Perylene-3,4,9,10-tetracarboxylic Dianhydride Molecules Research Articles

Ultrafast and stable molten salt aluminum organic batteries

Aluminum-organic batteries (AIBs) have gained significant popularity for large-scale energy storage due to their abundance of aluminum reserves, cost-effectiveness, and environmental friendliness. However, the current aluminum-organic batteries primarily relied on ionic liquid electrolytes suffer from slow reaction kinetics and limited cycle life. Herein, we report a novel and efficient aluminum-organic battery that addresses these limitations by utilizing a molten salt electrolyte and designing a strongly interacting organic cathode. By enhancing π-π stacking interactions, we induced a transition in commercial PTCDA (Perylene-3,4,9,10-tetracarboxylic dianhydride) molecules from the β-phase to the highly interactive α-phase, known as PA450. This transformation not only stabilizes the structure of the PA450 electrode, preventing dissolution in the molten salt electrolyte, but also significantly improves electron conductivity. The Al||PA450 molten salt battery demonstrates exceptional electrochemical performance, exhibiting a high reversible capacity of 135 mAh g–1 and outstanding cyclability for up to 2000 cycles at 10 A g−1. Additionally, the structural rearrangement and ion transport properties induced by the co-intercalation of Al3+ and AlCl2+ were studied are investigated. This work provides deep insights into the unique characteristics of organic materials for ultrafast energy storage in molten salt electrolytes.

From a free electron gas to confined states: A mixed island of PTCDA and copper phthalocyanine on Ag(111).

When perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA) is deposited on the Ag(111) surface at submonolayer coverage, it forms islands under which the native Shockley state of the Ag(111) surface can no longer be found. Previous work has shown that this state shifts upwards to form a new interface state starting at 0.6 V above the Fermi level, having properties of a two-dimensional electron gas (2DEG). We investigated mixed islands of PTCDA and copper phthalocyanine (CuPc) to study the change in the electronic state with the addition of an electron donor. We no longer observe a 2DEG state and instead identify states at 0.46 and 0.79 V. While one state appears in dI/dV images as an array of one-dimensional quantum wells, our analysis shows that this state does not act as a free electron gas and that the features are instead localized above individual PTCDA molecules.

The synthesis and characterization of PTCDA-Co(II), and PTCDA-La(III) fluorescent MOFs

Metal organic frameworks (MOFs) are unique porous materials with a high surface area employing variety of organic ligands and metal ion components. Moreover, the possibility of developing different additional features, such as magnetic, thermo-responsive, and fluorescent properties that come from the organic ligands and/or metal ions can methodically increase the industrial application of MOF structures. In this paper, perylene 3,4,9,10 tetracarboxylic dianhydride (PTCDA) based MOFs with fluorescent properties were synthesized using Co(II) and La(III) metal ions as nodules. The disappearance of carbonyl group peaks at 1756 cm−1 from PTCDA molecules confirmed the synthesis of PTCDA-based Co(II) and La(III) MOFs. The SEM image revealed that the prepared PTCDA-Co(II) MOFs are in ellipsoidal shapes, whereas the PTCDA-La(III) MOFs are in rod or fiber-like shapes. The BET surface area of prepared PTCDA-Co(II) and PTCDA-La(III) MOFs were determined as 125.9 m2/g and 29.9 m2/g, respectively. The prepared PTCDA-based Co(II) and La(III) MOF exhibit fluorescent properties, e.g., upon exposure to 465 nm excitation wavelength, they have fluorescence emission intensity of 10,500 and 13,000 (a.u) at 514 and 510 nm wavelength, respectively. The quenching activity of Cu(II), Ni(II), As(III), and Hg(II) metal ions on fluorescence properties of PTCDA-La(III) MOFs were examined. Moreover, it was observed that the prepared PTCDA-Co(II) and PTCDA-La(III) MOF show 82.9 ± 0.4 and 95.4 ± 4.1 % Fe(II) chelating activity at 1400 µg/mL concentration of PTCDA-Co(II) and PTCDA-La(III). Lastly, Quantum yield was calculated as 52 ± 1 % for PTCDA-La(III) MOF.

Molecular-Scale Investigation of the Thermal and Chemical Stability of Monolayer PTCDA on Cu(111) and Cu(110).

Perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA) has been intensively investigated for decades because of its unique electronic and optical properties and its applications in organic electronics and surface engineering and passivation of 2D materials. Recently, the high demand for achieving selective area deposition in device fabrications drives the research of utilizing organic molecules as a passivation layer on metals in the semiconductor industry. PTCDA molecules show promising potential to be used as a passivation layer on a metal surface because of their ability to form self-assembled compact lying-down layers with the well-exposed inert conjugated molecular π-plane. However, the thermal and chemical stabilities of monolayer PTCDA on metal surfaces have not been thoroughly studied. In this paper, we demonstrate that monolayer PTCDA on Cu(110) and Cu(111) surfaces exhibit good thermal and chemical stabilities, as revealed through the combination of in situ X-ray photoelectron spectroscopy and in situ low-temperature scanning tunneling microscopy measurements. We show that monolayer PTCDA on copper is stable up to 220 °C and decomposes to perylene at higher temperature. Monolayer PTCDA also shows good chemical stability when exposed to O2 and water, demonstrating good potential for its future applications as passivation layers in selective area deposition.

Highly Selective Gas Sensors Based on Graphene Nanoribbons Grown by Chemical Vapor Deposition.

Despite the recent advances in bottom-up synthesis of different kinds of atomically precise graphene nanoribbons (GNRs) with very diverse physical properties, the translation of these GNRs into electronic devices remains challenging. Among other factors, the electronic characterization of GNRs is hampered by their complex synthesis that often requires custom-made organic precursors and the need for their transfer to dielectric substrates compatible with the conventional device fabrication procedures. In this paper, we demonstrate that uniform electrically conductive GNR films can be grown on arbitrary high-temperature-resistant substrates, such as metals, Si/SiO2, or silica glasses, by a simple chemical vapor deposition (CVD) approach based on thermal decomposition of commercially available perylenetetracarboxylic dianhydride molecules. The results of spectroscopic and microscopic characterization of the CVD-grown films were consistent with the formation of oxygen-terminated N = 5 armchair GNRs. The CVD-grown nanoribbon films exhibited an ambipolar electric field effect and low on-off ratios, which were in agreement with the predicted metallic properties of N = 5 armchair GNRs, and remarkable gas sensing properties to a variety of volatile organic compounds (VOCs). We fabricated a GNR-based electronic nose system that could reliably recognize VOCs from different chemical classes including alcohols (methanol, ethanol, and isopropanol) and amines (n-butylamine, diethylamine, and triethylamine). The simplicity of the described CVD approach and its compatibility with the conventional device fabrication procedures, as well as the demonstrated sensitivity of the GNR devices to a variety of VOCs, warrant further investigation of CVD-grown nanoribbons for sensing applications.

TEMPOL-enhanced MRI Reveals Distinct Redox State In Aggressive Phenotypes of Prostate Cancer

Synthesis and adsorption studies of the SBA-15 immobilizing perylene and pyrene dyes are described in this work. The functionalization is carried out with amine groups through post-synthesis using amino-propyl triethoxysilane (APTES) and ethanol or toluene as solvent. The resulting functionalized material is investigated as a matrix for the immobilization of perylene-3,4,9,10-tetracarboxylic dianhydride (PDA). Further exploration of the immobilization of 1-Pyrenecarboxaldehyde (PCA) is detailed. The obtained materials were characterized by FTIR and fluorescence spectroscopy, nitrogen adsorption analysis and X-ray diffraction (XRD). The textural characterization of the functionalized samples shows the decrement of the average pore sizes and the surface area as consequence of the APTES and fluorescent dyes immobilization. Compared with the pristine SBA-15, the solids obtained by functionalization with PDA yielded red-coloured samples, which show absorption bands at λ = 670 nm in solid state and λ = 570 nm in solution. The PDA dye is bonded to the SBA-15 network and it shows absorption or emissions properties for the new hybrid solids. The fluorescence of these species are preserved if the PDA molecules remains with a more flexible structure.

Surface passivation of black phosphorus via van der Waals stacked PTCDA

Two-dimensional (2D) black phosphorus (BP) has received great attention due to its anisotropic mechanical, optical and electronic properties. However, the air-instability of BP seriously limits its further applications. Various approaches have been explored to improve the device stability of BP, including the encapsulation by inert 2D counterparts, and surface passivation by AlOxvia atomic layer deposition and by organic layers either van der Waals stacked or covalently bonded onto the surface. Here we systematically investigate the surface passivation effect of perylenetetracarboxylic dianhydride (PTCDA) on BP through a variety of in-situ characterization techniques. PTCDA molecule on BP adopts a lying down configuration with the molecular π-plane almost parallel to the BP surface, arising from the formation of multiple intermolecular hydrogen bonds. The evaporation of PTCDA on BP does not modify the intrinsic structure and electrical transport property of BP, as revealed by in-situ ultraviolet photoelectron spectroscopy (UPS)/x-ray photoelectron spectroscopy (XPS), and further corroborated by in-situ field-effect-transistor (FET) evaluation. After the air-exposure of PTCDA covered BP in dark, no obvious degradation on BP was observed by XPS. However, the electron mobility of the passivated BP FET significantly decreased by 80% after 20 h exposure despite lifetime of the passivated device was prolonged.

Solvent effect on adsorption and fluorescence properties of perylene and pyrene dyes bonded to SBA-15 network

Abstract Synthesis and adsorption studies of the SBA-15 immobilizing perylene and pyrene dyes are described in this work. The functionalization is carried out with amine groups through post-synthesis using amino-propyl triethoxysilane (APTES) and ethanol or toluene as solvent. The resulting functionalized material is investigated as a matrix for the immobilization of perylene-3,4,9,10-tetracarboxylic dianhydride (PDA). Further exploration of the immobilization of 1-Pyrenecarboxaldehyde (PCA) is detailed. The obtained materials were characterized by FTIR and fluorescence spectroscopy, nitrogen adsorption analysis and X-ray diffraction (XRD). The textural characterization of the functionalized samples shows the decrement of the average pore sizes and the surface area as consequence of the APTES and fluorescent dyes immobilization. Compared with the pristine SBA-15, the solids obtained by functionalization with PDA yielded red-coloured samples, which show absorption bands at λ = 670 nm in solid state and λ = 570 nm in solution. The PDA dye is bonded to the SBA-15 network and it shows absorption or emissions properties for the new hybrid solids. The fluorescence of these species are preserved if the PDA molecules remains with a more flexible structure.

Differences in self-assembly of spherical C60 and planar PTCDA on rippled graphene surfaces

It was recently recognized that two-dimensional (2D) graphene exhibits nonplanar aberrations such as a rippled surface. Understanding the self-assembly of organic semiconductor molecules on monolayer 2D curved graphene surfaces is a paramount issue for ultimate application in semiconductor and optoelectronic devices. Herein, we report on the preparation of fullerene, C60 and perylenetetracarboxylic dianhydride (PTCDA) molecules adsorbed on a rippled graphene surface. We find that the spherical C60 molecules form a quasi-hexagonal close packed (hcp) structure, while the planar PTCDA molecules form a disordered herringbone structure. These 2D layer systems have been characterized by experimental scanning tunneling microscope (STM) imaging and computational density functional theory (DFT) approaches. The DFT computational results exhibit interaction energies for adsorbed molecule/rippled graphene complexes located in the 2D graphene valley sites that are significantly larger in comparison with adsorbed idealized planar/molecule graphene 2D complexes. In addition, we report that the adsorbed PTCDA molecules prefer different orientations when the rippled graphene peak regions are compared to the valley regions. This difference in orientations causes the PTCDA molecules to form a disordered herringbone structure on the rippled graphene surface. The results of this study clearly illustrate significant differences in C60 and PTCDA molecular packing on rippled graphene surfaces.

PTCDA growth on Ge(111)- surfaces: a scanning tunneling microscopy study

The initial stages of growth of PTCDA (3,4,9,10 perylene tetracarboxylic dianhydride) at room temperature (RT) on Ge(111)- surfaces have been studied by means of scanning tunneling microscopy (STM) under ultrahigh vacuum conditions. The results show that PTCDA molecules have a high mobility at RT on the well ordered areas of the semiconductor substrate, since nucleation is only observed in domain walls, steps and surface defects. However, no molecular ordering has been detected at submonolayer coverage. For higher coverages, the formation of three-dimensional (3D) molecular islands has been observed. These 3D islands present a crystalline nature as demostrated by molecularly resolved STM images. According to these STM measurements, PTCDA molecules are ordered in a herringbone structure, similar to the one observed in PTCDA bulk crystals. Moreover, the 3D crystallites are grown on top of a disordered molecular layer, which acts as a passivating layer.

The Analysis of Element and Measure Analysis of NMR Spectrum and XRD Spectrum for High Purity 3,4,9,10 Perylenetetracarboxylic Dianhydride-PTCDA

vacuum sublimation method was used to purify the homegrown 3,4,9,10 perylenetetracarboxylic dianhydride(PTCDA)powder with a purity of 98% in its sublimation point of 450 ℃. With Bill’s law and ultraviolet-visible spectrophotometer testing analysis, its purity reached to 99.8%. Meanwhile, the contents of C and H elements in the pre-and post-purified molecules were also measured by using elemental analyzer. The measured results indicate that the contents of C and H elements in the post-purified the molecules are very close to the theoretical value. H element in the molecular structure was investigated with nuclear magnetic resonance (NMR) spectroscopy and the results demonstrated that there are an equal number of H atoms in two different chemical environments and it can only be located on the aromatic ring. By discussing the chemical bond formation of PTCDA molecules, the C, H and O atoms in high purity PTCDA molecules are mainly covalent bonds. The crystalline state and crystal structure of this organic material were tested and analyzed by X-ray diffractometer. The results suggest that the post-purified PTCDA power existed α-PTCDA and β-PTCDA two phases, in which α-PTCDA phase is major component while β-PTCDA phase accounts for about one five of the total ingredients. Besides, the crystal cell belonged to bottom-centered monoclinal structure. Meanwhile, the crystal state, grain size and band structure of PTCDA single crystal thin films formed on the surface of p-type silicon in its sublimation point are investigated in detail. During the high-purity α-PTCDA forming organic single thin film on the surface of p-type single silicon, the π-electron cloud covered on the top, bottom and two sides of its thin film’s molecular layer plane. Due to the formation of delocalized bond that attributed to the overlap of the outermost valence electron orbital of C, H, O atom, the valence electrons generate co-movement and the energy level splitting for the band. The energy difference between valence band and the first tight binding is 2.2 eV which lead to this organic material possessing the properties of semiconductor conduction. In addition, this organic material with the intrinsic carrier concentration for 1014 cm-3 belong to weak p-type organic semiconductor material. This organic material combines with the surface of p-type silicon to form hetehomo-type heterojunction which is provided with excellent response for visible light to near infrared wavelengths of light.

Structure of vacant electronic states of an oxidized germanium surface upon deposition of perylene tetracarboxylic dianhydride films

This paper presents the results of the investigation of the interface potential barrier and vacant electronic states in the energy range of 5 to 20 eV above the Fermi level (EF) in the deposition of perylene tetracarboxylic dianhydride (PTCDA) films on the oxidized germanium surface ((GeO2)Ge). The concentration of oxide on the (GeO2)Ge surface was determined by X-ray photoelectron spectroscopy. In the experiments, we used the recording of the reflection of a test low-energy electron beam from the surface, implemented in the mode of total current spectroscopy. The theoretical analysis involves the calculation of the energy and spatial distribution of the orbitals of PTCDA molecules by the density functional theory (DFT) using B3LYP functional with the basis 6-31G(d), followed by the scaling of the calculated values of the orbital energy according to the procedure well-proven in the studies of small organic conjugated molecules. The pattern of changes in the fine structure of the total current spectra with increasing thickness of the PTCDA coating on the (GeO2)Ge surface to 6 nm was studied. At energies below 9 eV above EF, there is a maximum of the density of unoccupied electron states in the PTCDA film, formed mainly by π* molecular orbitals. The higher density maxima of unoccupied states are of σ* nature. The formation of the interface potential barrier in the deposition of PTCDA at the (GeO2)Ge surface is accompanied by an increase in the work function of the surface, Evac–EF, from 4.6 ± 0.1 to 4.9 ± 0.1 eV. This occurs when the PTCDA coating thickness increases to 3 nm, and upon further deposition of PTCDA, the work function of the surface does not change, which corresponds to the model of formation of a limited polarization layer in the deposited organic film.

Tuning molecule-substrate coupling via deposition of metal adatoms.

Organic-inorganic hybrids constitute an important class of functional materials. The fundamentals at the molecular levels are, however, relatively unexplored. PTCDA (perylene-3,4,9,10-tetracarboxylic dianhydride) is a colorant and extensively applied in organic-based optoelectronic devices. PTCDA/Cu(111) and Fe-PTCDA/Cu(111) metal-organic hybrid monolayers are studied by low temperature scanning tunneling microscopy and spectroscopy (STS) and density functional theory (DFT). The former exhibits Moiré pattern-modulated molecular density of states while the latter adapts a commensurate adlattice. Both imaging and spectroscopic results suggest a strong hybridization between PTCDA molecules and Cu(111) substrate. Weak PTCDA-Cu(111) coupling can be obtained by the introduction of Fe adatoms. Compared to PTCDA/Cu(111), STS spectra of Fe-PTCDA/Cu(111) exhibit a higher energy and sharper features of the frontier orbitals. Together with the DFT results, we found that the PTCDA-Cu(111) coupling is attenuated by the presence of Fe adatoms and Fe-PTCDA coordination.

Photoinduced decomposition of PTCDA molecules and desorption of their fragments from the films formed on the GaAs(110) surface

Photoinduced fragmentation and desorption of thin films of perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA) vacuum-deposited on the GaAs(110) surface were studied by time-of-flight (TOF) mass spectroscopy under ultrahigh vacuum conditions. The main effects under pulsed laser light irradiation (pulse duration 10 ns, photon energy 2.34 eV, laser fluence 0.5–7 mJ/cm2) were the fragmentation of the PTCDA molecule and desorption of the resulting fragments in vacuum, whereas no desorption of the intact PTCDA molecule was recorded. The fragments included the perylene core C20H8, its half C10H4, carbon dioxide and monooxide, and atomic oxygen. The desorbed fragments of different types have significantly different kinetic energies of translational motion in the gas phase because of the nonthermal mechanism of photofragmentation and photodesorption.

Modification of electronic properties during adsorption of conjugate organic molecules on the surface of polycrystalline SnO2

The modification of the electronic structure during adsorption of ultrathin copper phthalocyanine (CuPc) and 3, 4, 9, 10 perylene-tetracarboxylic-dianhydride (PTCDA) coatings on the surface of polycrystalline tin dioxide is traced. Auger electron spectroscopy is employed to find changes in the atomic composition of the surface. It is found with the help of low-energy electron total current spectroscopy using a testing beam of electrons with energies up to 30 eV that the total current spectra typical of organic films are formed when the thickness of the coating being deposited is 2–7 nm. The formation of an interface layer 1.5–2.0 nm in thickness is detected, in which the intensity of the structure of the total current spectra decreases and the effect of interaction of PTCDA molecules with the SnO2 surface is manifested.

Effect of nitrogen-containing substituents on fragmentation of perylene derivatives under laser irradiation

The effect of nitrogen-containing substituents such as phenyl imide and actyl imide on the character of fragmentation of perylene derivative molecules under laser irradiation has been studied by laser desorption (LD) mass spectrometry. Replacement of the central oxygen atom by a nitrogen atom in anhydride carboxy groups in perylene tetracarboxylic dianhydride (PTCDA) molecule results in the suppression of CO2 desorption and predominant desorption of CO. The LD mass spectrum exhibits peaks that correspond to fragments of the perylene nucleus and those of the aromatic and aliphatic substituents. Intact PTCDA molecules are present in the desorbed flux in insignificant amounts.

Structural analysis of PTCDA monolayers on epitaxial graphene with ultra-high vacuum scanning tunneling microscopy and high-resolution X-ray reflectivity

Epitaxial graphene, grown by thermal decomposition of the SiC (0001) surface, is a promising material for future applications due to its unique and superlative electronic properties. However, the innate chemical passivity of graphene presents challenges for integration with other materials for device applications. Here, we present structural characterization of epitaxial graphene functionalized by the organic semiconductor perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA). A combination of ultra-high vacuum scanning tunneling microscopy (STM) and high-resolution X-ray reflectivity (XRR) is used to extract lateral and vertical structures of 0, 1, and 2 monolayer (ML) PTCDA on epitaxial graphene. Both Fienup-based phase-retrieval algorithms and model-based least-squares analyses of the XRR data are used to extract an electron density profile that is interpreted in terms of a stacking sequence of molecular layers with specific interlayer spacings. Features in the STM and XRR analysis indicate long-range molecular ordering and weak π–π* interactions binding PTCDA molecules to the graphene surface. The high degree of both lateral and vertical ordering of the self-assembled film demonstrates PTCDA functionalization as a viable route for templating graphene for the growth and deposition of additional materials required for next-generation electronics and sensors.

Laser stimulated fragmentation and desorption from the surface of organic films: Perylene derivatives

The mass spectra of laser desorption from the surface of perylene-tetracarboxylic dianhydride (PTCDA) films deposited in vacuum onto indium arsenide (InAs) and gallium arsenide (GaAs) substrates have been studied. The desorption was induced by 10-ns pulses of neodymium laser radiation (quantum energy, 2.34 eV) with the energy density E varied within 0.5–20 mJ/cm2. It is established that laser radiation produces fragmentation of PTCDA molecules and desorption of the molecular fragments. The main fragments observed in the mass spectra are identified. Initially, carboxy and dianhydride groups are detached, decomposed, and desorbed in the form of CO, CO2, and a small amount of atomic oxygen species. An increase in the laser pulse power leads to the desorption of the perylene nucleus (M = 248 amu) and its halves (M = 124 amu). No evidence for laser-stimulated desorption of intact PTCDA molecules was observed. The possible mechanisms of photostimulated fragmentation of PTCDA molecules and the subsequent desorption of fragments are discussed.

Dianhydride-Amine Hydrogen Bonded Perylene Tetracarboxylic Dianhydride and Tetraaminobenzene Rows

We have investigated the coadsorption of perylene tetracarboxylic dianhydride (PTCDA) and tetraaminobenzene (TAB) on the Ag/Si(111)-square root(3) x square root(3) R30 degree surface using scanning tunneling microscopy. At room temperature, PTCDA islands with square and herringbone ordering are formed which, on exposure to TAB, are converted into an intermixed phase in which PTCDA and TAB form alternating rows. From our images, we determine the relative placement of TAB and PTCDA molecules and conclude that the row structure is stabilized by hydrogen bonding between dianhydride and diamine groups. We confirm that this hydrogen bonding junction is stable using ab initio calculations and show that the proposed geometry is consistent with calculated intermolecular dimensions.

Formation of small-diameter carbon nanotubes from PTCDA arranged inside the single-wall carbon nanotubes

A systematic study was carried out on the doping of perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA) to the single-wall carbon nanotubes (SWNTs). After the doping reaction, the interior space of SWNTs was fully filled with the dopant. The heat treatment at high temperature in vacuum of this PTCDA-filled SWNTs induced new Raman signals ranging between 300 and 400 cm −1, which was assigned to the radial breathing mode of vibration associated with the inner tubes. Furthermore, transmission electron microscopy clearly showed the existence of one-dimensionally arranged PTCDA molecules in the tube and the secondary inner tubes formed after the high-temperature treatment.