Intrinsic efficiency limits in low-bandgap non-fullerene acceptor organic solar cells.

In bulk heterojunction (BHJ) organic solar cells (OSCs) both the electron affinity (EA) and ionization energy (IE) offsets at the donor-acceptor interface should equally control exciton dissociation. Here, we demonstrate that in low-bandgap non-fullerene acceptor (NFA) BHJs ultrafast donor-to-acceptor energy transfer precedes hole transfer from the acceptor to the donor and thus renders the EA offset virtually unimportant. Moreover, sizeable bulk IE offsets of about 0.5 eV are needed for efficient charge transfer and high internal quantum efficiencies, since energy level bending at the donor-NFA interface caused by the acceptors' quadrupole moments prevents efficient exciton-to-charge-transfer state conversion at low IE offsets. The same bending, however, is the origin of the barrier-less charge transfer state to free charge conversion. Our results provide a comprehensive picture of the photophysics of NFA-based blends, and show that sizeable bulk IE offsets are essential to design efficient BHJ OSCs based on low-bandgap NFAs.

Ultralow Self-Doping in Two-dimensional Hybrid Perovskite Single Crystals.

Unintentional self-doping in semiconductors through shallow defects is detrimental to optoelectronic device performance. It adversely affects junction properties and it introduces electronic noise. This is especially acute for solution-processed semiconductors, including hybrid perovskites, which are usually high in defects due to rapid crystallization. Here, we uncover extremely low self-doping concentrations in single crystals of the two-dimensional perovskites (C6H5C2H4NH3)2PbI4·(CH3NH3PbI3)n-1 (n = 1, 2, and 3), over three orders of magnitude lower than those of typical three-dimensional hybrid perovskites, by analyzing their conductivity behavior. We propose that crystallization of hybrid perovskites containing large organic cations suppresses defect formation and thus favors a low self-doping level. To exemplify the benefits of this effect, we demonstrate extraordinarily high light-detectivity (1013 Jones) in (C6H5C2H4NH3)2PbI4·(CH3NH3PbI3)n-1 photoconductors due to the reduced electronic noise, which makes them particularly attractive for the detection of weak light signals. Furthermore, the low self-doping concentration reduces the equilibrium charge carrier concentration in (C6H5C2H4NH3)2PbI4·(CH3NH3PbI3)n-1, advantageous in the design of p-i-n heterojunction solar cells by optimizing band alignment and promoting carrier depletion in the intrinsic perovskite layer, thereby enhancing charge extraction.

Double Charged Surface Layers in Lead Halide Perovskite Crystals.

Understanding defect chemistry, particularly ion migration, and its significant effect on the surface's optical and electronic properties is one of the major challenges impeding the development of hybrid perovskite-based devices. Here, using both experimental and theoretical approaches, we demonstrated that the surface layers of the perovskite crystals may acquire a high concentration of positively charged vacancies with the complementary negatively charged halide ions pushed to the surface. This charge separation near the surface generates an electric field that can induce an increase of optical band gap in the surface layers relative to the bulk. We found that the charge separation, electric field, and the amplitude of shift in the bandgap strongly depend on the halides and organic moieties of perovskite crystals. Our findings reveal the peculiarity of surface effects that are currently limiting the applications of perovskite crystals and more importantly explain their origins, thus enabling viable surface passivation strategies to remediate them.

Real-Space Mapping of Surface Trap States in CIGSe Nanocrystals Using 4D Electron Microscopy.

Surface trap states in copper indium gallium selenide semiconductor nanocrystals (NCs), which serve as undesirable channels for nonradiative carrier recombination, remain a great challenge impeding the development of solar and optoelectronics devices based on these NCs. In order to design efficient passivation techniques to minimize these trap states, a precise knowledge about the charge carrier dynamics on the NCs surface is essential. However, selective mapping of surface traps requires capabilities beyond the reach of conventional laser spectroscopy and static electron microscopy; it can only be accessed by using a one-of-a-kind, second-generation four-dimensional scanning ultrafast electron microscope (4D S-UEM) with subpicosecond temporal and nanometer spatial resolutions. Here, we precisely map the collective surface charge carrier dynamics of copper indium gallium selenide NCs as a function of the surface trap states before and after surface passivation in real space and time using S-UEM. The time-resolved snapshots clearly demonstrate that the density of the trap states is significantly reduced after zinc sulfide (ZnS) shelling. Furthermore, the removal of trap states and elongation of carrier lifetime are confirmed by the increased photocurrent of the self-biased photodetector fabricated using the shelled NCs.

Engineering of CH3 NH3 PbI3 Perovskite Crystals by Alloying Large Organic Cations for Enhanced Thermal Stability and Transport Properties.

The number of studies on organic-inorganic hybrid perovskites has soared in recent years. However, the majority of hybrid perovskites under investigation are based on a limited number of organic cations of suitable sizes, such as methylammonium and formamidinium. These small cations easily fit into the perovskite's three-dimensional (3D) lead halide framework to produce semiconductors with excellent charge transport properties. Until now, larger cations, such as ethylammonium, have been found to form 2D crystals with lead halide. Here we show for the first time that ethylammonium can in fact be incorporated coordinately with methylammonium in the lattice of a 3D perovskite thanks to a balance of opposite lattice distortion strains. This inclusion results in higher crystal symmetry, improved material stability, and markedly enhanced charge carrier lifetime. This crystal engineering strategy of balancing opposite lattice distortion effects vastly increases the number of potential choices of organic cations for 3D perovskites, opening up new degrees of freedom to tailor their optoelectronic and environmental properties.

A layer-by-layer ZnO nanoparticle-PbS quantum dot self-assembly platform for ultrafast interfacial electron injection.

Absorbent layers of semiconductor quantum dots (QDs) are now used as material platforms for low-cost, high-performance solar cells. The semiconductor metal oxide nanoparticles as an acceptor layer have become an integral part of the next generation solar cell. To achieve sufficient electron transfer and subsequently high conversion efficiency in these solar cells, however, energy-level alignment and interfacial contact between the donor and the acceptor units are needed. Here, the layer-by-layer (LbL) technique is used to assemble ZnO nanoparticles (NPs), providing adequate PbS QD uptake to achieve greater interfacial contact compared with traditional sputtering methods. Electron injection at the PbS QD and ZnO NP interface is investigated using broadband transient absorption spectroscopy with 120 femtosecond temporal resolution. The results indicate that electron injection from photoexcited PbS QDs to ZnO NPs occurs on a time scale of a few hundred femtoseconds. This observation is supported by the interfacial electronic-energy alignment between the donor and acceptor moieties. Finally, due to the combination of large interfacial contact and ultrafast electron injection, this proposed platform of assembled thin films holds promise for a variety of solar cell architectures and other settings that principally rely on interfacial contact, such as photocatalysis.

The Impact of Grain Alignment of the Electron Transporting Layer on the Performance of Inverted Bulk Heterojunction Solar Cells.

This report presents a new strategy for improving solar cell power conversion efficiencies (PCEs) through grain alignment and morphology control of the ZnO electron transport layer (ETL) prepared by radio frequency (RF) magnetron sputtering. The systematic control over the ETL's grain alignment and thickness is shown, by varying the deposition pressure and operating substrate temperature during the deposition. Notably, a high PCE of 6.9%, short circuit current density (J(sc)) of 12.8 mA cm(-2), open circuit voltage (V(oc)) of 910 mV, and fill factor of 59% are demonstrated using the poly(benzo[1,2-b:4,5-b']dithiophene-thieno[3,4-c]pyrrole-4,6-dione):[6,6]-phenyl-C(71) -butyric acid methyl ester polymer blend with ETLs prepared at room temperature exhibiting oriented and aligned rod-like ZnO grains. Increasing the deposition temperature during the ZnO sputtering induces morphological cleavage of the rod-like ZnO grains and therefore reduced conductivity from 7.2 × 10(-13) to ≈1.7 × 10(-14) S m(-1) and PCE from 6.9% to 4.28%. An investigation of the charge carrier dynamics by femtosecond (fs) transient absorption spectroscopy with broadband capability reveals clear evidence of faster carrier recombination for a ZnO layer deposited at higher temperature, which is consistent with the conductivity and device performance.

Real-time observation of ultrafast electron injection at graphene-Zn porphyrin interfaces.

We report on the ultrafast interfacial electron transfer (ET) between zinc(II) porphyrin (ZnTMPyP) and negatively charged graphene carboxylate (GC) using state-of-the-art femtosecond laser spectroscopy with broadband capabilities. The steady-state interaction between GC and ZnTMPyP results in a red-shifted absorption spectrum, providing a clear indication for the binding affinity between ZnTMPyP and GC via electrostatic and π-π stacking interactions. Ultrafast transient absorption (TA) spectra in the absence and presence of three different GC concentrations reveal (i) the ultrafast formation of singlet excited ZnTMPyP*, which partially relaxes into a long-lived triplet state, and (ii) ET from the singlet excited ZnTMPyP* to GC, forming ZnTMPyP˙(+) and GC˙(-), as indicated by a spectral feature at 650-750 nm, which is attributed to a ZnTMPyP radical cation resulting from the ET process.

Carrier dynamics of a visible-light-responsive Ta3N5 photoanode for water oxidation.

The physicochemical properties of a tantalum nitride (Ta3N5) photoanode were investigated in detail to understand the fundamental aspects associated with the photoelectrochemical (PEC) water oxidation. The Ta3N5 thin films were synthesized using DC magnetron sputtering followed by annealing in air and nitridation under ammonia (NH3). A polycrystalline structure with a dense morphology of the monoclinic Ta3N5 films was obtained. A relatively low absorption coefficient (10(4) to 10(5) cm(-1)) in the visible light range was measured for Ta3N5, consistent with the nature of the indirect band-gap. Ultra-fast spectroscopic measurements revealed that the Ta3N5 with different thicknesses films possess low transport properties and fast carrier recombination (<10 ps). These critical kinetic properties of Ta3N5 as a photoanode may necessitate high overpotentials to achieve appreciable photocurrents for water oxidation (onset ∼0.6 V vs. RHE).

To what extent can charge localization influence electron injection efficiency at graphene-porphyrin interfaces?

Controlling the electron transfer process at donor-acceptor interfaces is a research direction that has not yet seen much progress. Here, with careful control of the charge localization on the porphyrin macrocycle using ß-cyclodextrin as an external cage, we are able to improve the electron injection efficiency from cationic porphyrin to graphene carboxylate by 120%. The detailed reaction mechanism is also discussed.

Quantum confinement-tunable ultrafast charge transfer at the PbS quantum dot and phenyl-C61-butyric acid methyl ester interface.

Quantum dot (QD) solar cells have emerged as promising low-cost alternatives to existing photovoltaic technologies. Here, we investigate charge transfer and separation at PbS QDs and phenyl-C61-butyric acid methyl ester (PCBM) interfaces using a combination of femtosecond broadband transient absorption (TA) spectroscopy and steady-state photoluminescence quenching measurements. We analyzed ultrafast electron injection and charge separation at PbS QD/PCBM interfaces for four different QD sizes and as a function of PCBM concentration. The results reveal that the energy band alignment, tuned by the quantum size effect, is the key element for efficient electron injection and charge separation processes. More specifically, the steady-state and time-resolved data demonstrate that only small-sized PbS QDs with a bandgap larger than 1 eV can transfer electrons to PCBM upon light absorption. We show that these trends result from the formation of a type-II interface band alignment, as a consequence of the size distribution of the QDs. Transient absorption data indicate that electron injection from photoexcited PbS QDs to PCBM occurs within our temporal resolution of 120 fs for QDs with bandgaps that achieve type-II alignment, while virtually all signals observed in smaller bandgap QD samples result from large bandgap outliers in the size distribution. Taken together, our results clearly demonstrate that charge transfer rates at QD interfaces can be tuned by several orders of magnitude by engineering the QD size distribution. The work presented here will advance both the design and the understanding of QD interfaces for solar energy conversion.

Impact of metal ions in porphyrin-based applied materials for visible-light photocatalysis: key information from ultrafast electronic spectroscopy.

Protoporphyrin IX-zinc oxide (PP-ZnO) nanohybrids have been synthesized for applications in photocatalytic devices. High-resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), and steady-state infrared, absorption, and emission spectroscopies have been used to analyze the structural details and optical properties of these nanohybrids. Time-resolved fluorescence and transient absorption techniques have been applied to study the ultrafast dynamic events that are key to photocatalytic activities. The photocatalytic efficiency under visible-light irradiation in the presence of naturally abundant iron(III) and copper(II) ions has been found to be significantly retarded in the former case, but enhanced in the latter case. More importantly, femtosecond (fs) transient absorption data have clearly demonstrated that the residence of photoexcited electrons from the sensitizer PP in the centrally located iron moiety hinders ground-state bleach recovery of the sensitizer, affecting the overall photocatalytic rate of the nanohybrid. The presence of copper(II) ions, on the other hand, offers additional stability against photobleaching and eventually enhances the efficiency of photocatalysis. In addition, we have also explored the role of UV light in the efficiency of photocatalysis and have rationalized our observations from femtosecond- to picosecond-resolved studies.

Photophysics of organometallic platinum(II) derivatives of the diketopyrrolopyrrole chromophore.

A pair of diketopyrrolopyrrole (DPP) chromophores that are end-functionalized with platinum containing "auxochromes" were subjected to electrochemical and photophysical study. The chromophores contain either platinum acetylide or ortho-metalated 2-thienylpyridinyl(platinum) end-groups (DPP-Pt(CC) and DPP-Pt(acac), respectively). The ground state redox potentials of the chromophores were determined by solution electrochemistry, and the HOMO and LUMO levels were estimated. The chromophores' photophysical properties were characterized by absorption, photoluminescence, and time-resolved absorption spectroscopy on time scales from sub-picoseconds to microseconds. Density functional theory (DFT) computations were performed to understand the molecular orbitals involved in both the singlet and triplet excited state photophysics. The results reveal that in both platinum DPP derivatives the organometallic auxochromes have a significant effect on the chromophores' photophysics. The most profound effect is a reduction in the fluorescence yields accompanied by enhanced triplet yields due to spin-orbit coupling induced by the metal centers. The effects are most pronounced in DPP-Pt(acac), indicating that the orthometalated platinum auxochrome is able to induce spin-orbital coupling to a greater extent compared to the platinum acetylide units.

Tuning Solute-Redistribution Dynamics for Scalable Fabrication of Colloidal Quantum-Dot Optoelectronics.

Solution-processed colloidal quantum dots (CQDs) are attractive materials for the realization of low-cost and efficient optoelectronic devices. Although impressive CQD-solar-cell performance has been achieved, the fabrication of CQD films is still limited to laboratory-scale small areas because of the complicated deposition of CQD inks. Large-area, uniform deposition of lead sulfide (PbS) CQD inks is successfully realized for photovoltaic device applications by engineering the solute redistribution of CQD droplets. It is shown experimentally and theoretically that the solute-redistribution dynamics of CQD droplets are highly dependent on the movement of the contact line and on the evaporation kinetics of the solvent. By lowering the friction constant of the contact line and increasing the evaporation rate of the droplets, a uniform deposition of CQD ink in length and width over large areas is realized. By utilizing a spray-coating process, large-area (up to 100 cm2 ) CQD films are fabricated with 3-7% thickness variation on various substrates including glass, indium tin oxide glass, and polyethylene terephthalate. Furthermore, scalable fabrication of CQD solar cells is demonstrated with 100 cm2 CQD films which exhibits a notably high efficiency of 8.10%.

Ultralong Radiative States in Hybrid Perovskite Crystals: Compositions for Submillimeter Diffusion Lengths.

Organic-inorganic hybrid perovskite materials have recently evolved into the leading candidate solution-processed semiconductor for solar cells due to their combination of desirable optical and charge transport properties. Chief among these properties is the long carrier diffusion length, which is essential to optimizing the device architecture and performance. Herein, we used time-resolved photoluminescence (at low excitation fluence, 10.59 µJ·cm-2 upon two-photon excitation), which is the most accurate and direct approach to measure the radiative charge carrier lifetime and diffusion lengths. Lifetimes of about 72 and 4.3 µs for FAPbBr3 and FAPbI3 perovskite single crystals have been recorded, presenting the longest radiative carrier lifetimes reported to date for perovskite materials. Subsequently, carrier diffusion lengths of 107.2 and 19.7 µm are obtained. In addition, we demonstrate the key role of the organic cation units in modulating the carrier lifetime and its diffusion lengths, in which the defect formation energies for FA cations are much higher than those with the MA ones.

Temperature-Induced Lattice Relaxation of Perovskite Crystal Enhances Optoelectronic Properties and Solar Cell Performance.

Hybrid organic-inorganic perovskite crystals have recently become one of the most important classes of photoactive materials in the solar cell and optoelectronic communities. Albeit improvements have focused on state-of-the-art technology including various fabrication methods, device architectures, and surface passivation, progress is yet to be made in understanding the actual operational temperature on the electronic properties and the device performances. Therefore, the substantial effect of temperature on the optoelectronic properties, charge separation, charge recombination dynamics, and photoconversion efficiency are explored. The results clearly demonstrated a significant enhancement in the carrier mobility, photocurrent, charge carrier lifetime, and solar cell performance in the 60 ± 5 °C temperature range. In this temperature range, perovskite crystal exhibits a highly symmetrical relaxed cubic structure with well-aligned domains that are perpendicular to a principal axis, thereby remarkably improving the device operation. This finding provides a new key variable component and paves the way toward using perovskite crystals in highly efficient photovoltaic cells.

Amorphous Tin Oxide as a Low-Temperature-Processed Electron-Transport Layer for Organic and Hybrid Perovskite Solar Cells.

Chemical bath deposition (CBD) of tin oxide (SnO2) thin films as an electron-transport layer (ETL) in a planar-heterojunction n-i-p organohalide lead perovskite and organic bulk-heterojunction (BHJ) solar cells is reported. The amorphous SnO2 (a-SnO2) films are grown from a nontoxic aqueous bath of tin chloride at a very low temperature (55 °C) and do not require postannealing treatment to work very effectively as an ETL in a planar-heterojunction n-i-p organohalide lead perovskite or organic BHJ solar cells, in lieu of the commonly used ETL materials titanium oxide (TiO2) and zinc oxide (ZnO), respectively. Ultraviolet photoelectron spectroscopy measurements on the glass/indium-tin oxide (ITO)/SnO2/methylammonium lead iodide (MAPbI3)/2,2',7,7'-tetrakis(N,N-di-p-methoxyphenylamine)-9,9'-spirobifluorene device stack indicate that extraction of photogenerated electrons is facilitated by a perfect alignment of the conduction bands at the SnO2/MAPbI3 interface, while the deep valence band of SnO2 ensures strong hole-blocking properties. Despite exhibiting very low electron mobility, the excellent interfacial energetics combined with high transparency (Egap,optical > 4 eV) and uniform substrate coverage make the a-SnO2 ETL prepared by CBD an excellent candidate for the potentially low-cost and large-scale fabrication of organohalide lead perovskite and organic photovoltaics.

Zero-Dimensional Cs4PbBr6 Perovskite Nanocrystals.

Perovskite nanocrystals (NCs) have become leading candidates for solution-processed optoelectronics applications. While substantial work has been published on 3-D perovskite phases, the NC form of the zero-dimensional (0-D) phase of this promising class of materials remains elusive. Here we report the synthesis of a new class of colloidal semiconductor NCs based on Cs4PbBr6, the 0-D perovskite, enabled through the design of a novel low-temperature reverse microemulsion method with 85% reaction yield. These 0-D perovskite NCs exhibit high photoluminescence quantum yield (PLQY) in the colloidal form (PLQY: 65%), and, more importantly, in the form of thin film (PLQY: 54%). Notably, the latter is among the highest values reported so far for perovskite NCs in the solid form. Our work brings the 0-D phase of perovskite into the realm of colloidal NCs with appealingly high PLQY in the film form, which paves the way for their practical application in real devices.

Ultrahigh Carrier Mobility Achieved in Photoresponsive Hybrid Perovskite Films via Coupling with Single-Walled Carbon Nanotubes.

Organolead trihalide perovskites have drawn substantial interest for photovoltaic and optoelectronic applications due to their remarkable physical properties and low processing cost. However, perovskite thin films suffer from low carrier mobility as a result of their structural imperfections such as grain boundaries and pinholes, limiting their device performance and application potential. Here we demonstrate a simple and straightforward synthetic strategy based on coupling perovskite films with embedded single-walled carbon nanotubes. We are able to significantly enhance the hole and electron mobilities of the perovskite film to record-high values of 595.3 and 108.7 cm2 V-1 s-1 , respectively. Such a synergistic effect can be harnessed to construct ambipolar phototransistors with an ultrahigh detectivity of 3.7 × 1014 Jones and a responsivity of 1 × 104 A W-1 , on a par with the best devices available to date. The perovskite/carbon nanotube hybrids should provide a platform that is highly desirable for fields as diverse as optoelectronics, solar energy conversion, and molecular sensing.