Understanding and Control of Bipolar Doping in Copper Nitride
Angela N Fioretti, Craig P Schwartz, John Vinson, Dennis Nordlund, David Prendergast, Adele C Tamboli, Christopher M Caskey, Filip Tuomisto, Florence Linez, Ste… 展开作者
Angela N Fioretti, Craig P Schwartz, John Vinson, Dennis Nordlund, David Prendergast, Adele C Tamboli, Christopher M Caskey, Filip Tuomisto, Florence Linez, Steven T Christensen, Eric S Toberer, Stephan Lany, Andriy Zakutayev
Semiconductor materials that can be doped both n-type and p-type are desirable for diode-based applications and transistor technology. Copper nitride (Cu3N) is a metastable semiconductor with a solar-relevant bandgap that has been reported to exhibit bipolar doping behavior. However, deeper understanding and better control of the mechanism behind this behavior in Cu3N is currently lacking in the literature. In this work, we use combinatorial growth with a temperature gradient to demonstrate both conduction types of phase-pure, sputter-deposited Cu3N thin films. Room temperature Hall effect and Seebeck effect measurements show n-type Cu3N with 10^17 electrons/cm^3 for low growth temperature (~35 degrees C) and p-type with 10^15-10^16 holes/cm^3 for elevated growth temperatures (50-120 degrees C). Mobility for both types of Cu3N was ~0.1-1 cm^2/Vs. Additionally, temperature- dependent Hall effect measurements indicate that ionized defects are an important scattering mechanism in p-type films. By combining X-ray absorption spectroscopy and first-principles defect theory, we determined that V_Cu defects form preferentially in p-type Cu3N while Cu_i defects form preferentially in n-type Cu3N. Based on these theoretical and experimental results, we propose a kinetic defect formation mechanism for bipolar doping in Cu3N, that is also supported by positron annihilation experiments. Overall, the results of this work highlight the importance of kinetic processes in the defect physics of metastable materials, and provide a framework that can be applied when considering the properties of such materials in general.
We present a transfer-free preparation method for graphene on hexagonal boron nitride (h-BN) crystals by chemical vapor deposition of graphene via a catalytic proximity effect, i.e. activated by a Cu catalyst close-by . We demonstrate the full coverage by monolayer graphene of half-millimeter-sized hexagonal boron nitride crystals exfoliated on a copper foil prior to growth. We demonstrate that the proximity of the copper catalyst ensures high yield with the growth rate estimated between of 2μm/min to 5μm/min . Optical and electron microscopies together with confocal micro-Raman mapping confir…
The boron nitride nanomesh is a corrugated monolayer of hexagonal boron nitride (h-BN) on Rh(111), which so far has been studied mostly under ultrahigh vacuum conditions. Here, we investigate how copper underpotential deposition (upd) can be used to quantify defects in the boron nitride monolayer and to assess the potential window of the nanomesh, which is important to explore its functionality under ambient and electrochemical conditions. In dilute sulfuric acid, the potential window of h-BN/Rh(111) is close to 1 volt, i.e. larger than that of the Rh substrate, and is limited by molecular hyd…
Graphene-covered copper surfaces have been exposed to borazine, (BH)3(NH)3, with the resulting surfaces characterized by low-energy electron microscopy. Although the intent of the experiment was to form hexagonal boron nitride (h-BN) on top of the graphene, such layers were not obtained. Rather, in isolated surface areas, h-BN is found to form micrometer-size islands that substitute for the graphene. Additionally, over nearly the entire surface, the properties of the layer that was originally graphene is observed to change in a manner that is consistent with the formation of a mixed h-BN/graph…
Although the high impermeability of graphene makes it an excellent barrier to inhibit metal oxidation and corrosion, graphene can form a galvanic cell with the underlying metal that promotes corrosion of the metal in the long term. Boron nitride (BN) nanosheets which have a similar impermeability could be a better choice as protective barrier, because they are more thermally and chemically stable than graphene and, more importantly, do not cause galvanic corrosion due to their electrical insulation. In this study, the performance of commercially available BN nanosheets grown by chemical vapor …
We present a detailed first-principles DFT study of the equation of state (EOS), energy-optimized geometries, phase stabilities and electronic properties of bulk crystalline Cu3N, CuN and CuN2 in a set of twenty different structural phases. We analyzed different structural preferences for these three stoichiometries and determined their equilibrium structural parameters. Band-structure and density of states of the relatively most stable phases were carefully investigated. Further, we carried out GW0 calculations within the random-phase approximation (RPA) to the dielectric tensor to investigat…
We report on the unexpected uniform spin chain physics in CuNCN, the insulating nitride analog of copper oxides. Based on full-potential band structure calculations, we derive the relevant microscopic parameters, estimate individual exchange couplings, and establish a realistic spin model of this compound. The structure of CuNCN contains chains of edge-sharing CuN(4) squares. As a surprise, in contrast to analogous [CuO(2)] chains in "edge-sharing" cuprates, the leading magnetic interactions J ~ 2500 K run perpendicular to the structural [CuN(2)] chains via bridging NCN groups. The resulting s…
At a single atom thick, it is challenging to distinguish graphene from its substrate using conventional techniques. In this paper we show that friction force microscopy (FFM) is a simple and quick technique for identifying graphene on a range of samples, from growth substrates to rough insulators. We show that FFM is particularly effective for characterising graphene grown on copper where it can correlate the graphene growth to the three-dimensional surface topography and map the crystallographic orientation of the graphene nondestructively, reproducibly and at high resolution. We expect FFM t…
Copper interconnects in modern integrated circuits require ultra-thin barriers to prevent intermixing of Cu with surrounding dielectric materials. Conventional barriers rely on metals like TaN, however their finite thickness reduces the cross-sectional area and significantly increases the resistivity of nanoscale interconnects. In this study, a new class of two-dimensional (2D) Cu diffusion barriers, hexagonal boron nitride (h-BN) and molybdenum disulfide (MoS2), is demonstrated for the first time. Using time-dependent dielectric breakdown measurements and scanning transmission electron micros…
Copper deposition has been carried out at various time span on glass slide and silicon substrate by using indigenously developed unbalanced type DC magnetron sputtering system. The main objective of this work is to study the crystalline structure of the deposited materials and also to calculate the crystallite grain size. As a transition metal, Copper nano-particles and structures have several utilities in the field of photo-catalytic and sensor applications. Such structures are utilized to provide free electrons that enhance optical and electrical properties of the photo-catalytic sensor mate…
Optically addressable spins in materials are important platforms for quantum technologies, such as repeaters and sensors. Identification of such systems in two-dimensional (2d) layered materials offers advantages over their bulk counterparts, as their reduced dimensionality enables more feasible on-chip integration into devices. Here, we report optically detected magnetic resonance (ODMR) from previously identified carbon-related defects in 2d hexagonal boron nitride (hBN). We show that single-defect ODMR contrast can be as strong as 6% and displays a magnetic-field dependence with both positi…
Luminescent defect-centers in hexagonal boron nitride (hBN) have emerged as a promising 2D-source of single photon emitters (SPEs) due to their high brightness and robust operation at room temperature. The ability to create such emitters with well-defined optical properties is a cornerstone towards their integration into on-chip photonic architectures. Here, we report an effective approach to fabricate hBN single photon emitters (SPEs) with desired emission properties in two isolated spectral regions via the manipulation of boron diffusion through copper during atmospheric pressure chemical va…
Two dimensional materials are an emerging class of materials which is transforming the present day research activity on a phenomenal scale. Hexagonal boron nitride is a wide band gap 2D material which is an excellent substrate for graphene based electronics. To achieve the full potential of hBN scalable and high yield growth procedures are required. Here, we demonstrate the synthesis of hBN by reactive R.F magnetron sputtering over copper foil. Copper foil preparation conditions determines the phase selectivity of BN films. Deposition of hBN on non-electropolished Cu foils with predominant (10…
We report a bipolar field effect tunneling transistor that exploits to advantage the low density of states in graphene and its one atomic layer thickness. Our proof-of-concept devices are graphene heterostructures with atomically thin boron nitride acting as a tunnel barrier. They exhibit room temperature switching ratios ~50, a value that can be enhanced further by optimizing the device structure. These devices have potential for high frequency operation and large scale integration.
The review of studies on memristive properties or effect of resistive switchings in four classes of high temperature superconductors is presented in order to reveal functional properties of HTSCs which become apparent in the effects under discussion, prospects of usage of high temperature superconductors based memristors in applications and search for new mechanisms of strongly correlated nature to realize new generation memristors. The properties are: undergoing metal insulator transition at oxygen doping, transport anisotropy, existence of charge reservoirs through which doping of conductive…
The effect of monolayers of oxygen (O) and hydrogen (H) on the possibility of material transfer at aluminium/titanium nitride (Al/TiN) and copper/diamond (Cu/C$_{\text{dia}}$) interfaces, respectively, were investigated within the framework of density functional theory (DFT). To this end the approach, contact, and subsequent separation of two atomically flat surfaces consisting of the aforementioned pairs of materials were simulated. These calculations were performed for the clean as well as oxygenated and hydrogenated Al and C$_{\text{dia}}$ surfaces, respectively. Various contact configurati…
The emergence of two-dimensional (2D) materials has attracted a great deal of attention due to their fascinating physical properties and potential applications for future nanoelectronic devices. Since the first isolation of graphene, a Dirac material, a large family of new functional 2D materials have been discovered and characterized, including insulating 2D boron nitride, semiconducting 2D transition metal dichalcogenides and black phosphorus, and superconducting 2D bismuth strontium calcium copper oxide, molybdenum disulphide and niobium selenide, etc. Here, we report the identification of …
