Oxford Terahertz Photonics Group

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 delta H-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.

Halogen mixing in lead-halide perovskites is an effective route for tuning the band gap in light emission and multijunction solar cell applications. Here we report the effect of halogen mixing on the optoelectronic properties of lead-halide perovskites from theory and experiment. We applied the virtual crystal approximation within density functional theory, the GW approximation, and the Betheâ€“Salpeter equation to calculate structural, vibrational, and optoelectronic properties for a series of mixed halide perovskites. We separately perform spectroscopic measurements of these properties and analyze the impact of halogen mixing on quasiparticle band gaps, effective masses, absorption coefficients, charge-carrier mobilities, and exciton binding energies. Our joint theoreticalâ€“experimental study demonstrates that iodideâ€“bromide mixed-halide perovskites can be modeled as homovalent alloys, and local structural distortions do not play a significant role for the properties of these mixed species. Our study outlines a general theoreticalâ€“experimental framework for future investigations of novel chemically mixed systems.

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 Cu-4x(AgBi)(1-x)I-4). 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.

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 MAPbI(3) 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 MAPbI(3). 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 MAPbI(3), phonon lifetimes were significantly longer and phonon frequencies shifted less with temperature, compared with polycrystalline MAPbI(3). We attribute these differences to increased crystalline disorder, associated with grain boundaries and strain in the polycrystalline MAPbI(3). Thus we provide fundamental insight into the photoexcitation and electron-phonon coupling in MAPbI(3).

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 cm(2) V-1 s(-1) at room temperature because of low energetic barriers to formation and transport. Together with a low exciton binding energy of similar to 29 meV and a direct band gap near 2.1 eV, these findings highlight Cu2AgBiI6 as an attractive lead-free material for photovoltaic applications.

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 charge-carrier 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-carrier scattering in single crystals and polycrystalline films of CH3NH3PbI3. We show that Frohlich 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-carrier 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 light-emitting diodes and modulators.

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 cm(2) 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.

Understanding the electronic energy landscape in metal halide perovskites is essential for further improvements in their promising performance in thin-film photovoltaics. Here, we uncover the presence of above-bandgap oscillatory features in the absorption spectra of formamidinium lead triiodide thin films. We attribute these discrete features to intrinsically occurring quantum confinement effects, for which the related energies change with temperature according to the inverse square of the intrinsic lattice parameter, and with peak index in a quadratic manner. By determining the threshold film thickness at which the amplitude of the peaks is appreciably decreased, and through ab initio simulations of the absorption features, we estimate the length scale of confinement to be 10-20 nm. Such absorption peaks present a new and intriguing quantum electronic phenomenon in a nominally bulk semiconductor, offering intrinsic nanoscale optoelectronic properties without necessitating cumbersome additional processing steps. Oscillatory features in the absorption spectra of formamidinium lead triiodide perovskite thin films reveal the occurrence of intrinsic quantum confinement effects with confinement on the scale of tens of nanometres.

Trap-related charge-carrier recombination fundamentally limits the performance of perovskite solar cells and other optoelectronic devices. While improved fabrication and passivation techniques have reduced trap densities, the properties of trap states and their impact on the charge-carrier dynamics in metal-halide perovskites are still under debate. Here, a unified model is presented of the radiative and nonradiative recombination channels in a mixed formamidinium-cesium lead iodide perovskite, including charge-carrier trapping, de-trapping and accumulation, as well as higher-order recombination mechanisms. A fast initial photoluminescence (PL) decay component observed after pulsed photogeneration is demonstrated to result from rapid localization of free charge carriers in unoccupied trap states, which may be followed by de-trapping, or nonradiative recombination with free carriers of opposite charge. Such initial decay components are shown to be highly sensitive to remnant charge carriers that accumulate in traps under pulsed-laser excitation, with partial trap occupation masking the trap density actually present in the material. Finally, such modelling reveals a change in trap density at the phase transition, and disentangles the radiative and nonradiative charge recombination channels present in FA(0.95)Cs(0.05)PbI(3,)accurately predicting the experimentally recorded PL efficiencies between 50 and 295 K, and demonstrating that bimolecular recombination is a fully radiative process.

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 MAPbBr(3) 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 MAPbBr(3) 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.

The production of highly efficient single- and multijunction metal halide perovskite (MHP) solar cells requires careful optimization of the optical and electrical properties of these devices. Here, precise control of CH3NH3PbI3 perovskite layers is demonstrated in solar cell devices through the use of dual source coevaporation. Light absorption and device performance are tracked for incorporated MHP films ranging from approximate to 67 nm to approximate to 1.4 mu m thickness and transfer-matrix optical modeling is utilized to quantify optical losses that arise from interference effects. Based on these results, a device with 19.2% steady-state power conversion efficiency is achieved through incorporation of a perovskite film with near-optimum predicted thickness (approximate to 709 nm). Significantly, a clear signature of photon reabsorption is observed in perovskite films that have the same thickness (approximate to 709 nm) as in the optimized device. Despite the positive effect of photon recycling associated with photon reabsorption, devices with thicker (>750 nm) MHP layers exhibit poor performance owing to competing nonradiative charge recombination in a "dead-volume" of MHP. Overall, these findings demonstrate the need for fine control over MHP thickness to achieve the highest efficiency cells, and accurate consideration of photon reabsorption, optical interference, and charge transport properties.

An understanding of the factors driving halide segregation in lead mixed-halide perovskites is required for their implementation in tandem solar cells with existing silicon technology. Here we report that the halide segregation dynamics observed in the photoluminescence from CH3NH3Pb(Br0.5I0.5)(3) is strongly influenced by the atmospheric environment, and that encapsulation of films with a layer of poly(methyl methacrylate) allows for halide segregation dynamics to be fully reversible and repeatable. We further establish an empirical model directly linking the amount of halide segregation observed in the photoluminescence to the fraction of charge carriers recombining through trap-mediated channels, and the photon flux absorbed. From such quantitative analysis we show that under pulsed illumination, the frequency of the modulation alone has no influence on the segregation dynamics. Additionally, we extrapolate that working CH3NH3Pb(Br0.5I0.5)(3) perovskite cells would require a reduction of the trap-related charge carrier recombination rate to less than or similar to 10(5)s(-1) in order for halide segregation to be sufficiently suppressed.

Photovoltaic devices based on metal halide perovskites are rapidly improving in efficiency. Once the Shockley-Queisser limit is reached, charge-carrier extraction will be limited only by radiative bimolecular recombination of electrons with holes. Yet, this fundamental process, and its link with material stoichiometry, is still poorly understood. Here we show that bimolecular charge-carrier recombination in methylammonium lead triiodide perovskite can be fully explained as the inverse process of absorption. By correctly accounting for contributions to the absorption from excitons and electron-hole continuum states, we are able to utilise the van Roosbroeck-Shockley relation to determine bimolecular recombination rate constants from absorption spectra. We show that the sharpening of photon, electron and hole distribution functions significantly enhances bimolecular charge recombination as the temperature is lowered, mirroring trends in transient spectroscopy. Our findings provide vital understanding of band-to-band recombination processes in this hybrid perovskite, which comprise direct, fully radiative transitions between thermalized electrons and holes.

Perovskite thin-film solar cells are one of the most promising emerging renewable energy technologies because of their potential for low-cost, large-area fabrication combined with high energy conversion efficiencies. Recently, formamidinium lead triiodide ($rm {FAPbI_3}$) and other formamidinium (CH(NH$_2$)$_2$) based perovskites have been explored as interesting alternatives to methylammonium lead triiodide ($rm {MAPbI_3}$), because they exhibit better thermal stability. However at present a major challenge is up-scaling of perovskite solar cells from small test-cells to full solar modules. We show that co-evaporation is a scalable method for the deposition of homogeneous $rm FAPbI_3$ thin-films over large areas. The method allows precise control over film thickness and results in highly uniform, pin-hole free layers. Our films exhibited a high charge-carrier mobility of 26,$rm cm^2 V^{-1}s^{-1}$, excellent optical properties and a bimolecular recombination constant of $7times10^{-11}$,cm$^3$s$^{-1}$. Solar cells fabricated using these vapor-deposited layers within a regular device architecture produced stabilized power conversion efficiencies of up to 14.2,$rm%$. Thus we demonstrate that efficient $rm FAPbI_3$ solar cells can be vapor-deposited, which opens up a pathway towards large-area stable perovskite photovoltaics.

Traps limit the photovoltaic efficiency and affect the charge transport of optoelectronic devices based on hybrid lead halide perovskites. Understanding the nature and energy scale of these trap states is therefore crucial for the development and optimization of solar cell and laser technology based on these materials. Here, the low-temperature photoluminescence of formamidinium lead triiodide (HC(NH2)(2)PbI3) is investigated. A power-law time dependence in the emission intensity and an additional low-energy emission peak that exhibits an anomalous relative Stokes shift are observed. Using a rate-equation model and a Monte Carlo simulation, it is revealed that both phenomena arise from an exponential trap-density tail with characteristic energy scale of approximate to 3 meV. Charge-carrier recombination from sites deep within the tail is found to cause emission with energy downshifted by up to several tens of meV. Hence, such phenomena may in part be responsible for open-circuit voltage losses commonly observed in these materials. In this high-quality hybrid perovskite, trap states thus predominantly comprise a continuum of energetic levels (associated with disorder) rather than discrete trap energy levels (associated, e.g., with elemental vacancies). Hybrid perovskites may therefore be viewed as classic semiconductors whose band-structure picture is moderated by a modest degree of energetic disorder.

Phonon scattering limits charge-carrier mobilities and governs emission line broadening in hybrid metal halide perovskites. Establishing how charge carriers interact with phonons in these materials is therefore essential for the development of high-efficiency perovskite photovoltaics and low-cost lasers. Here we investigate the temperature dependence of emission line broadening in the four commonly studied formamidinium and methylammonium perovskites, HC(NH2)(2)PbI3, HC(NH2)(2)PbBr3, CH3NH3PbI3 and CH3NH3PbBr3, and discover that scattering from longitudinal optical phonons via the Frohlich interaction is the dominant source of electron-phonon coupling near room temperature, with scattering off acoustic phonons negligible. We determine energies for the interacting longitudinal optical phonon modes to be 11.5 and 15.3 meV, and Frohlich coupling constants of similar to 40 and 60 meV for the lead iodide and bromide perovskites, respectively. Our findings correlate well with first-principles calculations based on many-body perturbation theory, which underlines the suitability of an electronic band-structure picture for describing charge carriers in hybrid perovskites.

Hybrid metal-halide perovskites have emerged as a leading class of semiconductors for optoelectronic devices because of their desirable material properties and versatile fabrication methods. However, little is known about the chemical transformations that occur in the initial stages of perovskite crystal formation. Here we follow the real-time formation dynamics of MAPbI3 from a bilayer of lead iodide (PbI2) and methylammonium iodide (MAI) deposited through a two-step thermal evaporation process. By lowering the substrate temperature during deposition, we are able to initially inhibit intermixing of the two layers. We subsequently use infrared and visible light transmission, X-ray diffraction, and photoluminescence lifetime measurements to reveal the room-temperature transformations that occur in vacuum and ambient air, as MAI diffuses into the PbI2 lattice to form MAPbI3. In vacuum, the transformation to MAPbI3 is incomplete as unreacted MAI is retained in the film. However, exposure to moist air allows for conversion of the unreacted MAI to MAPbI3, demonstrating that moisture is essential in making MAI more mobile and thus aiding perovskite crystallization. These dynamic processes are reflected in the observed charge-carrier lifetimes, which strongly fluctuate during periods of large ion migration but steadily increase with improving crystallinity.

Liquid-crystalline polymers are materials of considerable scientific interest and technological value(1-3). An important subset of these materials exhibit rubber-like elasticity, combining the optical properties of liquid crystals with the mechanical properties of rubber. Moreover, they exhibit behaviour not seen in either type of material independently(2), and many of their properties depend crucially on the particular mesophase employed. Such stretchable liquid-crystalline polymers have previously been demonstrated in the nematic, chiral-nematic, and smectic mesophases(2,4). Here, we report the fabrication of a stretchable gel of blue phase I, which forms a self-assembled, three-dimensional photonic crystal that remains electro-optically switchable under a moderate applied voltage, and whose optical properties can be manipulated by an applied strain. We also find that, unlike its undistorted counterpart, a mechanically deformed blue phase exhibits a Pockels electro-optic effect, which sets out new theoretical challenges and possibilities for low-voltage electro-optic devices.

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Dr Adam Wright

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