A bolaamphiphilic amino acid appended photo-switching supramolecular gel and tuning of photo-switching behaviour.

Self-assembled bolaamphiphilic perylene bisimide (PBI) containing an amino acid appended fluorescent semiconducting soft material (hydrogel) has been discovered at physiological pH. This new organic material based on self-assembled perylene bisimide appended amino acid-based bolaamphiphile (PBI-C11-Y) has been well characterized using various techniques including UV-Vis, fluorescence, X-ray diffraction, FT-IR, transmission electron microscopic (TEM) and atomic force microscopic (AFM) studies. Interestingly, the UV-Vis absorption properties of the soft-material are dependent on the pH of the medium. This PBI-conjugated amino acid appended gelator molecule contains a centrally located perylene bisimide moiety as well as an aromatic amino acid l-tyrosine at the side chains, which are extremely useful for interacting with the delocalized large π-surface of GO (graphene oxide) or RGO (reduced graphene oxide) to form a GO/RGO containing hybrid hydrogel. Graphene oxide and reduced graphene oxide have been successfully incorporated into the nanofibrillar network structure of the PBI-C11-Y based gel to make nanohybrid systems. The I-V profile of the semiconducting photo-responsive soft-material of the PBI-C11-Y has been successfully tuned upon the incorporation of GO and RGO within the gel-based soft material. This PBI-C11-Y xerogel based structure shows photo-switching behaviour upon exposure to white light. The ON/OFF ratio of the PBI-C11-Y can be modulated upon the inclusion of GO and RGO within the hydrogel matrix. Furthermore, the OFF state stability of the PBI-C11-Y xerogel material has been increased upon the inclusion of RGO. Regulation of the photo-switching behaviour of the PBI-C11-Y based xerogel holds promise for making PBI-containing amino acid appended biomaterials with interesting properties in future.

Surface modification of halide perovskite using EDTA-complexed SnO2 as electron transport layer in high performance solar cells.

The long-term performance of metal halide perovskite solar cells (PSCs) can be significantly improved by tuning the surface characteristics of the perovskite layers. Herein, low-temperature-processed ethylenediaminetetraacetic acid (EDTA)-complexed SnO2 (E-SnO2) is successfully employed as an electron transport layer (ETL) in PSCs, enhancing the efficiency and stability of the devices. The effects of EDTA treatment on SnO2 are investigated for different concentrations: comparing the solar cells' response with 15%-2.5% SnO2 and E-SnO2 based ETLs, and it was found that 7.5% E-SnO2 provided the best results. The improved surface properties of the perovskite layer on E-SnO2 are attributed to the presence of small amount of PbI2 which contributes to passivate the defects at the grain boundaries and films' surface. However, for the excess PbI2 based devices, photocurrent dropped, which could be attributed to the generation of shallow traps due to excess PbI2. The better alignment between the Fermi level of E-SnO2 and the conduction band of perovskite is another favorable aspect that enables increased open-circuit potential (VOC), from 0.82 V to 1.015 V, yielding a stabilized power conversion efficiency of 15.51%. This complex ETL strategy presented here demonstrates the enormous potential of E-SnO2 as selective contact to enhance the perovskite layer properties and thereby allow stable and high-efficiency PSCs.

MXene-Enhanced Nanoscale Photoconduction in Perovskite Solar Cells Revealed by Conductive Atomic Force Microscopy.

The use of MXene materials in perovskite solar cells (PSCs) has received significant interest due to their distinct features that result from the termination of functional groups and the oxidation of MXene. Herein, we have used photoconductive atomic force microscopy (pcAFM) to map the local (nanoscale) photovoltaic performances of the Ti3C2Tx MXene nanosheet-integrated TiO2 (MXene@TiO2) electron transport layer-based PSCs to determine the influence of the treatment on the microscopic charge flow inside the devices. At different applied voltages, the morphology and current have been simultaneously measured with nanoscale resolution from the top surfaces of the solar cells without back contacts. The PSCs based on MXene@TiO2 exhibit more enhanced current flow across the grains than the only TiO2-based PSCs. At zero applied bias, the average local photocurrent for MXene-integrated PSCs is several times higher than the reference PSCs and decreases gradually when the positive bias is increased until the open circuit voltage. Considerable differences were also observed in the short circuit current among different locations that appear identical in AFM topography. Our findings reveal the potential of MXene-integrated ETLs to enhance the nanoscale photoconduction and inherent characteristics of the active layers, thereby improving the performance of the polycrystalline photovoltaic devices.

Toward Stable Solution-Processed High-Mobility p-Type Thin Film Transistors Based on Halide Perovskites.

Organolead halide perovskites have drawn significant attention from the scientific community as one of the most attractive materials in optoelectronics, especially in the field of photovoltaics. In this study, we focus on using halide perovskites in processing thin film transistors (TFTs). Halide perovskites have high solution processability and excellent carrier transport characteristics, in particular for holes. The present work aims to fill a gap in oxide-based technology. It concerns the process of using high-stable and reliable p-type oxide-based devices to target CMOS technology (complementary metal-oxide-semiconductor). We report on a solution-processed high-performance TFT based on methylammonium lead iodide (CH3NH3PbI3) perovskite semiconductor films, which shows promise for devices that can be simple to manufacture with high reliability, reproducibility, and excellent stability in atmospheric conditions. To achieve a highly stable perovskite semiconductor film, we introduce diethylsulfide in the perovskite precursor. The TFT shows a stable p-type behavior when operated at low voltages (≤-2 V) and has a current modulation of >104, an almost negligible hysteresis, and average saturation mobility of about 18.8 cm2 V-1 s-1, taken over 50 devices tested (the highest one measured was ∼23.2 cm2 V-1 s-1). This is the highest value until now reported in the literature. In addition, we demonstrate that perovskite TFTs can be fabricated at temperatures as low as 150 °C on flexible substrates with a saturation mobility of ∼11.5 cm2 V-1 s-1. The high-performance perovskite TFT with excellent stability is a promising candidate for the next generation of p-type transistors for a plethora of low-cost electronics applications.

Imaging the Anomalous Charge Distribution Inside CsPbBr3 Perovskite Quantum Dots Sensitized Solar Cells.

Highly luminescent CsPbBr3 perovskite quantum dots (QDs) have gained huge attention in research due to their various applications in optoelectronics, including as a light absorber in photovoltaic solar cells. To improve the performances of such devices, it requires a deeper knowledge on the charge transport dynamics inside the solar cell, which are related to its power-conversion efficiency. Here, we report the successful fabrication of an all-inorganic CsPbBr3 perovskite QD sensitized solar cell and the imaging of anomalous electrical potential distribution across the layers of the cell under different illuminations using Kelvin probe force microscopy. Carrier generation, separation, and transport capacity inside the cells are dependent on the light illumination. Large differences in surface potential between electron and hole transport layers with unbalanced carrier separation at the junction have been observed under white light (full solar spectrum) illumination. However, under monochromatic light (single wavelength of solar spectrum) illumination, poor charge transport occurred across the junction as a consequence of less difference in surface potential between the active layers. The outcome of this study provides a clear idea on the carrier dynamic processes inside the cells and corresponding surface potential across the layers under the illumination of different wavelengths of light to understand the functioning of the solar cells and ultimately for the improvement of their photovoltaic performances.

Oxide-Based Solar Cell: Impact of Layer Thicknesses on the Device Performance.

A ZnO/Cu2O-based combinatorial heterojunction device library was successfully fabricated by a simple spray pyrolysis technique using ITO-coated glass as the substrate. The combinatorial approach was introduced to analyze the impact of the ZnO and Cu2O layer thicknesses on the performance of the solar cells. The thickness of the ZnO layer was varied from ∼50 to 320 nm, and the Cu2O layer was deposited orthogonal to the ZnO thickness gradient. In the case of Cu2O, the thickness varied from ∼200 to 800 nm. The photovoltaic performance of the cells is strongly dependent on the absorber layer thickness for a particular window layer thickness and reaches a maximum short-circuit current density of 3.9 mA/cm2 when the absorber layer thickness just crosses ∼700 nm. Reducing the thicknesses of the active layers leads to a sharp decrease in the device performance. It is shown that the entire built-in bias of the heterojunction is created in the absorber layer due to low carrier density. The poor performance of the devices having lower thicknesses is attributed to different interfacial phenomena such as optical losses due to the thin Cu2O layer, back-contact recombination of the carriers due to the low layer thickness because a minimum heterojunction thickness is required for the formation of the full built-in bias that slows down the recombination of the carriers, and other factors.

Observation of Space Charge Dynamics Inside an All Oxide Based Solar Cell.

The charge transfer dynamics at interfaces are fundamental to know the mechanism of photovoltaic processes. The internal potential in solar cell devices depends on the basic processes of photovoltaic effect such as charge carrier generation, separation, transport, recombination, etc. Here we report the direct observation of the surface potential depth profile over the cross-section of the ZnO nanorods/Cu2O based solar cell for two different layer thicknesses at different wavelengths of light using Kelvin probe force microscopy. The topography and phase images across the cross-section of the solar cell are also observed, where the interfaces are well-defined on the nanoscale. The potential profiling results demonstrate that under white light illumination, the photoinduced electrons in Cu2O inject into ZnO due to the interfacial electric field, which results in the large difference in surface potential between two active layers. However, under a single wavelength illumination, the charge carrier generation, separation, and transport processes between two active layers are limited, which affect the surface potential images and corresponding potential depth profile. Because of changes in the active layer thicknesses, small variations have been observed in the charge carrier transport mechanism inside the device. These results provide the clear idea about the charge carrier distribution inside the solar cell in different conditions and show the perfect illumination condition for large carrier transport in a high performance solar cell.

Metal-free doping process to enhance the conductivity of zinc oxide nanorods retaining the transparency.

The well-ordered metal oxide nanostructures can be synthesized successfully, but the conductance of these structures is limited, which is a disadvantage for applying these in photovoltaic and display devices. Conductivity of a semiconductor can be improved by using metal doping, but the issue becomes a major challenge in nanostructures since their high surface energy usually hinders any metal doping process. Here we show an entirely new metal-free doping strategy to enhance the current conduction of ZnO nanorods' (NRs) arrays through a sulphidation technique. The process is based on the electronegativity difference between S and O because of which one can expect a rigorous bond rearrangement at the interface and a ZnOS-ZnS composite is formed as O is being partially replaced by S. The current conduction by the metal oxide NRs arrays is significantly enhanced by nearly 4 orders of magnitude without sacrificing the transparency of the NRs arrays. The increased current conduction is assigned due to an increase in the Zn(i) concentration as evidenced from the electron paramagnetic resonance measurements. The composite layer grown on p-Si forms a photodiode which is highly sensitive to visible light with a very fast response time.

Core-shell TiO2@ZnO nanorods for efficient ultraviolet photodetection.

Core-shell TiO(2)@ZnO nanorods (NRs) have been fabricated by a simple two step method: growth of ZnO NRs' array by an aqueous chemical technique and then coating of the NRs with a solution of titanium isopropoxide [Ti(OC(3)H(7))(4)] followed by a heating step to form the shell. The core-shell nanocomposites are composed of single-crystalline ZnO NRs, coated with a thin TiO(2) shell layer obtained by varying the number of coatings (one, three and five times). The ultraviolet (UV) emission intensity of the nanocomposite is largely quenched due to an efficient electron-hole separation reducing the band-to-band recombinations. The UV photoconductivity of the core-shell structure with three times TiO(2) coating has been largely enhanced due to photoelectron transfer between the core and the shell. The UV photosensitivity of the nanocomposite becomes four times larger while the photocurrent decay during steady UV illumination has been decreased almost by 7 times compared to the as-grown ZnO NRs indicating high efficiency of these core-shell structures as UV sensors.

Morphology driven ultraviolet photosensitivity in ZnO-CdS composite.

Semiconductors in the form of composite yields immense possibilities for the study of charge transfer processes at the interface. We have designed CdS nanoparticles (NPs) capped ZnO nanostructures using two morphologies of the latter namely nanorods arrays (NRAs) and nanocrystalline film to form a composite NRAs and composite films respectively. The photocurrent values in both the composites have been increased but to a different extent when these are illuminated with the ultraviolet (UV) light. More interestingly, the resultant UV photosensitivity in the composite NRAs is decreased while that in the composite films is increased as compared to the values of the respective uncapped samples. A different charge transfer process at the interface is occurred due to the difference in the morphologies resulting in a contrast change in the UV sensitivity. The photoluminescence results also show that the change in the emission property is morphology-dependent. Therefore, our results imply that the choice of the morphology while making a nanocomposite is crucial to tune its UV sensitivity as well as optical properties.

Ordered dispersion of ZnO quantum dots in SiO2 matrix and its strong emission properties.

ZnO nanoparticles in the form of quantum dots (QDs) have been dispersed in SiO(2) matrix using StÖber method to form ZnO QDs-SiO(2) nanocomposites. Addition of tetraethyl orthosilicate (TEOS) to an ethanolic solution of ZnO nanoparticles produces random dispersion. On the other hand, addition of ZnO nanoparticles to an already hydrolyzed ethanolic TEOS solution results in a chain-like ordered dispersion. The photoluminescence spectra of the as-grown nanocomposites show strong emission in the ultraviolet region. When annealed at higher temperature, depending on the sample type, these show strong red or white emission. Interestingly, when the excitation is removed, the orderly dispersed ZnO QDs-SiO(2) composite shows a very bright blue fluorescence visible by naked eyes for few seconds indicating their promise for display applications. The emission property has been explained in the light of structure-property relationship.

Encapsulation of 2-3-nm-sized ZnO quantum dots in a SiO2 matrix and observation of negative photoconductivity.

Quantum dots (QDs) of ZnO of 2-4 nm size have been encapsulated within a SiO(2) matrix using aqueous chemically grown ZnO nanoparticles in a precursor of tetraethyl orthosilicate. The microstructure shows almost a uniform embedment of the QDs in the SiO(2) matrix, resulting in a ZnO QDs-SiO(2) composite structure. The photocurrent transients of the composite show an instant fall in the current followed by an exponential decay under ultraviolet (UV) illumination, causing negative photoconductivity (NPC), in contrast to the positive photoconductivity in only ZnO nanoparticles. The interface defect states due to the presence of the SiO(2) network around ZnO act as charge trap centers for the photoexcited electrons and are responsible for the NPC. The presence of interface-trapped charges under UV illumination has been further confirmed from capacitance-voltage measurements.