Flexible Gallium Nitride for High‐Performance,Strainable Radio‐Frequency Devices

Flexible gallium nitride (GaN) thin films can enable future strainable and conformal devices for transmission of radio‐frequency (RF) signals over large distances for more efficient wireless communication. For the first time, strainable high‐frequency RF GaN devices are demonstrated, whose exceptional performance is enabled by epitaxial growth on 2D boron nitride for chemical‐free transfer to a soft, flexible substrate. The AlGaN/GaN heterostructures transferred to flexible substrates are uniaxially strained up to 0.85% and reveal near state‐of‐the‐art values for electrical performance, with electron mobility exceeding 2000 cm² V^?1 s^?1 and sheet carrier density above 1.07 × 10¹³ cm^?2. The influence of strain on the RF performance of flexible GaN high‐electron‐mobility transistor (HEMT) devices is evaluated, demonstrating cutoff frequencies and maximum oscillation frequencies greater than 42 and 74 GHz, respectively, at up to 0.43% strain, representing a significant advancement toward conformal, highly integrated electronic materials for RF applications.     

Strain engineering of piezoelectric properties of strontium titanate thin films

The in-plane and out-of-plane piezoelectric properties of (001) strontium titanate (SrTiO₃, STO) epitaxial thin films on pseudo-cubic (001) substrates are computed as a function of in-plane misfit strain. A nonlinear thermodynamic model is employed, which takes into account the appropriate mechanical boundary conditions, the electromechanical coupling between the polarization and the in-plane lattice mismatch, and the self-strains of the ferroelastic and ferroelectric phase transformations. The piezoelectric behavior of epitaxial STO films is described in various strain-induced ferroelectric phase fields in a temperature range from ?50 to 50 °C. The calculations show that by carefully tailoring in-plane misfit strains in both tensile and compressive ranges, piezoelectric coefficients that are of the order of prototypical lead zirconate titanate and other lead-based piezoceramics can be realized. These results indicate that strain engineered STO films may be employed in a variety of sensor and actuator applications as well as surface acoustic wave devices and thin-film bulk acoustic resonators.     

Periodic Wrinkle-Patterned Single-Crystalline Ferroelectric Oxide Membranes with Enhanced Piezoelectricity

Self-assembled membranes with periodic wrinkled patterns are the critical building blocks of various flexible electronics, where the wrinkles are usually designed and fabricated to provide distinct functionalities. These membranes are typically metallic and organic materials with good ductility that are tolerant of complex deformation. However, the preparation of oxide membranes, especially those with intricate wrinkle patterns, is challenging due to their inherently strong covalent or ionic bonding, which usually leads to material crazing and brittle fracture. Here, wrinkle-patterned BaTiO₃ (BTO)/poly(dimethylsiloxane) membranes with finely controlled parallel, zigzag, and mosaic patterns are prepared. The BTO layers show excellent flexibility and can form well-ordered and periodic wrinkles under compressive in-plane stress. Enhanced piezoelectricity is observed at the sites of peaks and valleys of the wrinkles where the largest strain gradient is generated. Atomistic simulations further reveal that the excellent elasticity and the correlated coupling between polarization and strain/strain gradient are strongly associated with ferroelectric domain switching and continuous dipole rotation. The out-of-plane polarization is primarily generated at compressive regions, while the in-plane polarization dominates at the tensile regions. The wrinkled ferroelectric oxides with differently strained regions and correlated polarization distributions would pave a way toward novel flexible electronics.     

Novel room temperature multiferroics for random access memory elements

We have fabricated a variety of PZT-PFW (P bZr?.??Ti?.??O?)1-x(PbFe?/?W?/?O?)x [PZTFWx; 0.2 < x <0.4] single-phase tetragonal ferroelectrics via chemical solution deposition [polycrystalline] and pulsed laser deposition [epitaxial] onto Pt/Ti/SiO2/Si(100) and SrTiO?/Si substrates. These exhibit ferroelectricity and (weak) ferromagnetism above room temperature with strain coupling via electrostriction and magnetostriction. Application of modest magnetic field strength (μ?H < 1.0 T) destabilizes the long-range ferroelectric ordering and switches the polarization from approximately 22 μC/cm2 (0.22 C/m2) to zero (relaxor state). This offers the possibility of three-state logic (+P, 0, -P) and magnetically switched polarizations. Because the switching is of large magnitude (unlike the very small nanocoulomb per centimeter squared values in terbium manganites) and at room-temperature, commercial devices should be possible.     

Atomic Origins of Enhanced Ferroelectricity in Nanocolumnar PbTiO3/PbO Composite Thin Films

Nanocomposite films hold great promise for multifunctional devices by integrating different functionalities within a single film. The microstructure of the precipitate/secondary phase is an essential element in designing composites’ properties. The interphase strain between the matrix and secondary phase is responsible for strain-mediated functionalities, such as magnetoelectric coupling and ferroelectricity. However, a quantitative microstructure-dependent interphase strain characterization has been scarcely studied. Here, it is demonstrated that the PbTiO₃(PTO)/PbO composite system can be prepared in nano-spherical and nanocolumnar configurations by tuning the misfit strain, confirmed by a three-dimensional reconstructive microscopy technique. With the atomic resolution quantitative microscopy with a depth resolution of a few nanometers, it is discovered that the strained region in PTO is much larger and more uniform in nanocolumnar compared to nano-spherical composites, resulting in much enhanced ferroelectric properties. The interphase strain between PbO and PTO in the nanocolumnar structure leads to a giant c/a ratio of 1.20 (bulk value of 1.06), accompanied by a Ti polarization displacement of 0.48 Å and an effective ferroelectric polarization of 241.7 µC cm⁻², three times compared to the bulk value. The quantitative atomic-scale strain and polarization analysis on the interphase strain provides an important guideline for designing ferroelectric nanocomposites.     

Fabrication of single crystal PZT thin films on glass substrates

 We have successfully transferred heteroepitaxial Pb(Zr,Ti)O₃ (PZT) thin films from MgO substrates on to glass substrates. The transferred PZT thin films exhibit single crystal structure with ferroelectric properties similar to the as-grown epitaxial films. The transferring process comprises coating of Cr-metallized surface of epitaxial PZT thin films, pressing and cementing the Cr-metallized surface on to the glass substrates by silicone rubber, and removing the MgO substrates by chemical etching. This process realizes a fabrication of high-temperature processed PZT thin films onto the glass at room temperature. The process is also available for the transformation of PZT thin films on organic film sheet. The present transfer process reduces the effects of the inevitable strain and/or constraint to rigid substrates for heteroepitaxial growth and has a potential for integration of single crystal piezoelectric PZT devices onto a wide variety of MEMS.     

Modulations in structural and ferroelectric properties due to tensile strain in BiFeO3 films on MgAl2O4 substrates induced by thermal-expansion

The effect of tensile strain on structural and ferroelectric properties of BiFeO₃ epitaxial films was investigated. The films grown by pulsed laser deposition on MgAl₂O₄ (0 0 1) substrates revealed monoclinic structure deviated from the bulk rhombohedral structure due to a tensile strain along the in-plane direction. The strain is induced by the difference in thermal expansion coefficients between the film and the substrate. A Poisson ratio is calculated from the in-plain and out-of-plain lattice constants at different temperatures measured by reciprocal space maps of X-ray diffraction. The small Poisson ratio compared to the bulk suggests a weaker elastic response at high temperature. The ferroelectric polarization of the tensile-strained film along the (0 0 1) is also decreased from the bulk value.     

Tuning Susceptibility via Misfit Strain in Relaxed Morphotropic Phase Boundary PbZr1‐xTixO3 Epitaxial Thin Films

Epitaxial strain is a powerful tool to manipulate the properties of ferroelectric materials. But despite extensive work in this regard, few studies have explored the effect of epitaxial strain on PbZr_0.52Ti_0.48O₃. Here we explore how epitaxial strain impacts the structure and properties of 75 nm thick films of the morphotropic phase boundary composition. Single‐phase, fully epitaxial films are found to possess “relaxed” or nearly “relaxed” structures despite growth on a range of substrates. Subsequent studies of the dielectric and ferroelectric properties reveal films with low leakage currents facilitating the measurement of low‐loss hysteresis loops down to measurement frequencies of 30 mHz and dielectric response at background dc bias fields as large as 850 kV/cm. Despite a seeming insensitivity of the crystal structure to the epitaxial strain, the polarization and switching characteristics are found to vary with substrate. The elastic constraint from the substrate produces residual strains that dramatically alter the electric‐field response including quenching domain wall contributions to the dielectric permittivity and suppressing field‐induced structural reorientation. These results demonstrate that substrate mediated epitaxial strain of PbZr_0.52Ti_0.48O₃ is more complex than in conventional ferroelectrics with discretely defined phases, yet can have a marked effect on the material and its responses.     

Ferroelectric properties of epitaxial Bi3.15Nd0.85Ti3O12 films on SiO2/Si using biaxially oriented MgO as templates

High quality epitaxial Bi_3.15Nd_0.85Ti₃O₁₂ (BNT) thin films with thicknesses from 30 to 80 nm have been integrated on SiO₂/Si substrates. MgO templates deposited by ion-beam-assisted deposition and SrRuO₃ (SRO) buffer layers processed by pulsed laser deposition have been used to initiate the epitaxial growth of BNT films on the amorphous SiO₂/Si substrates. The structural and ferroelectric properties were investigated. Microstructural studies by X-ray diffraction and transmission electron microscopy revealed high quality crystalline with an epitaxial relationship of (001)_BNT||(001)_SRO||(001)_MgO and [100]_BNT||[110]_SRO||[110]_MgO. A ferroelectric hysteresis loop with a remanent polarization of 3.1 μC/cm² has been observed for a 30 nm thick film. The polarization exhibits a fatigue-free characteristic up to 1.44 × 10¹⁰ switching cycles.     

Giant sharp and persistent converse magnetoelectric effects in multiferroic epitaxial heterostructures

Magnetoelectric coupling between magnetic and electrical properties presents valuable degrees of freedom for applications. The two most promising scenarios are magnetic-field sensors that could replace low-temperature superconducting quantum interference devices, and electric-write magnetic-read memory devices that combine the best of ferroelectric and magnetic random-access memory. The former scenario requires magnetically induced continuous and reversible changes in electrical polarization. These are commonly observed, but the coupling constants thus obtained are invalid for data-storage applications, where the more difficult to achieve and rarely studied magnetic response to an electric field is required. Here, we demonstrate electrically induced giant, sharp and persistent magnetic changes (up to 2.3 x 10(-7) s m(-1)) at a single epitaxial interface in ferromagnetic 40 nm La(0.67)Sr(0.33)MnO(3) films on 0.5 mm ferroelectric BaTiO(3) substrates. X-ray diffraction confirms strain coupling via ferroelastic non-180( composite function) BaTiO(3) domains. Our findings are valid over a wide range of temperatures including room temperature, and should inspire further study with single epitaxial interfaces.     

Ultrathin Crystalline Silicon Nano and Micro Membranes with High Areal Density for Low-Cost Flexible Electronics

Ultrathin crystalline silicon is widely used as an active material for high-performance, flexible, and stretchable electronics, from simple passive and active components to complex integrated circuits, due to its excellent electrical and mechanical properties. However, in contrast to conventional silicon wafer-based devices, ultrathin crystalline silicon-based electronics require an expensive and rather complicated fabrication process. Although silicon-on-insulator (SOI) wafers are commonly used to obtain a single layer of crystalline silicon, they are costly and difficult to process. Therefore, as an alternative to SOI wafers-based thin layers, here, a simple transfer method is proposed for printing ultrathin multiple crystalline silicon sheets with thicknesses between 300 nm to 13 µm and high areal density (>90%) from a single mother wafer. Theoretically, the silicon nano/micro membrane can be generated until the mother wafer is completely consumed. In addition, the electronic applications of silicon membranes are successfully demonstrated through the fabrication of a flexible solar cell and flexible NMOS transistor arrays.     

Review of magnetoelectric perovskite–spinel self-assembled nano-composite thin films

Two-phase multiferroic nano-composite thin films have been a topic of research interests in the last few years. This is because of their expected magnetoelectric coupling, as well as potential applications. This review focuses on recent findings in self-assembled nano-structure composite thin films, and various efforts to realize and improve their magnetoelectricity. Topics include: (i) nano-pillar and maze structures, and their formation mechanisms, and a nano-belt structure oriented in-plane found by our research group; (ii) the ferroelectric properties of composite thin films, and how they can be enhanced by epitaxial engineering; (iii) a magnetic anisotropy that is induced by constraint stress, and by the nano-structures of the ferromagnetic phase; and (iv) a magnetoelectric coupling that was first observed via a change in magnetization near the Curie temperature of the ferroelectric phase, a magnetization switching assisted by electric field, and recently direct measurements using a magnetic cantilever method yielding values of 18 mV/cm Oe in BiFeO₃–CoFe₂O₄.     

Study on adhesion and wear resistance of multi-element (AlCrTaTiZr)N coatings

Multi-element (AlCrTaTiZr)N films were deposited on cemented carbide and M2 steel substrates by reactive RF magnetron sputtering. Prior to nitride film deposition, an interlayer between the film and the substrate was introduced to improve adhesion property. The influence of interlayer materials (Ti, Cr, and AlCrTaTiZr alloy) and interlayer thickness (0–400 nm) on the adhesion and tribological properties of films was investigated. In this study, the nitride film deposited at R_N = 20% exhibited the highest hardness (35.2 GPa) and the lowest residual compressive stress (? 1.52 GPa), and was prepared as the top layer for further testing. The interlayer materials can effectively improved the film adhesion onto the cemented carbide substrates, and the adhesive failure was not observed even under the normal load of 100 N. For M2 steel substrates, only the Cr interlayer can slightly improve the film adhesion, and the cohesive and adhesive failure can be found at relatively lower applied load. The optimal interlayer thickness was 100–200 nm for the 1 µm-thick (AlCrTaTiZr)N film and can be related to the stress evolution. The friction coefficient and wear rate for the (AlCrTaTiZr)N film were 0.82 and 4.9 × 10^? 6 mm³/Nm, respectively, and almost kept constant under different interlayer materials and thickness. The worn-through event of the nitride film during tribological test occurred easily owing to its poor adhesion behavior, and can be improved by interlayer additions.     

Organic photodiodes on flexible substrates

The fabrication of organic photodiodes on solution cast indium tin oxide (ITO) bottom electrodes on flexible substrates is described. ITO coatings with a sheet resistance of 2 to 3 kΩ/sq are produced by gravure printing process on PEN (polyethylene 2,6-naphthalate) films. The ITO films are directly used as transparent bottom electrodes for organic photodiodes (OPD). Furthermore, first experiments to integrate one of these OPDs in an all-organic opto-chemical sensor are successfully demonstrated. The implementation of OPDs as detectors in applications such as integrated sensors demands a fabrication of these devices on flexible substrates. For these applications the OPDs on printed ITO on PEN are especially suitable.     

Graphene–Mesoporous Si Nanocomposite as a Compliant Substrate for Heteroepitaxy

The ultimate performance of a solid state device is limited by the restricted number of crystalline substrates that are available for epitaxial growth. As a result, only a small fraction of semiconductors are usable. This study describes a novel concept for a tunable compliant substrate for epitaxy, based on a graphene–porous silicon nanocomposite, which extends the range of available lattice constants for epitaxial semiconductor alloys. The presence of graphene and its effect on the strain of the porous layer lattice parameter are discussed in detail and new remarkable properties are demonstrated. These include thermal stability up to 900 °C, lattice tuning up to 0.9 % mismatch, and compliance under stress for virtual substrate thicknesses of several micrometers. A theoretical model is proposed to define the compliant substrate design rules. These advances lay the foundation for the fabrication of a compliant substrate that could unlock the lattice constant restrictions for defect‐free new epitaxial semiconductor alloys and devices.     

Effect of film thickness on ferroelectric domain structure and properties of Pb(Zr0.35Ti0.65)O3/SrRuO3/SrTiO3 heterostructures

Epitaxial Pb(Zr_0.35Ti_0.65)O₃ (PZT) thin films with tetragonal symmetry and thicknesses ranging from 45 to 230 nm were grown at 540 °C on SrRuO₃-coated (001)SrTiO₃ substrates by pulse-injected metalorganic chemical vapor deposition. The effect of the film thickness on the ferroelectric domain structure and the dielectric and ferroelectric properties were systematically investigated. Domain structure analysis of epitaxial PZT films was accomplished with high-resolution X-ray diffraction reciprocal space mapping and high-resolution transmission electron microscopy. Fully polar-axis (c-axis)-oriented epitaxial PZT thin films with high ferroelectric polarization values [e.g., remanent polarization (P _r) ~ 90 μC/cm²] were observed for film thicknesses below 70 nm. Films thicker than 70 nm had a c/a/c/a polydomain structure and the relative volume fraction of c-domains monotonously decreased to about 72% on increasing the film thickness up to 230 nm , and finally P _r diminished to about 64 μC/cm² for the 230-nm-thick epitaxial film. These polarization values were in good agreement with the estimated values taking into account the volume fraction of the c-axis-oriented domains while assuming a negligible contribution of 90° domain reorientation caused by an externally applied electric field.     

Ionic Gel Modulation of RKKY Interactions in Synthetic Anti‐Ferromagnetic Nanostructures for Low Power Wearable Spintronic Devices

To meet the demand of developing compatible and energy‐efficient flexible spintronics, voltage manipulation of magnetism on soft substrates is in demand. Here, a voltage tunable flexible field‐effect transistor structure by ionic gel (IG) gating in perpendicular synthetic anti‐ferromagnetic nanostructure is demonstrated. As a result, the interlayer Ruderman–Kittel–Kasuya–Yosida (RKKY) interaction can be tuned electrically at room temperature. With a circuit gating voltage, anti‐ferromagnetic (AFM) ordering is enhanced or converted into an AFM–ferromagnetic (FM) intermediate state, accompanying with the dynamic domain switching. This IG gating process can be repeated stably at different curvatures, confirming an excellent mechanical property. The IG‐induced modification of interlayer exchange coupling is related to the change of Fermi level aroused by the disturbance of itinerant electrons. The voltage modulation of RKKY interaction with excellent flexibility proposes an application potential for wearable spintronic devices with energy efficiency and ultralow operation voltage.     

Flexible copper-7,7,8,8 tetracyanochinodimethane memory devices — Operation, cross talk and bending

Non-volatile memory devices based on the charge transfer complex copper-7,7,8,8 tetracyanochinodimethane were fabricated on ridged and flexible substrates with special emphasis on their general functionality and cross talk behaviour in 4 × 4 passive matrix arrays. Device characteristics have been investigated at elevated temperatures during operation (ranging from room temperature to 120 °C) under ambient conditions without encapsulation. To explore the influence of mechanical stress on device performance, the memory cells on flexible polyethylene terephthalate substrates were bended during operation, up to a convex and concave radius of 4 mm. The detected shift of the switching voltages and the decrease of reliability can be attributed to stress induced cracks in the active layer.     

Optimal growth windows of multiferroic BiFeO3 films and characteristics of ferroelectric domain structures

Multiferroic BiFeO₃ films of smooth surface and fully-saturated ferroelectric hysteresis loops have been grown by RF magnetron sputtering. The (001)-oriented epitaxial films showed a large remanent polarisation of 61 µC/cm². A strategy to grow BiFeO₃ films of good ferroelectric property was demonstrated, that was using fast growth rate to achieve accurate stoichiometry for the BiFeO₃ phase and at the same time to avoid the formation of impurity phases associated with the fast growth by accurate control of thermodynamic parameters such as oxygen partial pressure and temperature, as well as proper selection of substrates. Piezoresponse force microscopy revealed fine spontaneous domains for highly resistive epitaxial films, which were switchable under DC biases. For the polycrystalline films of increased density of free carriers, single-domain grains of about 200 nm in diameter were observed due to effective compensation of depolarisation field by free carriers and therefore allowing larger domains.     

Flexoelectric rotation of polarization in ferroelectric thin films

Strain engineering enables modification of the properties of thin films using the stress from the substrates on which they are grown. Strain may be relaxed, however, and this can also modify the properties thanks to the coupling between strain gradient and polarization known as flexoelectricity. Here we have studied the strain distribution inside epitaxial films of the archetypal ferroelectric PbTiO(3), where the mismatch with the substrate is relaxed through the formation of domains (twins). Synchrotron X-ray diffraction and high-resolution scanning transmission electron microscopy reveal an intricate strain distribution, with gradients in both the vertical and, unexpectedly, the horizontal direction. These gradients generate a horizontal flexoelectricity that forces the spontaneous polarization to rotate away from the normal. Polar rotations are a characteristic of compositionally engineered morphotropic phase boundary ferroelectrics with high piezoelectricity; flexoelectricity provides an alternative route for generating such rotations in standard ferroelectrics using purely physical means.