As an abundant and non-toxic wide band gap semiconductor with a high electron mobility, ZnO in the form of nanowires has emerged as an important electron transporting material in a vast number of nanostructured solar cells. ZnO nanowires are grown by low-cost chemical deposition techniques and their integration into solar cells presents, in principle, significant advantages including efficient optical absorption through light trapping phenomena and enhanced charge carrier separation and collection. However, they also raise some significant issues related to the control of the interface properties and to the technological integration. The present review is intended to report a detailed analysis of the state-of-the-art of all types of nanostructured solar cells integrating ZnO nanowires, including extremely thin absorber solar cells, quantum dot solar cells, dye-sensitized solar cells, organic and hybrid solar cells, as well as halide perovskite-based solar cells.

A statistical analysis of the electrical properties of selective area grown O- and Zn-polar ZnO nanorods by chemical bath deposition is performed by four-point probe resistivity measurements in patterned metal contact and multiprobe scanning tunneling microscopy configurations. We show that ZnO nanorods with either polarity exhibit a bulklike electrical conduction in their core and are highly conductive. O-polar ZnO nanorods with a smaller mean electrical conductivity have a nonmetallic or metallic electrical conduction, depending on the nano-object considered, while the vast majority of Zn-polar ZnO nanorods with a larger mean electrical conductivity present a metallic electrical conduction. We reveal, from Raman scattering and spatially resolved 5 K cathodoluminescence measurements, that the resulting high carrier density of ZnO nanorods with O or Zn polarity is due to the massive incorporation of hydrogen in the form of interstitial hydrogen in bond-centered sites (HBC), substitutional hydrogen on the oxygen lattice site (HO), and multiple O–H bonds in a zinc vacancy (VZn–H n ). While HBC is largely incorporated in ZnO nanorods with either polarity, HO and (VZn–H n ) defect complexes appear as the dominant hydrogen-related species in O- and Zn-polar ZnO nanorods, respectively. These findings reveal that polarity greatly affects the electrical and optical properties of ZnO nanorods. They further cast a light on the dominant role of hydrogen when ZnO nanorods are grown by the widely used chemical bath deposition technique. This work should be considered for any strategy for thoroughly controlling their physical properties as a prerequisite for their efficient integration into nanoscale engineering devices.

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Polarity is known to affect the growth and properties of ZnO single crystals and epitaxial films, but its effects are mostly unknown in ZnO nanorods. To leave polarity as the only varying parameter, ZnO nanorods are grown by chemical bath deposition under identical conditions and during the same run on O- and Zn-polar ZnO single crystals patterned by electron beam lithography with the same pattern consisting of 15 different domains. The resulting well-ordered O- and Zn-polar ZnO nanorod arrays with high structural uniformity are formed on all the domains. The comparison of their typical dimensions unambiguously reveals that Zn-polar ZnO nanorods have much higher growth rates than O-polar ZnO nanorods for all the hole diameter and period combinations. The distinct growth rates are explained in the framework of the surface reaction-/diffusive transport-limited elongation regime analysis, which yields a much larger surface reaction rate constant for Zn-polar ZnO nanorods. The origin of the difference is attributed to polarity-dependent dangling bond configurations at the top polar c-faces of ZnO nanorods, which may further be affected by polarity-dependent interactions with the ionic species in aqueous solution. These findings show the relevance of considering polarity as an important quantity in ZnO nanorods.

An original self-powered UV photodetector integrating ZnO/CuCrO 2 core-shell nanowire heterostructures is fabricated using low-cost and scalable chemical deposition techniques operating at moderate temperatures. A 35 nm thick delafossite phase CuCrO 2 shell is formed with high uniformity by aerosol-assisted chemical vapor deposition over an array of vertically aligned ZnO nanowires grown by chemical bath deposition. The CuCrO 2 shell consists of columnar grains at the top of ZnO nanowires as well as nanograins with some preferential orientations on their vertical sidewalls. The ZnO/CuCrO 2 core-shell nanowire heterostructures exhibit significant diode behavior, with a rectification ratio approaching 1.2 × 10 4 at 1 V and -1 V, as well as a high optical absorptance above 85% in the UV part of the electromagnetic spectrum. A high UV responsivity at zero bias under low-power illumination of up to 3.43 mA W -1 under a 365 nm UV lamp, and up to 5.87 mA W -1 at 395 nm from spectrally resolved measurements, alongside a high selectivity with a UV-to-visible (395-550 nm) rejection ratio of 106 is measured. The short rise and decay times of 32 and 35 µs, respectively, both measured at zero bias, further establish these devices as promising candidates for cost-efficient, all-oxide self-powered UV photodetectors.

Controlling the formation of ZnO nanowire (NW) arrays on a wide variety of substrates is crucial for their efficient integration into nanoscale devices. While their nucleation and growth by chemical bath deposition (CBD) have intensively been investigated on non-polar and polar c-plane ZnO surfaces, their formation on alternatively oriented ZnO surfaces has not been addressed yet. In this work, the standard CBD technique of ZnO is investigated on and semipolar ZnO single crystal surfaces. A uniform nanostructured layer consisting of tilted ZnO NWs is formed on the surface while elongated nanostructures are coalesced into a two-dimensional compact layer on the surface. By further combining the CBD with selective area growth (SAG) using electron beam-assisted lithography, highly tilted well-ordered ZnO NWs with high structural uniformity are grown on the patterned surface. The structural analysis reveals that ZnO NWs are homoepitaxially grown along the polar c-axis. The occurrence of quasi-transverse and -longitudinal optical phonon modes in Raman spectra is detected and their origin and position are explained in the framework of the Loudon’s model. These results highlight the possibility to form ZnO NWs on original semipolar ZnO surfaces. It also opens the way for comprehensively understanding the nucleation and growth of ZnO NW arrays on poorly and highly textured polycrystalline ZnO seed layers composed of nanoparticles with a wide range of non-polar, semipolar, and polar plane orientations. Eventually, the possibility to tune both the inclination and dimensions of well-ordered ZnO NW arrays by using SAG on semipolar surfaces is noteworthy for photonic and optoelectronic nanoscale devices.

The successive ionic layer adsorption and reaction (SILAR) technique is found to be of high potential for the formation of ZnO core–shell nanowire heterostructures with high uniformity at moderate temperature.

Polarity-controlled growth of ZnO by chemical bath deposition provides a method for controlling the crystal orientation of vertical nanorod arrays. The ability to define the morphology and structure of the nanorods is essential to maximizing the performance of optical and electrical devices such as piezoelectric nanogenerators; however, well-defined Schottky contacts to the polar facets of the structures have yet to be explored. In this work, we demonstrate a process to fabricate metal–semiconductor–metal device structures from vertical arrays with Au contacts on the uppermost polar facets of the nanorods and show that the O-polar nanorods (∼0.44 eV) have a greater effective barrier height than the Zn-polar nanorods (∼0.37 eV). Oxygen plasma treatment is shown by cathodoluminescence spectroscopy to affect midgap defects associated with radiative emissions, which improves the Schottky contacts from weakly rectifying to strongly rectifying. Interestingly, the plasma treatment is shown to have a much greater effect in reducing the number of carriers in O-polar nanorods through quenching of the donor-type substitutional hydrogen on oxygen sites (HO) when compared to the zinc-vacancy-related hydrogen defect complexes (VZn−nH) in Zn-polar nanorods that evolve to lower-coordinated complexes. The effect on HO in the O-polar nanorods coincides with a large reduction in the visible-range defects, producing a lower conductivity and creating the larger effective barrier heights. This combination can allow radiative losses and charge leakage to be controlled, enhancing devices such as dynamic photodetectors, strain sensors, and light-emitting diodes while showing that the O-polar nanorods can outperform Zn-polar nanorods in such applications.