Synthesis and characterization of the semiconductor Li0.93Cu0.07Nb3O8: Application to oxygen evolution under visible light

The semiconductor Li_0.93Cu_0.07Nb₃O₈ is prepared by soft chemistry in aqueous electrolyte via Cu²⁺ → Li⁺ exchange between copper nitrate and LiNb₃O₈. The substituted niobate crystallizes in an orthorhombic symmetry and the semiconducting and photo-electrochemical properties are investigated for the first time. The oxide exhibits a dark brown color and the UV–Visible spectroscopy gives an optical gap of 1.42 eV, due to the crystal field splitting of Cu²⁺ in octahedral site. The thermal variation of the conductivity shows that Nb: 4d-electrons are localized and the data are fitted by a small-polaron hopping model σ = σ_o exp {−0.053 eV/kT} with a carrier density thermally activated. The capacitance measurement done in ionic electrolyte (Na₂SO₄, 10⁻² M) indicates n type semiconductor with mixed valences Nb^5+/4+, due to the hetero-valent substitution Li⁺/Cu²⁺, with a flat band potential of 0.28 V_SCE and electrons density of 2.17×10¹⁷ cm⁻³. The Nyquist diagram shows mainly the bulk contribution with a diffusion process. The valence band (6.39 eV below vacuum) derives from O^2-: 2p orbital with a small admixture of Cu²⁺: 3d character while the conduction band is made up of Nb⁵⁺: 4d orbital. The material is successfully tested for the oxygen generation with an evolution rate of 87 µmol mn⁻¹ g⁻¹ under visible light (29 mW cm⁻²) and a quantum yield of 0.35%.     

Preparation and characterization of the semiconductor CuMnO2 by sol-gel route

Nano crystallites of the crednerite CuMnO₂ are prepared by sol–gel method with two-step annealing process. The powder heated at 450 °C under air flow shows a mixture of CuO, Mn₂O₃ and Cu_xMn_3−xO₄. However, when calcined at 900 °C under N₂ atmosphere, the crednerite CuMnO₂ with a monoclinic structure (space group: C2/m) is obtained. The Raman spectrum shows a single peak at 679 cm⁻¹ assigned to A_1g mode whereas the infrared analysis confirms the linearity of CuO₂³⁻ units. The optical transition at 1.70 eV, determined from the diffuse reflectance is attributed to the inter-band d-d transition of Cu⁺ ion. The oxide exhibits semiconducting properties with an activation energy of 0.21 eV. The photo-electrochemical measurement shows p-type conduction due to O²⁻ insertion in the two dimensional lattice. The flat band potential (+0.12 V_SCE), indicates a cationic character of both valence and conduction bands deriving from Cu⁺: 3d orbital.     

Preparation and physical properties of the layered niobate Cu0.5Nb3O8: Application to photocatalytic hydrogen evolution

The new layered niobate Cu_0.5Nb₃O₈ is synthesized by soft chemistry in aqueous electrolyte via Cu²⁺→H⁺ exchange between copper nitrate and HNb₃O₈·H₂O. The characterization of the exchanged product is made by means of thermal gravimetry, chemical analysis, X-ray diffraction and IR spectroscopy. Thermal analysis shows a conversion to anhydrous compound above 500 °C. The oxide displays a semiconductor like behavior; the thermal variation of the conductivity shows that d electrons are strongly localized and the conduction is thermally activated with activation energy of 0.13 eV. The temperature dependence of the thermopower is indicative of an extrinsic conductivity; the electrons are dominant carriers in conformity with an anodic photocurrent. Indeed, the Mott–Schottky plot confirms n-type conduction from which a flat band potential of −0.82 V_SCE, an electronic density of 8.72×10¹⁹ m⁻³ and a depletion width of 4.4 nm are determined. The upper valence band, located at ~5.8 eV below vacuum is made up predominantly of Cu²⁺: 3d with a small admixture of O²⁻: 2p orbitals whereas the conduction band consists of empty Nb⁵⁺: 5s level. The energy band diagram shows the feasibility of the oxide for the photocatalytic hydrogen production upon visible light (29 mW cm⁻²) with a rate evolution of 0.31 mL g⁻¹ min⁻¹.     

Synthesis and semiconducting properties of Na2MnPO4F. Application to degradation of Rhodamine B under UV-light

Na₂MnPO₄F is synthesized by hydrothermal route at 453 K and the physical properties and photo-electrochemical characterizations are reported. The compound crystallizes in a monoclinic system (SG: P 2₁/n) with the lattice constants: a=13.7132 Å, b=5.3461 Å, c=13.7079 Å, β=119.97°. The UV–visible spectroscopy shows an indirect optical transition at 2.68 eV; a further direct transition occurs at 3.70 eV, due to the charge transfer O²⁻: 2p → Mn²⁺: e_g. The thermal variation of the electrical conductivity is characteristic of a semiconducting behavior with activation energy of 39 meV and an electron mobility (µ_318 K=5.56×10⁻⁴ cm² V⁻¹ s⁻¹), thermally activated. The flat band potential (+0.47 V_SCE) indicates that the valence band derives mainly from O²⁻: 2p orbital with a small admixture of F⁻ character while the conduction band is made up of Mn²⁺: t_2g orbital. The electrochemical impedance spectroscopy shows the contribution of both the bulk and grains boundaries. The photocatalytic performance of Na₂MnPO₄F for the degradation of Rhodamine B (RhB) is demonstrated on the basis of the energy diagram. 88% of the initial concentration is degraded under UV light and the oxidation follows a first order kinetic with a rate constant of 0.516 h⁻¹. Neither adsorption nor photolysis is observed. The photoactivity results from the electron transition from the hybridized band (O²⁻, F⁻) to the Mn²⁺: e_g orbital, occurring in the UV region. The catalyst was subjected to three successive photocatalytic cycles, thus proving its long term stability.     

Preparation and characterization of the brownmillerite Sr2Co2O5 as novel photocatalyst in the hydrogen generation

Sr₂Co₂O₅ is a semiconductor belonging to the brownmillerite family; it is prepared by nitrate route and the photo-electrochemical properties are assessed for the first time for the photocatalytic hydrogen production. Thermal analysis indicates the formation of the semiconductor phase at 750 °C. An optical transition at 1.10 eV, directly allowed is obtained from the diffuse reflectance spectrum, due to the internal Co³⁺: d-d transition in octahedral coordination. A flat band potential of 0.037 V_SCE is determined in KOH solution (0.1 M) from the Mott-Schottky characteristic and the results are relevant for the water reduction. The conduction band of Sr₂Co₂O₅ (−0.85 V_SCE), deriving from Co³⁺: 3d orbital is more cathodic than the potential of H₂O/H₂ couple and hydrogen is successfully evolved under visible light. A rate evolution of 68 µmol (g catalyst)⁻¹ min⁻¹ at pH ∼ 12 and a light-to-chemical energy efficiency of 0.82% are determined.     

Electrical and optical properties of Cu2ZnSnS4 grown by a thermal co-evaporation method and its diode application

Cu₂ZnSnS₄ (CZTS) is low cost and constitutes non-toxic materials abundant in the earth crust. Environment friendly solar cell absorber layers were fabricated by a thermal co-evaporation technique. Elemental composition of the film was stated by energy dispersive spectroscopy (EDS). Some optical and electrical properties such as absorption of light, absorption coefficient, optical band gap charge carrier density, sheet resistance and mobility were extracted. Optical band gap was found to be as 1.44 eV, besides, charge carrier density, resistivity and mobility were found as 2.14×10¹⁹ cm⁻³, 8.41×10⁻⁴ Ω cm and 3.45×10² cm² V⁻¹ s⁻¹, respectively. In this study Ag/CZTS/n-Si Schottky diode was fabricated and basic diode parameters including barrier height, ideality factor, and series resistance were concluded using current–voltage and capacitance–voltage measurements. Barrier height and ideality factor values were found from the measurements as 0.81 eV and 4.76, respectively, for Ag/CZTS/n-Si contact.     

Sulfur stoichiometry driven chalcopyrite and pyrite structure of spray pyrolyzed Cu-alloyed FeS2 thin films

We report on fabrication of Cu_xFe_1−xS₂ (CFS) thin films using chemical spray pyrolysis followed by post-sulfurization. Post-sulfurized CFS films were grown with compact and good crystalline texture. The sulfur stoichiometry in CFS films was found to be crucial for determination of its crystal structure. The sulfur deficient CFS films were driven to chalcopyrite CFS (CH-CFS) structure whereas the sulfur cured CFS films were grown with Cu-incorporated pyrite CFS (P-CFS) structure which was confirmed by X-ray diffraction and Raman spectroscopy analysis along with UV–vis spectroscopy measurement. Electrical characterizations of both types of CFS films revealed p-type conductivity with carrier concentration in the range of 10¹⁸–10²⁰ cm⁻³ and mobility of 0.5–9 cm² V⁻¹ s⁻¹. The band gaps of CFS films of CH-CFS structure (0.885–0.949 eV) were found to be less than that of P-CFS structure (0.966–1.156 eV), which indicates its potential application for thermoelectric and photovoltaic devices.     

A study on phase transformation of SnOx thin films prepared by reactive magnetron sputtering

In the paper, SnO_x thin films were deposited by reactive magnetron sputtering from a tin target in O₂ containing working gas. The evolution from Sn-containing SnO to tetravalent SnO₂ films was investigated. The films could be classified into three groups according to their optical band gaps, which are E_g<2.5 eV, E_g=3.0–3.3 eV and E_g>3.7 eV. The electric measurements show that high conductivity can be obtained much easier in SnO₂ than in SnO films. A high electron mobility of 15.7 cm² V⁻¹ s⁻¹, a carrier concentration of 1.43×10²⁰ cm⁻³ and a resistivity of 2.8×10⁻³ Ω cm have been achieved in amorphous SnO₂ films. Films with the optical band gap of 3.0–3.3 eV remain amorphous though the substrate temperature is as high as 300 °C, which implies that °btaining high mobility in p-type SnO is more challenging in contrast to n-type SnO₂ films.     

Structural and optical properties of Cu2FeSnS4 thin film synthesized via a simple chemical method

Cu₂FeSnS₄ thin film, with potential as an effective photovoltaic absorber, was prepared by sulfurizing a (Cu,Sn)S/FeS-structured precursor prepared via successive ionic layer absorption and reaction combined with chemical bath deposition. X-Ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy, and UV-vis-NIR absorbance measurements showed that the Cu₂FeSnS₄ thin film exhibits large agglomeration of rod-shaped grains, a bandgap of E_g=1.22 eV, and a high optical absorption coefficient (>10⁴ cm⁻¹).     

Structural,optical and transport properties of SxZnO

In this paper, S-doped ZnO (S_xZnO) was prepared using sol-gel method at different S amounts. The structural, optical and transport properties were investigated. The introduction of S atoms into the ZnO network was found to lower the crystallization level which results in reducing the crystallite size up to x=0.3. The doping process is confirmed by the observed peak at ~610 cm⁻¹ in the ATR spectrum related to the Zn-S linking. EDX mapping shows a homogeneous distribution of S atoms on the particles surface. The best compromise between the band gap (Eg=2.96 eV), the charge carriers (N_A=2.139×10²² cm⁻³), the conductivity (σ=5.56×10⁻⁴ Ω⁻¹ m⁻¹) and the mobility (µ=16.26×10⁻¹⁴ m² V⁻¹ s⁻¹) is obtained for x=0.1. The conduction mechanism is assumed by small hopping polaron. The S-doping has impacted positively the photocatalytic activity of ZnO, with particularly high performance for S_0.2ZnO.     

Electrochemical growth of tin(II) oxide films: Application in photocatalytic degradation of methylene blue

We have investigated the semiconducting and photoelectrochemical properties of SnO films grown potentiostatically on tin substrate. The oxide is characterized by X-ray diffraction, scanning electron microscopy and Raman spectroscopy. The anodic process corresponds to the formation of SnO·nH₂O pre-passive layer that is removed upon increasing potential due to surface etching at the metal/oxide interface. SnO films deposited for long durations (>50 mn) are uniform and well adhered; they thicken up to ~50 nm by diffusion-controlled process and the growth follows a direct logarithmic law. The thickness is determined by coulometry and the X-ray diffraction indicates the tetragonal SnO phase (SG: P4/mmm) with a crystallite size of 32 nm. The Mott–Schottky plot is characteristic of n type conductivity with an electrons density of 5.72×10¹⁸ cm⁻³, a flat band potential of −0.09 V_SCE and a depletion width of ~10 nm. The valence band, located at 5.91 eV below, vacuum is made up of hybridized O²⁻:2p Sn²⁺:5s while the conduction band (4.45 eV) derives from Sn²⁺:5p orbital. The electrochemical impedance spectroscopy (EIS) measured in the range (10⁻²–10⁵ Hz) shows the contribution of the bulk and grain boundaries. The energy band diagram predicts the photodegradation of methylene blue on SnO films. 67% of the initial concentration (10 mg L⁻¹) disappears after 3 h of exposure to visible light (9 mW cm⁻²) with a quantum yield of 0.072.     

Effects of RTA temperatures on conductivity and micro-structures of boron-doped silicon nanocrystals in Si-rich oxide thin films

In this work, the B-doped Si rich oxide (SRO) thin films were deposited and then annealed using rapid thermal annealing (RTA) to form SiO₂-matrix silicon nanocrystals (Si NCs). The effects of the RTA temperatures on the structural properties, conduction mechanisms and electrical properties of B-doped SRO thin films (BSF) were investigated systematically using Hall measurements, Fourier transform infrared spectroscopy and Raman spectroscopy. Results showed that the crystalline fraction of annealed BSF increased from 41.3% to 62.8%, the conductivity was increased from 4.48×10⁻³ S/cm to 0.16 s/cm, the carrier concentration was increased from 8.74×10¹⁷ cm⁻³ to 4.9×10¹⁸ cm⁻³ and the carrier mobility was increased from 0.032 cm² V⁻¹ s⁻¹ to 0.2 cm² V⁻¹ s⁻¹ when the RTA temperatures increased from 1050 °C to 1150 °C. In addition, the fluctuation induced tunneling (FIT) theory was applicable to the conduction mechanisms of SiO₂-matrix boron-doped Si-NC thin films.     

Theoretical insight into the electronic and photocatalytic properties of Cu2O from a hybrid density functional theory

A comprehensive first-principle investigation, based on hybrid density functional theory, produces strong evidence that the Cu₂O band-edges do satisfy the requirements of the H⁺/H₂ and O₂/H₂O redox levels, demonstrating that it has enough driving force for photocatalytic overall water splitting. The calculated band gap of Cu₂O is 2.184 eV, which is consistent with the experimental value of 2.17 eV. The highly dispersive s–s hybrid states at the conduction band bottom result in a small effective mass of the electron, which is favorable to carrier separation and the carrier transfer to surface, and thus facilitate the reduction of H⁺ to H₂. The strong optical absorption of Cu₂O is beneficial to overall water splitting under visible light irradiation. Possible reasons for no observation of H₂ in some experiments are also discussed. The results address the ongoing controversy associated with photocatalytic overall water splitting of Cu₂O.     

Photo-electrochemical characterization of porous material Fe-FSM-16. Application for hydrogen production

We describe in the present work the photo-electrochemical characterization of iron/folded-sheets mesoporous materials (Fe-FSM-16, Si/Fe=60) synthesized by microwave-assisted hydrothermal (M-H) method and its application for the hydrogen evolution upon visible light. The mesoporous catalyst consists of small Fe₂O₃ particles (～2 nm) spread on SiO₂ with specific surface area of ～800 m² g^?1. The capacitance measurements reveal an iron deficiency and the oxide exhibit p type conductivity with activation energy of 0.07 eV. The optical gap of the hematite (α-Fe₂O₃) is evaluated at 3.24 eV from the diffuse reflectance spectrum. The flat band potential V_fb (?0.54 V_SCE) and the holes density N_D (9.56×10¹⁴ cm^?3) of the hematite are obtained respectively by extrapolating the linear part to C^?2=0 and the slope of the Mott Schottky plot. At pH=7, the conduction band (?0.47 V_SCE) is suitably positioned with respect to the H₂O/H₂ level (?0.59 V_SCE) leading to a spontaneous water reduction. The oxide is stabilized by hole consumption involving SO₃^2? and S₂O₃^2? species and spectacular improvement of the hydrogen evolution is reported with evolution rates of ～461 and 163 μ mol respectively.     

Defect characterization of Tl4GaIn3Se2S6 layered single crystals by photoluminescence

Photoluminescence (PL) spectra of Tl₄GaIn₃Se₂S₆ layered crystals grown by the Bridgman method have been studied in the energy region of 2.02–2.35 eV and in the temperature range of 16–45 K. A broad PL band centered at 2.20 eV was observed at T=16 K. Variations of emission band has been studied as a function of excitation laser intensity in the 0.1 to 149.9 mW cm⁻² range. Radiative transitions from shallow donor level located at 10 meV below the bottom of conduction band to moderately deep acceptor level located at 180 meV above the top of the valence band were suggested to be responsible for the observed PL band. An energy level diagram showing transitions in the band gap of the crystal was plotted taking into account the results of present work and previously reported paper on thermally stimulated current measurements carried out below room temperature. Analysis of the transmission and reflection measurements performed in the wavelength range of 400–1030 nm at room temperature revealed the presence of indirect transitions with 2.22 eV band gap energy.     

Fabric electrodes coated with polypyrrole nanorods for flexible supercapacitor application prepared via a reactive self-degraded template

Wearable energy storage devices that can be used in the garment industry are strongly required to power E-textiles. In this article, polypyrrole (PPy) nanorods were deposited on cotton fabrics via in situ polymerization of pyrrole in the presence of the fibrillar complex of FeCl₃ and methyl orange as a reactive self-degraded template. The obtained fabrics could be directly used as supercapacitor electrodes, with a maximum specific capacitance of 325 F g⁻¹ and an energy density of 24.7 Wh kg⁻¹ at a current density of 0.6 mA cm⁻². The capacitance remained higher than 200 F g⁻¹ after 500 cycles.     

Metal-catalyzed synthesis of ultralong tin dioxide nanobelts: Electrical and optical properties with oxygen vacancy-related orange emission

Tin dioxide (SnO₂) ultralong nanobelts were fabricated on silicon substrate by metal catalyzed Chemical Vapor Deposition (CVD) approach. An optical bandgap of 3.66 eV was calculated by optical absorbance data. Three Raman active modes peaks were observed at 474.4, 633 and 774.4 cm⁻¹. Room temperature photoluminescence (PL) exhibited an orange emission at 600 nm. A vapor–liquid–solid (VLS) process based growth mechanism for the formation of SnO₂ nanobelts was proposed and discussed briefly. Electrical transport characteristics of nanobelts were studied in dark and under ultraviolet (UV) laser. The fabricated device exhibited high photo-response properties under UV light, indicating their potential application as photo-switches and UV detectors.     

2,2-Dicyanovinyl-end-capped oligothiophenes as electron acceptor in solution processed bulk-heterojunction organic solar cells

Three 2,2-dicyanovinyl (DCV) end-capped A-π-D-π-A type oligothiophenes (DCV-OTs) containing dithieno[3,2-b:2′,3′-d]silole (DTSi), cyclopenta[1,2-b:3,4-b′]dithiophene (DTCP) or dithieno[3,2-b:2′,3′-d]pyrrole (DTPy) unit as the central donor part, mono-thiophene as the π-conjugation bridge were synthesized. The absorption spectroscopies, cyclic voltammetry of these compounds were characterized. Results showed that all these compounds have intensive absorption band over 500–680 nm with a LUMO energy level around −3.80 eV, which is slightly higher than that of [6,6]phenyl-C₆₁-butyric acid methyl ester (PC₆₁BM, E_LUMO = −4.01 eV), but lower than that of poly(3-hexylthiophene) (P3HT, E_LUMO = −2.91 eV). Solution processed bulk heterojunction “all-thiophene” solar cells using P3HT as electron donor and the above mentioned oligothiophenes as electron acceptor were fabricated and tested. The highest power conversion efficiency (PCE) of 1.31% was achieved for DTSi-cored compound DTSi(THDCV)₂, whereas PTB7:DTSi(THDCV)₂ based device showed slightly higher PCE of 1.56%. Electron mobilities of these three compounds were measured to be around 10⁻⁵ cm² V⁻¹ s⁻¹ by space charge limited current method, which is much lower than that of PC₆₁BM, and was considered as one of the reason for the low photovoltaic performance.     

Star-shaped self-assembly of an organic thin film transistor sensor in the presence of Cu2+ and CN− ions

In this study we developed organic thin film transistors (OTFTs) for the sensing of metal ions and anions through the self-assembly of a pentacene/Schiff base pyrene derivative. Our bilayer OTFTs displayed attractive device parameters: an electron mobility (μ) of 0.12 cm² V⁻¹ s⁻¹, a threshold voltage (V_th) of 22.20 V, and a five-orders-of-magnitude on/off ratio. This device was sensitive toward Cu²⁺ among 13 metal cations and toward CN⁻ among nine anions, as measured through changes in the values of V_th and I_off in the presence of Cu²⁺ cations and a change in the value of I_sat in the presence of CN⁻ anions. We observed selectivity toward both of these ions in mixed ion solutions, with sensitivity over different concentrations (from 20 to 350 μM for Cu²⁺; from 100 to 350 μM for CN⁻) as well as in sea water. The pyrene derivative self-assembled through pyrene–pyrene^* coordination in the presence of Cu²⁺ ions; the rods of the pyrene derivative broke into smaller pieces upon formation of benzoxazole rings in the presence of CN⁻ ions, as confirmed using atomic force microscopy and fourier transform attenuated total reflection spectroscopy.     

D–A copolymer with high ambipolar mobilities based on dithienothiophene and diketopyrrolopyrrole for polymer solar cells and organic field-effect transistors

Donor–acceptor (D–A) type conjugated polymers have been developed to absorb longer wavelength light in polymer solar cells (PSCs) and to achieve a high charge carrier mobility in organic field-effect transistors (OFETs). PDTDP, containing dithienothiophene (DTT) as the electron donor and diketopyrrolopyrrole (DPP) as the electron acceptor, was synthesized by stille polycondensation in order to achieve the advantages of D–A type conjugated polymers. The polymer showed optical band gaps of 1.44 and 1.42 eV in solution and in film, respectively, and a HOMO level of 5.09 eV. PDTDP and PC₇₁BM blends with 1,8-diiodooctane (DIO) exhibited improved performance in PSCs with a power conversion efficiency (PCE) of 4.45% under AM 1.5G irradiation. By investigating transmission electron microscopy (TEM), atomic force microscopy (AFM), and the light intensity dependence of J_SC and V_OC, we conclude that DIO acts as a processing additive that helps to form a nanoscale phase separation between donor and acceptor, resulting in an enhancement of μ_h and μ_e, which affects the J_SC, EQE, and PCE of PSCs. The charge carrier mobilities of PDTDP in OFETs were also investigated at various annealing temperatures and the polymer exhibited the highest hole and electron mobilities of 2.53 cm² V⁻¹ s⁻¹ at 250 °C and 0.36 cm² V⁻¹ s⁻¹ at 310 °C, respectively. XRD and AFM results demonstrated that the thermal annealing temperature had a critical effect on the changes in the crystallinity and morphology of the polymer. The low-voltage device was fabricated using high-k dielectric, P(VDF-TrFE) and P(VDF-TrFE-CTFE), and the carrier mobility of PDTDP was reached 0.1 cm² V⁻¹ s⁻¹ at V_d = −5 V. PDTDP complementary inverters were fabricated, and the high ambipolar characteristics of the polymer resulted in an output voltage gain of more than 25.