Peter J. Diemer

Vibration‐Assisted Crystallization Improves Organic/Dielectric Interface in Organic Thin‐Film Transistors

Solution processability of organic semiconductors allows high-throughput fabrication on arbitrary substrates at low-cost, but the films often exhibit low performance. Here, we report on a new method for device fabrication, vibration assisted crystallization (VAC) that produces superior films, which approach the fundamental performance limits shown in corresponding single-crystal measurements.

Quantitative analysis of the density of trap states at the semiconductor-dielectric interface in organic field-effect transistors

The electrical properties of organic field-effect transistors are governed by the quality of the constituting layers, and the resulting interfaces. We compare the properties of the same organic semiconductor film, 2,8-difluoro- 5,11-bis (triethylsilylethynyl) anthradithiophene, with bottom SiO2 dielectric and top Cytop dielectric and find a 10× increase in charge carrier mobility, from 0.17 ± 0.19 cm2 V−1 s−1 to 1.5 ± 0.70 cm2 V−1 s−1, when the polymer dielectric is used. This results from a significant reduction of the trap density of states in the semiconductor band-gap, and a decrease in the contact resistance.

Oriented Liquid Crystalline Polymer Semiconductor Films with Large Ordered Domains

Large strains are applied to liquid crystalline poly(2,5-bis(3-tetradecylthiophen-2yl)thieno(3,2-b)thiophene) (pBTTT) films when held at elevated temperatures resulting in in-plane polymer alignment. We find that the polymer backbone aligns significantly in the direction of strain, and that the films maintain large quasi-domains similar to that found in spun-cast films on hydrophobic surfaces, highlighted by dark-field transmission electron microscopy imaging. The highly strained films also have nanoscale holes consistent with dewetting. Charge transport in the films is then characterized in a transistor configuration, where the field effect mobility is shown to increase in the direction of polymer backbone alignment, and decrease in the transverse direction. The highest saturated field-effect mobility was found to be 1.67 cm(2) V(-1) s(-1), representing one of the highest reported mobilities for this material system. The morphology of the oriented films demonstrated here contrast significantly with previous demonstrations of oriented pBTTT films that form a ribbon-like morphology, opening up opportunities to explore how differences in molecular packing features of oriented films impact charge transport. Results highlight the role of grain boundaries, differences in charge transport along the polymer backbone and π-stacking direction, and structural features that impact the field dependence of charge transport.

Crossover from band-like to thermally activated charge transport in organic transistors due to strain-induced traps

Significance The operation of organic field-effect transistors is governed by the processes taking place at the device interfaces. The mismatch in the coefficients of thermal expansion of the consecutive layers can induce inhomogeneous strain in the organic semiconductor layer and reduce performance by increasing the electronic trap density. We show that a high-quality organic semiconductor layer is necessary, but not sufficient, to obtain efficient charge-carrier transport, and we propose a device design strategy that allows us to achieve the intrinsic performance limits of a given organic semiconductor regardless of the relative thermal expansions of the constituent layers. The temperature dependence of the charge-carrier mobility provides essential insight into the charge transport mechanisms in organic semiconductors. Such knowledge imparts critical understanding of the electrical properties of these materials, leading to better design of high-performance materials for consumer applications. Here, we present experimental results that suggest that the inhomogeneous strain induced in organic semiconductor layers by the mismatch between the coefficients of thermal expansion (CTE) of the consecutive device layers of field-effect transistors generates trapping states that localize charge carriers. We observe a universal scaling between the activation energy of the transistors and the interfacial thermal expansion mismatch, in which band-like transport is observed for similar CTEs, and activated transport otherwise. Our results provide evidence that a high-quality semiconductor layer is necessary, but not sufficient, to obtain efficient charge-carrier transport in devices, and underline the importance of holistic device design to achieve the intrinsic performance limits of a given organic semiconductor. We go on to show that insertion of an ultrathin CTE buffer layer mitigates this problem and can help achieve band-like transport on a wide range of substrate platforms.

The Influence of Isomer Purity on Trap States and Performance of Organic Thin‐Film Transistors

Organic field-effect transistor (OFET) performance is dictated by its composition and geometry, as well as the quality of the organic semiconductor (OSC) film, which strongly depends on purity and microstructure. When present, impurities and defects give rise to trap states in the bandgap of the OSC, lowering device performance. Here, 2,8-difluoro-5,11-bis(triethylsilylethynyl)-anthradithiophene is used as a model system to study the mechanism responsible for performance degradation in OFETs due to isomer coexistence. The density of trapping states is evaluated through temperature dependent current-voltage measurements, and it is discovered that OFETs containing a mixture of syn- and anti-isomers exhibit a discrete trapping state detected as a peak located at ~ 0.4 eV above the valence-band edge, which is absent in the samples fabricated on single-isomer films. Ultraviolet photoelectron spectroscopy measurements and density functional theory calculations do not point to a significant difference in electronic band structure between individual isomers. Instead, it is proposed that the dipole moment of the syn-isomer present in the host crystal of the anti-isomer locally polarizes the neighboring molecules, inducing energetic disorder. The isomers can be separated by applying gentle mechanical vibrations during film crystallization, as confirmed by the suppression of the peak and improvement in device performance.

Solution-Processed Organic and Halide Perovskite Transistors on Hydrophobic Surfaces

Solution-processable electronic devices are highly desirable due to their low cost and compatibility with flexible substrates. However, they are often challenging to fabricate due to the hydrophobic nature of the surfaces of the constituent layers. Here, we use a protein solution to modify the surface properties and to improve the wettability of the fluoropolymer dielectric Cytop. The engineered hydrophilic surface is successfully incorporated in bottom-gate solution-deposited organic field-effect transistors (OFETs) and hybrid organic-inorganic trihalide perovskite field-effect transistors (HTP-FETs) fabricated on flexible substrates. Our analysis of the density of trapping states at the semiconductor-dielectric interface suggests that the increase in the trap density as a result of the chemical treatment is minimal. As a result, the devices exhibit good charge carrier mobilities, near-zero threshold voltages, and low electrical hysteresis.

Low-temperature phase transitions in a soluble oligoacene and their effect on device performance and stability

The use of organic semiconductors in high-performance organic field-effect transistors requires a thorough understanding of the effects that processing conditions, thermal, and bias-stress history have on device operation. Here, we evaluate the temperature dependence of the electrical properties of transistors fabricated with 2,8-difluoro-5,11-bis(triethylsilylethynyl)anthradithiophene, a material that has attracted much attention recently due to its exceptional electrical properties. We have discovered a phase transition at T = 205 K and discuss its implications on device performance and stability. We examined the impact of this low-temperature phase transition on the thermodynamic, electrical, and structural properties of both single crystals and thin films of this material. Our results show that while the changes to the crystal structure are reversible, the induced thermal stress yields irreversible degradation of the devices.

Organic thin-film transistor fabrication using a laser printer (Conference Presentation)

Organic electronic materials are desirable due to facile and low-cost manufacturing through solution deposition. However, the inherit difficulties of reproducibility and solvent compatibility, as well as the hazards associated with the solvents, have stifled the progress of realizing practical solution-deposition methods. As a result, organic thin-films used in industry are typically produced by thermal evaporation techniques, which largely negate the benefits due to the higher cost and complexity of vacuum and evaporation equipment. Here we report the use of a conventional office laser printer to electrophotographically deposit the organic semiconductor layer in thin-film transistors. We have successfully used this solvent-free, low-cost method to produce the first laser-printed organic semiconductor layer in thin-film transistors. We printed on flexible and transparent polyethylene terephthalate (PET) substrates. We used the highly hydrophobic fluoropolymer Cytop as the dielectric in a bottom-gate, bottom-contact configuration, a feat that is not possible with traditional solution-deposition. The organic semiconductor layer consisted of a toner powder based on triisopropylsilylethynyl pentacene (TIPS Pn). Grazing incidence wide-angle X-ray scattering (GIWAXS) images indicated both edge- and face-on orientations of the semiconductor for these devices while electrical measurements revealed field-effect mobilities up to 10-3 cm2V¬-1s-1 and on/off current ratio of 103. Our method has the combined advantages of low temperature and ambient pressure deposition while eliminating the drawbacks of solvents or the high cost of evaporation equipment. Further, as a digital printing method, the laser-printed layer is easily patternable as designed by any convenient graphics software. Since the powder is transferred in a dry state, surface dewetting is no longer an issue, which opens the door to even more substrate/dielectric materials that would otherwise reject solutions from adhering.