Modulation of surface solubility and wettability for high-performance inkjet-printed organic transistors

The surface solubility and wettability of photosensitive layers of polystyrene (PS) were engineered to evaluate its effect on the crystalline microstructure and film morphology of inkjet-printed 6,13-bis(triisopropylsiylethynyl) pentacene (TIPS-pentacene). UV exposure proved to be a simple and effective method for modulating the solubility of PS films with controllable crosslinking. As compared with the untreated PS film, the film morphology of the printed semiconductor on the UV-irradiated crosslinked PS films was significantly optimized. The optimal degree of crosslinking and solubility of the PS film were achieved by UV irradiation at a dose of 0.417 J cm⁻². Field-effect transistors fabricated using well-organized crystals on the optimal crosslinked PS film exhibited a maximum mobility of 0.48 cm² V⁻¹ s⁻¹ and an average value of 0.19 cm² V⁻¹ s⁻¹. The performance is clearly superior to that of devices prepared on a pristine PS film (0.02 cm² V⁻¹ s⁻¹).     

A new diketopyrrolopyrrole-based co-polymer for ambipolar field-effect transistors and solar cells

A new thieno[3,2-b]thiophenediketopyrrolopyrrole-benzo[1,2-b:4,5-b′]dithiophene based narrow optical gap co-polymer (PTTDPP-BDT) has been synthesized and characterized for field-effect transistors and solar cells. In field-effect transistors the polymer exhibited ambipolar charge transport behaviour with maximum hole and electron mobilities of 10⁻³ cm² V⁻¹ s⁻¹ and 10⁻⁵ cm² V⁻¹ s⁻¹, respectively. The respectable charge transporting properties of the polymer were consistent with X-ray diffraction measurements that showed close molecular packing in the solid state. The difference in hole and electron mobilities was explained by density functional theory calculations, which showed that the highest occupied molecular orbital was delocalized along the polymer backbone with the lowest unoccupied molecular orbital localized on the bis(thieno[3,2-b]thiophene)diketopyrrolopyrrole units. Bulk heterojunction photovoltaic devices with the fullerene acceptor PC₇₀BM were fabricated and delivered a maximum conversion efficiency of 3.3% under AM1.5G illumination.     

Interface optimization using diindenoperylene for C60 thin film transistors with high electron mobility and stability

C₆₀-based organic thin film transistors (OTFTs) with high electron mobility and high operational stability are achieved with (1 1 1) oriented C₆₀ films grown by using template effects of diindenoperylene (DIP) under layer on the SiO₂ gate insulator. The electron mobility of the C₆₀ transistor is significantly increased from 0.21 cm² V⁻¹ s⁻¹ to 2.92 cm² V⁻¹ s⁻¹ by inserting the template-DIP layer. Moreover much higher operational stability is also observed for the DIP-template C₆₀ OTFTs. A grazing incidence X-ray diffraction and ultrahigh-sensitivity photoelectron spectroscopy measurements indicate that the improved electron mobility and stability arise from the decreased density of trap states in the C₆₀ film due to increased (1 1 1) orientation of C₆₀-grains and their crystallinity on the DIP template.     

Toward High Mobility Green Solvent-Processable Conjugated Polymers: A Systematic Study on Chalcogen Effect in Poly(Diketopyrrolopyrrole-alt-Terchalcogenophene)s

Nine diketopyrrolopyrrole (DPP)-based conjugated polymers (CPs), that is, poly(diketopyrrolopyrrole-alt-terchalcogenophene)s, via combinations of furanyl-(FDPP), thienyl-(TDPP), selenophenyl-DPP (SeDPP) and furan, thiophene, selenophene comonomers, are synthesized to explore the chalcogen effect on the solubility, film morphology/microstructure, and charge transport property of the resultant polymers. All polymers except for SeDPP-Se are soluble in non-chlorinated solvents such as o-xylene and tetralin. Flanking of DPP with furan in FDPP-F, FDPP-T, and FDPP-Se enables even good solubility in green solvent anisole. TDPP-Se exhibits the highest reliable hole mobility over 10 cm² V⁻¹ s⁻¹ in organic thin film transistors (OTFTs) bar-coated from o-xylene/tetralin (20/80 v/v) solution. With anisole as the processing solvent, FDPP-F-based bar-coated OTFTs displays a reliable hole mobility up to 3.50 cm² V⁻¹ s⁻¹. This is the first report on green solvent processed OTFTs with mobility above 1 cm² V⁻¹ s⁻¹. Charge transport property of all the polymers is correlated with the film morphology and microstructure that are noticeably influenced by the type and position of chalcogenophenes. The current work sheds light on the design of high mobility CPs processable with green solvents.     

Using unsorted single-wall carbon nanotubes to enhance mobility of diketopyrrolopyrrole-quarterthiophene copolymer in thin-film transistors

Organic thin film transistors (OTFTs) were fabricated for the first time using a semiconductor copolymer of diketopyrrolopyrrole-quarterthiophene (DPP-QT) and unsorted single walled carbon nanotubes (SWCNTs). Three different SWCNTs having different tube diameters, length, and shape were used to investigate the effects of carbon nanotubes’ properties on dispersion of the SWCNTs in DPP-QT polymer, as well as the mobility and current on/off ratio of the OTFTs. The DPP-QT polymer was able to selectively disperse two types of SWCNTs. An optimal SWCNT loading was found to be 1.5–2.5 wt% for these SWCNTs, before the on/off ratio fell below 10⁵ due to increased metallic tube content of the film. At this optimal loading, the field effect mobility was improved by a factor of two, with the maximum mobility reaching 1.3 cm² V⁻¹ s⁻¹, when the SWCNTs with a short length and small tube diameter were used.     

A simple droplet pinning method for polymer film deposition for measuring charge transport in a thin film transistor

Thin-film field-effect transistors (FETs) are widely used to evaluate charge transport properties of semiconducting polymers. Discovery of high performance materials require design and synthesis of new polymers. However, most polymers require multi-step synthesis and are difficult to be obtained in a large scale for comprehensive device evaluations. Here, we report a simple method to cast semiconducting polymer films from solutions with polymer concentration as low as 0.5 mg/mL, which is substantially less than typical values (∼10 mg/mL) used in conventional spin coating method. Here, we demonstrate that using this method, our cast films of a previously-reported polymer (PDPP-TT2T) exhibited field-effect mobility (μ_hole = 0.89 ± 0.13 cm² V⁻¹ s⁻¹, μ_e = 0.025 ± 0.005 cm² V⁻¹ s⁻¹), which is comparable to the reported values using the same device geometry. Furthermore, we extend this method to examine cast films of a pair of polymers (PDPP-3T-Ref, PDPP-3T-Si) to study the effect of siloxane substitution in the side chains on the molecular packing and their subsequent FET performance. We observed that shorter π-stacking distance (3.61 Å) for the siloxane-terminated polymer, when compared to that for the reference polymer (3.73 Å), resulted in improved FET performance (e.g., μ_hole = 0.63 ± 0.046 cm² V⁻¹ s⁻¹ for PDPP-3T-Si vs μ_hole = 0.17 ± 0.062 cm² V⁻¹ s⁻¹ for PDPP-3T-Ref). Taken together, this work presents an efficient alternative film-casting approach to produce polymer FETs that consumes much less material for their fabrication, lending viability for evaluation of various polymeric materials.     

Photo-Patternable Stretchable Semi-Interpenetrating Polymer Semiconductor Network Using Thiol–Ene Chemistry for Field-Effect Transistors

Stretchable polymer semiconductors are an essential component for skin-inspired electronics. However, the lack of scalable patterning capability of stretchable polymer semiconductors limits the development of stretchable electronics. To address this issue, photo-curable stretchable polymer blends consisting of a high-mobility donor–acceptor conjugated polymer and an elastic rubber through thiol–ene chemistry are developed. The thiol–ene reaction can selectively cross-link the rubber with alkene or vinyl groups without damaging the electronic properties of the conjugated polymer. The conjugated polymer chains embedded in the elastic polymer matrix induce a semi-interpenetrating polymer network (SIPN). The thiol–ene-cross-linked network provides great solvent resistance and enhances stretchability for the embedded conjugated polymer. The well-defined patterned film with a feature size of ≈10 µm can be obtained using UV light at 365 nm through conventional photolithography processes. Furthermore, the SIPN-based transistors show increased mobilities from 0.61 to 1.18 cm² V⁻¹ s⁻¹ when applying the strain from 0% to 100%. Moreover, the hole mobility can still maintain at 0.87 cm² V⁻¹ s⁻¹ after 1000 strain-and-release cycles at the strain of 25%. This study sheds light on the molecular design of photo-curable polymer semiconductors for the mass production of stretchable circuits.     

BODIPY derivatives as n-type organic semiconductors: Isomer effect on carrier mobility

In the present work, two dipyrro-boradiazaindacenes (BODIPY) derivatives functioning as novel high-performance organic semiconductors are investigated by theoretical method. These two isomeric complexes are demonstrated to have large electron-transfer mobility, which means they are favor to be n-type organic semiconductors. The highest electron-transfer mobility appears at the same packing style in two crystals. The intermolecular distances of the packing style are nearly same, 4.994 Å in crystal 1 and 5.283 Å in crystal 2. However, their electron-transfer mobility changes significantly. The mobility of crystal 2 with better planar molecular structure is 0.291 cm² V⁻¹ s⁻¹, which is 13 times larger than that of crystal 1 as 0.022 cm² V⁻¹ s⁻¹. The significant difference of carrier mobility is ascribed to the little structural difference of these two isomers. It has been demonstrated that both crystal 1 and 2 show remarkable anisotropic behavior. This study will undoubtedly provide a new understanding of isomerization on designing novel organic semiconductors.     

Benzodithiophene and benzotrithiophene-based conjugated polymers for organic thin-film transistors application: Impact of conjugated- and acyl-side chain

A series of benzodithiophene (BDT) and benzotrithiophene (BTT)-based conjugated polymers (P1–P4), with/without conjugated- and acyl-side chain, have been synthesized by Stille cross-coupling reaction. Their thermal, photophysical, electrochemical properties, devices performances, and microstructure have been investigated. Conjugated-side chain can significantly raise the thermal stability and acyl-side chain can lower HOMO/LUMO energy levels. Organic thin-film transistors (OTFTs) based on conjugated polymers were fabricated and the transistor electrical characterization showed the device performance was sensitive to the conjugated- and acyl-side chain substituent of polymers. A maximum hole mobility of 1.70 × 10⁻³ cm² V⁻¹ s⁻¹ was obtained for P1-based devices, which is an order of magnitude higher than those of P3 and P4-based devices. The corresponding microstructures were investigated by grazing-incidence X-ray diffraction (GIXD) to correlate with conjugated- and acyl-side chain dependent carrier mobility of P1–P4. The results showed that the conjugated- and acyl-side chain have an impact on the polymer packing models and device performances.     

Effect of Non‐Chlorinated Mixed Solvents on Charge Transport and Morphology of Solution‐Processed Polymer Field‐Effect Transistors

Using non‐chlorinated solvents for polymer device fabrication is highly desirable to avoid the negative environmental and health effects of chlorinated solvents. Here, a non‐chlorinated mixed solvent system, composed by a mixture of tetrahydronaphthalene and p­‐xylene, is described for processing a high mobility donor‐acceptor fused thiophene‐diketopyrrolopyrrole copolymer (PTDPPTFT4) in thin film transistors. The effects of the use of a mixed solvent system on the device performance, e.g., charge transport, morphology, and molecular packing, are investigated. p‐Xylene is chosen to promote polymer aggregation in solution, while a higher boiling point solvent, tetrahydronaphthalene, is used to allow a longer evaporation time and better solubility, which further facilitates morphological tuning. By optimizing the ratio of the two solvents, the charge transport characteristics of the polymer semiconductor device are observed to significantly improve for polymer devices deposited by spin coating and solution shearing. Average charge carrier mobilities of 3.13 cm² V^?1 s^?1 and a maximum value as high as 3.94 cm² V^?1 s^?1 are obtained by solution shearing. The combination of non‐chlorinated mixed solvents and the solution shearing film deposition provide a practical and environmentally‐friendly approach to achieve high performance polymer transistor devices.     

Controlling aggregation and crystallization of solution processed diketopyrrolopyrrole based polymer for high performance thin film transistors by pre-metered slot die coating process

The organic semiconductors have attracted much attention for plastic electronics due to their good solution processability, low temperature deposition, and compatible with large-area printing technology. The charge transport properties of polymer based field effect transistors are limited by their amorphous domains and weakly interaction between polymer chains. In this study, antisolvent like methanol is introduced to promote polymer chain aggregation, and slot die coating is used to finely tune the film morphology. The effects of anti-solvent introduction and slot die coating process on the device performance, e.g. charge transport, surface morphology, and solid state packing, were investigated in details. By optimizing the antisolvent ratio and polymer chain aggregation, the charge transport properties of the polymer devices were observed to be significantly improved. An average charge carrier mobility of 3.76 cm² V⁻¹ s⁻¹ and a maximum mobility of 4.10 cm² V⁻¹ s⁻¹ were achieved under optimized conditions. The controlling the aggregation degree by combining the mixed solvent system and slot die coating technique provides a convenient and practical approach to achieve high performance polymer field effect transistor.     

Downscaling of n-channel organic field-effect transistors with inkjet-printed electrodes

In this contribution we demonstrate for the first time a downscaled n-channel organic field-effect transistors based on N,N′-dialkylsubstituted-(1,7&1,6)-dicyanoperylene-3,4:9,10-bis(dicarboximide) with inkjet printed electrodes. First we demonstrate that the use of a high boiling point solvent is critical to achieve extended crystalline domains in spin-coated thin films and thus high electron mobility >0.1 cm² V⁻¹ s⁻¹ in top-gate devices. Then inkjet-printing is employed to realize sub-micrometer scale channels by dewetting of silver nanoparticles off a first patterned gold contact. By employing a 50 nm crosslinked fluoropolymer gate dielectric, ∼200 nm long channel transistors can achieve good current saturation when operated <5 V with good bias stress stability.     

Organic nonvolatile memory transistors based on fullerene and an electron-trapping polymer

We report for the first time organic n-type nonvolatile memory transistors based on a fullerene (C₆₀) semiconductor and an electron-trapping polymer, poly(perfluoroalkenyl vinyl ether) (CYTOP). The transistors with a Si++/SiO₂/CYTOP/C₆₀/Al structure show good n-type transistor performance with a threshold voltage (V_th) of 2.8 V and an electron mobility of 0.4 cm² V⁻¹ s⁻¹. Applying gate voltages of 50 or −45 V for about 0.1 s to the devices induces the reversible shifts in their transfer characteristics, which results in a large memory window (ΔV_th) of 10 V. A memory on/off ratio of 10⁵ at a small reading voltage below 5 V and a retention time greater than 10⁵ s are achieved. The memory effect in the transistor is ascribed to electrons trapped at the CYTOP/SiO₂ interface. Because of the use of high-electron-mobility C₆₀, the switching voltages of our memory transistors become significantly lower than those of conventional memory transistors based on pentacene.     

High performance p-type organic thin film transistors with an intrinsically photopatternable,ultrathin polymer dielectric layer

A high-performing bottom-gate top-contact pentacene-based oTFT technology with an ultrathin (25–48 nm) and electrically dense photopatternable polymeric gate dielectric layer is reported. The photosensitive polymer poly((±)endo,exo-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid, diphenylester) (PNDPE) is patterned directly by UV-exposure (λ = 254 nm) at a dose typical for conventionally used negative photoresists without the need for any additional photoinitiator. The polymer itself undergoes a photo-Fries rearrangement reaction under UV illumination, which is accompanied by a selective cross-linking of the macromolecules, leading to a change in solubility in organic solvents. This crosslinking reaction and the negative photoresist behavior are investigated by means of sol–gel analysis. The resulting transistors show a field-effect mobility up to 0.8 cm² V⁻¹ s⁻¹ at an operation voltage as low as −4.5 V. The ultra-low subthreshold swing in the order of 0.1 V dec⁻¹ as well as the completely hysteresis-free transistor characteristics are indicating a very low interface trap density. It can be shown that the device performance is completely stable upon UV-irradiation and development according to a very robust chemical rearrangement. The excellent interface properties, the high stability and the small thickness make the PNDPE gate dielectric a promising candidate for fast organic electronic circuits.     

Bottom-contact small-molecule n-type organic field effect transistors achieved via simultaneous modification of electrode and dielectric surfaces

Low-voltage, n-type organic field effect transistors (OFETs) with simultaneously modified bottom-contact (BC) electrodes and dielectric were compared to their top-contact (TC) counterparts. The devices modified with 6-phenoxyhexylphosphonic acid (Ph6PA) self-assembled monolayer (SAM) showed similar performance, morphology, and contact resistance. Electron mobility of C₆₀ devices were 0.212 and 0.320 cm² V⁻¹ s⁻¹ and [6,6]-phenyl-C₆₁-butyric acid methyl ester (PCBM) devices were 0.04 and 0.06 cm² V⁻¹ s⁻¹ for TC and BC devices, respectively. Low contact resistance between 11 and 45 kΩ cm was found regardless of device architecture or n-type semiconductor used. This work shows it is possible to fabricate solution processable low-voltage bottom-contact devices with performance that is similar or better than their top-contact counterparts without the addition of complex and time-consuming processing steps.     

Hydrated bovine serum albumin as the gate dielectric material for organic field-effect transistors

Bovine serum albumin (BSA) is a natural protein with good hydration ability which contains acidic and basic amino acid residues of ca. 34% in total. In vacuum, pentacene organic field-effect transistors (OFETs) with BSA as the gate dielectric exhibits a field-effect mobility value (μ_FE,sat) of 0.3 cm² V⁻¹ s⁻¹ in the saturation regime and a threshold voltage (V_TH) of ca. −16 V. BSA is easy to be hydrated in air ambient. Electrical properties of BSA in vacuum and hydrated BSA in air ambient are characterized. Similar to polyelectrolyte, hydrated BSA may act the gate dielectric with the formation of electric double-layer capacitors (EDLCs) to improve the device performance. In a relative humidity of 47%, the μ_FE,sat value increases to 4.7 cm² V⁻¹ s⁻¹ and the V_TH reduces to −0.7 V. Generation of mobile ions in hydrated BSA and the formation of EDLCs are discussed.     

Molecular Packing‐Induced Transition between Ambipolar and Unipolar Behavior in Dithiophene‐4,9‐dione‐Containing Organic Semiconductors

By changing the packing motif of the conjugated cores and the thin‐film microstructures, unipolar organic semiconductors may be converted into ambipolar materials. A combined experimental and theoretical investigation is conducted on the thin‐film organic field‐effect transistors (OFETs) of three organic semiconductors that have the same conjugated core structure of s‐indaceno[1,2‐b:5,6‐b′]dithiophene‐4,9‐dione but with different n‐alkyl groups. The optical and electrochemical measurements suggest that the three organic semiconductors have very similar energy levels; however, their OFETs exhibit dramatically different transport characteristics. Transistors based on compound 1a or 1c show ambipolar transport properties, while those based on compound 1b show p‐type unipolar behavior. Specifically, compound 1c is characterized as a good ambipolar semiconductor with the highest electron mobility of 0.22 cm² V^?1 s^?1 and the highest hole mobility of 0.03 cm² V^?1 s^?1. Complementary metal oxide semiconductor (CMOS) inverters incorporated with compound 1c show sharp inversions with high gains above 50. Theoretical investigations reveal that the drastic difference in the transport properties of the three materials is due to the difference in their molecular packing and film microstructures.     

Materials and interfaces issues in pentacene/PTCDI-C8 ambipolar organic field-effect transistors with solution-based gelatin dielectric

Gelatin is a natural protein, which works well as the gate dielectric for pentacene/N,N-dioctyl-3,4,9,10-perylene tetracarboxylic diimide (PTCDI-C₈) ambipolar organic field-effect transistors (OFETs) in air ambient and in vacuum. An aqueous solution process was used to form the gelatin gate dielectric film on poly(ethylene terephthalate) (PET) by spin-coating and subsequent casting. Pentacene morphology and interface roughness are two major factors affecting the electron and hole field-effect mobility (μ_FE) values of pentacene/PTCDI-C₈ ambipolar OFETs in vacuum and in air ambient. In contrast, water absorption in gelatin has higher contribution to the electron and hole μ_FE values in air ambient. The ambipolar performance of pentacene/PTCDI-C₈ ambipolar OFETs depends on their layer sequence. For example, when PTCDI-C₈ is deposited onto pentacene, i.e. in the structure of PTCDI-C₈/pentacene, unbalanced ambipolar characteristics appear. In contrast, better ambipolar performance occurs in the structure of pentacene/PTCDI-C₈. The optimum ambipolar characteristics with electron μ_FE of 0.85 cm² V⁻¹ s⁻¹ and hole μ_FE of 0.95 cm² V⁻¹ s⁻¹ occurs at the condition of pentacene (40 nm)/PTCDI-C₈ (40 nm). Surprisingly, water absorption plays a crucial role in ambipolar performance. The device performance changes tremendously in pentacene/PTCDI-C₈ ambipolar OFETs due to the removal of water out of gelatin in vacuum. The optimum ambipolar characteristics with electron μ_FE of 0.008 cm² V⁻¹ s⁻¹ and hole μ_FE of 0.007 cm² V⁻¹ s⁻¹ occurs at the condition of pentacene (65 nm)/PTCDI-C₈ (40 nm). The roles of layer sequence, relative layer thickness, and water absorption are proposed to explain the ambipolar performance.     

Alcohol as a Processing Solvent of Polymeric Semiconductors to Fabricate Environmentally Benign and High Performance Polymer Field Effect Transistors

Here, a novel strategy is reported to develop polymer field effect transistors using ethanol, propanol, and butanol—the most environmentally benign solvent except water—as processing solvents. From such environmentally benign processes, for the first time high‐mobility (>1 cm² V^?1 s^?1) polymer field effect transistors are demonstrated. These mobility values realized from “really green solvents” exceed those of conventional hydrogenated amorphous silicon semiconductors. To achieve this 1) stable sub‐microparticles of conjugated polymers dispersed in alcohols are fabricated, 2) an aldehyde‐assisted surface tension‐depression methodology is developed to successfully form thin films from alcohol, and 3) the structural information of alcohol‐dispersed sub‐microparticles of semiconducting polymers is carefully characterized.     

Methylated conjugated polymers based on diketopyrrolopyrrole and dithienothiophene for high performance field-effect transistors

In this work, a series of conjugated polymers based on diketopyrrolopyrrole (DPP) and dithienothiophene were designed for application in field-effect transistors (FETs). Owing to the synthetic nature of DPP units, the DPP polymers here contain different aromatic linkers with thiophene and methylthiophene, resulting in non-methylated and methylated DPP polymers. Methylated DPP polymers were found to show good crystalline properties and provide high hole mobilties up to 5.32 cm² V⁻¹ s⁻¹ in FETs, while non-methylated polymer exhibits a hole mobility of 3.16 cm² V⁻¹ s⁻¹. Especially, the polymer containing asymmetric linkers presents “face-on” orientation in thin films but provides the highest mobility. Our results reveal that the polymers incorporating methyl units as side chains can be used to realize high carrier mobility in FETs.