Ligand-engineered bandgap stability in mixed-halide perovskite LEDs.

Lead halide perovskites are promising semiconductors for light-emitting applications because they exhibit bright, bandgap-tunable luminescence with high colour purity1,2. Photoluminescence quantum yields close to unity have been achieved for perovskite nanocrystals across a broad range of emission colours, and light-emitting diodes with external quantum efficiencies exceeding 20 per cent-approaching those of commercial organic light-emitting diodes-have been demonstrated in both the infrared and the green emission channels1,3,4. However, owing to the formation of lower-bandgap iodide-rich domains, efficient and colour-stable red electroluminescence from mixed-halide perovskites has not yet been realized5,6. Here we report the treatment of mixed-halide perovskite nanocrystals with multidentate ligands to suppress halide segregation under electroluminescent operation. We demonstrate colour-stable, red emission centred at 620 nanometres, with an electroluminescence external quantum efficiency of 20.3 per cent. We show that a key function of the ligand treatment is to 'clean' the nanocrystal surface through the removal of lead atoms. Density functional theory calculations reveal that the binding between the ligands and the nanocrystal surface suppresses the formation of iodine Frenkel defects, which in turn inhibits halide segregation. Our work exemplifies how the functionality of metal halide perovskites is extremely sensitive to the nature of the (nano)crystalline surface and presents a route through which to control the formation and migration of surface defects. This is critical to achieve bandgap stability for light emission and could also have a broader impact on other optoelectronic applications-such as photovoltaics-for which bandgap stability is required.

Lanthanide-doped inorganic nanoparticles turn molecular triplet excitons bright.

The generation, control and transfer of triplet excitons in molecular and hybrid systems is of great interest owing to their long lifetime and diffusion length in both solid-state and solution phase systems, and to their applications in light emission1, optoelectronics2,3, photon frequency conversion4,5 and photocatalysis6,7. Molecular triplet excitons (bound electron-hole pairs) are 'dark states' because of the forbidden nature of the direct optical transition between the spin-zero ground state and the spin-one triplet levels8. Hence, triplet dynamics are conventionally controlled through heavy-metal-based spin-orbit coupling9-11 or tuning of the singlet-triplet energy splitting12,13 via molecular design. Both these methods place constraints on the range of properties that can be modified and the molecular structures that can be used. Here we demonstrate that it is possible to control triplet dynamics by coupling organic molecules to lanthanide-doped inorganic insulating nanoparticles. This allows the classically forbidden transitions from the ground-state singlet to excited-state triplets to gain oscillator strength, enabling triplets to be directly generated on molecules via photon absorption. Photogenerated singlet excitons can be converted to triplet excitons on sub-10-picosecond timescales with unity efficiency by intersystem crossing. Triplet exciton states of the molecules can undergo energy transfer to the lanthanide ions with unity efficiency, which allows us to achieve luminescent harvesting of the dark triplet excitons. Furthermore, we demonstrate that the triplet excitons generated in the lanthanide nanoparticle-molecule hybrid systems by near-infrared photoexcitation can undergo efficient upconversion via a lanthanide-triplet excitation fusion process: this process enables endothermic upconversion and allows efficient upconversion from near-infrared to visible frequencies in the solid state. These results provide a new way to control triplet excitons, which is essential for many fields of optoelectronic and biomedical research.

Approaching disorder-free transport in high-mobility conjugated polymers.

Conjugated polymers enable the production of flexible semiconductor devices that can be processed from solution at low temperatures. Over the past 25 years, device performance has improved greatly as a wide variety of molecular structures have been studied. However, one major limitation has not been overcome; transport properties in polymer films are still limited by pervasive conformational and energetic disorder. This not only limits the rational design of materials with higher performance, but also prevents the study of physical phenomena associated with an extended π-electron delocalization along the polymer backbone. Here we report a comparative transport study of several high-mobility conjugated polymers by field-effect-modulated Seebeck, transistor and sub-bandgap optical absorption measurements. We show that in several of these polymers, most notably in a recently reported, indacenodithiophene-based donor-acceptor copolymer with a near-amorphous microstructure, the charge transport properties approach intrinsic disorder-free limits at which all molecular sites are thermally accessible. Molecular dynamics simulations identify the origin of this long sought-after regime as a planar, torsion-free backbone conformation that is surprisingly resilient to side-chain disorder. Our results provide molecular-design guidelines for 'disorder-free' conjugated polymers.

Electroluminescence from Solution-Processed Pinhole-Free Nanometer-Thickness Layers of Conjugated Polymers.

We report the formation of robust, reproducible, pinhole-free, thin layers of fluorinated polyfluorene conjugated copolymers on a range of polymeric underlayers via a simple solution processing method. This is driven by the different characters of the fluorinated and nonfluorinated sections of these polymers. Photothermal deflection spectroscopy is used to determine that these layers are 1-2 nm thick, corresponding to a molecularly thin layer. Evidence that these layers are continuous and pinhole-free is provided by electroluminescence data from polymer LED devices that incorporate these layers within the stacked LED structure. These reveal, remarkably, light emission solely from these molecularly thin layers.

Exciton-Phonon Interactions Govern Charge-Transfer-State Dynamics in CdSe/CdTe Two-Dimensional Colloidal Heterostructures.

CdSe/CdTe core-crown type-II nanoplatelet heterostructures are two-dimensional semiconductors that have attracted interest for use in light-emitting technologies due to their ease of fabrication, outstanding emission yields, and tunable properties. Despite this, the exciton dynamics of these complex materials, and in particular how they are influenced by phonons, is not yet well understood. Here, we use a combination of femtosecond vibrational spectroscopy, temperature-resolved photoluminescence (PL), and temperature-dependent structural measurements to investigate CdSe/CdTe nanoplatelets with a thickness of four monolayers. We show that charge-transfer (CT) excitons across the CdSe/CdTe interface are formed on two distinct time scales: initially from an ultrafast (∼70 fs) electron transfer and then on longer time scales (∼5 ps) from the diffusion of domain excitons to the interface. We find that the CT excitons are influenced by an interfacial phonon mode at ∼120 cm-1, which localizes them to the interface. Using low-temperature PL spectroscopy we reveal that this same phonon mode is the dominant mechanism in broadening the CT PL. On cooling to 4 K, the total PL quantum yield reaches close to unity, with an ∼85% contribution from CT emission and the remainder from an emissive sub-band-gap state. At room temperature, incomplete diffusion of domain excitons to the interface and scattering between CT excitons and phonons limit the PL quantum yield to ∼50%. Our results provide a detailed picture of the nature of exciton-phonon interactions at the interfaces of 2D heterostructures and explain both the broad shape of the CT PL spectrum and the origin of PL quantum yield losses. Furthermore, they suggest that to maximize the PL quantum yield both improved engineering of the interfacial crystal structure and diffusion of domain excitons to the interface, e.g., by altering the relative core/crown size, are required.

Visualizing excitations at buried heterojunctions in organic semiconductor blends.

Interfaces play a crucial role in semiconductor devices, but in many device architectures they are nanostructured, disordered and buried away from the surface of the sample. Conventional optical, X-ray and photoelectron probes often fail to provide interface-specific information in such systems. Here we develop an all-optical time-resolved method to probe the local energetic landscape and electronic dynamics at such interfaces, based on the Stark effect caused by electron-hole pairs photo-generated across the interface. Using this method, we found that the electronically active sites at the polymer/fullerene interfaces in model bulk-heterojunction blends fall within the low-energy tail of the absorption spectrum. This suggests that these sites are highly ordered compared with the bulk of the polymer film, leading to large wavefunction delocalization and low site energies. We also detected a 100 fs migration of holes from higher- to lower-energy sites, consistent with these charges moving ballistically into more ordered polymer regions. This ultrafast charge motion may be key to separating electron-hole pairs into free charges against the Coulomb interaction.

High operational and environmental stability of high-mobility conjugated polymer field-effect transistors through the use of molecular additives.

Due to their low-temperature processing properties and inherent mechanical flexibility, conjugated polymer field-effect transistors (FETs) are promising candidates for enabling flexible electronic circuits and displays. Much progress has been made on materials performance; however, there remain significant concerns about operational and environmental stability, particularly in the context of applications that require a very high level of threshold voltage stability, such as active-matrix addressing of organic light-emitting diode displays. Here, we investigate the physical mechanisms behind operational and environmental degradation of high-mobility, p-type polymer FETs and demonstrate an effective route to improve device stability. We show that water incorporated in nanometre-sized voids within the polymer microstructure is the key factor in charge trapping and device degradation. By inserting molecular additives that displace water from these voids, it is possible to increase the stability as well as uniformity to a high level sufficient for demanding industrial applications.

Organic Cation Rotation and Immobilization in Pure and Mixed Methylammonium Lead-Halide Perovskites.

Three-dimensional lead-halide perovskites have attracted a lot of attention due to their ability to combine solution processing with outstanding optoelectronic properties. Despite their soft ionic nature these materials demonstrate a surprisingly low level of electronic disorder resulting in sharp band edges and narrow distributions of the electronic energies. Understanding how structural and dynamic disorder impacts the optoelectronic properties of these perovskites is important for many applications. Here we combine ultrafast two-dimensional vibrational spectroscopy and molecular dynamics simulations to study the dynamics of the organic methylammonium (MA) cation orientation in a range of pure and mixed trihalide perovskite materials. For pure MAPbX3 (X = I, Br, Cl) perovskite films, we observe that the cation dynamics accelerate with decreasing size of the halide atom. This acceleration is surprising given the expected strengthening of the hydrogen bonds between the MA and the smaller halide anions, but can be explained by the increase in the polarizability with the size of halide. Much slower dynamics, up to partial immobilization of the organic cation, are observed in the mixed MAPb(ClxBr1-x)3 and MAPb(BrxI1-x)3 alloys, which we associate with symmetry breaking within the perovskite unit cell. The observed dynamics are essential for understanding the effects of structural and dynamical disorder in perovskite-based optoelectronic systems.

Partial oxidation of the absorber layer reduces charge carrier recombination in antimony sulfide solar cells.

We investigate the effect of a post heat treatment of the absorber layer in air for antimony sulfide (Sb2S3) sensitized solar cells. Phenomenologically, exposing the Sb2S3 surface of sensitised solar cells to air at elevated temperatures is known to improve device performance. Here, we have investigated the detailed origins of this improvement. To this end, samples were annealed in air for different time periods and the build-up of an antimony oxide layer was monitored by XPS. A very short heat treatment resulted in an increase in power conversion efficiency from η = 1.4% to η = 2.4%, while longer annealing decreased the device performance. This improvement was linked to a reduction in charge carrier recombination at the interface of Sb2S3 with the organic hole conductor, arising from the oxide barrier layer, as demonstrated by intensity modulated photovoltage spectroscopy (IMVS).

What Controls the Rate of Ultrafast Charge Transfer and Charge Separation Efficiency in Organic Photovoltaic Blends.

In solar energy harvesting devices based on molecular semiconductors, such as organic photovoltaics (OPVs) and artificial photosynthetic systems, Frenkel excitons must be dissociated via charge transfer at heterojunctions to yield free charges. What controls the rate and efficiency of charge transfer and charge separation is an important question, as it determines the overall power conversion efficiency (PCE) of these systems. In bulk heterojunctions between polymer donor and fullerene acceptors, which provide a model system to understand the fundamental dynamics of electron transfer in molecular systems, it has been established that the first step of photoinduced electron transfer can be fast, of order 100 fs. But here we report the first study which correlates differences in the electron transfer rate with electronic structure and morphology, achieved with sub-20 fs time resolution pump-probe spectroscopy. We vary both the fullerene substitution and donor/fullerene ratio which allow us to control both aggregate size and the energetic driving force for charge transfer. We observe a range of electron transfer times from polymer to fullerene, from 240 fs to as short as 37 fs. Using ultrafast electro-optical pump-push-photocurrent spectroscopy, we find the yield of free versus bound charges to be weakly dependent on the energetic driving force, but to be very strongly dependent on fullerene aggregate size and packing. Our results point toward the importance of state accessibility and charge delocalization and suggest that energetic offsets between donor and acceptor levels are not an important criterion for efficient charge generation. This provides design rules for next-generation materials to minimize losses related to driving energy and boost PCE.

Blue-Green Color Tunable Solution Processable Organolead Chloride-Bromide Mixed Halide Perovskites for Optoelectronic Applications.

Solution-processed organo-lead halide perovskites are produced with sharp, color-pure electroluminescence that can be tuned from blue to green region of visible spectrum (425-570 nm). This was accomplished by controlling the halide composition of CH3NH3Pb(BrxCl1-x)3 [0 ≤ x ≤ 1] perovskites. The bandgap and lattice parameters change monotonically with composition. The films possess remarkably sharp band edges and a clean bandgap, with a single optically active phase. These chloride-bromide perovskites can potentially be used in optoelectronic devices like solar cells and light emitting diodes (LEDs). Here we demonstrate high color-purity, tunable LEDs with narrow emission full width at half maxima (FWHM) and low turn on voltages using thin-films of these perovskite materials, including a blue CH3NH3PbCl3 perovskite LED with a narrow emission FWHM of 5 nm.

Electronic Structure of Low-Temperature Solution-Processed Amorphous Metal Oxide Semiconductors for Thin-Film Transistor Applications.

The electronic structure of low temperature, solution-processed indium-zinc oxide thin-film transistors is complex and remains insufficiently understood. As commonly observed, high device performance with mobility >1 cm2 V-1 s-1 is achievable after annealing in air above typically 250 °C but performance decreases rapidly when annealing temperatures ≤200 °C are used. Here, the electronic structure of low temperature, solution-processed oxide thin films as a function of annealing temperature and environment using a combination of X-ray photoelectron spectroscopy, ultraviolet photoelectron spectroscopy, and photothermal deflection spectroscopy is investigated. The drop-off in performance at temperatures ≤200 °C to incomplete conversion of metal hydroxide species into the fully coordinated oxide is attributed. The effect of an additional vacuum annealing step, which is beneficial if performed for short times at low temperatures, but leads to catastrophic device failure if performed at too high temperatures or for too long is also investigated. Evidence is found that during vacuum annealing, the workfunction increases and a large concentration of sub-bandgap defect states (re)appears. These results demonstrate that good devices can only be achieved in low temperature, solution-processed oxides if a significant concentration of acceptor states below the conduction band minimum is compensated or passivated by shallow hydrogen and oxygen vacancy-induced donor levels.

Phosphonic anchoring groups in organic dyes for solid-state solar cells.

We report the synthesis and the optoelectronic characterization of three new 4H-pyran-4-ylidene and thiazole derivatives (pyt) as metal-free organic dyes for solid-state dye-sensitized solar cells (DSSCs). We investigate the performance and the long-term stability of devices employing pyt dyes functionalized with carboxylic and phosphonic acids as TiO2 anchoring groups. In contrast to reports on liquid electrolyte DSSCs, we show that solid-state DSSCs prepared with phosphoric pyt derivatives can achieve similar power conversion efficiency to their carboxyl analogues. We make use of the Mott-Schottky analysis and equivalent circuit models to demonstrate that a phosphonic group induces a significant increase in built-in voltage at the TiO2-hole transporter interface, which results in a higher open circuit voltage.

Improved Exciton Dissociation at Semiconducting Polymer:ZnO Donor:Acceptor Interfaces via Nitrogen Doping of ZnO.

Exciton dissociation at the zinc oxide/poly(3-hexylthiophene) (ZnO/P3HT) interface as a function of nitrogen doping of the zinc oxide, which decreases the electron concentration from approximately 1019 cm-3 to 1017 cm-3, is reported. Exciton dissociation and device photocurrent are strongly improved with nitrogen doping. This improved dissociation of excitons in the conjugated polymer is found to result from enhanced light-induced de-trapping of electrons from the surface of the nitrogen-doped ZnO. The ability to improve the surface properties of ZnO by introducing a simple nitrogen dopant has general applicability.

Formation of Iodide-Rich Domains During Halide Segregation in Lead-Halide Perovskite Nanocrystals.

Mixed iodide-bromide methylammonium lead perovskite (MAPbIxBr3-x) nanocrystals (NCs) hold promise for use in light-emitting applications owing to the size- and composition-tunability of their bandgap. However, the segregation of halides during light exposure causes their band gaps to become unstable and narrow. Here, we use transient absorption spectroscopy to track excited-state dynamics during photoinduced halide segregation. The Auger recombination dynamics are observed to accelerate as the bandgap narrows, suggesting enhanced electron-hole overlap. We simulate the motion of iodide within the NC and estimate the evolving bandgap and electron-hole overlap during two possible mechanisms of halide segregation. Our results support a segregation mechanism in which iodide anions form a domain within the NC, rather than a mechanism in which iodide anions independently segregate toward the NC surface. Such mechanistic insight will contribute to future NC bandgap stabilization strategies.

Tin Sulfide (SnS) Films Deposited by an Electric Field-Assisted Continuous Spray Pyrolysis Technique with Application as Counter Electrodes in Dye-Sensitized Solar Cells.

The deposition of tin sulfide (SnS) nanostructured films using a continuous spray pyrolysis technique is reported with an electric field present at the nozzle for influencing the atomization and the subsequent film deposition. In the absence of the electric field, the X-ray diffraction pattern shows the orthorhombic phase of SnS with a crystallographic preferred orientation along the (040) plane. The application of the electric field results in significant improvement in the morphology and a reduction in surface roughness (28 nm from 37 nm). The direct optical band gap of the films deposited with and without the electric field is estimated to be 1.5 and 1.7 eV, respectively. The photothermal deflection spectroscopy studies show a lower energetic disorder (no Urbach tail), which indicates an annealing effect in the SnS films deposited under the electric field. The improvement in the film properties is reflected in the expected improvement in the power conversion efficiency (PCE) of dye-sensitized solar cells fabricated using the SnS film as a counter electrode. An enhancement of PCE from 2.07% for the film deposited without the electric field to 2.89% for the film deposited with the electric field shows the role of the electric field in the fabrication of improved SnS films.

Charge transport physics of a unique class of rigid-rod conjugated polymers with fused-ring conjugated units linked by double carbon-carbon bonds.

We investigate the charge transport physics of a previously unidentified class of electron-deficient conjugated polymers that do not contain any single bonds linking monomer units along the backbone but only double-bond linkages. Such polymers would be expected to behave as rigid rods, but little is known about their actual chain conformations and electronic structure. Here, we present a detailed study of the structural and charge transport properties of a family of four such polymers. By adopting a copolymer design, we achieve high electron mobilities up to 0.5 cm2 V-1 s-1 Field-induced electron spin resonance measurements of charge dynamics provide evidence for relatively slow hopping over, however, long distances. Our work provides important insights into the factors that limit charge transport in this unique class of polymers and allows us to identify molecular design strategies for achieving even higher levels of performance.

Anisotropy of Charge Transport in a Uniaxially Aligned Fused Electron-Deficient Polymer Processed by Solution Shear Coating.

Precise control of the microstructure in organic semiconductors (OSCs) is essential for developing high-performance organic electronic devices. Here, a comprehensive charge transport characterization of two recently reported rigid-rod conjugated polymers that do not contain single bonds in the main chain is reported. It is demonstrated that the molecular design of the polymer makes it possible to achieve an extended linear backbone structure, which can be directly visualized by high-resolution scanning tunneling microscopy (STM). The rigid structure of the polymers allows the formation of thin films with uniaxially aligned polymer chains by using a simple one-step solution-shear/bar coating technique. These aligned films show a high optical anisotropy with a dichroic ratio of up to a factor of 6. Transport measurements performed using top-gate bottom-contact field-effect transistors exhibit a high saturation electron mobility of 0.2 cm2 V-1 s-1 along the alignment direction, which is more than six times higher than the value reported in the previous work. This work demonstrates that this new class of polymers is able to achieve mobility values comparable to state-of-the-art n-type polymers and identifies an effective processing strategy for this class of rigid-rod polymer system to optimize their charge transport properties.

Proton-transfer-induced 3D/2D hybrid perovskites suppress ion migration and reduce luminance overshoot.

Perovskite light-emitting diodes (PeLEDs) based on three-dimensional (3D) polycrystalline perovskites suffer from ion migration, which causes overshoot of luminance over time during operation and reduces its operational lifetime. Here, we demonstrate 3D/2D hybrid PeLEDs with extremely reduced luminance overshoot and 21 times longer operational lifetime than 3D PeLEDs. The luminance overshoot ratio of 3D/2D hybrid PeLED is only 7.4% which is greatly lower than that of 3D PeLED (150.4%). The 3D/2D hybrid perovskite is obtained by adding a small amount of neutral benzylamine to methylammonium lead bromide, which induces a proton transfer from methylammonium to benzylamine and enables crystallization of 2D perovskite without destroying the 3D phase. Benzylammonium in the perovskite lattice suppresses formation of deep-trap states and ion migration, thereby enhances both operating stability and luminous efficiency based on its retardation effect in reorientation.

Charge extraction via graded doping of hole transport layers gives highly luminescent and stable metal halide perovskite devices.

One source of instability in perovskite solar cells (PSCs) is interfacial defects, particularly those that exist between the perovskite and the hole transport layer (HTL). We demonstrate that thermally evaporated dopant-free tetracene (120 nm) on top of the perovskite layer, capped with a lithium-doped Spiro-OMeTAD layer (200 nm) and top gold electrode, offers an excellent hole-extracting stack with minimal interfacial defect levels. For a perovskite layer interfaced between these graded HTLs and a mesoporous TiO2 electron-extracting layer, its photoluminescence yield reaches 15% compared to 5% for the perovskite layer interfaced between TiO2 and Spiro-OMeTAD alone. For PSCs with graded HTL structure, we demonstrate efficiency of up to 21.6% and an extended power output of over 550 hours of continuous illumination at AM1.5G, retaining more than 90% of the initial performance and thus validating our approach. Our findings represent a breakthrough in the construction of stable PSCs with minimized nonradiative losses.