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Chalcogenide-based semiconductors have recently emerged as promising candidates for optoelectronic devices, benefiting from their low-cost, solution processability, excellent stability and tunable optoelectronic properties. However, the understanding of their fundamental optoelectronic properties is far behind the success of device performance and starts to limit their further development. To fill this gap, we conduct a comparative study of chalcogenide absorbers across a wide material space, in order to assess their suitability for different types of applications. We utilize optical-pump terahertz-probe spectroscopy and time-resolved microwave conductivity techniques to fully analyze their charge-carrier dynamics. We show that antimony-based chalcogenide thin films exhibit relatively low charge-carrier mobilities and short lifetimes, compared with bismuth-based chalcogenides. In particular, AgBiS2 thin films possess the highest mobility, and Sb2S3 thin films have less energetic disorder, which are beneficial for photovoltaic devices. On the contrary, Bi2S3 showed ultralong carrier lifetime and high photoconductive gain, which is beneficial for designing photoconductors.

Funder: Alexander von Humboldt Foundation, Funder: Experienced Researcher Fellowship, Funder: DFG Collaborative, Funder: PAPIIT, Funder: Danish National Research Foundation, Funder: JSPS, Funder: STFC Centre for Instrumentation, Funder: UKSA Centre for Earth, Funder: Leverhulme Trust; doi: http://dx.doi.org/10.13039/501100000275, Funder: NRF, Funder: Royal Society; doi: http://dx.doi.org/10.13039/501100000288, Funder: Australian Government; doi: http://dx.doi.org/10.13039/100015539, Funder: Cancer Research UK; doi: http://dx.doi.org/10.13039/501100000289, Funder: University of Warwick; doi: http://dx.doi.org/10.13039/501100000741, Terahertz (THz) radiation encompasses a wide spectral range within the electromagnetic spectrum that extends from microwaves to the far infrared (100 GHz–∼30 THz). Within its frequency boundaries exist a broad variety of scientific disciplines that have presented, and continue to present, technical challenges to researchers. During the past 50 years, for instance, the demands of the scientific community have substantially evolved and with a need for advanced instrumentation to support radio astronomy, Earth observation, weather forecasting, security imaging, telecommunications, non-destructive device testing and much more. Furthermore, applications have required an emergence of technology from the laboratory environment to production-scale supply and in-the-field deployments ranging from harsh ground-based locations to deep space. In addressing these requirements, the research and development community has advanced related technology and bridged the transition between electronics and photonics that high frequency operation demands. The multidisciplinary nature of THz work was our stimulus for creating the 2017 THz Science and Technology Roadmap (Dhillon et al 2017 J. Phys. D: Appl. Phys. 50 043001). As one might envisage, though, there remains much to explore both scientifically and technically and the field has continued to develop and expand rapidly. It is timely, therefore, to revise our previous roadmap and in this 2023 version we both provide an update on key developments in established technical areas that have important scientific and public benefit, and highlight new and emerging areas that show particular promise. The developments that we describe thus span from fundamental scientific research, such as THz astronomy and the emergent area of THz quantum optics, to highly applied and commercially and societally impactful subjects that include 6G THz communications, medical imaging, and climate monitoring and prediction. Our Roadmap vision draws upon the expertise and perspective of multiple international specialists that together provide an overview of past developments and the likely challenges facing the field of THz science and technology in future decades. The document is written in a form that is accessible to policy makers who wish to gain an overview of the current state of the THz art, and for the non-specialist and curious who wish to understand available technology and challenges. A such, our experts deliver a ‘snapshot’ introduction to the current status of the field and provide suggestions for exciting future technical development directions. Ultimately, we intend the Roadmap to portray the advantages and benefits of the THz domain and to stimulate further exploration of the field in support of scientific research and commercial realisation.

As perovskite-based photovoltaics near commercialization, it is imperative to develop industrial-scale defect-passivation techniques. Vapor deposition is a solvent-free fabrication technique that is widely implemented in industry and can be used to fabricate metal-halide perovskite thin films. We demonstrate markably improved growth and optoelectronic properties for vapor-deposited [CH(NH2)2]0.83Cs0.17PbI3 perovskite solar cells by partially substituting PbI2 for PbCl2 as the inorganic precursor. We find the partial substitution of PbI2 for PbCl2 enhances photoluminescence lifetimes from 5.6 ns to over 100 ns, photoluminescence quantum yields by more than an order of magnitude, and charge-carrier mobility from 46 cm2/(V s) to 56 cm2/(V s). This results in improved solar-cell power conversion efficiency, from 16.4% to 19.3% for the devices employing perovskite films deposited with 20% substitution of PbI2 for PbCl2. Our method presents a scalable, dry, and solvent-free route to reducing nonradiative recombination centers and hence improving the performance of vapor-deposited metal-halide perovskite solar cells.

With power conversion efficiencies of perovskite-on-silicon and all-perovskite tandem solar cells increasing at rapid pace, wide bandgap (> 1.7 eV) metal-halide perovskites (MHPs) are becoming a major focus of academic and industrial photovoltaic research. Compared to their lower bandgap (< 1.6 eV) counterparts, these types of perovskites suffer from higher levels of non-radiative losses in both the bulk material and in device configurations, constraining their efficiencies far below their thermodynamic potential. In this work, we investigate the energy losses in methylammonium (MA) free high-Br-content widegap perovskites by using a combination of THz spectroscopy, steady-state and time-resolved photoluminescence, coupled with drift-diffusion simulations. The investigation of this system allows us to study charge-carrier recombination in these materials and devices in the absence of halide segregation due to the photostabilty of formamidinium-cesium based lead halide perovskites. We find that these perovskites are characterised by large non-radiative recombination losses in the bulk material and that the interfaces with transport layers in solar cell devices strongly limit their open-circuit voltage. In particular, we discover that the interface with the hole transport layer performs particularly poorly, in contrast to 1.6 eV bandgap MHPs which are generally limited by the interface with the electron-transport layer. To overcome these losses, we incorporate and investigate the recombination mechanisms present with perovskites treated with the ionic additive 1-butyl-1-methylpipiderinium tetrafluoroborate. We find that this additive not only improves the radiative efficiency of the bulk perovskite, but also reduces the non-radiative recombination at both the hole and electron transport layer interfaces of full photovoltaic devices. In addition to unravelling the beneficial effect of this specific treatment, we further optimise our solar cells by introducing an additional LiF interface treatment at the electron transport layer interface. Together these treatments enable MA-free 1.79 eV bandgap perovskite solar cells with open-circuit voltages of 1.22 V and power conversion efficiencies approaching 17 %, which is among the highest reported for this material system.

Achieving the long-term stability of perovskite solar cells is arguably the most important challenge required to enable widespread commercialization. Understanding the perovskite crystallization process and its direct impact on device stability is critical to achieving this goal. The commonly employed dimethyl-formamide/dimethyl-sulfoxide solvent preparation method results in a poor crystal quality and microstructure of the polycrystalline perovskite films. In this work, we introduce a high-temperature dimethyl-sulfoxide-free processing method that utilizes dimethylammonium chloride as an additive to control the perovskite intermediate precursor phases. By controlling the crystallization sequence, we tune the grain size, texturing, orientation (corner-up versus face-up) and crystallinity of the formamidinium (FA)/caesium (FA)yCs1–yPb(IxBr1–x)3 perovskite system. A population of encapsulated devices showed improved operational stability, with a median T80 lifetime (the time over which the device power conversion efficiency decreases to 80% of its initial value) for the steady-state power conversion efficiency of 1,190 hours, and a champion device showed a T80 of 1,410 hours, under simulated sunlight at 65 °C in air, under open-circuit conditions. This work highlights the importance of material quality in achieving the long-term operational stability of perovskite optoelectronic devices.

The generation and control of terahertz pulses is vital for realizing the potential of terahertz radiation in several sectors, including 6G communication, security and imaging. In this work, we present the topological Dirac semimetal cadmium arsenide as a novel helicity-dependent terahertz source. We show both broadband (single-cycle) and narrowband (multi-cycle) terahertz pulses upon near-infrared photoexcitation at oblique incidence. By varying the incident angle of the photoexcitation pulse, control of the emission frequency can also be achieved, providing a candidate for a tuneable narrowband terahertz source.

Spintronic metal thin films excited by femtosecond laser pulses have recently emerged as excellent broadband sources of terahertz (THz) radiation. Unfortunately, these emitters transmit a significant proportion of the incident excitation laser, which causes two issues: first, the transmitted light can interfere with measurements and so must be attenuated; second, the transmitted light is effectively wasted as it does not drive further THz generation. Here, we address both issues with the inclusion of a high-reflectivity (HR) coating made from alternating layers of SiO2 and Ta2O5. Emitters with the HR coating transmit less than 0.1% of the incident excitation pulse. Additionally, we find that the HR coating increases the peak THz signal by roughly 35%, whereas alternative attenuating elements, such as cellulose nitrate films, reduce the THz signal. To further improve the emission, we study the inclusion of an anti-reflective coating to the HR-coated emitters and find the peak THz signal is enhanced by a further 4%.

Mixed-halide perovskites offer ideal bandgaps for tandem solar cells, but photoinduced halide segregation compromises photovoltaic device performance. This study explores the influence of a hole-transport layer, necessary for a full device, by monitoring halide segregation through in situ, concurrent X-ray diffraction and photoluminescence measurements to disentangle compositional and optoelectronic changes. This work demonstrates that top coating FA0.83Cs0.17Pb(Br0.4I0.6)3 perovskite films with a poly(triaryl)amine (PTAA) hole-extraction layer surprisingly leads to suppression of halide segregation because photogenerated charge carriers are rapidly trapped at interfacial defects that do not drive halide segregation. However, the generation of iodide-enriched regions near the perovskite/PTAA interface enhances hole back-transfer from the PTAA layer through improved energy level offsets, increasing radiative recombination losses. It is further found that while passivation with a piperidinium salt slows halide segregation in perovskite films, the addition of a PTAA top-coating accelerates such effects, elucidating the specific nature of trap types that are able to drive the halide segregation process. This work highlights the importance of selective passivation techniques for achieving efficient and stable wide-bandgap perovskite photovoltaic devices.

Vacuumdepositionis a solvent-free method suitable for growing thin films of metal halideperovskite(MHP) semiconductors. However, most reports of high-efficiencysolarcellsbased on suchvacuum-deposited MHP films incorporate solution-processed hole transport layers (HTLs), thereby complicating prospects of industrial upscaling and potentially affecting the overall devicestability. In this work, we investigate organometallic copper phthalocyanine (CuPc) and zinc phthalocyanine (ZnPc) as alternative, low-cost, and durable HTLs in all-vacuum-deposited solvent-free formamidinium-cesium lead triodide [CH(NH2)2]0.83Cs0.17PbI3(FACsPbI3)perovskitesolarcells. We elucidate that the CuPc HTL, when employed in an “inverted” p–i–nsolarcell configuration, attains asolar-to-electrical power conversion efficiency of up to 13.9%. Importantly, unencapsulated devices as large as 1 cm2exhibited excellent long-termstability, demonstrating no observable degradation in efficiency after more than 5000 h in storage and 3700 h under 85 °C thermal stressing in N2atmosphere.

Cs2AgBiBr6 is a promising metal halide double perovskite offering the possibility of efficient photovoltaic devices based on lead-free materials. Here, we report on the evolution of photoexcited charge carriers in Cs2AgBiBr6 using a combination of temperature-dependent photoluminescence, absorption and optical pump–terahertz probe spectroscopy. We observe rapid decays in terahertz photoconductivity transients that reveal an ultrafast, barrier-free localization of free carriers on the time scale of 1.0 ps to an intrinsic small polaronic state. While the initially photogenerated delocalized charge carriers show bandlike transport, the self-trapped, small polaronic state exhibits temperature-activated mobilities, allowing the mobilities of both to still exceed 1 cm2 V–1 s–1 at room temperature. Self-trapped charge carriers subsequently diffuse to color centers, causing broad emission that is strongly red-shifted from a direct band edge whose band gap and associated exciton binding energy shrink with increasing temperature in a correlated manner. Overall, our observations suggest that strong electron–phonon coupling in this material induces rapid charge-carrier localization.

Owing to the bandgap-bowing effect, mixed lead-tin halide perovskites provide ideal bandgaps for the bottom subcell of all-perovskite tandem photovoltaic devices that offer fundamentally elevated power-conversion efficiencies. However, these materials suffer from degradation in ambient air, which worsens their optoelectronic properties and hinders their usability for photovoltaic applications. Such degradation pathways are not yet fully understood, especially for the perovskites in the middle of the APbxSn1-xI3 solid solution line, which offer the narrowest bandgaps across the range. This study unravels the degradation mechanisms of APbxSn1-xI3 perovskites, reporting clear differences between mixed lead-tin (x = 0.5) and tin-only (x = 0) perovskites. The dynamic optoelectronic properties, electronic structure, crystal structure, and decomposition products of the perovskite thin films are examined in situ during air exposure. Both perovskite compositions suffer from the formation of defects over the timescale of hours, as indicated by a significant reduction in their charge-carrier diffusion lengths. For tin-only perovskite, degradation predominantly causes the formation of energetically shallow tin vacancies and hole doping. However, for mixed lead-tin perovskite, deep trap states are formed that significantly accelerate charge-carrier recombination, yet leave mobilities relatively unaffected. These findings highlight the need for passivation strategies tailored specifically to mixed lead-tin iodide perovskites.

Lead halide perovskites are leading candidates for photovoltaic and light-emitting devices, owing to their excellent and widely tunable optoelectronic properties. Nanostructure control has been central to their development, allowing for improvements in efficiency and stability, and changes in electronic dimensionality. Recently, formamidinium lead triiodide (FAPbI3) has been shown to exhibit intrinsic quantum confinement effects in nominally bulk thin films, apparent through above-bandgap absorption peaks. Here, we show that such nanoscale electronic effects can be controlled through partial replacement of the FA cation with Cs. We find that Cs-cation exchange causes a weakening of quantum confinement in the perovskite, arising from changes in the bandstructure, the length scale of confinement, or the presence of δH-phase electronic barriers. We further observe photon emission from quantum-confined regions, highlighting their potential usefulness to light-emitting devices and single-photon sources. Overall, controlling this intriguing quantum phenomenon will allow for its suppression or enhancement according to need.

Suitable execution of moderation policy is challenging but crucial for the trustworthiness and credibility of internal high-stakes assessment systems. In formal education, policies are rarely implemented as intended. Instead, they are enacted in ways influenced by mediating factors including the internal and external contexts of organisations. Ball, Maguire and Braun’s (2012) contextual-dimensions heuristic provides a conceptualisation of organisation-specific contexts, which is useful when the organisation is the unit of analysis. However, comprehensive analysis of policy enactment—including that relating to moderation—warrants consideration of contexts narrower in scope than whole organisations and wider in scope than individual organisations. In this article, we modify Ball and colleagues’ heuristic, incorporating Biggs’ (1993) application of systems theory, to develop a new contextual framework for moderation that is applicable on multiple scales and enables such analysis. This framework is applied to a selection of contemporary moderation studies with scopes that vary from one course, to jurisdiction-wide, to illustrate its utility. Our framework captures the hierarchy of embedded, interacting systems within which moderation is enacted and makes contextual relationships visible, allowing consideration of perspectives between units of analysis. Our framework provides a nuanced conceptualisation of context that distinguishes between material and human factors, and intrinsic and extrinsic contexts. We present potential uses of the framework for education organisations, central agencies and researchers including as a tool for identifying contextual factors involved in executing moderation initiatives and identifying possible pressures, tensions and enablers.

Using ultrafast optical-pump terahertz-probe spectroscopy (OPTP) and ultrafast terahertz emission spectroscopy, we showcase the electron and hole dynamics in Cd 3 As 2 nanowires (NWs), a well-known 3D Dirac semimetal a subgroup of the newly discovered. A temperature-dependent photoconductivity measurement was carried out yielding an incredibly high electron mobility ~ 16,000 cm2/Vs at 5K. Strong THz emission due to helicity-dependent surface photocurrents was also observed for both nanowires and single crystal (SC) which is highly desirable for devices such as THz sources.

Although metal halide perovskite photovoltaics have shown an unprecedented rise in power conversion efficiency (PCE), they remain far from their theoretical PCE limit. Among the highest efficiencies to date are delivered when polycrystalline films are enhanced via “molecular passivation”, but this can introduce new instabilities, in particular under severe accelerated aging conditions (e.g., at 85 °C in the dark or under full spectrum simulated sunlight). Here, we utilize a benzylammonium bromide passivation treatment to improve device performance, achieving the champion stabilized power output (SPO) of 19.5 % in a p-i-n device architecture. We correlate the improved device performance with a significant increase in charge carrier diffusion lengths, mobilities, and lifetimes. Furthermore, treated devices maintain an increased performance during 120 h combined stressing under simulated full spectrum sunlight at 85 °C, indicating that enhancement from this passivation treatment is sustained under harsh accelerated aging conditions. This is a crucial step toward real-world operation-relevant passivation treatments.

Successful chemical doping of metal halide perovskites with small amounts of heterovalent metals has attracted recent research attention because of its potential to improve long-term material stability and tune absorption spectra. However, some additives have been observed to impact negatively on optoelectronic properties, highlighting the importance of understanding charge-carrier behavior in doped metal halide perovskites. Here, we present an investigation of charge-carrier trapping and conduction in films of MAPbBr3 perovskite chemically doped with bismuth. We find that the addition of bismuth has no effect on either the band gap or exciton binding energy of the MAPbBr3 host. However, we observe a substantial enhancement of electron-trapping defects upon bismuth doping, which results in an ultrafast charge-carrier decay component, enhanced infrared emission, and a notable decrease of charge-carrier mobility. We propose that such defects arise from the current approach to Bi-doping through addition of BiBr3, which may enhance the presence of bromide interstitials.

Silver-bismuth based semiconductors represent a promising new class of materials for optoelectronic applications because of their high stability, all-inorganic composition, and advantageous optoelectronic properties. In this study, charge-carrier dynamics and transport properties are investigated across five compositions along the AgBiI4–CuI solid solution line (stoichiometry Cu4x(AgBi)1−xI4). The presence of a close-packed iodide sublattice is found to provide a good backbone for general semiconducting properties across all of these materials, whose optoelectronic properties are found to improve markedly with increasing copper content, which enhances photoluminescence intensity and charge-carrier transport. Photoluminescence and photoexcitation-energy-dependent terahertz photoconductivity measurements reveal that this enhanced charge-carrier transport derives from reduced cation disorder and improved electronic connectivity owing to the presence of Cu+. Further, increased Cu+ content enhances the band curvature around the valence band maximum, resulting in lower charge-carrier effective masses, reduced exciton binding energies, and higher mobilities. Finally, ultrafast charge-carrier localization is observed upon pulsed photoexcitation across all compositions investigated, lowering the charge-carrier mobility and leading to Langevin-like bimolecular recombination. This process is concluded to be intrinsically linked to the presence of silver and bismuth, and strategies to tailor or mitigate the effect are proposed and discussed.

In New Zealand, education organisations that internally assess against nationally-set standards must engage in national moderation—such as that conducted by the New Zealand Qualifications Authority (NZQA)—to quality assure those assessments. How policies are enacted by organisations is influenced by multiple factors and enactment may diverge from intent. One such factor is the people involved in policy work within organisations; however, little research has been done into their perspectives. In this mixed-methods study, we collected perception data from a sample of 215 academic leaders from three organisation types via an online survey. We explored their understandings of the functions of NZQA moderation and differences in views according to organisation type. We found that leaders perceive NZQA moderation to function in the areas of assessment quality, professional learning opportunities, organisational quality assurance and maintaining public confidence. Leaders from different organisation types mostly shared similar views in terms of the functions; however, those from private training enterprises considered NZQA moderation to place stronger emphasis on organisational quality assurance and to hold broader improvement functions than did those from other organisations. These findings are useful for informing the policy work of education organisations (and making better use of the opportunities afforded by moderation) and for NZQA, including to guide suitable framing of moderation communications to enhance alignment between policy intent and policy enactment. Such uses remain relevant in New Zealand’s current climate of educational reform, irrespective of any changes made to NZQA moderation policy.

Metal-halide perovskite semiconductors have attracted intense interest over the past decade, particularly for applications in photovoltaics. Low-energy optical phonons combined with significant crystal anharmonicity play an important role in charge-carrier cooling and scattering in these materials, strongly affecting their optoelectronic properties. We have observed optical phonons associated with Pb–I stretching in both MAPbI3 single crystals and polycrystalline thin films as a function of temperature by measuring their terahertz conductivity spectra with and without photoexcitation. An anomalous bond hardening was observed under above-bandgap illumination for both single-crystal and polycrystalline MAPbI3. First-principles calculations reproduced this photo-induced bond hardening and identified a related lattice contraction (photostriction), with the mechanism revealed as Pauli blocking. For single-crystal MAPbI3, phonon lifetimes were significantly longer and phonon frequencies shifted less with temperature, compared with polycrystalline MAPbI3. We attribute these differences to increased crystalline disorder, associated with grain boundaries and strain in the polycrystalline MAPbI3. Thus we provide fundamental insight into the photoexcitation and electron–phonon coupling in MAPbI3.

Measuring terahertz (THz) conductivity on an ultrafast time scale is an excellent way to observe charge-carrier dynamics in semiconductors as a function of time after photoexcitation. However, a conductivity measurement alone cannot separate the effects of charge-carrier recombination from effective mass changes as charges cool and experience different regions of the electronic band structure. Here we present a form of time-resolved magneto-THz spectroscopy which allows us to measure cyclotron effective mass on a picosecond time scale. We demonstrate this technique by observing electron cooling in the technologically-significant narrow-bandgap semiconductor indium antimonide (InSb). A significant reduction of electron effective mass from 0.032$m_\mathrm{e}$ to 0.017$m_\mathrm{e}$ is observed in the first 200ps after injecting hot electrons. Measurement of electron effective mass in InSb as a function of photo-injected electron density agrees well with conduction band non-parabolicity predictions from ab initio calculations of the quasiparticle band structure.

Polarization encoding for pulsed terahertz (THz) systems are highly desired. For example, polarization-resolved THz time-domain spectroscopy (THz-TDS) allows studying the anisotropic dielectric properties of materials and even lead to new techniques such as the THz optical-Hall effect and THz polarimetry [1] . The polarization information of THz pulsed imaging helps correct the artifacts associated with birefringence and scattering from sample edge that enables high-resolution THz tomography. However, currently available measurement schemes for polarization sensing in pulsed THz systems are not practical. The existing polarization-sensitive detectors suffer from crosstalk between detection channels while polarization-insensitive detectors based on wire-grid THz polarizers are bulky and time-consuming. Thus, we propose a cross-nanowire detector structure [2] that enables fast and precise detection of the full polarization state of THz pulses.

Tin-iodide perovskites are an important group of semiconductors for photovoltaic applications, promising higher intrinsic charge-carrier mobilities and lower toxicity than their lead-based counterparts. Controllable tin vacancy formation and the ensuing hole doping provide interesting opportunities to investigate dynamic intraband transitions of charge carriers in these materials. Here, we present for the first time an experimental implementation of a novel Optical-Pump–IR-Push–THz-Probe spectroscopic technique and demonstrate its suitability to investigate the intraband relaxation dynamics of charge carriers brought into non-equilibrium by an infrared “push” pulse. We observe a push-induced decrease of terahertz conductivity for both chemically- and photodoped FA0.83Cs0.17SnI3 thin films and show that these effects derive from stimulated THz emission. We use this technique to reveal that newly photogenerated charge carriers relax within the bands of FA0.83Cs0.17SnI3 on a sub-picosecond timescale when a large, already fully thermalized (cold) population of charge-carriers is present. Such rapid dissipation of the initial charge-carrier energy suggests that the propensity of tin halide perovskites towards unintentional self-doping resulting from tin vacancy formation makes these materials less suited to implementation in hot-carrier solar cells than their lead-based counterparts.

Lead-free silver–bismuth semiconductors have become increasingly popular materials for optoelectronic applications, building upon the success of lead halide perovskites. In these materials, charge-lattice couplings fundamentally determine charge transport, critically affecting device performance. In this study, we investigate the optoelectronic properties of the recently discovered lead-free semiconductor Cu2AgBiI6 using temperature-dependent photoluminescence, absorption, and optical-pump terahertz-probe spectroscopy. We report ultrafast charge-carrier localization effects, evident from sharp THz photoconductivity decays occurring within a few picoseconds after excitation and a rise in intensity with decreasing temperature of long-lived, highly Stokes-shifted photoluminescence. We conclude that charge carriers in Cu2AgBiI6 are subject to strong charge-lattice coupling. However, such small polarons still exhibit mobilities in excess of 1 cm2 V–1 s–1 at room temperature because of low energetic barriers to formation and transport. Together with a low exciton binding energy of ∼29 meV and a direct band gap near 2.1 eV, these findings highlight Cu2AgBiI6 as an attractive lead-free material for photovoltaic applications.

Mixed-halide perovskites offer bandgap tunability essential for multijunction solar cells; however, a detrimental halide segregation under light is often observed. Here we combine simultaneous in situ photoluminescence and X-ray diffraction measurements to demonstrate clear differences in compositional and optoelectronic changes associated with halide segregation in MAPb(Br0.5I0.5)3 and FA0.83Cs0.17Pb(Br0.4I0.6)3 films. We report evidence for low-barrier ionic pathways in MAPb(Br0.5I0.5)3, which allow for the rearrangement of halide ions in localized volumes of perovskite without significant compositional changes to the bulk material. In contrast, FA0.83Cs0.17Pb(Br0.4I0.6)3 lacks such low-barrier ionic pathways and is, consequently, more stable against halide segregation. However, under prolonged illumination, it exhibits a considerable ionic rearrangement throughout the bulk material, which may be triggered by an initial demixing of A-site cations, altering the composition of the bulk perovskite and reducing its stability against halide segregation. Our work elucidates links between composition, ionic pathways, and halide segregation, and it facilitates the future engineering of phase-stable mixed-halide perovskites.

Semiconducting polycrystalline thin films are cheap to produce and can be deposited on flexible substrates, yet high-performance electronic devices usually utilize single-crystal semiconductors, owing to their superior electrical mobilities and longer diffusion lengths. Here we show that the electrical performance of polycrystalline films of metal-halide perovskites (MHPs) approaches that of single crystals at room temperature. Combining temperature-dependent terahertz conductivity measurements and ab initio calculations we uncover a complete picture of the origins of charge scattering in single crystals and polycrystalline films of CH$_3$NH$_3$PbI$_3$. We show that Fr\"ohlich scattering of charge carriers with multiple phonon modes is the dominant mechanism limiting mobility, with grain-boundary scattering further reducing mobility in polycrystalline films. We reconcile the large discrepancy in charge diffusion lengths between single crystals and films by considering photon reabsorption. Thus, polycrystalline films of MHPs offer great promise for devices beyond solar cells, including transistors and modulators., Comment: 33 pages, 4 figures (including the toc figure)

Semiconductor Nanowires (NWs) have revolutionized photonics by providing minimal footprint optoelectronic devices and coherent light sources. However, given their nanoscale dimensions, their integration with nanophotonic systems is a significant challenge. To overcome this issue, we have developed a hybrid nanofabrication technique, known as nanoscale transfer-printing, permitting the accurate integration of individually-selected NWs at target positions onto desired surfaces. Examples of nanophotonic systems enabled by our technique include 1D/2D NW laser arrays and on-chip waveguide-coupled NW laser systems. We have also recently demonstrated a nanophotonic circuit for THz signal detection formed by a 3D semiconductor NW network coupled with a metallic antenna structure.

Metal halide perovskites have fascinated the research community over the past decade, and demonstrated unprecedented success in optoelectronics. In particular, perovskite single crystals have emerged as promising candidates for ionization radiation detection, due to the excellent opto-electronic properties. However, most of the reported crystals are grown in organic solvents and require high temperature. In this work, we develop a low-temperature crystallization strategy to grow CsPbBr3 perovskite single crystals in water. Then, we carefully investigate the structure and optoelectronic properties of the crystals obtained, and compare them with CsPbBr3 crystals grown in dimethyl sulfoxide. Interestingly, the water grown crystals exhibit a distinct crystal habit, superior charge transport properties and better stability in air. We also fabricate X-ray detectors based on the CsPbBr3 crystals, and systematically characterize their device performance. The crystals grown in water demonstrate great potential for X-ray imaging with enhanced performance metrics., Perovskite single crystals are commonly grown in organic solvents, which require relatively high temperature condition. Here, the authors develop a low-temperature crystallisation strategy to grow CsPbBr3 single crystals in water with improved charge transport properties and stability.

Hybrid halide perovskites have great potential for application in optoelectronic devices. However, an understanding of some basic properties, such as charge-carrier transport, remains inconclusive, mainly due to the mixed ionic and electronic nature of these materials. Here, we perform temperature-dependent pulsed-voltage space-charge-limited current measurements to provide a detailed look into the electronic properties of methylammonium lead tribromide (${\mathrm{MA}\mathrm{Pb}\mathrm{Br}}_{3}$) and methylammonium lead triiodide (${\mathrm{MA}\mathrm{Pb}\mathrm{I}}_{3}$) single crystals. We show that the background carrier density in these crystals is orders of magnitude higher than that expected from thermally excited carriers from the valence band. We highlight the complexity of the system via a combination of experiments and drift-diffusion simulations and show that different factors, such as thermal injection from the electrodes, temperature-dependent mobility, and trap and ion density, influence the free-carrier concentration. We experimentally determine effective activation energies for conductivity of (349 \ifmmode\pm\else\textpm\fi{} 10) meV for ${\mathrm{MA}\mathrm{Pb}\mathrm{Br}}_{3}$ and (193 \ifmmode\pm\else\textpm\fi{} 12) meV for ${\mathrm{MA}\mathrm{Pb}\mathrm{I}}_{3}$, which includes the sum of all of these factors. We point out that fitting the dark current density-voltage curve with a drift-diffusion model allows for the extraction of intrinsic parameters, such as mobility and trap and ion density. From simulations, we determine a charge-carrier mobility of 12.9 cm${}^{2}$/Vs, a trap density of 1.52 \ifmmode\times\else\texttimes\fi{} 10${}^{13}$ cm${}^{\ensuremath{-}3}$, and an ion density of 3.19 \ifmmode\times\else\texttimes\fi{} 10${}^{12}$ cm${}^{\ensuremath{-}3}$ for ${\mathrm{MA}\mathrm{Pb}\mathrm{Br}}_{3}$ single crystals. Insights into charge-carrier transport in metal-halide perovskite single crystals will be beneficial for device optimization in various optoelectronic applications.

This roadmap on Nanotechnology for Catalysis and Solar Energy Conversion focuses on the application of nanotechnology in addressing the current challenges of energy conversion: ‘high efficiency, stability, safety, and the potential for low-cost/scalable manufacturing’ to quote from the contributed article by Nathan Lewis. This roadmap focuses on solar-to-fuel conversion, solar water splitting, solar photovoltaics and bio-catalysis. It includes dye-sensitized solar cells (DSSCs), perovskite solar cells, and organic photovoltaics. Smart engineering of colloidal quantum materials and nanostructured electrodes will improve solar-to-fuel conversion efficiency, as described in the articles by Waiskopf and Banin and Meyer. Semiconductor nanoparticles will also improve solar energy conversion efficiency, as discussed by Boschloo et al in their article on DSSCs. Perovskite solar cells have advanced rapidly in recent years, including new ideas on 2D and 3D hybrid halide perovskites, as described by Spanopoulos et al ‘Next generation’ solar cells using multiple exciton generation (MEG) from hot carriers, described in the article by Nozik and Beard, could lead to remarkable improvement in photovoltaic efficiency by using quantization effects in semiconductor nanostructures (quantum dots, wires or wells). These challenges will not be met without simultaneous improvement in nanoscale characterization methods. Terahertz spectroscopy, discussed in the article by Milot et al is one example of a method that is overcoming the difficulties associated with nanoscale materials characterization by avoiding electrical contacts to nanoparticles, allowing characterization during device operation, and enabling characterization of a single nanoparticle. Besides experimental advances, computational science is also meeting the challenges of nanomaterials synthesis. The article by Kohlstedt and Schatz discusses the computational frameworks being used to predict structure–property relationships in materials and devices, including machine learning methods, with an emphasis on organic photovoltaics. The contribution by Megarity and Armstrong presents the ‘electrochemical leaf’ for improvements in electrochemistry and beyond. In addition, biohybrid approaches can take advantage of efficient and specific enzyme catalysts. These articles present the nanoscience and technology at the forefront of renewable energy development that will have significant benefits to society.

In this study, a novel type of broadband polarization-sensitive photoconductive terahertz detectors based on crossed nanowire networks is demonstrated, enabling fast and precise polarization terahertz time-domain spectroscopy measurements.

We employ ultrafast optical-pump terahertz-probe spectroscopy and ultrafast THz emission spectroscopy to investigate the ultrafast charge carrier dynamics in the 3D Dirac semi-metal Cd 3 As 2 . We extract the temperature-dependent electron mobility (16,000cm2V−1s−1 at 5K) for Cd 3 As 2 nanowire ensemble. We also demonstrate strong THz emission from both Cd 3 As 2 single crystal and nanowires, whose polarity depends strongly on incident angle and pump polarisation.

We have explored the high frequency properties of semiconductor nanowires using optical pump terahertz probe spectroscopy and used this knowledge to create a range of nanowire-based THz devices. Here we present nanowire devices for THz polarimetry including a novel cross-nanowire detector.