A critical review on the contributions of chemical and physical factors toward the nucleation and growth of large-area graphene

Since the first isolation of graphene over a decade ago, research into graphene has exponentially increased due to its excellent electrical, optical, mechanical and chemical properties. Graphene has been shown to enhance the performance of various electronic devices. In addition, graphene can be simply produced through chemical vapor deposition (CVD). Although the synthesis of graphene has been widely researched, especially the CVD growth method, the lack of understanding of various synthetic parameters still limits the fabrication of large-area and defect-free graphene films. This report critically reviews various parameters affecting the quality of CVD grown graphene to understand the relationship between these parameters and thechoice of metal substrates and to provide a point of reference for future studies of large-area, CVD-grown graphene

Graphene and chiral nematic liquid crystals: A focus on lasing

© The Royal Society of Chemistry 2015. This work presents the interaction of self-assembled liquid crystalline (LC) unidimensional photonic structures on the surface of polycrystalline graphene. Further, this surface effect is studied through different substrate geometries in the test devices. Primarily, these devices are characterised through polarizing optical microscopy (POM) and their laser emission features in the dye-doped chiral systems. Then the conductive nature of graphene is utilized to apply external electric fields to the photonic medium and its effect is envisaged. These graphene-based devices demonstrate a unique result in polarizing optical micrographs and electro-optic responses which indicates the presence of multidirectional domain formations. Additionally, the LC band-edge lasing from graphene cells is found to be anisotropic and depends on the directionality of the optical pump. This work attempts to lay the foundation for the implementation of a new class of defused chiral nematic liquid crystal based devices e.g. optical filters, notch filters, colour reflectors, and light shutters and may add toward the knowledge base necessary in the substitution of Indium Tin Oxide (ITO) with graphene in traditional LC based display devices.This work was carried out under the GRAPHTED project which is funded by the Engineering and Physical Sciences Research Council UK (project ref. EP/K016636/1, Grant No. EP/H047565/ 1). A. A. K. would like to thank the Higher Education of Pakistan (HEC), P. R. K. acknowledges Lindemann Trust Fellowship. A. A. K. and P. R. K. acknowledge the Cambridge Commonwealth, European and International Trust and for the nancial suppo

Formation of physical-gel redox electrolytes through self-assembly of discotic liquid crystals: Applications in dye sensitized solar cells

The self-assembly of small molecules into ordered structures is of significant interest in electronic applications due to simpler device fabrication and better performance. Here we present work on the development of self-assembled fibrous networks of thermotropic triphenylene discotic liquid crystals, where 2,3,6,7,10,11-Hexakishexyloxytriphenylene (HAT6) is studied. The formation of interconnected molecular fibres in acetonitrile-based solvents facilitates thermally-reversible physical-gel (non-covalent) preparation, with the HAT6 network providing mechanical support and containment of the solvent. Furthermore, gel formation is also achieved using an acetonitrile-based iodide/tri-iodide redox liquid electrolyte, and the resulting gel mixture is utilised as an electrolyte in dye-sensitized solar cells (DSSCs). Our results show that it is indeed possible to achieve in situ gel formation in DSSCs, allowing for easy cell fabrication and electrolyte filling. In addition, the gel phase is found to increase device lifetime by limiting solvent evaporation. Differential scanning calorimetry (DSC) and polarising optical microscopy (POM) are used to study gel formation, and it is identified that the thermally reversible gels are stable up to working temperatures of 40 °C. It is found that DSSCs filled with gel electrolyte exhibit longer electron lifetime in the TiO 2 photo-anode (≈8.4 ms in the liquid electrolyte to ≈11.4 ms in the gel electrolytes), most likely due to electron screening from the electrolyte by HAT6. Current-Voltage (I–V) and electrochemical impedance spectroscopy (EIS) are used to study the effect of gel formation on conductivity and electrochemical properties, and it is found that confinement of the liquid electrolyte into a gel phase does not significantly reduce ionic conductivity, a problem common with solid-state polymer electrolytes. A 3.8 mM HAT6 gel electrolyte DSSC exhibited a PCE of 6.19% vs. a 5.86% liquid electrolyte reference. Extended device lifetimes studies showed that the gels increase stability of the DSSCs by reducing the rate of solvent evaporation.Cambridge Commonwealth European and International Trust (CCEIT), Higher Education Commission of Pakistan (HEC

Self-assembled liquid crystalline nanotemplates and their incorporation in dye-sensitised solar cells

Liquid junction dye-sensitised solar cells (DSSCs) suffer from solvent evaporation and leakage which limit their large-scale production. Here, we have prepared DSSC using a simple and cheap fabrication process with improved photovoltaic parameters and stability. A binary mixture of Smectic A (SmA) and Nematic Liquid Crystal (NLC) was used to provide a self-assembled template for a polymerisable reactive mesogen LC. The layered structure of SmA combined with a low viscosity NLC forms a polygonal structure that provides an ordered and continuous template for reactive mesogens. Once the reactive mesogen is polymerised under UV light, the SmA:NLC mixture is washed away, resulting in a polymer network template containing nanochannels. We demonstrate the incorporation of these templates into DSSCs and find that DSSCs containing these nanochannels show improved open-circuit voltage (V$_{OC}$) (0.705 V) and short-circuit current (J$_{SC}$) (13.25 mA cm$^{-2}$) compared to that of the liquid electrolyte (V$_{OC}$ = 0.694 V and JSC = 10.46 mA cm$^{-2}$). The highest obtained power conversion efficiency with Sm-PE was 5.94% which is higher than that of the reference solar cell (5.51%). These can be attributed to the improved ionic conductivity and ionic diffusion of Sm-PE where the presence of the nanochannels aided the ionic conduction in the polymer electrolyte. In addition, it is hypothesized that the light scattering effect of the polymerised reactive mesogen also contributed to the improved performance of the photovoltaic devices. This finding is important because it is known fact that when a polymer is added to liquid electrolyte, the ionic conductivity will decrease although the stability is improved.A.A.K. and G.R. would like to thank the Cambridge Commonwealth Trust for financial support. A.A.K. would also like to thank the HEC (Pakistan) for financial support. C.W would like to thank EPSRC Integrated Photonics and Electronics Systems funding

Enhanced Crystallization by Methanol Additive in Antisolvent for Achieving High‐Quality MAPbI3 Perovskite Films in Humid Atmosphere

Perovskite solar cells have attracted considerable attention owing to their easy and low‐cost solution manufacturing process with high power conversion efficiency. However, the fabrication process is usually performed inside a glovebox to avoid moisture, as organometallic halide perovskites are easily dissolved in water. In this study, we propose a one‐step fabrication of high‐quality MAPbI3 perovskite films in around 50% relative humidity (RH) humid ambient air by using diethyl ether as an antisolvent and methanol as an additive into this antisolvent. Because of the presence of methanol, the water molecules can be efficiently removed from the gaps of the perovskite precursors and the perovskite film formation can be slightly controlled, leading to pinhole‐free and low roughness films. Concurrently, methanol can be used to tune the DMSO ratio in the intermediate perovskite phase to regulate perovskite formation. Planar solar cells fabricated by using this method exhibited the best efficiency of 16.4% with a reduced current density–voltage hysteresis. This efficiency value is approximately 160% higher than the devices fabrication by using only diethyl ether treatment. From the impedance measurement, it is also found that the recombination reaction is suppressed when the device is prepared with methanol additive in the antisolvent. This method presents a new path for controlling the growth and morphology of perovskite films in humid climates and laboratories with uncontrolled environments

Addition Effect of Pyreneammonium Iodide to Methylammonium Lead Halide Perovskite‐2D/3D Heterostructured Perovskite with Enhanced Stability

Despite the eminent performance of the organometallic halide perovskite solar cells (PSCs), the poor stability for humidity and ultraviolet irradiation is still major problem for the commercialization of PSCs. Herein, a novel functional organic compound 1‐(ammonium acetyl)pyrene is successfully introduced for preparing the 2D/3D heterostructured MAPbI3 perovskite. Because of the functional organic pyrene group with high humidity resistance and strong absorption in the ultraviolet region, the 2D/3D perovskite film shows notable stability with no degradation in ≈60% relative humidity after even six months and exhibits a high ultraviolet irradiation stability which keeps nearly no degradation after 1 h in the UV Ozone treatment. Planar PSCs are fabricated in the ≈60% relative humidity air outside glovebox. The champion efficiency of (PEY2PbI4)0.02MAPbI3 perovskite solar cells is 14.7% with nearly no hysteresis which is equal performance of 3D MAPbI3 devices (15.0%). This work presents a new direction for enhancing the solar cells\u27 performance and stability by incorporating a functional organic aromatic compound into the perovskite layer

Dependence of acetate based anti-solvent for high humidity fabrication of CH3NH3PbI3 perovskite devices in ambient atmosphere

High-efficiency perovskite solar cells (PSCs) need to be fabricated in the nitrogen-filled glovebox by the atmosphere-controlled crystallization process. However, the use of the glovebox process is of great concern for mass level production of PSCs. In this work, notable efficient CH3NH3PbI3 solar cells can be obtained in high humidity ambient atmosphere (60–70% relative humidity) by using acetate as the antisolvent, in which dependence of methyl, ethyl, propyl, and butyl acetate on the crystal growth mechanism is discussed. It is explored that acetate screens the sensitive perovskite intermediate phases from water molecules during perovskite film formation and annealing. It is revealed that relatively high vapor pressure and high water solubility of methyl acetate (MA) leads to the formation of highly dense and pinhole free perovskite films guiding to the best power conversion efficiency (PCE) of 16.3% with a reduced hysteresis. The devices prepared using MA showed remarkable shelf life stability of more than 80% for 360 h in ambient air condition, when compared to the devices fabricated using other antisolvents with low vapor pressure and low water solubility. Moreover, the PCE was still kept at 15.6% even though 2 vol % deionized water was added in the MA for preparing the perovskite layer

Performance Enhancement of Mesoporous TiO2-Based Perovskite Solar Cells by SbI3 Interfacial Modification Layer

TiO2 is commonly used as an electron-transporting material in perovskite photovoltaic devices due to its advantages, including suitable band gap, good photoelectrochemical stability, and simple preparation process. However, there are many oxygen vacancies or defects on the surface of TiO2 and thus this affects the stability of TiO2-based perovskite solar cells under UV light. In this work, a thin (monolayer) SbI3 modification layer is introduced on the mesoporous TiO2 surface and the effect at the interface between of TiO2 and perovskite is monitored by using a quartz crystal microbalance system. We demonstrate that the SbI3-modified TiO2 electrodes exhibit superior electronic properties by reducing electronic trap states, enabling faster electron transport. This approach results in higher performances compared with electrodes without the SbI3 passivation layer. CH3NH3PbI3 perovskite solar cells with a maximum power conversion efficiency of 17.33% in air, accompanied by a reduction in hysteresis and enhancement of the device stability, are reported

Melamine Hydroiodide Functionalized MAPbI3 Perovskite with Enhanced Photovoltaic Performance and Stability in Ambient Atmosphere

Despite the remarkable performance of organometallic halide perovskite solar cells (PSCs), their ultimate stability is still a major issue that inhibits the commercialization of this eminent technology. Herein, melamine hydroiodide (MLAI) is added to function methyl ammonium (CH3NH3+, MA+) lead iodide perovskite for fabricating structured perovskite with enhanced photovoltaic performance and stability in the harsh ambient atmosphere (35 °C, 60–70% relative humidity). Nearly no new phase formed even incorporated 25 mol.% MLAI induces the strain in the perovskite crystal structure. The MLAI‐structured perovskite film shows a denser and smoother surface than the pristine MAPbI3 perovskite. Planar PSCs based on 2 mol.% MLAI‐functionalized perovskite show 17.2% power conversion efficiency with nearly no hysteresis which is much higher than pristine MAPbI3 PSCs. Most importantly, the solar cell devices based on 2 mol.% MLAI‐functionalized perovskite still retain over 90% of the initial performance after being kept in ambient atmosphere for more than 560 h without encapsulation

Magnesium-Doped MAPbI3 Perovskite Layers for Enhanced Photovoltaic Performance in Humid Air Atmosphere

Despite the high efficiency of MAPbI3 perovskite solar cells, the long term stability and degradation in humid atmosphere are issues that still needed to be addressed. In this work, magnesium iodide (MgI2) was first successfully used as a dopant into MAPbI3 perovskite prepared in humid air atmosphere. Mg doping decreased the valence band level, which was determined from photoelectron yield spectroscopy. Compared to the pristine MAPbI3 perovskite film, the 1.0% Mg-doped perovskite film showed increased crystal grain size and formation of pinhole-free perovskite film. Performance of the solar cell was increased from 14.2% of the doping-free solar cell to 17.8% of 1.0% Mg-doped device. Moreover, 90% of the original power conversion efficiency was still retained after storage in 30–40% relative humidity for 600 h