Flexomagnetism, the coupling of magnetic ordering to strain gradients, provides access to novel symmetry-broken magnetic phases that cannot be accessed via uniform strain. However, flexomagnetism is hard to understand because it is extremely difficult to control a spatially varying strain. Here, we develop a top-down strategy to pattern transverse strain gradients using helium ion implantation through a lithographically defined mask. Using epitaxial films of the antiferromagnetic nodal line semimetal GdAuGe, we demonstrate that transverse strain gradients ∂ε_zz/∂ x induce near-room-temperature ferromagnetic response, compared to the retained para or antiferromagnetism for homogeneously strained GdAuGe. We spatially correlate the magnetic response with the regions of largest strain gradient, via magnetic force microscopy and nanobeam x-ray diffraction, respectively, to confirm the flexomagnetic response. Our approach opens new avenues for the precise control of magnetic phases in thin films of quantum materials via a patterned strain gradient.

Wrapping polymers are useful for sorting high purity suspensions of semiconducting carbon nanotubes (CNTs) in organic solvents, but for many microelectronic applications the wroapping polymer needs to be removed. Coating wrapped CNTs with yttrium metal, followed by oxidation and removal with dilute aqueous acid, has been used to etch wrapping polymer, but the mechanism, selectivity, extent of etching, and range of conditions over which etching occurs have not been reported. We use spectroscopic and physical measurements to characterize this process on thin films of an archetypical conjugated wrapping polymer (PFO-BPy), its amorphous char residue, CNTs (average diameter 1.5 nm), graphene, and other organic films. Exposure of a yttrium overcoated film of PFO-BPy to ambient air at 20 degrees C oxidizes a similar to 0.5 nm layer of polymer, forming carbonate, carboxylate, and/or carbonyl groups that dissolve in dilute acid. Thicker layers of polymer are removed by repeated cycles. Similar results are observed for other organic films at 20 degrees C whereas CNTs and graphene are unaltered, providing the selectivity needed to remove carbon-based contaminants from sp(2) carbon based nanostructures. Increasing temperature to 250 degrees C increases polymer oxidation and removal to similar to 2.5 nm per cycle; however, the CNTs and graphene are damaged.

The growth of hexagonal boron nitride (hBN) directly onto semiconducting substrates, like Ge and Ge on Si, promises to advance the integration of hBN into microelectronics. However, a detailed understanding of the growth and characteristics of hBN islands and monolayers on these substrates is lacking. Here, we present the growth of hBN on Ge and Ge epilayers on Si via high-vacuum chemical vapor deposition from borazine and study the effects of Ge sublimation, surface orientation, and vicinality on the shape and alignment of hBN islands. We find that suppressing Ge sublimation is essential for growing high quality hBN and that the Ge surface orientation and vicinality strongly affect hBN alignment. Interestingly, 95% of hBN islands are unidirectionally aligned on Ge(111), which may be a path toward metal- and transfer-free, single-crystalline hBN. Finally, we extend the growth time and borazine partial pressure to grow monolayer hBN on Ge and Ge epilayers on Si. These findings provide new insights into the growth of high-quality hBN on semiconducting substrates.

Remote and van der Waals epitaxy are promising approaches for synthesizing single crystalline membranes for flexible electronics and discovery of new properties via extreme strain; however, a fundamental challenge is that most materials do not wet the graphene surface. We develop a cold seed approach for synthesizing smooth intermetallic films on graphene that can be exfoliated to form few nanometer thick single crystalline membranes. Our seeded GdAuGe films have narrow X-ray rocking curve widths of 9-24 arc seconds, which is 2 orders of magnitude lower than their counterparts grown by typical high temperature methods, and have atomically sharp interfaces observed by transmission electron microscopy. Upon exfoliation and rippling, strain gradients in GdAuGe membranes induce an antiferromagnetic to ferri/ferromagnetic transition. Our smooth, ultrathin membranes provide a clean platform for discovering new flexomagnetic effects in quantum materials.

The synthesis of graphene nanoribbons (GNRs) can be realized via CH4 4 chemical vapor deposition (CVD) on substrates such as Ge(001) that promote highly anisotropic growth. Small polycyclic aromatic hydrocarbons (PAHs) are first sublimed onto Ge at relatively low temperature to form graphene-like seeds that subsequently initiate GNR growth with CH4 4 exposure at 1173 K. The behaviors of PAHs between their sublimation onto Ge and GNR growth are unclear. Here, we study an archetypical PAH - perylene-3,4,9,10-tetracarboxyl acid dianhydride (PTCDA) - on Ge(001) using both scanning tunneling microscopy (STM) and density functional theory (DFT) to characterize PAH configuration, surface diffusivity, and clustering. PTCDA becomes mobile above 673 K, consistent with a DFT diffusion barrier of 1.74 eV. The mobile PTCDA molecules meet, cluster, and fuse at Ge step edges, dehydrogenating at higher temperatures. These clusters have a height of 0.4 nm, similar to small graphene islands, and grow laterally with increasing temperature - reaching 1.2-2.1 nm in width at 1173 K, consistent with extrapolated CVD experiments. These results provide a plausible picture for how PTCDA forms seeds for anisotropic GNR CVD and show that PAHs with reduced surface diffusivity and inter-molecular reactivity are needed to enable more monodisperse PAH-seeded GNR synthesis.

Understanding the sticking coefficient $\sigma$, i.e., the probability of an adatom sticking to a surface, is essential for controlling the stoichiometry during epitaxial film growth. However, $\sigma$ on monolayer graphene-covered surfaces and its impact on remote epitaxy are not understood. Here, using molecular-beam epitaxial (MBE) growth of the magnetic shape memory alloy Ni$_2$MnGa, we show that the sticking coefficients for metals on graphene-covered MgO (001) are less than one and are temperature and element dependent, as revealed by ion backscattering spectrometry (IBS) and energy dispersive x-ray spectroscopy (EDS). This lies in stark contrast with most transition metals sticking on semiconductor and oxide substrates, for which $\sigma$ is near unity at typical growth temperatures ($T<800\degree$C). By initiating growth below $400 \degree$ C, where the sticking coefficients are closer to unity and wetting on the graphene surface is improved, we demonstrate epitaxy of Ni$_2$MnGa films with controlled stoichiometry that can be exfoliated to produce freestanding membranes. Straining these membranes tunes the magnetic coercive field. Our results provide a route to synthesize membranes with complex stoichiometries whose properties can be manipulated via strain.

We use epitaxial lateral overgrowth (ELO) to produce semimetallic graphene nanostructures embedded in a semiconducting GaAs matrix for potential applications in plasmonics, THz generation and detection, and tunnel junctions in multijunction solar cells. We show that (1) the combination of low sticking coefficient and fast surface diffusion on graphene enhances nucleation selectivity at exposed regions of the substrate and (2) high growth temperatures favor efficient lateral overgrowth, coalescence, and planarization of epitaxial GaAs films over the graphene nanostructures. Our work provides a more complete understanding of ELO using graphene masks, as opposed to more conventional dielectric masks, and enables new types of metal/semiconductor nanocomposites.

Remote epitaxy is promising for the synthesis of lattice-mismatched materials, exfoliation of membranes, and reuse of expensive substrates. However, clear experimental evidence of a remote mechanism remains elusive. Alternative mechanisms such as pinhole-seeded epitaxy or van der Waals epitaxy can often explain the resulting films. Here, we show that growth of the Heusler compound GdPtSb on clean graphene/sapphire produces a 30° rotated (R30) superstructure that cannot be explained by pinhole epitaxy. With decreasing temperature, the fraction of this R30 domain increases, compared to the direct epitaxial R0 domain, which can be explained by a competition between remote versus pinhole epitaxy. Careful graphene/substrate annealing and consideration of the relative lattice mismatches are required to obtain epitaxy to the underlying substrate across a series of other Heusler films, including LaPtSb and GdAuGe. The R30 superstructure provides a possible experimental fingerprint of remote epitaxy, since it is inconsistent with the leading alternative mechanisms.

We quantify the mechanisms for manganese (Mn) diffusion through graphene in Mn/graphene/Ge (001) and Mn/graphene/GaAs (001) heterostructures for samples prepared by graphene layer transfer versus graphene growth directly on the semiconductor substrate. These heterostructures are important for applications in spintronics; however, challenges in synthesizing graphene directly on technologically important substrates such as GaAs necessitate layer transfer and annealing steps, which introduce defects into the graphene. In situ photoemission spectroscopy measurements reveal that Mn diffusion through graphene grown directly on a Ge (001) substrate is 1000 times lower than Mn diffusion into samples without graphene (Dgr,direct ∼ 4 × 10-18 cm2/s, Dno-gr ∼ 5 × 10-15 cm2/s at 500 °C). Transferred graphene on Ge suppresses the Mn in Ge diffusion by a factor of 10 compared to no graphene (Dgr,transfer ∼ 4 × 10-16 cm2/s). For both transferred and directly grown graphene, the low activation energy (Ea ∼ 0.1-0.5 eV) suggests that Mn diffusion through graphene occurs primarily at graphene defects. This is further confirmed as the diffusivity prefactor, D0, scales with the defect density of the graphene sheet. Similar diffusion barrier performance is found on GaAs substrates; however, it is not currently possible to grow graphene directly on GaAs. Our results highlight the importance of developing graphene growth directly on functional substrates to avoid the damage induced by layer transfer and annealing.

Indium monoselenide (InSe) is an emerging two-dimensional semiconductor with superlative electrical and optical properties whose full potential for high-performance electronics and optoelectronics has been limited by the lack of reliable large-area thin-film synthesis methods. The difficulty in InSe synthesis lies in the complexity of the indium-selenium phase diagram and inadequate understanding of how this complexity is manifested in the growth of thin films. Herein, we present a systematic method for synthesizing InSe thin films by pulsed laser deposition followed by vacuum thermal annealing. The controlled phase evolution of the annealed InSe thin films is elucidated using a comprehensive set of in situ and ex situ characterization techniques. The annealing temperature is identified as the key parameter in controlling phase evolution with pure thin films of InSe developed within a window of 325 °C to 425 °C. To exert finer stoichiometric control over the as-deposited InSe thin film, a co-deposition scheme utilizing InSe and In2Se3 pulsed laser deposition targets is employed to mitigate the effects of mass loss during annealing, ultimately resulting in the synthesis of centimeter-scale, thickness-tunable ε-InSe thin films with high crystallinity. The optimized InSe thin films possess a strong optoelectronic response, exhibited by phototransistors with high responsivities up to 103 A/W. Additionally, enhancement-mode InSe field-effect transistors are fabricated over large areas with device yields exceeding 90% and high on/off current modulation greater than 104, realizing a degree of electronic uniformity previously unattained in InSe thin-film synthesis.

Spiking neural networks exploit spatiotemporal processing, spiking sparsity, and high interneuron bandwidth to maximize the energy efficiency of neuromorphic computing. While conventional silicon-based technology can be used in this context, the resulting neuron-synapse circuits require multiple transistors and complicated layouts that limit integration density. Here, we demonstrate unprecedented electrostatic control of dual-gated Gaussian heterojunction transistors for simplified spiking neuron implementation. These devices employ wafer-scale mixed-dimensional van der Waals heterojunctions consisting of chemical vapor deposited monolayer molybdenum disulfide and solution-processed semiconducting single-walled carbon nanotubes to emulate the spike-generating ion channels in biological neurons. Circuits based on these dual-gated Gaussian devices enable a variety of biological spiking responses including phasic spiking, delayed spiking, and tonic bursting. In addition to neuromorphic computing, the tunable Gaussian response has significant implications for a range of other applications including telecommunications, computer vision, and natural language processing.

Memristive systems offer biomimetic functions that are being actively explored for energy-efficient neuromorphic circuits. In addition to providing ultimate geometric scaling limits, 2D semiconductors enable unique gate-tunable responses including the recent realization of hybrid memristor and transistor devices known as memtransistors. In particular, monolayer MoS(2)memtransistors exhibit nonvolatile memristive switching where the resistance of each state is modulated by a gate terminal. Here, further control over the memtransistor neuromorphic response through the introduction of a second gate terminal is gained. The resulting dual-gated memtransistors allow tunability over the learning rate for non-Hebbian training where the long-term potentiation and depression synaptic behavior is dictated by gate biases during the reading and writing processes. Furthermore, the electrostatic control provided by dual gates provides a compact solution to the sneak current problem in traditional memristor crossbar arrays. In this manner, dual gating facilitates the full utilization and integration of memtransistor functionality in highly scaled crossbar circuits. Furthermore, the tunability of long-term potentiation yields improved linearity and symmetry of weight update rules that are utilized in simulated artificial neural networks to achieve a 94% recognition rate of hand-written digits.

Mixed-dimensional heterojunctions (MDHJs) combine the characteristics of component materials such as the discrete orbital energies of zero-dimensional (0D) molecules and the extended band structure of two-dimensional (2D) semiconductors. Here, time-resolved spectroscopy reveals sub-picosecond photoinduced hole-transfer and sub-320 fs photoinduced electron-transfer processes at the interfaces of type-II copper and free-base phthalocyanine/monolayer MoS2 MDHJs. In CuPc/MoS2 heterojunctions, charge separation lasts as long as 70 ns, which is a factor of 17 longer than that in H2Pc/MoS2 heterojunctions and a factor of 40 longer than that in previously reported transition-metal dichalcogenide-based heterojunctions. Preservation of the charge-separated state is attributed to the face-on orientation of CuPc on the MoS2 surface, which templates stacking of CuPc molecules and facilitates hole migration away from the interface, whereas H2Pc molecules adopt a mixed edge-on and face-on orientation. This work highlights the role of molecular structure in determining the interfacial geometry and, ultimately, charge-transfer dynamics in 0D/2D heterojunctions.