Research Update: Bismuth-based perovskite-inspired photovoltaic materials

Bismuth-based compounds have recently gained interest as solar absorbers with the potential to have low toxicity, be efficient in devices, and be processable using facile methods. We review recent theoretical and experimental investigations into bismuth- based compounds, which shape our understanding of their photovoltaic potential, with particular focus on their defect-tolerance. We also review the processing methods that have been used to control the structural and optoelectronic properties of single crystals and thin films. Additionally, we discuss the key factors limiting their device perfor- mance, as well as the future steps needed to ultimately realize these new materials for commercial applications.L.C.L. would like to acknowledge funding from the EPSRC Centre for Doctoral Training in New and Sustainable Photovoltaics. T.N.H. acknowledges funding from the EPSRC Centre for Doctoral Training in Graphene Technology (No. EP/L016087/1). R.L.Z.H. acknowledges support from Magdalene College, Cambridge. All authors acknowledge support from the Winton Programme for the Physics of Sustainability

Ti Alloyed α -Ga 2 O 3: Route towards Wide Band Gap Engineering

The suitability of Ti as a band gap modifier for α-Ga2O3 was investigated, taking advantage of the isostructural α phases and high band gap difference between Ti2O3 and Ga2O3. Films of (Ti,Ga)2O3 were synthesized by atomic layer deposition on sapphire substrates, and characterized to determine how crystallinity and band gap vary with composition for this alloy. We report the deposition of high quality α-(TixGa1−x)2O3 films with x = 3.7%. For greater compositions the crystalline quality of the films degrades rapidly, where the corundum phase is maintained in films up to x = 5.3%, and films containing greater Ti fractions being amorphous. Over the range of achieved corundum phase films, that is 0% ≤ x ≤ 5.3%, the band gap energy varies by ∼270 meV. The ability to maintain a crystalline phase at low fractions of Ti, accompanied by a modification in band gap, shows promising prospects for band gap engineering and the development of wavelength specific solar-blind photodetectors based on α-Ga2O3

Role of ALD Al2O3 Surface Passivation on the Performance of p-Type Cu2O Thin Film Transistors

High-performance p- type oxide thin film transistors (TFTs) have great potential for many semiconductor applications. However, these devices typically suffer from low hole mobility and high off-state currents. We fabricated p-type TFTs with a phase-pure polycrystalline Cu2O semiconductor channel grown by atomic layer deposition (ALD). The TFT switching characteristics were improved by applying a thin ALD Al2O3 passivation layer on the Cu2O channel, followed by vacuum annealing at 300 degrees C. Detailed characterization by transmission electron microscopy-energy dispersive X-ray analysis and X-ray photoelectron spectroscopy shows that the surface of Cu2O is reduced following Al2O3 deposition and indicates the formation of a 1-2 nm thick CuAlO2 interfacial layer. This, together with field-effect passivation caused by the high negative fixed charge of the ALD Al2O3, leads to an improvement in the TFT performance by reducing the density of deep trap states as well as by reducing the accumulation of electrons in the semiconducting layer in the device off-state.Peer reviewe

Rapid Vapor-Phase Deposition of High-Mobility p-Type Buffer Layers on Perovskite Photovoltaics for Efficient Semi-Transparent Devices

Perovskite solar cells (PSCs) with transparent electrodes can be integrated with existing solar panels in tandem configurations to increase the power conversion efficiency. A critical layer in semi-transparent PSCs is the inorganic buffer layer, which protects the PSC against damage when the transparent electrode is sputtered on top. The development of n-i-p structured semi-transparent PSCs has been hampered by the lack of suitable p-type buffer layers. In this work we develop a p-type CuOx buffer layer, which can be grown uniformly over the perovskite device without damaging the perovskite or organic hole transport layer. The CuOx layer has high hole mobility (4.3 ± 2 cm2 V-1 s-1), high transmittance (>95%), and a suitable ionization potential for hole extraction (5.3 ± 0.2 eV). Semi-transparent PSCs with efficiencies up to 16.7% are achieved using the CuOx buffer layer. Our work demonstrates a new approach to integrate n-i-p structured PSCs into tandem configurations, as well as enable the development of other devices that need high quality, protective p-type layers.EPSRC Department Training Partnership studentship (No: EP/N509620/1), as well as Bill Welland. T.N.H. acknowledges funding from the EPSRC Centre for Doctoral Training in Graphene Technology (No. EP/L016087/1) and the Aziz Foundation. W.-W.L. and J.L.M.-D. acknowledge support from the EPSRC (Nos.: EP/L011700/1, EP/N004272/10), and the Isaac Newton Trust (Minute 13.38(k)). M.N. and J.L.M.-D. acknowledge financial support from EPSRC (No. EP/P027032/1). S. D. S. acknowledges support from the Royal Society and Tata Group (UF150033). R.L.Z.H. acknowledges support from the Royal Academy of Engineering under the Research Fellowship scheme (No.: RF\201718\1701), the Centre of Advanced Materials for Integrated Energy Systems (EPSRC Grant No. EP/P007767/1), the Isaac Newton Trust (Minute 19.07(d)), and the Kim and Juliana Silverman Research Fellowship at Downing College, Cambridge

Identifying and Reducing Interfacial Losses to Enhance Color-Pure Electroluminescence in Blue-Emitting Perovskite Nanoplatelet Light-Emitting Diodes.

Perovskite nanoplatelets (NPls) hold promise for light-emitting applications, having achieved photoluminescence quantum efficiencies approaching unity in the blue wavelength range, where other metal-halide perovskites have typically been ineffective. However, the external quantum efficiencies (EQEs) of blue-emitting NPl light-emitting diodes (LEDs) have reached only 0.12%. In this work, we show that NPl LEDs are primarily limited by a poor electronic interface between the emitter and hole injector. We show that the NPls have remarkably deep ionization potentials (≥6.5 eV), leading to large barriers for hole injection, as well as substantial nonradiative decay at the NPl/hole-injector interface. We find that an effective way to reduce these nonradiative losses is by using poly(triarylamine) interlayers, which lead to an increase in the  EQE of the blue (464 nm emission wavelength) and sky-blue (489 nm emission wavelength) LEDs to 0.3% and 0.55%, respectively. Our work also identifies the key challenges for further efficiency increases

Developing next generation, non-toxic, inorganic materials for photovoltaics and thin-film transistors

The focus of this thesis is on developing two next-generation inorganic materials for thin-film device applications, namely photovoltaics and thin-film transistors. Both of these device applications are crucial in today’s technology-based society with photovoltaics enabling sustainable generation of electricity whilst advancements in thin-film transistors allow for development of low-power, efficient electronic devices. BiOI, a non-toxic, perovskite-inspired material is investigated for photovoltaics (PVs) whilst Cu2O, with a reasonably high predicted hole mobility is developed for *p*-type thin-film transistors (TFTs). These novel materials are fabricated with scalable processing techniques which enable lower manufacturing costs and improve energy efficiency. In the first results chapter, the suitability of non-toxic BiOI as a photovoltaic material is investigated. Dense BiOI films grown by thermal chemical vapour deposition (CVD) incorporated into an all-inorganic ITO/NiO*x*/BiOI/ZnO/Al stack demonstrate high external quantum efficiencies (80% at 450 nm wavelength). However, the 1.9 eV band gap of BiOI is not matched to terrestrial solar spectra; the PVs achieve 1.8% power conversion efficiency. Owing to improved spectral matching with indoor light spectra, BiOI devices improve in efficiency to 4.37% under 1000 lux white light emitting diode indoor illumination, and millimetre-area BiOI devices are sufficient to power novel carbon nanotube inverters. The factor limiting further efficiency gains is downwards band-bending at the BiOI/NiO*x* interface owing to NiO*x* having a lower work function. In the second chapter, MoS2 is investigated as an alternative to NiO*x* where the work function of MoS2 is tuned through oxygen plasma treatment to increase its work function. The experimental examination of defect tolerance of BiOI is conducted in chapter three. BiOI films are vacuum-annealed to induce surface composition changes. Large changes in surface atomic fractions (reduction in iodine and bismuth by 40% and 5% respectively, and increase in oxygen by >45%) are observed. These significant changes do not affect the electronic and optoelectronic properties, in contrast to traditional covalent semiconductors. The applicability of low-temperature (≤ 200 °C) atmospheric pressure spatial atomic layer deposited (AP-SALD) Cu2O for use in *p*-type TFTs is explored in chapter four. The performance of AP-SALD Cu2O is comparable to atomic layer deposition (ALD) grown Cu2O with an I*ON*/I*OFF* ratio of 103, and field-effect mobility between 10-4 - 10-3 cm2·V-1·s-1, illustrating the potential of AP-SALD grown films for integration with flexible substrates.PragmatIC Aziz Foundatio

Research Update: Bismuth-based perovskite-inspired photovoltaic materials

Bismuth-based compounds have recently gained interest as solar absorbers with the potential to have low toxicity, be efficient in devices, and be processable using facile methods. We review recent theoretical and experimental investigations into bismuth- based compounds, which shape our understanding of their photovoltaic potential, with particular focus on their defect-tolerance. We also review the processing methods that have been used to control the structural and optoelectronic properties of single crystals and thin films. Additionally, we discuss the key factors limiting their device perfor- mance, as well as the future steps needed to ultimately realize these new materials for commercial applications.L.C.L. would like to acknowledge funding from the EPSRC Centre for Doctoral Training in New and Sustainable Photovoltaics. T.N.H. acknowledges funding from the EPSRC Centre for Doctoral Training in Graphene Technology (No. EP/L016087/1). R.L.Z.H. acknowledges support from Magdalene College, Cambridge. All authors acknowledge support from the Winton Programme for the Physics of Sustainability

Nickel oxide thin films grown by chemical deposition techniques: Potential and challenges in next‐generation rigid and flexible device applications

Funder: Aziz FoundationFunder: Downing College, CambridgeFunder: Isaac Newton Trust; Id: http://dx.doi.org/10.13039/501100004815Abstract: Nickel oxide (NiO x ), a p‐type oxide semiconductor, has gained significant attention due to its versatile and tunable properties. It has become one of the critical materials in wide range of electronics applications, including resistive switching random access memory devices and highly sensitive and selective sensor applications. In addition, the wide band gap and high work function, coupled with the low electron affinity, have made NiO x widely used in emerging optoelectronics and p‐n heterojunctions. The properties of NiO x thin films depend strongly on the deposition method and conditions. Efficient implementation of NiO x in next‐generation devices will require controllable growth and processing methods that can tailor the morphological and electronic properties of the material, but which are also compatible with flexible substrates. In this review, we link together the fundamental properties of NiO x with the chemical processing methods that have been developed to grow the material as thin films, and with its application in electronic devices. We focus solely on thin films, rather than NiO x incorporated with one‐dimensional or two‐dimensional materials. This review starts by discussing how the p‐type nature of NiO x arises and how its stoichiometry affects its electronic and magnetic properties. We discuss the chemical deposition techniques for growing NiO x thin films, including chemical vapor deposition, atomic layer deposition, and a selection of solution processing approaches, and present examples of recent progress made in the implementation of NiO x thin films in devices, both on rigid and flexible substrates. Furthermore, we discuss the remaining challenges and limitations in the deposition of device‐quality NiO x thin films with chemical growth methods. imag

Research Update: Bismuth-based perovskite-inspired photovoltaic materials

Bismuth-based compounds have recently gained interest as solar absorbers with the potential to have low toxicity, be efficient in devices, and be processable using facile methods. We review recent theoretical and experimental investigations into bismuth-based compounds, which shape our understanding of their photovoltaic potential, with particular focus on their defect-tolerance. We also review the processing methods that have been used to control the structural and optoelectronic properties of single crystals and thin films. Additionally, we discuss the key factors limiting their device performance, as well as the future steps needed to ultimately realize these new materials for commercial applications