CO2 doping of organic interlayers for perovskite solar cells.

In perovskite solar cells, doped organic semiconductors are often used as charge-extraction interlayers situated between the photoactive layer and the electrodes. The π-conjugated small molecule 2,2',7,7'-tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9-spirobifluorene (spiro-OMeTAD) is the most frequently used semiconductor in the hole-conducting layer1-6, and its electrical properties considerably affect the charge collection efficiencies of the solar cell7. To enhance the electrical conductivity of spiro-OMeTAD, lithium bis(trifluoromethane)sulfonimide (LiTFSI) is typically used in a doping process, which is conventionally initiated by exposing spiro-OMeTAD:LiTFSI blend films to air and light for several hours. This process, in which oxygen acts as the p-type dopant8-11, is time-intensive and largely depends on ambient conditions, and thus hinders the commercialization of perovskite solar cells. Here we report a fast and reproducible doping method that involves bubbling a spiro-OMeTAD:LiTFSI solution with CO2 under ultraviolet light. CO2 obtains electrons from photoexcited spiro-OMeTAD, rapidly promoting its p-type doping and resulting in the precipitation of carbonates. The CO2-treated interlayer exhibits approximately 100 times higher conductivity than a pristine film while realizing stable, high-efficiency perovskite solar cells without any post-treatments. We also show that this method can be used to dope π-conjugated polymers.

A Promising Carbon/g-C3 N4 Composite Negative Electrode for a Long-Life Sodium-Ion Battery.

2D graphitic carbon nitride (g-C3 N4 ) nanosheets are a promising negative electrode candidate for sodium-ion batteries (NIBs) owing to its easy scalability, low cost, chemical stability, and potentially high rate capability. However, intrinsic g-C3 N4 exhibits poor electronic conductivity, low reversible Na-storage capacity, and insufficient cyclability. DFT calculations suggest that this could be due to a large Na+ ion diffusion barrier in the innate g-C3 N4 nanosheet. A facile one-pot heating of a mixture of low-cost urea and asphalt is strategically applied to yield stacked multilayer C/g-C3 N4 composites with improved Na-storage capacity (about 2 times higher than that of g-C3 N4 , up to 254 mAh g-1 ), rate capability, and cyclability. A C/g-C3 N4 sodium-ion full cell (in which sodium rhodizonate dibasic is used as the positive electrode) demonstrates high Coulombic efficiency (ca. 99.8 %) and a negligible capacity fading over 14 000 cycles at 1 A g-1 .

Stable Graphene-Two-Dimensional Multiphase Perovskite Heterostructure Phototransistors with High Gain.

Recently, two-dimensional (2D) organic-inorganic perovskites emerged as an alternative material for their three-dimensional (3D) counterparts in photovoltaic applications with improved moisture resistance. Here, we report a stable, high-gain phototransistor consisting of a monolayer graphene on hexagonal boron nitride (hBN) covered by a 2D multiphase perovskite heterostructure, which was realized using a newly developed two-step ligand exchange method. In this phototransistor, the multiple phases with varying bandgap in 2D perovskite thin films are aligned for the efficient electron-hole pair separation, leading to a high responsivity of ∼105 A W-1 at 532 nm. Moreover, the designed phase alignment method aggregates more hydrophobic butylammonium cations close to the upper surface of the 2D perovskite thin film, preventing the permeation of moisture and enhancing the device stability dramatically. In addition, faster photoresponse and smaller 1/f noise observed in the 2D perovskite phototransistors indicate a smaller density of deep hole traps in the 2D perovskite thin film compared with their 3D counterparts. These desirable properties not only improve the performance of the phototransistor, but also provide a new direction for the future enhancement of the efficiency of 2D perovskite photovoltaics.

Chemically Engineered Titanium Oxide Interconnecting Layer for Multijunction Polymer Solar Cells.

We report chemically tunable n-type titanium oxides using ethanolamine as a nitrogen dopant source. As the amount of ethanolamine added to the titanium oxide precursor during synthesis increases, the Fermi level of the resulting titanium oxides (ethanolamine-incorporated titanium oxides) significantly changes from -4.9 eV to -4.3 eV, and their free charge carrier densities are enhanced by two orders of magnitudes, reaching up to 5 × 1018 cm-3. Unexpectedly, a basic ethanolamine reinforces not only the n-type properties of titanium oxides, but also their basicity, which facilitates acid-base ionic junctions in contact with acidic materials. The enhanced charge carrier density and basicity of the chemically tuned titanium oxides enable multi-junction solar cells to have interconnecting junctions consisting of basic n-type titanium oxides and acidic p-type PEDOT:PSS to gain high open-circuit voltages of 1.44 V and 2.25 V from tandem and triple architectures, respectively.

Building mechanism for a high open-circuit voltage in an all-solution-processed tandem polymer solar cell.

Additional post-processing techniques, such as post-thermal annealing and UV illumination, were found to be required to obtain desirable values of the cell parameters in a tandem polymer solar cell incorporated with solution-processed basic n-type titanium sub-oxide (TiO(x))/acidic p-type poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) interlayers. Subsequent to the fabrication of the tandem polymer solar cells, the open-circuit voltage (V(OC)) of the cells exhibited half of the expected value. Only after the application of the post-treatments, the V(OC) of a tandem cell increased from the initial half-cell value (∼0.6 V) to its full-cell value (∼1.2 V). The selective light-biased incident photon-to-current efficiency (IPCE) measurements indicated that the initial V(OC) originated from the back subcell and that the application of the post-processing treatments revived the front subcell, such that the net photocurrent of the tandem cell was finally governed by a recombination process of holes from the back subcell and electrons from the front subcell. Based on our experimental results, we suggest that a V(OC) enhancement could be ascribed to two types of subsequent junction formations at the interface between the TiO(x) and PEDOT:PSS interlayers: an 'ion-mediated dipole junction', resulting from the electro-kinetic migration of cationic ions in the interlayers during post-thermal annealing in the presence of a low-work-function metal cathode, and a 'photoinduced Schottky junction', formed by increasing the charge carrier density in the n-type TiO(x) interlayer during UV illumination process. The two junctions separately contributed to the formation of a recombination junction through which the electrons in TiO(x) and the holes in PEDOT:PSS were able to recombine without substantial voltage drops.

Hydrothermally Grown Dual-Phase Heterogeneous Electrocatalysts for Highly Efficient Rechargeable Metal-Air Batteries with Long-Term Stability.

Metal-air batteries as alternatives to the existing lithium-ion battery are becoming increasingly attractive sources of power due to their high energy-cost competitiveness and inherent safety; however, their low oxygen evolution and reduction reaction (OER/ORR) performance and poor operational stability must be overcome prior to commercialization. Herein, it is demonstrated that a novel class of hydrothermally grown dual-phase heterogeneous electrocatalysts, in which silver-manganese (AgMn) heterometal nanoparticles are anchored on top of 2D nanosheet-like nickel vanadium oxide (NiV2 O6 ), allows an enlarged surface area and efficient charge transfer/redistribution, resulting in a bifunctional OER/ORR superior to those of conventional Pt/C or RuO2 . The dual-phase NiV2 O6 /AgMn catalysts on the air cathode of a zinc-air battery lead to a stable discharge-charge voltage gap of 0.83 V at 50 mA cm-2 , with a specific capacity of 660 mAh g-1 and life cycle stabilities of more than 146 h at 10 mA cm-2 and 11 h at 50 mA cm-2 . The proposed new class of dual-phase NiV2 O6 /AgMn catalysts are successfully applied as pouch-type zinc-air batteries with long-term stability over 33.9 h at 10 mA cm-2 .

Identifying optimal photovoltaic technologies for underwater applications.

Improving solar energy collection in aquatic environments would allow for superior environmental monitoring and remote sensing, but the identification of optimal photovoltaic technologies for such applications is challenging as evaluation requires either field deployment or access to large water tanks. Here, we present a simple bench-top characterization technique that does not require direct access to water and therefore circumvents the need for field testing during initial trials of development. Employing LEDs to simulate underwater solar spectra at various depths, we compare Si and CdTe solar cells, two commercially available technologies, with GaInP cells, a technology with a wide bandgap close to ideal for underwater solar harvesting. We use this method to show that while Si cells outperform both CdTe and GaInP cells under terrestrial AM1.5G solar irradiance, CdTe and GaInP cells outperform Si cells at depths >2 m, with GaInP cells operating with underwater efficiencies approaching 54%.

Analog memory and spike-timing-dependent plasticity characteristics of a nanoscale titanium oxide bilayer resistive switching device.

We demonstrated analog memory, synaptic plasticity, and a spike-timing-dependent plasticity (STDP) function with a nanoscale titanium oxide bilayer resistive switching device with a simple fabrication process and good yield uniformity. We confirmed the multilevel conductance and analog memory characteristics as well as the uniformity and separated states for the accuracy of conductance change. Finally, STDP and a biological triple model were analyzed to demonstrate the potential of titanium oxide bilayer resistive switching device as synapses in neuromorphic devices. By developing a simple resistive switching device that can emulate a synaptic function, the unique characteristics of synapses in the brain, e.g. combined memory and computing in one synapse and adaptation to the outside environment, were successfully demonstrated in a solid state device.

Mechanically strong and electrically conductive multilayer MXene nanocomposites.

Polymer nanocomposites offer the opportunity to bridge properties of nanomaterials to the macroscale. In this work, layer-by-layer (LbL) assembly is used to demonstrate nanocomposites of 2D titanium carbide nanosheets (MXene) and clay nanoplatelets (montmorillonite) to fabricate freestanding thin films with unique multifunctional properties. These thin films can be tuned by adjusting the thickness to exhibit a tensile strength of 138 MPa-225 MPa, EMI specific shielding effectiveness normalized to thickness and density up to 24 550 dB cm2 g-1, and sheet resistance from 855 Ω sq-1-3.27 kΩ sq-1 (corresponding to a range of conductivity from 53 S m-1 to 125 S m-1). This composite is the strongest MXene-based LbL film prepared to date, in part due to the nacre-like brick-and-mortar structure. Ultra-strong, multifunctional films of this nature are desirable for many applications ranging from membranes, to structural and multifunctional composites, energy harvesting and storage, and materials for aerospace.

Potential Dip in Organic Photovoltaics Probed by Cross-sectional Kelvin Probe Force Microscopy.

Cross-sectional potential distribution of high open-circuit voltage bulk heterojunction photovoltaic device was measured using Kelvin probe force microscopy. Potential drop confined at cathode interface implies that photo-active layer is an effective p-type semiconductor. Potential values in field-free region show wide variation according to log-normal distribution. This potential dip prone to have holes captured during the diffusive motion, which can increase bimolecular recombination, while potential gradient in depletion region makes this potential dip smaller and the captured holes easily escape from dip region by Schottky barrier lowering.

Three-Phase Morphology Evolution in Sequentially Solution-Processed Polymer Photodetector: Toward Low Dark Current and High Photodetectivity.

Sequentially solution-processed polymer photodetectors (SSP PPDs) based on poly(3-hexylthiophene-2,5-diyl) (P3HT)/[6,6]-phenyl C71-butyric acid methyl ester (PC71BM) are fabricated by depositing the top layers of PC71BM from an appropriate cosolvent of 2-chlorophenol (2-CP)/o-dichlorobenzene (ODCB) onto the predeposited bottom layers of P3HT. By adjusting the ratio of 2-CP/ODCB in the top PC71BM layers, the resulting SSP PPD shows a decreased dark current and an increased photocurrent, leading to a maximum detectivity of 1.23 × 1012 Jones at a wavelength of 550 nm. This value is 5.3-fold higher than that of the conventional bulk heterojunction PPD. Morphology studies reveal that the PC71BM partially penetrates the predeposited P3HT layer during the spin-coating process, resulting in an optimal three-phase morphology with one well-mixed interdiffusion P3HT/PC71BM phase in the middle of the bulk and two pure phases of P3HT and PC71BM at the two electrode sides. We show that the pure phases form high Schottky barriers (>2.0 eV) at the active layer/electrodes interface and efficiently block unfavorable reverse charge carrier injection by significantly decreasing the dark current. The interdiffussion phase enlarges the donor-acceptor interfacial area leading to a large photocurrent. We also reveal that the improved performance of SSP PPDs is also due to the enhanced optical absorption, improved P3HT crystallinity, increased charge carrier mobilities, and suppressed bimolecular recombination.

Spray coating of the PCBM electron transport layer significantly improves the efficiency of p-i-n planar perovskite solar cells.

The p-i-n structure for perovskite solar cells has recently shown significant advantages in minimal hysteresis effects, and scalable manufacturing potential using low-temperature solution processing. However, the power conversion efficiency (PCE) of the perovskite p-i-n structure remains low mainly due to limitations using a flat electron transport layer (ETL). In this work, we demonstrate a new approach using spray coating to fabricate the [6,6]-phenyl-C(61)-butyric acid methyl ester (PCBM) ETL. By creating a rough surface, we effectively improve the light trapping properties inside the PCBM ETL. We reveal that the spray coated PCBM can form a cross-linked network, which may facilitate better charge transport and enhance extraction efficiency. By improving the contact between the perovskite film and the PCBM ETL, a reduction in the trap states is observed resulting in a PCE increase from 13% to >17%.

PEOz-PEDOT:PSS Composite Layer: A Route to Suppressed Hysteresis and Enhanced Open-Circuit Voltage in a Planar Perovskite Solar Cell.

The successful commercialization of perovskite solar cells (Pvs-SCs) calls for the need to find low-temperature processable interlayers with outstanding charge-transport features. In this work, we strategically blend poly(2-ethyl-2-oxazoline) (PEOz) with PEDOT:PSS as the modified hole transport layer (HTL) to achieve high-efficiency P-I-N CH3NH3PbI3 Pvs-SCs. The PEOz-PEDOT:PSS HTL exhibits enhanced features over the conventional layer including the following: (1) promoting perovskite with enlarged grain sizes to decrease the perovskite layer's recombination, (2) increasing the work function of the HTL, and (3) decreasing the noncapacitive current in Pvs-SCs. Remarkably, we demonstrate a 17.39% power conversion efficiency with very low hysteresis and high Voc values of 1.075 V for Pvs-SCs with PEOz-PEDOT:PSS.

Perovskite solar cells with a DMSO-treated PEDOT:PSS hole transport layer exhibit higher photovoltaic performance and enhanced durability.

Despite being the most commonly used hole transport layer for p-i-n perovskite solar cells, the conventional PEDOT:PSS layer is far from being optimal for the best photovoltaic performance. Herein, we demonstrate highly conductive thin DMSO-doped PEDOT:PSS layers which significantly enhance the light harvesting, charge extraction, and photocurrent production of organo-lead iodide devices. Both imaging and X-ray analysis reveal that the perovskite thin films grown on DMSO-doped PEDOT:PSS exhibit larger grains with increased crystallinity. Altogether, these improvements result in a 37% boost in the power conversion efficiency (PCE) compared to standard p-i-n photovoltaics with pristine PEDOT:PSS. Furthermore, we demonstrate that DMSO-doped PEDOT:PSS devices possess enhanced PCE durability over time which we attribute primarily to fill factor stability.

High-Performance Integrated Perovskite and Organic Solar Cells with Enhanced Fill Factors and Near-Infrared Harvesting.

Highly efficient P-I-N type perovskite/bulk-heterojunction (BHJ) integrated solar cells (ISCs) with enhanced fill factor (FF) (≈80%) and high near-infrared harvesting (>30%) are demonstrated by optimizing the BHJ morphology with a novel n-type polymer, N2200, and a new solvent-processing additive. This work proves the feasibility of highly efficient ISCs with panchromatic absorption as a new photovoltaic architecture and provides important design rules for optimizing ISCs.

Simplified tandem polymer solar cells with an ideal self-organized recombination layer.

A new tandem architecture for printable photovoltaics using a versatile organic nanocomposite containing photoactive and interfacial materials is demonstrated. The nanocomposite forms an ideal self-organized recombination layer via a spontaneous vertical phase separation, which yields a simplified tandem structure fabricated with only four component layers and a high tandem efficiency of 10.8%.

Top-down approach for nanophase reconstruction in bulk heterojunction solar cells.

"Top-Down" nanophase reconstruction via a post-additive soaking process is first presented with various BHJ binary composites. By simply rinsing as-cast BHJ films with a solvent mixture containing a few traces of a nanophase-control reagent such as 1,8-diiodooctane, oversized fullerene-rich clusters (>100 nm in dia-meter) in the BHJ film are instataneously disassembled and entirely reorganized into finely intermixed donor/acceptor nanophases (ca. 10 nm) with a 3D compositional homogeneity, without surface segregation.

Long-term stable polymer solar cells with significantly reduced burn-in loss.

The inferior long-term stability of polymer-based solar cells needs to be overcome for their commercialization to be viable. In particular, an abrupt decrease in performance during initial device operation, the so-called 'burn-in' loss, has been a major contributor to the short lifetime of polymer solar cells, fundamentally impeding polymer-based photovoltaic technology. In this study, we demonstrate polymer solar cells with significantly improved lifetime, in which an initial burn-in loss is substantially reduced. By isolating trap-embedded components from pristine photoactive polymers based on the unimodality of molecular weight distributions, we are able to selectively extract a trap-free, high-molecular-weight component. The resulting polymer component exhibits enhanced power conversion efficiency and long-term stability without abrupt initial burn-in degradation. Our discovery suggests a promising possibility for commercial viability of polymer-based photovoltaics towards real solar cell applications.