Study of Martensitic Phase Transformation in a NiTiCu Thin‐Film Shape‐Memory Alloy Using Photoelectron Emission Microscopy

Thermally induced martensitic phase transformation in a polycrystalline NiTiCu thin‐film shape‐memory alloy is probed using photoelectron emission microscopy (PEEM). In situ PEEM images reveal distinct changes in microstructure and photoemission intensity at the phase‐transition temperatures. In particular, images of the low‐temperature, martensite phase are brighter than that of the high‐temperature, austenite phase, because of the lower work function of the martensite. UV photoelectron spectroscopy shows that the effective work‐function changes by about 0.16 eV during thermal cycling. In situ PEEM images also show that the network of trenches observed on the room‐temperature film disappears suddenly during heating and reappears suddenly during subsequent cooling. These trenches are also characterized using atomic force microscopy at selected temperatures. The implications of these observations with respect to the spatial distribution of phases during thermal cycling in this thin‐film shape‐memory alloy are discussed.     

High‐Strain Shape‐Memory Polymers

Shape‐memory polymers (SMPs) are self‐adjusting, smart materials in which shape changes can be accurately controlled at specific, tailored temperatures. In this study, the glass transition temperature (T_g) is adjusted between 28 and 55 °C through synthesis of copolymers of methyl acrylate (MA), methyl methacrylate (MMA), and isobornyl acrylate (IBoA). Acrylate compositions with both crosslinker densities and photoinitiator concentrations optimized at fractions of a mole percent demonstrate fully recoverable strains at 807% for a T_g of 28 °C, at 663% for a T_g of 37 °C, and at 553% for a T_g of 55 °C. A new compound, 4,4′‐di(acryloyloxy)benzil (referred to hereafter as Xini) in which both polymerizable and initiating functionalities are incorporated in the same molecule, was synthesized and polymerized into acrylate shape‐memory polymers, which were thermomechanically characterized yielding fully recoverable strains above 500%. The materials synthesized in this work were compared to an industry standard thermoplastic SMP, Mitsubishi's MM5510, which showed failure strains of similar magnitude, but without full shape recovery: residual strain after a single shape‐memory cycle caused large‐scale disfiguration. The materials in this study are intended to enable future applications where both recoverable high‐strain capacity and the ability to accurately and independently position T_g are required.     

Shape‐Memory Microfluidics

Materials with embedded vascular networks afford rapid and enhanced control over bulk material properties including thermoregulation and distribution of active compounds such as healing agents or stimuli. Vascularized materials have a wide range of potential applications in self‐healing systems and tissue engineering constructs. Here, the application of vascularized materials for accelerated phase transitions in stimuli‐responsive microfluidic networks is reported. Poly(ester amide) elastomers are hygroscopic and exhibit thermo‐mechanical properties (T_g ≈ 37 °C) that enable heating or hydration to be used as stimuli to induce glassy‐rubbery transitions. Hydration‐dependent elasticity serves as the basis for stimuli‐responsive shape‐memory microfluidic networks. Recovery kinetics in shape‐memory microfluidics are measured under several operating modes. Perfusion‐assisted delivery of stimulus to the bulk volume of shape‐memory microfluidics dramatically accelerates shape recovery kinetics compared to devices that are not perfused. The recovery times are 4.2 ± 0.1 h and 8.0 ± 0.3 h in the perfused and non‐perfused cases, respectively. The recovery kinetics of the shape‐memory microfluidic devices operating in various modes of stimuli delivery can be accurately predicted through finite element simulations. This work demonstrates the utility of vascularized materials as a strategy to reduce the characteristic length scale for diffusion, thereby accelerating the actuation of stimuli‐responsive bulk materials.     

Strong,Tailored, Biocompatible Shape‐Memory Polymer Networks

Shape‐memory polymers are a class of smart materials that have recently been used in intelligent biomedical devices and industrial applications for their ability to change shape under a predetermined stimulus. In this study, photopolymerized thermoset shape‐memory networks with tailored thermomechanics are evaluated to link polymer structure to recovery behavior. Methyl methacrylate (MMA) and poly(ethylene glycol) dimethacrylate (PEGDMA) are copolymerized to create networks with independently adjusted glass transition temperatures (T_g) and rubbery modulus values ranging from 56 to 92 °C and 9.3 to 23.0 MPa, respectively. Free‐strain recovery under isothermal and transient temperature conditions is highly influenced by the T_g of the networks, while the rubbery moduli of the networks has a negligible effect on this response. The magnitude of stress generation of fixed‐strain recovery correlates with network rubbery moduli, while fixed‐strain recovery under isothermal conditions shows a complex evolution for varying T_g. The results are intended to help aid in future shape‐memory device design and the MMA‐co‐PEGDMA network is presented as a possible high strength shape‐memory biomaterial.     

Self‐Assembled Shape‐Memory Fibers of Triblock Liquid‐Crystal Polymers

New thermoplastic liquid‐crystalline elastomers have been synthesized using the telechelic principle of microphase separation in triblock copolymers. The large central block is made of a main‐chain nematic polymer renowned for its large spontaneous elongation along the nematic director. The effective crosslinking is established by small terminal blocks formed of terphenyl moieties, which phase separate into semicrystalline micelles acting as multifunctional junction points of the network. The resulting transient network retains the director alignment and shows a significant shape‐memory effect, characteristic and exceeding that of covalently bonded nematic elastomers. Its plasticity at temperatures above the nematic–isotropic transition allows drawing thin well‐aligned fibers from the melt. The fibers have been characterized and their thermal actuator behavior—reversible contraction of heating and elongation on cooling—has been investigated.     

Dependence of Transformation Temperatures of NiTi‐based Shape‐Memory Alloys on the Number and Concentration of Valence Electrons

Dependence of transformation temperatures of ternary and quaternary NiTi‐based shape memory alloys on the number (e_v/a) and concentration (c_v) of valence electrons is investigated. Two distinct trends of transformation temperatures with respect to the number of valence electrons per atom are found depending on whether e_v/a = 7 or e_v/a ≠ 7. Clear correlations between transformation temperatures and c_v exist. M_s and A_s decrease consistently from 900 to ?100 °C, and 950 to ?30 °C, respectively, with increasing c_v from 0.145 to 0.296. The relationship of electron concentration on the elastic moduli of the NiTi‐based alloys is discussed. The possible influence of the atomic size of alloying elements on transformation hysteresis is introduced.     

Temperature‐Memory Effect of Copolyesterurethanes and their Application Potential in Minimally Invasive Medical Technologies

Minimally invasive surgery often requires devices that can change their geometry or shape when placed inside the body. Here, the potential of thermoplastic temperature‐memory polymers (TMP) for the design of intelligent devices, which can be programmed by the clinician to individually adapt their shifting geometry and their response temperature T_sw to the patient's needs, is explored. Poly(ω‐pentadecalactone) as hard segments and poly(?‐caprolactone) segments acting as crystallizable controlling units for the temperature‐memory effect (TME) are chosen to form multiblock copolymers PDLCL. These components are selected according to their thermal properties and their good biocompatibility. Response temperatures obtained under stress‐free and constant strain recovery can be systematically adjusted by variation of the deformation temperature in a temperature range from 32 °C to 65 °C, which is the relevant temperature range for medical applications. The working principle of TMP based instruments for minimally invasive surgical procedures is successfully demonstrated using three temperature‐memory catheter concepts: individually programmable TM‐catheter, an in‐situ programmable TM‐catheter, and an intelligent drainage catheter for gastroenterology.     

A New Prototype Two‐Phase (TiNi)–(β‐W) SMA System with Tailorable Thermal Hysteresis

The Ti–Ni–W two‐phase shape memory alloy (SMA) thin film system is presented as a prototype for new SMAs with tailorable thermal transformation hysteresis (ΔT). The concept is to combine the SMA TiNi with almost insoluble W to create the two‐phase system (TiNi)–(β‐W). This system behaves like a pseudobinary TiNi system. Phase transformation behavior for compositions above the solubility limit of W in TiNi exhibit a B2–R phase transformation with characteristically small ΔT. Moreover, ΔT is dependent on the amount of W and it can be tailored to zero and even negative. This phenomenon is rationalized as being due to the mechanical interaction between the phases B2‐TiNi and β‐W. The presented results are very promising for the development of high‐speed Ti–Ni‐based SMA actuators.     

Coupling of Micromagnetic and Structural Properties Across the Martensite and Curie Temperatures in Miniaturized Ni‐Mn‐Ga Ferromagnetic Shape Memory Alloys

Micromagnetic structure evolution in Ni‐Mn‐Ga ferromagnetic shape memory thin films is investigated by means of temperature dependent magnetic force microscopy (TD‐MFM). The center of interest is the magnetic properties of epitaxial Ni‐Mn‐Ga thin films on MgO substrates across thermally induced phase transitions. Experimental results are discussed within the framework of competing magnetic interactions arising in stressed thin ferromagnetic films. Measurements on 14M martensite specimens are supplemented by three‐dimensional micromagnetic simulations. Corresponding calculated MFM micrographs are compared to experimental data. The influence of twin variant dimension and orientation on micromagnetic domain formation and wall structure is depicted from a theoretical point of view. A micromagnetic model system of partial flux closure is proposed and calculated analytically to estimate a stress induced magneto crystalline anisotropy constant in austenite Ni‐Mn‐Ga.     

Magnetic Field‐Enhanced Thermoelectric Performance in Dirac Semimetal Cd3As2 Crystals with Different Carrier Concentrations

The magneto‐thermoelectric figure of merit (ZT) in crystals of the topological Dirac semimetal Cd₃As₂ with different carrier concentrations is studied. The ZTs for all the crystals increase with the temperature and show maxima at high temperatures. Meanwhile, the temperatures corresponding to the ZT maxima increase with the carrier concentration. The limit to the improvement in ZT(T) at high temperature could be related to the unusual large enhancement in thermal conductivity at elevated temperatures. The bipolar effect and Dirac liquid behavior are presented as processes possibly responsible for the peculiar behavior of the thermal conductivity. Applying a transverse magnetic field initially leads to a dramatic enhancement and, subsequently, to a slight reduction in ZT for all the crystals. The maximum ZT achieved in a magnetic field increases with the carrier concentration and reaches 1.24 at 450 K in a magnetic field of 9 T for the crystal with the highest carrier concentration. It is expected that this work will be beneficial to the current interests in optimizing the thermoelectric properties of quantum topological materials.     

Controllable Shifts in Threshold Voltage of Top‐Gate Polymer Field‐Effect Transistors for Applications in Organic Nano Floating Gate Memory

Organic field‐effect transistor (FET) memory is an emerging technology with the potential to realize light‐weight, low‐cost, flexible charge storage media. Here, solution‐processed poly[9,9‐dioctylfluorenyl‐2,7‐diyl]‐co‐(bithiophene)] (F8T2) nano floating gate memory (NFGM) with a top‐gate/bottom‐contact device configuration is reported. A reversible shift in the threshold voltage (V_Th) and reliable memory characteristics was achieved by the incorporation of thin Au nanoparticles (NPs) as charge storage sites for negative charges (electrons) at the interface between polystyrene and cross‐linked poly(4‐vinylphenol). The F8T2 NFGM showed relatively high field‐effect mobility (µ_FET) (0.02 cm² V^?1 s^?1) for an amorphous semiconducting polymer with a large memory window (ca. 30 V), a high on/off ratio (more than 10⁴) during writing and erasing with an operation voltage of 80 V of gate bias in a relatively short timescale (less than 1 s), and a retention time of a few hours. This top‐gated polymer NFGM could be used as an organic transistor memory element for organic flash memory.     

A New Carbazole‐Constructed Hyperbranched Polymer: Convenient One‐Pot Synthesis,Hole‐Transporting Ability,and Field‐Effect Transistor Properties

A new hyperbranched polymer ( HB‐car ), constructed fully by carbazole moieties, is successfully synthesized through a one‐pot Suzuki coupling reaction. The resultant polymer is well‐characterized, and its hole‐transporting ability is studied carefully. The device, in which HB‐car is utilized as a hole‐transporting layer and tris‐(8‐hydroxyquinoline) aluminum as an electron‐emitting layer as well as electron‐transporting layer, gives a much higher efficiency (3.05 cd A^–1), than that of a poly(N‐vinylcarbazole) based device (2.19 cd A^–1) under similar experimental conditions. The remarkable performance is attributed to its low energy barrier and enhanced hole‐drifting ability in the HB‐car based device. In addition, for the first time, a field‐effect transistor (FET) based on the hyperbranched polymer is fabricated, and the organic FET device shows that HB‐car is a typical p‐type FET material with a saturation mobility of 1 × 10^–5 cm² V^–1 s^–1, a threshold voltage of –47.1 V, and an on‐to‐off current ratio of 10³.     

Manipulating the Hysteresis in Poly(vinyl alcohol)‐Dielectric Organic Field‐Effect Transistors Toward Memory Elements

The origins of hysteresis in organic field‐effect transistors (OFETs) and its applications in organic memory devices is investigated. It is found that the orientations of the hydroxyl groups in poly(vinyl alcohol) (PVA) gate dielectrics are correlated with the hysteresis of transfer characteristics in pentacene‐based OFETs under the forward and backward scan. The applied gate bias partially aligns the orientations of the hydroxyl groups perpendicular to the substrate as characterized by reflective absorption Fourier transform infrared spectroscopy (RA‐FTIR), in which the field‐induced surface dipoles at the pentacene/PVA interface trap charges and cause the hysteresis. Treating PVA with an anhydrous solvent eliminates the residual moisture in the dielectrics layer, allowing for more effective control of the induced dipoles by the applied gate bias. OFETs of dehydrated‐PVA dielectrics present a pronounced shift of the threshold voltage (ΔV_Th) of 35.7 V in transfer characteristics, higher than that of 18.5 V for untreated devices and results in sufficient dynamic response for applications in memory elements. This work highlights the usage of non‐ferroelectric gate dielectrics to fabricate OFET memory elements by manipulating the molecular orientations in the dielectrics layer.     

Voltage‐Induced Coercivity Reduction in Nanoporous Alloy Films: A Boost toward Energy‐Efficient Magnetic Actuation

Magnetic data storage and magnetically actuated devices are conventionally controlled by magnetic fields generated using electric currents. This involves significant power dissipation by Joule heating effect. To optimize energy efficiency, manipulation of magnetic information with lower magnetic fields (i.e., lower electric currents) is desirable. This can be accomplished by reducing the coercivity of the actuated material. Here, a drastic reduction of coercivity is observed at room temperature in thick (≈600 nm), nanoporous, electrodeposited Cu–Ni films by simply subjecting them to the action of an electric field. The effect is due to voltage‐induced changes in the magnetic anisotropy. The large surface‐area‐to‐volume ratio and the ultranarrow pore walls of the system allow the whole film, and not only the topmost surface, to effectively contribute to the observed magnetoelectric effect. This waives the stringent “ultrathin‐film requirement” from previous studies, where small voltage‐driven coercivity variations were reported. This observation expands the already wide range of applications of nanoporous materials (hitherto in areas like energy storage or catalysis) and it opens new paradigms in the fields of spintronics, computation, and magnetic actuation in general.     

A Semi‐Floating Memory with 535% Enhancement of Refresh Time by Local Field Modulation

The recently proposed semi‐floating gate memory technology shows the potential to balance conflicts between writing speed and data storage. Although the introduction of the p–n junction greatly improves device writing speed, the inevitable junction leakage limits the further extension of data retention time. A local nonvolatile electric field is introduced by exploiting the polarization of ferroelectric gate dielectric HfZrO₄ to modulate the charge leakage speed of the p–n junction since the carrier density of 2D materials can be efficiently regulated. The refresh time is greatly prolonged more than 535%, solving the bottleneck problem of relatively short retention time of previous semi‐floating gate memory. In addition, the characteristics of device under low operation voltage is also explored, which can serve for further power reducing. This design realizes the combination of ultrafast writing operation and significant enhanced data retention ability, which provides a new idea of the development for high speed non‐volatile memory technology.     

Identification of Quaternary Shape Memory Alloys with Near‐Zero Thermal Hysteresis and Unprecedented Functional Stability

Improving the functional stability of shape memory alloys (SMAs), which undergo a reversible martensitic transformation, is critical for their applications and remains a central research theme driving advances in shape memory technology. By using a thin‐film composition‐spread technique and high‐throughput characterization methods, the lattice parameters of quaternary Ti–Ni–Cu–Pd SMAs and the thermal hysteresis are tailored. Novel alloys with near‐zero thermal hysteresis, as predicted by the geometric non‐linear theory of martensite, are identified. The thin‐film results are successfully transferred to bulk materials and near‐zero thermal hysteresis is observed for the phase transformation in bulk alloys using the temperature‐dependent alternating current potential drop method. A universal behavior of hysteresis versus the middle eigenvalue of the transformation stretch matrix is observed for different alloy systems. Furthermore, significantly improved functional stability, investigated by thermal cycling using differential scanning calorimetry, is found for the quaternary bulk alloy Ti_50.2Ni_34.4Cu_12.3Pd_3.1.     

A Die‐Selection Method Using Search‐Space Conditions for Yield Enhancement in 3D Memory

Three‐dimensional (3D) memories using through‐silicon vias (TSVs) as vertical buses across memory layers will likely be the first commercial application of 3D integrated circuit technology. The memory dies to stack together in a 3D memory are selected by a die‐selection method. The conventional die‐selection methods do not result in a high‐enough yields of 3D memories because 3D memories are typically composed of known‐good‐dies (KGDs), which are repaired using self‐contained redundancies. In 3D memory, redundancy sharing between neighboring vertical memory dies using TSVs is an effective strategy for yield enhancement. With the redundancy sharing strategy, a known‐bad‐die (KBD) possibly becomes a KGD after bonding. In this paper, we propose a novel die‐selection method using KBDs as well as KGDs for yield enhancement in 3D memory. The proposed die‐selection method uses three search‐space conditions, which can reduce the search space for selecting memory dies to manufacture 3D memories. Simulation results show that the proposed die‐selection method can significantly improve the yield of 3D memories in various fault distributions.