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The alpha phase of hematite (α-Fe2O3) is one of the most promising catalysts for photoelectrochemical (PEC) water splitting among several photoanode materials due to its suitable band gap and stability in aqueous solutions. The surface structure and morphology of films play pivotal roles in the enhancement of water oxidation reaction kinetics. In this work, α-Fe2O3 films were produced via either spray pyrolysis (SP), chemical vapor deposition (CVD), or aerosol-assisted chemical vapor deposition (AACVD). Their structural and morphological properties were subsequently characterized by powder x-ray diffraction (PXD), scanning electron microscopy (SEM), and Raman spectroscopy. High-quality thin films were best achieved by AACVD annealed at 525 °C, possessing an average thickness of 0.75 µm with 85% transmittance and an optical absorption onset at 650 nm. The results showed that the thermal oxidation process achieved at 525 °C eliminated undesired impurity phases, such as FeO and Fe3O4 , and enabled the microstructure to be optimized to facilitate the generation and transport of photogenerated charge carriers. The optimized α-Fe2O3 film showed a stable PEC water oxidation current density of ~1.23 mA cm-2 at 1.23 V (vs. RHE), with an onset potential of 0.76 V, under AM 1.5 irradiation. The obtained higher current density of pristine α-Fe2O3 thin films obtained by the AACVD method is unique, and the films presented good photocurrent stability with 92% retention after 6 h. Data from electrochemical impedance spectroscopy (EIS) corroborated these results, identifying fast charge transfer kinetics with decreased resistance and an electron lifetime of 175 µs. Quantitative measurements showed that 1.2 μmol cm-2 of oxygen could be produced at the photoanode in 6 h.

Herein, we successfully synthesized high-quality Hf-ZnO thin films with various Hf contents (0, 3, 6, 9, 12, and 15 at. %), which showed both superhydrophilic (6% Hf-ZnO) and ultrahydrophobic (15% Hf-ZnO) wetting behavior. Different characterization methods were opted to recognize the structural (XRD, SEM, AFM) and defect properties (XPS) of the pristine and doped materials, to understand the mechanisms underlying the tuning of wetting behavior (contact angle). Hafnium doping plays a noteworthy role in tuning the morphology of the ZnO nanostructures, roughness of the material surface, generation of defects, Lewis acid-base interactions, and wettability properties. We achieved a superhydrophilic surface with 6% Hf-ZnO owing to a smooth surface, less basicity, and maximum concentration of oxygen vacancies, and also an ultrahydrophobic surface with 15% Hf-ZnO because of the rough surface, high basicity, and minimum concentration of oxygen vacancies. The as prepared Hf-ZnO samples showed stable performance (stability, wearability, weatherability, and antifouling) under real-life conditions marking them multifunctional and biosafe material to be effectively used in solar and building's window. A wetting mechanism was established to relate the wetting behavior of the samples to oxygen vacancies (active sites for water dissociation: resulted due to charge mismatch of host cation (Zn2+) by the doped cation (Hf4+)), roughness (smooth surface (Wenzel) with minimum Rrms (0.588) portraying hydrophilic property and rough caltropic surface (Cassie-Baxter) with maximum Rrms (2.522) portraying hydrophobic property), basicity (H2O: Lewis Base; ZnO: Lewis acid; HfO2: Lewis base) and morphology (tube-like structure (0-6% Hf-ZnO) and caltrop-like structure (12-15% Hf-ZnO)).

The development of low-cost, durable and efficient photocatalyst for overall photoelectrochemical water splitting is in demand to overcome the renewable energy crises. Herein, we demonstrate the efficient photoelectrochemical water splitting by cobalt (Co) incorporated zinc oxide (Zn1-xCoxO) thin films deposited via aerosol assisted chemical vapour deposition (AACVD) technique. The as-deposited Co incorporated ZnO thin films were characterised by powdered X-ray diffraction (pXRD), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM) and ultra violet-visible spectroscopy (UV-Vis). These films with different concentration of cobalt were investigated for water splitting applications and the best results were achieved for the films with 15% Co incorporation.

Nanostructured Bi2WO6 thin film electrodes with enhanced solar energy conversion and photocatalytic properties have been fabricated using Aerosol-Assisted Chemical Vapor Deposition (AACVD). By conveniently controlling the deposition process parameters, Bi2WO6 electrodes were fabricated with nanoplates and hierarchical buckyball-shaped microsphere structures morphology. A detailed study has been conducted to correlate the structure and morphology with the photoelectrochemical (PEC) and photocatalytic dye degradation performance. The PEC investigations revealed that the hierarchical buckyball-shaped microsphere structured Bi2WO6 electrodes have shown the photocurrent density of 220 &mu, Acm&minus, 2 while nanoplates have a photocurrent density of 170 &mu, 2 at 0.23 V (vs. Ag/AgCl/3M KCl) under AM1.5 illumination. The PEC characterization of Bi2WO6 electrodes also reveals that the photocurrent density and photocurrent onset potential is strongly dependent on the orientation and morphology, hence the deposition parameters. Similarly, the methylene blue (MB) and rhodamine B (RhB) photodegradation performance of Bi2WO6 electrodes also show a strong correlation with morphology. This finding provides an appropriate route to engineer the energetic and interfacial properties of Bi2WO6 electrode to enhance solar energy conversion and the photocatalytic performance of semiconductor materials.

Acanthite (Ag2S) thin films were fabricated on fluorine doped tin oxide coated conducting glass substrates by aerosol assisted chemical vapor deposition (AACVD) using silver cluster [Ag4{S2CN(C2H5)2}3(C5H5N)2]n·nNO3·2nH2O (1) [where (S2CN(C2H5)2) = diethyldithiocarbamate, C5H5N = pyridine] as a single source precursor. Cluster (1) was synthesized by the reaction of sodium diethyldithiocarbamate with silver nitrate in a mixture of acetone and pyridine. (1) was analyzed by melting point, elemental analysis, Fourier transform infrared spectroscopy, proton nuclear magnetic resonance spectroscopy, thermogravimetry and single crystal X-ray studies. Single crystal X-ray studies showed that (1) crystallizes in the triclinic crystal system with a = 11.4372(3), b = 11.6768(3), and c = 16.3672(4) A and α = 105.817(3), β = 97.891(3), and γ = 93.274(3)° in the space group P-1. Thermogravimetric analysis revealed that (1) undergoes facile thermal decomposition at 400 °C to give a stable residual mass consistent with the formation of Ag2S. Thin films grown from a 0.02 M solution of (1) in pyridine at 350 and 400 °C using AACVD technique were characterized by powder X-ray diffraction, field emission scanning electron microscopy (FESEM), energy dispersive X-ray and ultraviolet-visible spectrophotometry. FESEM images of the films exhibited well-defined nanorods with length > 1000 nm and diameter 100–150 nm grown without any cracks, fractures or directional preference. A band gap of 1.05 eV was estimated by extrapolating the linear part of a Tauc plot recorded for the films. The photoelectrochemical (PEC) characteristics recorded under Air Mass 1.5 illumination indicated a photocurrent density of 220 μA cm− 2 at 0.0 V vs Ag/AgCl/3 M KCl. The optical and PEC characteristics of the deposited thin films proved their suitability for PEC applications.

New hexanuclear zinc complex, Zn6(OAc)8(μ-O)2(dmae)4 (1) (OAc = acetato, dmae = N,N-dimethyl aminoethanolato) has been synthesized and characterized by its melting point, elemental analysis, Fourier transform infrared spectroscopy, atmospheric-pressure chemical-ionization mass spectrometry, thermal gravimetric analysis, and single crystal X-ray analysis. The complex (1) crystallizes in the monoclinic space group C2/c. The high solubility of complex (1) in organic solvents such as alcohol, THF, and toluene and low decomposition temperature as compared to Zn(OAc)2 make it a promising single source candidate for the deposition of nanostructured ZnO thin films by aerosol-assisted chemical vapor deposition. Films with various nanostructures, morphology, and crystallographic orientation have been deposited by controlling the deposition temperature. The deposited films have been characterized by X-ray diffraction, scanning electron microscopy, and energy dispersive X-ray analysis. The optical characterization of...

A single molecular heterobimetallic complex, [Co2Ti(m3-O)(TFA)6(THF)3] (1) [TFA=trifluoroacetate, THF=tetrahydrofuran], was synthesized, structurally and spectroscopically characterized and implemented as a single-source precursor for the preparation of CoTiO3–CoO composite thin films by aerosol-assisted chemical vapour deposition (AACVD). The precursor complex was prepared by interaction of Co(OAc)2.4H2O [OAc=(CH3COO � )] with Ti(iso-propoxide)4 in the presence of trifluoroacetic acid in THF, and was analysed by melting point, CHN, FT-IR, single-crystal X-ray diffraction and thermogravimetric analysis. The precursor complex thermally decomposed at 480 � C to give a residual mass corresponding to a CoTiO3–CoO composite material. Good-quality crystalline CoTiO3–CoO composite thin films deposited at 500 � C by AACVD and characterized through powder X-ray diffraction and scanning electron microscopy/energy-dispersive X-ray spectroscopy shows that the crystallites have a rose-flower-like morphology with an average petal size in the range of 2–6mm. Copyright © 2012 John Wiley & Sons, Ltd.

A heterobimetallic single molecular precursor, [Fe2Ti4(μ-O)6(TFA)8(THF)6] (1) [TFA = trifluoroacetate, THF = tetrahydrofuran], was synthesized by the simple reaction of [Fe3O(OAc)6(H2O)3]NO3·4H2O [OAc = acetato] with tetrakis(2-ethoxyethanalato)titanium(IV) in the presence of trifluoroacetic acid in THF. The synthesized precursor was analyzed by melting point, CHN analysis, FTIR, single crystal X-ray diffraction and thermogravimetric analysis. Complex (1) crystallizes in the orthorhombic space group Pca21 with cell dimensions a = 19.2114(14), b = 20.4804(15) and c = 17.2504(12) A, and the complex undergoes thermal decomposition at 490 °C to give a residual mass corresponding to an Fe2TiO5–TiO2 composite mixture. The synthesized precursor was utilized for deposition of Fe2TiO5–TiO2 composite thin films by aerosol-assisted chemical vapor deposition (AACVD) on glass substrates at 500 °C using argon as the carrier gas. Scanning electron microscopy (SEM), energy dispersive X-ray (EDX) and X-ray powder diffraction (XRD) analyses of the thin films suggest the formation of good quality crystalline thin films of an Fe2TiO5–TiO2 composite with an average grain size of 0.105–0.120 μm.

Semiconducting nanocrystalline ZnFe 2 O 4 thin films were deposited by aerosol-assisted chemical vapour deposition (AACVD) for photoelectrochemical (PEC) water splitting. The effect of deposition parameters such as solvent type, temperature and deposition time on PEC properties has been investigated. The SEM analysis illustrated that the morphology of the films changes significantly with the change of solvent. The films deposited from ethanolic precursor solution have a morphology consisting of interconnected cactus-like ZnFe 2 O 4 structure growing vertically from the FTO substrate. The current–voltage characterization proved that the nanocrystalline ZnFe 2 O 4 electrodes exhibit n -type semiconducting behaviour and the photocurrent was found strongly dependent on the deposition solvent, deposition temperature and deposition time. The maximum photocurrent density of 350 μA/cm 2 at 0.23 V vs. Ag/AgCl/3 M KCl (∼1.23 V vs. RHE) was obtained for the ZnFe 2 O 4 electrode synthesized using the optimum deposition temperature of 450 °C, the deposition time of 35 min, and 0.1 M solution of ( 1 ) in ethanol. The electrode gave an incident photon to electron conversion efficiency of 13.5% at an applied potential of 0.23 V vs. Ag/AgCl/3 M KCl at 350 nm. The donor density of the ZnFe 2 O 4 was 3.24 × 10 24 m −3 and the flatband potential is approximately −0.17 V, which remarkably agrees with the photocurrent onset potential of −0.18 V vs. Ag/AgCl/3 M KCl.

Bi2S3 nanotubes and nanoparticle in the form of thin films were deposited on fluorine doped SnO2 (FTO) coated conducting glass substrates by Aerosol Assisted Chemical Vapor Deposition (AACVD) using tris-(N,N-diethyldithiocarbamato)bismuth(III), [Bi(S2CN(C2H5)2)3]2 (1) as a precursor. Thin films were deposited from solutions of (1) in either chloroform, dichloromethane, or a 1:1 mixture of chloroform and toluene at temperature between 350 to 450 °C and characterized by X-ray diffraction (XRD), UV−vis spectroscopy, field emission gun scanning electron microscopy (FEGSEM), and energy dispersive X-ray (EDX) analysis. FEGSEM images of films deposited from chloroform or dichloromethane exhibit well-defined and evenly distributed nanotubes with an average internal diameter of 40 nm. Films deposited from chloroform/toluene, on the other hand, have compact nanostuctured morphology. Bandgaps of 1.85 and 1.8 eV were estimated for nanotubes and nanoparticles, respectively, by extrapolating the linear part of the Tauc...

A single source heterobimetallic complex [Fe 2 (acac) 4 (dmaeH) 2 ][ZnCl 4 ] ( 1 ) (acac = 2,4-pentanedionate, dmaeH = N,N-dimethylaminoethanol), was synthesized in high yield. The complex was analyzed by melting point, Fourier transfer infrared spectroscopy (FT-IR) and thermogravimetric analysis (TGA). The structure of the cation was established by single crystal X-ray analysis on a derivative, [Fe 2 (acac) 4 (dmaeH) 2 ][ZnCl 3 (THF)] 2 ·THF ( 1a ) (THF = tetrahydrofuran). TGA analysis showed that complex ( 1 ) undergoes facile thermal decomposition at 450 °C to give ZnFe 2 O 4 residue. In-house designed aerosol assisted chemical vapour deposition equipment was used to deposit thin films of ZnFe 2 O 4 on fluorine doped SnO 2 coated conducting glass substrate at 450 °C. X-ray diffraction analysis proved the formation of crystalline ZnFe 2 O 4 phase and scanning electron microscopy revealed the film morphology with well defined crystalline particles evenly distributed in the range 150–200 nm. The indirect and direct bandgap energies of the thin films were estimated to be 1.76 and 2.10 eV, respectively.

α-Fe2O3 thin film photoelectrodes were fabricated by aerosol-assisted chemical vapor deposition (AACVD) using a new hexanuclear iron precursor [Fe6(PhCOO)10(acac)2(O)2(OH)2]·3C7H8 (1) (where PhCOO = benzoate and acac = 2,4-pentanedionate). The precursor (1) designed for AACVD has a low decomposition temperature and sufficient solubility in organic solvents and was synthesized by simple chemical techniques in high yield. It was characterized by melting point, FT-IR, X-ray crystallography, and thermogravimetry (TGA). The TGA analysis proved that complex (1) undergoes facile thermal decomposition at 475 °C to give iron oxide residue. In-house designed AACVD equipment was used to deposit highly crystalline thin films of α-Fe2O3 on fluorine-doped SnO2 coated glass substrates at 475 °C in a single step. The material properties were characterized by XRD, XPS, and Raman spectroscopy, and the results confirmed that films were highly crystalline α-Fe2O3 and free from other phases of iron oxide. Further analysis of ...

Homobi-, -tri- and -tetranuclear copper(II) oligomeric complexes, [Cu(dmap)(OAc)(H2O)]2·H2O (1), [Cu3(dmae)3(acac)2Cl] (2) and [Cu(dmae)(TFA)]4 (3), have been prepared by reacting Cu(OAc)2·H2O with dmapH, [Cu(dmae)Cl]4 with Na(acac) and Cu(dmae)2 with Cu(TFA)2 [dmae = (N,N-dimethylamino)ethanolate, dmap = (N,N-dimethylamino)propanolate, TFA = trifluoroacetate, and acac = 2,4-pentanedionate], respectively and characterized by melting point, elemental analysis, FT-IR and single-crystal X-ray diffraction. The crystal analysis shows that bi- (1) and trinuclear (2) complexes crystallize in the triclinic, while the tetranuclear complex 3 belongs to the monoclinic crystal system. TGA and AACVD experiments prove that the complexes undergo facile thermal decomposition in the temperature range 300–460 °C to deposit thin films of pure copper metal. The SEM and XRD analyses of the thin films suggest the formation of Cu crystallites with grain sizes of 100–340 nm (for 1), 75.4–90.8 nm (for 2 and 3). (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

Nanostructured thin films of α-Fe2O3 were prepared through atmospheric chemical vapour deposition (APCVD) using ferrocene and iron pentacarbonyl as precursors. Higher optical absorption was observed for hematite films prepared using ferrocene, which was attributed to the higher packing density. Photoelectrochemical (PEC) studies of the films prepared using ferrocene showed superior performance to that of iron pentacarbonyl. Photocurrent density of 540 µA/cm2 and 1.5 µA/cm2 at 1.23 VRHE was achieved for hematite films prepared using ferrocene and iron pentacarbonyl, respectively. Our findings suggest that ferrocene can be used as a promising alternative to iron pentacarbonyl to prepare hematite photoelectrodes using APCVD.

The high nuclearity zinc complex, Zn-6(OAc)(8)(mu-OH)(2)(dmae)(2)(dmaeH)(2) (1) (OAc = acetate and dmaeH = N,N'-dimethylaminoethanol), having a low decomposition temperature and sufficiently high solubility in non-polar solvents, was synthesized by a simple chemical technique in high yield and analyzed by melting point, elemental analysis, FTIR, NMR, single crystal X-ray crystallography and thermal analysis. Aerosol-assisted chemical vapor deposition technique was used to deposit a high-quality thin film with good adhesion to the glass substrate at relatively low temperature (320 degrees C). Scanning electron microscopy of the film shows clearly distinct crystallites of uniform shape with 2.4-2.9 mu m size. Powder X-ray diffraction measurements have indicated the deposition of a crystalline phase of hexagonal ZnO with space group P63mc. (c) 2007 Elsevier B.V. All rights reserved.

Heterobimetallic molecular precursors [Ti4(dmae)6(mu-OH)(mu-O)6Cu6(OAc)9.H2O] (1) and [Zn7(OAc)10(mu-OH)6Cu5(dmae)4Cl4] (2) for the deposition of metal oxide thin films of Cu6Ti4O12 (Cu3TiO4, TiO2) and Cu5Zn7O12 (ZnO, CuO) were prepared by the interaction of Ti(dmae)4 with Cu(OAc)2.2H2O for 1 and tetrameric (N,N-dimethylamino)ethanolatocopper(II) chloride, [(dmae)CuCl]4 [where dmae = (N,N-dimethylamino)ethanolate] with Zn(OAc)2.2H2O (where OAc = acetate) for 2 in dry toluene. Both complexes were characterized by melting point, elemental analysis, Fourier transform IR, fast atom bombardment mass spectrometry, thermal analysis (TGA), and single-crystal X-ray diffraction. TGA and XRD prove that complexes 1 and 2 undergo facile thermal decomposition at 300 and 460 degrees C to form thin films of Cu/Ti and Cu/Zn mixed-metal oxides, respectively. Scanning electron microscopy and XRD of the thin films suggest the formation of impurity-free crystallite mixtures of Cu3TiO4 and TiO2, with average crystallite sizes of 22.2 nm from complex 1 and of ZnO and CuO with average crystallite sizes of 26.1 nm from complex 2.

Rate constants for recombination and hole transfer during oxygen evolution at illuminated alpha-Fe(2)O(3) electrodes were measured by intensity-modulated photocurrent spectroscopy and found to be remarkably low. Treatment of the electrode with a Co(II) solution suppressed surface recombination but did not catalyse hole transfer. Intermediates in the reaction were detected spectroscopically.

The mixed metal complex [Zn(TFA)(3)(μ-OH)Cu(3)(dmae)(3)Br]·THF (1) and its isostructural analogues ([Zn(TFA)(3)(μ-OH)Cu(3)(dmae)(3)Cl]·THF (2) and [Zn(TFA)(3)(μ-OH)Cu(3)(dmae)(3)Cl/Br]·THF (3)) have been prepared by a simple metal ligand assembly method and were characterized by their melting points, elemental analysis, IR spectroscopy, thermogravimetry and single crystal X-ray structures. The compounds are distinguished only by the nature of the halide ions and are made up of the same [Zn(TFA)(3)(μ-OH)Cu(3)(dmae)(3)X]·THF molecular building block with Cu(3)ZnO(4) cubane moieties as the central core in which the four metal ions and four oxygen atoms are joined together in alternate positions of the cuboid. All the complexes crystallize with similar packing and crystallographically related symmetry settings, distinguished mainly by the degree of disorder within the complexes and the ordering of the complexes in the structures. The triclinic cell of (1) emulates the monoclinic cell of (2) and is pseudomerohedrally twinned by a symmetry operation of the monoclinic cell. The molecules in (2) are 1:1 disordered around a crystallographic mirror plane. The structure of the mixed halogen compound (3) in turn is a superstructure of the less symmetric structures of (1) and (2) formed by ordering of the complexes along the longest axis of (3). Aerosol-assisted chemical vapour deposition (AACVD) experiments showed that they are promising precursors to deposit thin films of crystalline Cu/ZnO composites. The surface morphology, microstructure, chemical composition and crystallinity of the resulting Cu/ZnO composite thin films were analysed by scanning electron microscopy (SEM), X-ray diffraction (XRD) and energy dispersive X-ray analysis (EDAX), which suggest that the films are thin, crystalline, uniform, smooth and tightly adherent to the substrates with average crystallite sizes in a range between 40.2 and 80.0 nm. Particle sizes, shapes and film morphology were investigated as a function of precursor and decomposition temperature.

A single-source heterobimetallic complex Ni2Ti2(OEt)2(mu-OEt)6(acac)4 (1) (acac=2,4-pentanedionate), having a low decomposition temperature and sufficient solubility in organic solvents, was synthesized by simple chemical techniques in high yield and analyzed by melting point, FTIR, single crystal X-ray analysis and thermal analysis. The TGA analysis proved that complex (1) underwent facile thermal decomposition at 500 degrees C to give NiTiO3 residue. In-house designed aerosol assisted chemical vapor deposition equipment was used to deposit high quality thin films of NiTiO3 on a SnO2 coated conducting glass substrate at 500 degrees C. An XRD analysis of the thin films proved the formation of crystalline NiTiO3 with average grain size 42 nm. Scanning electron microscopic studies (SEM) show that the thin films consist of flat, plate-like nanoparticles. The current-potential characteristics recorded under AM1.5 illumination indicate that NiTiO3 thin films are anodic and the photocurrent density at 1.23 V vs RHE (Reversible Hydrogen Electrode) is about 40 microA cm(-2).

Heterobimetallic molecular precursors [Ti(4)(dmae)(6)(mu-OH)(mu-O)(6)Cu(6)(benzoate)(9)] (1) and [Ti(4)(dmae)(6)(mu-OH)(mu-O)(6)Cu(6)(2-methylbenzoate)(9)] (2) were prepared by the interaction of Ti(dmae)(4) [dmae=N,N-dimethylaminoethanolate] with Cu(benzoate)(2).2H(2)O for (2) and Cu(2-methylbenzoate)(2).2H(2)O for (2), respectively, in dry toluene, for selective deposition of Cu/Ti oxide thin films for possible technological applications. Both the complexes were characterized by melting point, elemental analysis, FT-IR, thermal analysis and single crystal X-ray analysis. Complex (1) crystallizes in the triclinic space group P-1 and complex (2) in the rhombohedral space group R-3. The TGA analysis proves that complexes (1) and (2) undergo facile thermal decomposition at 550 degrees C to form copper titanium mixed metal oxides. The SEM/EDX and XRD analyses suggest the formation of carbonaceous impurity free good quality thin films of crystalline mixtures of beta-Cu(3)TiO(4) and TiO(2) for both (1) and (2), with average grain sizes of 0.29 and 0.74 microm, respectively. Formation of two different homogeneously dispersed oxide phases is also supported by electrical impedance measurements.

Ba(dmae)2 (dmaeH=N,N-dimethylaminoethanol, C4H11NO) reacts with Co(acac)2 (acac=2,4-pentanedionate) to produce the trinuclear coordination complex [Ba2Co(acac)4(dmae)3(dmaeH)] in an 85% yield. Spectroscopic and single-crystal X-ray diffraction experiments indicate that the complex possesses a structure in which two barium atoms and a cobalt atom are bridged by acac and dmae groups. The barium centers are eight and nine coordinate with BaO7N and BaO7N2 coordination spheres while the cobalt is a more regular CoO5N octahedron. This 2:1 heterobimetallic molecular complex was investigated as precursor for the deposition of thin film by AACVD. The film was characterized by SEM and XRD. TGA shows that the complex starts thermal decomposition upon heating in nitrogen atmosphere at 105 degrees C to produce barium cobalt oxide material of a Ba2CoO3 composition with an orthorhombic structure. The synthetic approach detailed here represents a unique route to the formation of a heterobimetallic barium cobalt coordination complex.

A simple method of depositing morphology- and phase-tailored thin films of copper(i) oxide and metallic copper from [Cu(dmae)(TFA)]4·CH2Cl2 (1), where dmae is N,N-dimethylaminoethanolato and TFA is trifluoroacetato, on glass substrates by aerosol-assisted chemical vapour deposition is demonstrated. The tetrameric precursor 1 was synthesized and its structure was determined by single-crystal X-ray crystallography. Precursor 1 was applied for the deposition of nanostructured thin films of copper(i) oxide and copper nanowires at 250 and 375°C respectively. The deposited thin films were characterized by powder X-ray diffraction, field emission scanning electron microscopy, energy-dispersive X-ray diffraction, and ultraviolet–visible spectroscopy. The results indicate that the phase and morphology of the deposited material are strongly dependent on deposition temperature. UV-vis studies reveal that copper(i) oxide films with a band gap of 2.48 eV may find possible applications in tandem photoelectrochemical devices as light-absorbing material.

Heterobimetallic molecular Cu–Ni and Cu–Co complexes [Cu2Ni4(acac)2(dmae)2(dmaeH)2(OH)(TFA)6] (1) and [Cu2Co4(acac)2(dmae)2(dmaeH)2(OH)(TFA)6] (2) [dmae = N,N-dimethylaminoethanol, TFA = trifluoroacetic acid and acac = 2,4-pentanedionate] were prepared and tested as precursors for the deposition of mixed metal oxide composite thin films. The complexes were synthesized by reaction of the tetrameric copper(II) complex [Cu(dmae)(TFA)]4 with M(acac)2·xH2O [M = Ni, x = 2; Co, x = 1] in THF and were characterized by melting point, elemental analysis, FT-IR spectroscopy, TG/DTG and single-crystal X-ray diffraction. The complexes are isomorphous and crystallize in the triclinic centrosymmetric space group P. Aerosol assisted chemical vapour deposition (AACVD) studies carried out on (1) and (2) showed that they are promising precursors for the deposition of thin films of crystalline CuO–NiO and Cu2O–CoO composites, respectively. The size, shape, surface morphology, microstructure, chemical composition and crystallinity of the resulting mixed-metal oxide composite thin films were analysed by scanning electron microscopy (SEM) and X-ray diffraction (XRD). The analysis proved that the thin films are crystalline, uniform, smooth and tightly adherent to the substrates.

Heterobimetallic molecular precursors [Ba(dmap)4Cu4(OAc)6·THF] (1) and [Ba(dmap)4Cu4(TFA)6·THF] (2) [dmap = N,N-dimethylaminopropanolate, OAc = acetate and TFA = trifluoroacetate] for the deposition of barium–copper composite oxide thin films, were prepared by the interaction of Ba(dmap)2 with Cu(OAc)2 for 1 and Cu(TFA)2 for 2, in THF. Both heterobimetallic complexes were characterized by melting point, elemental analysis, FT-IR spectroscopy, mass spectrometry and single crystal X-ray diffraction. X-Ray crystallography shows that complex 1 crystallizes in the orthorhombic space groupP212121 with the cell dimensions a = 11.2621(11) A, b = 18.2768(17) A and c = 24.541(2) A, while complex 2 crystallizes in the monoclinic space groupC2/c with a = 23.9288(14) A, b = 19.8564(12) A, c = 25.5925(15) A and β = 112.4390(10)°. Thermal gravimetric analysis shows that both complexes 1 and 2 undergo controlled thermal decomposition at 450 °C and 400 °C, respectively, to give mixed metal oxide composite thin films. Scanning electron microscopy (SEM), energy dispersive X-ray (EDX) and X-ray powder diffraction (XRD) analyses of the thin films suggest the formation of good quality crystalline thin films of BaCuO2–CuO composites from both 1 and 2, with average grain sizes of 105 to 175 nm and 110 to 205 nm, respectively.