Abstract: Point defects in diamond, promising candidates for nanoscale pressure- and temperature-sensing applications, are potentially scalable in polycrystalline diamond fabricated using the microwave plasma-enhanced chemical vapor deposition (MW PE CVD) technique. However, this approach introduces residual stress in the diamond films, leading to variations in the characteristic zero phonon line (ZPL) of the point defect in diamond. Here, we report the effect of residual stress on germanium-vacancy (GeV) centers in MW PE CVD nanocrystalline diamond (NCD) films fabricated using single crystal Ge as the substrate and solid dopant source. GeV ensemble formation indicated by the zero phonon line (ZPL) at similar to 602 nm is confirmed by room temperature (RT) photoluminescence (PL) measurements. PL mapping results show spatial nonuniformity in GeV formation along with other defects, including silicon-vacancy centers in the diamond films. The residual stress in NCD results in shifts in the PL peak positions. By estimating a stress shift coefficient of (2.9 +/- 0.9) nm/GPa, the GeV PL peak position in the NCD film is determined to be between 598.7 and 603.2 nm. A larger ground state splitting due to the strain on a GeV-incorporated NCD pillar at a low temperature (10 K) is also reported. We also report the observation of intense ZPLs at RT that in some cases could be related to low Ge concentration and the surrounding crystalline environment. In addition, we also observe thicker microcrystalline diamond (MCD) films delaminate from the Ge substrate due to film residual stress and graphitic phase at the diamond/Ge substrate interface (confirmed by electron energy loss spectroscopy). Using this approach, a free-standing color center incorporated MCD film with dimensions up to 1 x 1 cm(2) is fabricated. Qualitative analysis using time-of-flight secondary ion mass spectroscopy reveals the presence of impurities, including Ge and silicon, in the MCD film. Our experimental results will provide insights into the scalability of GeV fabrication using the MW PE CVD technique and effectively implement NCD-based nanoscale-sensing applications.

Abstract: Lead based bulk piezoelectric materials, e.g., PbZrxTi1-xO3 (PZT), are widely used in electromechanical applications, sensors, and transducers, for which optimally performing thin films are needed. The results of a multi-domain Landau-Ginzberg-Devonshire model applicable to clamped ferroelectric thin films are used to predict the lattice symmetry and properties of clamped PZT thin films on different substrates. Guided by the thermal strain phase diagrams that are produced by this model, experimentally structural transitions are observed. These can be related to changes of the piezoelectric properties in PZT(x = 0.6) thin films that are grown on CaF2, SrTiO3 (STO) and 70% PbMg1/3Nb2/3O3-30% PbTiO3 (PMN-PT) substrates by pulsed laser deposition. Through temperature en field dependent in situ X-ray reciprocal space mapping (RSMs) and piezoelectric force microscopy (PFM), the low symmetry monoclinic phase and polarization rotation are observed in the film on STO and can be linked to the measured enhanced properties. The study identifies a monoclinic -rhombohedral M-C-M-A-R crystal symmetry path as the polarization rotation mechanism. The films on CaF2 and PMN-PT remain in the same symmetry phase up to the ferroelectric-paraelectric phase transition, as predicted. These results support the validity of the multi-domain model which provides the possibility to predict the behavior of clamped, piezoelectric PZT thin films, and design films with enhanced properties.

Abstract: Diamond electrochemistry is primarily influenced by quantities of sp3-carbon, surface terminations, and crystalline structure. In this work, a new dimension is introduced by investigating the effect of using substrate-interlayers for diamond growth. Boron and nitrogen co-doped nanocrystalline diamond (BNDD) films are grown on Si substrate without and with Ti and Ta as interlayers, named BNDD/Si, BNDD/Ti/Si, and BNDD/Ta/Ti/Si, respectively. After detailed characterization using microscopies, spectroscopies, electrochemical techniques, and density functional theory simulations, the relationship of composition, interfacial structure, charge transport, and electrochemical properties of the interface between diamond and metal is investigated. The BNDD/Ta/Ti/Si electrodes exhibit faster electron transfer processes than the other two diamond electrodes. The interlayer thus determines the intrinsic activity and reaction kinetics. The reduction in their barrier widths can be attributed to the formation of TaC, which facilitates carrier tunneling, and simultaneously increases the concentration of electrically active defects. As a case study, the BNDD/Ta/Ti/Si electrode is further employed to assemble a redox-electrolyte-based supercapacitor device with enhanced performance. In summary, the study not only sheds light on the intricate relationship between interlayer composition, charge transfer, and electrochemical performance but also demonstrates the potential of tailored interlayer design to unlock new capabilities in diamond-based electrochemical devices. Diamond electrochemistry is revealed to be affected by the interlayers between boron/nitrogen co-doped nanocrystalline diamond (BNDD) film and a Si substrate. A BNDD/Ta/Ti/Si electrode exhibits faster electron transfer processes and smaller electron transfer resistance of redox probes for [Fe(CN)6]3-/4- and [Ru(NH3)6]3+/2+ than the other electrodes, because the interlayer thus determines the intrinsic activity and reaction kinetics of diamond films. image