Effect of humidity on the a.c. impedance of CH3NH3SnCl3 hybrid films

Impedance spectroscopy measurements show that complex conductivity of thermally ablated CH₃NH₃SnCl₃ films is strongly enhanced when humidity increases. Coplanar two-electrode test devices are modeled through an equivalent circuit comprising one resistance and two constant phase elements. It is shown that the influence of ambient humidity is mainly resistive. The dynamic responses of the devices to humidification/dehumidification cycles point out that the a.c. current varies by more than three orders of magnitude when humidity is varied between dry air and 80% relative humidity. The rise times are few hundred seconds while fall times are as short as few tens of seconds. This observation suggests that impedance variations are determined by mechanisms involving loosely bound water molecules physisorbed at the surface of the hybrid film. The results obtained are discussed in terms of protonic conduction.     

致密度对填充skutterudite化合物La0.75Fe3CoSb12热电性能的影响

研究了致密度对填充skutterudite化合物La_0.75Fe₃CoSb₁₂热电性能的影响.La_0.75Fe₃CoSb₁₂表现为p型传导，载流子迁移率随着致密度的增加而升高.由于样品中空洞的散射作用，致使电阻率ρ随着致密度的降低而升高，同时造成热导率κ的下降，但塞贝克系数α与致密度关系不大，致密度造成电阻率ρ升高的比率与热导率κ下降的比率相当，致密度不同的样品具有相当的ZT 关键词： 致密度 填充式skutterudite化合物 热电性能     

Humidity controlled crystallization of thin CH3NH3PbI3 films for high performance perovskite solar cell

Control of crystallization of a solution‐processed perovskite layer is of prime importance for high performance solar cells. In spite of the negative effect of water on perovskite solar energy conversion in several previous works, we observed that humidity plays a critical role to develop a thin uniform, dense perovskite film with preferred crystals, in particular, in a device with architecture of ITO/PEDOT:PSS/CH₃NH₃PbI₃/ PC₇₁BM/LiF/Al fabricated by two‐step sequential spin‐coating process. Humidity controlled spin‐coating of CH₃NH₃I on the pre‐formed PbI₂ layer was the most influential process and systematic structural investigation as a function of humidity revealed that grains of CH₃NH₃PbI₃ perovskite crystals increase in size with their preferred orientation while film surface becomes roughened as the humidity increases. The performance of a device was closely related to the humidity dependent film morphology and in 40% relative humidity, the device exhibited the maximum power conversion efficiency of approximately 12% more than 10 times greater than that of a device fabricated at 20% humidity. The results suggest that our process with controlled humidity can be another efficient route for high performance and reliable perovskite solar cells. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Large grained and high charge carrier lifetime CH3NH3PbI3 thin-films: implications for perovskite solar cells

Spin coated perovskite thin films are known to have an issue of pinholes & poor morphology control which lead to poor device-to-device repeatability, that is an impediment to scale-up. In this work, Methylamine vapor annealing process is demonstrated which consistently leads to high-quality perovskite thin-films with an average grain-size of 10–15 μm. The improvement in film morphology enables improvement in effective carrier recombination lifetime, from 21 μs in as-deposited films to 54 μs in vapor-annealed films. The annealed films with large-grains are also more stable in ambient conditions. Devices made on annealed perovskite films are very consistent, with a standard deviation of only 0.7%. Methylamine vapor annealing process is a promising method of depositing large-grain CH₃NH₃PbI₃ films with high recombination lifetime and the devices with improved performance.     

Study of ion transport and materials properties of K+-ion conducting solid polymer electrolyte (SPE): [(1-x) PEO: xCH3COOK]

Study of ion transport behavior in K⁺-ion conducting solid polymer electrolyte (SPE) films: [(1-x) PEO: xCH₃COOK] has been reported. Poly (ethylene oxide) PEO has been used as polymeric host and potassium acetate: CH₃COOK as complexing salt. SPE films in varying salt concentrations have been prepared by hot-press cast method. SPE film: [95PEO: 5CH₃COOK] has been identified as Optimum Conducting Composition (OCC) with room temperature conductivity (σ _rt) ~ 2.74 × 10⁻⁷ S/cm. As a consequence of salt complexation in polymeric host, σ _rt-enhancement of approximately two orders of magnitude was achieved in SPE OCC film. Ion transport property has been characterized in terms of ionic conductivity (σ), total ionic (t _ion)/cation (t ₊) transference numbers using different ac/dc techniques. Temperature-dependent conductivity measurement was done to explain mechanism of ion transport and to evaluate activation energy (E _a). XRD, FTIR, and DSC techniques were used to study materials property in SPE OCC film which also confirmed the complexation of salt in the polymeric host as well as increase in degree of amorphousity.

     

Structural and thermal studies of PVA:NH4I

Proton-conducting polymer electrolytes based on poly vinyl alcohol (PVA; 88% hydrolyzed) and ammonium iodide (NH₄I) has been prepared by solution casting method with different molar ratios of polymer and salt using DMSO as solvent. DMSO has been chosen as a solvent due its high dielectric constant and also its plasticizing nature. The ionic conductivity has been found to increase with increasing salt concentration up to 25 mol% beyond which the conductivity decreases and the highest ambient temperature conductivity has been found to be 2.5×10⁻³ S cm⁻¹. The conductivity enhancement with addition of NH₄I has been well correlated with the increase in amorphous nature of the films confirmed from XRD and differential scanning calorimetry (DSC) analyses. The temperature-dependent conductivity follows the Arrhenius relation. The polymer-proton interactions have been analyzed by FTIR spectroscopy.     

Multistep spin–spray deposition of large-grain-size CH3NH3PbI3 with bilayer structure for conductive-carbon-based perovskite solar cells

Large-grain-size and void-free CH₃NH₃PbI₃ films with bilayer structure are fabricated by spin-coating a PbI₂ layer onto a mesoporous TiO₂ layer and sequentially spraying CH₃NH₃I (methylammonium iodide, MAI) multilayers. The sprayer is controlled by a homemade three-axis computer numerical control machine; thus, the substrates are coated by successive parallel passes achieved by moving the nozzle. Spray deposition at the optimal spray rate and substrate temperature produces a large-grain-size and void-free methylammonium lead iodide (MAPbI₃) bilayer structure. The mesoporous TiO₂ layer plays an important role in electron transport by preventing the return of electrons to the perovskite layer and decreasing the contact resistance at the perovskite/compact TiO₂/fluorine tin oxide interface. When the films are incorporated into a solar cell device with a conductive carbon counter electrode, a maximum power conversion efficiency of 10.58% is realised.     

Reactive ion etching of FePt using inductively coupled plasma

We propose a reactive ion etching (RIE) process of an L1₀-FePt film which is expected as one of the promising materials for the perpendicular magnetic recording media. The etching was carried out using an inductively coupled plasma (ICP) RIE system and an etching gas combination of CH₄/O₂/NH₃ was employed. The L1₀-FePt films were deposited on (1 0 0)-oriented MgO substrates using a magnetron sputtering system. The etching masks of Ti were patterned on the FePt films lithographically. The etch rates of ∼16 and ∼0 nm/min were obtained for the FePt film and the Ti mask, respectively. The atomic force microscopy (AFM) analyses provided the average roughness (R_a) value of 0.95 nm for the etched FePt surface, that is, a very flat etched surface was obtained. Those results show that the highly selective RIE process of L1₀-FePt was successfully realized in the present study.     

Photovoltaic activity in a ZnSe/PEO–chitosan blend electrolyte junction

Thin films of ZnSe and PEO–chitosan blend polymer doped with NH₄I and iodine crystals were prepared to form the two sides of a semiconductor electrolyte junction. ZnSe was electrodeposited on indium tin oxide (ITO) conducting glass. The polymer is a blend of 50 wt% chitosan and 50 wt% polyethylene oxide. The polymer blend was complexed with ammonium iodide (NH₄I), and some iodine crystals were added to the polymer–NH₄I solution to provide the I⁻/I³⁻redox couple. The room temperature ionic conductivity of the polymer electrolyte is 4.32 × 10⁻⁶ S/cm. The polymer film was sandwiched between the ZnSe semiconductor and an ITO glass to form a ZnSe/polymer electrolyte/ITO photovoltaic cell. The open circuit voltage (V _oc) of the fabricated cells ranges between 200 to 400 mV and the short circuit current between 7 to 10 μA.     

Effects of OH concentration and temperature on NO emission characteristics of turbulent non-premixed CH4/NH3/air flames in a two-stage gas turbine like combustor at high pressure

This study examined the effects of OH concentration and temperature on the NO emission characteristics of turbulent, non-premixed methane (CH₄)/ammonia (NH₃)/air swirl flames in two-stage combustors at high pressure. Emission data were obtained using large-eddy simulations with a finite-rate chemistry method from model flames based on the energy fraction of NH₃ (E_NH3) in CH₄/NH₃ mixtures. Although NO emissions at the combustor exit were found to be significantly higher than those generated by CH₄/air and NH₃/air flames under both lean and stoichiometric primary zone conditions, these emissions could be lowered to approximately 300 ppm by employing far-rich equivalence ratios (?) of 1.3 to 1.4 in the primary zone. This effect was possibly due to the lower OH concentrations under far-rich conditions. An analysis of local flame characteristics using a newly developed mixture fraction equation for CH₄/NH₃/air flames indicated that the local temperature and NO and OH concentration distributions with local ? were qualitatively similar to those in NH₃/air flames. That is, the maximum local NO and OH concentrations appeared at local ? of 0.9, although the maximum temperature was observed at local ? of 1.0. Both the temperature and OH concentration were found to gradually decrease with the partial replacement of CH₄ with NH₃. Consequently, NO emissions from CH₄/NH₃ flames were maximized at E_NH3 in the range of 20% to 30%, after which the emissions decreased. Above 2100 K, the NO emissions from CH₄/NH₃ flames increased exponentially with temperature, which was not observed in NH₃/air flames because of the lower flame temperatures in the latter. But, the maximum NO concentration in CH₄/NH₃ flames was occurred at a temperature slightly below the maximum temperature, just as in NH₃/air flames. The apparent exponential increase in NO emissions from CH₄/NH₃ flames is attributed to a similar trend in the OH concentration at high temperatures.     

Neutron scattering study of the structure and dynamics of butane adsorbed on graphite2

Inelastic and elastic neutron scattering have been used to study the dynamics and structure of monolayer films of butane (CH₃(CH₂)₂CH₃) adsorbed on a graphitized carbon powder at 77 K. In addition to the intramolecular torsional modes found in the bulk solid, the inelastic spectra of the films contain new excitations associated with coupling of the molecular motion to the substrate. Model calculations are described which show the monolayer excitation spectrum to be sensitive to the orientation of the adsorbed butane molecule and the location and strength of the bonds to the substrate. For butane we infer that the molecule is adsorbed with the plane of the carbon skeleton parallel to the graphite layers. We have also used elastic neutron diffraction to investigate the possibility of long-range order in the butane films. Although we have not found Bragg peaks indicative of an ordered two-dimensional structure in a 1.5 layer film at 81 K, a large modulation of the graphite 002 Bragg reflection is observed. The experimental approach discussed here would seem to be applicable to the study of the dynamics, molecular orientation, and bonding of other hydrogenous adsorbates as a function of film thickness and temperature. Measurements are presently being extended to propane (CH₃CH₂CH₃) and ethane (CH₃CH₃) adsorbed on graphite.     

Electrical conditioning of diamond-like carbon films for the formation of coated field emission cathodes

Diamond-like carbon (DLC) films deposited on different substrates by plasma enhanced chemical vapour deposition were investigated. Bonding states and film quality were characterized by FT-IR spectroscopy. The influence of the power of plasma and the deposition time on the sp²/sp³ ratio as well as the concentration of CH_n bonds was studied. The influence of sp²/sp³ ratio on the formation process of conducting channels in diamond-like carbon films as a result of electrical breakdown was determined. Reproducible increase of diamond-like carbon film conductivity, with initial sp²/sp³ ratio larger than 0.16, was observed after electrical breakdown.     

Chemical bath-deposited ZnS thin films: Preparation and characterization

Chemical bath deposition of ZnS thin films from NH₃/SC(NH₂)₂/ZnSO₄ solutions has been studied. The effect of various process parameters on the growth and the film quality are presented. The influence on the growth rate of solution composition and the structural, optical properties of the ZnS thin films deposited by this method have been studied. The XRF analysis confirmed that volume of oxygen of the as-deposited film is very high. The XRD analysis of as-deposited films shows that the films are cubic ZnS structure. The XRD analysis of annealed films shows the annealed films are cubic ZnS and ZnO mixture structure. Those results confirmed that the as-deposited films have amorphous Zn(OH)₂. SEM studies of the ZnS thin films grown on various growth phases show that ZnS film formed in the none-film phase is discontinuous. ZnS film formed in quasi-linear phase shows a compact and a granular structure with the grain size about 100 nm. There are adsorbed particles on films formed in the saturation phase. Transmission measurement shows that an optical transmittance is about 90% when the wavelength over 500 nm. The band gap (E_g) value of the deposited film is about 3.51 eV.     

Optical anisotropy of Langmuir-Blodgett films of long-chain acetylenic acids

The optical anisotropy of Langmuir-Blodgett films, along with its variation in the course of polymerization under UV radiation, is studied by ellipsometry at a fixed wavelength of 632.8 nm for several angles of incidence of light. Films of the Cd and Pb salts of acetylenic acids with internal and terminal triple bonds—HC≡ C(CH₂)₂₁COOH (I) and CH₃(CH₂)₁₈C≡CCOOH (II)—are studied. The refractive indices and thicknesses of the films are determined on the basis of a model of a biaxial anisotropic film. It is found that the films of the Pb salt of acid II are biaxial, while the films of the Cd salt of acid II and of the Cd and Pb salts of acid I have nearly uniaxial anisotropy. The calculated thicknesses of monolayers coincide with the thicknesses determined from small-angle x-ray scattering. The anisotropy of the films is shown to vary under UV irradiation. After polymerization of the films, the anisotropy in the plane of the layer virtually vanishes, while that in the direction perpendicular to the interface is retained.     

Emission properties of sequentially deposited ultrathin CH3NH3PbI3/MoS2 heterostructures

Hybrid organic-inorganic perovskite materials have obtained considerable attention due to their exotic optoelectronic properties and extraordinarily high performance in photovoltaic devices. Herein, we successively converted the ultrathin PbI₂/MoS₂ into the CH₃NH₃PbI₃/MoS₂ heterostructures via CH₃NH₃I vapor processing. Atomic force microscopy (AFM)、Scanning electron microscopy (SEM) and X-ray photoemission spectroscopy (XPS) measurements prove the high-quality of the converted CH₃NH₃PbI₃/MoS₂. Both MoS₂ and CH₃NH₃PbI₃ related photoluminescence (PL) intensity quenching in CH₃NH₃PbI₃/MoS₂ implies a Type-II energy level alignment at the interface. Temperature-dependent PL measurements show that the emission peak position shifting trend of CH₃NH₃PbI₃ is opposite to that of MoS₂ (traditional semiconductors) due to the thermal expansion and electron-phonon coupling effects. The CH₃NH₃PbI₃/TMDC heterostructures are useful in fabricating innovative devices for wider optoelectronic applications.     

制备工艺对p型碲化铋基合金热电性能的影响

利用区熔法、机械合金化、放电等离子烧结(SPS)技术、热压法等多种工艺制备了p型碲化铋基热电材料.在300—500K的温度范围内测量了各热电性能参数，包括电导率(σ)、塞贝克系数(α)和热导率(κ)，研究了制备工艺对热电性能的影响.结果表明，所制备的块体材料与同组成区熔晶体相比，性能优值ZT均有不同程度的提高.其中，利用区熔法结合SPS技术可获得热电性能最佳的块体材料，其ZT值达1.15. 关键词： 碲化铋 放电等离子烧结 区熔法 热电性能     

GeC薄膜的射频磁控反应溅射制备及性质

用射频磁控反应溅射法在ZnS衬底上制备了GeC薄膜,研究了工艺参数对Ge靶溅射及GeC薄膜红外透射性能的影响.衬底温度较低时GeC薄膜中含有H,形成了CH₂,CH₃,Ge-CH₃等,使薄膜产生红外吸收;随衬底温度升高,薄膜红外吸收明显减小.靶基距、射频功率、Ar:CH₄气体流量比、总气压对靶面中毒及溅射影响较大,但对GeC薄膜红外吸收影响较小.靶面中毒严重时,所制备无氢GeC薄膜附着性能差,随靶中毒减弱薄膜附着性能变好.优化工艺后,在ZnS衬底上制备了附着性能良好的无氢GeC薄膜,其折射率约为1.78,薄膜中C的含量比Ge的大,二者主要形成了C—Ge键.所制备的GeC/GaP红外增透保护膜系对ZnS衬底有良好的增透效果. 关键词： GeC薄膜 红外透射光谱 射频磁控溅射 XPS     

Microstructural properties of GaN grown on a Si(110) substrate by gas-source molecular beam epitaxy: Dependence on the ammonia flux

The microstructural properties of a GaN thin film grown on a Si(110) substrate under various ammonia (NH₃)-flux conditions were observed to study growth mode and defect evolution. The surface flatness of GaN thin films was improved with the increase of the NH₃ flux while the thickness was decreased by increasing the NH₃ flux. In addition, the crystalline quality of the GaN film grown under the lower NH₃ flux (100 sccm) was better than that of the film under the higher NH₃ flux (400 sccm). The different dislocation behaviors depending on NH₃ fluxes were observed; the low density of dislocations was measured and most of dislocations penetrating the thin film was mixed- and edge-type dislocations when GaN was grown under the low NH₃ flux condition while the high density of dislocation and many mixed- and screw-type dislocations penetrating the film were observed in the GaN film grown under the high NH₃ flux. These phenomena are demonstrated by using a kinetic model related to the role of NH₃.     

Surface morphology, growth rate and quality of diamond films synthesized in hot filament CVD system under various methane concentrations

Hot filament chemical vapor deposition (CVD) technique has been used to deposit diamond films on silicon substrate. In the present study, diamond films were grown at various vol.% CH₄ in H₂ from 0.5% to 3.5%, at substrate temperature and pressure of 850 °C and 80 torr, respectively. Scanning electron microscopy, X-ray diffraction and Raman spectroscopy were employed to analyze the properties of deposited films. The formation of methyl radicals as a function of vol.% CH₄ not only changes film morphology but also increase film growth rate. At low, intermediate and high vol.% CH₄, cluster, faceted cubes and pyramidal features growth, were dominant. By increasing vol.% CH₄ from 0.5% to 3.5%, as the growth rate improved from ∼0.25 μm/h to ∼2.0 μm/h. Raman studies features revealed high purity diamond films at intermediate range of vol.% CH₄ and grain density increased by increasing CH₄ concentration. The present study represents experimentally surface morphology, growth rate and quality of diamond films grown in hot filament CVD system at various CH₄ concentrations.     

Sonochemical synthesis of CH3NH3PbI3 perovskite ultrafine nanocrystal sensitizers for solar energy applications

The organic–inorganic hybrid perovskite CH₃NH₃PbI₃ is becoming an interesting material in the field of energy harvesting. This material is one of the cleanest and cheapest components in solar cells which is available in ample amounts. However, most of the previous research work was done on thin film of this material. In the present work we describe the preparation of a powder containing nanoparticles of CH₃NH₃PbI₃ using a sonochemical method. Characterization of the product was done by various methods, such as HRTEM, FTIR, PL, DLS and XRD. The particles were found to be highly crystalline (tetragonal crystal structure), polygonal in shape and having diameters of 10–40 nm.