| 1. |
- Bakoglidis, Konstantinos D., et al.
(författare)
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Low-temperature growth of low friction wear-resistant amorphous carbon nitride thin films by mid-frequency, high power impulse, and direct current magnetron sputtering
- 2015
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Ingår i: Journal of Vacuum Science & Technology. A. Vacuum, Surfaces, and Films. - : American Vacuum Society. - 0734-2101 .- 1520-8559. ; 33:5
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Tidskriftsartikel (refereegranskat)abstract
- Amorphous carbon nitride (a-CNx) thin films were deposited on steel AISI52100 and Si(001) substrates using mid-frequency magnetron sputtering (MFMS) with an MF bias voltage, high power impulse magnetron sputtering (HiPIMS) with a synchronized HiPIMS bias voltage, and direct current magnetron sputtering (DCMS) with a DC bias voltage. The films were deposited at a low substrate temperature of 150 °C and a N2/Ar flow ratio of 0.16 at the total pressure of 400 mPa. The negative bias voltage (Vs) was varied from 20 V to 120 V in each of the three deposition modes. The microstructure of the films was characterized by high-resolution transmission electron microscopy (HRTEM) and selected area electron diffraction (SAED), while the film morphology was investigated by scanning electron microscopy (SEM). All films possessed amorphous microstructure with clearly developed columns extending throughout the entire film thickness. Layers grown with the lowest substrate bias of 20 V exhibited pronounced intercolumnar porosity, independent of the technique used. Voids closed and dense films formed at Vs ≥ 60 V, Vs ≥ 100 V and Vs = 120 V for MFMS, DCMS and HiPIMS, respectively. X-ray photoelectron spectroscopy (XPS) revealed that the nitrogen-to-carbon ratio, N/C, of the films ranged between 0.2 and 0.24. Elastic recoil detection analysis (ERDA) showed that Ar content varied between 0 and 0.8 at% and increases as a function of Vs for all deposition techniques. All films exhibited compressive residual stress, σ, which depends on the growth method; HiPIMS produces the least stressed films with stress between – 0.4 and – 1.2 GPa for all Vs values, while for CNx films deposited by MFMS σ = – 4.2 GPa. Nanoindentation showed a significant increase in film hardness and reduced elastic modulus with increasing Vs for all techniques. The harder films were produced by MFMS with hardness as high as 25 GPa. Low friction coefficients, between 0.05 and 0.06, were recorded for all films. Furthermore, CNx films produced by MFMS and DCMS at Vs = 100 V and 120 V presented a high wear resistance with wear coefficients of k ≤ 2.3 x 10-5 mm3/Nm.
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| 2. |
- Boyd, Robert, et al.
(författare)
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Double oxide shell layer formed on a metal nanoparticle as revealed by aberration corrected (scanning) transmission electron microscopy
- 2014
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Ingår i: Materials Research Express. - : IOP Publishing. - 2053-1591. ; 1:2, s. Art. no. 025016-
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Tidskriftsartikel (refereegranskat)abstract
- Determining the extent of oxidation in batches of metal nanoparticles is essential to predict the behaviour of the material. Using aberration corrected transmission electron microscopy (TEM) it was possible to detect the formation of an oxide shell, of thickness 3 nm, on the surface of copper nanoparticles. Further analysis showed that this shell actually consists of two layers, both of which were polycrystalline in nature with domains in the size range of 1-2 nm, and having a thickness of 1.5 nm each. Energy dispersive x-ray spectroscopy confirms that the layers arise due to the formation of oxides, but it was not possible to determine their exact nature. Analysis of the intensity variation within images obtained via probe corrected scanning TEM combined with a high angle annular dark field detector indicates that the shell consists of an inner layer of cuprous oxide (Cu2O) and an outer layer of cupric oxide (CuO). This work was complemented by conventional TEM which provided size distribution and revealed that the majority of particles have a core consisting of a single crystal of copper. This demonstrates the ability of TEM to help to determine the oxidation state of nanoparticles and its potential to be applied to a wide range of homogenous and heterogeneous nanoparticles.
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| 3. |
- Chubarov, Mikhail, et al.
(författare)
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Polytype pure sp2-BN thin films as dictated by the substrate crystal structure
- 2015
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Ingår i: Chemistry of Materials. - Washington : American Chemical Society (ACS). - 0897-4756 .- 1520-5002. ; 27:5, s. 1640-1645
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Tidskriftsartikel (refereegranskat)abstract
- Boron nitride (BN) is a promising semiconductor material, but its current exploration is hampered by difficulties in growth of single crystalline phase-pure thin films. We compare the growth of sp2-BN by chemical vapor deposition on (0001) 6H-SiC and on (0001) α-Al2O3 substrates with an AlN buffer layer. Polytype-pure rhombohedral BN (r-BN) with a thickness of 200 nm is observed on SiC whereas hexagonal BN (h-BN) nucleates and grows on the AlN buffer layer. For the latter case after a thickness of 4 nm, the h-BN growth is followed by r-BN growth to a total thickness of 200 nm. We find that the polytype of the sp2-BN films is determined by the ordering of Si-C or Al-N atomic pairs in the underlying crystalline structure (SiC or AlN). In the latter case the change from h-BN to r-BN is triggered by stress relaxation. This is important for the development of BN semiconductor device technology.
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| 4. |
- Das, Prasanna, et al.
(författare)
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Near-UV-to-Near-IR Hyperbolic Photonic Dispersion in Epitaxial (Hf,Zr)N/ScN Metal/Dielectric Superlattices
- 2022
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Ingår i: ACS Applied Energy Materials. - : AMER CHEMICAL SOC. - 2574-0962. ; 5:4, s. 3898-3904
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Tidskriftsartikel (refereegranskat)abstract
- Hyperbolic metamaterials (HMMs) with extreme dielectric anisotropy have shown great promise in nanophotonic applications such as superlensing, enhancement of spontaneous emission, negative refraction, and the diverging photonic density of states. Noble metal-based metal/dielectric multilayers (e.g., Au/ SiO2 and Ag/TiO2) and metallic (Au and Ag) nanowires embedded inside a dielectric matrix have been traditionally used to demonstrate HMM properties and for implementations into devices. Noble metals are, however, unstable at high temperatures, complementary metal oxide semiconductor incompatible, and difficult to deposit in thin-film form due to their high surface energies that limit their potential applications. TiN has emerged as an alternative plasmonic material to Au in recent years, and epitaxial TiN/Al0.72Sc0.28N metal/semiconductor superlattices were developed that exhibit excellent HMM properties. As TiN exhibits epsilon-near-zero (ENZ) at similar to 500 nm, TiN/Al0.72Sc0.28N HMM also operates from similar to 500 nm to long-wavelength regions. However, for several energy-conversion-related applications as well as for fundamental studies, it is desirable to achieve HMM wavelengths from the near-UV to the near-IR region of the spectrum. In this article, we demonstrate hyperbolic photonic dispersion in (Hf,Zr)N/ScN, a class of metal/semiconducting superlattice metamaterial that covers the near-UV to the near-IR spectral range. Epitaxial HfN/ScN, ZrN/ScN, and Hf0.5Zr0.5N/ScN superlattices are deposited on (001) MgO substrates and characterized with synchrotron-radiation X-ray diffraction as well as high-resolution electron microscopy techniques. Superlattices grow with cube-on-cube epitaxy and with sharp interfaces. Optical characterization reveals both type-I and type-II hyperbolic photonic dispersions as well as low losses and high figures-of-merit. Along with its high-temperature thermal stability, demonstration of HMM properties in (Hf,Zr)N/ScN metal/dielectric superlattices makes them potential candidates for HMM devices.
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| 5. |
- Elofsson, Viktor, et al.
(författare)
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Structure formation in Ag-X (X = Au, Cu) alloys synthesized far-from-equilibrium
- 2018
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Ingår i: Journal of Applied Physics. - New York : A I P Publishing LLC. - 0021-8979 .- 1089-7550. ; 123:16
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Tidskriftsartikel (refereegranskat)abstract
- We employ sub-monolayer, pulsed Ag and Au vapor fluxes, along with deterministic growth simulations, and nanoscale probes to study structure formation in miscible Ag-Au films synthesized under far-from-equilibrium conditions. Our results show that nanoscale atomic arrangement is primarily determined by roughness build up at the film growth front, whereby larger roughness leads to increased intermixing between Ag and Au. These findings suggest a different structure formation pathway as compared to the immiscible Ag-Cu system for which the present study, in combination with previously published data, reveals that no significant roughness is developed, and the local atomic structure is predominantly determined by the tendency of Ag and Cu to phase-separate.
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| 6. |
- Garbrecht, Magnus, et al.
(författare)
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Dislocation-pipe diffusion in nitride superlattices observed in direct atomic resolution
- 2017
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Ingår i: Scientific Reports. - : NATURE PUBLISHING GROUP. - 2045-2322. ; 7
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Tidskriftsartikel (refereegranskat)abstract
- Device failure from diffusion short circuits in microelectronic components occurs via thermally induced migration of atoms along high-diffusivity paths: dislocations, grain boundaries, and free surfaces. Even well-annealed single-grain metallic films contain dislocation densities of about 1014 m-2; hence dislocation-pipe diffusion (DPD) becomes a major contribution at working temperatures. While its theoretical concept was established already in the 1950s and its contribution is commonly measured using indirect tracer, spectroscopy, or electrical methods, no direct observation of DPD at the atomic level has been reported. We present atomically-resolved electron microscopy images of the onset and progression of diffusion along threading dislocations in sequentially annealed nitride metal/semiconductor superlattices, and show that this type of diffusion can be independent of concentration gradients in the system but governed by the reduction of strain fields in the lattice.
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| 7. |
- Garbrecht, Magnus, et al.
(författare)
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Microstructural evolution and thermal stability of HfN/ScN, ZrN/ScN, and Hf0.5Zr0.5N/ScN metal/semiconductor superlattices
- 2016
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Ingår i: Journal of Materials Science. - : SPRINGER. - 0022-2461 .- 1573-4803. ; 51:17, s. 8250-8258
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Tidskriftsartikel (refereegranskat)abstract
- Nitride-based metal/semiconductor superlattices for possible applications as thermoelectric, plasmonic, and hard coating materials have been grown by magnetron sputtering. Since long-time thermal stability of the superlattices is crucial for these applications, the atomic scale microstructure and its evolution under annealing to working temperatures were investigated with high-resolution transmission electron microscopy methods. We report on epitaxial growth of three cubic superlattice systems (HfN/ScN, ZrN/ScN, and Hf0.5Zr0.5N/ScN) that show long-time thermal stability (annealing up to 120 h at 950 degrees C) as monitored by scanning transmission electron microscopy-based energy-dispersive X-ray spectroscopy. No interdiffusion between the metal and semiconductor layers could be observed for any of the present systems under long-time annealing, which is in contrast to earlier attempts on similar superlattice structures based on TiN as the metallic compound. Atomically resolved high-resolution transmission electron microscopy imaging revealed that even though the superlattice curves towards the substrate at regular interval column boundaries originating from threading dislocations close to the substrate interface, the cubic lattice continues coherently across the boundaries. It is found that the boundaries themselves are alloyed along the entire growth direction, while in their vicinity nanometer-size inclusions of metallic phases are observed that could be identified as the zinc blende phase of same stoichiometry as the parent rock salt transition metal nitride phase. Our results demonstrate the longtime thermal stability of metal/semiconductor superlattices based on Zr and Hf nitrides.
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| 8. |
- Garbrecht, Magnus, et al.
(författare)
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Quantitative atom column position analysis at the incommensurate interfaces of a (PbS)(1.14)NbS2 misfit layered compound with aberration-corrected HRTEM
- 2011
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Ingår i: Ultramicroscopy. - : Elsevier. - 0304-3991 .- 1879-2723. ; 111:3, s. 245-250
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Tidskriftsartikel (refereegranskat)abstract
- Aberration-corrected HRTEM is applied to explore the potential of NCSI contrast imaging to quantitatively analyse the complex atomic structure of misfit layered compounds and their incommensurate interfaces. Using the (PbS)(1.14)NbS2 misfit layered compound as a model system it is shown that atom column position analyses at the incommensurate interfaces can be performed with precisions reaching a statistical accuracy of +/- 6 pm. The procedure adopted for these studies compares experimental images taken from compound regions free of defects and interface modulations with a structure model derived from XRD experiments and with multi-slice image simulations for the corresponding NCSI contrast conditions used. The high precision achievable in such experiments is confirmed by a detailed quantitative analysis of the atom column positions at the incommensurate interfaces, proving a tetragonal distortion of the monochalcogenide sublattice. (C) 2010 Elsevier B.V. All rights reserved.
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| 9. |
- Garbrecht, Magnus, et al.
(författare)
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Tailoring of surface plasmon resonances in TiN/(Al0.72Sc0.28)N multilayers by dielectric layer thickness variation
- 2018
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Ingår i: Journal of Materials Science. - : SPRINGER. - 0022-2461 .- 1573-4803. ; 53:6, s. 4001-4009
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Tidskriftsartikel (refereegranskat)abstract
- Alternative designs of plasmonic metamaterials for applications in solar energy-harvesting devices are necessary due to pure noble metal-based nanostructures incompatibility with CMOS technology, limited thermal and chemical stability, and high losses in the visible spectrum. In the present study, we demonstrate the design of a material based on a multilayer architecture with systematically varying dielectric interlayer thicknesses that result in a continuous shift of surface plasmon energy. Plasmon resonance characteristics of metal/semiconductor TiN/(Al,Sc)N multilayer thin films with constant TiN and increasing (Al,Sc)N interlayer thicknesses were analyzed using aberration-corrected and monochromated scanning transmission electron microscopy-based electron energy loss spectroscopy (EELS). EEL spectrum images and line scans were systematically taken across layer interfaces and compared to spectra from the centers of the respective adjacent TiN layer. While a constant value for the TiN bulk plasmon resonance of about 2.50 eV was found, the surface plasmon resonance energy was detected to continuously decrease with increasing (Al,Sc)N interlayer thickness until 2.16 eV is reached. This effect can be understood to be the result of resonant coupling between the TiN bulk and surface plasmons across the dielectric interlayers at very low (Al,Sc)N thicknesses. That energy interval between bulk and decreasing surface plasmon resonances corresponds to wavelengths in the visible spectrum. This shows the potential of tailoring the materials plasmonic response by controlling the (Al,Sc)N interlayer thickness, making TiN-based multilayers good prospects for plasmonic metamaterials in energy devices.
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| 10. |
- Garbrecht, Magnus, et al.
(författare)
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Void-mediated coherency-strain relaxation and impediment of cubic-to-hexagonal transformation in epitaxial metastable metal/semiconductor TiN/Al0.72Sc0.28N multilayers
- 2017
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Ingår i: Physical Review Materials. - : AMER PHYSICAL SOC. - 2475-9953. ; 1:3
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Tidskriftsartikel (refereegranskat)abstract
- Bulk metastable phases can be stabilized during thin-film growth by employing substrates with similar crystal structure and lattice parameter, albeit over a thickness range limited by coherency-strain relaxation. Expanding that strategy, growth of superlattices comprising one stable and another metastable compound with similar crystal structure and lattice parameters are known to yield epitaxial stabilization over a few nanometers of thickness. In this work, the high-pressure rocksalt (B1) phase of Al0.72Sc0.28N was stabilized epitaxially in a multilayer with TiN with thicknesses of up to 26 nm. In order to investigate the microstructural changes leading to the phase transformation of the metastable B1 phase to its wurtzite allomorph, we demonstrate a design based on a multilayer architecture with systematically varying thicknesses of the metastable compound within a constant-thickness lattice of stable metallic TiN with the cubic rocksalt structure. The multilayer films show an increasing hardness and elastic modulus for decreasing period thickness, in correspondence with both coherency-strain and Koehler hardening. The phase transition is accompanied by an increase of lattice strain with increasing multilayer periods, and resulting ultimately in coherency-strain relaxation upon phase transformation. Further, we show that the phase transformation is mediated by voids decorating the {130} planes that separate regions of different growth rates and act as additional growth fronts for wurtzite growth during the phase transformation. The TiN/(Al, Sc) N interfaces themselves remain atomically sharp and smooth until the interface structure roughens along with the epitaxial rocksalt to wurtzite transition of (Al, Sc) N. These results show the strong influence of the voids on controlling the target thickness of epitaxially stabilized thin-film growth to the range relevant for applications, such as coatings, plasmonic materials, and electronic device technology, where the mechanical integrity of the material is critical.
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