Nanoscale Patterns Research Articles

Direct-Write of Nanoscale Domains with Tunable Metamagnetic Order in FeRh Thin Films.

We have directly written nanoscale patterns of magnetic ordering in FeRh films using focused helium-ion beam irradiation. By varying the dose, we pattern arrays with metamagnetic transition temperatures that range from the as-grown film temperature to below room temperature. We employ transmission electron microscopy, X-ray diffraction, and temperature-dependent transport measurements to characterize the as-grown film, and magneto-optic Kerr effect imaging to quantify the He+ irradiation-induced changes to the magnetic order. Moreover, we demonstrate temperature-dependent optical microscopy and conductive atomic force microscopy as indirect probes of the metamagnetic transition that are sensitive to the differences in dielectric properties and electrical conductivity, respectively, of FeRh in the antiferromagnetic (AF) and ferromagnetic (FM) states. Using density functional theory, we quantify strain- and defect-induced changes in spin-flip energy to understand their influence on the metamagnetic transition temperature. This work holds promise for in-plane AF-FM spintronic devices, by reducing the need for multiple patterning steps or different materials, and potentially eliminating interfacial polarization losses due to cross material interfacial spin scattering.

Measurement of Ehrlich-Schwoebel barrier contribution to the self-organized formation of ordered surface patterns on Ge(001)

Normal incidence 1 keV Ar$^+$ ion bombardment leads to amorphization and ultrasmoothing of Ge at room temperature, but at elevated temperatures the Ge surface remains crystalline and is unstable to the formation of self-organized nanoscale patterns of ordered pyramid-shaped pits. The physical phenomenon distinguishing the high temperature patterning from room temperature ultrasmoothing is believed to be a surface instability due to the Ehrlich-Schwoebel barrier for diffusing vacancies and adatoms, which is not present on the amorphous material. This real-time GISAXS study compares smoothing of a pre-patterned Ge sample at room temperature with patterning of an initially flat Ge sample at an elevated temperature. In both experiments, when the nanoscale structures are relatively small in height, the average kinetics can be explained by a linear theory. The linear theory coefficients, indicating surface stability or instability, were extracted for both experiments. A comparison between the two measurements allows estimation of the contribution of the Ehrlich-Schwoebel barrier to the self-organized formation of ordered nanoscale patterns on crystalline Ge surfaces.

Using DNA origami to produce nanoscale patterns and structures

The review article provides an overview of the DNA origami technique for fabricating nanomaterials with specific patterns and structures.

Etch characteristics of magnetic tunnel junction materials using H2/NH3 reactive ion beam

Magnetic tunneling junction (MTJ) materials such as CoFeB, Co, Pt, MgO, and the hard mask material such as W and TiN were etched with a reactive ion beam etching (RIBE) system using H2/NH3. By using gas mixtures of H2 and NH3, especially with the H2/NH3( 2:1) ratio, higher etch rates of MTJ related materials and higher etch selectivities over mask materials (>30) could be observed compared to those etching using pure H2( no etching) and NH3. In addition, no significant chemical and physical damages were observed on etched magnetic materials surfaces and, for CoPt and MTJ nanoscale patterns etched by the H2/NH3( 2:1) ion beam, highly anisotropic etch profiles >83° with no sidewall redeposition could be observed. The higher etch rates of magnetic materials such as CoFeB by the H2/NH3( 2:1) ion beam compared to those by H2 ion beam or NH3 ion beam are believed to be related to the formation of volatile metal hydrides (MH, M = Co, Fe, etc) through the reduction of M-NHx( x = 1 ∼ 3) formed in the CoFeB surface by the exposure to NH3 ion beam. It is believed that the H2/NH3 RIBE is a suitable technique in the etching of MTJ materials for the next generation nanoscale spin transfer torque magnetic random access memory (STT-MRAM) devices.

A perspective on nanoscale pattern formation at surfaces by ion-beam irradiation

The formation of periodic patterns on the surfaces of many solid materials undergoing ion-beam irradiation has long been known. The advent of high resolution characterization techniques elucidated the nanoscopic traits of this self-organization process, enabling a wide range of applications for the nanostructures thus produced, from optoelectronic to biomedical. Meanwhile, full theoretical understanding of the technique has been challenged by its multiscale nature, whereby the external perturbation implemented by the ion beam acts at a much slower rate (typically, one ion arrives per square-nm every second) than the microscopic processes, like collision cascades and material transport, which try to relax such external perturbations (collision cascades or surface diffusion attempts usually relax after a few picoseconds). Here, we present a Perspective on the main developments that have led to the current understanding of nanoscale pattern formation at surfaces by ion-beam irradiation, from the points of view of experiments, applications, and theory, and offer an outlook on future steps that may eventually facilitate full harnessing of such a versatile avenue to materials nanostructuring.

Nanostructural evolution in vapor deposited phase-separating binary alloy films of non-equimolar compositions: Insights from a 3D phase-field approach

A rich variety of self-organized nanoscale patterns evolve during physical vapor deposition of phase-separating alloy films. However, our limited understanding of the fundamental mechanisms of morphological evolution during the vapor deposition of multi-component metallic films is a major hurdle in optimizing their mechanical and functional properties. Diffuse interface approaches, such as the phase-field method, can enable the prediction of nanostructured morphologies in a broad class of immiscible binary alloys by achieving a fundamental understanding of self-assembly mechanisms down to the nanometer scale. Here, we adopt a three-dimensional phase-field approach to numerically investigate the role of alloy compositions, deposition rates, and temperature on the morphological self-assembly of nanostructures in vapor deposited alloy films. We explain the influence of alloy composition and deposition parameters on the evolution of novel film morphologies such as perforated layered and aligned rods. Following an extensive parametric study, we construct morphology maps that help expand our knowledge of the different combinations of processing conditions that generate distinct nanoscaled morphologies. Finally, we expand and elucidate a theory based on the minimization of interfacial energy that underpins the mechanisms of morphological transitions in vapor deposition of immiscible alloy films for an entire composition range.

Progress and prospects for ultrathin solar cells

Ultrathin solar cells with thicknesses at least 10 times lower than conventional solar cells could have the unique potential to efficiently convert solar energy into electricity while enabling material savings, shorter deposition times and improved carrier collection in defective absorber materials. Efficient light absorption and hence high power conversion efficiency could be retained in ultrathin absorbers using light-trapping structures that enhance the optical path. Nevertheless, several technical challenges prevent the realization of a practical device. Here we review the state-of-the-art of c-Si, GaAs and Cu(In,Ga)(S,Se)2 ultrathin solar cells and compare their optical performances against theoretical light-trapping models. We then address challenges in the fabrication of ultrathin absorber layers and in nanoscale patterning of light-trapping structures and discuss strategies to ensure efficient charge collection. Finally, we propose practical architectures for ultrathin solar cells that combine photonic and electrical constraints, and identify future research directions and potential applications of ultrathin photovoltaic technologies. Ultrathin solar cells attract interest for their relatively low cost and potential novel applications. Here, Massiot et al. discuss their performance and the challenges in the fabrication of ultrathin absorbers, patterning of light trapping structures and ensuring efficient charge-carrier collection.

Hydroxypropyl Cellulose Adhesives for Transfer Printing of Carbon Nanotubes and Metallic Nanostructures.

Transfer printing is one of the key nanofabrication techniques for the large-scale manufacturing of complex device architectures. It provides acost-effective and high-throughput route for the integration of independently processed materials into spatially tailored architectures. Furthermore, this method enables the fabrication of flexible and curvilinear devices, paving the way for the fabrication of a new generation of technologies for optics, electronics, and biomedicine. In this work, hydroxypropyl cellulose (HPC) membranes are used as water soluble adhesives for transfer printing processes with improved performance and versatility compared to conventional silicone alternatives. The high-water solubility and excellent mechanical properties of HPC facilitate transfer printing with high yield for both metal and carbon nanotubes (CNTs) inks. In the case of metal inks, crack-free stripping of silver films and the simple fabrication of Moiré Plasmonic architectures of different geometries are demonstrated. Furthermore, HPC membranes are used to transfer print carbon nanotube films with different thicknesses and up to 77% transparency in the visible and near infrared region with potential applications as transparent conductive substrates. Finally, the use of prepatterned HPC membranes enables nanoscale patterning of CNT with feature resolution down to 1µm.

Direct X-ray and electron-beam lithography of halogenated zeolitic imidazolate frameworks.

Metal-organic frameworks (MOFs) offer disruptive potential in micro- and optoelectronics because of the unique properties of these microporous materials. Nanoscale patterning is a fundamental step in the implementation of MOFs in miniaturized solid-state devices. Conventional MOF patterning methods suffer from low resolution and poorly defined pattern edges. Here, we demonstrate the resist-free, direct X-ray and electron-beam lithography of MOFs. This process avoids etching damage and contamination and leaves the porosity and crystallinity of the patterned MOFs intact. The resulting high-quality patterns have excellent sub-50-nm resolution, and approach the mesopore regime. The compatibility of X-ray and electron-beam lithography with existing micro- and nanofabrication processes will facilitate the integration of MOFs in miniaturized devices.

Magnon polaron formed by selectively coupled coherent magnon and phonon modes of a surface patterned ferromagnet

Strong coupling between two quanta of different excitations leads to the formation of a hybridized state which paves a way for exploiting new degrees of freedom to control phenomena with high efficiency and precision. A magnon polaron is the hybridized state of a phonon and a magnon, the elementary quanta of lattice vibrations and spin waves in a magnetically-ordered material. A magnon polaron can be formed at the intersection of the magnon and phonon dispersions, where their frequencies coincide. The observation of magnon polarons in the time domain has remained extremely challenging because the weak interaction of magnons and phonons and their short lifetimes jeopardize the strong coupling required for the formation of a hybridized state. Here, we overcome these limitations by spatial matching of magnons and phonons in a metallic ferromagnet with a nanoscale periodic surface pattern. The spatial overlap of the selected phonon and magnon modes formed in the periodic ferromagnetic structure results in a high coupling strength which, in combination with their long lifetimes allows us to find clear evidence of an optically excited magnon polaron. We show that the symmetries of the localized magnon and phonon states play a crucial role in the magnon polaron formation and its manifestation in the optically excited magnetic transients.

Nanopatterning of the (001) surface of crystalline Ge by ion irradiation at off-normal incidence: Experiment and simulation

Intricate topographical patterns can form on the surface of crystalline Ge(001) subject to low-energy ion irradiation in the reverse epitaxy regime, i.e., at elevated temperatures which enable dynamic recrystallization. We compare such nanoscale patterns produced by irradiation from varied polar and azimuthal ion incidence angles with corresponding calculated surface topographies. To this end, we propose a continuum equation including both anisotropic erosive and anisotropic diffusive effects. Molecular dynamics simulations provide the coefficients of angle-dependent sputter erosion for the calculations. By merely changing these coefficients accordingly, the experimentally observed surface morphologies can be reproduced, except for extreme ion incidence angles. Angle-dependent sputter erosion is thereby identified as a dominant mechanism in ion-induced pattern formation on crystalline surfaces under irradiation from off-normal incidence angles.

A correlative super-resolution protocol to visualise structural underpinnings of fast second-messenger signalling in primary cell types.

Nanometre-scale cellular information obtained through super-resolution microscopies are often unaccompanied by functional information, particularly transient and diffusible signals through which life is orchestrated in the nano-micrometre spatial scale. We describe a correlative imaging protocol which allows the ubiquitous intracellular second messenger, calcium (Ca2+), to be directly visualised against nanoscale patterns of the ryanodine receptor (RyR) Ca2+ channels which give rise to these Ca2+ signals in wildtype primary cells. This was achieved by combining total internal reflection fluorescence (TIRF) imaging of the elementary Ca2+ signals, with the subsequent DNA-PAINT imaging of the RyRs. We report a straightforward image analysis protocol of feature extraction and image alignment between correlative datasets and demonstrate how such data can be used to visually identify the ensembles of Ca2+ channels that are locally activated during the genesis of cytoplasmic Ca2+ signals.

Hyperbolic dispersion metasurfaces for molecular biosensing

AbstractSensor technology has become increasingly crucial in medical research and clinical diagnostics to directly detect small numbers of low-molecular-weight biomolecules relevant for lethal diseases. In recent years, various technologies have been developed, a number of them becoming core label-free technologies for detection of cancer biomarkers and viruses. However, to radically improve early disease diagnostics, tracking of disease progression and evaluation of treatments, today’s biosensing techniques still require a radical innovation to deliver high sensitivity, specificity, diffusion-limited transport, and accuracy for both nucleic acids and proteins. In this review, we discuss both scientific and technological aspects of hyperbolic dispersion metasurfaces for molecular biosensing. Optical metasurfaces have offered the tantalizing opportunity to engineer wavefronts while its intrinsic nanoscale patterns promote tremendous molecular interactions and selective binding. Hyperbolic dispersion metasurfaces support high-kmodes that proved to be extremely sensitive to minute concentrations of ultralow-molecular-weight proteins and nucleic acids.

Nanoscale patterning at the Si/SiO2/graphene interface by focused He+ beam

We have studied the capability of He+ focused ion beam (He+-FIB) patterning to fabricate defect arrays on the Si/SiO2/Graphene interface using a combination of atomic force microscopy (AFM) and Raman imaging to probe damage zones. In general, an amorphized ‘blister’ region of cylindrical symmetry results upon exposing the surface to the stationary focused He+ beam. The topography of the amorphized region depends strongly on the ion dose, DS , (ranging from 103 to 107ions/spot) with craters and holes observed at higher doses. Furthermore, the surface morphology depends on the distance between adjacent irradiated spots, LS . Increasing the dose leads to (enhanced) subsurface amorphization and a local height increase relative to the unexposed regions. At the highest areal ion dose, the average height of a patterned area also increases as ∼1/LS . Correspondingly, in optical micrographs, the µm2-sized patterned surface regions change appearance. These phenomena can be explained by implantation of the He+ ions into the subsurface layers, formation of helium nanobubbles, expansion and modification of the dielectric constant of the patterned material. The corresponding modifications of the terminating graphene monolayer have been monitored by micro Raman imaging. At low ion doses, DS , the graphene becomes modified by carbon atom defects which perturb the 2D lattice (as indicated by increasing D/G Raman mode ratio). Additional x-ray photoionization spectroscopy (XPS) measurements allow us to infer that for moderate ion doses, scattering of He+ ions by the subsurface results in the oxidation of the graphene network. For largest doses and smallest LS values, the He+ beam activates extensive Si/SiO2/C bond rearrangement and a multicomponent material possibly comprising SiC and silicon oxycarbides, SiOC, is observed. We also infer parameter ranges for He+-FIB patterning defect arrays of potential use for pinning transition metal nanoparticles in model studies of heterogeneous catalysis.

Sacrificial layer-assisted nanoscale transfer printing

Transfer printing is an emerging assembly technique for flexible and stretchable electronics. Although a variety of transfer printing methods have been developed, transferring patterns with nanometer resolution remains challenging. We report a sacrificial layer-assisted nanoscale transfer printing method. A sacrificial layer is deposited on a donor substrate, and ink is prepared on and transferred with the sacrificial layer. Introducing the sacrificial layer into the transfer printing process eliminates the effect of the contact area on the energy release rate (ERR) and ensures that the ERR for the stamp/ink-sacrificial layer interface is greater than that for the sacrificial layer/donor interface even at a slow peel speed (5 mm s−1). Hence, large-area nanoscale patterns can be successfully transferred with a yield of 100%, such as Au nanoline arrays (100 nm thick, 4 mm long and 47 nm wide) fabricated by photolithography techniques and PZT nanowires (10 mm long and 63 nm wide) fabricated by electrohydrodynamic jet printing, using only a blank stamp and without the assistance of any interfacial chemistries. Moreover, the presence of the sacrificial layer also enables the ink to move close to the mechanical neutral plane of the multilayer peel-off sheet, remarkably decreasing the bending stress and obviating cracks or fractures in the ink during transfer printing.

Dispersity effects on phase behavior and structural evolution in ultrathin films of a deuterated polystyrene-block-poly(methyl methacrylate) diblock copolymer

We report the unique phase behavior and structural transitions in thin films of a distorted network (DNW) nanostructure, which is an equilibrium phase contained in the bulk of a nearly-symmetric deuterated polystyrene-block-poly (methyl methacrylate), dPS-b-PMMA, block copolymer. The DNW is due to a broad dispersity for the PMMA block. Grazing incidence small-angle X-ray scattering, neutron reflectometry, atomic force microscopy and transmission electron microscopy techniques were used to characterize thermally-annealed dPS-b-PMMA ultrathin films with neutral boundaries at both the free surface and substrate interface. Brief thermal annealing imposed on the ultrathin films leads to perpendicular lamellae (L⊥). Upon increasing the duration of thermal annealing, the dPS-b-PMMA ultrathin films exhibit thickness dependence of phase transition kinetics and different irreversible routes of phase transition. As a result, the protracted thermal annealing of the thin films of various thicknesses produces either hexagonal arrays of perpendicular PMMA cylinders (HEX-C⊥) or disordered PMMA nanostructures (DIS). The phase transition routes and kinetics in ultrathin films suggest various possibilities to obtain diverse nanoscale patterns via thin film self-assembly.

Effect of reactant dosing on selectivity during area-selective deposition of TiO2 via integrated atomic layer deposition and atomic layer etching

A key hallmark of atomic layer deposition (ALD) is that it proceeds via self-limiting reactions. For a good ALD process, long reactant exposure times beyond that required for saturation on planar substrates can be useful, for example, to achieve conformal growth on high aspect ratio nanoscale trenches, while maintaining consistent deposition across large-area surfaces. Area-selective deposition (ASD) is becoming an enabling process for nanoscale pattern modification on advanced nanoelectronic devices. Herein, we demonstrate that during area-selective ALD, achieved by direct coupling of ALD and thermal atomic layer etching (ALE), excess reactant exposure can have a substantially detrimental influence on the extent of selectivity. As an example system, we study ASD of TiO2 on hydroxylated SiO2 (Si–OH) vs hydrogen-terminated (100) Si (Si–H) using TiCl4/H2O for ALD and WF6/BCl3 for ALE. Using in situ spectroscopic ellipsometry and ex situ x-ray photoelectron spectroscopy, we show that unwanted nucleation can be minimized by limiting the water exposure during the ALD steps. Longer exposures markedly increased the rate of nucleation and growth on the desired non-growth region, thereby degrading selectivity. Specifically, transmission electron microscopy analysis demonstrated that near-saturated H2O doses enabled 32.7 nm thick TiO2 patterns at selectivity threshold S > 0.9 on patterned Si/SiO2 substrates. The correlation between selectivity and reactant exposure serves to increase fundamental insights into the effects of sub-saturated self-limiting surface reactions on the quality and effectiveness of ASD processes and methods.

Understanding of the Mechanism for Laser Ablation-Assisted Patterning of Graphene/ITO Double Layers: Role of Effective Thermal Energy Transfer

Demand for the fabrication of high-performance, transparent electronic devices with improved electronic and mechanical properties is significantly increasing for various applications. In this context, it is essential to develop highly transparent and conductive electrodes for the realization of such devices. To this end, in this work, a chemical vapor deposition (CVD)-grown graphene was transferred to both glass and polyethylene terephthalate (PET) substrates that had been pre-coated with an indium tin oxide (ITO) layer and then subsequently patterned by using a laser-ablation method for a low-cost, simple, and high-throughput process. A comparison of the results of the laser ablation of such a graphene/ITO double layer with those of the ITO single-layered films reveals that a larger amount of effective thermal energy of the laser used is transferred in the lateral direction along the graphene upper layer in the graphene/ITO double-layered structure, attributable to the high thermal conductivity of graphene. The transferred thermal energy is expected to melt and evaporate the lower ITO layer at a relatively lower threshold energy of laser ablation. The transient analysis of the temperature profiles indicates that the graphene layers can act as both an effective thermal diffuser and converter for the planar heat transfer. Raman spectroscopy was used to investigate the graphite peak on the ITO layer where the graphene upper layer was selectively removed because of the incomplete heating and removal process for the ITO layer by the laterally transferred effective thermal energy of the laser beam. Our approach could have broad implications for designing highly transparent and conductive electrodes as well as a new way of nanoscale patterning for other optoelectronic-device applications using laser-ablation methods.

Computational proximity lithography with extreme ultraviolet radiation.

The potential of extreme ultraviolet (EUV) computational proximity lithography for fabrication of arbitrary nanoscale patterns is investigated. We propose to use a holographic mask (attenuating phase shifting mask) consisting of structures of two phase levels. This approach allows printing of arbitrary, non-periodic structures without using high-resolution imaging optics. The holographic mask is designed for a wavelength of 13.5 nm with a conventional high-resolution electron beam resist as the phase shifting medium (pixel size 50 nm). The imaging performance is evaluated by using EUV radiation with different degrees of spatial coherence. Therefore exposures on identical masks are carried out with both undulator radiation at a synchrotron facility and plasma-based radiation at a laboratory setup.

Enhanced magnetic signal along edges of embedded epitaxial La0.7Sr0.3MnO3 nanostructures

When thin films are patterned to realize nanoscale device geometries, maintaining their structural integrity is key to the quality of their functional properties. The introduction of new surfaces and interfaces by lateral modifications may alter material properties as well as the expected device functionality. In this study, two different techniques for nanoscale patterning of epitaxial thin films of La0.7Sr0.3MnO3 are used to investigate the effects on their ferromagnetic properties and film crystalline structure. Nanomagnets are realized as free-standing structures and embedded ferromagnets in a paramagnetic matrix, respectively. We find that the magnetic dichroism signal in x-ray spectomicroscopy is stronger along the edges of the embedded magnets close to TC. X-ray-diffraction measurements reveal a reduction of their in-plane lattice parameters. We discuss how in-plane stress from the nanomagnet surroundings can affect the magnetic properties in these structures.