Heteroepitaxial thin film of iron phthalocyanine on Ag(1 1 1)

Ordering of submonolayer iron phthalocyanine (FePc) molecules deposited on Ag(1 1 1) was investigated using scanning tunneling microscopy. The room temperature deposition of FePc alone, without any annealing, results in no ordered overlayers. However, posterior annealing the substrate to 475 K leads to the formation of a two-dimensional oblique lattice with the lattice constants of 16.2 ± 0.3 Å and the angle of 78 ± 1° between them. The resulting FePc lattice is commensurate to the substrate lattice. In addition, the nearest neighbor distance in the lattice is significantly increased through a distinctive molecular orientation of the FePc molecules within the unit cell. The commensurate lattice with a large intermolecular distance is in sharp contrast to that observed from a close-packed square lattice that many other metallo-phthalocyanine molecules often self-assemble into. A possible reasoning behind this intriguing structure is discussed.     

FePc与TiO2(110)及C60界面电子结构研究

基于C₆₀受体和有机分子给体的太阳能电池是目前非常重要的一个研究热点, 利用同步辐射真空紫外光电子能谱(SRUPS) 技术研究了酞菁铁(FePc)与TiO₂(110)及C₆₀的界面电子结构, 以及FePc与C₆₀分子混合薄膜的电子结构. SRUPS价带谱显示, FePc沉积在化学计量比与还原态两种不同的TiO₂(110)表面时, FePc分子的HOMO能级均随FePc厚度的变化发生了移动, 而在化学计量比的TiO₂(110)表面位移较大, 同时发生界面能带弯曲, 说明存在从有机层向衬底的电子转移. 在FePc/C₆₀和C₆₀/FePc界面形成过程中, FePc与C₆₀分子的最高占据分子轨道(HOMO)位移大小基本相同. 由界面能级排列发现, 在FePc与C₆₀的混合薄膜中, FePc分子的HOMO与C₆₀分子的最高占据分子轨道能级差较大, 这有利于提高器件开路电压, 改善器件性能.     

Effect of doping with iron on the charge ordering in La0.33Ca0.67Mn1−y Fe y O3 (y = 0, 0.05) manganites

The formation and specific features of the superstructure in La_0.33Ca_0.67Mn_1?y Fe _y O₃ (y = 0, 0.05) manganites doped with iron are investigated using transmission electron microscopy. The electron diffraction patterns of the manganites are studied in the temperature range 90–300 K, and the high-resolution electron microscope images recorded at temperatures of 91–92 K are analyzed. In both manganites, the structural transition that is accompanied by the formation of the superstructure and which is directly observed from the appearance of additional peaks in the electron diffraction patterns occurs at a temperature that is in close agreement with the charge ordering temperature T _CO determined from the temperature dependences of the magnetization M(T). In the temperature range 90 < T < 200 K, the undoped compound has a commensurate superstructure characterized by the vector q = 1/3a* and triple the unit cell «3a × b × c» (where a ≈ b ≈ √2a _c , c ≈ 2a _c , and a _c ～ 3.9 Å is the lattice parameter of a simple perovskite). The doping with iron (5 at. %) brings about a decrease in the charge ordering temperature T _CO by 50 K and the formation of an incommensurate structure for which the magnitude of the vector q is smaller by approximately 15%. The unit cell of the superstructure in the iron-doped compound is not triple the unit cell but involves defects of ordering, such as quadrupling of the unit cell, numerous translations by a _c √2 along the a direction, and dislocation-type defects in the stripe structure of the charge ordering. These pseudoperiodic defects lead to a decrease in the magnitude of the vector q and are responsible for the incommensurability of the structure. A decrease in the charge ordering temperature T _CO due to the doping with iron and the incommensurability of the superstructure correlate with the change in the concentration of Mn³⁺ Jahn-Teller ions as a result of their replacement by Fe³⁺ non-Jahn-Teller ions.     

Probing the molecular orbitals of FePc near the chemical potential using electron energy-loss spectroscopy

We have studied the electronic structure of iron phthalocyanine (FePc) films at low temperature using electron energy-loss spectroscopy. The electronic excitation spectrum of FePc is rather complex and comprises both π-π^* transitions of the phthalocyanine ligand and transitions that involve the Fe 3d orbitals. The C 1s core excitations provide so far unidentified information on the molecular orbitals. They demonstrate that the Fe 3d orbital with e_g symmetry is energetically located in between the highest occupied and the lowest unoccupied ligand state and that it is not fully occupied.     

Influence of CO molecule on structure stability and electronic properties of silver nanotube

Influence of CO molecule on structure stability and electronic properties of silver nanotube (AgNT) has been systematically investigated by using first-principles calculations based on the density-functional theory. The results indicate that the top site is the most stable for CO adsorption, which is energetically favorable than the bridge site (B1) on the AgNT's surface. The AgNT undergoes a slight structural distortion after the CO adsorption. The binding mechanism between CO and AgNT can be described by the Blyholder's model, and the donation–backdonation process between the CO and Ag states leads to the formation of bonding/antibonding pairs, 5σ_b/5σ_a and 2π_b*/2π_a*. The quantum conductance of the AgNT decreases 1G₀ after CO adsorption, which is promising for the application of CO sensor.     

A shortcut for determining growth mode

Thin and thick films of iron phthalocyanine （FePc） molecules are deposited on a Ag （110） surface. The nature of the FePc growth and the interaction with the substrate have been studied by X-ray photoelectron spectroscopy （XPS）. All of the core level spectra exhibit rigid shifts towards lower binding energies following the deposition of the organic films, each by a different magnitude. A greater change and a larger shift in the Fe2p level as compared to Cls core level reveals that the adsorbate interacts with the substrate mainly via the Fe atom, located at the center of the molecule. An increase/decrease in the intensity of C1 s/Ag3d level is found to be exponentially linked to the overlayer molecular coverage. Finally, the so- called growth/decay curve indicates that FePc thin films initially develop following the FM growth mode and then transform to SK mode, resulting in 3D island aggregation.     

Role of buffer layer in electronic structures of iron phthalocyanine molecules on Au(111)

We investigate the electronic structures of one and two monolayer iron phthalocyanine (FePc) molecules on Au(111) surfaces. The first monolayer FePc is lying flat on the Au(111) substrate, and the second monolayer FePc is tilted at～15° relative to the substrate plane along the nearest neighbour [101ˉ] direction with a lobe downward to the central hole of the unit cell in the first layer. The structural information obtained by first-principles calculations is in agreement with the experiment results. Furthermore, it is demonstrated that the electronic structures of FePc molecules in one-monolayer FePc/Au(111) system are perturbed significantly, while the electronic structures of FePc molecules in the second monolayer in two-monolayer FePc/Au(111) system remain almost unchanged due to the screening of the buffer layer on Au(111).     

Indium-induced superstructures formed on Si(1 1 0) surfaces

Si(1 1 0) surfaces covered with small amounts of In deposit and then annealed at high temperature were investigated by RHEED, and two kinds of superstructures with A = 3a and B = −a + 4b, and A = 3a − 2b and B = −2a + 4b as primitive translational vectors are reported to form on the surfaces.     

The synthesis and photophysical properties of novel cationic tetra pyridiloxy substituted aluminium, silicon and titanium phthalocyanines in water

This work reports on the synthesis, characterisation and photophysical properties of new unquaternized β-2,(3)-tetra-(2 pyridiloxy) aluminium(III) (3a), silicon(IV) (3b), titanium(IV) (3c) phthalocyanines and their water-soluble quaternized counterparts, 4a, 4b and 4c, respectively. The water-soluble silicon(IV) (4b) and titanium(IV) (4c) phthalocyanine derivatives were found to be aggregated in aqueous media but were partially or fully disaggregated in the presence of a surfactant Cremophor^® EL (CEL). The photophysical properties of aggregated complexes were investigated both in the presence of CEL and in pH 11 alone. Low triplet and fluorescence yield were obtained in pH 11 but an improvement was achieved upon addition of CEL for the aggregated complexes. The unquaternized silicon(IV) phthalocyanine complex (3b) gave the highest triplet quantum yield of 0.77 in DMF followed by its quaternized derivative (4b) with triplet yield of 0.73 in pH 11 plus CEL. The highest triplet lifetime of 220 μs was obtained for 4b in the presence of CEL. Higher fluorescence yields of 0.23 were obtained for quaternized water-soluble aluminium(III) phthalocyanine derivative (4a) in the presence of CEL.     

An STM investigation of the interaction and ordering of pentacene molecules on the Ag/Si(1 1 1)-(√3×√3)R30° surface

Scanning tunneling microscopy has been used to study the ordering of pentacene (C₂₂H₁₄) molecules on the Ag/Si(1 1 1)-(√3×√3)R30° surface at room temperature. Two solid phases, S1 and S2, are observed at coverages of ∼0.35 monolayer (ML) and ∼1.0 ML respectively. It is shown that the solid phase S1 has a high-order commensurate lattice, Ag/Si(1 1 1)-(25 × 25)-pentacene, containing 75 molecules. The structure of this phase is determined from STM measurements at very low coverages where it is possible to image both the pentacene molecules and the structure of the Ag/Si(1 1 1) substrate. Two adsorption sites are identified, a three-fold hollow site at the centre of a Ag-trimer (CA-site) and a six-fold hollow site at the centre of the hexagonal arrangement of silver atoms (CB-site). A higher pentacene coverage of ∼1 ML lead to a molecular reorganization and forms a new commensurate structure Ag/Si(1 1 1)-(2 × 3)-pentacene, containing two molecules per unit cell. Because low energy electron diffraction patterns were not obtainable for this system, the structure of this second phase is determined by using the bias voltage as a tunable parameter to “focus” on either the molecular film or on the substrate. In this phase adsorption takes place exclusively on the Ag-trimer (CA) site and the CB-site is lost because of strong lateral molecule-molecule interactions. The role of competition between intermolecular and molecule-substrate interactions and the nature of the adsorption sites in determining the structure of the pentacene layers is discussed.     

X-ray diffraction study of a sequence of phase transitions in Cs2HgCl4 crystals

The temperature behavior of lattice parameters and diffraction patterns of the reciprocal lattice in Cs₂HgCl₄ crystals is studied by x-ray diffraction in the temperature range from 4.2 to 300 K. A sequence of phase transitions is observed and attributed to the evolution of incommensurate and commensurate modulations along the crystallographic a and c axes of a unit cell in the initial Pnma structure.     

First-principles study on the electronic structures of iron phthalocyanine monolayer

The electronic band structure and magnetic properties of iron phthalocyanine (FePc) monolayer were investigated by using the first-principles all-electron full-potential linearized augmented plane wave energy band method. It is found that the ferromagnetic FePc monolayer is energetically more stable than the paramagnetic one. The exchange interaction, which splits the majority and minority bands, influences strongly on the electronic structure near the Fermi level (E_F). Magnetic moment of the central Fe atom is calculated to 1.95 μ_B. The range of the positive polarization of Fe site is larger in the out-of-plane than in the in-plane direction. The FePc ligand remains paramagnetic. The presence of states at E_F indicates the metallic character of FePc monolayer both for the paramagnetic and ferromagnetic states. However, the large density of states at E_F of the majority spins in the ferromagnetic state is expected to cause a phase transition to insulating antiferromagnetic state from the metallic ferromagnetic one.     

Surface-modification of TiO2 with new metalloporphyrins and their photocatalytic activity in the degradation of 4-notrophenol

A new mono-functionalized porphyrin derivative, 5-mono-[4-(2-(4-hydroxy)-phenoxy)ethoxy]-10,15,20-triphenylporphyrin (3) and its Cu(II) (3a), Zn(II) (3b) and Ni(II) (3c) metalloporphyrins were synthesized and characterized by using various spectroscopic techniques. The corresponding 3a, 3b, 3c-TiO₂ photocatalysts were then prepared and characterized by means of FT-IR and diffused reflectance spectra, X-ray diffraction (XRD) and scanning electron microscopy (SEM). The photocatalytic activities of 3a, 3b, 3c-TiO₂ were investigated by testing the photodegradation of 4-nitrophenol (4-NP) in aqueous solution under the halogen lamp irradiation. The results indicated that all the 3a, 3b, 3c enhanced the photocatalytic efficiency of bare TiO₂ in photodegrading the 4-NP, and 3a-TiO₂ exhibited the highest photocatalytic activity. The result is considered a combined action of potential match of 3a with TiO₂ CB and effective impregnated of 3a onto the surface of TiO₂.     

Adsorbed states of substituted α‐aminophosphinic acids on a silver electrode surface: comparison with a colloidal silver substrate

We investigated the interfacial structures of various aromatic (each compound contains one or two phenyls) di‐α‐amino ( L¹ – L³ ) and α‐amino‐α‐hydroxyphosphinic ( L⁴ – L⁶ ) acids immobilized onto an electrochemically roughened silver electrode surface in an aqueous solution using surface‐enhanced Raman scattering (SERS). These structures were compared to those on a colloidal silver surface to determine the relationship between adsorption strength and geometry. The presence of an enhanced ν_19a ring band in the SERS spectra of L⁶ , L² , and L³ on the electrode indicated that the benzene rings of those molecules interact with the electrode surface through localized CC bond(s). We observed significant band broadening of the benzene ring modes for all α‐hydroxyphosphinic acids on both substrates, except for L¹ deposited onto the electrode surface. This suggests the possibility of direct interaction between the ring and Ag, although the benzene ring–surface π overlap is weaker for the colloidal silver than for the Ag electrode. The downward shift in wavenumber and alternations in the enhancement of a ν₁₂ ring band indicate a general increase of tilt angle on both silver substrates in the order L³ < L⁴ < L⁵ < L⁶ . The altered enhancement of the bands due to the vibrations of the  NH₂ and O PO fragments, a finding observed on both silver substrates, strongly suggests that the groups interact with different strength and geometry with these substrates. Copyright © 2009 John Wiley & Sons, Ltd.     

Photoelectron (He(I), He(II) and X-ray) spectroscopy of γ-pyrone and its related sulphur derivatives: valence and core ionization energies and shake-up satellites

The photoelectron He(I) and He(II) spectra of 4H-pyran-4-one (1), 4H-thiopyran-4-one (2), 4H-pyran-4-thione (3) and 4H-thiopyran-4-thione (4) are reported. The assignments are based on experimental evidence, taking into account the results of theoretical calculations. The outermost orbital sequences proposed (X = O, S) are n_X (σ), 3b₁ (π), 1a₂(π) for 1, 2 and 4; and 3b₁(π), n_X(σ) and 1a₂(π) for 3. The shifts of the core-ionization energy values for 1–4 are ascribed to a drift of π-charge from the intracyclic heteroatom towards the carbonyl or thiocarbonyl group. Low-energy shake-up satellites (up to 25% with respect to the main line) are observed in the various energy regions of the XPS spectra. They are qualitatively reproduced by CNDO/2 calculations. The most important satellites derive from the transition in the ion corresponding to the 3b₁ (π) → 4b₁(π*) transition in the UV-visible spectra of the neutral molecules. Charge rearrangements accompanying this transition lead to charge depletion of the core-ionized atom.     

The magnetic phases of NdCu2

The magnetic phase diagram of a NdCu₂ single crystal is investigated by means of specific-heat measurements and neutron diffraction as a function of temperature and external magnetic field applied along the crystallographic b-direction. In the low temperature region we observe three commensurate phases AF1, F1, and F2. Their magnetic structures all consist of ferromagnetic (bc)-planes with different stacking sequences along the a-direction comprising 5, 3 and 8 chemical unit cells, respectively. Above 2.8 T the system is in a ferromagnetically aligned state (F3). Furthermore, there is an incommensurate phase AF3 between the low temperature commensurate phases and the paramagnetic state and, in a very narrow temperature region of only 0.2 K, an intermediate phase AF2 between AF1 and AF3. The Nd-moments are oriented along the b-direction in all phases.     

Adsorption behavior of iron phthalocyanine at the initial stage on Cu(100) surface

The adsorption behavior of iron phthalocyanine (FePc) on the Cu(100) surface at the initial stage has been investigated by combining scanning tunneling microscopy (STM) and density functional theory (DFT) calculations. At low coverage, FePc molecules deposited on the sample surface at room temperature tend to adsorb dispersedly with their molecular planes parallel to the crystallographic directions of the substrate. Another interesting STM observation for the sub-monolayer coverage is that the molecular axes of FePc are aligned along [037] (as well as $\left[0\overline{3}7\right]$) azimuth. At the monolayer coverage and elevated temperature, two types of ordered structures are observed. The FePc adsorption sites for the experimentally observed two distinct ordered domains have been revealed through DFT calculations. With further increasing the coverage, molecular clusters are formed particularly near the step edges.     

Iron phthalocyanine oligomer/Fe3O4 hybrid microspheres and their microwave absorption property

The novel nano-scale iron phthalocyanine oligomer/Fe₃O₄ (FePc/Fe₃O₄) hybrid microspheres were synthesized from iron phthalocyanine oligomer and FeCl₃·6H₂O via a solvent-thermal crystallization route. The morphology and structure of the hybrid microspheres were characterized by Fourier transform infrared spectrophotometer, X-ray diffraction, scanning electron microscopy and transmission electron microscopy. These results showed that the hybrids were monodisperse microspheres and the morphology can be adjusted by controlling pre-polymerization time. The saturation magnetization increased with increase in the pre-polymerization time, while the coercivities decreased. The FePc/Fe₃O₄ hybrid microspheres exhibited novel microwave electromagnetic properties: the dielectric loss was enhanced when the pre-polymerization time increased and a new microwave loss peak appeared at high frequency. The microwave absorbing properties enhanced with increase in the pre-polymerization time and a maximum reflection loss of −29.7 dB was obtained at 11.7 GHz with 6 h of pre-polymerization time when the matching thickness was 3.0 mm. The novel hybrid materials are believed to have potential applications as microwave absorbing materials.     

Effect of oxygen segregation on the surface structure of single-crystalline niobium films on sapphire

Single-crystalline Nb films are grown on (1120) oriented sapphire substrates by electron-beam evaporation in ultra-high vacuum. The films are studied in-situ by RHEED and Auger analysis. At a substrate temperature T _S=750° C the RHEED pattern shows a smooth growth of bcc-Nb in the [110] direction. In addition to the fundamental streaks, we observe superlattice streaks of fractional order in several azimuthal directions. The reciprocal lattice of the surface is determined. The basic vectors of the superlattice in real space are given by b ₁=2a ₁, b ₂=–a ₁+3a ₂ where a ₁ and a ₂ are the basic vectors of the Nb (110) surface. Auger analysis shows that the surface of these films is contaminated with oxygen. Therefore, the superstructure is attributed to a modified surface structure due to segregated oxygen, possibly having diffused from the sapphire to the film surface. The superstructure dissappears during further evaporation of Nb at T _S<450° C with a concomitant decrease of the oxygen signal. Nb films on sapphire with a clean, oxygen-free surface can only be prepared at lower temperatures in an island-growth mode.     

Syntheses and structure characterization of inorganic/organic coordination polymers: Ag(dpa), Co(O3PH)(4,4′-bpy)(H2O), Zn(O3PH)(4,4′-bpy)0.5 and Mn[O2PH(C6H5)]2(4,4′-bpy) (dpa=2,2′-dipyridylamine; 4,4′-bpy=4,4′-bipyridine)

Four novel coordination polymers: Ag(dpa) I, Co(O₃PH)(4,4′-bpy)(H₂O) II, Zn(O₃PH)(4,4′-bpy)_0.5 III and Mn[O₂PH(C₆H₅)]₂(4,4′-bpy) IV (dpa=2,2′-dipyridylamine; 4,4′-bpy=4,4′-bipyridine), were synthesized by microwave heating and characterized by X-ray crystallography. I crystallizes in monoclinic space group P21/n with a=11.576(2) Å, b=5.585(2) Å, c=15.243(4) Å, β=109.00(2)°, V=931.8(3) ų. II crystallizes in monoclinic Cc space group with a=22.477(7) Å, b=5.280(1) Å, c=10.404(4) Å, β=96.08(3)°, V=1227.8(7) ų. III crystallizes in monoclinic P21/c space group with a=9.758(2) Å, b=7.449(3) Å, c=10.277(2) Å, β=100.02(2)°, V=735.6(4) ų. IV crystallizes in monoclinic space group P2/c with a=10.174(1) Å, b=11.817(3) Å, c=18.784(4) Å, β=102.14(1)°, V=2207.8(8) ų. I consists of linear metal–metal chains wrapped by dpa ligands. II and III consist of two-dimensional M^II(O₃PH) inorganic sheets cross-linked by 4,4′-bpy ligands, while IV is formed by Mn[O₂PH(C₆H₅)]₂ sheets cross-linked by 4,4′-bpy ligands. I exhibits two-step thermal decomposition at ~200 and ~250°C, resulting in the reduction of Ag⁺ to Ag metal. II loses its coordination water at ~100°C, leaving vacant coordination sites at Co²⁺ ions, while the original framework remains intact. The removal of 4,4′-bpy in II–IV occurs at elevated temperatures above 250, 200 and 400°C respectively.