Maximum Hole Mobility Research Articles

Enhanced Carrier Transport Performance of Monolayer Hafnium Disulphide by Strain Engineering.

For semiconducting two-dimensional transition metal dichalcogenides (TMDs), the carrier transport properties of the material are affected by strain engineering. In this study, we investigate the carrier mobility of monolayer hafnium disulphide (HfS2) under different biaxial strains by first-principles calculations combined with the Kubo-Greenwood mobility approach and the compact band model. The decrease/increase in the effective mass of the conduction band (CB) of monolayer HfS2 caused by biaxial tensile/compressive strain is the major reason for the enhancement/degradation of its electron mobility. The lower hole effective mass of the valence bands (VB) in monolayer HfS2 under biaxial compressive strain improves its hole transport performance compared to that under biaxial tensile strain. In summary, biaxial compressive strain causes a decrease in both the effective mass and phonon scattering rate of monolayer HfS2, resulting in an increase in its carrier mobility. Under the biaxial compressive strain reaches 4%, the electron mobility enhancement ratio of the CB of monolayer HfS2 is ~90%. For the VB of monolayer HfS2, the maximum hole mobility enhancement ratio appears to be ~13% at a biaxial compressive strain of 4%. Our results indicate that the carrier transport performance of monolayer HfS2 can be greatly improved by strain engineering.

(Invited) An Unsymmetrical 5,15-Disubstituted Tetrabenzoporphyrin: Effect of Molecular Symmetry on the Packing Structure and Charge Transporting Property

One of the key issues in the development of organic field-effect transistor (OFET) materials is the improvement of charge mobility. Since charge mobility depends on intermolecular interactions in solid state, it is important to control the crystal structure. In the current mainstream OFET materials, such as acenes and heteroacenes, which have one-dimensionally (1D) extended polycyclic aromatic frameworks, the effect of substitution on the crystal structure has been intensively studied. On the other hand, some bulky (trialkylsilyl)ethynyl-substituted derivatives such as 6,13-bis(triisopropylsilylethynyl)pentacene (TIPS-pentacene) have been known to afford brickwork packing. In comparison, two-dimensionally (2D) extended π-conjugated molecules tend to form a sandwich herringbone, a co-facial herringbone, and a 1D columnar structure, due to their enhanced π−π interaction. The molecular design strategy to control the crystal structure of two-dimensional (2D) π-extended organic semi-conductors has not been intensively explored.We synthesized an unsymmetric tetrabenzoporphyrin derivative (TIPS-Ph-BP) to demonstrate the effect of molecular symmetry on crystal packing.1 An unsymmetric structure would make 2D π-stacking more stable than a one-dimensional (1D) columnar structure to counteract steric and electronic imbalance in the crystal. TIPS-Ph-BP formed an antiparallel slipped π-stacking and 2D herringbone-like structure as expected, but, it formed a dimeric herringbone packing consisting of slipped π-stacking in an antiparallel manner in the crystal. OFETs using TIPS-Ph-BP achieved the maximum hole mobility of 0.71 cm2 V-1 s-1 due to the partially 2D packing structure.Although TIPS-Ph-BP gave dimeric herringbone packing, this strategy could be used to control the crystal structures of various 2D extended π-conjugated systems. Further modification of the porphyrin substituents is ongoing. Reference K. Miyazaki, K. Matsuo, H. Hayashi, M. Yamauchi, N. Aratani, H. Yamada, Org. Lett. 2023, 25, 7354-7358

Metal-modulated epitaxy of Mg-doped Al0.80In0.20N-based layer for application as the electron blocking layer in deep ultraviolet light-emitting diodes

This work reports the growth and characterization of p-AlInN layers doped with Mg by plasma-assisted molecular beam epitaxy (PAMBE). AlInN was grown with an Al molar fraction of 0.80 by metal-modulated epitaxy (MME) with a thickness of 180 nm on Si(111) substrates using AlN as buffer layers. Low substrate temperatures were used to enhance the incorporation of indium atoms into the alloy without clustering, as confirmed by X-ray diffraction (XRD). Cathodoluminescence measurements revealed ultraviolet (UV) range emissions. Meanwhile, Hall effect measurements indicated a maximum hole mobility of 146 cm2/(V∙s), corresponding to a free hole concentration of 1.23 × 1019 cm−3. The samples were analyzed by X-ray photoelectron spectroscopy (XPS) estimating the alloy composition and extracting the Fermi level by valence band analysis. Mg-doped AlInN layers were studied for use as the electron-blocking layer (EBL) in LED structures. We varied the Al composition in the EBL from 0.84 to 0.96 molar fraction to assess its theoretical effects on electroluminescence, carrier concentration, and electric field, using SILVACO Atlas. The results from this study highlight the importance and capability of producing high-quality Mg-doped p-AlInN layers through PAMBE. Our simulations suggest that an Al content of 0.86 is optimal for achieving desired outcomes in electroluminescence, carrier concentration, and electric field.

Polymeric Semiconductor in Field-Effect Transistors Utilizing Flexible and High-Surface Area Expanded Poly(tetrafluoroethylene) Membrane Gate Dielectrics.

Organic field-effect transistors (OFETs) were fabricated using three high-surface area and flexible expanded-poly(tetrafluoroethylene) (ePTFE) membranes in gate dielectrics, along with the semiconducting polymer poly[2,5-bis(2-octyldodecyl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione-3,6-diyl)-alt-(2,2':5',2″:5″,2‴-quaterthiophen-5,5‴-diyl)] (PDPP4T). The transistor behavior of these devices was investigated following annealing at 50, 100, 150, and 200 °C, all sustained for 1 h. For annealing temperatures above 50 °C, the OFETs displayed improved transistor behavior and a significant increase in output current while maintaining similar magnitudes of Vth shifts when subjected to static voltage compared to those kept at ambient temperature. We also tested the response to NO2 gas for further characterization and for possible applications. The ePTFE-PDPP4T interface of each membrane was characterized via scanning electron microscopy for all four annealing temperatures to derive a model for the hole mobility of the ePTFE-PDPP4T OFETs that accounts for the microporous structure of the ePTFE and consequently adjusts the channel width of the OFET. Using this model, a maximum hole mobility of 1.8 ± 1.0 cm2/V s was calculated for the polymer in an ePTFE-PDPP4T OFET annealed at 200 °C, whereas a PDPP4T OFET using only the native silicon wafer oxide as a gate dielectric exhibited a hole mobility of just 0.09 ± 0.03 cm2/V s at the same annealing condition. This work demonstrates that responsive semiconducting polymer films can be deposited on nominally nonwetting and extremely bendable membranes, and the charge carrier mobility can be significantly increased compared to their as-prepared state by using thermally durable polymer membranes with unique microstructures as gate dielectrics.

Temperature dependence of hole mobility in methylated germanane field-effect transistor

Methylated germanane, a layered material in which single-layer germanium is terminated by methyl groups, was utilized as a channel material of back-gate-type FETs. Titanium (Ti) and nickel (Ni) were used as source and drain electrodes of FETs, and the FET with the Ti electrode showed ambipolar characteristics, whereas that with the Ni electrode showed p-type characteristics. The maximum hole mobility at RT is 380 cm2V−1s−1, which is higher than those of typical transition metal dichalcogenides. The mobility changes with temperature T according to the T −3/2 law at temperatures ranging from 243 to 343 K, suggesting that the major scattering factor of holes is acoustic phonons.

Theoretical investigations of the substituent effect on the opto-electronic properties of the linearly fused napthadithiophene-based molecules.

The optoelectronic and charge transport properties of eight linearly fused Napthadithiophene (NDT) molecules with different electron-withdrawing (EWG) and electron-donating (EDG) substituents are studied using the density functional theory (DFT) methods. The effect of the substitution of EWG and EDG on the molecular structure, frontier molecular orbitals, ionization energy, electron affinity, reorganization energy, crystal packing, and charge carrier mobility are studied. The crystal structure simulation method is used to optimize the possible crystal packing arrangements for the studied molecules. The energy and distribution of electron density on the frontier molecular orbitals are strongly influenced by the substitution of EWG and EDG, thereby changes in the absorption spectrum and charge transport properties. The unsubstituted NDT molecule possesses a maximum hole mobility of 2.8 cm2 V-1 s-1, which is due to the strong intermolecular interactions. Therefore, the NDT molecule can be used as a p-type semiconducting material. Among the studied molecules, the CCH-substituted NDT molecule, NDT-CCH, possesses a higher electron mobility of 1.13 cm2 V-1 s-1. The C2H5-substituted NDT molecule, NDT-C2H5, possesses ambipolar behavior with mobility of 4.77 × 10-2 cm2 V-1 s-1 and 1.70 × 10-2 cm2 V-1 s-1 for hole and electron, respectively.

Reversible Transition of Semiconducting PtSe2 and Metallic PtTe2 for Scalable All-2D Edge-Contacted FETs.

Two-dimensional (2D) transition metal dichalcogenide (TMD) layers are highly promising as field-effect transistor (FET) channels in the atomic-scale limit. However, accomplishing this superiority in scaled-up FETs remains challenging due to their van der Waals (vdW) bonding nature with respect to conventional metal electrodes. Herein, we report a scalable approach to fabricate centimeter-scale all-2D FET arrays of platinum diselenide (PtSe2) with in-plane platinum ditelluride (PtTe2) edge contacts, mitigating the aforementioned challenges. We realized a reversible transition between semiconducting PtSe2 and metallic PtTe2 via a low-temperature anion exchange reaction compatible with the back-end-of-line (BEOL) processes. All-2D PtSe2 FETs seamlessly edge-contacted with transited metallic PtTe2 exhibited significant performance improvements compared to those with surface-contacted gold electrodes, e.g., an increase of carrier mobility and on/off ratio by over an order of magnitude, achieving a maximum hole mobility of ∼50.30 cm2 V-1 s-1 at room temperature. This study opens up new opportunities toward atomically thin 2D-TMD-based circuitries with extraordinary functionalities.

(Invited) Effect of Oxygen on Activation Annealing of Mg-Doped GaN

The effects of N2 and O2:N2 (1:1) as ambient gases during activation annealing of Mg as p-type doping of GaN grown by MOCVD are investigated. The purpose is to understand the mechanisms involved and especially the impact of O2 on the resulting free hole concentration and hole mobility. The addition of O2 to the ambient gas during annealing is very effective in reducing the H level of the Mg-doped GaN layer, especially at lower activation temperatures, but the maximum achievable hole concentration and mobility, as determined by Hall characterization, is still higher with pure N2.The difference between activation in pure N2 or O2:N2 (1:1) ambient a is explained by an in-diffusion of O to the GaN layer acting as n-dopant and thus giving rise to a compensation effect. It is found that to a large degree only the Mg-H complexes at substitutional (MgGa), i.e., the electrically active acceptor sites that provide free holes, are activated by annealing with N2 only as ambient gas, while annealing with O2:N2 (1:1) also dissociates electrically inactive Mg-H complexes resulting in much less residual H. Thus, the residual H level in relation to the Mg level after activation annealing with N2 only may provide a representative measure of the resulting free hole concentration of the Mg-doped GaN layer.An additional factor to be taken into account for in order to maximize the hole concentration is the growth pressure. At the lower growth pressure of 150 mbar compared to higher growth pressure of 300 mbar, an increasing carbon incorporation leads to a compensation effect drastically reducing the free hole concentration while the mobility is unaffected. Conclusions Addition of O2 during RTP is very effective in reducing the H level however, the maximum hole concentration and mobility are still higher with pure N2.Mg-H complexes at substitutional (MgGa) electrically active acceptor are preferentially dissociated by annealing with N2 as ambient gas.By employing a higher growth pressure, carbon incorporation that leads to a compensation effect drastically reducing the free hole concentration can be minimized.By activation annealing with N2 the residual H level provides a measure of the free hole concentration. Figure 1

Quaternary, layered, 2D chalcogenide, Mo1−x W x SSe: thickness dependent transport properties

Highly oriented, single crystalline, quaternary alloy chalcogenide crystal, Mo x W1−x S2y Se2(1−y), is synthesized using a high temperature chemical vapor transport technique and its transport properties studied over a wide temperature range. Field effect transistors (FET) with bottom gated configuration are fabricated using Mo0.5W0.5SSe flakes of different thicknesses, from a single layer to bulk. The FET characteristics are thickness tunable, with thin flakes (1–4 layers) exhibiting n-type transport behaviour while ambipolar transfer characteristics are observed for thicker flakes (>90 layers). Ambipolar behavior with the dominance of n-type over p-type transport is noted for devices fabricated with layers between 9 and 90. The devices with flake thickness ∼9 layers exhibit a maximum electron mobility 63 ± 4 cm2 V−1s−1 and an I ON/I OFF ratio >108. A maximum hole mobility 10.3 ± 0.4 cm2 V−1s−1 is observed for the devices with flake thickness ∼94 layers with I ON/I OFF ratio >102–103 observed for the hole conduction. A maximum I ON/I OFF for hole conduction, 104 is obtained for the devices fabricated with flakes of thickness ∼7–19 layers. The electron Schottky barrier height values are determined to be ∼23.3 meV and ∼74 meV for 2 layer and 94 layers flakes respectively, as measured using low temperature measurements. This indicates that an increase in hole current with thickness is likely to be due to lowering of the band gap as a function of thickness. Furthermore, the contact resistance (R ct) is evaluated using transmission line model (TLM) and is found to be 14 kohm.μm. These results suggest that quaternary alloys of Mo0.5W0.5SSe are potential candidates for various electronic/optoelectronic devices where properties and performance can be tuned within a single composition.

A study of bottom-contact organic thin-film transistors based on source/drain tunneling structure

During recent years, OLED display has become one of the important products for consuming electronics and industrial domains. For AMOLED display, thin film transistor (TFT) is necessary for driving OLED devices. As the polysilicon and amorphous silicon TFTs have become mainstreams, organic thin film transistors (OTFTs) have also been proposed and shown their advantages in low-temperature process compatible with flexible substrates. However, OTFTs applicable to drive OLED generally adopt bottom-contact configuration. The performance of bottom-contact OTFTs are often inferior relative to top-contact OTFTs, due primarily to the high contact resistance of bottom-contact OTFTs. To overcome this disadvantage, the source/drain tunneling structure is proposed in this article. This tunneling structure can not only decorate the electrode/organic semiconductor interface to obtain a good metal-semiconductor contact, but also can form a MOS configuration at source/drain contact, so as to increase the carrier concentration at the contact to further reduce contact resistance. In this paper, a typical P-type high-mobility small molecule material of Pentacene is employed as the active layer of the OTFT, while CuO film, Polystyrene (PS) film is separately selected as the tunneling layer at source/drain contact. The diverse parameters, especially field effect mobility, were analyzed by analyzing electrical characteristics of the top-contact and bottom-contact OTFTs. In addition, the contact resistances were confirmed by line transfer method. The bottom-contact OTFTs incorporating tunneling layer own a maximum hole mobility of 0.143cm2/V·s.This suggested that the source/drain tunneling structure can indeed improve the electrical characteristics of bottom-contact OTFT, and further improvement is necessitated to achieve the high performance comparable to top-contact device.

Donor-Acceptor-Based Organic Polymer Semiconductor Materials to Achieve High Hole Mobility in Organic Field-Effect Transistors.

Organic polymer semiconductor materials are conveniently tuned to energy levels because of their good chemically modifiable properties, thus enhancing their carrier transport capabilities. Here, we have designed and prepared a polymer with a donor-acceptor structure and tested its potential as a p-type material for organic field-effect transistor (OFET) applications using a solution-processing method. The conjugated polymers, obtained via the polymerization of the two monomers relying on the Stille coupling reaction, possess extremely high molecular weights and thermodynamic stability. Theoretical-based calculations show that PDPP-2S-Se has superior planarity, which is favorable for carrier transport within the main chain. Photophysical and electrochemical measurements systematically investigated the properties of the material and the energy levels with respect to the theoretical values. The maximum hole mobility of the PDPP-2S-Se-based OFET device is 0.59 cm2 V-1 s-1, which makes it a useful material for potential organic electronics applications.

Indolocarbazoles with Sterically Unrestricted Electron-Accepting Anchors Showcasing Aggregation-Induced Thermally Activated Delayed Mechanoluminescence for Host-Free Organic Light-Emitting Diodes.

We investigated the effects of sterically nonrestricted electron-accepting substituents of three isomeric indolocarbazole derivatives on their aggregation-induced emission enhancement, mechanochromic luminescence and thermally activated delayed fluorescence. The compounds are potentially efficient emitters for host-free organic light-emitting diodes. The films of indolocarbazole derivatives exhibit emissions with wavelengths of fluorescence intensity maxima from 483 to 500 nm and photoluminescence quantum yields from 31 to 58%. The ionization potentials of the solid samples, measured by photoelectron emission spectrometry, are in the narrow range of 5.78-5.99 eV. The electron affinities of the solid samples are in the range of 2.99-3.19 eV. The layers of the derivatives show diverse charge-transporting properties with maximum hole mobility reaching 10-4 cm2/Vs at high electric fields. An organic light-emitting diode with a light-emitting layer of neat compound shows a turn-on voltage of 4.1 V, a maximum brightness of 24,800 cd/m2, a maximum current efficiency of 12.5 cd/A and an external quantum efficiency of ca. 4.8%. When the compounds are used as hosts, green electroluminescent devices with an external quantum efficiency of ca. 11% are obtained. The linking topology of the isomeric derivatives of indolo[2,3-a]carbazole and indolo[3,2-b]carbazole and the electron-accepting anchors influences their properties differently, such as aggregation-induced emission enhancement, mechanochromic luminescence, thermally activated delayed fluorescence, charge-transporting, and electroluminescent properties. The derivative indolo[3,2-b]carbazole displays good light-emitting properties, while the derivatives of indolo[2,3-a]carbazole show good hosting properties, which make them useful for application in electroluminescent devices.

P-Type Conjugated Polymers Containing Electron-Deficient Pentacyclic Azepinedione.

Bisthienoazepinedione (BTA) has been reported for constructing high-performing p-type conjugated polymers in organic electronics, but the ring extended version of BTA is not well explored. In this work, we report a new synthesis of a key building block to the ring expanded electron-deficient pentacyclic azepinedione (BTTA). Three copolymers of BTAA with benzodithiophene substituted by different side chains are prepared. These polymers exhibit similar energy levels and optical absorption in solution and solid state, while significant differences are revealed in their film morphologies and behavior in transistor and photovoltaic devices. The best-performing polymers in transistor devices contained alkylthienyl side chains on the BDT unit (pBDT-BTTA-2 and pBDT-BTTA-3) and demonstrated maximum saturation hole mobilities of 0.027 and 0.017 cm2 V-1 s-1. Blends of these polymers with PC71BM exhibited a best photovoltaic efficiency of 6.78% for pBDT-BTTA-3-based devices. Changing to a low band gap non-fullerene acceptor (BTP-eC9) resulted in improved efficiency of up to 13.5%. Our results are among the best device performances for BTA and BTTA-based p-type polymers and highlight the versatile applications of this electron-deficient BTTA unit.

Acceptor activation of Mg-doped GaN—Effects of N2/O2 vs N2 as ambient gas during annealing

Here, we investigate the effects of O2:N2 (1:1) as ambient gas as compared with pure N2 during activation annealing of Mg as p-type doping in GaN layers grown by MOCVD. The purpose is to understand the impact of O2 on the resulting free hole concentration and hole mobility using SIMS, XRD, STEM, AFM, and Hall effect measurements. Even though the presence of O2 in the ambient gas during annealing is very effective in reducing the H level of the Mg-doped GaN layers, the maximum achievable hole concentration and mobility is still higher with pure N2. The differences are explained by an in-diffusion of O to the GaN layer acting as n-dopant and, thus, giving rise to a compensation effect. The Mg–H complexes at substitutional (MgGa), i.e., the electrically active acceptor sites that provide free holes, are preferentially activated by annealing with N2 only as ambient gas, while annealing with O2:N2 (1:1) also dissociates electrically inactive Mg–H complexes resulting in much less residual H. At the lower growth pressure of 150 mbar compared to higher growth pressure of 300 mbar, an increasing carbon incorporation leads to a compensation effect drastically reducing the free hole concentration while the mobility is unaffected.

Thickness-dependent carrier transport of PdSe2 films grown by plasma-assisted metal selenization

Atomically thin narrow-bandgap layered PdSe2 has attracted much attention due to its rich and unique electrical properties. For silicon-compatible device integration, direct wafer-scale preparation of high-quality PdSe2 thin film on a silicon substrate is highly desired. Here, we present the low-temperature synthesis of large-area polycrystalline PdSe2 films grown on SiO2/Si substrates by plasma-assisted metal selenization and investigate their charge carrier transport behaviors. Raman analysis, depth-dependent x-ray photoelectron spectroscopy, and cross-sectional transmission electron microscopy were used to reveal the selenization process. The results indicate a structural evolution from initial Pd to intermediate PdSe2–x phase and eventually to PdSe2. The field-effect transistors fabricated from these ultrathin PdSe2 films exhibit strong thickness-dependent transport behaviors. For thinner films (4.5 nm), a record high on/off ratio of 104 was obtained. While for thick ones (11 nm), the maximum hole mobility is about 0.93 cm2 V−1 S−1, which is the record high value ever reported for polycrystalline films. These findings suggest that our low-temperature-metal-selenized PdSe2 films have high quality and show great potential for applications in electrical devices.

Designing of anthracene-arylamine hole transporting materials for organic and perovskite solar cells

This study focuses on the creation of 5 small donor molecules (A102W1-A102W5) by substituting the one-sided methoxy group of model (A102R) with different thiophene bridged acceptor moieties. B3LYP/6–31**G (d,p) model has been employed for computational analysis. The best miscibility was found for A102W3 in dichloromethane (DCM) solvent, where its λmax was also found to be at 753 nm, its Eg was found to be 1.55 eV as well as dipole moment in DCM was 21.47 D. The percentage of PCE among all the variants was greatest for A102W2 (25.31%). The electron reorganization energy shown by A102W4 was 0.00470 eV, whereas the hole reorganization energy investigated in A102W2 was 0.00586 eV representing their maximum electron and hole mobility respectively amongst all. Results validate the value of specified techniques, opening a new door to create efficient small donors for OSCs and HTMs for PSCs.

Synthesis and properties of 10,20-bis(triisopropylsilylethynyl)-tetrabenzo-5,15-diazaporphine

A 10,20-bis(triisopropylsilylethynyl)tetrabenzo-5,15-diazaporphine (TIPS-TBDAP) was synthesized by the metal-template aza-annulation reaction. TIPS-TBDAP showed intense far-red fluorescence at 723 nm with a fluorescence quantum yield of 31% in chloroform solution. X-ray diffraction analysis revealed that TIPS-TBDAP forms a one-dimensional slipped [Formula: see text]-stacking structure in the single crystal state. TIPS-TBDAP is soluble in common organic solvents owing to the bulky substituents and solution-processed field-effect transistors (FETs) could be fabricated. Dip-coating and single-crystal FETs showed the maximum hole mobilities of 1.5× 10[Formula: see text] and 0.16 cm2 V[Formula: see text] s[Formula: see text], respectively.

π-Extended Rubrenes via Dearomative Annulative π-Extension Reaction.

Among a large variety of organic semiconducting materials, rubrene (5,6,11,12-tetraphenyltetracene) represents one of the most prominent molecular entities mainly because of its unusually high carrier mobility. Toward finding superior rubrene-based organic semiconductors, several synthetic strategies for related molecules have been established. However, despite its outstanding properties and significant attention in the field of materials science, late-stage functionalizations of rubrene remains undeveloped, thereby limiting the accessible chemical space of rubrene-based materials. Herein, we report on a late-stage π-extension of rubrene by dearomative annulative π-extension (DAPEX), leading to the generation of rubrene derivatives having an extended acene core. The Diels-Alder reaction of rubrene with 4-methyl-1,2,4-triazoline-3,5-dione occurred to give 1:1 and 1:2 cycloadducts which further underwent iron-catalyzed annulative diarylation. The thus-formed 1:1 and 1:2 adducts were subjected to radical-mediated oxidation and thermal cycloreversion to furnish one-side and two-side π-extended rubrenes, respectively. These π-extended rubrenes displayed a marked red shift in absorption and emission spectra, clearly showing that the acene π-system of rubrene was extended not only structurally but also electronically. The X-ray crystallographic analysis uncovered interesting packing modes of these π-extended rubrenes. Particularly, two-side π-extended rubrene adopts a brick-wall packing structure with largely overlapping two-dimensional face-to-face π-π interactions. Finally, organic field-effect transistor devices using two-side π-extended rubrene were fabricated, and their carrier mobilities were measured. The observed maximum hole mobility of 1.49 × 10-3 cm2V-1 s-1, which is a comparable value to that of the thin-film transistor using rubrene, clearly shows the potential utility of two-side π-extended rubrene in organic electronics.

How does changing substituents affect the hole transport characteristic of butterfly-shaped materials based on fluorene–dithiophene core for perovskite photovoltaics

Ten butterfly-shaped compounds based on fluorene–dithiophene (FDT) core containing para-substituted N,N-phenylamine moieties were designed as hole transporting materials (HTMs) for perovskite solar cells (PSCs). Among different HTMs, only HOMO level of NO2 containing molecule was placed lower than the that of CH3NH3PbI3 (MAPbI3) perovskite which confirmed all materials but the NO2 substituted compound could efficiently inject holes from the MAPbI3 towards the Au cathode electrode. Also, the LUMO levels of all HTMs indicated higher energies compared to that of MAPbI3 verifying inhibited electron backward transport to the Au cathode electrode. The HTM with NMe2 substituent showed maximum hole mobility of 1.033 × 10−3 cm2V−1s−1 which was greater than those of the reference FDT-OMe HTM and Spiro-OMeTAD. The FDT-H illustrated the biggest open-circuit voltage (VOC), fill factor (FF) and power conversion efficiency (PCE) of 1.149 V, 0.895 and 23.342%, respectively, establishing it could be the best HTM candidate for high performance MAPbI3-based PSCs. The photovoltaic parameters of PSCs containing formamidinium lead iodide (FAPbI3) and FDT-core or Spiro-OMeTAD HTMs were superior to those of the MAPbI3-based solar cells.

Alkyl-Substituted N,S-Embedded Heterocycloarenes with a Planar Aromatic Configuration for Hosting Fullerenes and Organic Field-Effect Transistors.

Cycloarenes and heterocycloarenes display unique physical structures and hold great potential as organic semiconductors. However, the synthesis of (hetero)cycloarenes remains a big challenge, and there are limited reports on their applications. Herein, a series of nitrogen- and sulfur-codoped cycloarenes NS-Octulene-n (n = 2, 3, 4) with branched alkyl substituents containing linear spacer groups from C2 to C4 have been conveniently synthesized. Compared with their isoelectronic analogues Octulene and S-Octulene, both having a saddle-shaped configuration, the coincorporation of two nitrogen atoms and two sulfur atoms leads to a fully coplanar aromatic backbone structure. Each of these three planar heterocycloarenes acts as a supramolecular host for encapsulation of both fullerenes C60 and C70 with a stronger donor-acceptor interaction for the complexation between the heterocycloarene and C70 due to the unique molecular geometry and defined cavity. Meanwhile, the electron-rich nitrogen atoms also slightly increase the energies of both highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) in this series of planar heterocycloarenes, indicating that they can be used as p-type semiconductors. Most importantly, benefitting from the planar π-conjugated backbone structure accompanied by excellent crystallinity and ordered molecular packing, as well as upon the engineering of the alkyl chain branching position, thin-film field-effect transistors of NS-Octulene-3 with moderate alkyl branching point exhibit the maximum hole mobility of 0.86 cm2 V-1 s-1, which is the highest for (hetero)cycloarene-based organic semiconductors. This study will shed new light on designing novel high-performance macrocyclic polycyclic aromatic hydrocarbon (PAH) semiconductors.