A Study of the Drift Phenomena of Gate-Functionalized Biosensors and Dual-Gate-Functionalized Biosensors in Human Serum.

In this paper, we study the drift behavior of organic electrochemical transistor (OECT) biosensors in a phosphate-buffered saline (PBS) buffer solution and human serum. Theoretical and experimental methods are illustrated in this paper to understand the origin of the drift phenomenon and the mechanism of ion diffusion in the sensing layer. The drift phenomenon is explained using a first-order kinetic model of ion adsorption into the gate material and shows very good agreement with experimental data on drift in OECTs. We show that the temporal current drift can be largely mitigated using a dual-gate OECT architecture and that dual-gate-based biosensors can increase the accuracy and sensitivity of immuno-biosensors compared to a standard single-gate design. Specific binding can be detected at a relatively low limit of detection, even in human serum.

Selective Detection of Functionalized Carbon Particles based on Polymer Semiconducting and Conducting Devices as Potential Particulate Matter Sensors.

This paper reports a new mechanism for particulate matter detection and identification. Three types of carbon particles are synthesized with different functional groups to mimic the real particulates in atmospheric aerosol. After exposing polymer-based organic devices in organic field effect transistor (OFET) architectures to the particle mist, the sensitivity and selectivity of the detection of different types of particles are shown by the current changes extracted from the transfer curves. The results indicate that the sensitivity of the devices is related to the structure and functional groups of the organic semiconducting layers, as well as the morphology. The predominant response is simulated by a model that yielded values of charge carrier density increase and charge carriers delivered per unit mass of particles. The research points out that polymer semiconductor devices have the ability to selectively detect particles with multiple functional groups, which reveals a future direction for selective detection of particulate matter.

Blended Conjugated Host and Unconjugated Dopant Polymers Towards N-type All-Polymer Conductors and High-ZT Thermoelectrics.

N-Type thermoelectrics typically consist of small molecule dopant+polymer host. Only a few polymer dopant+polymer host systems have been reported, and these have lower thermoelectric parameters. N-type polymers with high crystallinity and order are generally used for high-conductivity ( σ ${\sigma }$ ) organic conductors. Few n-type polymers with only short-range lamellar stacking for high-conductivity materials have been reported. Here, we describe an n-type short-range lamellar-stacked all-polymer thermoelectric system with highest σ ${\sigma }$ of 78 S-1 , power factor (PF) of 163 µW m-1 K-2 , and maximum Figure of merit (ZT) of 0.53 at room temperature with a dopant/host ratio of 75 wt%. The minor effect of polymer dopant on the molecular arrangement of conjugated polymer PDPIN at high ratios, high doping capability, high Seebeck coefficient (S) absolute values relative to σ ${\sigma }$ , and atypical decreased thermal conductivity ( κ ${\kappa }$ ) with increased doping ratio contribute to the promising performance.

Chemical and Biomolecule Sensing with Organic Field-Effect Transistors.

The strong and controllable chemical sensitivity of organic semiconductors (OSCs) and the amplification capability of transistors in circuits make use of OSC-based field-effect transistors compelling for chemical sensors. Analytes detected and assayed range from few-atom gas-phase molecules that may have adverse health and security implications to biomacromolecules (proteins, nucleic acids) that may be markers for physiological processes and medical conditions. This review highlights recent progress in organic field-effect transistor (OFET) chemical sensors, emphasizing advances from the past 5 years and including aspects of OSC morphology and the role of adjacent dielectrics. Design elements of the OSCs and various formats for the devices are illustrated and evaluated. Challenges associated with the present state of the art and future opportunities are also discussed.

3,4,5-Trimethoxy Substitution on an N-DMBI Dopant with New N-Type Polymers: Polymer-Dopant Matching for Improved Conductivity-Seebeck Coefficient Relationship.

Achieving high electrical conductivity and thermoelectric power factor simultaneously for n-type organic thermoelectrics is still challenging. By constructing two new acceptor-acceptor n-type conjugated polymers with different backbones and introducing the 3,4,5-trimethoxyphenyl group to form the new n-type dopant 1,3-dimethyl-2-(3,4,5-trimethoxyphenyl)-2,3-dihydro-1H-benzo[d]imidazole (TP-DMBI), high electrical conductivity of 11 S cm-1 and power factor of 32 µW m-1 K-2 are achieved. Calculations using Density Functional Theory show that TP-DMBI presents a higher singly occupied molecular orbital (SOMO) energy level of -1.94 eV than that of the common dopant 4-(1, 3-dimethyl-2, 3-dihydro-1H-benzoimidazol-2-yl) phenyl) dimethylamine (N-DMBI) (-2.36 eV), which can result in a larger offset between the SOMO of dopant and lowest unoccupied molecular orbital (LUMO) of n-type polymers, though that effect may not be dominant in the present work. The doped polymer films exhibit higher Seebeck coefficient and power factor than films using N-DMBI at the same doping levels or similar electrical conductivity levels. Moreover, TP-DMBI doped polymer films offer much higher electron mobility of up to 0.53 cm2 V-1 s-1 than films with N-DMBI doping, demonstrating the potential of TP-DMBI, and 3,4,5-trialkoxy DMBIs more broadly, for high performance n-type organic thermoelectrics.

Correction: Solid-state electrical applications of protein and peptide based nanomaterials.

Correction for 'Solid-state electrical applications of protein and peptide based nanomaterials' by Sayak Subhra Panda et al., Chem. Soc. Rev., 2018, 47, 3640-3658.

Analytical Platform To Characterize Dopant Solution Concentrations, Charge Carrier Densities in Films and Interfaces, and Physical Diffusion in Polymers Utilizing Remote Field-Effect Transistors.

Characterizing doping effects in a conductive polymer and physical diffusion in a passive polymer were performed using a remote-gate field-effect transistor (RG FET) detection system that was able to measure the electrical potential perturbation of a polymer film coupled to the gate of a silicon FET. Poly(3-hexylthiophene) (P3HT) film doped using various concentrations of 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ) solutions imposed additional positive potentials on the P3HT RG, resulting in a lower threshold voltage ( Vth) on the n-channel silicon FET. Changes in Vth were related to the induced hole concentrations and hole mobility in P3HT films by using our Vth shifting model for the RG FET. We discovered that the electron-donating P3HT and even inorganic materials, indium tin oxide and gold, showed similar electrical potential perturbations dependent on the concentration of F4TCNQ in overlying solutions as the dopant radical anions maximally covered the surfaces. This suggests that there are limited electroactive sites for F4TCNQ binding on electron donor surfaces which results in a similar number of positive charges in film materials forming dipoles with the F4TCNQ radical counteranions. The effect of electron acceptors such as 7,7,8,8-tetracyanoquinodimethane and tetracyanoethylene was compared to that of F4TCNQ in terms of Vth shift using our analytical tool, with differences attributed to acceptor size and reduction potential. Meanwhile, this FET analysis tool offered a means of monitoring the physical diffusion of small molecules, exemplified by F4TCNQ, in the passive polymer polystyrene, driven by concentration gradients. The technique allows for nondestructive, nonspectroscopic, ambient characterization of electron donor-acceptor interactions at surfaces.

Solid-state electrical applications of protein and peptide based nanomaterials.

The field of organic electronics continues to be driven by new charge-transporting materials that are typically processed from toxic organic solvents incompatible with biological environments. Over the past few decades, powerful examples of electrical transport as mediated through protein-based macromolecules have fueled the emerging area of organic bioelectronics. These attractive bioinspired architectures have enabled several important applications that draw on their functional electrical properties, ranging from field-effect transistors to piezoelectrics. In addition to naturally occurring protein biomacromolecules, unnatural oligopeptide self-assemblies and peptide-π conjugates also exhibit interesting electrical applications. This review provides an overview of electrical transport and electrical polarization in specialized biomaterials as manifested in solid-state device architectures.

Direct Detection of Dilute Solid Chemicals with Responsive Lateral Organic Diodes.

Organic field-effect transistors (OFETs) have emerged as promising sensors targeting chemical analytes in vapors and liquids. However, the direct detection of solid chemicals by OFETs has not been achieved. Here for the first time, we describe the direct detection of solid chemical analytes by organic electronics. An organic diode structure based on a horizontal side-by-side p-n junction was adopted and shown to be superior to OFETs for this purpose. The diodes showed more than 40% current decrease upon exposure to 1 ppm melamine powders. The estimated detection limit to melamine can potentially reach the ppb range. This is the first demonstration of an electronic signal from an interaction between a solid and an organic p-n junction directly, which suggests that our lateral organic diodes are excellent platforms for the development of future sensors when direct detection of solid chemicals is needed. The approach developed here is general and can be extended to chemical sensors targeting various analytes, opening unprecedented opportunities for the development of low-cost and high-performance solid chemical sensors.

Modification of the Poly(bisdodecylquaterthiophene) Structure for High and Predominantly Nonionic Conductivity with Matched Dopants.

Four p-type polymers were synthesized by modifying poly(bisdodecylquaterthiophene) (PQT12) to increase oxidizability by p-dopants. A sulfur atom is inserted between the thiophene rings and dodecyl chains, and/or 3,4-ethylenedioxy groups are appended to thiophene rings of PQT12. Doped with NOBF4, PQTS12 (with sulfur in side chains) shows a conductivity of 350 S cm-1, the highest reported nonionic conductivity among films made from dopant-polymer solutions. Doped with tetrafluorotetracyanoquinodimethane (F4TCNQ), PDTDE12 (with 3,4-ethylenedioxy groups on thiophene rings) shows a conductivity of 140 S cm-1. The converse combinations of polymer and dopant and formulations using a polymer with both the sulfur and ethylenedioxy modifications showed lower conductivities. The conductivities are stable in air without extrinsic ion contributions associated with PEDOT:PSS that cannot support sustained current or thermoelectric voltage. Efficient charge transfer, tighter π-π stacking, and strong intermolecular coupling are responsible for the conductivity. Values of nontransient Seebeck coefficient and conductivity agree with empirical modeling for materials with these levels of pure hole conductivity; the power factor compares favorably with prior p-type polymers made by the alternative process of immersion of polymer films into dopant solutions. Models and conductivities point to significant mobility increases induced by dopants on the order of 1-5 cm2 V-1 s-1, supported by field-effect transistor studies of slightly doped samples. The thermal conductivities were in the range of 0.2-0.5 W m-1 K-1, typical for conductive polymers. The results point to further enhancements that could be obtained by increasing doped polymer mobilities.

Extended Solution Gate OFET-based Biosensor for Label-free Glial Fibrillary Acidic Protein Detection with Polyethylene Glycol-Containing Bioreceptor Layer.

A novel organic field effect transistor (OFET) -based biosensor is described for label-free glial fibrillary acidic protein (GFAP) detection. We report the first use of an extended solution gate structure where the sensing area and the organic semiconductor are separated, and a reference electrode is not needed. Different molecular weight polyethylene glycols (PEGs) are mixed into the bio-receptor layer to help extend the Debye screening length. The drain current change was significantly increased with the help of higher molecular weight PEGs, as they are known to reduce the dielectric constant. We also investigated the sensing performance under different gate voltage (Vg). The sensitivity increased after we decreased Vg from -5 V to -2 V, because the lower Vg is much closer to the OFET threshold voltage and the influence of attached negatively charged proteins become more apparent. Finally, the selectivity experiments toward different interferents were performed. The stability and selectivity are promising for clinical applications.

Molecular Switching via Multiplicity-Exclusive E/Z Photoisomerization Pathways.

Mutual exclusivity in the nature of forward and reserve isomerization pathways holds promise for predictably controlling responses of photoswitchable materials according to molecular structure or external stimuli. Herein we have characterized the E/Z photoisomerization mechanisms of the visible-light-triggered switch 1,2-dithienyl-1,2-dicyanoethene (4TCE) in chlorobenzene with ultrafast transient absorption spectroscopy. We observe that switching mechanisms occur exclusively by relaxation through electronic manifolds of different spin multiplicity: trans-to-cis isomerization only occurs via electronic relaxation within the singlet manifold on a time scale of 40 ps; in contrast, cis-to-trans isomerization is not observed above 440 nm, but occurs via two rapid ISC processes into and out of the triplet manifold on time scales of ∼2 ps and 0.4 ns, respectively, when excited at higher energies (e.g., 420 nm). Observation of ultrafast ISC in cis-4TCE is consistent with photoinduced dynamics of related thiophene-based oligomers. Interpretation of the photophysical pathways underlying these isomerization reactions is supported by the observation that cis-to-trans isomerization occurs efficiently via triplet-sensitized energy transfer, whereas trans-to-cis isomerization does not. Quantum-chemical calculations reveal that the T1 potential energy surface is barrierless along the coordinate of the central ethylene dihedral angle (θ) from the cis Franck-Condon region (θ = 175°) to geometries that are within the region of the trans ground-state well; furthermore, the T1 and S1 surfaces cross with a substantial spin-orbital coupling. In total, we demonstrate that E/Z photoswitching of 4TCE operates by multiplicity-exclusive pathways, enabling additional means for tailoring switch performance by manipulating spin-orbit couplings through variations in molecular structure or physical environment.

A High-Capacitance Salt-Free Dielectric for Self-Healable, Printable, and Flexible Organic Field Effect Transistors and Chemical Sensor.

Printable and flexible electronics attract sustained attention for their low cost, easy scale up, and potential application in wearable and implantable sensors. However, they are susceptible to scratching, rupture, or other damage from bending or stretching due to their "soft" nature compared to their rigid counterparts (Si-based electronics), leading to loss of functionality. Self-healing capability is highly desirable for these "soft" electronic devices. Here, a versatile self-healing polymer blend dielectric is developed with no added salts and it is integrated into organic field transistors (OFETs) as a gate insulator material. This polymer blend exhibits an unusually high thin film capacitance (1400 nF cm -2 at 120 nm thickness and 20-100 Hz). Furthermore, it shows pronounced electrical and mechanical self-healing behavior, can serve as the gate dielectric for organic semiconductors, and can even induce healing of the conductivity of a layer coated above it together with the process of healing itself. Based on these attractive properties, we developed a self-healable, low-voltage operable, printed, and flexible OFET for the first time, showing promise for vapor sensing as well as conventional OFET applications.

Through thick and thin: tuning the threshold voltage in organic field-effect transistors.

Organic semiconductors (OSCs) constitute a class of organic materials containing densely packed, overlapping conjugated molecular moieties that enable charge carrier transport. Their unique optical, electrical, and magnetic properties have been investigated for use in next-generation electronic devices, from roll-up displays and radiofrequency identification (RFID) to biological sensors. The organic field-effect transistor (OFET) is the key active element for many of these applications, but the high values, poor definition, and long-term instability of the threshold voltage (V(T)) in OFETs remain barriers to realization of their full potential because the power and control circuitry necessary to compensate for overvoltages and drifting set points decrease OFET practicality. The drifting phenomenon has been widely observed and generally termed "bias stress." Research on the mechanisms responsible for this poor V(T) control has revealed a strong dependence on the physical order and chemical makeup of the interfaces between OSCs and adjacent materials in the OFET architecture. In this Account, we review the state of the art for tuning OFET performance via chemical designs and physical processes that manipulate V(T). This parameter gets to the heart of OFET operation, as it determines the voltage regimes where OFETs are either ON or OFF, the basis for the logical function of the devices. One obvious way to decrease the magnitude and variability of V(T) is to work with thinner and higher permittivity gate dielectrics. From the perspective of interfacial engineering, we evaluate various methods that we and others have developed, from electrostatic poling of gate dielectrics to molecular design of substituted alkyl chains. Corona charging of dielectric surfaces, a method for charging the surface of an insulating material using a constant high-voltage field, is a brute force means of shifting the effective gate voltage applied to a gate dielectric. A gentler and more direct method is to apply surface voltage to dielectric interfaces by direct contact or postprocess biasing; these methods could also be adapted for high throughput printing sequences. Dielectric hydrophobicity is an important chemical property determining the stability of the surface charges. Functional organic monolayers applied to dielectrics, using the surface attachment chemistry made available from "self-assembled" monolayer chemistry, provide local electric fields without any biasing process at all. To the extent that the monolayer molecules can be printed, these are also suitable for high throughput processes. Finally, we briefly consider V(T) control in the context of device integration and reliability, such as the role of contact resistance in affecting this parameter.

Visible-light-triggered molecular photoswitch based on reversible E/Z isomerization of a 1,2-dicyanoethene derivative.

A designed bis(dithienyl) dicyanoethene-based, strictly E/Z photoswitch (4TCE) operates through state-selective (E and Z isomer) photoactivation with visible light. The E and Z isomers of 4TCE exhibit remarkably different spectroscopic characteristics, including a large separation (70 nm) in their absorption maxima (λ(max)) and a 2.5-fold increase in molar extinction coefficient from cis to trans. The energetically stable trans form can be completely converted to the cis form within minutes when exposed to white light, whereas the reverse isomerization occurs readily upon irradiation by blue light (λ<480 nm) or completely by thermal conversion at elevated temperatures. These features together with excellent thermal stability and photostability of both isomers make this new E/Z photoswitch a promising building block for photoswitchable materials that operate without the need for UV light.

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.

Field-effect-tuned lateral organic diodes.

The operation of organic diodes in solar cells and light-emitting displays strongly depends on the properties of the interfaces between hole- and electron-carrying organic semiconductors. Such interfaces are difficult to characterize, as they are usually buried under the surface or exist as an irregular "bulk heterojunction." Using a unique fluorinated barrier layer-based lithographic technique, we fabricated a lateral organic p-n junction, allowing the first observation of the potential at an organic p-n interface simultaneously with the charge transport measurements. We find that the diode characteristics of the device (current output and rectification ratio) are consistent with the changes in the surface potentials near the junction, and the current-voltage curves and junction potentials are strongly and self-consistently modulated by a third, gate electrode. The generality of our technique makes this an attractive method to investigate the physics of organic semiconductor junctions. The lithographic technique is applicable to a wide variety of soft material patterns. The observation of built-in potentials makes an important connection between organic junctions and textbook descriptions of inorganic devices. Finally, these kinds of potentials may prove to be controlling factors in charge separation efficiency in organic photovoltaics.

Permittivity Threshold and Thermodynamics of Integer Charge-Transfer Complexation for an Organic Donor-Acceptor Pair.

Molecular charge doping involves the formation of donor-acceptor charge-transfer complexes (CTCs) through integer or partial electron transfer; understanding how local chemical environment impacts complexation is important for controlling the properties of organic materials. We present steady-state and temperature-dependent spectroscopic investigations of the p-dopant 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ) complexed with the electron donor and hole transport material N,N'-diphenyl-N,N'-di-p-tolylbenzene-1,4-diamine (MPDA). Equilibrium formation constants (KCT) were determined for donor-acceptor pairs dissolved in a series of solvents covering a range of values of permittivity. A threshold for highly favorable complex formation was observed to occur at ϵ ∼ 8-9, with large (>104) and small (<103) values of KCT obtained in solvents of higher and lower permittivity, respectively, but with chloroform (ϵ = 4.81) exhibiting an anomalously high formation constant. Temperature-dependent formation constants were determined in order to evaluate the thermodynamics of complex formation. In 1,2-dichloroethane (ϵ = 10.36) and chlorobenzene (ϵ = 5.62), complex formation is both enthalpically and entropically favorable, with higher enthalpic and entropic stabilization in the solvent with higher permittivity. Complexation in chloroform is exothermic and entropically disfavored, indicating that specific, inner-shell solvent-solute interactions stabilize the charge-separated complex and result in a net increase in local solution structure. Our results provide insight into how modification to the chemical environment may be utilized to support stable integer charge transfer for molecular doping applications and requiring only modest changes in local permittivity.

Highly sensitive NH3 detection based on organic field-effect transistors with tris(pentafluorophenyl)borane as receptor.

We have increased organic field-effect transistor (OFET) NH(3) response using tris(pentafluorophenyl)borane (TPFB) as a receptor. OFETs with this additive could detect concentrations of 450 ppb v/v, with a limit of detection of 350 ppb, the highest sensitivity reported to date for semiconductor films; in comparison, when triphenylmethane (TPM) or triphenylborane (TFB) was used as an additive, no obvious improvement in the sensitivity was observed. These OFETs also showed considerable selectivity with respect to common organic vapors and stability toward storage. Furthermore, excellent memory of exposure was achieved by keeping the exposed devices in a sealed container stored at -30 °C, the first such capability demonstrated with OFETs.

Stabilization and Specification in Polymer Field-Effect Transistor Semiconductors.

The strong and varied chemical interactions between polymer semiconductors and small molecules, and the electronic consequences of these interactions, make polymer organic field-effect transistors (OFETs) attractive as vapor sensing elements. Two hindrances to their wider acceptance and use are their environmental drift and the poor specificity of individual OFETs. Approaches to addressing these two present drawbacks are presented in this Spotlight on Applications. They include the use of semiconducting polymers with greater inherent stability, circuits that add further stability, and arrays that generate patterns that are much more specific to analyte vapors of interest than the individual responses.