Using a combination of complementary in situ X-ray photoelectron spectroscopy and X-ray diffraction, we study the fundamental mechanisms underlying the chemical vapor deposition (CVD) of hexagonal boron nitride (h-BN) on polycrystalline Cu. The nucleation and growth of h-BN layers is found to occur isothermally, i.e., at constant elevated temperature, on the Cu surface during exposure to borazine. A Cu lattice expansion during borazine exposure and B precipitation from Cu upon cooling highlight that B is incorporated into the Cu bulk, i.e., that growth is not just surface-mediated. On this basis we suggest that B is taken up in the Cu catalyst while N is not (by relative amounts), indicating element-specific feeding mechanisms including the bulk of the catalyst. We further show that oxygen intercalation readily occurs under as-grown h-BN during ambient air exposure, as is common in further processing, and that this negatively affects the stability of h-BN on the catalyst. For extended air exposure Cu oxidation is observed, and upon re-heating in vacuum an oxygen-mediated disintegration of the h-BN film via volatile boron oxides occurs. Importantly, this disintegration is catalyst mediated, i.e., occurs at the catalyst/h-BN interface and depends on the level of oxygen fed to this interface. In turn, however, deliberate feeding of oxygen during h-BN deposition can positively affect control over film morphology. We discuss the implications of these observations in the context of corrosion protection and relate them to challenges in process integration and heterostructure CVD.
Recording atomic-resolution transmission electron microscopy (TEM) images is becoming increasingly routine. A new bottleneck is then analyzing this information, which often involves time-consuming manual structural identification. A deep learning-based algorithm for recognition of the local structure in TEM images was developed, which is stable to microscope parameters and noise. The neural network is trained entirely from simulation but is capable of making reliable predictions on experimental images. The method is applied to single sheets of defected graphene, and to metallic nanoparticles on an oxide support.
Recently developed lead‐free incipient piezoceramics are promising candidates for off‐resonance actuator applications with their exceptionally large electromechanical strains. Their commercialization currently faces two major challenges: high electric field required for activating the large strains and large strain hysteresis. It is demonstrated that design of a relaxor/ferroelectric composite provides a highly effective way to resolve both challenges. Experimental results in conjunction with numerical simulations provide key parameters for the development of viable incipient piezoceramics.
A lead‐free piezoelectric 0.91(Bi1/2Na1/2)TiO3–0.06BaTiO3–0.03(K0.5Na0.5)NbO3 ceramic with high strain was examined in situ under an applied electric field using the transmission electron microscope. No domain structure is observed without an electric field, but an alternating electric field leads to the reversible formation of a lamellar domain structure. Correlations to polarization and strain hysteresis loop measurements indicate an electric field‐induced phase transition from a nonpolar to a ferroelectric state and vice versa.
Prior studies have shown that a field-induced ferroelectricity in ceramics with general chemical formula (1−x−y)(Bi1/2Na1/2)TiO3-xBaTiO3-y(K0.5Na0.5)NbO3 and a very low remanent strain can produce very large piezoelectric strains. Here we show that both the longitudinal and transverse strains gradually change with applied electric fields even during the transition from the nonferroelectric to the ferroelectric state, in contrast to known Pb-containing antiferroelectrics. Hence, the volume change and, in turn, the phase transition can be affected using uniaxial compressive stresses, and the effect on ferroelectricity can thus be assessed. It is found that the 0.94(Bi1/2Na1/2)TiO3-0.05BaTiO3-0.01(K0.5Na0.5)NbO3ceramic (largely ferroelectric), with a rhombohedral R3c symmetry, displays large ferroelectric domains, significant ferroelastic deformation, and large remanent electrical polarizations even at a 250 MPa compressive stress. In comparison, the 0.91(Bi1/2Na1/2)TiO3-0.07BaTiO3-0.02(K0.5Na0.5)NbO3ceramic (largely nonferroelectric) possesses characteristics of a relaxor ferroelectricceramic, including a pseudocubic structure, limited ferroelastic deformation, and low remanent polarization. The results are discussed with respect of the proposed antiferroelectric nature of the nonferroelectric state. Prior studies have shown that a field-induced ferroelectricity in ceramics with general chemical formula ͑1−x − y͒͑Bi 1/2 Na 1/2 ͒TiO 3 -xBaTiO 3 -y͑K 0.5 Na 0.5 ͒NbO 3 and a very low remanent strain can produce very large piezoelectric strains. Here we show that both the longitudinal and transverse strains gradually change with applied electric fields even during the transition from the nonferroelectric to the ferroelectric state, in contrast to known Pb-containing antiferroelectrics. Hence, the volume change and, in turn, the phase transition can be affected using uniaxial compressive stresses, and the effect on ferroelectricity can thus be assessed. It is found that the 0.94͑Bi 1/2 Na 1/2 ͒TiO 3 -0.05BaTiO 3 -0.01͑K 0.5 Na 0.5 ͒NbO 3 ceramic ͑largely ferroelectric͒, with a rhombohedral R3c symmetry, displays large ferroelectric domains, significant ferroelastic deformation, and large remanent electrical polarizations even at a 250 MPa compressive stress. In comparison, the 0.91͑Bi 1/2 Na 1/2 ͒TiO 3 -0.07BaTiO 3 -0.02͑K 0.5 Na 0.5 ͒NbO 3 ceramic ͑largely nonferroelectric͒ possesses characteristics of a relaxor ferroelectric ceramic, including a pseudocubic structure, limited ferroelastic deformation, and low remanent polarization. The results are discussed with respect of the proposed antiferroelectric nature of the nonferroelectric state.
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