Multiobjective Optimization of Silver-Nanowire Deposition for Flexible Transparent Conducting Electrodes.

Optimizing the spin coating of silver nanowires to form transparent conducting electrodes (TCE) is guided by machine learning (ML). A good TCE has two competing characteristics: high transmittance and high conductance. Optimization using a scalar figure of merit, as often done in the field, cannot satisfy the independent requirements for transmittance and conductance imposed by specific applications. By performing a Pareto front analysis based on ML models, we show that the desired outcomes of transmittance ≥ 75% and sheet resistance ≤ 15 Ω/sq are challenging but can be achieved using processing parameters identified by ML analysis.

Heterojunction Transistors Printed via Instantaneous Oxidation of Liquid Metals.

Semiconducting transparent metal oxides are critical high mobility materials for flexible optoelectronic devices such as displays. We introduce the continuous liquid metal printing (CLMP) technique to enable rapid roll-to-roll compatible deposition of semiconducting two-dimensional (2D) metal oxide heterostructures. We leverage CLMP to deposit 10 cm2-scale nanosheets of InOx and GaOx in seconds at a low process temperature (T < 200 °C) in air, fabricating heterojunction thin film transistors with 100× greater Ion/Ioff, 4× steeper subthreshold slope, and a 50% increase in mobility over pure InOx channels. Detailed nanoscale characterization of the heterointerface by X-ray photoelectron spectroscopy, UV-vis, and Kelvin probe elucidates the origins of enhanced electronic transport in these 2D heterojunctions. This combination of CLMP with the electrostatic control induced by the heterostructure architecture leads to high performance (µlin up to 22.6 cm2/(V s)) while reducing the process time for metal oxide transistors by greater than 100× compared with sol-gels and vacuum deposition methods.

The effect of solvent on determining highest occupied molecular orbital energies of semiconducting organic molecules: Insight from a combined computational approach.

Although cyclic voltammetry (CV) measurements in solution have been widely used to determine the highest occupied molecular orbital energy (EHOMO ) of semiconducting organic molecules, an understanding of the experimentally observed discrepancies due to the solvent used is lacking. To explain these differences, we investigate the solvent effects on EHOMO by combining density functional theory and molecular dynamics calculations for four donor molecules with a common backbone moiety. We compare the experimental EHOMO values to the calculated values obtained from either implicit or first solvation shell theories. We find that the first solvation shell method can capture the EHOMO variation arising from the functional groups in solution, unlike the implicit method. We further applied the first solvation shell method to other semiconducting organic molecules measured in solutions for different solvents. We find that the EHOMO obtained using an implicit method is insensitive to solvent choice. The first solvation shell, however, produces EHOMO values that are sensitive to solvent choices and agrees with published experimental results. The solvent sensitivity arises from a hierarchy of three effects: (1) the solute electronic state within a surrounding dielectric continuum, (2) ambient temperature or solvent atoms changing the solute geometry, and (3) electronic interactions between the solute and solvents. The implicit method, on the other hand, only captures the effect of a dielectric environment. Our findings suggest that EHOMO obtained by CV measurements should account for the influence of solvent when the results are reported, interpreted, or compared to other molecules.

Stable and Bright Electroluminescent Devices utilizing Emissive 0D Perovskite Nanocrystals Incorporated in a 3D CsPbBr3 Matrix.

The 0D cesium lead halide perovskite Cs4 PbBr6 has drawn remarkable interest due to its highly efficient robust green emission compared to its 3D CsPbBr3 counterpart. However, seizing the advantages of the superior photoluminescence properties for practical light-emitting devices remains elusive. To date, Cs4 PbBr6 has been employed only as a higher-bandgap nonluminescent matrix to passivate or provide quantum/dielectric confinement to CsPbBr3 in light-emitting devices and to enhance its photo-/thermal/environmental stability. To resolve this disparity, a novel solvent engineering method to incorporate highly luminescent 0D Cs4 PbBr6 nanocrystals (perovskite nanocrystals (PNCs)) into a 3D CsPbBr3 film, forming the active emissive layer in single-layer perovskite light-emitting electrochemical cells (PeLECs) is designed. A dramatic increase of the maximum external quantum efficiency and luminance from 2.7% and 6050 cd m-2 for a 3D-only PeLEC to 8.3% and 11 200 cd m-2 for a 3D-0D PNC device with only 7% by weight of 0D PNCs is observed. The majority of this increase is driven by the efficient inherent emission of the 0D PNCs, while the concomitant morphology improvement also contributes to reduced leakage current, reduced hysteresis, and enhanced operational lifetime (half-life of 129 h), making this one of the best-performing LECs reported to date.

Metal Oxide-Induced Instability and Its Mitigation in Halide Perovskite Solar Cells.

Halide perovskite solar cells (PSCs) have emerged as a promising photovoltaic technology for sustainable energy solutions because of their impressive power conversion efficiency and a path to be manufactured by low-cost, high-throughput methods. To reach PSCs' full potential for practical implementation, it is crucial to solve the issues related to long-term operational stability. Given that PSCs consist of many layers of dissimilar materials which form multiple internal interfaces, it is prudent to examine whether there exist interfacial interactions, most importantly between transport layers and perovskite absorbers, that can trigger instability and affect device performance. In this Perspective, we bring to the attention of the PSC research community the lesser-known interfacial degradation of halide perovskites promoted by contact with metal oxide transport layers and highlight the deleterious effects on the PSCs' performance and stability. We also discuss various mitigation strategies that have shown promise for achieving high-performing and stable PSCs.

Opposite Polarity Surface Photovoltage of MoS2 Monolayers on Au Nanodot versus Nanohole Arrays.

We prepared MoS2 monolayers on Au nanodot (ND) and nanohole (NH) arrays. Both these sample arrays exhibited enhanced photoluminescence intensity compared with that of a bare SiO2/Si substrate. The reflectance spectra of MoS2/ND and MoS2/NH had clear features originating from excitation of localized surface plasmon and propagating surface plasmon polaritons. Notably, the surface photovoltages (SPV) of these hybrid plasmonic nanostructures had opposite polarities, indicating negative and positive charging at MoS2/ND and MoS2/NH, respectively. Surface potential maps, obtained by Kelvin probe force microscopy, suggested that the potential gradient led to a distinct spatial distribution of photo-generated charges in these two samples under illumination. Furthermore, the local density of photo-generated excitons, as predicted from optical simulations, explained the SPV spectra of MoS2/ND and MoS2/NH. We show that the geometric configuration of the plasmonic nanostructures modified the polarity of photo-generated excess charges in MoS2. These findings point to a useful means of optimizing optoelectronic characteristics and improving the performance of MoS2-based plasmonic devices.

Solution Synthesis, Processing, and Applications of Semiconducting Nanomaterials.

Nanomaterials have contributed to the forefront of materials research in the past two decades, and are used today in sensors, solar cells, light emitting diodes, electronics, and biomedical devices [...].

Mg Doped CuCrO2 as Efficient Hole Transport Layers for Organic and Perovskite Solar Cells.

The electrical and optical properties of the hole transport layer (HTL) are critical for organic and halide perovskite solar cell (OSC and PSC, respectively) performance. In this work, we studied the effect of Mg doping on CuCrO2 (CCO) nanoparticles and their performance as HTLs in OSCs and PSCs. CCO and Mg doped CCO (Mg:CCO) nanoparticles were hydrothermally synthesized. The nanoparticles were characterized by various experimental techniques to study the effect of Mg doping on structural, chemical, morphological, optical, and electronic properties of CCO. We found that Mg doping increases work function and decreases particle size. We demonstrate CCO and Mg:CCO as efficient HTLs in a variety of OSCs, including the first demonstration of a non-fullerene acceptor bulk heterojunction, and CH3NH3PbI3 PSCs. A small improvement of average short-circuit current density with Mg doping was found in all systems.

Integrated Experimental-Theoretical Approach To Determine Reliable Molecular Reaction Mechanisms on Transition-Metal Oxide Surfaces.

By combining experimental and theoretical approaches, we investigate the quantitative relationship between molecular desorption temperature and binding energy on d and f metal oxide surfaces. We demonstrate how temperature-programmed desorption can be used to quantitatively correlate the theoretical surface chemistry of metal oxides (via on-site Hubbard U correction) to gas surface interactions for catalytic reactions. For this purpose, both CO and NO oxidation mechanisms are studied in a step-by-step reaction process for perovskite and mullite-type oxides, respectively. Additionally, we show solutions for over-binding issues found in COx, NOx, SOx, and other covalently bonded molecules that must be considered during surface reaction modeling. This work shows the high reliability of using TPD and density functional theory in conjunction to create accurate surface chemistry information for a variety of correlated metal oxide materials.

Stable and Active Oxidation Catalysis by Cooperative Lattice Oxygen Redox on SmMn2O5 Mullite Surface.

The correlation between lattice oxygen (O) binding energy and O oxidation activity imposes a fundamental limit in developing oxide catalysts, simultaneously meeting the stringent thermal stability and catalytic activity standards for complete oxidation reactions under harsh conditions. Typically, strong O binding indicates a stable surface structure, but low O oxidation activity, and vice versa. Using nitric oxide (NO) catalytic oxidation as a model reaction, we demonstrate that this conflicting correlation can be avoided by cooperative lattice oxygen redox on SmMn2O5 mullite oxides, leading to stable and active oxide surface structures. The strongly bound neighboring lattice oxygen pair cooperates in NO oxidation to form bridging nitrate (NO3-) intermediates, which can facilely transform into monodentate NO3- by a concerted rotation with simultaneous O2 adsorption onto the resulting oxygen vacancy. Subsequently, monodentate NO3- species decompose to NO2 to restore one of the lattice oxygen atoms that act as a reversible redox center, and the vacancy can easily activate O2 to replenish the consumed one. This discovery not only provides insights into the cooperative reaction mechanism but also aids the design of oxidation catalysts with the strong O binding region, offering strong activation of O2, high O activity, and high thermal stability in harsh conditions.

Effects of Environmental Water Absorption by Solution-Deposited Al2O3 Gate Dielectrics on Thin Film Transistor Performance and Mobility.

In recent years, many solution-processed oxide transistors have been reported with mobility rivaling or exceeding their vacuum-deposited counterparts. Here, we show that water absorption from the environment by solution-processed dielectric materialsexplains this enhanced mobility. By monitoring the water content of Al2O3, ZrO2, and bilayer dielectric materials, we demonstrate how water absorption by the dielectric affects electrical characteristics in solution-processed metal oxide transistors. These effects, including capacitance-frequency dispersion, counterclockwise hysteresis in transfer curves, and high channel mobility, are elucidated by electron transfer between the gate/channel and trap states within the band gap of the dielectric created by the water.

Tunable Electrical and Optical Properties of Nickel Oxide (NiO x) Thin Films for Fully Transparent NiO x-Ga2O3 p-n Junction Diodes.

One of the major limitations of oxide semiconductors technology is the lack of proper p-type materials to enable devices such as pn junctions, light-emitting diodes, and photodetectors. This limitation has resulted in an increased research focus on these materials. In this work, p-type NiO x thin films with tunable optical and electrical properties as well as its dependence with oxygen pressure during pulsed laser deposition are demonstrated. The control of NiO x films resistivity ranged from ∼109 to ∼102 Ω cm, showing a p-type behavior with Eg tuning from 3.4 to 3.9 eV. Chemical composition and the resulting band diagrams are also discussed. The all-oxide NiO x-Ga2O3 pn junction showed very low leakage current, an ideality factor of ∼2, 105 on/off ratio, and 0.6 V built-in potential. Its J- V temperature dependence is also analyzed. C- V measurements demonstrate diodes with a carrier concentration of 1015 cm-3 for the Ga2O3 layer, which is fully depleted. These results show a stable, promising diode, attractive for future photoelectronic devices.

Combustion Synthesis of p-Type Transparent Conducting CuCrO2+x and Cu:CrOx Thin Films at 180 °C.

Low-temperature solution processing of p-type transparent conducting oxides (TCOs) will open up new opportunities for applications on flexible substrates that utilize low-cost, large-area manufacturing. Here, we report a facile solution synthesis method that produces two p-type TCO thin films: copper chromium oxide and copper-doped chromium oxide. Using combustion chemistry, both films are solution processed at 180 °C, which is lower than most recent efforts. While adopting the same precursor preparation and annealing temperature, we find that annealing environment (solvent vapor vs open air) dictates the resulting film phase, hence the optoelectronic properties. The effect of annealing environment on the reaction mechanism is discussed. We further characterize the electronic, optical, and transport properties of the two materials, and compare the differences. Their applications in optoelectronic devices are successfully demonstrated in transparent p-n junction diodes and as hole transport layers in organic photovoltaic devices.

Thermal stability of mullite RMn2O5 (R = Bi, Y, Pr, Sm or Gd): combined density functional theory and experimental study.

Understanding and effectively predicting the thermal stability of ternary transition metal oxides with heavy elements using first principle simulations are vital for understanding performance of advanced materials. In this work, we have investigated the thermal stability of mullite RMn2O5 (R = Bi, Pr, Sm, or Gd) structures by constructing temperature phase diagrams using an efficient mixed generalized gradient approximation (GGA) and the GGA + U method. Simulation predicted stability regions without corrections on heavy elements show a 4-200 K underestimation compared to our experimental results. We have found the number of d/f electrons in the heavy elements shows a linear relationship with the prediction deviation. Further correction on the strongly correlated electrons in heavy elements could significantly reduce the prediction deviations. Our corrected simulation results demonstrate that further correction of R-site elements in RMn2O5 could effectively reduce the underestimation of the density functional theory-predicted decomposition temperature to within 30 K. Therefore, it could produce an accurate thermal stability prediction for complex ternary transition metal oxide compounds with heavy elements.

Effects of Contact-Induced Doping on the Behaviors of Organic Photovoltaic Devices.

Substrates can significantly affect the electronic properties of organic semiconductors. In this paper, we report the effects of contact-induced doping, arising from charge transfer between a high work function hole extraction layer (HEL) and the organic active layer, on organic photovoltaic device performance. Employing a high work function HEL is found to increase doping in the active layer and decrease photocurrent. Combined experimental and modeling investigations reveal that higher doping increases polaron-exciton quenching and carrier recombination within the field-free region. Consequently, there exists an optimal HEL work function that enables a large built-in field while keeping the active layer doping low. This value is found to be ~0.4 eV larger than the pinning level of the active layer material. These understandings establish a criterion for optimal design of the HEL when adapting a new active layer system and can shed light on optimizing performance in other organic electronic devices.

Solution Synthesized p-Type Copper Gallium Oxide Nanoplates as Hole Transport Layer for Organic Photovoltaic Devices.

p-Type metal-oxide hole transport layer (HTL) suppresses recombination at the anode and hence improves the organic photovoltaic (OPV) device performance. While NiOx has been shown to exhibit good HTL performance, very thin films (<10 nm) are needed due to its poor conductivity and high absorption. To overcome these limitations, we utilize CuGaO2, a p-type transparent conducting oxide, as HTL for OPV devices. Pure delafossite phase CuGaO2 nanoplates are synthesized via microwave-assisted hydrothermal reaction in a significantly shorter reaction time compared to via conventional heating. A thick CuGaO2 HTL (∼280 nm) in poly(3-hexylthiophene):[6,6]-phenyl-C61-butyric acid methyl ester (P3HT:PCBM) devices achieves 3.2% power conversion efficiency, on par with devices made with standard HTL materials. Such a thick CuGaO2 HTL is more compatible with large-area and high-volume printing process.

Impurities and Electronic Property Variations of Natural MoS2 Crystal Surfaces.

Room temperature X-ray photoelectron spectroscopy (XPS), inductively coupled plasma mass spectrometry (ICPMS), high resolution Rutherford backscattering spectrometry (HR-RBS), Kelvin probe method, and scanning tunneling microscopy (STM) are employed to study the properties of a freshly exfoliated surface of geological MoS2 crystals. Our findings reveal that the semiconductor 2H-MoS2 exhibits both n- and p-type behavior, and the work function as measured by the Kelvin probe is found to vary from 4.4 to 5.3 eV. The presence of impurities in parts-per-million (ppm) and a surface defect density of up to 8% of the total area could explain the variation of the Fermi level position. High resolution RBS data also show a large variation in the MoSx composition (1.8 < x < 2.05) at the surface. Thus, the variation in the conductivity, the work function, and stoichiometry across small areas of MoS2 will have to be controlled during crystal growth in order to provide high quality uniform materials for future device fabrication.

HfSe2 thin films: 2D transition metal dichalcogenides grown by molecular beam epitaxy.

In this work, we demonstrate the growth of HfSe2 thin films using molecular beam epitaxy. The relaxed growth criteria have allowed us to demonstrate layered, crystalline growth without misfit dislocations on other 2D substrates such as highly ordered pyrolytic graphite and MoS2. The HfSe2 thin films exhibit an atomically sharp interface with the substrates used, followed by flat, 2D layers with octahedral (1T) coordination. The resulting HfSe2 is slightly n-type with an indirect band gap of ∼ 1.1 eV and a measured energy band alignment significantly different from recent DFT calculations. These results demonstrate the feasibility and significant potential of fabricating 2D material based heterostructures with tunable band alignments for a variety of nanoelectronic and optoelectronic applications.

Molecular weight dependence of the morphology in P3HT:PCBM solar cells.

In polymer-based photovoltaic devices, optimizing and controlling the active layer morphology is important to enhancing the device efficiency. Using poly(3-hexylthiophene) (P3HT) with well-defined molecular weights (MWs), synthesized by the Grignard metathesis (GRIM) method, we show that the morphology of the photovoltaic active layer and the absorption and crystal structure of P3HT are dependent on the MW. Differential scanning calorimetry showed that the crystallinity of P3HT reached a maximum for intermediate MWs. Grazing-incidence wide-angle X-ray diffraction showed that the spacing of the (100) planes of P3HT increased with increasing MW, while the crystal size decreased. Nonlinear crystal lattice expansions were found for both the (100) and (020) lattice planes, with an unusual π-π-stacking enhancement observed between 50 and 100 °C. The melting point depression for P3HT, when mixed with [6,6]-phenyl-C61-butyric acid methyl ester (PCBM), and, hence, the Flory-Huggins interaction parameter depended on the MW. PCBM was found to perturb the ordering of P3HT chains. In photovoltaic devices, P3HT with a MW of ∼20K showed the best device performance. The morphologies of these blends were studied by grazing-incidence small-angle X-ray scattering (GISAXS) and resonant soft X-ray scattering. In GISAXS, we observed that the low-molecular-weight P3HT more readily crystallizes, promoting a phase-separated morphology.

Solution processed ZnO hybrid nanocomposite with tailored work function for improved electron transport layer in organic photovoltaic devices.

We demonstrate improved organic photovoltaic device performance using solution processed electron transport layers of ZnO nanoparticle (NP) films containing organic additives, poly(vinylpyrrolidone) (PVP), or diethanolamine (DEA), that do not require post processing after film deposition. Inclusion of PVP or DEA decreased the ZnO work function by 0.4 eV through interfacial dipole formation. While PVP did not change the ZnO NP shape or size, DEA modified the ZnO shape from 5 nm × 15 nm nanorods to 5 nm nanoparticles. At an optimized PVP concentration of 0.7 wt %, ZnO NP:PVP electron transport layers (ETLs) improved the efficiency of inverted P3HT:PCBM devices by 37%, primarily through higher fill factor. ZnO NP:PVP and ZnO NP:DEA ETLs increased the open circuit voltage of inverted P3HT:ICBA devices by 0.07 V due to decreasing ETL work function, leading to enhanced built-in field. The relationship between ZnO nanocomposite ETL work function, donor-acceptor energy offset, and device performance is discussed. The effects of the two additives are compared.