Photoluminescence measurement of ruby excited by duty ratio-controlled pulse light-emitting diodes (LED) light source.

Photoluminescence (PL) spectra from ruby were obtained using a highly stable LED light source, employing pulse width modulation technique for excitation. The temporal variation in PL intensity caused by the increasing temperature of the LED used for excitation can be mitigated by adjusting the duty ratio (%) of the pulsed LED light to below 10% for cooling the LED. Stable PL spectra measurements were achieved with a duty ratio of less than 10% using a duty ratio-controlled pulsed LED light source, as temperature fluctuations in LED light intensity are minimized at duty ratios less than 10%. Furthermore, fluctuations in the measured PL intensity were diminished by setting the frequency of the pulsed LED light source to greater than 1 kHz. This method enables more reliable, cost-effective, and stable PL measurements for material characterization in semiconductors, photonics, and nanotechnology.

A Hemispherical Image Sensor Array Fabricated with Organic Photomemory Transistors.

Hemispherical image sensors simplify lens designs, reduce optical aberrations, and improve image resolution for compact wide-field-of-view cameras. To achieve hemispherical image sensors, organic materials are promising candidates due to the following advantages: tunability of optoelectronic/spectral response and low-temperature low-cost processes. Here, a photolithographic process is developed to prepare a hemispherical image sensor array using organic thin film photomemory transistors with a density of 308 pixels per square centimeter. This design includes only one photomemory transistor as a single active pixel, in contrast to the conventional pixel architecture, consisting of select/readout/reset transistors and a photodiode. The organic photomemory transistor, comprising light-sensitive organic semiconductor and charge-trapping dielectric, is able to achieve a linear photoresponse (light intensity range, from 1 to 50 W m-2 ), along with a responsivity as high as 1.6 A W-1 (wavelength = 465 nm) for a dark current of 0.24 A m-2 (drain voltage = -1.5 V). These observed values represent the best responsivity for similar dark currents among all the reported hemispherical image sensor arrays to date. A transfer method was further developed that does not damage organic materials for hemispherical organic photomemory transistor arrays. These developed techniques are scalable and are amenable for other high-resolution 3D organic semiconductor devices.

Fluorescence-enhanced Si photodiodes for ultraviolet C rays (UVC) measurements.

The ultraviolet C rays (UVC, wavelength λ = 100-280 nm) light generated by a Hg lamp (λ = 254 nm) and UVC light-emitting diodes (LEDs, λ = 265 and 275 nm) was detected using a fluorescence-enhanced silicon photodiode (FE-PD). Ce-doped yttrium aluminum garnet (YAG:Ce), YAG:Pr, YAG:Eu, YAG:Tb, YAG:Cr, Al2O3:Ti, Al2O3:Cr, MgAl2O4:Ti, MgAl2O4:Cr, MgAl2O4:Mn, and commercial fluorescent acrylic resins were tested as phosphor sources to enhance the output signal intensity of the FE-PD irradiated with UVC light. The resulting output signal intensity increased linearly with the UVC light strength, which was adjusted by raising the input current of the UVC LEDs from 0 to 40 mA. The sensitivity of the fabricated UVC detectors, assessed based on the calibration curve slope, varied depending on the phosphor materials. The phosphors effectively enhanced the output signal intensity of the FE-PD, which was up to six times greater than that of the visible and near infrared Si-PD without phosphors; the stronger output signal intensity was achieved using YAG:Tb, YAG:Cr, and a red fluorescent acrylic resin. The visible light emitted by phosphors under UVC irradiation is useful for detecting UVC light by the eye when using FE-PD.

High-frequency and intrinsically stretchable polymer diodes.

Skin-like intrinsically stretchable soft electronic devices are essential to realize next-generation remote and preventative medicine for advanced personal healthcare1-4. The recent development of intrinsically stretchable conductors and semiconductors has enabled highly mechanically robust and skin-conformable electronic circuits or optoelectronic devices2,5-10. However, their operating frequencies have been limited to less than 100 hertz, which is much lower than that required for many applications. Here we report intrinsically stretchable diodes-based on stretchable organic and nanomaterials-capable of operating at a frequency as high as 13.56 megahertz. This operating frequency is high enough for the wireless operation of soft sensors and electrochromic display pixels using radiofrequency identification in which the base-carrier frequency is 6.78 megahertz or 13.56 megahertz. This was achieved through a combination of rational material design and device engineering. Specifically, we developed a stretchable anode, cathode, semiconductor and current collector that can satisfy the strict requirements for high-frequency operation. Finally, we show the operational feasibility of our diode by integrating it with a stretchable sensor, electrochromic display pixel and antenna to realize a stretchable wireless tag. This work is an important step towards enabling enhanced functionalities and capabilities for skin-like wearable electronics.

Fluorescence thermometry application of photoluminescence image from Cr-doped YAG.

The temperature dependence of a photoluminescence (PL) image from a Cr-doped Y3Al5O12 (YAG:Cr) crystal was evaluated for a fluorescence thermometry application. The brightness of a red PL image of YAG:Cr was found to be increased by increasing the temperature. Temperature variations of the peak intensity and peak area of red PL related to the PL peaks at λ = 680, 690, 708, and 725 nm were evaluated to reveal the cause of the increase in brightness of the PL image. While intensities of the PL peaks at λ = 690, 690, and 708 nm decreased with temperature due to thermal quenching, the peak intensity at λ = 725 nm and the peak area increased with temperature up to 250 °C. The latter factor greatly affects the temperature variation of the brightness of PL images. The increase in the brightness of the PL image with temperature is evidently linked with the thermal excitation of electrons at the 2E level responsible for the increase in the PL peak area. Cr concentration suitable for the temperature sensor is suggested based on the temperature variation of the PL peak area.

Genetically targeted chemical assembly of functional materials in living cells, tissues, and animals.

The structural and functional complexity of multicellular biological systems, such as the brain, are beyond the reach of human design or assembly capabilities. Cells in living organisms may be recruited to construct synthetic materials or structures if treated as anatomically defined compartments for specific chemistry, harnessing biology for the assembly of complex functional structures. By integrating engineered-enzyme targeting and polymer chemistry, we genetically instructed specific living neurons to guide chemical synthesis of electrically functional (conductive or insulating) polymers at the plasma membrane. Electrophysiological and behavioral analyses confirmed that rationally designed, genetically targeted assembly of functional polymers not only preserved neuronal viability but also achieved remodeling of membrane properties and modulated cell type-specific behaviors in freely moving animals. This approach may enable the creation of diverse, complex, and functional structures and materials within living systems.

Stretchable self-healable semiconducting polymer film for active-matrix strain-sensing array.

Skin-like sensory devices should be stretchable and self-healable to meet the demands for future electronic skin applications. Despite recent notable advances in skin-inspired electronic materials, it remains challenging to confer these desired functionalities to an active semiconductor. Here, we report a strain-sensitive, stretchable, and autonomously self-healable semiconducting film achieved through blending of a polymer semiconductor and a self-healable elastomer, both of which are dynamically cross-linked by metal coordination. We observed that by controlling the percolation threshold of the polymer semiconductor, the blend film became strain sensitive, with a gauge factor of 5.75 × 105 at 100% strain in a stretchable transistor. The blend film is also highly stretchable (fracture strain, >1300%) and autonomously self-healable at room temperature. We proceed to demonstrate a fully integrated 5 × 5 stretchable active-matrix transistor sensor array capable of detecting strain distribution through surface deformation.

Non-destructive evaluation of tomato based on optical scattering.

Equipment for the non-destructive evaluations of a tomato has been developed based on the scattering spectra, the angular distributions of the scattering intensities, and the scattering images from the specimens. The sugar concentrations of tomato can be estimated optically based on the scattering intensities using a halogen lamp, a white light-emitting diode (white LED), a yellow LED, a red LED, and near infrared LEDs (λ = 850 nm and 940 nm) as the incident lights. The scattering intensity is found to vary linearly with sugar concentrations of tomato with any wavelengths at which the scattering light can be observed. The gradient of calibration lines of the sugar concentrations against the scattering intensities varies with scattering angles, θ. Evaluations at around θ = 160° are found to be suitable because of the large gradient and good linearity with the correlation coefficient, R, close to 1.

Multi-scale ordering in highly stretchable polymer semiconducting films.

Stretchable semiconducting polymers have been developed as a key component to enable skin-like wearable electronics, but their electrical performance must be improved to enable more advanced functionalities. Here, we report a solution processing approach that can achieve multi-scale ordering and alignment of conjugated polymers in stretchable semiconductors to substantially improve their charge carrier mobility. Using solution shearing with a patterned microtrench coating blade, macroscale alignment of conjugated-polymer nanostructures was achieved along the charge transport direction. In conjunction, the nanoscale spatial confinement aligns chain conformation and promotes short-range π-π ordering, substantially reducing the energetic barrier for charge carrier transport. As a result, the mobilities of stretchable conjugated-polymer films have been enhanced up to threefold and maintained under a strain up to 100%. This method may also serve as the basis for large-area manufacturing of stretchable semiconducting films, as demonstrated by the roll-to-roll coating of metre-scale films.

X-ray detector based on Mn doped MgAl2O4 and Si photodiode.

Luminescence properties of Mn doped MgAl2O4 crystals connected with the Si PIN photodiode (PD) have been evaluated for X-ray detector applications. Mn doped MgAl2O4 crystals emit green colored luminescence peaking at around λ = 520 nm with CuKα irradiation. The intensity of the output signal from Si PD increases linearly with the X-ray intensity of CuKα generated with the X-ray tube at a current from 2 mA to 40 mA. The intensity of the X-ray excited luminescence is strongest in the specimen with 3.0 mol. % Mn. Afterglow luminescence is weak in the specimen with 2.0 mol. % Mn. Mn doped MgAl2O4 crystals connected with the Si PD is considered to be a useful X-ray detector.

An integrated self-healable electronic skin system fabricated via dynamic reconstruction of a nanostructured conducting network.

Electronic skin devices capable of monitoring physiological signals and displaying feedback information through closed-loop communication between the user and electronics are being considered for next-generation wearables and the 'Internet of Things'. Such devices need to be ultrathin to achieve seamless and conformal contact with the human body, to accommodate strains from repeated movement and to be comfortable to wear. Recently, self-healing chemistry has driven important advances in deformable and reconfigurable electronics, particularly with self-healable electrodes as the key enabler. Unlike polymer substrates with self-healable dynamic nature, the disrupted conducting network is unable to recover its stretchability after damage. Here, we report the observation of self-reconstruction of conducting nanostructures when in contact with a dynamically crosslinked polymer network. This, combined with the self-bonding property of self-healing polymer, allowed subsequent heterogeneous multi-component device integration of interconnects, sensors and light-emitting devices into a single multi-functional system. This first autonomous self-healable and stretchable multi-component electronic skin paves the way for future robust electronics.

Tough and Water-Insensitive Self-Healing Elastomer for Robust Electronic Skin.

An electronic (e-) skin is expected to experience significant wear and tear over time. Therefore, self-healing stretchable materials that are simultaneously soft and with high fracture energy, that is high tolerance of damage or small cracks without propagating, are essential requirements for the realization of robust e-skin. However, previously reported elastomers and especially self-healing polymers are mostly viscoelastic and lack high mechanical toughness. Here, a new class of polymeric material crosslinked through rationally designed multistrength hydrogen bonding interactions is reported. The resultant supramolecular network in polymer film realizes exceptional mechanical properties such as notch-insensitive high stretchability (1200%), high toughness of 12 000 J m-2 , and autonomous self-healing even in artificial sweat. The tough self-healing materials enable the wafer-scale fabrication of robust and stretchable self-healing e-skin devices, which will provide new directions for future soft robotics and skin prosthetics.

Deformable Organic Nanowire Field-Effect Transistors.

Deformable electronic devices that are impervious to mechanical influence when mounted on surfaces of dynamically changing soft matters have great potential for next-generation implantable bioelectronic devices. Here, deformable field-effect transistors (FETs) composed of single organic nanowires (NWs) as the semiconductor are presented. The NWs are composed of fused thiophene diketopyrrolopyrrole based polymer semiconductor and high-molecular-weight polyethylene oxide as both the molecular binder and deformability enhancer. The obtained transistors show high field-effect mobility >8 cm2 V-1 s-1 with poly(vinylidenefluoride-co-trifluoroethylene) polymer dielectric and can easily be deformed by applied strains (both 100% tensile and compressive strains). The electrical reliability and mechanical durability of the NWs can be significantly enhanced by forming serpentine-like structures of the NWs. Remarkably, the fully deformable NW FETs withstand 3D volume changes (>1700% and reverting back to original state) of a rubber balloon with constant current output, on the surface of which it is attached. The deformable transistors can robustly operate without noticeable degradation on a mechanically dynamic soft matter surface, e.g., a pulsating balloon (pulse rate: 40 min-1 (0.67 Hz) and 40% volume expansion) that mimics a beating heart, which underscores its potential for future biomedical applications.

Intrinsically stretchable and healable semiconducting polymer for organic transistors.

Thin-film field-effect transistors are essential elements of stretchable electronic devices for wearable electronics. All of the materials and components of such transistors need to be stretchable and mechanically robust. Although there has been recent progress towards stretchable conductors, the realization of stretchable semiconductors has focused mainly on strain-accommodating engineering of materials, or blending of nanofibres or nanowires into elastomers. An alternative approach relies on using semiconductors that are intrinsically stretchable, so that they can be fabricated using standard processing methods. Molecular stretchability can be enhanced when conjugated polymers, containing modified side-chains and segmented backbones, are infused with more flexible molecular building blocks. Here we present a design concept for stretchable semiconducting polymers, which involves introducing chemical moieties to promote dynamic non-covalent crosslinking of the conjugated polymers. These non-covalent crosslinking moieties are able to undergo an energy dissipation mechanism through breakage of bonds when strain is applied, while retaining high charge transport abilities. As a result, our polymer is able to recover its high field-effect mobility performance (more than 1 square centimetre per volt per second) even after a hundred cycles at 100 per cent applied strain. Organic thin-film field-effect transistors fabricated from these materials exhibited mobility as high as 1.3 square centimetres per volt per second and a high on/off current ratio exceeding a million. The field-effect mobility remained as high as 1.12 square centimetres per volt per second at 100 per cent strain along the direction perpendicular to the strain. The field-effect mobility of damaged devices can be almost fully recovered after a solvent and thermal healing treatment. Finally, we successfully fabricated a skin-inspired stretchable organic transistor operating under deformations that might be expected in a wearable device.

Fiber-optic thermometer application of thermal radiation from rare-earth end-doped SiO2 fiber.

Visible light thermal radiation from SiO2 glass doped with Y, La, Ce, Pr, Nd, Eu, Tb, Dy, Ho, Er, Tm, Yb, and Lu were studied for the fiber-optic thermometer application based on the temperature dependence of thermal radiation. Thermal radiations according to Planck's law of radiation are observed from the SiO2 fibers doped with Y, La, Ce, Pr, Eu, Tb, and Lu at the temperature above 1100 K. Thermal radiations due to f-f transitions of rare-earth ions are observed from the SiO2 fibers doped with Nd, Dy, Ho, Er, Tm, and Yb at the temperature above 900 K. Peak intensities of thermal radiations from rare-earth doped SiO2 fibers increase sensitively with temperature. Thermal activation energies of thermal radiations by f-f transitions seen in Nd, Dy, Ho, Er, Tm, and Yb doped SiO2 fibers are smaller than those from SiO2 fibers doped with Y, La, Ce, Pr, Eu, Tb, and Lu. Thermal radiation due to highly efficient f-f transitions in Nd, Dy, Ho, Er, Tm, and Yb ions emits more easily than usual thermal radiation process. Thermal radiations from rare-earth doped SiO2 are potentially applicable for the fiber-optic thermometry above 900 K.

Fiber-optic thermometry using thermal radiation from Tm end doped SiO2 fiber sensor.

Fiber-optic thermometry based on temperature dependence of thermal radiation from Tm(3+) ions was studied using Tm end doped SiO2 fiber sensor. Visible light radiation peaks due to f-f transition of Tm(3+) ion were clearly observed at λ = 690 and 790 nm from Tm end doped SiO2 fibers sensor at the temperature above 600 °C. Thermal radiation peaks are assigned with f-f transition of Tm(3+) ion, (1)D2-(3)H6, and (1)G4-(3)H6. Peak intensity of thermal radiation from Tm(3+) ion increases with temperature. Intensity ratio of thermal radiation peaks at λ = 690 nm against that at λ = 790 nm, I790/690, is suitable for the temperature measurement above 750 °C. Two-dimensional temperature distribution in a flame is successfully evaluated by Tm end doped SiO2 fiber sensor.

Synthesis and charge/discharge properties of polyacetylenes carrying 2,2,6,6-tetramethyl-1-piperidinoxy radicals.

The 2,2,6,6-tetramethyl-1-piperidinoxy (TEMPO)-containing acetylenic monomers HC[triple bond]CC(6)H(3)-p,m-(CONH-4-TEMPO)(2) (1), HC[triple bond]CC(6)H(3)-p,m-(COO-4-TEMPO)(2) (2), (S,S,S,S)-HC[triple bond]CC(6)H(3)-p,m-[CO-NHCH{COO-(4-TEMPO)}CH(2)COO-(4-TEMPO)](2) (3), (S,S)-HC[triple bond]CC(6)H(4)CO-NHCH{COO-(4-TEMPO)}CH(2)COO-(4-TEMPO) (4), HC[triple bond]CC(6)H(4)-p-OCO-4-TEMPO (5), HC[triple bond]CCH(2)C(CH(3))(CH(2)OCO-4-TEMPO)(2) (6), HC[triple bond]CCH(2)NHCO-4-TEMPO (7), and HC[triple bond]CCH(2)OCO-4-TEMPO (8) were polymerized to afford novel polymers containing the TEMPO radical at high densities. Monomers 1, 3-6, and 8 provided polymers with average molecular weights of 10 000-136 500 in 62-99 % yield in the presence of a rhodium catalyst, whereas monomers 2 and 7 gave insoluble polymers in 100 % yield. The formed polymers were thermally stable up to approximately 274 degrees C according to thermogravimetric analysis (TGA). All the TEMPO-containing polymers demonstrated reversible charge/discharge processes, whose discharge capacities were 21.3-108 A h kg(-1). In particular, the capacity of poly(1)-, poly(4)-, and poly(5)-based cells reached 108, 96.3, and 89.3 A h kg(-1), respectively, which practically coincided with their theoretical values.