In Situ Grown Nanocrystalline Si Recombination Junction Layers for Efficient Perovskite-Si Monolithic Tandem Solar Cells: Toward a Simpler Multijunction Architecture.

The perovskite-Si tandem is an attractive avenue to attain greater power conversion efficiency (PCE) than their respective single-junction solar cells. However, such devices generally employ complex stacks with numerous deposition steps, which are rather unattractive from an industrial perspective. Here, we develop a simplified tandem architecture consisting of a perovskite n-i-p stack on a silicon heterojunction structure without applying the typically used indium-tin-oxide (ITO) recombination junction (RJ) layer between the top and bottom cells. It is demonstrated that an n-type hydrogenated nanocrystalline silicon (nc-Si:H) grown in situ on an amorphous silicon hole contact layer of the bottom cell acts as an efficient RJ layer, leading to a high open-circuit voltage (VOC) of >1.8 V and a PCE of 21.4% without optimizing the optical design. Compared to the tandem cell with an ITO RJ layer, the nc-Si:H RJ layer not only improves light management but also achieves a higher VOC due to superior contact properties with an overlying SnO2 electron transport layer of the perovskite top cell. Omitting the costly material and its deposition step offers the opportunity toward realizing industrially feasible high-efficiency tandem solar cells.

A Sodium Chloride Modification of SnO2 Electron Transport Layers to Enhance the Performance of Perovskite Solar Cells.

A sodium chloride modification was applied where different amounts of sodium chloride was physically blended in a tin oxide colloid solution to passivate the interface between the electron transport layer (ETL) and perovskite layer and improve the performance of perovskite solar cells. Sodium chloride-modified tin oxide was utilized as the electron transport material to fabricate perovskite solar cells. It was found that sodium chloride-modified tin oxide as an ETL could considerably enhance the performance of the device compared to pristine tin oxide. The power conversion efficiency of the perovskite solar cell displayed 8.8% remarkable improvement from 18.7 ± 0.4% to 20.3 ± 0.3% on average and 9.5% improvement from 18.9 to 20.7% in champion devices because of the considerable enhancement of the fill factor when 25 mM sodium chloride-modified tin oxide as the ETL was used in comparison with pristine tin oxide.

Insights into Microscopic Crystal Growth Dynamics of CH3NH3PbI3 under a Laser Deposition Process Revealed by In Situ X-ray Diffraction.

The process dynamics for the vacuum deposition of methylammonium lead iodide (MAPbI3) perovskite was analyzed by in situ X-ray diffraction using synchrotron radiation. MAPbI3 was fabricated by alternatingly supplying PbI2 and methylammonium iodide via a laser deposition system installed at the synchrotron beamline BL46XU at SPring-8, and in situ crystallization analysis was conducted. Microscopic insights into the crystallization were obtained, including observation of Laue oscillation during the PbI2 growth and octahedral unit (PbI6) rotation during the transformation into perovskite. On the basis of this analysis, conditions that favor the construction of atomically flat MAPbI3 perovskite films were deduced.

Cesium iodide post-treatment of organic-inorganic perovskite crystals to improve photovoltaic performance and thermal stability.

Organic-inorganic perovskites were treated with a CsI solution to improve the photovoltaic performance and stability. Due to the formation of CsPbI3 and trap filling in Cs0.05(FA0.83MA0.17)0.95Pb(I0.83Br0.17)3 perovskites by CsI treatment, the power conversion efficiency was improved to 20.48%. The CsI-treated perovskites exhibited slower degradation under heating at 180 °C than the untreated perovskites.

Electron band tuning of organolead halide perovskite materials by methylammonium and formamidinium halide post-treatment for high-efficiency solar cells.

Perovskite crystals post-treated with methylammonium and formamidinium halide materials were compared. The bandgap energy of perovskites changed upon incorporation of CH5N2+, Br-, and Cl- ions. Perovskites treated with formamidinium iodide yielded the best efficiency of 20.06% due to an increase in photocurrent density by decreased bandgap energy.

Tuning Methylammonium Iodide Amount in Organolead Halide Perovskite Materials by Post-Treatment for High-Efficiency Solar Cells.

In this study, the composition of organic-inorganic perovskite materials is tuned by methylammonium iodide (MAI) post-treatment for high photovoltaic performance. By spin-coating MAI solutions of different concentrations, the amounts of PbI2 and MAI in perovskite layers are tuned. In perovskites, the removal of PbI2 through a reaction with MAI decreases the hysteresis in photocurrent density-voltage curves. Further, by treating perovskites with a high-concentration MAI solution, the excess MAI is incorporated into the perovskites. These perovskites with excess MAI show better power conversion efficiencies (of up to 20.7%) than perovskites with excess PbI2 because of the decrease in trap density. Since the present post-treatment can control perovskite composition without affecting the morphology and crystallinity of the perovskite crystals, this technique would be a useful tool to improve the photovoltaic performance of perovskite solar cells.

Constructing Nanostructured Donor/Acceptor Bulk Heterojunctions via Interfacial Templates for Efficient Organic Photovoltaics.

We demonstrate that a poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate)/diindenoperylene (PEDOT:PSS/DIP) interfacial bilayer could serve as a structural template to enable the morphological control of bulk heterojunctions (BHJs) by co-evaporation of tetraphenyldibenzoperiflanthene:fullerene (DBP:C60), which greatly improves the device performances. Especially, we show that isolated crystalline domains of C60 can be well-controlled at the nanoscale during the co-evaporation. Photoluminescence spectra indicate the realization of DIP/DBP cascade energy architecture, which significantly facilitates both the energy transfer and photocurrent generation. In addition, with bias-dependent external quantum efficiency analysis, we reveal that such a cascade energy device architecture greatly suppresses the energy recombination in both carrier and exciton transfer, resulting in a high open-circuit voltage and a high fill factor. By carefully optimizing the interfacial and BHJ layers, we achieved a high-performance organic photovoltaic cell with a power conversion efficiency of 5.0 ± 0.3%.

Adjustment of Conduction Band Edge of Compact TiO2 Layer in Perovskite Solar Cells Through TiCl4 Treatment.

Perovskite solar cells (PSCs) without a mesoporous TiO2 layer, that is, planar-type PSCs exhibit poorer cell performance as compared to PSCs with a porous TiO2 layer, owing to inefficient electron transfer from the perovskite layer to the compact TiO2 layer in the former case. The matching of the conduction band levels of perovskite and the compact TiO2 layer is thus essential for enhancing PSC performance. In this study, we demonstrate the shifting of the conduction band edge (CBE) of the compact TiO2 layer through a TiCl4 treatment, with the aim of improving PSC performance. The CBE of the compact TiO2 layer was shifted to a higher level through the TiCl4 treatment and then shifted in the opposite direction, that is, to a lower level, through a subsequent heat treatment. These shifts in the CBE were reflected in the PSC performance. The TiCl4-treated PSC showed an increase in the open-circuit voltage of more than 150 mV, as well as a decrease of 100 mV after being heated at 450 °C. On the other hand, the short-circuit current decreased after the treatment but increased after heating at temperatures higher than 300 °C. The treated PSC subjected to subsequent heating at 300 °C exhibited the best performance, with the power conversion efficiency of the PSC being 17% under optimized conditions.

Highly Controlled Codeposition Rate of Organolead Halide Perovskite by Laser Evaporation Method.

Organolead-halide perovskites can be promising materials for next-generation solar cells because of its high power conversion efficiency. The method of precise fabrication is required because both solution-process and vacuum-process fabrication of the perovskite have problems of controllability and reproducibility. Vacuum deposition process was expected to achieve precise control; however, vaporization of amine compound significantly degrades the controllability of deposition rate. Here we achieved the reduction of the vaporization by implementing the laser evaporation system for the codeposition of perovskite. Locally irradiated continuous-wave lasers on the source materials realized the reduced vaporization of CH3NH3I. The deposition rate was stabilized for several hours by adjusting the duty ratio of modulated laser based on proportional-integral control. Organic-photovoltaic-type perovskite solar cells were fabricated by codeposition of PbI2 and CH3NH3I. A power-conversion efficiency of 16.0% with reduced hysteresis was achieved.

Crystallization Dynamics of Organolead Halide Perovskite by Real-Time X-ray Diffraction.

We analyzed the crystallization process of the CH3NH3PbI3 perovskite by observing real-time X-ray diffraction immediately after combining a PbI2 thin film with a CH3NH3I solution. A detailed analysis of the transformation kinetics demonstrated the fractal diffusion of the CH3NH3I solution into the PbI2 film. Moreover, the perovskite crystal was found to be initially oriented based on the PbI2 crystal orientation but to gradually transition to a random orientation. The fluctuating characteristics of the crystallization process of perovskites, such as fractal penetration and orientational transformation, should be controlled to allow the fabrication of high-quality perovskite crystals. The characteristic reaction dynamics observed in this study should assist in establishing reproducible fabrication processes for perovskite solar cells.

Understanding device-structure-induced variations in open-circuit voltage for organic photovoltaics.

We investigate the structural influences on the device performance, especially on open-circuit voltage (V(OC)) in squaraine (SQ)/fullerene (C60) bilayer cells. Simply changing the SQ thickness could lead to 40% variation in V(OC) from 0.62 to 0.86 V. The ionization potential (IP) of SQ films and recombination at the anode surface as well as donor/acceptor (D/A) interface sensitively vary with film thicknesses, which account for the shifts in V(OC). The anode recombination can be effectively suppressed by preventing direct contact between C60 and the anode with a buffer layer, delivering an elevated V(OC). Through polarized infrared-multiple-angle incidence resolution spectroscopy measurement, the molecular structure of SQ films is found to gradually evolve from lying-down on indium-tin oxide substrates with noncentrosymmetric orientation at low thicknesses to random structure at high thicknesses. The different molecular orientation may yield different strengths of electronic coupling, which affects the charge-carrier recombination and thus V(OC). Moreover, the oriented SQ films would spontaneously compose aligned dipole moments at the D/A interface because of the strong dipolar effects in SQ molecules identified by density functional theory calculations, whereas no aligned interfacial dipole moment exists in the random structure. The resulting interfacial dipole moments would form an electric field at the D/A interface, leading to variations in the IP and thus impacting V(OC). Our findings demonstrate that V(OC) in organic photovoltaic cells is critically associated with the molecular orientation that affects the charge-carrier recombination and interfacial dipole alignment, which should be seriously taken into consideration for the design of organic molecules and optimization of the cell efficiency.

Simple push coating of polymer thin-film transistors.

Solution processibility is a unique advantage of organic semiconductors, permitting the low-cost production of flexible electronics under ambient conditions. However, the solution affinity to substrate surfaces remains a serious dilemma; liquid manipulation is more difficult on highly hydrophobic surfaces, but the use of such surfaces is indispensable for improving device characteristics. Here we demonstrate a simple technique, which we call 'push coating', to produce uniform large-area semiconducting polymer films over a hydrophobic surface with eliminating material loss. We utilize a poly(dimethylsiloxane)-based trilayer stamp whose conformal contact with the substrate enables capillarity-induced wetting of the surface. Films are formed through solvent sorption and retention in the stamp, allowing the stamp to be peeled perfectly from the film. The planar film formation on hydrophobic surfaces also enables subsequent fine film patterning. The technique improves the crystallinity and field-effect mobility of stamped semiconductor films, constituting a major step towards flexible electronics production.

Soluble fullerene-based n-channel organic thin-film transistors printed by using a polydimethylsiloxane stamp.

A polydimethylsiloxane stamp was applied for the first time to the fabrication of n-channel thin-film transistors based on soluble small molecule organic semiconducting materials. The stamping method was found to facilitate film transfer onto a gate insulator surface irrespective of its surface free energy. We used [6,6]-phenyl-C(61)-butyric acid methyl ester (PCBM) and C(60)-fused N-methylpyrrolidine-meta-dodecyl phenyl (C60MC12) as n-channel materials. The stamped thin-film transistors of C60MC12 achieved a high electron mobility of 0.39 cm(2)/(V s) and a current on-off ratio of 1 × 10(7). The mobility of the stamped C60MC12 thin-film transistors did not depend much on the surface free energy of the SiO(2) gate insulator with and without surface treatment using a silane-coupling reagent. In particular, the stamped C60MC12 thin-film transistor exhibited a relatively high mobility of 0.1 cm(2)/(V s) on a high energy surface of untreated SiO(2). In addition, a complementary inverter composed of an n-channel and a p-channel stamped thin-film transistor was demonstrated for the first time, which exhibits a maximum gain of 63 at a supply voltage of 50 V.

Crystal structure of friction-transferred poly(2,5-dioctyloxy-1,4-phenylenevinylene).

Poly(2,5-dioctyloxy-1,4-phenylenevinylene) (DOPPV) was found to form a highly oriented film by a friction-transfer technique. Structural investigation of friction-transferred DOPPV was studied by means of polarized ultraviolet-visible (UV-vis) absorption spectroscopy, polarized photoluminescence (PL) spectroscopy, and synchrotron-sourced grazing incident X-ray diffraction (GIXD) analysis. The polarized UV-vis absorption and PL spectra indicate clear axial alignment. DOPPV backbones in friction-transferred film are highly aligned along the drawing direction of the friction-transfer. Further information of the molecular arrangement in friction-transferred DOPPV film was investigated by both the out-of-plane and the in-plane GIXD analyses with synchrotron source. The DOPPV molecules in friction-transferred films were perfectly arranged three-dimensionally: the backbones aligned along the drawing direction of friction-transfer, the alkyl side chains lay in the film plane, and the planar backbones were arranged parallel to the film surface. Additionally, two neighboring DOPPV molecules along the direction of inter-backbones separation by alkyl side chains were found to be shifted with respect to one another by the mean distance of half of a monomeric repeat.