Browse
Submit Data
Databases
API
Help

Dataset Information

16 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Mapping the Chiroptical Properties of Local Domains in Thin Films of Chiral Silicon Phthalocyanines by CD Imaging.

ABSTRACT: The first example of uniformly chiral thin films of silicon phthalocyanines (SiPcs) are reported. The local domains of the films are mapped using circular dichroism (CD) imaging (CDi) technique available at the Diamond B23 beamline. The CDi allowed us to increase the spatial resolution up to 525× when compared with benchtop spectrometers. The results indicate formation on-surface of chiral and stable supramolecular assemblies with homogenous distribution. Chemical functionalization and solvent choice for deposition allow controllable chiroptical properties to be obtained. The method and technique reported in this work could be applied to prepare and characterize a wide variety of chiral thin films.

SUBMITTER: Rasadean DM

PROVIDER: S-EPMC7767354 | biostudies-literature | 2020 Dec

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Mapping the Chiroptical Properties of Local Domains in Thin Films of Chiral Silicon Phthalocyanines by CD Imaging.

Răsădean Dora-M DM Gianga Tiberiu-M TM Jávorfi Tamás T Hussain Rohanah R Siligardi Giuliano G Pantoș G Dan GD

Molecules (Basel, Switzerland) 20201221 24

The first example of uniformly chiral thin films of silicon phthalocyanines (SiPcs) are reported. The local domains of the films are mapped using circular dichroism (CD) imaging (CD<i>i</i>) technique available at the Diamond B23 beamline. The CD<i>i</i> allowed us to increase the spatial resolution up to 525× when compared with benchtop spectrometers. The results indicate formation on-surface of chiral and stable supramolecular assemblies with homogenous distribution. Chemical functionalization ...[more]

PMID: 33371353

Similar Datasets

Chlorosubstituted Copper Phthalocyanines: Spectral Study and Structure of Thin Films.

Project description:In this work, the tetra-, octa- and hexadecachloro-substituted copper phthalocyanines CuPcClx (where x can equal 4, 8 or 16) were investigated by the methods of vibrational (IR and Raman) spectroscopy and X-ray diffraction. The assignment of the most intense bands, both in IR and Raman spectra, was carried out on the basis of DFT calculations. The structure of a CuPcCl4 single crystal grown by sublimation in vacuum was refined for the first time. The effect of chloro-substitution on the structure of CuPcClx thin films deposited in a vacuum onto a glass substrate at 50 and 200 °C was studied. It was shown that CuPcCl4 formed polycrystalline films with the preferential orientation of the (100) crystallographic plane of crystallites parallel to the substrate surface when deposited on a substrate at 50 °C. Introduction of more Cl-substituents into the phthalocyanine macrocycle leads to the formation of amorphous films on the substrates at 50 °C. At the elevated substrate temperature, the growth of polycrystalline disordered films was observed for all three copper phthalocyanines.

| S-EPMC7181266 | biostudies-literature

Optically modified second harmonic generation in silicon oxynitride thin films via local layer heating.

Project description:Strong second harmonic generation (SHG) in silicon nitride has been extensively studied-among others, in terms of laser-induced SHG enhancement in Si3N4 waveguides. This enhancement has been ascribed to the all-optical poling induced by the coherent photogalvanic effect. Yet, an analogous process for Si3N4 thin films has not been reported. Our article reports on the observation of laser-induced threefold SHG enhancement in Si3N4 thin films. The observed enhancement has many features similar to all-optical poling, such as highly nonlinear power dependence, cumulative effect, or connection to the Si3N4-Si interface. However, identical experiments for low-oxygen silicon oxynitride thin films lead to complex behavior, including laser-induced SHG reduction. Following a thorough experimental study, including the effects of repetition rate or pulse length, the observed results were ascribed to heat-induced SHG variation. In addition to revealing a new mechanism of laser-induced SHG variation, our results also provide a means to identify this mechanism.

| S-EPMC10227052 | biostudies-literature

Spatiotemporal Mapping of Efficient Chiral Induction by Helicene-Type Additives in Copolymer Thin Films.

Project description:We observed efficient induction of chirality in polyfluorene copolymer thin films by mixing with helicene-type chiral additives based on the dibenzo[c,h]acridine motif. Images obtained from circular dichroism (CD) and circularly polarized luminescence (CPL) microscopy provide information about the chiral arrangements in the thin films with diffraction-limited resolution. The CD signal shows a characteristic dependence on the film thickness, which supports a supramolecular origin of the strong chiral response of the copolymer. In particular, we demonstrate the discrimination between films of opposite chirality based on their ultrafast transient chiral response through the use of femtosecond broadband CD spectroscopy and a newly developed setup for transient CPL spectroscopy with 28 ps time resolution. A systematic variation of the enantiomeric excess of the chiral additive shows that the "Sergeants and Soldiers" concept and "Majority Rules" are not obeyed.

| S-EPMC9401025 | biostudies-literature

Relation between Morphology and Chiroptical Properties in Chiral Conducting Polymer Films: A Case Study in Chiral PEDOT.

Project description:The electronic properties of conducting polymers are influenced by their micro- and macrostructural orders, which can be tailored by substituent modification. However, while the effect of substituents on conducting polymers is extensively investigated, chiral substituents are far less studied. Furthermore, many chiral conducting polymers have regioirregular structures, which result in polymer films with inferior properties. In this work, we apply electronic circular dichroism (ECD) spectroscopy to study the morphological changes to the chiral polymers under different polymerization conditions. For this purpose, we investigated 3,4-ethylenedioxythiophene (EDOT) derivatives having two stereogenic centers on each monomer and bearing methyl or phenyl side groups (dimethyl-EDOT and diphenyl-EDOT, respectively). Polymerizing the enantiomerically pure monomers produces regioregular and stereoregular dimethyl-PEDOT and diphenyl-PEDOT, respectively. The effect of the electrolyte and solvent on polymer film morphology was studied using scanning electron microscopy (SEM) and ECD, showing a correlation between the polymer's morphology and the chiroptical properties of its films. We found that, for diphenyl-PEDOT, the combination of perchlorate anion electrolyte and acetonitrile solvent resulted in a unique morphology characterized by significant intermolecular interactions. These interactions were clearly observable in the ECD spectra in the form of exciton couplings, whose presence was supported by TD-DFT calculations. A small enantiomeric excess was sufficient to induce very intense ECD signals, demonstrating chiral amplification in electropolymerized films.

| S-EPMC7660938 | biostudies-literature

Spin-Polarized Photoemission from Chiral CuO Catalyst Thin Films.

Project description:The chirality-induced spin selectivity (CISS) effect facilitates a paradigm shift for controlling the outcome and efficiency of spin-dependent chemical reactions, for example, photoinduced water splitting. While the phenomenon is established in organic chiral molecules, its emergence in chiral but inorganic, nonmolecular materials is not yet understood. Nevertheless, inorganic spin-filtering materials offer favorable characteristics, such as thermal and chemical stability, over organic, molecular spin filters. Chiral cupric oxide (CuO) thin films can spin polarize (photo)electron currents, and this capability is linked to the occurrence of the CISS effect. In the present work, chiral CuO films, electrochemically deposited on partially UV-transparent polycrystalline gold substrates, were subjected to deep-UV laser pulses, and the average spin polarization of photoelectrons was measured in a Mott scattering apparatus. By energy resolving the photoelectrons and changing the photoexcitation geometry, the energy distribution and spin polarization of the photoelectrons originating from the Au substrate could be distinguished from those arising from the CuO film. The findings reveal that the spin polarization is energy dependent and, furthermore, indicate that the measured polarization values can be rationalized as a sum of an intrinsic spin polarization in the chiral oxide layer and a contribution via CISS-related spin filtering of electrons from the Au substrate. The results support efforts toward a rational design of further spin-selective catalytic oxide materials.

| S-EPMC9413420 | biostudies-literature

Interface-induced nonswitchable domains in ferroelectric thin films.

Project description:Engineering domains in ferroelectric thin films is crucial for realizing technological applications including non-volatile data storage and solar energy harvesting. Size and shape of domains strongly depend on the electrical and mechanical boundary conditions. Here we report the origin of nonswitchable polarization under external bias that leads to energetically unfavourable head-to-head domain walls in as-grown epitaxial PbZr(0.2)Ti(0.8)O3 thin films. By mapping electrostatic potentials and electric fields using off-axis electron holography and electron-beam-induced current with in situ electrical biasing in a transmission electron microscope, we show that electronic band bending across film/substrate interfaces locks local polarization direction and further produces unidirectional biasing fields, inducing nonswitchable domains near the interface. Presence of oxygen vacancies near the film surface, as revealed by electron-energy loss spectroscopy, stabilizes the charged domain walls. The formation of charged domain walls and nonswitchable domains reported in this study can be an origin for imprint and retention loss in ferroelectric thin films.

| S-EPMC8491438 | biostudies-literature

Pulsed Laser Porosification of Silicon Thin Films.

Project description:We present a new and simple laser-based process to porosify thin film silicon using a pulsed laser. During deposition, we incorporate gas atoms or molecules into the Si thin film. Pulsed laser radiation of wavelength λ = 532 nm heats up thin film Si beyond its melting point. Upon heating, gas atoms or molecules form nm-sized thermally expanding gas bubbles in the silicon melt, until they explosively exit the film, leaving pores behind. Rapid heating and fast cooling during pulsed laser processing enable re-solidification of the liquid Si before the created pores contract and pore closure occurs within the liquid phase. Optimized plasma-enhanced chemical vapor deposition or sputtering of amorphous Si thin films on stainless steel substrate incorporates the necessary concentration of gas atoms or molecules. We are able to tailor the pore size between 50 and 550 nm by changing laser pulse energy density and film deposition parameters. Evaporated silicon containing no gas atoms forms only a few very large μ m-sized gas bubbles due to laser-induced vapor formation of evaporated solid material at the substrate-silicon interface.

| S-EPMC5456937 | biostudies-other

Photoprogrammable circularly polarized phosphorescence switching of chiral helical polyacetylene thin films.

Project description:The developments of pure organic room-temperature phosphorescence (RTP) materials with circularly polarized luminescence (CPL) have significantly facilitated the future integration and systemization of luminescent material in fundamental science and technological applications. Here, a type of photoinduced circularly polarized RTP materials are constructed by homogeneously dispersing phosphorescent chiral helical substituted polyacetylenes into a processable poly(methyl methacrylate) (PMMA) matrix. These substituted polyacetylenes play vital roles in the propagation of CPL and present prominently optical characteristics with high absorption and luminescent dissymmetric factors up to 0.029 (gabs) and 0.019 (glum). The oxygen consumption properties of the films under UV light irradiation endow materials with dynamic chiro-optical functionality, which can leverage of light to precisely control and manipulate the circularly polarized RTP properties with the remarkable advantages of being contactless, wireless and fatigue-resistant. Significantly, the distinct materials with dynamic properties can be used as anti-counterfeiting materials involving photoprogrammability.

| S-EPMC9772410 | biostudies-literature

Natural optical activity as the origin of the large chiroptical properties in π-conjugated polymer thin films.

Project description:Polymer thin films that emit and absorb circularly polarised light have been demonstrated with the promise of achieving important technological advances; from efficient, high-performance displays, to 3D imaging and all-organic spintronic devices. However, the origin of the large chiroptical effects in such films has, until now, remained elusive. We investigate the emergence of such phenomena in achiral polymers blended with a chiral small-molecule additive (1-aza[6]helicene) and intrinsically chiral-sidechain polymers using a combination of spectroscopic methods and structural probes. We show that - under conditions relevant for device fabrication - the large chiroptical effects are caused by magneto-electric coupling (natural optical activity), not structural chirality as previously assumed, and may occur because of local order in a cylinder blue phase-type organisation. This disruptive mechanistic insight into chiral polymer thin films will offer new approaches towards chiroptical materials development after almost three decades of research in this area.

| S-EPMC7708482 | biostudies-literature

Thin Films of Chlorinated Vanadyl Phthalocyanines as Active Layers of Chemiresistive Sensors for the Detection of Ammonia.

Project description:Halogenated metal phthalocyanines are promising materials for the manufacture of active layers of chemiresistive sensors for the detection of various gases. Despite the high interest in such sensors, there are few systematic studies of the position of halogen substituents in phthalocyanine macroring on the chemiresistive response of their films to gases. In this work, we prepared and studied films of novel tetrachlorosubstituted vanadyl phthalocyanine derivatives with Cl substituents in the peripheral (VOPcCl4-p) and nonperipheral (VOPcCl4-np) positions of the phthalocyanine ring as active layers of chemiresistive sensors to reveal the effect of the position of substituents on their structure and sensor response to low concentrations of NH3. It was shown that the films of VOPcCl4-p exhibited a noticeably higher sensor response to NH3 than the VOPcCl4-np ones. The limit of detection of NH3 was 0.7 ppm. The sensing layers demonstrated a reversible sensor response at room temperature with fairly low response/recovery times. It was also demonstrated that NH3 can be detected in the presence of various interfering gases (CO2 and H2) and some volatile organic vapors, as well as in a mixture of gases with a composition close to exhaled air.

| S-EPMC10534441 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

Tweets

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data