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The relaxation of the above-gap ("hot") carriers in lead halide perovskites (LHPs) is important for applications in photovoltaics and offers insights into carrier-carrier and carrier-phonon interactions. However, the role of quantum confinement in the hot carrier dynamics of nanosystems is still disputed. Here, we devise a single approach, ultrafast pump- push-probe spectroscopy, to study carrier cooling in six different size-controlled LHP nanomaterials. In cuboidal nanocrystals, we observe only a weak size effect on the cooling dynamics. In contrast, two-dimensional systems show suppression of the hot phonon bottleneck effect common in bulk perovskites. The proposed kinetic model describes the intrinsic and density-dependent cooling times accurately in all studied perovskite systems using only carrier-carrier, carrier-phonon, and excitonic coupling constants. This highlights the impact of exciton formation on carrier cooling and promotes dimensional confinement as a tool for engineering carrier-phonon and carrier-carrier interactions in LHP optoelectronic materials., ACS Nano, 17 (7), ISSN:1936-0851, ISSN:1936-086X

In contemporary organic solar cell (OSC) research, small A-D-A molecules comprising electron donor (D) and acceptor (A) units are increasingly used as a means to control the optoelectronic properties of photovoltaic blends. Slight structural variations to these A-D-A molecules can result in profound changes to the performance of the OSCs. Herein, we study two A-D-A molecules, BTCN-O and BTCN-M, which are identical in structure apart from a subtle difference in the position of alkyl chains, which force the molecules to adopt different equilibrium conformations. These steric effects cause the respective molecules to work better as an electron donor and acceptor when blended with benchmark acceptor and donor materials (PC71BM and PBDB-T). We study the photophysics of these “D:A” blends and devices using a combination of steady-state and time-resolved spectroscopic techniques. Time-resolved photoluminescence reveals the impact of the molecular conformation on the quenching of the A-D-A emission when BTCN-O and BTCN-M are blended with PBDB-T or PC71BM. Ultrafast broadband transient absorption spectroscopy demonstrates that the dynamics of charge separation are essentially identical when comparing BTCN-M and BTCN-O based blends, but the recombination dynamics are quite dissimilar. This suggests that the device performance is ultimately determined by the morphology of the blends imposed by the A-D-A conformation. This notion is supported by X-ray scattering data from the “D:A” films, and electroluminescence data and pump-push-photocurrent spectroscopy on the “D:A” devices. Our findings provide insight into the remarkable structure-function relationship in A-D-A molecules, and emphasize the need for careful morphological and energetic considerations when designing high-performance OSCs.

The behavior of hot carriers in metal-halide perovskites (MHPs) present a valuable foundation for understanding the details of carrier-phonon coupling in the materials as well as the prospective development of highly efficient hot carrier and carrier multiplication solar cells. Whilst the carrier population dynamics during cooling have been intensely studied, the evolution of the hot carrier properties, namely the hot carrier mobility, remain largely unexplored. To address this, we introduce a novel ultrafast visible pump - infrared push - terahertz probe spectroscopy (PPP-THz) to monitor the real-time conductivity dynamics of cooling carriers in methylammonium lead iodide. We find a decrease in mobility upon optically depositing energy into the carriers, which is typical of band-transport. Surprisingly, the conductivity recovery dynamics are incommensurate with the intraband relaxation measured by an analogous experiment with an infrared probe (PPP- IR), and exhibit a negligible dependence on the density of hot carriers. These results and the kinetic modelling reveal the importance of highly-localized lattice heating on the mobility of the hot electronic states. This collective polaron-lattice phenomenon may contribute to the unusual photophysics observed in MHPs and should be accounted for in devices that utilize hot carriers., Comment: 28 pages, 4 figures, 77 references

Here we provide a comprehensive review of a newly developed lighting technology based on metal halide perovskites (i.e. perovskite light-emitting diodes) encompassing the research endeavours into materials, photophysics and device engineering. At the outset we survey the basic perovskite structures and their various dimensions (namely three-, two- and zero-dimensional perovskites), and demonstrate how the compositional engineering of these structures affects the perovskite light-emitting properties. Next, we turn to the physics underpinning photo- and electroluminescence in these materials through their connection to the fundamental excited states, energy/charge transport processes and radiative and non-radiative decay mechanisms. In the remainder of the review, we focus on the engineering of perovskite light-emitting diodes, including the history of their development as well as an extensive analysis of contemporary strategies for boosting device performance. Key concepts include balancing the electron/hole injection, suppression of parasitic carrier losses, improvement of the photoluminescence quantum yield and enhancement of the light extraction. Overall, this review reflects the current paradigm for perovskite lighting, and is intended to serve as a foundation to materials and device scientists newly working in this field.

The relaxation of high-energy “hot” carriers in semiconductors is known to involve the redistribution of energy between hot and cold carriers, as well as the transfer of energy from hot carriers to phonons. Over the past few years, these two processes have been identified in lead-halide perovskites (LHPs) using ultrafast pump–probe experiments, but their interplay is not fully understood. Here we present a practical and intuitive kinetic model that accounts for the effects of both hot and cold carriers on carrier relaxation in LHPs. We apply this model to describe the dynamics of hot carriers in bulk and nanocrystalline CsPbBr3 as observed by multi-pulse “pump–push–probe” spectroscopy. The model captures the slowing of the relaxation dynamics in the materials as the number of hot carriers increases, which has previously been explained by a “hot-phonon bottleneck” mechanism. The model also correctly predicts an acceleration of the relaxation kinetics as the number of cold carriers in the samples is increased. Using a series of natural approximations, we reduce our model to a simple form containing terms for the carrier–carrier and carrier–phonon interactions. The model can be instrumental for evaluating the details of carrier relaxation and carrier–phonon couplings in LHPs and other soft optoelectronic materials. ISSN:1463-9084 ISSN:1463-9076

Nano Letters, 20 (4), ISSN:1530-6984, ISSN:1530-6992

Lead-halide perovskites are currently the highest-performing solution-processable semiconductors for solar energy conversion, with record efficiencies rapidly approaching that of the Shockley-Queisser limit for single-junction solar cells. Further progress in the development of lead-halide perovskite solar cells must overcome this limit, which largely stems from the ultrafast relaxation of high-energy hot carriers above the bandedge. In this contribution, we use a highly-specialized pump-push-probe technique to unravel the key parameters which control hot carrier cooling in bulk and nanocrystal (NC) lead bromide perovskites with different material composition, NC diameter and surface treatment. All samples exhibit slower cooling for higher hot carrier densities, which we assign to a phonon bottleneck mechanism. By comparing this density-dependent cooling behavior in the different samples, we find that the weak quantum confinement of electronic states and the surface defects in the NCs play no observable role in the hot carrier relaxation. Meanwhile, in accordance with our previous observations for bulk perovskites, we show that the cation plays a critical role towards carrier cooling in the perovskite NCs, as evidenced by the faster overall cooling in the hybrid FAPbBr3 NCs with respect to the all-inorganic CsPbBr3 NCs. These observations highlight the crucial role of the cations toward the phononic properties of lead-halide perovskites, and further point towards the defect tolerance of these emerging solution-processed semiconductors.

Junction-functionalized donor-acceptor (D-A) block copolymers (BCPs) enable spatial and electronic control over interfacial charge dynamics in excitonic devices such as solar cells. Here, we present the design, synthesis, morphology, and electronic characterization of block junction-functionalized, all-conjugated, all-crystalline D-A BCPs. Poly(3-hexylthiophene) (P3HT), a single thienylated diketopyrrolopyrrole (Th xDPPTh x, x = 1 or 2) unit, and poly{[ N, N'-bis(2-octyldodecyl)-naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl]- alt-5,5'-(2,2'-bithiophene)} (PNDIT2) are used as donor, interfacial unit, and acceptor, respectively. Almost all C-C coupling steps are accomplished by virtue of C-H activation. Synthesis of the macroreagent H-P3HT-Th xDPPTh x, with x determining its C-H reactivity, is key to the synthesis of various BCPs of type H-P3HT-Th xDPPTh x- block-PNDIT2. Morphology is determined from a combination of calorimetry, transmission electron microscopy (TEM), and thin-film scattering. Block copolymer crystallinity of P3HT and PNDIT2 is reduced, indicating frustrated crystallization. A long period lp is invisible from TEM, but shows up in resonant soft X-ray scattering experiments at a length scale of lp ∼ 60 nm. Photoluminescence of H-P3HT-Th xDPPTh x indicates efficient transfer of the excitation energy to the DPP chain end, but is quenched in BCP films. Transient absorption and pump-push photocurrent spectroscopies reveal geminate recombination (GR) as the main loss channel in as-prepared BCP films independent of junction functionalization. Melt annealing increases GR as a result of the low degree of crystallinity and poorly defined interfaces and additionally changes backbone orientation of PNDIT2 from face-on to edge-on. These morphological effects dominate solar cell performance and cause an insensitivity to the presence of the block junction.

Non-fullerene acceptors (NFAs) have recently outperformed their fullerene counterparts in binary bulk-heterojunction (BHJ) organic solar cells (OSCs). Further development of NFA OSCs may benefit other novel OSC device structures that alter or extend the standard BHJ concept. Here, we report such a new processing route that forms a BHJ-like morphology between sequentially processed polymer donor and NFA with high power conversion efficiencies in excess of 10%. Both devices show similar charge generation and recombination behaviours, supporting formation of similar BHJ active layers. We correlate the approximate to 30 meV smaller open-circuit voltage in sq-BHJ devices to more substantial non-radiative recombination by voltage loss analysis. We also determine the exciton diffusion length of benchmark polymer PBDB-T to be 10 +/- 3 nm. Our results demonstrate high-efficiency OSC devices using sequential deposition method and provide new opportunities to further improve performance of state-of-the-art OSCs. Funding Agencies|Engineering and Physical Sciences Research Council; Science and Technology Facilities Council [RB1800095]; China Scholarship Council [201503170255]; SPIE Optics and Photonics Education Scholarship; NSFC [91633301]; MOST of China [2014CB643502]; [2016-02051]

Understanding the photophysics of charge generation in organic semiconductors is a critical step toward the further optimization of organic solar cells. The separation of electron–hole pairs in systems with large energy offsets is relatively well-understood; however, the photophysics in blends with low driving energy remains unclear. Herein, we use the material system PffBT4T-2OD:PC71BM as an example to show that the built-in electric field plays a critical role toward long-range charge separation in high-performance devices. By using steady-state and time-resolved spectroscopic techniques, we show that in neat films an energetic barrier impedes polymer exciton dissociation, preventing charge transfer to the fullerene acceptor. In complete devices, this barrier is diminished due to the built-in electric field provided by the interlayers/contacts and accompanying space-charge distribution. The observed behavior could also be relevant to other systems with low driving energy and emphasizes the importance of using complete devices, rather than solely films, for photophysical studies.

The rapid relaxation of above-band-gap “hot” carriers (HCs) imposes the key efficiency limit in lead-halide perovskite (LHP) solar cells. Recent studies have indicated that HC cooling in these systems may be sensitive to materials composition, as well as the energy and density of excited states. However, the key parameters underpinning the cooling mechanism are currently under debate. Here we use a sequence of ultrafast optical pulses (visible pump–infrared push–infrared probe) to directly compare the intraband cooling dynamics in five common LHPs: FAPbI3, FAPbBr3, MAPbI3, MAPbBr3, and CsPbBr3. We observe ∼100–900 fs cooling times, with slower cooling at higher HC densities. This effect is strongest in the all-inorganic Cs-based system, compared to the hybrid analogues with organic cations. These observations, together with band structure calculations, allow us to quantify the origin of the “hot-phonon bottleneck” in LHPs and assert the thermodynamic contribution of a symmetry-breaking organic cation toward rapid HC cooling.

Correction for ‘Efficient non-fullerene organic solar cells employing sequentially deposited donor–acceptor layers’ by Jiangbin Zhang et al., J. Mater. Chem. A, 2018, 6, 18225–18233.

The energetic offset between the initial photo excited state and charge-transfer (CT) state in organic heterojunction solar cells influences both charge generation and open-circuit voltage (V-oc). Here, we use time-resolved spectroscopy and voltage loss measurements to analyze the effect of the exciton-CT state offset on charge transfer, separation, and recombination processes in blends of a low-band-gap polymer (INDT-S) with fullerene derivatives of different electron affinity (PCBM and KL). For the lower exciton-CT state offset blend (INDT-S:PCBM), both photocurrent generation and non-radiative voltage losses are lower. The INDT-S:PCBM blend shows different excited-state dynamics depending on whether the donor or acceptor is photoexcited. Surprisingly, the charge recombination dynamics in INDT-S:PCBM are distinctly faster than those in INDT-S:KL upon excitation of the donor. We reconcile these observations using a kinetic model and by considering hybridization between the lowest excitonic and CT states. The modeling results show that this hybridization can significantly reduce V-oc losses while still allowing reasonable charge generation efficiency.

The open-circuit voltage of organic solar cells is usually lower than the values achieved in inorganic or perovskite photovoltaic devices with comparable bandgaps. Energy losses during charge separation at the donor–acceptor interface and non-radiative recombination are among the main causes of such voltage losses. Here we combine spectroscopic and quantum-chemistry approaches to identify key rules for minimizing voltage losses: (1) a low energy offset between donor and acceptor molecular states and (2) high photoluminescence yield of the low-gap material in the blend. Following these rules, we present a range of existing and new donor–acceptor systems that combine efficient photocurrent generation with electroluminescence yield up to 0.03%, leading to non-radiative voltage losses as small as 0.21 V. This study provides a rationale to explain and further improve the performance of recently demonstrated high-open-circuit-voltage organic solar cells. Key optoelectronic properties for donor and acceptor organic semiconductors are identified to obtain organic solar cells with reduced open-circuit voltage losses and high power conversion efficiencies.