorption range for sensing purposes. The formation of new electronic states observed here offers a novel approach for band gap modification in perovskites for photocatalytic and photovoltaic applications.

On the evolution of the plant phytochrome chromophore biosynthesis.

Phytochromes are biliprotein photoreceptors present in plants, algae, certain bacteria, and fungi. Land plant phytochromes use phytochromobilin (PΦB) as the bilin chromophore. Phytochromes of streptophyte algae, the clade within which land plants evolved, employ phycocyanobilin (PCB), leading to a more blue-shifted absorption spectrum. Both chromophores are synthesized by ferredoxin-dependent bilin reductases (FDBRs) starting from biliverdin IXα (BV). In cyanobacteria and chlorophyta, BV is reduced to PCB by the FDBR phycocyanobilin:ferredoxin oxidoreductase (PcyA), whereas, in land plants, BV is reduced to PФB by phytochromobilin synthase (HY2). However, phylogenetic studies suggested the absence of any ortholog of PcyA in streptophyte algae and the presence of only PФB biosynthesis-related genes (HY2). The HY2 of the streptophyte alga Klebsormidium nitens (formerly Klebsormidium flaccidum) has already indirectly been indicated to participate in PCB biosynthesis. Here, we overexpressed and purified a His6-tagged variant of K. nitens HY2 (KflaHY2) in Escherichia coli. Employing anaerobic bilin reductase activity assays and coupled phytochrome assembly assays, we confirmed the product and identified intermediates of the reaction. Site-directed mutagenesis revealed 2 aspartate residues critical for catalysis. While it was not possible to convert KflaHY2 into a PΦB-producing enzyme by simply exchanging the catalytic pair, the biochemical investigation of 2 additional members of the HY2 lineage enabled us to define 2 distinct clades, the PCB-HY2 and the PΦB-HY2 clade. Overall, our study gives insight into the evolution of the HY2 lineage of FDBRs.

A new non-fullerene acceptor based on an asymmetric electron-deficient core for indoor organic photovoltaic cells

Extending the number of fused aromatic rings in π-conjugated materials has proven to be an effective strategy to tailor the electronic, optical, and structural properties. In this work, the structure of the well-known Y6 was modified and a new asymmetric non-fullerene acceptor BIID was developed for organic photovoltaics. BIID was found to show a slightly blue-shifted absorption spectrum compared with Y6 in solid thin films. A high efficiency of 19.5% was achieved by using an BIID:PM6 bulk heterojunction blend film in a 1 cm2 device under indoor LED light, while an efficiency of 17.6% was achieved from the Y6:PM6 blend under the same conditions. Several characterization techniques were applied to study the structure–property relationships, and it was found that the BIID:PM6 blend has less trap-induced recombination, which led to a much higher open circuit voltage and higher device efficiency. With numerous possibilities for further structural optimization, such as attaching various substituents to the central electron-deficient core, BIID is considered to be a class of promising non-fullerene acceptors for indoor organic photovoltaics.

Synthesis and Unexpected Optical Properties of Ionic Phosphorus Heterocycles with P-Regulated Noncovalent Interactions.

Optoelectronic properties of organic chromophores (OCPs) are to a large extent dictated by the chemical structures. Herein, we synthesized a new series of ionic phosphorus(P)-heteropines via the methylation of the P(III) center. Our studies revealed that methylation is highly dependent on the P(III) environments (NPN, NPC, and CPC), in which adjacent nitrogen atoms greatly withdraw electron density of the P(III) center. The observation of noncovalent interactions between solvent molecules and the molecular backbones of the related P-heterocycle in the single crystal structure implied tunable molecular conformations. Different from the red-shifted absorption and emission spectra of ionic P-OCPs induced by either decreased lowest unoccupied molecular orbital (LUMO) or intramolecular charge transfer (ICT) state in previous studies, current ionic P-heterocycles exhibit blue-shifted absorption and emission spectra compared to the nonionic counterparts. Our experimental and theoretical studies suggest that the unexpected photophysical characters are probably due to the counter-anion induced structure twisting via intermolecular noncovalent interactions between NH-indole and O(OTf), and/or strong intermolecular O···F bonding between O(MI) and F(OTf). Our studies also revealed that the P-environments (NPN, NPC, and CPC) conjunctly impact the photophysical properties of the ionic P-heteropines. Overall, the fact that the P-environment-regulated noncovalent interactions induce the rich structure dynamics and photophysics offers us with a new and effective strategy to fine-tune the optical properties of OCPs.

Modulating the organic photovoltaic properties of non-fullerene acceptors by molecular modification based on Y6: a theoretical study.

Developing non-fullerene acceptors (NFAs) by modifying the backbone, side chains and end groups is the most important strategy to improve the power conversion efficiency of organic solar cells (OSCs). Among numerous developed NFAs, Y6 and its derivatives are famous NFAs in the OSC field due to their good performance. Herein, in order to understand the mechanism of tuning the photovoltaic performance by modifying the Y6's center backbone, π-spacer and side-chains, we selected the PM6:Y6 OSC as a reference and systematically studied PM6:AQx-2, PM6:Y6-T, PM6:Y6-2T, PM6:Y6-O, PM6:Y6-1O and PM6:Y6-2O OSC systems based on extensive quantum chemistry calculations. The results indicate that introducing quinoxaline to substitute thiadiazole in the backbone induces a blue-shift of absorption spectra, reduces the charge transfer (CT) distance (Δd) and average electrostatic potential (ESP), and increases the singlet-triplet energy gap (ΔEST), CT excitation energy and the number of CT states in low-lying excitations. Inserting thienyl and dithiophenyl as π spacers generates a red-shift of absorption spectra, enlarges Δd and average ESP, and reduces ΔEST and the number of CT states. Introducing furo[3,2-b]furan for substituting one thieno[3,2-b]thiophene unit in the Y6's backbone causes a red-shift of absorption spectra and increases ΔEST, Δd and average ESP as well as CT excitation energy. Introducing alkoxyl as a side chain results in a blue-shift of absorption spectra, and increases ΔEST, Δd, average ESP, CT excitation energy and the number of CT states. The rate constants calculated using Marcus theory suggest that all the molecular modifications of Y6 reduce the exciton dissociation and charge recombination rates at the heterojunction interface, while introducing furo[3,2-b]furan and alkoxyl enlarges CT rates.

First principle study of hybrid materials based on conjugated polymers and zirconium oxide as a proficient sensor for H2S gas

A density functional-based study of polymer/zirconium oxide composites has been carried out to explore their optical and electronic properties for developing an efficient sensor for the HS analyte. Composites of Zirconium oxide (ZrO) with three different conjugated polymers; polythiophene (PTh), polypyrrole (PPy), and polyaniline (PAni) have been designed. Narrowing of the band gap, favorable interaction, and shift of charge density from the polymer unit to the metal oxide evidenced the stability and suitability of designed composites for sensing applications. The natural bond orbital (NBO) analysis, frontier orbital pictures, and configuration establish that electron density shifts from the polymer unit to the ZrO in optimised composites. Perturbation in electronic and optical properties after binding of HS on composite surfaces supports the sensing ability of composites toward H. The high magnitude of binding energy and significant blue shifts in absorption spectra confirm the sensing of the H analyte by the designed composites.

Double Narrowband Induced Perfect Absorption Photonic Sensor Based on Graphene–Dielectric–Gold Hybrid Metamaterial

Double narrowband induced perfect absorption in the terahertz region is achieved in a graphene–dielectric–gold hybrid metamaterial, whose physical mechanism is analyzed using the coupled-mode theory (CMT), which agreed well with the finite-difference time-domain (FDTD) simulation. This study found that the Fermi level of graphene can be adjusted to improve the absorptivity when the refractive index (RI) nd of the chosen dielectric cannot achieve a good absorption effect. In addition, the blue shift of absorption spectrum can be used in the design of dual-frequency electro-optical switches, of which the modulation degree of amplitude (MDA) can reach as high as 94.05% and 93.41%, indicating that this is a very promising electro-optical switch. Most significantly, the RI sensing performance is investigated, which shows an ultra-high absorption sensitivity SA = 4.4°/RIU, wavelength sensitivity Sλ = 9.8°/RIU, and phase shift sensitivity Sφ = 2691°/RIU. At last, an interesting finding is that the two peaks (R1 and R2) of plasmon-induced absorption (PIA) show different polarization characteristics (insensitive or sensitive) to the incident light angle; this polarization-sensitive is particularly important for the PIT/PIA-based optical polarizers. Undoubtedly, this paper is of great significance to the research and design of terahertz photonic devices and sensors.

Room-Temperature Ferromagnetism in Cu/Co Co-Doped ZnO Nanoparticles Prepared by the Co-Precipitation Method: For Spintronics Applications

In current work, pure ZnO and Zn0.96–xCu0.04CoxO (0 ≤ x ≤ 0.05) nanoparticles were synthesized by the co-precipitation method. Structural analysis and phase determination of the formed nanoparticles was carried out using X-ray diffraction (XRD) and Williamson–Hall plots. The hexagonal wurtzite structure was manifested by all the samples with divergent microstructures. The change in lattice parameters, bond length, dislocation density, and lattice strain indicates that Cu and Co were successfully incorporated. Average crystallite size was found to be in the range of 32.16–45.42 nm for various doping concentrations. Field emission scanning electron microscopy results exhibited that the surface morphology is an amalgam of spherical-like and hexagon-like structures. Spherical-shaped grains were homogeneous and evenly distributed all over the structure. Fourier transform infrared spectra indicated that the absorption bands were blue-shifted with increasing Co concentration. The UV–visible absorption spectra showed high absorption in the UV region and weak absorption in the visible region. An increase in the energy band gap for the maximum absorption peak was observed from 3.49 eV for ZnO to 3.88 eV for Zn0.91Cu0.04Co0.05O. The Burstein–Moss effect explained the noticed blue shift in absorption spectra and energy band gaps. The vibrating sample magnetometer study revealed the change in the diamagnetic behavior of pure ZnO to the ferromagnetic behavior of the prepared nanoparticles at room temperature for different doping concentrations. In the current study, we have developed the room-temperature ferromagnetism (RTFM) for Cu and Co co-doped ZnO nanoparticles. Since RTFM is the key objective for dilute magnetic semiconductors, therefore it can be served as the desirable expectant for spintronics applications with improved functionalities and device concepts.

A C 54 B 2 Polycyclic π-System with Bilayer Assembly and Multi-Redox Activity

A C ₅₄ B ₂ Polycyclic π-System with Bilayer Assembly and Multi-Redox Activity

Exploring structural, electronic, optical, magnetic, and thermoelectric properties of Pt doped and Pt-Cu/Au co-doped GaN

We present a computational research on investigating the structural, electronic, optical, magnetic, and thermoelectric properties of Pt doped and Pt-Cu/Au co-doped GaN using the Wien2k code. The PBE-GGA approximation is employed in Wien2k code using density functional theory. Study of electronic properties reveals that the d-states of Pt, Cu, and Au atoms participate actively in transferring electron from valence to conduction band and their addition as mono and co-doped formation turns the non-magnetic character of GaN to magnetic. A blueshift in absorption spectrum appear and absorption is more pronounced for Pt-Cu/Au co-doped GaN, suggesting the use of these materials for high energy UV optoelectronics, spintronics, photonic, and sensing devices. However, lower reflection and enhanced conductivity of Pt-Cu/Au co-doped materials in the UV region extends their potential applications in high frequency electronics. Moreover, higher ZT value of Pt@GaN suggest it a better thermoelectric source other than Pt-Cu/Au@GaN.

Calix[4]pyrrole based scrupulous probe for track on of tryptophan: Host-guest interaction, in silico modeling and molecular docking insights

• Novel aromatic calix[4]pyrrole, i.e. ABCP is synthesized by microwave as well as conventional method. • Synthesized ABCP is selective towards tryptophan in comparison to other amino-acids which is very well supported by absorption and computational studies i.e, the host–guest interaction analysis. • Insilico method favors the complexation with Tryptophan via H-bonding and π-π interaction. The natural Bonding Orbital analysis and other molecular properties support the charge transfer from tryptophan to ABCP via n1(O123) → σ*(N11-H61). The TDDFT support the charge transfer from HOMO-17 → LUMO, HOMO-11 → LUMO + 3, HOMO-3 → LUMO, and HOMO → LUMO + 4 transition with 17 nm blue shift. Interaction of a novel calix[4]pyrrole bearing carboxylic acid functionality (ABCP) has been investigated towards amino acids in methanol. The ABCP-Tryptophan complex produces a blue shift in absorption spectra based on charge transfer mediated recognition. Additionally, the density functional theory calculations could substantiate possible mechanism for the 1:1 binding of Tryptophan with ABCP theoretically. Moreover, other parameters such as stability, softness, hardness and chemical potential have been calculated to know about the binding behaviour of ABCP as host and Tryptophan as guest. The Natural Bond Orbital and TDDFT calculation facilitates to understand the proper binding mechanism in reference to experimental results.

Molecular engineering of the fused azacycle donors in the D-A-π-A metal-free organic dyes for efficient dye-sensitized solar cells

Four novel D-A-π-A metal-free organic sensitizers QL1–4 with the fused azacycle units as donors have been designed and synthesized to investigate the relationship between both the sizes and conjugations of azacycle and performances of dye-sensitized solar cells systematically. QL1 with the five-membered azacycle, i.e., with carbazole (Cz) as donor, exhibits the smallest molar extinction coefficients (ε). QL2 and QL3 with the seven-membered azacycle, i.e. with N-phenyl-iminostilbene (ISB) and N-phenyl-iminodibenzyl (IDB) as donors, respectively, show the red-shifted absorption spectra and higher ε compared to QL1. However, QL2 and QL3 with an only distinction in a single or double bond, display distinctive PCEs. QL4 with the six-membered azacycle, i.e., 9,9,10-triphenyl-9,10-dihydroacridine (TDD), exhibits a blue-shifted absorption spectrum due to a big dihedral angle, resulting in a lower photovoltaic performance. Especially, QL3 with the ISB donor is conducive to achieving a PCE of 6.22%, which is higher than QL2, due to its better planar structure and more conjugation. When co-adsorbed with CDCA, QL3 exhibits the highest PCE of 7.14% among all dyes, and up to 8.26% by co-sensitizing with dye WL5, which surpasses that of the reference dye N719 (7.75%). The results indicate that the size and conjugation of the fused azacycle donors may affect the photovoltaic performance significantly, and the ISB unit is demonstrated as a promising donor for efficient organic dyes.

Antibacterial activity and characteristics of silver nanoparticles biosynthesized from Carduus crispus

In recent years’ synthesis of metal nanoparticle using plants has been extensively studied and recognized as a non-toxic and efficient method applicable in biomedical field. The aim of this study is to investigate the role of different parts of medical plant Carduus crispus on synthesizing silver nanoparticles and characterize the produced nanoparticle. Our study showed that silver nanoparticles (AgNP) synthesized via whole plant extract exhibited a blue shift in absorption spectra with increased optical density, which correlates to a high yield and small size. Also, the results of zeta potential, X-ray diffraction, photon cross-correlation spectroscopy analysis showed the surface charge of − 54.29 ± 4.96 mV (AgNP-S), − 42.64 ± 3.762 mV (AgNP-F), − 46.02 ± 4.17 mV (AgNP-W), the crystallite size of 36 nm (AgNP-S), 13 nm (AgNP-F), 14 nm (AgNP-W) with face-centered cubic structure and average grain sizes of 145.1 nm, 22.5 nm and 99.6 nm. Another important characteristic, such as elemental composition and constituent capping agent has been determined by energy-dispersive X-ray spectroscopy and Fourier transform infrared. The silver nanoparticles were composed of ~ 80% Ag, ~ 15% K, and ~ 7.5% Ca (or ~ 2.8% P) elements. Moreover, the results of the FTIR measurement suggested that the distinct functional groups present in both AgNP-S and AgNP-F were found in AgNP-W. The atomic force microscopy analysis revealed that AgNP-S, AgNP-F and AgNP-W had sizes of 131 nm, 33 nm and 70 nm respectively. In addition, the biosynthesized silver nanoparticles were evaluated for their cytotoxicity and antibacterial activity. At 17 µg/ml concentration, AgNP-S, AgNP-F and AgNP-W showed very low toxicity on HepG2 cell line but also high antibacterial activity. The silver nanoparticles showed antibacterial activity on both gram-negative bacterium Escherichia coli (5.5 ± 0.2 mm to 6.5 ± 0.3 mm) and gram-positive bacterium Micrococcus luteus (7 ± 0.4 mm to 7.7 ± 0.5 mm). Our study is meaningful as a first observation indicating the possibility of using special plant organs to control the characteristics of nanoparticles.

Enhancing the photovoltaic performance with two similar structure polymers as donors by broadening the absorption spectrum and optimizing the molecular arrangement

Ternary organic photovoltaics (OPVs) were fabricated with two polymers (PM6 and D18) as the donor and the fullerene-free small molecule Y6 as the acceptor in an inverted structure. The blueshifted absorption spectrum of neat D18 relative to neat PM6 can enable harvesting of more short and medium wavelength photons in the ternary photoactive layer, which is beneficial to increasing the short-circuit current density ( J SC ). The enhancement of the open-circuit voltage ( V OC ) of the ternary OPVs can be explained by the deeper HOMO level of D18 than that of PM6, which is beneficial to broadening the energy bandgap. In addition, the combination of the cascade LUMO levels among D18, PM6 and Y6 and the enhanced crystallinity can lead to more efficient exciton dissociation and charge transport within the ternary films. As a result, the power conversion efficiency of the optimize ternary OPV is 15.85%, which is higher than those of the PM6:Y6- and D18:Y6-base binary OPVs (PCEs of 14.70% and 14.95%, respectively). The results indicate that ternary OPVs with a blend of two similar chemical structure polymers as the donor could achieve high performance by broadening the light spectrum and optimizing the phase separation and crystallinity. • D18 plays a dominant role in the light absorption and exciton dissociation. • The separation of exciton of D18 mainly occurs on the D18/PM6 interface. • The OPV based on D18 as third component materials exhibit a significant increase of 10% in PCE.

Investigations on electronic structure, magnetic and optical properties of C and Ti co-doped zincblende GaN for optoelectronic applications

In the current research, we perform a density functional theory study of C, Ti mono- doped (C-@GaN, Ti@GaN), and their co-doped GaN (C-Ti@GaN). We investigate the effect of C, Ti and their co-doping on the structural, electronic, magnetic, and optical properties using the Wien2K code. The formation energy of mono- and co-doped GaN is negative under the N-rich conditions and co-doped material is more stable than the mono-doped material. Optical absorption of mono-doped GaN is redshifted while the absorption of co-doped material is blue shifted. Our calculated results are in accordance with the already reported literature. Since, we did not find magnetism in the C-Ti@GaN material and because of blueshift in absorption spectrum; we suggest that co-doped GaN is more favorable for the UV optoelectronics, power electronics, and the UV solar cells applications than the co-doped materials.

First-Principles Study on the Photoelectric Properties of CsGeI3 under Hydrostatic Pressure

CsGeI3 has been widely studied as an important photoelectric material. Based on the density functional theory (DFT), we use first-principles to study the photoelectric properties of CsGeI3 by applying successive hydrostatic pressure. It has been found that CsGeI3 has an optimal optical band gap value of 1.37 eV when the applied pressure is −0.5 GPa, so this paper focuses on the comparative study of the photoelectric properties when the pressure is −0.5 GPa and 0 GPa. The results showed that CsGeI3 has a higher dielectric value, conductivity, and absorption coefficient and blue shift in absorption spectrum when the pressure is −0.5 GPa. By calculating and comparing the effective masses of electrons and holes and the exciton binding energy, it was found that their values are relatively small, which indicates that CsGeI3 is an efficient light absorbing material. CsGeI3 was found to be stable under both pressure conditions through multiple calculations of the Born Huang stability criterion, tolerance factor T, and phonon spectrum with or without virtual frequency. We also calculated the elastic modulus of both pressure conditions and found that they are both soft, ductile, and anisotropic. Finally, the thermal properties of CsGeI3 under two kinds of pressure were studied. It was found that the Debye temperature and heat capacity of CsGeI3 increased with the increase of thermodynamic temperature, and the Debye temperature increased rapidly after pressure, while the heat capacity slowly increased and finally stabilized. Through the calculation of enthalpy, entropy, and Gibbs free energy of CsGeI3, it was found that the Gibbs free energy decreases faster with the increase of temperature without applied pressure, which indicates that CsGeI3 has a higher stability without pressure. Through the comparative analysis of the photoelectric properties of CsGeI3 under pressure, it was found that CsGeI3 after applied pressure is a good photoelectric material and suitable for perovskite solar cells (PSCs) material.

Synthesis, Characterization and Dye-Sensitized Solar Cell Application of a Novel Symmetric Diphenylpyran Dye with Dual Rhodamine-3-acetic Acid Anchors

With simple three-step method, a new symmetrical metal free organic diphenylpyran dye containing dual rhodamine-3-acetic acid anchors was successfully synthesized, characterized and applied to dye-sensitized solar cells (DSSC). The dye has saturated methylene in its acceptor part, which makes the electron withdrawing group and the anchor group cannot be conjugated well. In addition, the exhibits lower molar extinction coefficients of the dye and its blue-shifted absorption spectrum also influenced the light capture ability. The resulting weaker intramolecular charge transfer and the electron coupling effect of the dye hindered the dye charge injection and shorten the electron lifetime, leading to an average power conversion efficiency of 0.65 % (Jsc = 2.32 mA cm−2, Voc = 448 mV and FF = 0.63). Further design of an efficient dye molecule needs efficient conjugation between the electron-withdrawing group and anchoring group, as well as an effective light harvest capability.