Room-temperature multiple ligands-tailored SnO2 quantum dots endow in situ dual-interface binding for upscaling efficient perovskite photovoltaics with high VOC.

The benchmark tin oxide (SnO2) electron transporting layers (ETLs) have enabled remarkable progress in planar perovskite solar cell (PSCs). However, the energy loss is still a challenge due to the lack of "hidden interface" control. We report a novel ligand-tailored ultrafine SnO2 quantum dots (QDs) via a facile rapid room temperature synthesis. Importantly, the ligand-tailored SnO2 QDs ETL with multi-functional terminal groups in situ refines the buried interfaces with both the perovskite and transparent electrode via enhanced interface binding and perovskite passivation. These novel ETLs induce synergistic effects of physical and chemical interfacial modulation and preferred perovskite crystallization-directing, delivering reduced interface defects, suppressed non-radiative recombination and elongated charge carrier lifetime. Power conversion efficiency (PCE) of 23.02% (0.04 cm2) and 21.6% (0.98 cm2, VOC loss: 0.336 V) have been achieved for the blade-coated PSCs (1.54 eV Eg) with our new ETLs, representing a record for SnO2 based blade-coated PSCs. Moreover, a substantially enhanced PCE (VOC) from 20.4% (1.15 V) to 22.8% (1.24 V, 90 mV higher VOC, 0.04 cm2 device) in the blade-coated 1.61 eV PSCs system, via replacing the benchmark commercial colloidal SnO2 with our new ETLs.

Charge Energetics and Electronic Level Changes At the Copper(II) Phthalocyanine/Fullerene Junction Upon Photoexcitation.

Energy offset at the donor (D)/acceptor (A) interface plays an important role in charge separation in organic photovoltaics. Its magnitude determines the charge separation process under illumination. Extensive studies have been carried out for elucidating the charge transfer (CT) process at different D/A junctions. These works lead to two different views: upon photoexcitation, energies would be (1) consumed in molecular polarization and orientation such that those opposite charges would overcome mutual Coulombic attractive potential at the interface and (2) spent on promoting charges to high-lying delocalized energy states (i.e., hot states), which is necessarily important prior to charge separation. Under these two scheme of studies, the electronic structures and the charge behaviors at the D/A interface should be different under photoexcitation, yet there is so far no direct experimental approach for probing the changes in electronics structures (i.e., Fermi level, vacuum level, frontier molecular orbitals, etc.) upon photoexcitation. Herein, a modified photoelectron spectroscopy (PES) system with an additional solar simulator is used to study the charge distributions and electronic interactions for a standard D/A heterojunction (i.e., copper phthalocyanine (CuPc)/ fullerene (C60)) under photoexcitation. CT states formed as a result of photon energy transfer at the CuPc/C60 junction. Subsequent superpositions of charge transfer and electron polarization effects increase the D/A energy level offsets from 0.75 (ground state measured in the dark) to 1.07 eV (high-lying state measured upon illumination). We showed that there is excess energy consumed for a subtle change in the energy level alignment of the CuPc/C60 junction under illumination, suggesting a new insight for the energy loss mechanism during the photocharge generation processes.

Organic-Inorganic Charge Transfer Complex with Charge Modulation after Electrical Pre-biasing.

Several breakthroughs in organic optoelectronic devices with new applications and performance improvement have been made recently by exploiting novel properties of charge transfer complexes (CTCs). In this work, a CTC film formed by coevaporating molybdenum(VI) oxide and pentacene (MoO3:pentacene) shows a strong dipole of 2.4 eV with direction controllability via pre-biasing with an external voltage. While CTCs are most widely known for their much red-shifted energy gaps, there is so far no report on their controllable dipoles. By controlling this dipole with an electrical pre-bias in a MoO3:pentacene CTC based device, current changes over 2 orders of magnitude can be achieved. Kelvin probe force microscopy further confirms that surface potential of the MoO3:pentacene film can be modulated by an external electric field. It is shown for the first time that a dipole of controllable direction can be set up inside a CTC layer by pre-biasing. This concept is further tested by incorporating the CTC layer in organic photovoltaic (OPV) devices. It was demonstrated that by pre-biasing the OPV devices in different directions, their open circuit voltages (Voc) can be significantly tuned via the built-in potentials.

Effects of Hydrogen Bonds between Polymeric Hole-Transporting Material and Organic Cation Spacer on Morphology of Quasi-Two-Dimensional Perovskite Grains and Their Performance in Light-Emitting Diodes.

Perovskite is emerging as a novel emitter in solution-processed light-emitting diodes (LEDs). In these LEDs, morphology, especially the grain size of perovskite, plays a key role in determining electroluminescence performance. Several studies have shown that sizes of the perovskite grains can be controlled by the contact angle between the perovskite solution and the substrate. In this work, we found that in the quasi-two-dimensional (2D) system, the perovskite grain size can be substantially refined when there are hydrogen bonding between the perovskite's organic spacer and the substrates. In fact, for quasi-2D perovskite, with the presence of such hydrogen bond, its effects on the perovskite grain size overshadow the contact angle's effect. We demonstrated that perovskite with refined grains can form amine- or carbazole-based polymers which can form N···H hydrogen bonding with the perovskite's organic spacer. Using these polymers as hole-transporting layers on poly(3,4-ethylenedioxythiophene):polystyrene sulfonate, external quantum efficiency of CsPbBr3-based LEDs can be enhanced from 1.5 to 10.0% without passivation treatment. This work suggests that bonding between perovskite precursors and the substrate can have significant influence on the morphology of the final perovskite grains and their optoelectronic performance.

A Lead Iodide Perovskite Based on a Large Organic Cation for Solar Cell Applications.

Methylammonium (CH3 NH3+ ) and formamidinium ((NH2 )2 CH+ ) based lead iodide perovskites are currently the two commonly used organic-inorganic lead iodide perovskites. There are still no alternative organic cations that can produce perovskites with band gaps spanning the visible spectrum (that is, <1.7 eV) for solar cell applications. Now, a new perovskite using large propane-1,3-diammonium cation (1,3-Pr(NH3 )22+ ) with a chemical structure of (1,3-Pr(NH3 )2 )0.5 PbI3 is demonstrated. X-ray diffraction (XRD) shows that the new perovskite exhibits a three-dimensional tetragonal phase. The band gap of the new perovskite is about 1.6 eV, which is desirable for photovoltaic applications. A (1,3-Pr(NH3 )2 )0.5 PbI3 perovskite solar cell (PSC) yields a power conversion efficiency (PCE) of 5.1 %. More importantly, this perovskite is composed of a large hydrophobic cation that provides better moisture resistance compared to CH3 NH3 PbI3 perovskite.

Stabilization of organometallic halide perovskite nanocrystals in aqueous solutions and their applications in copper ion detection.

Stabilization of two-dimensional (2D) PEA2PbI4 (PEA is phenethylammonium) perovskite nanocrystals (PNCs) in water is achieved. By inhibiting the desorption process, the PNCs show exceptional stability for more than 2 months in PEA+ aqueous solutions. Stabilized PNCs are successfully applied for probing Cu2+ in aqueous solution.

2D Perovskites with Short Interlayer Distance for High-Performance Solar Cell Application.

2D perovskites have emerged as one of the most promising photovoltaic materials owing to their excellent stability compared with their 3D counterparts. However, in typical 2D perovskites, the highly conductive inorganic layers are isolated by large organic cations leading to quantum confinement and thus inferior electrical conductivity across layers. To address this issue, the large organic cations are replaced with small propane-1,3-diammonium (PDA) cations to reduce distance between the inorganic perovskite layers. As shown by optical characterizations, quantum confinement is no longer dominating in the PDA-based 2D perovskites. This leads to considerable enhancement of charge transport as confirmed with electrochemical impedance spectroscopy, time-resolved photoluminescence, and mobility measurements. The improved electric properties of the interlayer-engineered 2D perovskites yield a power conversion efficiency of 13.0%. Furthermore, environmental stabilities of the PDA-based 2D perovskites are improved. PDA-based 2D perovskite solar cells (PSCs) with encapsulation can retain over 90% of their efficiency upon storage for over 1000 h, and PSCs without encapsulation can maintain their initial efficiency at 70 °C for over 100 h, which exhibit promising stabilities. These results reveal excellent optoelectronic properties and intrinsic stabilities of the layered perovskites with reduced interlayer distance.

Evidence on Enhanced Exciton Polarizability in Donor/Acceptor Bulk Heterojunction Organic Photovoltaics.

Using electroabsorption spectroscopy, we explore the polarizability of Frenkel excitons in both pristine donor and D/A blend films. We observe for the first time that the polarizability of excitonic states in pristine donors can be dramatically increased by adding an n-type acceptor. By investigating the dielectric effect in different organic semiconductor systems, we find that the polarizability of Frenkel excitons has direct correlation with the measured dielectric constant of the bulk heterojunction thin films. Our results disclose the difference in the nature of Frenkel excitons in pristine donor and D/A blend systems, revealing an important role of excitonic states in charge separation process of organic photovoltaic devices.

Heat Treatment for Regenerating Degraded Low-Dimensional Perovskite Solar Cells.

Organolead halide perovskite devices are reported to be susceptible to thermal degradation, which results from heat-induced fast ion diffusion and structural decomposition. In this work, it is found that the performances of degraded low-dimensional perovskite solar cells can be considerably improved (e.g., power conversion efficiency shows ∼10% increase over the fresh device) by a short-time heat treatment (85 °C, 3 min). Capacitance-frequency, X-ray diffraction, and ionic diffusion calculation results suggest that heat treatment can enhance the crystallinity of the degraded low-dimensional perovskite and minimize the detrimental effects caused by water molecules, leading to improved performances. Our results indicate that the heat treatment does not necessarily lead to the accelerated degradation but can also regenerate the degraded low-dimensional perovskite.

Effects of Small Polar Molecules (MA+ and H2O) on Degradation Processes of Perovskite Solar Cells.

Degradation mechanisms of methylammonium lead halide perovskite solar cells (PSCs) have drawn much attention recently. Herein, the bulk and surface degradation processes of the perovskite were differentiated for the first time by employing combinational studies using electrochemical impedance spectroscopy (EIS), capacitance frequency (CF), and X-ray diffraction (XRD) studies with particular attention on the roles of small polar molecules (MA+ and H2O). CF study shows that short-circuit current density of the PSCs is increased by H2O at the beginning of the degradation process coupled with an increased surface capacitance. On the basis of EIS and XRD analysis, we show that the bulk degradation of PSCs involves a lattice expansion process, which facilitates MA+ ion diffusion by creating more efficient channels. These results provide a better understanding of the roles of small polar molecules on degradation processes in the bulk and on the surface of the perovskite film.

Direct Free Carrier Photogeneration in Single Layer and Stacked Organic Photovoltaic Devices.

High performance organic photovoltaic devices typically rely on type-II P/N junctions for assisting exciton dissociation. Heremans and co-workers recently reported a high efficiency device with a third organic layer which is spatially separated from the active P/N junction; but still contributes to the carrier generation by passing its energy to the P/N junction via a long-range exciton energy transfer mechanism. In this study the authors show that there is an additional mechanism contributing to the high efficiency. Some bipolar materials (e.g., subnaphthalocyanine chloride (SubNc) and subphthalocyanine chloride (SubPc)) are observed to generate free carriers much more effectively than typical organic semiconductors upon photoexcitation. Single-layer devices with SubNc or SubPc sandwiched between two electrodes can give power conversion efficiencies 30 times higher than those of reported single-layer devices. In addition, internal quantum efficiencies (IQEs) of bilayer devices with opposite stacking sequences (i.e., SubNc/SubPc vs SubPc/SubNc) are found to be the sum of IQEs of single layer devices. These results confirm that SubNc and SubPc can directly generate free carriers upon photoexcitation without assistance from a P/N junction. These allow them to be stacked onto each other with reversible sequence or simply stacking onto another P/N junction and contribute to the photocarrier generation.

Evidence of Delocalization in Charge-Transfer State Manifold for Donor:Acceptor Organic Photovoltaics.

How charge-transfer states (CTSs) assist charge separation of a Coulombically bound exciton in organic photovoltaics has been a hot topic. It is believed that the delocalization feature of a CTS plays a crucial role in the charge separation process. However, the delocalization of the "hot" and the "relaxed" CTSs is still under debate. Here, with a novel frequency dependent charge-modulated electroabsorption spectroscopy (CMEAS) technique, we elucidate clearly that both "hot" and "relaxed" CTSs are loosely bound and delocalized states. This is confirmed by comparing the CMEAS results of CTSs with those of localized polaron states. Our results reveal the role of CTS delocalization on charge separation and indicate that no substantial delocalization gradient exists in CTSs.

Chlorine Incorporation for Enhanced Performance of Planar Perovskite Solar Cell Based on Lead Acetate Precursor.

We show the effects of chlorine incorporation in the crystallization process of perovskite film based on a lead acetate precursor. We demonstrate a fabrication process for fast grain growth with highly preferred {110} orientation upon only 5 min of annealing at 100 °C. By studying the correlation between precursor composition and morphology, the growth dynamic of perovskite film in the current system is discussed. In particular, we found that both lead acetate precursor and Cl incorporation are beneficial to perovskite growth. While lead acetate allows fast crystallization process, Cl improves perovskite crystallinity. Planar perovskite solar cells with optimized parameters deliver a best power conversion efficiency of 15.0% and average efficiency of 14.0% with remarkable reproducibility and good stability.

Ionic Charge Transfer Complex Induced Visible Light Harvesting and Photocharge Generation in Perovskite.

Organometal trihalide perovskite has recently emerged as a new class of promising material for high efficiency solar cells applications. While excess ions in perovskites are recently getting a great deal of attention, there is so far no clear understanding on both their formation and relating ions interaction to the photocharge generation in perovskite. Herein, we showed that tremendous ions indeed form during the initial stage of perovskite formation when the organic methylammonium halide (MAXa, Xa=Br and I) meets the inorganic PbXb2 (Xb=Cl, Br, I). The strong charge exchanges between the Pb2+ cations and Xa- anions result in formation of ionic charge transfer complexes (iCTC). MAXa parties induce empty valence electronic states within the forbidden bandgap of PbXb2. The strong surface dipole provide sufficient driving force for sub-bandgap electron transition with energy identical to the optical bandgap of forming perovskites. Evidences from XPS/UPS and photoluminescence studies showed that the light absorption, exciton dissociation, and photocharge generation of the perovskites are closely related to the strong ionic charge transfer interactions between Pb2+ and Xa- ions in the perovskite lattices. Our results shed light on mechanisms of light harvesting and subsequent free carrier generation in perovskites.

Surface Transfer Doping of Cubic Boron Nitride Films by MoO3 and Tetrafluoro-tetracyanoquinodimethane (F4-TCNQ).

Cubic boron nitride (cBN) has strong potential for the applications in high-temperature and high-power electronics and deep ultraviolet devices due to its outstanding combined physical and chemical properties. P-type surface transfer doping of heteroepitaxial cBN films was achieved by employing MoO3 and tetrafluoro-tetracyanoquinodimethane (F4-TCNQ) as the surface dopants. The surface conductivities of hydrogenated cBN films increased by 3-6 orders after the deposition of surface dopants. The photoemission spectroscopy (PES) measurements revealed the variation of electronic structures at the interface regions, which suggested that the electron transfer from cBN films to the surface dopants induced hole accumulation at the cBN surface and the increase of surface conductivity. Based on the PES results, the energy level diagrams at MoO3/cBN and F4-TCNQ/cBN interfaces were determined. The achievement provided a potential approach for fabricating cBN-based electronic devices, especially on micrometer and nanometer scales.

Charge-transfer complexes and their role in exciplex emission and near-infrared photovoltaics.

Charge transfer and interactions at organic heterojunctions (OHJs) are known to have critical influences on various properties of organic electronic devices. In this Research News article, a short review is given from the electronic viewpoint on how the local molecular interactions and interfacial energetics at P/N OHJs contribute to the recombination/dissociation of electron-hole pairs. Very often, the P-type materials donate electrons to the N-type materials, giving rise to charge-transfer complexes (CTCs) with a P(δ+) -N(δ-) configuration. A recently observed opposite charge-transfer direction in OHJs is also discussed (i.e., N-type material donates electrons to P-type material to form P(δ-) -N(δ+) ). Recent studies on the electronic structures of CTC-forming material pairs are also summarized. The formation of P(δ-) -N(δ+) -type CTCs and their correlations with exciplex emission are examined. Furthermore, the potential applications of CTCs in NIR photovoltaic devices are reviewed.

A multifunctional phosphine oxide-diphenylamine hybrid compound as a high performance deep-blue fluorescent emitter and green phosphorescent host.

A novel phosphine oxide-diphenylamine hybrid compound POA was designed and synthesized with the aim of developing new multifunctional blue fluorophores. POA is the first kind of compound that can be used as a high-efficiency deep-blue emitter (5.4% EQE) and a host to fabricate high-performance green phosphorescent OLEDs (18.1% EQE).

A versatile triphenylamine/fluoranthene-based derivative as a nondoped green-emitting, hole-transporting interlayer for electroluminescent devices.

A new triphenylamine-bridged fluoranthene derivative, 4-(7,10-diphenylfluoranthen-8-yl)-N-[4-(7,10-diphenylfluoranthen-8-yl)phenyl]-N-phenylaniline (BDPFPA), with a high glass transition temperature of 220 °C has been synthesized and characterized. BDPFPA is a highly fluorescent and versatile material that can be used as a nondoped green emitter and as a hole transporter. BDPFPA was used in a standard trilayer device as the emitting layer, which showed a low turn-on voltage (<3 V) and a high efficiency of 11.6 cd A(-1). The device also shows little efficiency roll-off at high brightness. For example, the efficiency can still be maintained at 11.4 cd A(-1) (5.4 lm W(-1)) at a brightness of 10,000 cd m(-2). These results are among the best reported for nondoped fluorescent green organic light-emitting diodes. A simple bilayer device, in which BDPFPA serves as a hole-transporting layer, has a maximum power efficiency of 3.3 lm W(-1) and the performance is nearly 40 % higher than that of an N,N'-bis(1-naphthyl)-N,N'- diphenyl-1,1'-biphenyl-4,4'-diamine (NPB)-based standard device.

Novel efficient blue fluorophors with small singlet-triplet splitting: hosts for highly efficient fluorescence and phosphorescence hybrid WOLEDs with simplified structure.

The exact hosts for F-P hybrid WOLEDs have been first demonstrated following a new design strategy for blue fluorophors with small singlet-triplet splitting. Two novel compounds DPMC and DAPSF exhibit efficient blue fluorescence, high triplet energies and good conductivities. These merits allow us to use new simplified device designs to achieve high efficiency, slow efficiency roll-off and stable emission color.