Large Electromechanical Response in a Polycrystalline Alkali-Deficient (K,Na)NbO3 Thin Film on Silicon.

The demand for large electromechanical performance in lead-free polycrystalline piezoelectric thin films is driven by the need for compact, high-performance microelectromechanical systems (MEMS) based devices operating at low voltages. Here we significantly enhance the electromechanical response in a polycrystalline lead-free oxide thin film by utilizing lattice-defect-induced structural inhomogeneities. Unlike prior observations in mismatched epitaxial films with limited low-frequency enhancements, we achieve large electromechanical strain in a polycrystalline (K,Na)NbO3 film integrated on silicon. This is achieved by inducing self-assembled Nb-rich planar faults with a nonstoichiometric composition. The film exhibits an effective piezoelectric coefficient of 565 pm V-1 at 1 kHz, surpassing those of lead-based counterparts. Notably, lattice defect growth is substrate-independent, and the large electromechanical response is extended to even higher frequencies in a polycrystalline film. Improved properties arise from unique lattice defect morphology and frequency-dependent relaxation behavior, offering a new route to remarkable electromechanical response in polycrystalline thin films.

Bond engineering of molecular ferroelectrics renders soft and high-performance piezoelectric energy harvesting materials.

Piezoelectric materials convert mechanical stress to electrical energy and thus are widely used in energy harvesting and wearable devices. However, in the piezoelectric family, there are two pairs of properties that improving one of them will generally compromises the other, which limits their applications. The first pair is piezoelectric strain and voltage constant, and the second is piezoelectric performance and mechanical softness. Here, we report a molecular bond weakening strategy to mitigate these issues in organic-inorganic hybrid piezoelectrics. By introduction of large-size halide elements, the metal-halide bonds can be effectively weakened, leading to a softening effect on bond strength and reduction in polarization switching barrier. The obtained solid solution C6H5N(CH3)3CdBr2Cl0.75I0.25 exhibits excellent piezoelectric constants (d33 = 367 pm/V, g33 = 3595 × 10-3 Vm/N), energy harvesting property (power density is 11 W/m2), and superior mechanical softness (0.8 GPa), promising this hybrid as high-performance soft piezoelectrics.

Origin of giant electric-field-induced strain in faulted alkali niobate films.

A large electromechanical response in ferroelectrics is highly desirable for developing high-performance sensors and actuators. Enhanced electromechanical coupling in ferroelectrics is usually obtained at morphotropic phase boundaries requiring stoichiometric control of complex compositions. Recently it was shown that giant piezoelectricity can be obtained in films with nanopillar structures. Here, we elucidate its origin in terms of atomic structure and demonstrate a different system with a greatly enhanced response. This is in non-stoichiometric potassium sodium niobate epitaxial thin films with a high density of self-assembled planar faults. A giant piezoelectric coefficient of ∼1900 picometer per volt is demonstrated at 1 kHz, which is almost double the highest ever reported effective piezoelectric response in any existing thin films. The large oxygen octahedral distortions and the coupling between the structural distortion and polarization orientation mediated by charge redistribution at the planar faults enable the giant electric-field-induced strain. Our findings demonstrate an important mechanism for realizing the unprecedentedly giant electromechanical coupling and can be extended to many other material functions by engineering lattice faults in non-stoichiometric compositions.

Intercalation-driven ferroelectric-to-ferroelastic conversion in a layered hybrid perovskite crystal.

Two-dimensional (2D) organic-inorganic hybrid perovskites have attracted intense interests due to their quantum well structure and tunable excitonic properties. As an alternative to the well-studied divalent metal hybrid perovskite based on Pb2+, Sn2+ and Cu2+, the trivalent metal-based (eg. Sb3+ with ns2 outer-shell electronic configuration) hybrid perovskite with the A3M2X9 formula (A = monovalent cations, M = trivalent metal, X = halide) offer intriguing possibilities for engineering ferroic properties. Here, we synthesized 2D ferroelectric hybrid perovskite (TMA)3Sb2Cl9 with measurable in-plane and out-of-plane polarization. Interestingly, (TMA)3Sb2Cl9 can be intercalated with FeCl4 ions to form a ferroelastic and piezoelectric single crystal, (TMA)4-Fe(iii)Cl4-Sb2Cl9. Density functional theory calculations were carried out to investigate the unusual mechanism of ferroelectric-ferroelastic crossover in these crystals.

Data-driven discovery of high performance layered van der Waals piezoelectric NbOI2.

Using high-throughput first-principles calculations to search for layered van der Waals materials with the largest piezoelectric stress coefficients, we discover NbOI2 to be the one among 2940 monolayers screened. The piezoelectric performance of NbOI2 is independent of thickness, and its electromechanical coupling factor of near unity is a hallmark of optimal interconversion between electrical and mechanical energy. Laser scanning vibrometer studies on bulk and few-layer NbOI2 crystals verify their huge piezoelectric responses, which exceed internal references such as In2Se3 and CuInP2S6. Furthermore, we provide insights into the atomic origins of anti-correlated piezoelectric and ferroelectric responses in NbOX2 (X = Cl, Br, I), based on bond covalency and structural distortions in these materials. Our discovery that NbOI2 has the largest piezoelectric stress coefficients among 2D materials calls for the development of NbOI2-based flexible nanoscale piezoelectric devices.

Tailoring the coercive field in ferroelectric metal-free perovskites by hydrogen bonding.

The miniaturization of ferroelectric devices in non-volatile memories requires the device to maintain stable switching behavior as the thickness scales down to nanometer scale, which requires the coercive field to be sufficiently large. Recently discovered metal-free perovskites exhibit advantages such as structural tunability and solution-processability, but they are disadvantaged by a lower coercive field compared to inorganic perovskites. Herein, we demonstrate that the coercive field (110 kV/cm) in metal-free ferroelectric perovskite MDABCO-NH4-(PF6)3 (MDABCO = N-methyl-N'-diazabicyclo[2.2.2]octonium) is one order larger than MDABCO-NH4-I3 (12 kV/cm) owing to the stronger intermolecular hydrogen bonding in the former. Using isotope experiments, the ferroelectric-to-paraelectric phase transition temperature and coercive field are verified to be strongly influenced by hydrogen bonds. Our work highlights that the coercive field of organic ferroelectrics can be tailored by tuning the strength of hydrogen bonding.

Fast Photostriction in Ferroelectrics.

Light-induced nonthermal strain, known as the photostrictive effect, offers a potential way to excite mechanical strain and acoustic wave remotely. The anisotropic photostrictive effect induced by the combination of bulk photovoltaic effect (BPVE) and converse piezoelectric effect in ferroelectric materials is known as too small and slow for the applications requiring a high strain rate, such as ultrasound generation and high-speed signal transmission. Here, a strategy to achieve high rate dynamic photostrictive strain by utilizing local fast responses under modulating continuous light excitation in the resonance condition is reported. A strain rate of 8.06 × 10-3  s-1 is demonstrated under continuous light excitation, which is at least one order of magnitude higher than previous studies on bulk samples as seen in the literature. The significant photostrictive response exists even in depoled ferroelectric material without overall polarization. The theoretical analyses show that fast ferroelectric photostriction can be obtained through the combinational interaction mechanism of local BPVE and local converse piezoelectric effect existing only in the microscopic scale, thus circumventing the slow and low efficient BPVE charging up process across the macroscopic electrical terminals. The achieved fast photostriction and new understandings will open new opportunities to realize future wireless signal transmission and light-acoustic devices.

Acceptor engineering of small-molecule fluorophores for NIR-II fluorescence and photoacoustic imaging.

Fluorescence imaging in the second near-infrared window (NIR-II) has been an emerging technique in diverse in vivo applications with high sensitivity/resolution and deep tissue penetration. To date, the design principle of the reported NIR-II organic fluorophores has heavily relied on benzo[1,2-c:4,5-c']bis([1,2,5]thiadiazole) (BBTD) as a strong electron acceptor. Here, we report the rational design and synthesis of a NIR-II fluorescent molecule with the rarely used [1,2,5]thiadiazolo[3,4-f]benzotriazole (TBZ) core to replace BBTD as the electron acceptor. Thanks to the weaker electron deficiency of the TBZ core than BBTD, the newly yielded NIR-II molecule (BTB) based nanoparticles have a higher mass extinction coefficient and quantum yield in water. In contrast, the nanoparticle suspension of its counterpart with BBTD as the core is nearly nonemissive. The NIR-II BTB nanoparticles allow video-rate fluorescence imaging for vasculature imaging in ears, hindlimbs, and the brain of the mouse. Additionally, its large absorptivity in the NIR-I region also promotes bioimaging using photoacoustic microscopy (PAM) and tomography (PAT). Upon surface conjugation with the Arg-Gly-Asp (RGD) peptide, the functionalized nanoparticles ensured targeted detection of integrin-overexpressed tumors through both imaging modalities in two- and three-dimensional views. Thus, our approach to engineering acceptors of organic fluorophores offers a promising molecular design strategy to afford new NIR-II fluorophores for versatile biomedical imaging applications.

Concave Array Ultrasonic Transducer From Multilayer Piezoelectric Ceramic for Photoacoustic Imaging.

Implementation of piezoelectric multilayer ceramic (MLC) is an effective way to reduce impedance and improve the performance of linear-array transducer for ultrasonic system applications. However, the ultrasonic image derived from a planar linear-array transducer generally suffers from degradation of lateral resolution and contrast. In this article, we designed and fabricated a focused 5-MHz 128-element linear-array ultrasonic transducer with concave structure using five-layered 0.1Pb (Ni1/3Nb2/3)O3 -0.35Pb(Zn1/3Nb2/3)O3 -0.15Pb(Mg1/3Nb2/3)O3-0.1PbZrO3-0.3PbTiO3 (PNN-PZN-PMN-PZ-PT) piezo- electric ceramic. The transducer showed a bandwidth of 63% at -6 dB and the lateral resolution up to 0.33 mm. An improved transmission signal of 90% higher than a commercial single-layer ceramic transducer was also achieved. We further demonstrated high-resolution photoacoustic imaging with the obtained concave linear-array transducer.

Ultrasonic Transducer From Piezoelectric Polymer Multilayer Through Electrophoretic Deposition for Photoacoustic Imaging.

Emerging ultrasound imaging modality based on optical-generated acoustic waves, such as photoacoustic (PA) imaging, has enabled novel functional imaging on biological samples. The performance of the ultrasonic transducer plays a critical role in producing higher quality PA images. However, the high electrical impedance of the small piezoelectric elements in the transducer array causes an electrical mismatch with external circuitry and results in degraded sensitivity. One effective method for reducing the electrical impedance is to implement a piezoelectric multilayer configuration instead of the conventional single layer for the transducer. In this work, we introduced an ultrasonic transducer comprising a piezoelectric polymer multilayer structure produced by an innovative multicycle powder-based electrophoretic deposition, using a suspension of polymer nanoparticles. The multicycle electrophoretic deposition overcomes the redissolution issue in solution-based methods. The ultrasonic transducer comprising the piezoelectric polymer multilayer exhibits significantly enhanced receiving sensitivity as compared to the ultrasonic transducer using a single layer. Ultrasonic transducer with multielement array configuration is obtained using the piezoelectric polymer multilayer, and PA imaging with improved resolution is demonstrated. Theoretical analysis shows that the enhanced transducer performance is mainly attributed to the improved electrical impedance match between the piezoelectric polymer element in the transducer and external receiving circuit.

Origin of High Thermoelectric Performance in Earth-Abundant Phosphide-Tetrahedrite.

Phosphide-based thermoelectrics are a relatively less studied class of compounds, primarily due to the presence of light elements, which result in high thermal conductivity and inherent stability problems. In this work, we present a stable phosphide-tetrahedrite, Ag6Ge10P12, which possesses the highest zT (∼0.7) among all known phosphides at intermediate temperatures (750 K). We examine the intrinsic electronic and thermal transport properties of this compound by expressing the transport properties in terms of weighted mobility (µW), transport coefficient (σE0), and material quality factor (B), from which we are able to elucidate that the origin of its high zT can be attributed to the platelike Fermi surface and high level of band multiplicity related to its complex band structure. Finally, we discuss the origin of the low lattice thermal conductivity observed in this compound using experimental sound velocity, elastic properties, and Debye-Callaway model, thus laying the foundation for similar stable phosphides as potentially earth-abundant and nontoxic intermediate-temperature thermoelectric materials.

Broadband Ultrasonic Array Transducer From Multilayer Piezoelectric Ceramic With Lowered Co-Firing Temperature.

Increasing array transducer bandwidth (BW) and signal-to-noise ratio (SNR) is a critical issue for producing a high-quality medical ultrasound image. However, array elements with small size tend to have poor sensitivity due to a much higher impedance compared with the electrical impedance of the transmitter and receiver circuit. Implementation of multilayer ceramic (MLC) is an effective way of reducing impedance, and thus, with a potential for improving SNR for an ultrasonic probe. In this work, we fabricated multilayer piezoelectric ceramic with a composition of 0.1Pb(Ni1/3Nb2/3)O3-0.35Pb(Zn1/3Nb2/3)O3-0.15Pb(Mg1/3Nb2/3)O3-0.1PbZrO3-0.3PbTiO3-4mol% excess NiO (PNN-PZN-PMN-PZ-PT), by a roll to roll tape casting process and co-fired with 90Ag/10Pd electrode at a low temperature of 950 °C. Using five-layer MLC (5L-MLC) as obtained, we designed and demonstrated a 5 MHz 32-element array transducer for ultrasonic and photoacoustic imaging. The five-layer transducer element exhibited a BW of 87% at -6 dB, substantially higher than 62% for single-layer ceramic (SLC) element. In addition, the insertion loss was improved by 16.2 dB over the SLC element with an external impedance of 50 Ω . Both the experimental results and theoretical analysis showed that our array transducer made of the PNN-PZN-PMN-PZ-PT MLC is promising for acquiring high-quality ultrasonic and photoacoustic images.

KNNS-BNZH Lead-Free 1-3 Piezoelectric Composite for Ultrasonic and Photoacoustic Imaging.

In this paper, lead-free 0.965(K0.45Na0.55) (Nb0.96Sb0.04)O3-0.0375Bi0.5Na0.5Zr0.85Hf0.15O3 (KNNS-BNZH)/epoxy 1-3 composite was designed and fabricated with the dice-and-fill method. The composite material exhibited a high thickness electromechanical coupling coefficient ( kt = 0.7 ), high piezoelectric constant ( d33 = 350 pC N-1), relatively low mechanical quality factor ( Qm = 5 ), and relatively low acoustic impedance. An ultrasonic transducer with a center frequency of 5 MHz was produced based on the 1-3 KNNS-BNZH/epoxy composite, showing a broad bandwidth of 80% (-6 dB) and two-way insertion loss of -30 dB. Ultrasonic and photoacoustic images were further demonstrated. The outstanding performance of the 1-3 KNNS-BNZH/epoxy composite transducer competitive to Pb(Zr1-xTix)O3 (PZT)-based transducers suggests that the lead-free material can serve as a promising alternative to Pb-based piezoelectric materials for ultrasonic applications.

Photoacoustic and Magnetic Resonance Imaging Bimodal Contrast Agent Displaying Amplified Photoacoustic Signal.

Progress in photoacoustic (PA) and magnetic resonance imaging (MRI) bimodal contrast agents has been achieved mainly by utilizing the imaging capability of single or multiple components and consequently realizing the desired application for both imaging modalities. However, the mechanism of the mutual influence between components within a single nanoformulation, which is the key to developing high-performance multimodal contrast agents, has yet to be fully understood. Herein, by integrating conjugated polymers (CPs) with iron oxide (IO) nanoparticles using an amphiphilic polymer, a bimodal contrast agent named CP-IO is developed, displaying 45% amplified PA signal intensity as compared to bare CP nanoparticle, while the performance of MRI is not affected. Further experimental and theoretical simulation results reveal that the addition of IO nanoparticles in CP-IO nanocomposites contributes to this PA signal amplification through a synergistic effect of additional heat generation and faster heat dissipation. Besides, the feasibility of CP-IO nanocomposites acting as PA-MRI bimodal contrast agents is validated through in vivo tumor imaging using mice models. From this study, it is demonstrated that a delicately designed structural arrangement of various components in a contrast agent could potentially lead to a superior performance in the imaging capability.

Bright Aggregation-Induced-Emission Dots for Targeted Synergetic NIR-II Fluorescence and NIR-I Photoacoustic Imaging of Orthotopic Brain Tumors.

Precise diagnostics are of significant importance to the optimal treatment outcomes of patients bearing brain tumors. NIR-II fluorescence imaging holds great promise for brain-tumor diagnostics with deep penetration and high sensitivity. This requires the development of organic NIR-II fluorescent agents with high quantum yield (QY), which is difficult to achieve. Herein, the design and synthesis of a new NIR-II fluorescent molecule with aggregation-induced-emission (AIE) characteristics is reported for orthotopic brain-tumor imaging. Encapsulation of the molecule in a polymer matrix yields AIE dots showing a very high QY of 6.2% with a large absorptivity of 10.2 L g-1 cm-1 at 740 nm and an emission maximum near 1000 nm. Further decoration of the AIE dots with c-RGD yields targeted AIE dots, which afford specific and selective tumor uptake, with a high signal/background ratio of 4.4 and resolution up to 38 µm. The large NIR absorptivity of the AIE dots facilitates NIR-I photoacoustic imaging with intrinsically deeper penetration than NIR-II fluorescence imaging and, more importantly, precise tumor-depth detection through intact scalp and skull. This research demonstrates the promise of NIR-II AIE molecules and their dots in dual NIR-II fluorescence and NIR-I photoacoustic imaging for precise brain cancer diagnostics.

Piezoelectric Nanotube Array for Broadband High-Frequency Ultrasonic Transducer.

Piezoelectric materials are vital in determining ultrasonic transducer and imaging performance as they offer the function for conversion between mechanical and electrical energy. Ultrasonic transducers with high-frequency operation suffer from performance degradation and fabrication difficulty of the demanded piezoelectric materials. Hence, we propose 1-D polymeric piezoelectric nanostructure with controlled nanoscale features to overcome the technical limitations of high-frequency ultrasonic transducers. For the first time, we demonstrate the integration of a well-aligned piezoelectric nanotube array to produce a high-frequency ultrasonic transducer with outstanding performance. We find that nanoconfinement-induced polarization orientation and unique nanotube structure lead to significantly improved piezoelectric and ultrasonic transducing performance over the conventional piezoelectric thin film. A large bandwidth, 126% (-6 dB), is achieved at high center frequency, 108 MHz. Transmission sensitivity of nanotube array is found to be 46% higher than that of the monolithic thin film transducer attributed to the improved electromechanical coupling effectiveness and impedance match. We further demonstrate high-resolution scanning, ultrasonic imaging, and photoacoustic imaging using the obtained nanotube array transducers, which is valuable for biomedical imaging applications in the future.

Nanoconfinement induced crystal orientation and large piezoelectric coefficient in vertically aligned P(VDF-TrFE) nanotube array.

Vertically aligned piezoelectric P(VDF-TrFE) nanotube array comprising nanotubes embedded in anodized alumina membrane matrix without entanglement has been fabricated. It is found that the crystallographic polar axes of the P(VDF-TrFE) nanotubes are oriented along the nanotubes long axes. Such a desired crystal orientation is due to the kinetic selection mechanism for lamellae growth confined in the nanopores. The preferred crystal orientation in nanotubes leads to huge piezoelectric coefficients of the P(VDF-TrFE). The piezoelectric strain and voltage coefficients of P(VDF-TrFE) nanotube array are observed to be 1.97 and 3.40 times of those for conventional spin coated film. Such a significant performance enhancement is attributed to the well-controlled polarization orientation, the elimination of the substrate constraint, and the low dielectric constant of the nanotube array. The P(VDF-TrFE) nanotube array exhibiting the unique structure and outstanding piezoelectric performance is promising for wide applications, including various electrical devices and electromechanical sensors and transducers.