In Situ Formation of Mixed-Dimensional Surface Passivation Layers in Perovskite Solar Cells with Dual-Isomer Alkylammonium Cations.

Dimensional engineering of perovskite solar cells has attracted significant research attention recently because of the potential to improve both device performance and stability. Here, a novel 2D passivation scheme for 3D perovskite solar cells is demonstrated using a mixed cation composition of 2D perovskite based on two different isomers of butylammonium iodide. The dual-cation 2D perovskite outperforms its single cation 2D counterparts in surface passivation quality, resulting in devices with an impressive open-circuit voltage of 1.21 V for a perovskite composition with an optical bandgap of ≈1.6 eV, and a champion efficiency of 23.27%. Using a combination of surface elemental analysis and valence electron spectra decomposition, it is shown that an in situ interaction between the 2D perovskite precursor and the 3D active layer results in surface intermixing of 3D and 2D perovskite phases, providing an effective combination of defect passivation and enhanced charge transfer, despite the semi-insulating nature of the 2D perovskite phase. The demonstration of the synergistic interaction of multiple organic spacer cations in a 2D passivation layer offers new opportunities for further enhancement of device performance with mixed dimensional perovskite solar cells.

Polymer Electrolyte Blend Gate Dielectrics for High-Performance Ultrathin Organic Transistors: Toward Favorable Polymer Blend Miscibility and Reliability.

We report on systematic mobility enhancements in electrolyte-gated organic field-effect transistors (OFETs) by thinning down the active layer and exploiting polymer solid-state electrolyte gate insulators (SEGIs). The SEGI is composed of homogeneous poly(vinylidene fluoride- co-hexafluoropropylene) [P(VDF-HFP)] polymer solution-ion gel blends of high areal capacitance of >10 µF cm-2 at 1 Hz. By scaling up the poly(3-hexylthiophene) (P3HT) semiconducting layer by 1 order of magnitude (5-50 nm), an ultraviolet photoelectron spectroscopy examination reveals a downward vacuum-level shift generating a substantial hole injection barrier that originates from different interfacial dipole layer formations. The ultrathin (5.1 nm) P3HT FETs outperformed the other devices, exhibiting stable device characteristics with a highest field-effect mobility of >2 cm2 V-1 s-1 (effective mobility of 0.83 ± 0.05 cm2 V-1 s-1), on/off ratio of ∼106, low threshold voltage of <-0.6 V, and low gate-leakage current levels of ∼105 below the on-current levels in 10 µm channel length devices. We observed a positive threshold voltage shift in the P3HT/SEGI FETs with decreasing semiconductor thickness. The aforementioned mobility is at least 10 times greater than that of neat P(VDF-HFP) devices. The significant FET performance is attributed to a better insulator/semiconductor interface, efficient hole injection from the Au electrode resulting in a low contact resistance of <500 Ω cm, and boosted charge-carrier densities in the transistor channel. This work demonstrates an excellent approach for carrier mobility enhancement and reliability assessment in low-voltage-operated electrolyte-gated OFETs.

Highly Sensitive Flexible NH3 Sensors Based on Printed Organic Transistors with Fluorinated Conjugated Polymers.

Understanding the sensing mechanism in organic chemical sensors is essential for improving the sensing performance such as detection limit, sensitivity, and other response/recovery time, selectivity, and reversibility for real applications. Here, we report a highly sensitive printed ammonia (NH3) gas sensor based on organic thin film transistors (OTFTs) with fluorinated difluorobenzothiadiazole-dithienosilole polymer (PDFDT). These sensors detected NH3 down to 1 ppm with high sensitivity (up to 56%) using bar-coated ultrathin (<4 nm) PDFDT layers without using any receptor additives. The sensing mechanism was confirmed by cyclic voltammetry, hydrogen/fluorine nuclear magnetic resonance, and UV/visible absorption spectroscopy. PDFDT-NH3 interactions comprise hydrogen bonds and electrostatic interactions between the PDFDT polymer backbone and NH3 gas molecules, thus lowering the highest occupied molecular orbital levels, leading to hole trapping in the OTFT sensors. Additionally, density functional theory calculations show that gaseous NH3 molecules are captured via cooperation of fluorine atoms and dithienosilole units in PDFDT. We verified that incorporation of functional groups that interact with a specific gas molecule in a conjugated polymer is a promising strategy for producing high-performance printed OTFT gas sensors.

Ultrahigh Mobility in Solution-Processed Solid-State Electrolyte-Gated Transistors.

A new concept of a high-capacitance polymeric dielectric based on high-k polymer and ion gel blends is reported. This solid-state electrolyte gate insulator enables remarkable field-effect mobilities exceeding 10 cm2 V-1 s-1 for common polymer and other semiconductor families at VG ≤ 2 V owing to high areal capacitance (>4 µF cm-2 ) from combined polarization of CF interface dipoles and electrical-double-layer formation.