Raman study of KMnF3 perovskite crystals doped by Na+

A study of the influence of cationic Na⁺ substitution in the archetype KMnF₃ perovskite crystal was performed using the Raman method. The Raman spectra of mixed K_1-xNa_xMnF₃ crystals with x = 0.029, 0.048 and 0.065 were recorded versus temperature and fully interpreted in terms of a “one mode” behaviour. In addition to the soft mode not completely vanishing close to Tc, attention was especially paid to evidence of static and dynamical disorder. From this point of view the behaviour of the hard Raman modes versus temperature has been studied together with two unexpected Raman bands in the cubic phase. The interpretation has been made within the more general framework of structural disorder existing in such perovskites with anisotropic interactions.     

Implantation as a tool for performing selective materials (application to solar energy conversion)

A selective solar material must absorb most of the solar spectrum, principally the visible light, and reflect the IR light.

Insulators are generally transparent in a wide part of the optical spectrum and the defects are revealed in these crystals by strong absorption bands. On the other hand, metals absorb much of the IR and near IR light and have a large reflection coefficient in the same region of the spectrum. In previous papers^1,2 it has been shown that metallic colloids, formed by precipitation of impurities in insulators, are responsible for a strong absorption band. Such metallic inclusions may be easily produced in most insulators by implantation. According to the nature of the implanted metal a selective absorption can be obtained. So a composite material (cermet) may be performed combining a colloidal absorption in the visible and a metallic reflection. We will discuss the different ways to achieve these properties using direct ion beam implantation.

Various cermets (LiF: Na, Au; MgO: Na, Au) have been studied as function of energy (0.1-1 MeV) and dose (10¹⁶-10¹⁷ ions/cm²). Colloids are completely developed by consecutive annealing.⁴

The modelization of these cermets requires a careful characterization by optical methods (spectrophotometry) and microscopic investigation (TEM, SEM, RBS, SIMS).⁷ These techniques are used to determine the filling factor and the concentration profile of metal in the insulating matrix.

With the help of the Maxwell-Garnett theory and using a single or multilayer model it is possible to suggest an interpretation of the optical properties.     

Impact of work function of back contact of perovskite solar cells without hole transport material analyzed by device simulation

The impact of the work function of a metal back contact on lead methylammonium tri-iodide based perovskite solar cells without hole transport material (HTM) was analyzed using device simulation. The elimination of the HTM is attractive in terms of the simplification of device structure and fabrication process. In the solar cell, a back junction is formed by the perovskite absorber and metal back contact. The device simulation revealed that the elimination of the HTM did not change the built-in voltage (V_bi) of the device when the work function of the metal back contact (?_M) was similar to the valence band maximum of the absorber (E_{v_absorber}). In the HTM-free structure, V_bi showed a high value if ?_M was equal to or deeper than E_{v_absorber}. In contrast, when ?_M was shallower than E_{v_absorber}, V_bi monotonically decreased, resulting in the decrease in open-circuit voltage of the device. The results showed the importance of the ?_M matching to maintain V_bi, which is useful guideline for the design of the HTM-free perovskite solar cells.     

Comparison of Activated Carbon,Multiwalled Carbon Nanotubes,and Cadmium Hydroxide Nanowire Loaded on Activated Carbon as Adsorbents for Kinetic and Equilibrium Study of Removal of Safranine O

Activated carbon (AC), multiwalled carbon nanotube (MWCNT), and cadmium hydroxide nanowire loaded on activated carbon (Cd(OH)₂-NW-AC) have been used for the removal of safranine O (SO) from wastewater. The effects of various parameters including pH, temperature, concentration of the dye, amount of adsorbents, and contact time on the SO adsorption efficiency for all adsorbents has been investigated. Graphical correlation of fitting experimental data to various adsorption isotherm models like those of Langmuir, Freundlich, Tempkin, and Dubinin–Radushkevich for all adsorbents have been calculated. It was found that safranine O adsorption on all adsorbents was endothermic and feasible in nature. Fitting the experimental data to different kinetic models suggests that the adsorption process follows pseudo-second-order kinetics with involvement of the particle diffusion mechanism.     

SMA-g-MPEG comb-like polymer as a dispersant for Al2O3 suspensions

SMA-g-MPEG comb-like polymer is first employed as the dispersant of Al₂O₃ suspensions in this paper. The comb-like polymer has anionic polycarboxylate backbone, which makes the polymer easily absorbed on the cationic surface of Al₂O₃ particles; on the other hand, the comb-like polymer has hydrophilic MPEG side chains, which extend into the solution to provide steric repulsion after the comb-like polymer is absorbed on the surface of Al₂O₃ particles. The adsorption behavior, zeta potential, apparent viscosity, granularity and TEM images of the Al₂O₃ suspensions using SMA-g-MPEG as dispersant are investigated. The addition of SMA-g-MPEG improves the dispersibility and decreases the apparent viscosity of the Al₂O₃ suspension observably. The impacts of the length of side chains on the dispersion of Al₂O₃ suspensions are particularly discussed. The adsorbed molecular number of the dispersant decreased by increasing the length of side chains. The zeta potential of Al₂O₃ suspension is more negative by using comb-like polymer with shorter side chains. Based on the steric repulsion and adsorbed molecular number, SMA-g-MPEG with moderate length of side chain is found to have the best dispersibility for Al₂O₃ suspension.     

Cocktail effect of Fe2O3 and TiO2 semiconductors for a high performance dye-sensitized solar cell

The bi-semiconductors of TiO₂ and Fe₂O₃ were used as a photoelectrode material in a high performance dye-sensitized solar cell due to cocktail effects from the two conduction bands. The size of the semiconductors was reduced by using a paint shaker to enlarge the contact area of the semiconductor with the dye or electrolyte. The fill factor and the efficiency of the prepared dye-sensitized solar cell were improved by over 16% and 300%, respectively; these parameters were measured from a current-voltage curve that was based on the effects of the Fe₂O₃ co-semiconductor and the size reduction. A mechanism is suggested wherein the conduction band of Fe₂O₃ works to prohibit the trapping effects of electrons in the conduction band of TiO₂. This result is attributed to the prevention of electron recombination between electrons in the TiO₂ conduction band with dye or electrolytes. The mechanism is suggested based on impedance results, which indicate improved electron transport at the interface of the TiO₂/dye/electrolyte.     

Pentacene as a hole transport material for high performance planar perovskite solar cells

A cost-effective and efficient organic semiconductor pentacene was developed as a hole transport layer (HTL) material to replace classical PEDOT:PSS for planar perovskite solar cells (PSCs). As expected, the pentacene based device exhibits power conversion efficiency (PCE) of 15.90% (J_sc of 19.44 mA/cm², V_oc of 1.07 V, and FF of 77%), comparable to the PEDOT:PSS based device (PCE of 15.65%, J_sc of 18.78 mA/cm², V_oc of 1.07 V, and FF of 77%) under the same experimental conditions. The excellent performance of vacuum deposited pentacene is mainly attributed to the high efficient charge extraction and transfer in device due to the high-quality perovskite film grown on the top of pentacene substrate and a favorable energy-level alignment together with a desired downward band bending formed at the perovskite/pentacene interface. Our research has confirmed that pentacene could be served as a promising HTL material to achieve effective and potentially economical planar type PSCs.     

Antiferromagnetism of perovskite EuZrO3 from a first-principles study

Electronic structure and magnetic properties of perovskite EuZrO₃ have been investigated using the ab initio density-functional calculations with local spin density approximation (LSDA) and LSDA+U methods. The results that are obtained reveal that the antiferromagnetic G-type arrangement is more stable than other possible configurations. The ground G-AFM state shows the insulator property with an energy gap of about 0.27 eV at U=0 eV. It is found that the energy gap strongly depends on the correction potential parameter of U due to the strong interaction of the f electrons of Eu in EuZrO₃. The spin magnetic moment of Eu ions is predited to be 6.82μ_B, which is in well agreement with the experimental result of 6.87μ_B.     

Influence of small-molecule material on performance of polymer solar cells based on MEH-PPV:PCBM blend

In this work,the influence of a small-molecule material,tris(8-hydroxyquinoline) aluminum (Alq 3),on bulk het-erojunction (BHJ) polymer solar cells (PSCs) is investigated in devices based on the blend of poly(2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene) (MEH-PPV) and [6,6]-phenyl-C 61-butyric acid methyl ester (PCBM).By dop-ing Alq 3 into MEH-PPV:PCBM solution,the number of MEH-PPV excitons can be effectively increased due to the energy transfer from Alq 3 to MEH-PPV,which probably induces the increase of photocurrent generated by excitons dissociation.However,the low carrier mobility of Alq 3 is detrimental to the efficient charge transport,thereby blocking the charge collection by the respective electrodes.The balance between photon absorption and charge transport in the active layer plays a key role in the performance of PSCs.For the case of 5 wt.% Alq 3 doping,the device performance is deteriorated rather than improved as compared with that of the undoped device.On the other hand,we adopt Alq 3 as a buffer layer instead of commonly used LiF.All the photovoltaic parameters are improved,yielding an 80% increase in power conversion efficiency (PCE) at the optimum thickness (1 nm) as compared with that of the device without any buffer layer.Even for the 5 wt.% Alq 3 doped device,the PCE has a slight enhancement compared with that of the standard device after modification with 1 nm (or 2 nm) thermally evaporated Alq 3.The performance deterioration of Alq 3-doped devices can be explained by the low solubility of Alq 3,which probably deteriorates the bicontinuous D-A network morphology;while the performance improvement of the devices with Alq 3 as a buffer layer is attributed to the increased light harvesting,as well as blocking the hole leakage from MEH-PPV to the aluminum (Al) electrode due to the lower highest occupied molecular orbital (HOMO) level of Alq 3 compared with that of MEH-PPV.     

Towards anode with low indium content as effective anode in organic solar cells

In₂O₃ thin films (100 nm thick) have been deposited by reactive evaporation of indium, in an oxygen partial atmosphere. Conductive (σ = 3.5 × 10³ S/cm) and transparent films are obtained using the following experimental conditions: oxygen partial pressure = 1 × 10⁻¹ Pa, substrate temperature = 300 °C and deposition rate = 0.02 nm/s. Layers of this In₂O₃ thick of 5 nm have been introduced in AZO/In₂O₃ and FTO/In₂O₃ multilayer anode structures. The performances of organic photovoltaic cells, based on the couple CuPc/C₆₀, are studied using the anode as parameter. In addition to these bilayers, other structures have been used as anode: AZO, FTO, AZO/In₂O₃/MoO₃, FTO/In₂O₃/MoO₃ and FTO/MoO₃. It is shown that the use of the In₂O₃ film in the bilayer structures improves significantly the cell performances. However the open circuit voltage is quite small while better efficiencies are achieved when MoO₃ is present. These results are discussed in the light of surface roughness and surface work function of the different anodes.     

The nature of antimony-enriched surface layer of Fe-Sb mixed oxides

Antimony segregation is a common feature in Fe-Sb mixed oxides, which have been widely applied as catalysts in selective oxidation and ammoxidation reactions. This paper attempts to shed a light on the cause of such a common feature and on the nature of the antimony-enriched surface layer over FeSbO₄ by means of XPS surface analysis. Single-phase FeSbO₄ samples prepared by different methods were studied, and the antimony in their surface layer is a mixture of both Sb⁵⁺ and Sb³⁺ rather than single Sb⁵⁺. Their surface composition is close to FeSb₂O₆, which could be described as (FeSbO₄)(Sb₂O₄)_δ, δ = 0.5, and it is not “Fe(II)Sb(V)₂O₆” as suggested in literature. Fe-Sb mixed oxides with Sb/Fe > 1 (mol/mol) are mixtures of FeSbO₄ and Sb₂O₄, and the surface of FeSbO₄ grains would be a layer of (FeSbO₄)(Sb₂O₄)_δ, δ ≥ 0.5. Fe-Sb mixed oxides with Sb/Fe < 1 are mixtures of FeSbO₄ and Fe₂O₃, and the surface of FeSbO₄ grains would be a layer of (FeSbO₄)(Sb₂O₄)_δ, δ ≤ 0.5, but the remaining Fe₂O₃ would be encapsulated by a layer of FeSbO₄.     

Recent progress in photoelectrochemical water splitting for solar hydrogen production

A water splitting photoelectrochemical (PEC) cell can convert solar energy to hydrogen fuels directly. The challenges for practical application are to fabricate photoelectrodes with high efficiency, good durability and low cost. In this review, we focus on recent progress of some promising photoelectrode materials, including BiVO₄${}_4$, α$\alpha$-Fe₂O₃, Ta₃N₅ photoanodes and Cu₂ZnSnS₄ photocathodes. Several new strategies to enhance the performance of a PEC cell, such as surface exfoliation, suppressing back reaction and loading dual-layer catalysts, are discussed.     

Identification of the high-temperature superconducting phase in the Y-Ba-Cu-O system as the perovskite YBa2Cu3O7±δ

The oxide responsible for high-temperature superconductivity (onset ∼100 K, zero resistance above liquid N₂ temperature) is found to be YBa₂Cu₃O₇±δ. Contribution No. 432 from the Solid State and Structural Chemistry Unit     

Synthesis of single-crystal perovskite PbCrO3 through a new reaction route at high pressure

As a new member in the family of Mott system, perovskite PbCrO₃ has recently been uncovered to exhibit fantastic structural transition under pressure, coupled with magnetic, electronic, and ferromagnetic transitions, which provide many opportunities for understanding of correlated system. However, it is still challenging to synthesize high-quality single-crystal PbCrO₃, leading to the limited exploration of this Mott compound. In this work, we formulate a new high-pressure reaction route for preparation of high-quality PbCrO₃ crystals between PbCl₂ and Na₂CrO₄ at high pressure of 5–10?GPa and at high temperature of 750–1500°C. Because of the formation of reaction byproduct NaCl, the final product can readily be separated by washing with water. The obtained sample is in the form of single crystal with crystallite size up to 200?μm. In addition, combined with X-ray diffraction measurement, a tentative pressure-temperature synthesis diagram of PbCrO₃ is mapped out from the reaction between PbCl₂ and Na₂CrO₄ and the reaction mechanism is also explored in detail.     

A solution-processable small-organic molecules containing carbazole or phenoxazine structure as hole-transport materials for perovskite solar cells

Three low molecular weight compounds bearing carbazole units (1,6-di{3-[2-(4-methylphenyl)vinyl]carbazol-9-yl}hexane and 9,9'-di{6-[3-(2-(4-methylphenyl)vinyl)-9-carbazol-9-yl]hexyl}-[3,3']bicarbazole) and phenoxazine structure (10-butyl-3,7-diphenylphenoxazine) were tested as hole-transporting materials in perovskite solar cells. Two of them were successfully applied as hole transporting layers in electroluminescent light emitted diodes. The examined compounds were high-thermally stable with decomposition temperature found at the range of 280–419 °C. Additionally, DSC measurement revealed that they can be converted into amorphous materials. The compounds possess adequate ionization potentials, to perovskite energy levels, being in the range of 5.15–5.36 eV. The significant increase in power conversion efficiency from 1.60% in the case of a device without hole-transporting layer, to 5.31% for device with 1,6-di{3-[2-(4-methylphenyl)vinyl]carbazol-9- yl}hexane was observed.     

Dielectric characteristics of cation deficient TbMnO3

Cation deficient polycrystalline Tb_1−xMnO₃ (x= 0.05, 0.10) and TbMn_1−yO₃ (y =0.05, 0.10) samples were fabricated by conventional solid-state reaction. The complex dielectric properties of the cation deficient TbMnO₃ were investigated as the function of temperature (77 K≤T≤350 K) and frequency (100 Hz≤ f≤ 200 kHz) separately. Compared to the parent TbMnO₃, the cation deficient TbMnO₃ samples exhibit not only high dielectric constant but also low dissipation factor. Nyquist plots of complex impedance show that the dielectric properties originate from two main relaxation sources, i.e. bulk contributions and grain boundary effects.     

Doctor-bladed Cu2ZnSnS4 light absorption layer for low-cost solar cell application

The doctor-blade method is investigated for the preparation of Cu₂ZnSnS₄ films for low-cost solar cell application. Cu₂ZnSnS₄ precursor powder, the main raw material for the doctor-blade paste, is synthesized by a simple ball-milling process. The doctor-bladed Cu₂ZnSnS₄ films are annealed in N₂ ambient under various conditions and characterized by X-ray diffraction, ultraviolent/vis spectrophotometry, scanning electron microscopy, and current-voltage (J-V) meansurement. Our experimental results indicate that (i) the X-ray diffraction peaks of the Cu₂ZnSnS₄ precursor powder each show a red shift of about 0.4°; (ii) the high-temperature annealing process can effectively improve the crystallinity of the doctor-bladed Cu₂ZnSnS₄, whereas an overlong annealing introduces defects; (iii) the band gap value of the doctor-bladed Cu₂ZnSnS₄ is around 1.41 eV; (iv) the short-circuit current density, the open-circuit voltage, the fill factor, and the efficiency of the best Cu₂ZnSnS₄ solar cell obtained with the superstrate structure of fluorine-doped tin oxide glass/TiO₂/In₂S₃/Cu₂ZnSnS₄/Mo are 7.82 mA/cm², 240 mV, 0.29, and 0.55%, respectively.     

Stabilization of formamidinium lead iodide perovskite precursor solution for blade-coating efficient carbon electrode perovskite solar cells

Formamidinium lead triiodide (FAPbI₃) is a research hotspot in perovskite photovoltaics due to its broad light absorption and proper thermal stability. However, quite a few researches focused on the stability of the FAPbI₃ perovskite precursor solutions. Besides, the most efficient FAPbI₃ layers are prepared by the spin-coating method, which is limited to the size of the device. Herein, the stability of FAPbI₃ perovskite solution with methylammonium chloride (MACl) or cesium chloride (CsCl) additive is studied for preparing perovskite film through an upscalable blade-coating method. Each additive works well for achieving a high-quality FAPbI₃ film, resulting in efficient carbon electrode perovskite solar cells (pero-SCs) in the ambient condition. However, the perovskite solution with MACl additive shows poor aging stability that no α-FAPbI₃ phase is observed when the solution is aged over one week. While the perovskite solution with CsCl additive shows promising aging stability that it still forms high-quality pure α-FAPbI₃ perovskite film even the solution is aged over one month. During the solution aging process, the MACl could be decomposed into methylamine which will form some unfavored intermediated phase inducing δ-phase FAPbI₃. Whereas, replacing MACl with CsCl could effectively solve this issue. Our founding shows that there is a great need to develop a non-MACl FAPbI₃ perovskite precursor solution for cost-effective preparation of pero-SCs.     

Electromagnetic and mechanical properties of Fe3O4-coated amorphous carbon nanotube/polyvinyl chloride composites

Electromagnetic wave absorbing properties of absorbing composites depend on the dielectric and magnetic loss generally. In this paper, using Fe₃O₄-coated amorphous carbon nanotubes (ACNTs-Fe₃O₄) fabricated using a chemical synthesis–hydrothermal treatment method as an absorber and polyvinyl chloride (PVC) as a matrix, electromagnetic and mechanical properties of ACNT-Fe₃O₄/PVC composite were investigated. The results showed that the dielectric and magnetic losses of ACNT-Fe₃O₄/PVC composite were significantly enhanced in 8.2–12.4 GHz compared to ACNT/PVC composite, which improved absorbing properties, while slightly changing the mechanical properties.