Vertical Organic Field‐Effect Transistors

Field‐effect transistors are the fundamental building blocks for electronic circuits and processors. Compared with inorganic transistors, organic field‐effect transistors (OFETs), featuring low cost, low weight, and easy fabrication, are attractive for large‐area flexible electronic devices. At present, OFETs with planar structures are widely investigated device structures in organic electronics and optoelectronics; however, they face enormous challenges in realizing large current density, fast operation speed, and outstanding mechanical flexibility for advancing their potential commercialized applications. In this context, vertical organic field‐effect transistors (VOFETs), composed of vertically stacked source/drain electrodes, could provide an effective approach for solving these questions due to their inherent small channel length and unique working principles. Since the first report of VOFETs in 2004, impressive progress has been witnessed in this field with the improvement of device performance. The aim of this review is to give a systematical summary of VOFETs with a special focus on device structure optimization for improved performance and potential applications demonstrated by VOFETs. An overview of the development of VOFETs along with current challenges and perspectives is also discussed. It is hoped that this review is timely and valuable for the next step in the rapid development of VOFETs and their related research fields.     

Star‐Shaped Oligothiophenes for Solution‐Processible Organic Field‐Effect Transistors

We have designed and successfully synthesized star‐shaped oligothiophenes, which could be used as semiconducting materials for solution‐processible organic field‐effect transistors (FETs). By systematically changing the chemical structure of the star‐shaped oligothiophenes we obtained the structural requirements needed for making working FETs from them. UV‐vis fluorescence measurements showed that a molecule of the star‐shaped compounds under consideration is not a fully conjugated molecule, but it has three independently conjugated oligothienyl‐phenylene blocks. A possible scheme of molecular packing of the star‐shaped oligothiophenes in a lamellar structure was proposed and confirmed by atomic force microscopy (AFM) and X‐ray diffraction (XRD) measurements. Although the star‐shaped semiconductors show a somewhat lower mobility than their linear analogs, they possess better solubility and film‐forming properties, leading to improved spin‐coating processing. The best FETs were made by spin‐coating 1,3,5‐tris(5″‐decyl‐2,2′:5′,2″‐terthien‐5‐yl)benzene from a chloroform solution, which resulted in a mobility of 2 × 10^–4 cm² V ^–1s^–1, a 10² on/off ratio at gate voltages of 0 V and –20 V, and a threshold voltage close to 0 V.     

Light‐Emitting Field‐Effect Transistors Consisting of Bilayer‐Crystal Organic Semiconductors

A novel device structure for organic light‐emitting field‐effect transistors has been developed. The devices comprise bilayer‐crystal organic semiconductors of a p‐type and an n‐type. The pn‐junction can readily be formed by successively laminating two crystals on top of a gate insulator. This structure enables the efficient injection and transport of electrons and holes, leading to their effective recombination. As a result, bright emissions are attained. The devices are operated by AC gate voltages. Gate‐voltage phase‐resolved drain‐current and emission‐intensity measurements enable us to study the relationship between the emissions and carrier transport. The maximum external quantum efficiency reaches 0.045%.     

N‐Type Self‐Assembled Monolayer Field‐Effect Transistors and Complementary Inverters

This work describes n‐type self‐assembled monolayer field‐effect transistors (SAMFETs) based on a perylene derivative which is covalently fixed to an aluminum oxide dielectric via a phosphonic acid linker. N‐type SAMFETs spontaneously formed by a single layer of active molecules are demonstrated for transistor channel length up to 100 μm. Highly reproducible transistors with electron mobilities of 1.5 × 10^?3 cm² V^?1 s^?1 and on/off current ratios up to 10⁵ are obtained. By implementing n‐type and p‐type transistors in one device, a complimentary inverter based solely on SAMFETs is demonstrated for the first time.     

Ionic‐Liquid Gating of InAs Nanowire‐Based Field‐Effect Transistors

Here, the operation of a field‐effect transistor based on a single InAs nanowire gated by an ionic liquid is reported. Liquid gating yields very efficient carrier modulation with a transconductance value 30 times larger than standard back gating with the SiO₂/Si₊₊ substrate. Thanks to this wide modulation, the controlled evolution from semiconductor to metallic‐like behavior in the nanowire is shown. This work provides the first systematic study of ionic‐liquid gating in electronic devices based on individual III–V semiconductor nanowires: this architecture opens the way to a wide range of fundamental and applied studies from the phase transitions to bioelectronics.     

Electrical Double‐Slope Nonideality in Organic Field‐Effect Transistors

The field effect transistor (FET) is arguably one of the most important circuit elements in modern electronics. Recently, a need has developed for flexible electronics in a variety of emerging applications. Examples include form‐fitting healthcare‐monitoring devices, flexible displays, and flexible radio frequency identification tags. Organic FETs (OFETs) are viable candidates for producing such flexible devices because they incorporate semiconducting π‐conjugated materials, including small molecules and conjugated polymers, which are intrinsically soft and mechanically compatible with flexible substrates. For OFETs to be industrially viable, however, they must achieve not only high charge carrier mobility, but also ideal and comprehensible electrical characteristics. Most recently, nonideal double‐slope characteristics in the transfer curves of OFETs (i.e., high slope at low gate voltage and low slope at high gate voltage), have stirred debate, which has led to different mechanistic rationales in the literature. This review focuses on the general observations, mechanistic understanding, and possible solutions associated with phenomena that result in FETs with double‐slope characteristics. By surveying and systematically summarizing in a single source relevant literature that deals with the issue of double slope, the experimental framework and theoretical basis for interpreting and avoiding this electrical nonideality in OFETs is provided.     

ReS2‐Based Field‐Effect Transistors and Photodetectors

Atomically thin 2D layered transition metal dichalcogenides (TMDs) have been extensively studied in recent years because of their appealing electrical and optical properties. Here, the fabrication of ReS₂ field‐effect transistors is reported via the encapsulation of ReS₂ nanosheets in a high‐κ Al₂O₃ dielectric environment. Low‐temperature transport measurements allow to observe a direct metal‐to‐insulator transition originating from strong electron–electron interactions. Remarkably, the photodetectors based on ReS₂ exhibit gate‐tunable photoresponsivity up to 16.14 A W^?1 and external quantum efficiency reaching 3168%, showing a competitive device performance to those reported in graphene, MoSe₂, GaS, and GaSe‐based photodetectors. This study unambiguously distinguishes ReS₂ as a new candidate for future applications in electronics and optoelectronics.     

Dual‐Gate Organic Field‐Effect Transistors as Potentiometric Sensors in Aqueous Solution

Buried electrodes and protection of the semiconductor with a thin passivation layer are used to yield dual‐gate organic transducers. The process technology is scaled up to 150‐mm wafers. The transducers are potentiometric sensors where the detection relies on measuring a shift in the threshold voltage caused by changes in the electrochemical potential at the second gate dielectric. Analytes can only be detected within the Debye screening length. The mechanism is assessed by pH measurements. The threshold voltage shift depends on pH as ΔV_th = (C_top/C_bottom) × 58 mV per pH unit, indicating that the sensitivity can be enhanced with respect to conventional ion‐sensitive field‐effect transistors (ISFETs) by adjusting the ratio of the top and bottom gate capacitances. Remaining challenges and opportunities are discussed.     

Gate Capacitance‐Dependent Field‐Effect Mobility in Solution‐Processed Oxide Semiconductor Thin‐Film Transistors

Solution‐processed oxide semiconductors (OSs) used as channel layer have been presented as a solution to the demand for flexible, cheap, and transparent thin‐film transistors (TFTs). In order to produce high‐performance and long‐sustainable portable devices with the solution‐processed OS TFTs, the low‐operational voltage driving current is a key issue. Experimentally, increasing the gate‐insulator capacitances by high‐k dielectrics in the OS TFTs has significantly improved the field‐effect mobility of the OS TFTs. But, methodical examinations of how the field‐effect mobility depends on gate capacitance have not been presented yet. Here, a systematic analysis of the field‐effect mobility on the gate capacitances in the solution‐processed OS TFTs is presented, where the multiple‐trapping‐and‐release and hopping percolation mechanism are used to describe the electrical conductivity of the nanocrystalline and amorphous OSs, respectively. An intuitive single‐piece expression showing how the field‐effect mobility depends on gate capacitance is developed based on the aforementioned mechanisms. The field‐effect mobility, depending on the gate capacitances, of the fabricated ZnO and ZnSnO TFTs clearly follows the theoretical prediction. In addition, the way in which the gate insulator properties (e.g., gate capacitance or dielectric constant) affect the field‐effect mobility maximum in the nanocrystalline ZnO and amorphous ZnSnO TFTs are investigated.     

An Amidine‐Type n‐Dopant for Solution‐Processed Field‐Effect Transistors and Perovskite Solar Cells

This study reports an effective amidine‐type n‐dopant of 1,8‐Diazabicyclo[5.4.0]undec‐7‐ene (DBU) that can universally dope electron acceptors, including PC₆₁BM, N2200, and ITIC, by mixing the dopant with the acceptors in organic solvents or exposing the acceptor films in the dopant vapor. The doping mechanism is due to its strong electron‐donating property that is also confirmed via the chemical reduction of PEDOT:PSS (yielding color change). The DBU doping considerably increases the electrical conductivity and shifts the Fermi levels up of the PC₆₁BM films. When the DBU‐doped PC₆₁BM is used as an electron‐transporting layer in perovskite solar cells, the n‐doping removes the “S‐shape” of J–V characteristics, which leads to the fill factor enhancement from 0.54 to 0.76. Furthermore, the DBU doping can effectively lower the threshold voltage and enhance the electron mobility of PC₆₁BM‐based n‐channel field‐effect transistors. These results show that the DBU can be a promising n‐dopant for solution‐processed electronics.     

Solution Processable Fluorenyl Hexa‐peri‐hexabenzocoronenes in Organic Field‐Effect Transistors and Solar Cells

The organization of organic semiconductor molecules in the active layer of organic electronic devices has important consequences to overall device performance. This is due to the fact that molecular organization directly affects charge carrier mobility of the material. Organic field‐effect transistor (OFET) performance is driven by high charge carrier mobility while bulk heterojunction (BHJ) solar cells require balanced hole and electron transport. By investigating the properties and device performance of three structural variations of the fluorenyl hexa‐peri‐hexabenzocoronene (FHBC) material, the importance of molecular organization to device performance was highlighted. It is clear from ¹H NMR and 2D wide‐angle X‐ray scattering (2D WAXS) experiments that the sterically demanding 9,9‐dioctylfluorene groups are preventing π–π intermolecular contact in the hexakis‐substituted FHBC 4 . For bis‐substituted FHBC compounds 5 and 6 , π–π intermolecular contact was observed in solution and hexagonal columnar ordering was observed in solid state. Furthermore, in atomic force microscopy (AFM) experiments, nanoscale phase separation was observed in thin films of FHBC and [6,6]‐phenyl‐C61‐butyric acid methyl ester (PC₆₁BM) blends. The differences in molecular and bulk structural features were found to correlate with OFET and BHJ solar cell performance. Poor OFET and BHJ solar cells devices were obtained for FHBC compound 4 while compounds 5 and 6 gave excellent devices. In particular, the field‐effect mobility of FHBC 6 , deposited by spin‐casting, reached 2.8 × 10^?3 cm² V^?1 s and a power conversion efficiency of 1.5% was recorded for the BHJ solar cell containing FHBC 6 and PC₆₁BM.     

Insulator Polarization Mechanisms in Polyelectrolyte‐Gated Organic Field‐Effect Transistors

Electrolyte‐gated organic field‐effect transistors (OFETs) hold promise for robust printed electronics operating at low voltages. The polarization mechanism of thin solid electrolyte films, the gate insulator in such OFETs, is still unclear and appears to limit the transient current characteristics of the transistors. Here, the polarization response of a thin proton membrane, a poly(styrenesulfonic acid) film, is controlled by varying the relative humidity. The formation of the conducting transistor channel follows the polarization of the polyelectrolyte, such that the drain transient current characteristics versus the time are rationalized by three different polarization mechanisms: the dipolar relaxation at high frequencies, the ionic relaxation (migration) at intermediate frequencies, and the electric double‐layer formation at the polyelectrolyte interfaces at low frequencies. The electric double layers of polyelectrolyte capacitors are formed in ～1 µs at humid conditions and an effective capacitance per area of 10 µF cm^?2 is obtained at 1 MHz, thus suggesting that this class of OFETs might operate at up to 1 MHz at 1 V.     

Heterogeneous Nucleation Promotes Carrier Transport in Solution‐Processed Organic Field‐Effect Transistors

A new way to investigate and control the growth of solution‐cast thin films is presented. The combination of in situ quartz crystal microbalance measurements with dissipation capabilities (QCM‐D) and in situ grazing‐incidence wide‐angle X‐ray scattering (GIWAXS) in an environmental chamber provides unique quantitative insights into the time‐evolution of the concentration of the solution, the onset of nucleation, and the mode of growth of the organic semiconductor under varied drying conditions. It is demonstrated that careful control over the kinetics of solution drying enhances carrier transport significantly by promoting phase transformation predominantly via heterogeneous nucleation and sustained surface growth of a highly lamellar structure at the solid‐liquid interface at the expense of homogeneous nucleation.     

Emission Color Tuning in Ambipolar Organic Single‐Crystal Field‐Effect Transistors by Dye‐Doping

The effect of dye‐doping in ambipolar light‐emitting organic field‐effect transistors (LE‐OFETs) is investigated from the standpoint of the carrier mobilities and the electroluminescence (EL) characteristics under ambipolar operation. Dye‐doping of organic crystals permits not only tuning of the emission color but also significantly increases the efficiency of ambipolar LE‐OFETs. A rather high external EL quantum efficiency (～0.64%) of one order of magnitude higher than that of a pure p‐distyrylbenzene (P3V2) single crystal is obtained by tetracene doping. The doping of tetracene molecules into a host P3V2 crystal has almost no effect on the electron mobility and the dominant carrier recombination process in the tetracene‐doped P3V2 crystal involves direct carrier recombination on the tetracene molecules.