Control over microstructure evolution and device performance in solution processable organic field-effect transistors

Die Arbeit beschäftigt sich mit der Kontrolle von Selbstorganisation und Mikrostruktur von organischen Halbleitern und deren Einsatz in OFETs. In Kapiteln 3, 4 und 5 eine neue Lösungsmittel-basierte Verabeitungsmethode, genannt als Lösungsmitteldampfdiffusion, ist konzipiert, um die Selbstorganisation von Halbleitermolekülen auf der Oberfläche zu steuern. Diese Methode als wirkungsvolles Werkzeug erlaubt eine genaue Kontrolle über die Mikrostruktur, wie in Kapitel 3 am Beispiel einer D-A Dyad bestehend aus Hexa-peri-hexabenzocoronene (HBC) als Donor und Perylene Diimide (PDI) als Akzeptor beweisen. Die Kombination aus Oberflächenmodifikation und Lösungsmitteldampf kann die Entnetzungseffekte ausgleichen, so dass die gewüschte Mikrostruktur und molekulare Organisation auf der Oberfläche erreicht werden kann. In Kapiteln 4 und 5 wurde diese Methode eingesetzt, um die Selbstorganisation von Dithieno[2, 3-d;2’, 3’-d’] benzo[1,2-b;4,5-b’]dithiophene (DTBDT) und Cyclopentadithiophene -benzothiadiazole copolymer (CDT-BTZ) Copolymer zu steuern. Die Ergebnisse könnten weitere Studien stimulieren und werfen Licht aus andere leistungsfaähige konjugierte Polymere. rnIn Kapiteln 6 und 7 Monolagen und deren anschlieβende Mikrostruktur von zwei konjugierten Polymeren, Poly (2,5-bis(3-alkylthiophen-2-yl)thieno[3,2-b]thiophene) PBTTT und 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)) wurden auf steife Oberflächen mittels Tauchbeschichtung aufgebracht. Da sist das erste Mal, dass es gelungen ist, Polymer Monolagen aus der Lösung aufzubringen. Dieser Ansatz kann weiter auf eine breite Reihe von anderen konjugierten Polymeren ausgeweitet werden.rnIn Kapitel 8 wurden PDI-CN2 Filme erfolgreich von Monolagen zu Bi- und Tri-Schichten auf Oberflächen aufgebracht, die unterschiedliche Rauigkeiten besitzen. Für das erste Mal, wurde der Einfluss der Rauigkeit auf Lösungsmittel-verarbeitete dünne Schichten klar beschrieben.rn

Self-Assembled Monolayers (SAMs) in Organic Field-Effect Transistors

Organic printed electronics is attracting an ever-growing interest in the last decades because of its impressive breakthroughs concerning the chemical design of π-conjugated materials and their processing. This has an impact on novel applications, such as flexible-large-area displays, low- cost printable circuits, plastic solar cells and lab-on-a-chip devices. The organic field-effect transistor (OFET) relies on a thin film of organic semiconductor that bridges source and drain electrodes. Since its first discovery in the 80s, intensive research activities were deployed in order to control the chemico-physical properties of these electronic devices and consequently their charge. Self-assembled monolayers (SAMs) are a versatile tool for tuning the properties of metallic, semi-conducting, and insulating surfaces. Within this context, OFETs represent reliable instruments for measuring the electrical properties of the SAMs in a Metal/SAM/OS junction. Our experimental approach, named Charge Injection Organic-Gauge (CIOG), uses OTFT in a charge-injection controlled regime. The CIOG sensitivity has been extensively demonstrated on different homologous self-assembling molecules that differ in either chain length or in anchor/terminal group. One of the latest applications of organic electronics is the so-called “bio-electronics” that makes use of electronic devices to encompass interests of the medical science, such as biosensors, biotransducers etc… As a result, thee second part of this thesis deals with the realization of an electronic transducer based on an Organic Field-Effect Transistor operating in aqueous media. Here, the conventional bottom gate/bottom contact configuration is replaced by top gate architecture with the electrolyte that ensures electrical contact between the top gold electrode and the semiconductor layer. This configuration is named Electrolyte-Gated Field-Effect Transistor (EGOFET). The functionalization of the top electrode is the sensing core of the device allowing the detection of dopamine as well as of protein biomarkers with ultra-low sensitivity.

One-dimensional polyelectrolyte/polymeric semiconductor core/shell structure : sulfonated poly(arylene ether ketone)/polyaniline nanofibers for organic field-effect transistors

A polyelectrolyte/polymeric semiconductor core/shell structure is developed for organic field-effect transistors (OFETs) based on sulfonated poly(arylene ether ketone)/polyaniline core/shell nanofibers via electrospinning and solution-phase selective polymerization. The polyelectrolyte does not work as a gate dielectric, but can provide an internal modulation from the nanointerface of the 1D core/shell nanostructure. The transistor devices display very high mobilities.

Band gap tunable N-type molecules for organic field effect transistors

A series of four novel n-type molecules has been synthesized. Unlike previous approaches, the end group of these molecules was fixed and the molecular core was varied. The resulting materials were thoroughly analyzed. Electronic properties were derived from photoemission spectroscopy, optical properties were derived with the help of optical spectroscopy, and the structure of thin films on Au(111) was derived by scanning tunneling microscopy (STM). In addition, prototypical organic field-effect transistors (OFETs) (forming n-channels in OFETs) have been fabricated and tested. The correlation between the device performance of the respective OFETs (i.e., electron mobility) and their electronic as well as structural properties was investigated. It turned out that a combination of beneficial electronic and structural properties provides the best results. These findings are important for the design of new materials for future device applications.

Characteristics of high-performance ambipolar organic field-effect transistors based on a diketopyrrolopyrrole-benzothiadiazole copolymer

In this paper, we report the device characteristics of ambipolar thin-film transistors (TFTs) based on a diketopyrrolopyrrole-benzothiadiazole copolymer. This polymer semiconductor exhibits the largest comparable electron and hole mobility values in a single organic semiconductor. The key to realizing such high mobility values, which are $0.5&cm}{2}/\hbox{V}̇\hbox{s, is molecular design, i.e., the use of suitable surface treatments of the source/drain contact electrodes and device architectures, particularly top-gate configurations. The subthreshold characteristics of the TFT devices are greatly improved by the use of dual-gate device geometry. We also report the first measurement of the velocity distribution of electron and hole velocities in an ambipolar organic semiconductor.

A fluorenone based low band gap solution processable copolymer for air stable and high mobility organic field effect transistors

A fluorenone based alternating copolymer (PFN-DPPF) with a furan based fused aromatic moiety has been designed and synthesized. PFN-DPPF exhibits a small band gap with a lower HOMO value. Testing this polymer semiconductor as the active layer in organic thin-film transistors results in hole mobilities as high as 0.15 cm2 V-1 s-1 in air.

Isoindigo dye incorporated copolymers with naphthalene and anthracene: promising materials for stable organic field effect transistors

In this paper, we report the design and synthesis of isoindigo based low band gap polymer semiconductors, poly{N,N′-(2-octyldodecyl)-isoindigo-alt- naphthalene} (PISD-NAP) and poly{N,N′-(2-octyldodecyl)-isoindigo-alt- anthracene} (PISD-ANT). A series of donor-acceptor (D-A) copolymers can be prepared where donor and acceptor conjugated blocks can be attached alternately using organometallic coupling. In these polymers, an isoindigo dye acceptor moiety has been attached alternately with naphthalene and anthracene donor comonomer blocks by Suzuki coupling. PISD-NAP and PISD-ANT exhibit excellent solution processibility and good film-forming properties. Gel permeation chromatography exhibits a higher molecular mass with lower polydispersity. UV-vis-NIR absorption of these polymers exhibits a wide absorption band ranging from 300 nm to 800 nm, indicating the low band gap nature of the polymers. Optical band gaps calculated from the solid state absorption cutoff value for PISD-NAP and PISD-ANT are around 1.80 eV and 1.75 eV, respectively. Highest occupied molecular orbital (HOMO) values calculated respectively for PISD-NAP and PISD-ANT thin films on glass substrate by photoelectron spectroscopy in air (PESA) are 5.66 eV and 5.53 eV, indicative of the good stability of these materials in organic electronic device applications. These polymers exhibit p-channel charge transport characteristics when used as the active semiconductor in organic thin-film transistor (OTFT) devices in ambient conditions. The highest hole mobility of 0.013 cm2 V-1 s-1 is achieved in top contact and bottom-gate OTFT devices for PISD-ANT, whereas polymer PISD-NAP exhibited a hole mobility of 0.004 cm2 V -1 s-1. When these polymer semiconductors were used as a donor and PC71BM as an acceptor in OPV devices, the highest power conversion efficiency (PCE) of 1.13% is obtained for the PISD-ANT polymer.

Thiophene–tetrafluorophenyl–thiophene : a promising building block for ambipolar organic field effect transistors

A thiophene–tetrafluorophenyl–thiophene donor–acceptor–donor building block was used in combination with a furan-substituted diketopyrrolopyrrole for synthesizing the polymer semiconductor, PDPPF-TFPT. Due to the balance of tetrafluorophenylene/diketopyrrolopyrrole electron-withdrawing and furan/thiophene electron-donating moieties in the backbone, PDPPF-TFPT exhibits ambipolar behaviour in organic thin-film transistors, with hole and electron mobilities as high as 0.40 cm2 V−1 s−1 and 0.12 cm2 V−1 s−1.

Solution processable quinoxaline based molecular materials for organic field effect transistors

Three new solution processable quinoxaline based donor-acceptor-donor (D-A-D) type molecules have been synthesized for application in field effect transistors. These molecules were characterized by UV-visible spectroscopy, thermal gravimetric analysis, differential scanning calorimetry and cyclic voltammetry. DFT calculation gives deeper insight into the electronic structure of these molecules. The crystallinity and morphology features of thin film were investigated using X-ray diffraction. These molecules show liquid crystalline phase confirmed by DSC and optical polarizing microscopy. Investigation of their field effect transistor performance indicated that these molecules exhibited p-type mobility up to 9.7 x 10 (4) cm(2) V (1) s (1) and on/off ratio of 10(4). (C) 2012 Elsevier B.V. All rights reserved.

Diketopyrrolopyrrole-Diketopyrrolopyrrole-Based Conjugated Copolymer for High-Mobility Organic Field-Effect Transistors

In this communication, we report the synthesis of a novel diketopyrrolopyrrole-diketopyrrolopyrrole (DPP-DPP)-based conjugated copolymer and its application in high-mobility organic field-effect transistors. Copolymerization of DPP with DPP yields a copolymer with exceptional properties such as extended absorption characteristics (up to similar to 1100 nm) and field-effect electron mobility values of >1 cm(2) V-1 s(-1). The synthesis of this novel DPP-DPP copolymer in combination with the demonstration of transistors with extremely high electron mobility makes this work an important step toward a new family of DPP-DPP copolymers for application in the general area of organic optoelectronics.

π-Conjugated molecules with fused rings for organic field-effect transistors: design, synthesis and applications

π-Conjugated molecular materials with fused rings are the focus of considerable interest in the emerging area of organic electronics, since the combination of excellent charge carrier mobility and high stability may lead to their practical applications. This tutorial review discusses the synthesis, properties and applications of π-conjugated organic semiconducting materials, especially those with fused rings. The achievements to date, the remaining problems and challenges, and the key research that needs to be done in the near future are all discussed.