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ZnO/CdS core/shell nanorod arrays were fabricated by a two-step method. Single-crystalline ZnO nanorod arrays were first electrochemically grown on SnO(2):F (FTO) glass substrates. Then, CdS nanocrystals were deposited onto the ZnO nanorods, using the successive ion layer adsorption and reaction (SILAR) technique, to form core/shell nanocable architectures. Structural, morphological and optical properties of the nanorod heterojunctions were investigated. The results indicate that CdS single-crystalline domains with a mean diameter of about 7 nm are uniformly and conformally covered on the surface of the single-crystalline ZnO nanorods. ZnO absorption with a bandgap energy value of 3.30 ± 0.02 eV is present in all optical transmittance spectra. Another absorption edge close to 500 nm corresponding to CdS with bandgap energy values between 2.43 and 2.59 eV is observed. The dispersion in this value may originate in quantum confinement inside the nanocrystalline material. The appearance of both edges corresponds with the separation of ZnO and CdS phases and reveals the absorption increase due to CdS sensitizer. The photovoltaic performance of the resulting ZnO/CdS core/shell nanorod arrays has been investigated as solar cell photoanodes in a photoelectrochemical cell under white illumination. In comparison with bare ZnO nanorod arrays, a 13-fold enhancement in photoactivity was observed using the ZnO/CdS coaxial heterostructures.

Halide perovskite solar cells (PSCs) have already demonstrated power conversion efficiencies above 25%, which makes them one of the most attractive photovoltaic technologies. However, one of the main bottlenecks towards their commercialization is their long-term stability, which should exceed the 20-year mark. Additive engineering is an effective pathway for the enhancement of device lifetime. Additives applied as organic or inorganic compounds, improve crystal grain growth enhancing power conversion efficiency. The interaction of their functional groups with the halide perovskite (HP) absorber, as well as with the transport layers, results in defect passivation and ion immobilization improving device performance and stability [1][2][3][4].In this review, we briefly summarize the different types of additives recently applied in PSC to enhance not only efficiency but also long-term stability. We discuss the different mechanism behind additive engineering and the role of the functional groups of these additives for defect passivation. Special emphasis is given to their effect on the stability of PSCs under environmental conditions such as humidity, atmosphere, light irradiation (UV, visible) or heat, taking into account the recently reported ISOS protocols [5]. We also discuss the relation between deep defect passivation, non-radiative recombination and device efficiency, as well as the possible relation between shallow defect passivation, ion immobilization and device operational stability. Finally, insights into the challenge and criteria for additive selection are provided for the further stability enhancement of PSCs.

CdS quantum dots (QDs) decorated ZnO nanorod (NR) arrays were fabricated by a two-step method. The first step consisted in electrochemical growth of single-crystalline ZnO NR arrays, followed by the novel spin-coating assisted SILAR method for decorating the ZnO NRs with CdS QDs. Structural, morphological and optical characterization of CdS QDs/ZnO NR arrays were done. ZnO NRs had a single crystal wurtzite structure growing along the c-axis. The decorated CdS QDs had a quasi-spherical shape with a mean diameter of about 5 nm. The increase of CdS content produces an increase in the visible part of the absorption spectrum. Bandgap energy values for ZnO between 3.26–3.29 eV were obtained. For CdS the measured absorption edge values are between 2.35–2.65 eV (decreasing with the number of coating cycles). Numerical simulations based on effective medium approximation were done to verify these features. The Urbach tail parameter in CdS absorption edge is between 44–52 meV. The photovoltaic performance of ZnO and CdS QDs/ZnO NRs have been evaluated in a photoelectrochemical solar cell configuration with a polysulfide electrolyte under white illumination. The decoration of ZnO NRs with CdS QDs leads to a cell performance of JSC = 2.67 mA/cm2, VOC = 0.74 V, FF = 0.30 and η = 1.48%.

The effect of both a RF sputtered Al-doped ZnO (AZO) thin film seed layer onto a FTO/glass substrate and its growth time onto the morphological, structural and optical properties of the resulting electrochemically grown ZnO nanorod arrays (NRAs) have been studied. ZnO NRs grown onto the different AZO seed layers exhibit smaller mean diameter and length than those grown onto a bare FTO/glass substrate, but ZnO NR density presents an opposite behavior, by using an AZO seed layer ZnO nanorod density can be increased by a factor of six. ZnO nanorods are highly crystalline with a wurtzite hexagonal structure and with a preferential growth perpendicular to the substrate. The c-axis of most of the ZnO NRs grown onto an AZO seed layer is aligned within ±6 • from the substrate surface normal. Both NRAs mean length and density increases light scattering, without greatly affecting the spectra shape. The diffuse reflectance intensity is more sensitive to NR density variations than to length or diameter variations. NR diameter affects directly the shape of these diffuse reflectance spectra: they red-shifts and broadens when NR mean diameter increases. A small influence in the UV edge due to size quantization may be also present. In recent years, ZnO, a wide bandgap semiconductor with a direct bandgap of about 3.37 eV and high exciton binding energy (60 meV) at room temperature, has attracted increasing interest due to its unique ability to form a variety of nanostructures such as nanowires, nanorods, nanobelts, nanocombs, nanospheres, nano-tetrapods.1,2 Among them, the most interesting are nanorods and nanorod arrays (NRAs) vertically arranged with respect to the substrate.1 These ZnO nanostructures present a pseudo-one dimensional (1D) structure, with an enhanced surface-to-volume ratio and confinement effects.3 ZnO nanorods exhibit fewer defects than its thin-film structure, it is, therefore, a promising material for optoelectronic applications. 4 In fact, recently, single crystal ZnO nanowire and nanorod arrays have emerged as promising building blocks for a new generation of devices in different hi-tech domains such as optoelectronics, gas sensing, field emission, piezoelectrics and solar cells. 2,5,6 In particular, ZnO one dimensional nanostructures are good candidates for photovoltaic applications for three straightforward reasons: i) they have a low reflectivity that enhances the light absorption; ii) relatively high surface to volume ratio that enables interfacial charge separation and iii) fast electron transport along the crystalline 1D nanostructures that improves the charge collection efficiency. In fact, ZnO arrays of 1D nanostructures, such as nanowires and nanotubes, have been widely utilized as they provide a direct conduction pathway for the rapid collection of the photogenerated electrons, 7 reducing the non-radiative recombination and carrier scattering loss dramatically, 8 and providing as well a high junction area.9,10 Moreover, electron transport in the crystalline nanorod is expected to be several orde...