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.

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.

Modelling Interfaces in Thin-Film Photovoltaic Devices.

Developing effective device architectures for energy technologies-such as solar cells, rechargeable batteries or fuel cells-does not only depend on the performance of a single material, but on the performance of multiple materials working together. A key part of this is understanding the behaviour at the interfaces between these materials. In the context of a solar cell, efficient charge transport across the interface is a pre-requisite for devices with high conversion efficiencies. There are several methods that can be used to simulate interfaces, each with an in-built set of approximations, limitations and length-scales. These methods range from those that consider only composition (e.g. data-driven approaches) to continuum device models (e.g. drift-diffusion models using the Poisson equation) and ab-initio atomistic models (developed using e.g. density functional theory). Here we present an introduction to interface models at various levels of theory, highlighting the capabilities and limitations of each. In addition, we discuss several of the various physical and chemical processes at a heterojunction interface, highlighting the complex nature of the problem and the challenges it presents for theory and simulation.

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.