Effect of metal dopants on the electrochromic performance of hydrothermally-prepared tungsten oxide materials.

Electrochromic (EC) glass has the potential to significantly improve energy efficiency in buildings by controlling the amount of light and heat that the building exchanges with its exterior. However, the development of EC materials is still hindered by key challenges such as slow switching time, low coloration efficiency, short cycling lifetime, and material degradation. Metal doping is a promising technique to enhance the performance of metal oxide-based EC materials, where adding a small amount of metal into the host material can lead to lattice distortion, a variation of oxygen vacancies, and a shorter ion transfer path during the insertion and de-insertion process. In this study, we investigated the effects of niobium, gadolinium, and erbium doping on tungsten oxide using a single-step solvothermal technique. Our results demonstrate that both insertion and de-insertion current density of a doped sample can be significantly enhanced by metal elements, with an improvement of about 5, 4 and 3.5 times for niobium, gadolinium and erbium doped tungsten oxide, respectively compared to a pure tungsten oxide sample. Moreover, the colouration efficiency increased by 16, 9 and 24% when doping with niobium, gadolinium and erbium, respectively. These findings suggest that metal doping is a promising technique for improving the performance of EC materials and can pave the way for the development of more efficient EC glass for building applications.

Enhanced Carrier Collection in Cd/In-Based Dual Buffers in Kesterite Thin-Film Solar Cells from Nanoparticle Inks.

Increasing the power conversion efficiency (PCE) of kesterite Cu2ZnSn(S,Se)4 (CZTSSe) solar cells has remained challenging over the past decade, in part due to open-circuit voltage (VOC)-limiting defect states at the absorber/buffer interface. Previously, we found that substituting the conventional CdS buffer layer with In2S3 in CZTSSe devices fabricated from nanoparticle inks produced an increase in the apparent doping density of the CZTSSe film and a higher built-in voltage arising from a more favorable energy-band alignment at the absorber/buffer interface. However, any associated gain in VOC was negated by the introduction of photoactive defects at the interface. This present study incorporates a hybrid Cd/In dual buffer in CZTSSe devices that demonstrate an average relative increase of 11.5% in PCE compared to CZTSSe devices with a standard CdS buffer. Current density-voltage analysis using a double-diode model revealed the presence of (i) a large recombination current in the quasi-neutral region (QNR) of the CZTSSe absorber in the standard CdS-based device, (ii) a large recombination current in the space-charge region (SCR) of the hybrid buffer CZTSSe-In2S3-CdS device, and (iii) reduced recombination currents in both the QNR and SCR of the CZTSSe-CdS-In2S3 device. This accounts for a notable 9.0% average increase in the short-circuit current density (JSC) observed in CZTSSe-CdS-In2S3 in comparison to the CdS-only CZTSSe solar cells. Energy-dispersive X-ray, secondary-ion mass spectroscopy, and grazing-incidence X-ray diffraction compositional analysis of the CZTSSe layer in the three types of kesterite solar cells suggest that there is diffusion of elemental In and Cd into the absorbers with a hybrid buffer. Enhanced Cd diffusion concomitant with a double postdeposition heat treatment of the hybrid buffer layers in the CZTSSe-CdS-In2S3 device increases carrier collection and extraction and boosts JSC. This is evidenced by electron-beam-induced current measurements, where higher current generation and collection near to the p-n junction is observed, accounting for the increase in JSC in this device. It is expected that optimization of the heat treatment of the hybrid buffer layers will lead to further improvements in the device performance.

Biocompatible Ti3Au-Ag/Cu thin film coatings with enhanced mechanical and antimicrobial functionality.

BACKGROUND: Biofilm formation on medical device surfaces is a persistent problem that shelters bacteria and encourages infections and implant rejection. One promising approach to tackle this problem is to coat the medical device with an antimicrobial material. In this work, for the first time, we impart antimicrobial functionality to Ti3Au intermetallic alloy thin film coatings, while maintaining their superior mechanical hardness and biocompatibility. METHODS: A mosaic Ti sputtering target is developed to dope controlled amounts of antimicrobial elements of Ag and Cu into a Ti3Au coating matrix by precise control of individual target power levels. The resulting Ti3Au-Ag/Cu thin film coatings are then systematically characterised for their structural, chemical, morphological, mechanical, corrosion, biocompatibility-cytotoxicity and antimicrobial properties. RESULTS: X-ray diffraction patterns reveal the formation of a super hard ß-Ti3Au phase, but the thin films undergo a transition in crystal orientation from (200) to (211) with increasing Ag concentration, whereas introduction of Cu brings no observable changes in crystal orientation. Scanning and transmission electron microscopy analysis show the polyhedral shape of the Ti3Au crystal but agglomeration of Ag particles between crystal grains begins at 1.2 at% Ag and develops into large granules with increasing Ag concentration up to 4.1 at%. The smallest doping concentration of 0.2 at% Ag raises the hardness of the thin film to 14.7 GPa, a 360% improvement compared to the ∼4 GPa hardness of the standard Ti6Al4V base alloy. On the other hand, addition of Cu brings a 315-330% improvement in mechanical hardness of films throughout the entire concentration range of 0.5-7.1 at%. The thin films also show good electrochemical corrosion resistance and a > tenfold reduction in wear rate compared to Ti6Al4V alloy. All thin film samples exhibit very safe cytotoxic profiles towards L929 mouse fibroblast cells when analysed with Alamar blue assay, with ion leaching concentrations lower than 0.2 ppm for Ag and 0.08 ppm for Cu and conductivity tests reveal the positive effect of increased conductivity on myogenic differentiation. Antimicrobial tests show a drastic reduction in microbial survival over a short test period of < 20 min for Ti3Au films doped with Ag or Cu concentrations as low as 0.2-0.5 at%. CONCLUSION: Therefore, according to these results, this work presents a new antimicrobial Ti3Au-Ag/Cu coating material with excellent mechanical performance with the potential to develop wear resistant medical implant devices with resistance to biofilm formation and bacterial infection.

Routes to increase performance for antimony selenide solar cells using inorganic hole transport layers.

Simple compound antimony selenide (Sb2Se3) is a promising emergent light absorber for photovoltaic applications benefiting from its outstanding photoelectric properties. Antimony selenide thin film solar cells however, are limited by low open circuit voltage due to carrier recombination at the metallic back contact interface. In this work, solar cell capacitance simulator (SCAPS) is used to interpret the effect of hole transport layers (HTL), i.e., transition metal oxides NiO and MoO x thin films on Sb2Se3 device characteristics. This reveals the critical role of NiO and MoO x in altering the energy band alignment and increasing device performance by the introduction of a high energy barrier to electrons at the rear absorber/metal interface. Close-space sublimation (CSS) and thermal evaporation (TE) techniques are applied to deposit Sb2Se3 layers in both substrate and superstrate thin film solar cells with NiO and MoO x HTLs incorporated into the device structure. The effect of the HTLs on Sb2Se3 crystallinity and solar cell performance is comprehensively studied. In superstrate device configuration, CSS-based Sb2Se3 solar cells with NiO HTL showed average improvements in open circuit voltage, short circuit current density and power conversion efficiency of 12%, 41%, and 42%, respectively, over the standard devices. Similarly, using a NiO HTL in TE-based Sb2Se3 devices improved open circuit voltage, short circuit current density and power conversion efficiency by 39%, 68%, and 92%, respectively.

Ex situ Ge-doping of CZTS nanocrystals and CZTSSe solar absorber films.

Cu2ZnSn(S,Se)4 (CZTSSe) is a promising material for thin-film photovoltaics, however, the open-circuit voltage (VOC) deficit of CZTSSe prevents the device performance from exceeding 13% conversion efficiency. CZTSSe is a heavily compensated material that is rich in point defects and prone to the formation of secondary phases. The landscape of these defects is complex and some mitigation is possible by employing non-stoichiometric conditions. Another route used to reduce the effects of undesirable defects is the doping and alloying of the material to suppress certain defects and improve crystallization, such as with germanium. The majority of works deposit Ge adjacent to a stacked metallic precursor deposited by physical vapour deposition before annealing in a selenium rich atmosphere. Here, we use an established hot-injection process to synthesise Cu2ZnSnS4 nanocrystals of a pre-determined composition, which are subsequently doped with Ge during selenisation to aid recrystallisation and reduce the effects of Sn species. Through Ge incorporation, we demonstrate structural changes with a negligible change in the energy bandgap but substantial increases in the crystallinity and grain morphology, which are associated with a Ge-Se growth mechanism, and gains in both the VOC and conversion efficiency. We use surface energy-filtered photoelectron emission microscopy (EF-PEEM) to map the surface work function terrains and show an improved electronic landscape, which we attribute to a reduction in the segregation of low local effective work function (LEWF) Sn(II) chalcogenide phases.

Recovery Mechanisms in Aged Kesterite Solar Cells.

For successful long-term deployment and operation of kesterites Cu2ZnSn(S x Se1-x )4 (CZTSSe) as light-absorber materials for photovoltaics, device stability and recovery in kesterite solar cells are investigated. A low-temperature heat treatment is applied to overcome the poor charge extraction that developed in the natural aging process. It is suggested that defect states at aged CZTSSe/CdS heterojunctions were reduced, while apparent doping density in the CZTSSe absorber increased due to Cd/Zn interdiffusion at the heterojunction during the annealing process. In situ annealing experiments in a transmission electron microscope were used to investigate the elemental diffusion at the CZTSSe/CdS heterojunction. This study reveals the critical role of heat treatment to enhance the absorber/Mo back contact, improve the quality of the absorber/buffer heterojunction, and recover the device performance in aged kesterite thin-film solar cells.

Reducing series resistance in Cu2ZnSn(S,Se)4 nanoparticle ink solar cells on flexible molybdenum foil substrates.

Earth abundant Cu2ZnSnS4 nanoparticle inks were deposited on molybdenum foil substrates and subsequently converted to high quality thin film Cu2ZnSn(S,Se)4 photovoltaic absorbers. Integration of these absorbers within a thin film solar cell device structure yields a solar energy conversion efficiency which is comparable to identical devices processed on rigid glass substrates. Importantly, this is only achieved when a thin layer of molybdenum is first applied directly to the foil. The layer limits the formation of a thick Mo(S,Se) x layer resulting in a substantially reduced series resistance.

Implications of the negative capacitance observed at forward bias in nanocomposite and polycrystalline solar cells.

Four different types of solar cells prepared in different laboratories have been characterized by impedance spectroscopy (IS): thin-film CdS/CdTe devices, an extremely thin absorber (eta) solar cell made with microporous TiO2/In(OH)xSy/PbS/PEDOT, an eta-solar cell of nanowire ZnO/CdSe/CuSCN, and a solid-state dye-sensitized solar cell (DSSC) with Spiro-OMeTAD as the transparent hole conductor. A negative capacitance behavior has been observed in all of them at high forward bias, independent of material type (organic and inorganic), configuration, and geometry of the cells studied. The experiments suggest a universality of the underlying phenomenon giving rise to this effect in a broad range of solar cell devices. An equivalent circuit model is suggested to explain the impedance and capacitance spectra, with an inductive recombination pathway that is activated at forward bias. The deleterious effect of negative capacitance on the device performance is discussed, by comparison of the results obtained for a conventional monocrystalline Si solar cell showing the positive chemical capacitance expected in the ideal IS model of a solar cell.