Contact Resistance in Organic Field‐Effect Transistors: Conquering the Barrier

Organic semiconductors have sparked interest as flexible, solution processable, and chemically tunable electronic materials. Improvements in charge carrier mobility put organic semiconductors in a competitive position for incorporation in a variety of (opto‐)electronic applications. One example is the organic field‐effect transistor (OFET), which is the fundamental building block of many applications based on organic semiconductors. While the semiconductor performance improvements opened up the possibilities for applying organic materials as active components in fast switching electrical devices, the ability to make good electrical contact hinders further development of deployable electronics. Additionally, inefficient contacts represent serious bottlenecks in identifying new electronic materials by inhibiting access to their intrinsic properties or providing misleading information. Recent work focused on the relationships of contact resistance with device architecture, applied voltage, metal and dielectric interfaces, has led to a steady reduction in contact resistance in OFETs. While impressive progress was made, contact resistance is still above the limits necessary to drive devices at the speed required for many active electronic components. Here, the origins of contact resistance and recent improvement in organic transistors are presented, with emphasis on the electric field and geometric considerations of charge injection in OFETs.     

Introducing a Nonvolatile N‐Type Dopant Drastically Improves Electron Transport in Polymer and Small‐Molecule Organic Transistors

Molecular doping is a powerful yet challenging technique for enhancing charge transport in organic semiconductors (OSCs). While there is a wealth of research on p‐type dopants, work on their n‐type counterparts is comparatively limited. Here, reported is the previously unexplored n‐dopant (12a,18a)‐5,6,12,12a,13,18,18a,19‐octahydro‐5,6‐dimethyl‐ 13,18[1′,2′]‐benzenobisbenzimidazo [1,2‐b:2′,1′‐d]benzo[i][2.5]benzodiazo‐cine potassium triflate adduct (DMBI‐BDZC) and its application in organic thin‐film transistors (OTFTs). Two different high electron mobility OSCs, namely, the polymer poly[[N,N′‐bis(2‐octyldodecyl)‐naphthalene‐1,4,5,8‐ bis(dicarboximide)‐2,6‐diyl]‐alt‐5,5′‐(2′‐bithiophene)] and a small‐molecule naphthalene diimides fused with 2‐(1,3‐dithiol‐2‐ylidene)malononitrile groups (NDI‐DTYM2) are used to study the effectiveness of DMBI‐BDZC as a n‐dopant. N‐doping of both semiconductors results in OTFTs with improved electron mobility (up to 1.1 cm² V^?1 s^?1), reduced threshold voltage and lower contact resistance. The impact of DMBI‐BDZC incorporation is particularly evident in the temperature dependence of the electron transport, where a significant reduction in the activation energy due to trap deactivation is observed. Electron paramagnetic resonance measurements support the n‐doping activity of DMBI‐BDZC in both semiconductors. This finding is corroborated by density functional theory calculations, which highlights ground‐state electron transfer as the main doping mechanism. The work highlights DMBI‐BDZC as a promising n‐type molecular dopant for OSCs and its application in OTFTs, solar cells, photodetectors, and thermoelectrics.     

Oligothiophene‐Functionalized Truxene: Star‐Shaped Compounds for Organic Field‐Effect Transistors

Organic field‐effect transistors (OFETs) based on oligothiophene‐functionalized truxene derivatives have been fabricated for use as novel star‐shaped organic semiconductors in solution‐processible organic electronics. The electronic and optical properties of compounds 1 – 3 , with increasing numbers of thiophene rings at each of the three branches, have been investigated using scanning electron microscopy (SEM), X‐ray diffraction measurements, and ultraviolet–visible (UV‐vis) and photoluminescence spectroscopies. The results show that with a stepwise increase of the thiophene rings at every branch, a transition from a polycrystalline to an amorphous state is observed. The characteristics of compounds 1 , 2 , and 3 used for OFETs exhibit a significant difference. The mobility depends greatly on the morphology in the solid state, and decreases in going from 1 to 3 . Mobilities up to 1.03 × 10^–3 cm² V^–1 s^–1 and an on/off ratio of about 10³ for compound 1 have been achieved; these are the highest values for star‐shaped organic semiconductors used for OFETs so far. All the results demonstrate that the truxene core of the oligothiophene‐functionalized truxene derivatives not only extends the π‐delocalized system, but also leads to high mobilities for the compounds.     

Comparative Study of the N‐Type Doping Efficiency in Solution‐processed Fullerenes and Fullerene Derivatives

Molecular doping of organic semiconductors and devices represents an enabling technology for a range of emerging optoelectronic applications. Although p‐type doping has been demonstrated in a number of organic semiconductors, efficient n‐type doping has proven to be particularly challenging. Here, n‐type doping of solution‐processed C₆₀, C₇₀, [60]PCBM, [70]PCBM and indene‐C₆₀ bis‐adduct by 1H‐benzimidazole (N‐DMBI) is reported. The doping efficiency for each system is assessed using field‐effect measurements performed under inert atmosphere at room temperature in combination with optical absorption spectroscopy and atomic force microscopy. The highest doping efficiency is observed for C₆₀ and C₇₀ and electron mobilities up to ≈2 cm²/Vs are obtained. Unlike in substituted fullerenes‐based transistors where the electron mobility is found to be inversely proportional to N‐DMBI concentration, C₆₀ and C₇₀ devices exhibit a characteristic mobility increase by approximately an order of magnitude with increasing dopant concentration up to 1 mol%. Doping also appears to significantly affect the bias stability of the transistors. The work contributes towards understanding of the molecular doping mechanism in fullerene‐based semiconductors and outlines a simple and highly efficient approach that enables significant improvement in device performance through facile chemical doping.     

Inside Front Cover: High‐Performance and Stable Organic Thin‐Film Transistors Based on Fused Thiophenes (Adv. Funct. Mater. 3/2006)

A series of new organic semiconductors for organic thin‐film transistors using dithieno[3,2‐b:2′,3′‐d]thiophene as the core have been synthesized. In work reported by Liu, Zhu, and co‐workers on p. 426, the phenyl‐substituted compound exhibited a high mobility of 0.42 cm² V^–1 s^–1 and an on/off ratio of 5 × 10⁶. Weekly shelf‐life tests of the transistors based on the bis(diphenyl)‐substituted thiophene under ambient conditions showed that the mobility was almost unchanged after more than two months, demonstrating potential for applications in future organic electronics. A series of new organic semiconductors for organic thin‐film transistors (OTFTs) using dithieno[3,2‐b:2′,3′‐d]thiophene as the core are synthesized. Their electronic and optical properties are investigated using scanning electron microscopy (SEM), X‐ray diffraction (XRD), UV‐vis and photoluminescence spectroscopies, thermal gravimetric analysis (TGA), and differential scanning calorimetry (DSC). The compounds exhibit an excellent field‐effect performance with a high mobility of 0.42 cm² V^–1 s^–1 and an on/off ratio of 5 × 10⁶. XRD patterns reveal these films, grown by vacuum deposition, to be highly crystalline, and SEM reveals well‐interconnected, microcrystalline domains in these films at room temperature. TGA and DSC demonstrate that the phenyl‐substituted compounds possess excellent thermal stability. Furthermore, weekly shelf‐life tests (under ambient conditions) of the OTFTs based on the phenyl‐substituted compounds show that the mobility for the bis(diphenyl)‐substituted thiophene was almost unchanged for more than two months, indicating a high environmental stability.     

Systematic Study of Widely Applicable N‐Doping Strategy for High‐Performance Solution‐Processed Field‐Effect Transistors

A specific design for solution‐processed doping of active semiconducting materials would be a powerful strategy in order to improve device performance in flexible and/or printed electronics. Tetrabutylammonium fluoride and tetrabutylammonium hydroxide contain Lewis base anions, F^? and OH^?, respectively, which are considered as organic dopants for efficient and cost‐effective n‐doping processes both in n‐type organic and nanocarbon‐based semiconductors, such as poly[[N,N′‐bis(2‐octyldodecyl)‐naphthalene‐1,4,5,8‐bis(dicarboximide)‐2,6‐diyl]‐alt‐5,5′‐(2,2′‐bithiophene)] (P(NDI2OD‐T2)) and selectively dispersed semiconducting single‐walled carbon nanotubes by π‐conjugated polymers. The dramatic enhancement of electron transport properties in field‐effect transistors is confirmed by the effective electron transfer from the dopants to the semiconductors as well as controllable onset and threshold voltages, convertible charge‐transport polarity, and simultaneously showing excellent device stabilities under ambient air and bias stress conditions. This simple solution‐processed chemical doping approach could facilitate the understanding of both intrinsic and extrinsic charge transport characteristics in organic semiconductors and nanocarbon‐based materials, and is thus widely applicable for developing high‐performance organic and printed electronics and optoelectronics devices.     

2D Single‐Crystalline Molecular Semiconductors with Precise Layer Definition Achieved by Floating‐Coffee‐Ring‐Driven Assembly

2D organic materials with in‐plane van der Waals forces among molecules have unique characteristics that ensure a brilliant future for multifunctional applications. Soluble organic semiconductors can be used to achieve low‐cost and high‐throughput manufacturing of electronic devices. However, achieving solution‐processed 2D single‐crystalline semiconductors with uniform morphology remains a substantial challenge. Here, the fabrication of 2D molecular single‐crystal semiconductors with precise layer definition by using a floating‐coffee‐ring‐driven assembly is presented. In particular, bilayer molecular films exhibit single‐crystalline features with atomic smoothness and high film uniformity over a large area; field‐effect transistors yield average and maximum carrier mobilities of 4.8 and 13.0 cm² V^?1 s^?1, respectively. This work demonstrates the strong potential of 2D molecular crystals for low‐cost, large‐area, and high‐performance electronics.     

High‐Mobility Air‐Stable Solution‐Shear‐Processed n‐Channel Organic Transistors Based on Core‐Chlorinated Naphthalene Diimides

High charge carrier mobility solution‐processed n‐channel organic thin‐film transistors (OTFTs) based on core‐chlorinated naphthalene tetracarboxylic diimides (NDIs) with fluoroalkyl chains are demonstrated. These OTFTs were prepared through a solution shearing method. Core‐chlorination of NDIs not only increases the electron mobilities of OTFTs, but also enhances their air stability, since the chlorination in the NDI core lowers the lowest unoccupied molecular orbital (LUMO) levels. The air‐stability of dichlorinated NDI was better than that of the tetrachlorinated NDIs, presumably due to the fact that dichlorinated NDIs have a denser packing of the fluoroalkyl chains and less grain boundaries on the surface, reducing the invasion pathway of ambient oxygen and moisture. The devices of dichlorinated NDIs exhibit good OTFT performance, even after storage in air for one and a half months. Charge transport anisotropy is observed from the dichlorinated NDI. A dichlorinated NDI with ?CH₂C₃F₇ side chains reveals high mobilities of up to 0.22 and 0.57 cm² V^?1 s^?1 in parallel and perpendicular direction, respectively, with regard to the shearing direction. This mobility anisotropy is related to the grain morphology. In addition, we find that the solution‐shearing deposition affects the molecular orientation in the crystalline thin films and lowers the d(001)‐spacing (the out‐of‐plane interlayer spacing), compared to the vapor‐deposited thin films. Core‐chlorinated NDI derivatives are found to be highly suitable for n‐channel active materials in low‐cost solution‐processed organic electronics.     

High‐Performance and Stable Organic Thin‐Film Transistors Based on Fused Thiophenes

A series of new organic semiconductors for organic thin‐film transistors (OTFTs) using dithieno[3,2‐b:2′,3′‐d]thiophene as the core are synthesized. Their electronic and optical properties are investigated using scanning electron microscopy (SEM), X‐ray diffraction (XRD), UV‐vis and photoluminescence spectroscopies, thermal gravimetric analysis (TGA), and differential scanning calorimetry (DSC). The compounds exhibit an excellent field‐effect performance with a high mobility of 0.42 cm² V^–1 s^–1 and an on/off ratio of 5 × 10⁶. XRD patterns reveal these films, grown by vacuum deposition, to be highly crystalline, and SEM reveals well‐interconnected, microcrystalline domains in these films at room temperature. TGA and DSC demonstrate that the phenyl‐substituted compounds possess excellent thermal stability. Furthermore, weekly shelf‐life tests (under ambient conditions) of the OTFTs based on the phenyl‐substituted compounds show that the mobility for the bis(diphenyl)‐substituted thiophene was almost unchanged for more than two months, indicating a high environmental stability.     

Solution‐Processed Zinc Oxide as High‐Performance Air‐Stable Electron Injector in Organic Ambipolar Light‐Emitting Field‐Effect Transistors

Electron injection from the source–drain electrodes limits the performance of many n‐type organic field‐effect transistors (OFETs), particularly those based on organic semiconductors with electron affinities less than 3.5 eV. Here, it is shown that modification of gold source–drain electrodes with an overlying solution‐deposited, patterned layer of an n‐type metal oxide such as zinc oxide (ZnO) provides an efficient electron‐injecting contact, which avoids the use of unstable low‐work‐function metals and is compatible with high‐resolution patterning techniques such as photolithography. Ambipolar light‐emitting field‐effect transistors (LEFETs) based on green‐light‐emitting poly(9,9‐dioctylfluorene‐alt‐benzothiadiazole) (F8BT) and blue‐light‐emitting poly(9,9‐dioctylfluorene) (F8) with electron‐injecting gold/ZnO and hole‐injecting gold electrodes show significantly lower electron threshold voltages and several orders of magnitude higher ambipolar currents, and hence light emission intensities, than devices with bare gold electrodes. Moreover, different solution‐deposited metal oxide injection layers are compared. By spin‐coating ZnO from a low‐temperature precursor, processing temperatures could be reduced to 150 °C. Ultraviolet photoemission spectroscopy (UPS) shows that the improvement in transistor performance is due to reduction of the electron injection barrier at the interface between the organic semiconductor and ZnO/Au compared to bare gold electrodes.     

Bithienopyrroledione‐Based Copolymers,Versatile Semiconductors for Balanced Ambipolar Thin‐Film Transistors and Organic Solar Cells with V oc > 1 V

Conjugated polymer semiconductors P1 and P2 with bithienopyrroledione (bi‐TPD) as acceptor unit are synthesized. Their transistor and photovoltaic performances are investigated. Both polymers display high and balanced ambipolar transport behaviors in thin‐film transistors. P1‐ based devices show an electron mobility of 1.02 cm² V^?1 s^?1 and a hole mobility of 0.33 cm² V^?1 s^?1, one of the highest performance reported for ambipolar polymer transistors. The electron and hole mobilities of P2 transistors are 0.36 and 0.16 cm² V^?1 s^?1, respectively. The solar cells with PC₇₁BM as the electron acceptor and P1/P2 as the donor exhibit a high V _oc about 1.0 V, and a power conversion efficiency of 6.46% is observed for P1‐ based devices without any additives and/or post treatment. The high performance of P1 and P2 is attributed to their crystalline films and short π–π stacking distance (<3.5 Å). These results demonstrate (1) bi‐TPD is an excellent versatile electron‐deficient unit for polymer semiconductors and (2) bi‐TPD‐based polymer semiconductors have potential applications in organic transistors and organic solar cells.     

Design of Novel Dielectric Surface Modifications for Perylene Thin‐Film Transistors

Dielectric surface modifications (DSMs) can improve the performance of organic thin‐film transistors (OTFTs) significantly. In order to gain a deeper understanding of this performance enhancement and to facilitate high‐mobility transistors, perylene based devices utilizing novel dielectric surface modifications have been produced. Novel DSMs, based on derivates of tridecyltrichlorosilane (TTS) with different functional end‐groups as well as polymeric dielectrics have been applied to tailor the adhesion energy of perylene. The resulting samples were characterized by electronic transport measurements, scanning probe microscopy, and X‐ray diffraction (XRD). Measurements of the surface free energy of the modified dielectric enabled the calculation of the adhesion energy of perylene upon these novel DSMs by the equation‐of‐state approach. These calculations demonstrate the successful tailoring of the adhesion energy. With these novel DSMs, perylene thin‐films with a superior film quality were produced, which enabled high‐performance perylene‐based OTFTs with high charge‐carrier mobility.     

Quinoidal Molecules as a New Class of Ambipolar Semiconductor Originating from Amphoteric Redox Behavior

The two small molecules, quinoidal bithiophene (QBT) and quinoidal biselenophene (QBS), are designed based on a quinoid structure, and synthesized via a facile synthetic route. These quinoidal molecules have a reduced band gap and an amphoteric redox behavior, which is caused by an extended delocalization. Due to such properties, organic field‐effect transistors based on QBT and QBS have shown balanced ambipolar characteristics. After thermal annealing, the performances of the devices are enhanced by an increase in crystallinity. The field‐effect hole and electron mobilities are measured to be 0.031 cm² V^?1 s^?1 and 0.005 cm² V^?1 s^?1 for QBT, and 0.055 cm² V^?1 s^?1 and 0.021 cm² V^?1 s^?1 for QBS, respectively. In addition, we investigate the effect of chalcogen atoms (S and Se) on the molecular properties. The optical, electrochemical properties and electronic structures are mainly dominated by the quinoidal structure, whereas molecular properties are scarcely affected by either type of chalcogen atom. The main effect of the chalcogen atoms is ascribed to the difference of crystallinity. Due to a strong intermolecular interaction of the selenophene, QBS exhibits a higher degree of crystallinity, which leads to an enhancement of both hole and electron mobilities. Consequently, these types of quinoidal molecules are found to be promising for use as ambipolar semiconductors.     

Ambipolar Organic Field‐Effect Transistors from Cross‐Conjugated Aromatic Quaterthiophenes; Comparisons with Quinoidal Parent Materials

This contribution presents an electrochemical, Raman spectroscopic, and theoretical study probing the differences in molecular and electronic structure of two quinoidal oligothiophenes (3′,4′‐dibutyl‐5,5″‐bis(dicyanomethylene)‐5,5″‐dihydro‐2,2′:5′,2″‐terthiophene and 5,5′‐bis(dicyanomethylene)‐3‐hexyl‐2,5‐dihydro‐4,4′‐dihexyl‐2,2′,5,5′‐tetrahydro‐tetrathiophene) with terminal tetracyanomethylene functionalization and aromatic oligothiophenes where acceptor moieties are positioned at lateral positions along the conjugated chain (6,6′‐dibutylsulfanyl‐[2,2′‐bi‐[4‐dicyanovinylene‐4H‐cyclopenta[2,1‐b:3,4‐b′]dithiophene]). In this way, the consequences of linear and cross conjugation are compared and contrasted. From this analysis, it is apparent that organic field‐effect transistors fabricated with cross‐conjugated tetrathiophene semiconductors should combine the benefits of an electron‐donor aromatic chain with strongly electron‐accepting tetracyanomethylene substituents. The corresponding organic field‐effect transistors exhibit ambipolar transport with rather similar hole and electron mobilities. Moreover, n‐channel conduction is enhanced to yield one of the highest electron mobilities found to date for this type of material.     

A Highly Crystalline Fused‐Ring n‐Type Small Molecule for Non‐Fullerene Acceptor Based Organic Solar Cells and Field‐Effect Transistors

N‐type organic small molecules (SMs) are attracting attention in the organic electronics field, due to their easy purification procedures with high yield. However, only a few reports show SMs that perform well in both organic field‐effect transistors (OFETs) and organic solar cells (OSCs). Here, the synthesis and characterization of an n‐type small molecule with an indacenodithieno[3,2‐b]thiophene (IDTT) core unit and linear alkylated side chain (C₁₆) (IDTTIC) are reported. Compared to the state‐of‐the‐art n‐type molecule IDTIC, IDTTIC exhibits smaller optical bandgap and higher absorption coefficient, which is due to the enhanced intramolecular effect. After mixing with the polymer donor PBDB‐T, IDTIC‐based solar cells deliver a power conversion efficiency of only 5.67%. In stark contrast, the OSC performance of IDTTIC improves significantly to 11.2%. It is found that the superior photovoltaic properties of PBDB‐T:IDTTIC blends are mainly due to reduced trap‐assisted recombination and enhanced molecular packing coherence length and higher domain purity when compared to IDTIC. Moreover, a significantly higher electron mobility of 0.50 cm² V⁻¹ s⁻¹ for IDTTIC in OFET devices than for IDTIC (0.15 cm² V⁻¹ s⁻¹) is obtained. These superior performances in OSCs and OFETs demonstrate that SMs with extended π‐conjugation of the backbone possess a great potential for application in organic electronic devices.     

Polyelectrolyte Dielectrics for Flexible Low‐Voltage Organic Thin‐Film Transistors in Highly Sensitive Pressure Sensing

Organic thin‐film transistors (OTFTs) can provide an effective platform to develop flexible pressure sensors in wearable electronics due to their good signal amplification function. However, it is particularly difficult to realize OTFT‐based pressure sensors with both low‐voltage operation and high sensitivity. Here, controllable polyelectrolyte composites based on poly(ethylene glycol) (PEG) and polyacrylic acid (PAA) are developed as a type of high‐capacitance dielectrics for flexible OTFTs and ultrasensitive pressure sensors with sub‐1 V operation. Flexible OTFTs using the PAA:PEG dielectrics show good universality and greatly enhanced electrical performance under a much smaller operating voltage of ?0.7 V than those with a pristine PAA dielectric. The low‐voltage OTFTs also exhibit excellent flexibility and bending stability under various bending radii and long cycles. Flexible OTFT‐based pressure sensors with low‐voltage operation and superhigh sensitivity are demonstrated by using a suspended semiconductor/dielectric/gate structure in combination with the PAA:PEG dielectric. The sensors deliver a record high sensitivity of 452.7 kPa^?1 under a low‐voltage of ?0.7 V, and excellent operating stability over 5000 cycles. The OTFT sensors can be built into a wearable sensor array for spatial pressure mapping, which shows a bright potential in flexible electronics such as wearable devices and smart skins.     

n-Type acceptor-acceptor polymer semiconductors

Polymer semiconductors have aroused interests from both academic and industry due to their wide applications in electronic devices,such as organic thin-film transistors (OT-FTs)[1],polymer solar cells (PSCs)[2-6],organic thermoelectrics(OTEs)[7-11],and perovskite solar cells (PVSCs)[12-14].To date,great efforts have been devoted to developing p-type poly-mer semiconductors,while the development of n-type poly-mers lags far behind.In fact,n-type polymers are essential for organic electronic devices.     

Highly Efficient Three Primary Color Organic Single‐Crystal Light‐Emitting Devices with Balanced Carrier Injection and Transport

Organic single crystals have a great potential in the field of organic optoelectronics because of their advantages of high carrier mobility and high thermal stability. However, the application of the organic single crystals in light‐emitting devices (OLEDs) has been limited by single‐layered structure with unbalanced carrier injection and transport. Here, fabrication of a multilayered‐structure crystal‐based OLED constitutes a major step toward balanced carrier injection and transport by introducing an anodic buffer layer and electron transport layer into the device structure. Three primary color single‐crystal‐based OLEDs based on the multilayered structure and molecular doping exhibit a maximum luminance and current efficiency of 820 cd cm^?2 and 0.9 cd A^?1, respectively, which are the highest performance to date for organic single‐crystal‐based OLEDs. This work paves the way toward high‐performance organic optoelectronic devices based on the organic single crystals.     

Modulated Thermoelectric Properties of Organic Semiconductors Using Field‐Effect Transistors

Organic thermoelectric materials, which can transform heat flow into electricity, have great potential for flexible, ultra‐low‐cost and large‐area thermoelectric applications. Despite rapid developments of organic thermoelectric materials, exploration and investigation of promising organic thermoelectric semiconductors still remain as a challenge. Here, the thermoelectric properties of several p‐ and n‐type organic semiconductors are investigated and studied, in particular, how the electric field modulations of the Seebeck coefficient in organic field‐effect transistors (OFETs) compare with the Seebeck coefficient in chemically doped films. The extracted relationship between the Seebeck coefficient (S) and electrical conductivity (σ) from the field‐effect transistor (FET) geometry is in good agreement with that of chemically doped films, enabling the investigation of the trade‐off relationship among σ, S, carrier concentration, and charging level. The results make OFETs an effective candidate for the thermoelectric studies of organic semiconductors.     

Doped Organic Semiconductors: Trap‐Filling,Impurity Saturation,and Reserve Regimes

A typical human being carries billions of silicon‐based field‐effect transistors in his/her pockets. What makes these transistors work is Fermi level control, both by doping and field effect. Organic semiconductors are the core of a novel flexible electronics age, but the key effect of doping is still little understood. Here, precise handling is demonstrated for molar doping ratios as low as 10^?5 in p‐ and n‐doped organic thin‐films by vacuum co‐sublimation, allowing comprehensive studying of the Fermi level control over the whole electronic gap of an organic semiconductor. In particular, dopant saturation and reserve regimes are observed for the first time in organic semiconductors. These results will allow for completely new design rules of organic transistors with improved long term stability and precise parameter control.