One-side metal-coated pyramidal cantilever tips for highly reproducible tip-enhanced Raman spectroscopy.

Tip-enhanced Raman spectroscopy (TERS) has been recognized as a useful tool for nanoscale chemical analysis, and it can further reach down to the sub-nanometer scale in the gap-mode configuration. Using an atomic force microscopy (AFM) in gap-mode TERS for position control of a metallic tip, a unique and correlative analysis can be even realized at the single molecule level. However, one of crucial issues in AFM-based gap-mode TERS is the fabrication of reliable and reproducible cantilver metallic tips. Here, we propose a simple, cost-effective fabrication method of metal-coated tips for AFM-based gap-mode TERS by means of the physical vapor deposition technique in a reproducible way. Our plamonic tips have extremely smooth silver layers on one side of the pyramidal tip, which is totally different from the regular metallic tips that hold granular metallic structures randomly arranged on their bodies. Importantly, all fabricated tips exhibited a reasonably high enhancement factor of more than 104, which indicates that the reproducibility of our plasmonic tip is virtually 100% in the gap-mode configuration. The excellent reproducibility of gap-mode TERS measurement holds great promise for rendering AFM-based TERS as a powerful analytical technique in a broad range of fields.

Fine-Tuning the Performance of Ultraflexible Organic Complementary Circuits on a Single Substrate via a Nanoscale Interfacial Photochemical Reaction.

Flexible electronics has paved the way toward the development of next-generation wearable and implantable healthcare devices, including multimodal sensors. Integrating flexible circuits with transducers on a single substrate is desirable for processing vital signals. However, the trade-off between low power consumption and high operating speed is a major bottleneck. Organic thin-film transistors (OTFTs) are suitable for developing flexible circuits owing to their intrinsic flexibility and compatibility with the printing process. We used a photoreactive insulating polymer poly((±)endo,exo-bicyclo[2.2.1]hept-ene-2,3-dicarboxylic acid, diphenylester) (PNDPE) to modulate the power consumption and operating speed of ultraflexible organic circuits fabricated on a single substrate. The turn-on voltage (V on) of the p- and n-type OTFTs was controlled through a nanoscale interfacial photochemical reaction. The time-of-flight secondary ion mass spectrometry revealed the preferential occurrence of the PNDPE photochemical reaction in the vicinity of the semiconductor-dielectric interface. The power consumption and operating speed of the ultraflexible complementary inverters were tuned by a factor of 6 and 4, respectively. The minimum static power consumption was 30 ± 9 pW at transient and 4 ± 1 pW at standby. Furthermore, within the tuning range of the operating speed and at a supply voltage above 2.5 V, the minimum stage delay time was of the order of hundreds of microseconds. We demonstrated electromyogram measurements to emphasize the advantage of the nanoscale interfacial photochemical reaction. Our study suggests that a nanoscale interfacial photochemical reaction can be employed to develop imperceptible and wearable multimodal sensors with organic signal processing circuits that exhibit low power consumption.

Polarization Raman Imaging of Organic Monolayer Islands for Crystal Orientation Analysis.

An organic semiconductor film made of diphenyl derivative dinaphtho[2,3-b:2',3'-f]thieno[3,2-b]thiophene (DPh-DNTT) has high carrier mobility. However, this mobility may be greatly affected by the crystal orientation of the DPh-DNTT's first layer. Polarization Raman microscopy is widely used to quantitatively analyze the molecular orientation, and thus holds great potential as a powerful tool to investigate the crystal orientation of monolayer DPh-DNTT with high spatial resolution. In this study, we demonstrate polarization Raman imaging of monolayer DPh-DNTT islands for crystal orientation analysis. We found that the DPh-DNTT sample indicated a strong dependence of the Raman intensity on the incident polarization direction. Based on the polarization dependence, we developed an analytical method of determining the crystal orientation of the monolayer DPh-DNTT islands and experimentally confirmed that our technique was highly effective at imaging the islands' crystal orientation with a spatial resolution of a few hundred nanometers.

Heterogeneous Functional Dielectric Patterns for Charge-Carrier Modulation in Ultraflexible Organic Integrated Circuits.

Flexible electronics have gained considerable attention for application in wearable devices. Organic transistors are potential candidates to develop flexible integrated circuits (ICs). A primary technique for maximizing their reliability, gain, and operation speed is the modulation of charge-carrier behavior in the respective transistors fabricated on the same substrate. In this work, heterogeneous functional dielectric patterns (HFDP) of ultrathin polymer gate dielectrics of poly((±)endo,exo-bicyclo[2.2.1]hept-ene-2,3-dicarboxylic acid, diphenylester) (PNDPE) are introduced. The HFDP that are obtained via the photo-Fries rearrangement by ultraviolet radiation in the homogeneous PNDPE provide a functional area for charge-carrier modulation. This leads to programmable threshold voltage control over a wide range (-1.5 to +0.2 V) in the transistors with a high patterning resolution, at 2 V operational voltage. The transistors also exhibit high operational stability over 140 days and under the bias-stress duration of 1800 s. With the HFDP, the performance metrics of ICs, for example, the noise margin and gain of the zero-VGS load inverters and the oscillation frequency of ring oscillators are improved to 80%, 1200, and 2.5 kHz, respectively, which are the highest among the previously reported zero-VGS -based organic circuits. The HFDP can be applied to much complex and ultraflexible ICs.