Odd-Even Alkyl Chain Effects on the Structure and Charge Carrier Transport of Two-Dimensional Sn-Based Perovskite Semiconductors.

Oscillations in the chemical or physical properties of materials, composed of an odd or even number of connected repeating methylene units, are a well-known phenomenon in organic chemistry and materials science. So far, such behavior has not been reported for the important class of materials, perovskite semiconductors. This work reports a distinct odd-even oscillation of the molecular structure and charge carrier transport properties of phenylalkylammonium two-dimensional (2D) Sn-based perovskites in which the alkyl chains in the phenylalkylammonium cations contain varying odd and even carbon numbers. Density functional theory calculations and grazing-incidence wide-angle X-ray scattering characterization reveal that perovskites with organic ligands containing an alkyl chain with an odd number of carbon atoms display a disordered crystal lattice and tilted inorganic octahedra accompanied by reduced mobilities. In contrast, perovskites with cations of an even number of carbon atoms in the alkyl chain form more ordered crystal structures, resulting in improved charge carrier mobilities. Our findings disclose the importance of minor changes in the molecular conformation of organic cations have an effect on morphology, photophysical properties, and charge carrier transport of 2D layered perovskites, showcasing alkyl chain engineering of organic cations to control key properties, of layered perovskite semiconductors.

Unveiling the role of linear alkyl organic cations in 2D layered tin halide perovskite field-effect transistors.

Two-dimensional (2D) tin halide perovskites are promising semiconductors for field-effect transistors (FETs) owing to their fascinating electronic properties. However, the correlation between the chemical nature of organic cations and charge carrier transport is still far from understanding. In this study, the influence of chain length of linear alkyl ammonium cations on film morphology, crystallinity, and charge transport in 2D tin halide perovskites is investigated. The carbon chain lengths of the organic spacers vary from propylammonium to heptanammonium. The increase of alkyl chain length leads to enhanced local charge carrier transport in the perovskite film with mobilities of up to 8 cm2 V-1 s-1, as confirmed by optical-pump terahertz spectroscopy. A similar improved macroscopic charge transport is also observed in FETs, only to the chain length of HA, due to the synergistic enhancement of film morphology and molecular organization. While the mobility increases with the temperature rise from 100 K to 200 K due to the thermally activated transport mechanism, the device performance decreases in the temperature range of 200 K to 295 K because of ion migration. These results provide guidelines on rational design principles of organic spacer cations for 2D tin halide perovskites and contribute to other optoelectronic applications.

Bottom-up Solution Synthesis of Graphene Nanoribbons with Precisely Engineered Nanopores.

The incorporation of nanopores into graphene nanostructures has been demonstrated as an efficient tool in tuning their band gaps and electronic structures. However, precisely embedding the uniform nanopores into graphene nanoribbons (GNRs) at the atomic level remains underdeveloped especially for in-solution synthesis due to the lack of efficient synthetic strategies. Herein we report the first case of solution-synthesized porous GNR (pGNR) with a fully conjugated backbone via the efficient Scholl reaction of tailor-made polyphenylene precursor (P1) bearing pre-installed hexagonal nanopores. The resultant pGNR features periodic subnanometer pores with a uniform diameter of 0.6 nm and an adjacent-pores-distance of 1.7 nm. To solidify our design strategy, two porous model compounds (1 a, 1 b) containing the same pore size as the shortcuts of pGNR, are successfully synthesized. The chemical structure and photophysical properties of pGNR are investigated by various spectroscopic analyses. Notably, the embedded periodic nanopores largely reduce the π-conjugation degree and alleviate the inter-ribbon π-π interactions, compared to the nonporous GNRs with similar widths, affording pGNR with a notably enlarged band gap and enhanced liquid-phase processability.

Modification of Two-Dimensional Tin-Based Perovskites by Pentanoic Acid for Improved Performance of Field-Effect Transistors.

Understanding and controlling the nucleation and crystallization in solution-processed perovskite thin films are critical to achieving high in-plane charge carrier transport in field-effect transistors (FETs). This work demonstrates a simple and effective additive engineering strategy using pentanoic acid (PA). Here, PA is introduced to both modulate the crystallization process and improve the charge carrier transport in 2D 2-thiopheneethylammonium tin iodide ((TEA)2 SnI4 ) perovskite FETs. It is revealed that the carboxylic group of PA is strongly coordinated to the spacer cation TEAI and [SnI6 ]4- framework in the perovskite precursor solution, inducing heterogeneous nucleation and lowering undesired oxidation of Sn2+ during the film formation. These factors contribute to a reduced defect density and improved film morphology, including lower surface roughness and larger grain size, resulting in overall enhanced transistor performance. The reduced defect density and decreased ion migration lead to a higher p-channel charge carrier mobility of 0.7 cm2 V-1 s-1 , which is more than a threefold increase compared with the control device. Temperature-dependent charge transport studies demonstrate a mobility of 2.3 cm2 V-1 s-1 at 100 K due to the diminished ion mobility at low temperatures. This result illustrates that the additive strategy bears great potential to realize high-performance Sn-based perovskite FETs.

Enhanced Performance of Flexible Organic Photovoltaics Based on MoS2 Micro-Nano Array.

In this work, we investigated the influence of MoS2 functioning as an electron transport layer (ETL) on the inverted flexible organic photovoltaics (FOPVs). Three ETLs, including MoS2, lithium quinolate (Liq), and a MoS2/Liq bilayer, were evaporated onto ITO-integrated polyethylene terephthalate substrates (PET-ITO), and the properties of transmittance, water contact angle, and reflectivity of the films were analyzed. The results revealed that MoS2 was helpful to improve the lipophilicity of the surface of the ETL, which was conducive to the deposition of the active layer. In addition, the reflectivity of MoS2 to the light ranging from 400 to 600 nm was the largest among the pristine PET-ITO substrate and the PET-ITO coated with three ETLs, which promoted the efficient use of the light. The efficiency of the FOPV with MoS2/Liq ETL was 73% higher than that of the pristine device. This was attributed to the nearly two-fold amplification of the MoS2 array to the light field, which promoted the FOPV to absorb more light. Moreover, the efficiency of the FOPV with MoS2 was maintained under different illumination angles and bending angles. The results demonstrate the promising applications of MoS2 in the fabrication of FOPVs.

Efficient Organic Light Emitting Diodes Using Solution-Processed Alkali Metal Carbonate Doped ZnO as Electron Injection Layer.

In this study, we demonstrate highly efficient, inverted organic light-emitting diodes (IOLEDs) using solution-processed alkali metal carbonate doped ZnO as an electron injection layer (EIL) and tris-(8-hydroxyquinoline) aluminum (Alq3) as an emitter layer. In order to enhance the electron injection efficiency of the IOLEDs, the ZnO EIL layers were modified by doping various alkali metal carbonate materials, including Li2CO3, Na2CO3, K2CO3, and Cs2CO3, using the low-temperature wet-chemical method. Compared to the control neat ZnO EIL-based IOLEDs, the alkali metal carbonate doped ZnO EIL-based IOLEDs possess obviously improved device performance. An optimal current efficiency of 6.04 cd A-1 were realized from the K2CO3 doped ZnO EIL based IOLED, which is 54% improved compared to that of the neat ZnO EIL based device. The enhancement is ascribed to the increased electron mobility and reduced barrier height for more efficient electron injection. Our results indicate that alkali metal carbonate doped ZnO has promising potential for application in highly efficient solution-processed OLEDs.

Low energy consumption phosphorescent organic light-emitting diodes using phenyl anthracenone derivatives as the host featuring bipolar and thermally activated delayed fluorescence.

A novel host material featuring the characteristics of bipolarity and thermally activated delayed fluorescence, 10-(4-(5,5-dimethylbenzofuro[3,2-c]acridin-13(5H)-yl)phenyl)-10-phenylanthracen-9(10H)-one (DphAn-5BzAc), has been designed and synthesized. By employing this material as the host of green emitter Ir(ppy)2acac, we have fabricated phosphorescent organic light-emitting diodes (PhOLEDs) with two hosting schemes, which are the single host system consisting of DhAn-5BzAc and the co-host system with 1,3-bis(carbazolyl)benzene (mCP). We found that the co-host based PhOLED achieved very low energy consumption values at high brightnesses, which were only 0.5, 5.9 and 94.0 mW m-2 at 100, 1000 and 10 000 cd m-2, respectively. The extremely low energy consumption for DhAn-based PhOLEDs were attributed to the excellent bipolar transport properties and thermally activated delayed fluorescence characteristics.

Efficient and chromaticity-stable flexible white organic light-emitting devices based on organic-inorganic hybrid color-conversion electrodes.

We have developed a novel organic-inorganic hybrid color conversion electrode composed of Ag NWs/poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV) via a solution process, which is the first report on a color conversion electrode for applications in flexible optoelectronics. Using the Ag NWs/MEH-PPV composite film as the anode on polyethylene terephthalate substrate and combined with a blue organic light emitting devices (OLEDs) unit employing bis(3,5-difluoro-2-(2-pyridyl)phenyl-(2-carboxypyridyl)iridium(iii)) (Flrpic) in 1,3-bis(carbazol-9-yl)benzene (mCP) as the emitting layer, a highly efficient and chromaticity-stable color-conversion flexible white OLEDs (WOLEDs) is achieved with a maximum current efficiency of 20.5 cd A-1. To the best of our knowledge, this is the highest efficiency reported for color-conversion based flexible WOLEDs. Our work provides an approach to achieving high-performance flexible WOLEDs devices and demonstrates great potential for lighting and display applications.

Comparison of the Solution and Vacuum-Processed Squaraine:Fullerene Small-Molecule Bulk Heterojunction Solar Cells.

Squaraine dyes have shown promising properties for high performance organic solar cells owing to their advantages of intense absorption and high absorption coefficients in the visible and near-infrared (NIR) regions. In this work, to directly compare the photovoltaic performance of solution- and vacuum-processed small-molecule bulk heterojunction (SMBHJ) solar cells, we employed a squaraine small molecular dye, 2,4-bis[4-(N,N-diisobutylamino)-2,6-dihydroxyphenyl] squaraine (DIBSQ), as an electron donor combined with fullerene acceptors to fabricate SMBHJ cells either from solution or vacuum deposition process. The solution-processed SMBHJ cell possesses a power conversion efficiency (PCE) of ~4.3%, while the vacuum-processed cell provides a PCE of ~6.3%. Comparison of the device performance shows that the vacuum-processed SMBHJ cells possess higher short-circuit current density, fill factor and thus higher PCE than the solution-processed devices, which should be assigned to more efficient charge transport and charge extraction in the vacuum-processed SMBHJ cells. However, solution-processed SMBHJ cells demonstrate more pronounced temperature-dependent device performance and higher device stability. This study indicates the great potential of DIBSQ in photovoltaic application via both of solution and vacuum processing techniques.