nC Cm-2 Research Articles

Hierarchical Wrinkles with Piezopotential Enhanced Surface Tribopolarity for High-Performance Self-Powered Pressure Sensor.

Achieving both high sensitivity and wide detecting range is significant for the applications of triboelectric nanogenerator-based self-powered pressure sensors (TPSs). However, most of the previous designs with high sensitivity usually struggle in a narrow pressure detection range (<30 kPa) while expanding the detection range normally sacrifices the sensitivity. To overcome this well-known obstacle, herein, piezopotential enhanced triboelectric effect realized by a rationally designed PDMS/ZnO NWs hierarchical wrinkle structure was exploited to develop a TPS (PETPS) with both high sensitivity and wide detecting range. In this PETPS design, the piezopotential derived from the deformation of ZnO NWs enhances its tribo-charge transferring ability; meanwhile, the hierarchical structure helps to establish a dynamically self-adjustable contact area. Benefiting from these advantages, the PETPS simultaneously achieves high sensitivity (0.26 nC cm-2 kPa-1 from 1 to 25 kPa, and 0.02 nC cm-2 kPa-1 from 25 to 476 kPa), fast response (46 ms), wide sensing range (1 to 476 kPa), and good stability (over 4000 cycles). In addition, the output charge density that is independent of the speed rate of driven force was adopted as the sensing signal of PETPS to replace the commonly used peak voltage/current values, enabling it more adaptive to accurately detect pressure variation in real applications.

Observation of ferroelectric behaviour in non-symmetrical cholesterol-based bent-shaped dimers.

Non-symmetrical cholesterol-based dimers have emerged as crucial materials in the field of liquid crystal research, owing to their remarkable ability to stabilize various exotic mesophases, including the blue phases (BPIII, BPII, BPI), cholesteric nematic (N*) phase, smectic blue phase (SmBP), twist grain boundary (TGB) phase, smectic A/smectic A* (SmA/SmA*) phase, and smectic C/smectic C* (SmC/SmC*) phase. These mesophases have garnered considerable attention due to their diverse applications in spatial light modulation, chiro-optical devices, optical switching, thermochromic materials, and more. In this study, we present the synthesis and comprehensive characterization of a series of non-symmetrical cholesterol-based bent-shaped dimers (1/12, 1/14, 1/16) in which the cholesterol unit is intricately linked to an aromatic mesogenic core through a flexible spacer. These novel materials exhibit the intriguing ability to stabilize a variety of mesophases, including the N*, TGBA, SmA, and SmC* phases. The chiro-optical properties of the helical SmC* phase have been meticulously investigated through temperature-dependent chiro-optical measurements, shedding light on their potential for advanced optoelectronic applications. Additionally, we have conducted a thorough examination of the physical characteristics of these cholesterol-based dimers, including static permittivity measurements, dielectric spectroscopy, and electro-optical performance analysis. Remarkably, two homologues (1/14, 1/16) exhibit negative dielectric anisotropy, a crucial parameter for liquid crystal devices. Furthermore, our investigation reveals that these materials exhibit ferroelectric behaviour in the SmC* phase, with compounds 1/14 and 1/16 demonstrating substantial spontaneous polarization (PS) values of approximately 132 nC cm-2 and 149 nC cm-2, respectively. These findings underscore the potential of non-symmetrical cholesterol-based dimers as versatile components for the development of innovative electro-optical devices.

A Ferroelectric Metallomesogen Exhibiting Field-Induced Slow Magnetic Relaxation.

Magnetoelectric (ME) materials exhibiting coupled electric and magnetic properties are of significant interest because of their potential use in memory storage devices, new sensors, or low-consumption devices. Herein, we report a new category of ME material that shows liquid crystal (LC), ferroelectric (FE), and field-induced single molecule magnet (SMM) behaviors. Co(II) complex incorporating alkyl chains of type [Co(3C16 -bzimpy)2 ](BF4 )2 (1; 3C16 -bzimpy=2,2'-(4-hexadecyloxy-2,6-diyl)bis(1-hexadecyl-1H-benzo[d]imidazole)) displayed a chiral smectic C mesophase in the temperature range 321 K-458 K, in which distinct FE behavior was observed, with a remnant polarization (88.3 nC cm-2 ). Complex 1 also exhibited field-induced slow magnetic relaxation behavior that reflects the large magnetic anisotropy of the Co(II) center. Furthermore, the dielectric property of 1 was able to be tuned by an external magnetic field occurring from both spin-lattice coupling and molecular orientational variation. Clearly, this multifunctional compound, combining LC, FE, and SMM properties, represents an entry to the development of a range of next-generation ME materials.

Establishing Stability in Organic Semiconductor Photocathodes for Solar Hydrogen Production.

As organic semiconductors attract increasing attention to application in the fields of bioelectronics and artificial photosynthesis, understanding the factors that determine their robust operation in direct contact with aqueous electrolytes becomes a critical task. Herein we uncover critical factors that influence the operational stability of donor:acceptor bulk heterojunction photocathodes for solar hydrogen production and significantly advance their performance under operational conditions. First, using the direct photoelectrochemical reduction of aqueous Eu3+ and impedance spectroscopy, we determine that replacing the commonly used fullerene-based electron acceptor with a perylene diimide-based polymer drastically increases operational stability and identify that limiting the photogenerated electron accumulation at the organic/water interface to values of ca. 100 nC cm-2 is required for stable operation (>12 h). These insights are extended to solar-driven hydrogen production using MoS3, MoP, or RuO2 water reduction catalyst overlayers where it is found that the catalyst morphology strongly affects performance due to differences in charge extraction. Optimized performance of bulk heterojunction photocathodes coated with a MoS3:MoP composite gave 1 Sun photocurrent density up to 8.7 mA cm-2 at 0 V vs RHE (pH 1). However, increased stability was gained with RuO2 where initial photocurrent density (>8 mA cm-2) deceased only 15% or 33% during continuous operation for 8 or 20 h, respectively, thus demonstrating unprecedented robustness without a protection layer. This performance represents a new benchmark for organic semiconductor photocathodes for solar fuel production and advances the understanding of stability criteria for organic semiconductor/water-junction-based devices.

Continuous and Scalable Manufacture of Hybridized Nano-Micro Triboelectric Yarns for Energy Harvesting and Signal Sensing.

Textile-based triboelectric nanogenerators (TENG) that can effectively harvest biomechanical energy and sense multifunctional posture and movement have a wide range of applications in next-generation wearable and portable electronic devices. Hence, bulk production of fine yarns with high triboelectric output through a continuous manufacturing process is an urgent task. Here, an ultralight single-electrode triboelectric yarn (SETY) with helical hybridized nano-micro core-shell fiber bundles is fabricated by a facile and continuous electrospinning technology. The obtained SETY device exhibits ultralightness (0.33 mg cm-1), extra softness, and smaller size (350.66 μm in diameter) compared to those fabricated by conventional fabrication techniques. Based on such a textile-based TENG, high energy-harvesting performance (40.8 V, 0.705 μA cm-2, and 9.513 nC cm-2) was achieved by applying a 2.5 Hz mechanical drive of 5 N. Importantly, the triboelectric yarns can identify textile materials according to their different electron affinity energies. In addition, the triboelectric yarns are compatible with traditional textile technology and can be woven into a high-density plain fabric for harvesting biomechanical energy and are also competent for monitoring tiny signals from humans or insects.

Probing Contact-Electrification-Induced Electron and Ion Transfers at a Liquid-Solid Interface.

As a well-known phenomenon, contact electrification (CE) has been studied for decades. Although recent studies have proven that CE between two solids is primarily due to electron transfer, the mechanism for CE between liquid and solid remains controversial. The CE process between different liquids and polytetrafluoroethylene (PTFE) film is systematically studied to clarify the electrification mechanism of the solid-liquid interface. The CE between deionized water and PTFE can produce a surface charges density in the scale of 1 nC cm-2 , which is ten times higher than the calculation based on the pure ion-transfer model. Hence, electron transfer is likely the dominating effect for this liquid-solid electrification process. Meanwhile, as ion concentration increases, the ion adsorption on the PTFE hinders electron transfer and results in the suppression of the transferred charge amount. Furthermore, there is an obvious charge transfer between oil and PTFE, which further confirms the presence of electron transfer between liquid and solid, simply because there are no ions in oil droplets. It is demonstrated that electron transfer plays the dominant role during CE between liquids and solids, which directly impacts the traditional understanding of the formation of an electric double layer (EDL) at a liquid-solid interface in physical chemistry.

Ferroelectric Liquid Crystals: Synthesis and Thermal Behavior of Optically Active, Three-Ring Schiff Bases and Salicylaldimines.

The chiral ferroelectric smectic C (SmC*) phase, characterized by a helical superstructure, has been well exploited in developing high-resolution microdisplays that have been effectively employed in the fabrication of a wide varieties of portable devices. Although, an overwhelming number of optically active (chiral) liquid crystals (LCs) exhibiting a SmC* phase have been designed and synthesized, the search for new systems continues so as to realize mesogens capable of meeting technical necessities and specifications for their end-use. In continuation of our research work in this direction, herein we report the design, synthesis, and thermal behavior of twenty new optically active, three-ring calamitic LCs belonging to four series. The first two series comprise five pairs of enantiomeric Schiff bases whereas the other two series are composed of five pairs of enantiomeric salicylaldimines. In each pair of optical isomers, the configuration of a chiral center in one stereoisomer is opposite to that of the analogous center in the other isomer as they are derived from (3 S)-3,7-dimethyloctyloxy and (3 R)-3,7-dimethyloctyloxy tails. To probe the structure-property correlations in each series, the length of the n-alkoxy tail situated at the other end of the mesogens has been varied from n-octyloxy to n-dodecyloxy. The measurement of optical activity of these chiral mesogens was carried out by recording their specific rotations. As expected, enantiomers rotate plane polarized light in the opposite direction but by the same magnitude. The thermal behavior of the compounds was established by using a combination of optical polarizing microscopy, differential scanning calorimetry, and powder X-ray diffraction. These complementary techniques demonstrate the existence of the expected, thermodynamically stable, chiral smectic C (SmC*) LC phase besides blue phase I/II (BPI or BPII) and chiral nematic (N*) phase. However, as noted in our previous analogous study, the vast majority of the Schiff bases show an additional metastable, unfamiliar smectic (SmX) phase just below the SmC* phase. Notably, the SmC* phase persists over the temperature range ≈80-115 °C. Two mesogens chosen each from Schiff bases and salicylaldimines were investigated for their electrical switching behavior. The study reveals the ferroelectric switching characteristics of the SmC* phase featuring the spontaneous polarization (PS ) in the range 69-96 nC cm-2 . The helical twist sense of the SmC* phase as well as the N* phase formed by a pair of enantiomeric Schiff bases and salicylaldimines has been established with the help of circular dichroism (CD) spectroscopic technique. As expected, the SmC* and the N* phase of a pair of enantiomers showed mirror image CD signals. Most importantly, the reversal of helical handedness from left to right and vice versa has been evidenced during the N* to SmC* phase transition, implying that the screw sense of the helical array of the N* phase and the SmC* phase of an enantiomer is opposite.

Anomalous photovoltaic effect based on molecular chirality: influence of enantiomeric purity on the photocurrent response in π-conjugated ferroelectric liquid crystals.

(S)- and (R)-forms of chiral π-conjugated ferroelectric liquid crystals were synthesized. The dielectric properties in the ferroelectric liquid-crystalline (FLC) phases were evaluated using the Sawyer-Tower method. Spontaneous polarization of (S)-1 reached 68 nC cm-2 at 127 °C. Hole mobilities in the FLC phases estimated using the time-of-flight (TOF) method were on the order of 10-4 cm2 V-1 s-1. Each chiral π-conjugated compound exhibited a photovoltaic effect based on spontaneous polarization without p-n or Schottky junctions. This phenomenon could be attributed to an anomalous photovoltaic (APV) effect that has been observed in ferroelectric ceramics. In addition, liquid-crystalline enantiomeric mixtures of (S)-1 and (R)-1 were prepared and the APV response under UV illumination was studied. The APV response was enhanced with an increase in enantiomeric purity and was minimized in the racemic mixture. From this result, it was concluded that the APV effect in this FLC compound originated from the molecular chirality.

Low Molar Mass Organosiloxane Liquid Crystals for Telecommunication Applications

Mixtures of two proprietary low molar mass organosiloxane liquid crystals were studied in order to improve their alignment and optimize their electro-optic properties for telecommunication applications. Over a certain concentration range, mixtures exhibited an isotropic-chiral smectic A-chiral smectic C (Iso-SmA*-SmC*) phase sequence leading to exceptionally good alignment. At room temperature, the spontaneous polarization of these samples was reduced from 225 nC cm-2 in the pure SmC* liquid crystal to as low as 75 nC cm-2 in the mixture. Within this concentration range, the ferroelectric tilt angle could be varied between 35° and 15° , while the rise time decreased by 69.4%. The rise times were <;45 μs for moderate electric fields of ±10 V μm-1 in the SmC* phase and ∼4 μs, independent of electric field, in the SmA* phase. At λ = 1550 nm, these mixtures exhibited very large extinction ratios of ~60 dB for binary switching in the SmC* phase and ~55 dB continuous variable attenuation in the SmA* phase.

Effect of the variation of swallow-tailed groups on the mesomorphic and electro-optical properties of chiral compounds derived from (S)-2-(6-hydroxy-2-naphthyl)propionic acid

Three homologous series of chiral swallow-tailed compounds, alkyl (S)-2-{6-[4-(4′-alkoxyphenyl)benzoyloxy]-2-naphthyl}propionates, (S)HNP(p,n,q) derived from (S)-2-(6-hydroxy-2-naphthyl)propionic acid in conjugation with a variety of swallow-tailed groups, attached to the external side of the chiral centre, have been synthesized and their mesomorphic and electro-optical properties studied. Both (S)HNP(p,1,2) and (S)HNP(p,1,3) exhibited an enantiotropic antiferroelectric SmC*A phase. This implys that the swallow-tailed groups in the molecules favour zigzag pairing of the molecules in the smectic phase. The maximum P S values of compounds (S)HNP(p,1,2) in the antiferroelectric phase were measured in the range 21–30 nC cm-2; those of compounds (S)HNP(p,1,3) were in the range 15–23 nC cm-2, indicating that these chiral compounds possess low polarity. The electro-optical response of the compounds in the antiferroelectric SmC*A phase displayed thresholdless V-shaped switching.

Novel chiral swallow-tailed amide liquid crystals possessing antiferroelectricity

Novel chiral swallow-tailed amide materials, N,N-dipropyl-(S)-2-{6-[4-(4-alkoxyphenyl)benzoyloxy]-2-naphthyl}propionamides, DPmPBNPA (m=9-13), have been designed and synthesized for the investigation of mesomorphic properties. The materials DPmPBNPA (m=9-11) display a monotropic phase sequence of I-SmA*-SmCA*-Cr. The antiferroelectric SmCA* phase for the materials was characterized by microscopic texture, switching behaviour, dielectric permitivity and electro-optical response. The measured maximum P s values in the SmCA* phase of the materials are in the range 80–87 nC cm-2.

Antiferroelectric Switchable Mesophases of Nonchiral Bent-Core Liquid Crystals Containing Fluorinated Central Cores

A new series of liquid-crystalline bent-core molecules comprising a central 3,4‘-disubstituted biphenyl unit (biphenyl 3,4‘-bis-4-[4-dodecyl(oxy)benzoyloxy]benzoates) at which one, two, or even three H atoms in various positions were replaced by F atoms has been synthesized. The biphenyl cores were built up by orthometalation, followed by palladium-catalyzed cross-coupling reactions. The compounds were characterized by polarizing microscopy, DSC, X-ray scattering, and electro-optical investigations. Most compounds exhibit broad regions of antiferroelectrical switchable SmCPA phases, but also rectangular columnar mesophases have been observed for some representatives. Extremely large values of the spontaneous polarization (up to 2300 nC cm-2) have been found for some representatives. Additionally, for some smectic compounds a third peak was detected in the polarization current curve beside the two peaks corresponding to the antiferroelectric switching process. The coexistence of ferroelectric and antiferro...

Antiferroelectric liquid crystal from a banana-shaped achiral molecule

A new banana-shaped achiral compound, 1,3-phenylene bis[4-(3-fluoro-4-n-octyloxyphenyliminomethyl)benzoate] (PBFOB) was synthesized and its antiferroelectric liquid crystallinity determined. The PBFOB was characterized by differential scanning calorimetry, X-ray diffractometry in the small and wide angle regions, and polarizing optical microscopy; its polarization and antiferroelectric properties were also investigated. The presence of a lateral fluoro-substituent in the banana-shaped achiral molecules containing a Schiff's base mesogen induced a decrease in melting temperature and formation of the switchable smectic B2 phase in the melt. The spontaneous polarization for PBFOB was about 250 nC cm-2 and the polarization of this phase switched on the reversal of an applied electric field.

Stable frustrated phases in chiral liquid crystals derived from optically active (R)- and (S)-3-ethylmercapto-2-methylpropionic acids

Highly optically pure (R)- and (S)-3-ethylmercapto-2-methylpropionic acids were synthesized by using optically active (D)- and (L)-2,10-camphorsultams as chiral auxiliaries, respectively. Their derivatives, (R)- and (S)-EMMPNmB (m=6-12), were prepared for investigation. Microscopic texture observations demonstrated that the materials possess three stable frustrated phases: BP, TGBA* and TGBC* phases. Interestingly, it was found that the N* phase behaves as an intermediary phase between BP and TGBA* phases in a rather narrow temperature range (calc. 0.5-1.4°C). A study of the racemic mixture, (±)-EMMPNmB (m=10), indicated that the chirality of the molecule could suppress the formation of smectic phases in the heating process. An increase of alkyl chain length favoured the formation of the TGB phases particularly, in accompaniment with a change of TGB phases from monotropic to enantiotropic. Moderate maximum P S values (calc. 14-19 nC cm-2) and apparent tilt angle (calc. 20°) were obtained for the TGBC* phase in a surface stabilized ferroelectric liquid crystal geometry.

Molecular Design of Nonchiral Bent-Core Liquid Crystals with Antiferroelectric Properties

Novel bent-core (banana-shaped) liquid crystals without Schiff-base units have been synthesized and investigated by polarized light optical microscopy, differential scanning calorimetry, X-ray scattering, and electrooptical investigations. These molecules are 4-(4-alkylbenzoyloxy)benzoates and 4-(4-alkoxybenzoyloxy)benzoates of resorcinol, 3,4‘-dihydroxybiphenyl, and 4,4‘ ‘-dihydroxy-1,1‘:3‘,1‘ ‘-terphenyl. Three different mesophases were found depending on the molecular structure and the length of the terminal alkyl chains: a rectangular columnar phase, a highly ordered low-temperature mesophase, and an antiferroelectric switchable fluid smectic mesophase designated as SmCPA. The influence of the molecular structure on the occurrence of the SmCPA phase was investigated. The spontaneous polarization of these molecules is quite high (PS = 500−700 nC cm-2) and specially those molecules with long alkyl chains and short bent-core structures have low melting points and broad regions of this switchable mesophase. Furthermore, first examples of antiferroelectric switchable bent-core molecules with semifluorinated terminal chains will be described.

Synthesis of a novel antiferroelectric liquid crystal with high Ps

An antiferroelectric liquid crystal material, (S)-4-[4-(dodecyloxycarbonylphenoxy)-2-chloropropionyl] phenyl 4-{4-[2-chloro-3-(4-benzamidoacetyloxyphenyl)propionyloxy] benzoyloxy}benzoate (DCPCPB), has been designed and synthesized by using L-tyrosine as a chiral source. Preliminary investigations of the ferroelectric properties of the present material show a high magnitude of spontaneous polarization (190 nC cm-2) and response times (135mus) in the antiferroelectric SmC* phase. The possible molecular contributions towards the appearance A of the antiferroelectric phase are summarized.

Characterization of lead zirconate titanate thin film deposition onto Pt/Ti/SiO2/Si substrates

Lead zirconate titanate, (Pb(Zr0.52Ti0.48)O3PZT) thin films were deposited onto a Pt/Ti/SiO2/Si substrate using radio frequency (r.f.) planar magnetron sputtering in this study. The deposited PZT thin films were almost amorphous before the annealing processes and developed a perovskite structure after the annealing process. If the annealing temperature was too low or annealing time too short, pyrochlore would form. However, if the annealing temperature was too high or annealing time too long, the thin film structure would degrade due to the volatilization of PbO. The significant finding in this experiment is that high quality perovskite PZT thin films on Pt/Ti/SiO2/Si substrates can be obtained by adjusting the annealing temperature to a range of 650 °C to 850 °C and annealing time to a range from 5 to 80 min. In this experiment, the optimal annealing condition was an annealing temperature of 650 °C and time of 20 min. The properties of PZT thin film annealed at 650 °C for 20 min were dielectric constant ɛr = 869 free dielectric constant ɛT33 = 893 piezoelectric constant d33 = 2.03p m V-1 piezoelectric constant g33 = 2.57 x 10-4 V m N-1, remanent polarization P1 = 112.5 nC cm-2 and coercive field Ec= 0.061 kV cm-1.

Synthesis and SmC* properties of chiral liquid crystalline terephthalates

Chiral ester derivatives of terephthalic acid containing one, three, or five phenyl rings were prepared by using (S)-2-methylbutanol or (R)-2-chloropropanol as starting materials. The one-ring terephthalates did not exhibit any liquid crystalline phases, but one of them was used as a chiral dopant in ferroelectric mixtures. Elongation of the aromatic core structure to three and five phenyl rings stabilized the SmA phase, whereas a (monotropic) SmC* phase was detected in some three-ring and five-ring derivatives. In ferroelectric mixtures based on the terephthalates, spontaneous polarizations up to 340 nC cm2 were measured.

Highly sensitive measurement of surface charge distribution using the Pockels effect and an image lock-in amplifier

A visualization and a quantification technique for a latent electric charge image on a dielectric material has been developed by using the Pockels effect and a computer imaging technique. An optical phase modulation technique and a computer image lock-in amplifier technique were used to improve the signal-to-noise ratio. The measurement system has several improved performances; sensitivity of surface change of 1 nC cm-2, spatial resolution of 200 mu m and discrimination of charge polarity. The basic principle of advanced electro-optic surface charge measurement is described and the typical surface charge distribution of positive discharge streamer produced by a high impulse voltage (5 kVpeak) is demonstrated. Also, comparison is made between the modulation method and the non-modulation method.

Simultaneous stretching and corona poling of PVDF and P(VDF-TriFE) films. II

For pt.I see T. Kaura, R. Nath and M.M. Perlman, ibid., vol.24, p.1848 (1991). Copolymer films of 75/25 and 50/50 mol.% poly(vinylidene fluoride-trifluorethylene) P(VDF-TriFE) are simultaneously stretched and corona poled (SSCP) in batch mode at elevated temperatures. When poled under optimum conditions, the 75/25 films yield a piezo-electric constant d31 approximately 48 pC N-1 and a pyro-electric constant p approximately 5 nC cm-2 K-1, at 30 degrees C. Both of these values are about 1.7 times those reported for films that were poled after stretching and agree with previously predicted, but until now unobserved, maxima. A 'frozen-in' stress limits the beta phase content and hence the piezo- and pyro-activity in normally drawn films. Drawing at elevated temperatures during SSCP raises the yield level, and hence the ultimate activity. The stability of d31 was also improved by SSCP. The authors postulate that there is a contribution of ferroelectric domain rotation in these SSCP films. X-rays show that they have an enhanced beta phase over those that were poled after stretching. The 50/50 films yield roughly the same activities (d31 approximately 35-40 pC N-1 and p approximately 4.8 nC cm-2 K-1 at 30 degrees C) whether poled during or after stretching, in agreement with the maximum values obtained by others and predicted by the authors. A good correlation with dipole moment was found amongst the activities of the copolymers and 100% PVDF.