In Situ Measurement of Effective Gate Bias Voltage in Ionic Liquid-Gated Organic Field-Effect Transistors: Exploring Intrinsic Performance and Trap Density of States.

Electric double layer (EDL)-mediated transistors with ionic liquid (IL) gating have garnered substantial interest due to their exceptional properties, such as high transconductance and low-voltage operation, positioning them as promising candidates for organic electronics. In this study, we present an in situ measurement of effective gate bias voltage (VGS,eff) in IL-gated organic field-effect transistors (IL-OFETs) using a modified current-voltage measurement configuration. The results reveal a significant deviation between VGS,eff and the applied gate bias (VGS,app), indicating that the EDL at the gate/IL interface screens the applied voltage. It is observed that the screening effect varies depending on the specific cation and anion present in the IL. The evaluation of VGS,eff plays a pivotal role in understanding the intrinsic behavior of IL-OFETs and addresses the challenges associated with accurate performance assessment. Inherently, IL-OFETs demonstrate high transconductance, achieving values of approximately 9 mS while operating at a low threshold voltage of around 0.55 V. Through the acquisition of VGS,eff, we have successfully addressed the limitations impeding the numerical estimation of the trap density of states (trap DOS) in IL-OFETs. Remarkably, our calculations reveal an exceptionally low density of deep traps, which serves as a crucial factor contributing to the near-ideal subthreshold swing (61-68 mV dec-1) observed in IL-OFETs. Further investigations unveil the neutral electrical nature of the IL bulk during OFET operation, confirming the hypothesis that the applied gate bias voltage in electrolyte-gated OFETs drops across the EDLs formed at the interfaces. The impedance spectroscopic (IS) analysis confirms the low contact resistance (≈1 Ω·m) of IL-OFETs calculated using the transition voltage method. The IS analysis also reveals the low-transmissive nature of the IL/organic semiconductor interface. The knowledge gained from this study holds significant implications for realizing high-performance electrolyte-gated OFETs in various applications including digital electronics, energy storage, and sensing. By unraveling the factors influencing the device performance, such as VGS,eff and trap DOS, this research contributes to the advancement of organic electronics and paves the way for future developments in the field.

Covalently linked benzothiadiazole-fullerene adducts for organic optoelectronic devices: synthesis and characterization.

Fullerene adducts have attracted attention in a variety of applications including organic optoelectronic devices. In this regard, we have designed a covalently linked donor-acceptor dyad comprising a fluorobenzothiadiazole-thiophene (BTF2-Th) unit with the electron acceptor fullerene in an Acceptor-Donor-Acceptor (A-D-A) molecular arrangement. We synthesized and characterized two new covalently bonded benzothiadiazole-based fullerene molecules, mono-adduct, 7 (benzothiadiazole : PC61BM = 1 : 1, anchored terminally via esterification reaction) and multi-adduct, 10-I (benzothiadiazole : PC61BM = n : 1, where n ≥ 1, attached directly to the fullerene core via the Prato reaction) using different synthetic strategies. A broadening of the UV-visible spectra of the modified fullerene derivative with strong absorption from 350 to 500 nm and at low wavelengths is observed as compared to PC61BM. A suitable bandgap, good electronic conductivity, and appreciable solubility in solvents suggest their utility in optoelectronic devices. The mono-adduct 7 showed two-order higher electron mobility as compared to bis-adduct 10-I due to retention of extended conjugation in fullerene, as in the case of PC61BM. Experimentally determined optical properties and energy levels of the fullerene adducts were found to be in good agreement and supported by theoretical calculations. The presence of BTF2 affects the ground state dipole moments as well as the absorption strengths, most noticeable in the case of two attached BTF2 moieties. The HOMO and LUMO levels are found to be localized on the fullerene cage with the extension of the HOMO to the BTF2 unit more and the same is noticed in ground state dipole moment in the side-chain functionalized structure. Such structural arrangement provides easy charge transfer between acceptor and donor units to allow a concomitant effect of favorable optoelectronic properties, energy levels of the frontier orbitals, effective exciton dissociation, and charge transport which may reduce processing complexity to advance single material-based future optoelectronic devices.

Electrode and dielectric layer interface device engineering study using furan flanked diketopyrrolopyrrole-dithienothiophene polymer based organic transistors.

We successfully demonstrated a detailed and systematic enhancement of organic field effect transistors (OFETs) performance using dithienothiophene (DTT) and furan-flanked diketopyrrolopyrrole based donor-acceptor conjugated polymer semiconductor namely PDPPF-DTT as an active semiconductor. The self-assembled monolayers (SAMs) treatments at interface junctions of the semiconductor-dielectric and at the semiconductor-metal electrodes has been implemented using bottom gate bottom contact device geometry. Due to SAM treatment at the interface using tailored approach, the significant reduction of threshold voltage (Vth) from - 15.42 to + 5.74 V has been observed. In addition to tuning effect of Vth, simultaneously charge carrier mobility (µFET) has been also enhanced the from 9.94 × 10-4 cm2/Vs to 0.18 cm2/Vs. In order to calculate the trap density in each OFET device, the hysteresis in transfer characteristics has been studied in detail for bare and SAM treated devices. Higher trap density in Penta-fluoro-benzene-thiol (PFBT) treated OFET devices enhances the gate field, which in turn controls the charge carrier density in the channel, and hence gives lower Vth = + 5.74 V. Also, PFBT treatment enhances the trapped interface electrons, which helps to enhance the mobility in this OFET architecture. The overall effect has led to possibility of reduction in the Vth with simultaneous enhancements of µFET in OFETs, following systematic device engineering methodology.

Investigation of the buried planar interfaces in multi-layered inverted organic solar cells using x-ray reflectivity and impedance spectroscopy.

The hole and electron extracting interlayers in the organic solar cells (OSCs) play an important role in high performing devices. The present work focuses on an investigation of Zinc oxide/bulk heterojunction (ZnO/BHJ) and BHJ/MoO x (Molybdenum oxide) buried planar interfaces in inverted OSC devices using the optical contrast in various layers along with the electrical measurements. The x-ray reflectivity (XRR) analysis demonstrates the formation of additional intermixing layers at the interfaces of ZnO/BHJ and BHJ/MoO x . Our results indicate infusion of PC71BM into ZnO layer up to ~4 nm which smoothen the ZnO/BHJ interface. In contrast, thermally evaporated MoO x molecules diffuse into PTB7-Th dominant upper layers of BHJ active layer resulting in an intermixed layer at the interface of MoO x /BHJ. The high recombination resistance (~5 kΩ cm2) and electron lifetime (~70 µs), obtained from the impedance spectroscopy (IS), support such vertical segregation of PTB7-Th and PC71BM in the active layer. The OSC devices, processed in ambient condition, exhibit high power conversion efficiency of 6.4%. We consider our results have great significance to understand the structure of buried planar interfaces at interlayers and their correlation with the electrical parameters representing various interfacial mechanisms of OSCs.

Strategical Designing of Donor-Acceptor-Donor Based Organic Molecules for Tuning Their Linear Optical Properties.

Low-energy linear absorption spectrum of a series of 48 donor-acceptor-donor (D-A-D) scheme based thiophone-benzo(bis-)X-diazole molecules with X = O, S, Se, or Te are calculated using time dependent density functional theory in order to propose strategical design of molecules that can efficiently absorb light in the infrared and visible region of the solar spectrum. Our study establishes that optical properties of the D-A-D based organic molecules significantly depend on the donor-to-acceptor (D/A) ratio and the strength of the acceptor moiety. Thus, by choice of a suitable D/A ratio and type of the acceptor moiety, the linear absorption spectrum can be largely shifted, in general, while the optical gap can be engineered over a wide energy range of ∼0.2-2.3 eV, in particular. It is also noticed that the increase in acceptor units (i.e., when D/A ≤ 1) leads to increase in steric hindrance in between them. This, in turn, disrupts the effective conjugation length and increases the optical gap. However, this effect is found to dominate strongly in the bis-configurations of the molecules as compared to the nonbis compositions. In order to reduce this effect for rational designing of effective D-A-D type chromophores with less steric hindrance, the role of π-conjugated ethylene (-CH═CH-) linkage/spacer between the A-A units is explored further. Here, it is found that introduction of such linkage substantially decreases the steric hindrance and, thereby, the optical gap as well. Besides this, our study also highlights and explains the impact of the acceptor moiety in improving the absorption capabilities of these molecules in the low-energy region.

Vinylene and benzo[c][1,2,5]thiadiazole: effect of the π-spacer unit on the properties of bis(2-oxoindolin-3-ylidene)-benzodifuran-dione containing polymers for n-channel organic field-effect transistors.

Two polymers based on (3E,7E)-3,7-bis(2-oxoindolin-3-ylidene)benzo[1,2-b:4,5-b']difuran-2,6(3H,7H)-dione (BIBDF) coupled with (E)-2-(2-(thiophen-2-yl)vinyl)thiophene (TVT) or dithienylbenzothiadiazole (TBT), namely PBIBDF-TVT and PBIBDF-TBT were synthesized via the Stille coupling reaction. The effect of benzothiadiazole or vinylene-π spacer of the copolymers on optical properties, energy levels, electronic device performance and microstructure were studied. It was found that PBIBDF-TBT based OFET devices, annealed at 180 °C, showed better performance with the highest electron mobility of 2.9 × 10-2 cm2 V s-1 whereas PBIBDF-TVT polymer exhibited 5.0 × 10-4 cm2 V s-1. The two orders of magnitude higher electron mobility of PBIBDF-TBT over PBIBDT-TVT is a clear indicator of the better charge transport ability of this polymer semiconductor arising from its higher crystallinity and better donor-acceptor interaction.

A benzothiadiazole end capped donor-acceptor based small molecule for organic electronics.

A benzothiadiazole end-capped small molecule 3,6-bis(5-(benzo-[c][1,2,5]thiadiazol-4-yl)thiophen-2-yl)-2,5-bis(2-butyloctyl)pyrrolo-[3,4-c]pyrrole-1,4(2H,5H)-dione (BO-DPP-BTZ) using a fused aromatic moiety DPP (at the centre) is designed and synthesized. BO-DPP-BTZ is a donor­acceptor­donor (D­A­D) structure which possesses a band gap of 1.6 eV and exhibits a strong solid state ordering inferred from ~120 nm red shift of the absorption maxima from solution to thin film. Field-effect transistors utilizing a spin coated thin film of BO-DPP-BTZ as an active layer exhibited a hole mobility of 0.06 cm(2) V(-1) s(-1). Solution-processed bulk heterojunction organic photovoltaics employing a blend of BO-DPP-BTZ and [70]PCBM demonstrated a power conversion efficiency of 0.9%.

A furan-containing conjugated polymer for high mobility ambipolar organic thin film transistors.

Furan substituted diketopyrrolopyrrole (DBF) combined with benzothiadiazole based polymer semiconductor PDPP-FBF has been synthesized and evaluated as an ambipolar semiconductor in organic thin-film transistors. Hole and electron mobilities as high as 0.20 cm(2) V(-1) s(-1) and 0.56 cm(2) V(-1) s(-1), respectively, are achieved for PDPP-FBF.

Poly(2,5-bis(2-octyldodecyl)-3,6-di(furan-2-yl)-2,5-dihydro-pyrrolo[3,4-c]pyrrole-1,4-dione-co-thieno[3,2-b]thiophene): a high performance polymer semiconductor for both organic thin film transistors and organic photovoltaics.

A new diketopyrrolopyrrole (DPP)-containing donor-acceptor polymer, poly(2,5-bis(2-octyldodecyl)-3,6-di(furan-2-yl)-2,5-dihydro-pyrrolo[3,4-c]pyrrole-1,4-dione-co-thieno[3,2-b]thiophene) (PDBF-co-TT), is synthesized and studied as a semiconductor in organic thin film transistors (OTFTs) and organic photovoltaics (OPVs). High hole mobility of up to 0.53 cm(2) V(-1) s(-1) in bottom-gate, top-contact OTFT devices is achieved owing to the ordered polymer chain packing and favoured chain orientation, strong intermolecular interactions, as well as uniform film morphology of PDBF-co-TT. The optimum band gap of 1.39 eV and high hole mobility make this polymer a promising donor semiconductor for the solar cell application. When paired with a fullerene acceptor, PC71BM, the resulting OPV devices show a high power conversion efficiency of up to 4.38% under simulated standard AM1.5 solar illumination.

Annealing-free high-mobility diketopyrrolopyrrole-quaterthiophene copolymer for solution-processed organic thin film transistors.

A donor-acceptor polymer semiconductor, PDQT, comprising diketopyrrolopyrrole (DPP) and ß-unsubstituted quaterthiophene (QT) for organic thin film transistors (OTFTs) is reported. This polymer forms ordered layer-by-layer lamellar packing with an edge-on orientation in thin films even without thermal annealing. The strong intermolecular interactions arising from the fused aromatic DPP moiety and the DPP-QT donor-acceptor interaction facilitate the spontaneous self-assembly of the polymer chains into close proximity and form a large π-π overlap, which are favorable for intermolecular charge hopping. The well-interconnected crystalline grains form efficient intergranular charge transport pathways. The desirable chemical, electronic, and morphological structures of PDQT bring about high hole mobility of up to 0.97 cm(2)/(V·s) in OTFTs with polymer thin films annealed at a mild temperature of 100 °C and similarly high mobility of 0.89 cm(2)/(V·s) for polymer thin films even without thermal annealing.