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Vanadium dioxide (VO2) is a popular candidate for electronic and optical switching applications due to its well-known semiconductor-metal transition. Its study is notoriously challenging due to the interplay of long and short range elastic distortions, as well as the symmetry change, and the electronic structure changes. The inherent coupling of lattice and electronic degrees of freedom opens the avenue towards mechanical actuation of single domains. In this work, we show that we can manipulate and monitor the reversible semiconductor-to-metal transition of VO2 while applying a controlled amount of mechanical pressure by a nanosized metallic probe using an atomic force microscope. At a critical pressure, we can reversibly actuate the phase transition with a large modulation of the conductivity. Direct tunneling through the VO2-metal contact is observed as the main charge carrier injection mechanism before and after the phase transition of VO2. The tunneling barrier is formed by a very thin but persistently insulating surfacelayer of the VO2. The necessary pressure to induce the transition decreases with temperature. In addition, we measured the phase coexistence line in a hitherto unexplored regime. Our study provides valuable information on pressure-induced electronic modifications of the VO2 properties, as well as on nanoscale metal-oxide contacts, which can help in the future design of oxide electronics., Y.A.B. and K.S. contributed equally. 30 pages, 4 figures, Supplemental Material (28 pages, 16 figures)

It is challenging to develop a material that combines good mechanical properties and high translucency since these properties are generally not coincident in one material. In this study, we prepared ZrO2-SiO2 nanocrystalline glass-ceramics that combines the above two types of properties. Raw powder with 55 mol%, 65 mol%, and 75 mol% ZrO2 and each with 5 mol% yttrium as a dopant was prepared by sol-gel method, followed by spark plasma sintering to obtain dense glass-ceramics. XRD results demonstrated that the glass-ceramics with 65 mol% and 75 mol% ZrO2 were composed of tetragonal-ZrO2, whereas, that with 55 mol% ZrO2 was composed of cubic-ZrO2. The as-sintered glass-ceramics showed black/brown discoloration, but they obtained high translucency after thermal treatment. X-ray energy-dispersive spectrometry (EDS) results in scanning electron transmission microscopy (STEM) mode demonstrated yttrium dopants were predominately distributed in ZrO2 nanocrystallites. The glass-ceramics with 65 mol% ZrO2 had the highest flexural strength, achieving an average value of 673 MPa. The glass-ceramics with different compositions sintered at different temperatures showed fracture toughness values ranging from 5.25 MPa m1/2 to 6.69 MPa m1/2. The strong and translucent ZrO2-SiO2 nanocrystalline glass-ceramics showing great protentional to be used in many fields.

Carbothermal reduction of Zr-sucrose gels powders into nano-phase ZrC, or ZrC-Zr(C,O) core-shell powders, via a composite of 2–4 nm sized ZrO2 and amorphous carbon, is described. Samples with 1.7–20 sucrose-carbon:Zr ratio gels heated to 1495 °C at 10 °Cmin−1, with 3 and 30 min hold time were studied in detail using; TG, XRD, SEM, TEM, STEM-EDX, and XPS with Ar+-ion etching. After 1495 °C, 3 min, the samples with 12-20C:Zr ratios yielded weakly agglomerated 30 to 40 nm sized ZrC particles, surrounded by a dense 5 nm thick shell of Zr(C,O). With 5C:Zr significant amounts of ZrO2 was present after heating at 1495 °C for 3 min, while after 30 min annealing, ZrC particles without residual amorphous carbon was obtained. Minor amounts of zirconia was found in most samples, which in similarity with the 5 nm Zr(C,O) shell, is believed to stem from post synthesis oxidation.

Dentin hypersensitivity can be reduced by the use of a remineralization agent to hinder movement of fluids within the dentin tubules. Penetration of particles into the tubules and a continuous release of Ca2+ and phosphate ions can induce the mineralization of a material mimicking the mineral component of dentin, sealing the tubules. In this work, we have used complementary electron microscopy techniques to investigate the ultrastructure of dentin and crystallization and occlusion effects when using amorphous calcium magnesium phosphate (ACMP) microspheres on extracted human molars. Application of the particles in a gel intended for at-home use resulted in intra-tubular mineralization of a carbonate substituted hydroxyapatite (HA). Transmission electron microscopy (TEM) and scanning electron microscopy (SEM) showed that crystallization was initiated on the peritubular dentin (PTD) with undirected crystal growth leading to the formation of a porous material. We additionally investigated the effects from using a fluoride toothpaste to potentially improve the remineralization and anti-cariogenic properties of the ACMP microspheres. Energy dispersive x-ray spectroscopy (EDX) using TEM in scanning mode (STEM) showed that fluoride incorporation resulted in an increase in aspect ratio of the crystals, crystal growth directed towards the center of the tubule lumen and densification of the mineralized material. Thus, ACMP microspheres are promising alternatives as occluding agents and the efficacy of the particles could be further improved with the complementary use of a fluoride toothpaste.

Tungsten (W)-based materials attract significant attention due to their superior mechanical properties. Here, we present a chemical approach based on the addition of carbon (C) for increased strength via the combination of three strengthening mechanisms in W thin films. W:C thin films with C concentrations up to ~4 at.% were deposited by magnetron sputtering. All films exhibit a body-centred-cubic structure with strong texture and columnar growth behaviour. X-ray and electron diffraction measurements suggest the formation of supersaturated W:C solid solution phases. The addition of C reduced the average column width from ~133 nm for W to ~20 nm for the film containing ~4 at.% C. The column refinement is explained by a mechanism where C acts as re-nucleation sites. The W film is ~13 GPa hard, while the W:C films achieve a peak hardness of ~24 GPa. The W:C films are ~11 GPa harder than the W film, which is explained by a combination of grain refinement strengthening, solid solution strengthening and increased dislocation density. Additional micropillar compression tests showed that the flow stress increased upon C addition, from ~3.8 to ~8.3 GPa and no brittle fracture was observed., Materials & Design, 208, ISSN:0264-1275, ISSN:1873-4197

International audience; We report on the development of highly reflective back contacts (RBCs) made of multilayer stacks for ultrathin CIGS solar cells. Two architectures are compared: they are made of a silver mirror coated either with a single layer of In2O3:Sn (ITO) or with a bilayer of ZnO:Al/ITO. Due to the improvement of CIGS rear reflectance, both back contacts result in a significant external quantum efficiency enhancement, in agreement with optical simulations. However, solar cells fabricated with Ag/ITO back contacts exhibit a strong shunting behavior. The key role of the ZnO:Al layer to control the morphology of the top ITO layer and to avoid silver diffusion through the back contact is highlighted. For a 500-nm-thick CIGS layer, this optimized RBC leads to a best cell with a short-circuit current of 27.8 mA/cm2 (+2.2 mA/cm2 as compared to a Mo back contact) and a 12.2%-efficiency (+2.5% absolute).

Complex compound semiconductors, such as the emerging solar cell material Cu2ZnSn(S,Se)4 (CZTS), present major experimental challenges in terms of understanding and controlling growth processes and defect formation. This study aims to shed light upon the complicated interplay of the synthesis conditions and CZTS thin film properties. Composition-spread thin films are fabricated in different atmospheric conditions during the annealing step. The span of the single-phase region is identified by a phase analysis combining XRD and Raman mapping. The phase characterisation is strengthened by STEM-EDX analysis. Our results show that the stability of the CZTS phase is strongly affected by the process conditions which is observed as a shift in the secondary phase boundaries and different levels of maximum cation ordering achieved in the different samples. With regard to the photoluminescence intensity, all investigated samples show the same trends: regions with Cu3SnS4 secondary phase show the lowest intensity, while the presence of SnSx secondary phases greatly enhances the photoluminescence intensity. The single-phase region features an overall low photoluminescence intensity without a remarkable composition dependence and we propose the presence of deep defects in absence of secondary phases that limit the radiative recombination. We discuss implications for future efforts in defect engineering toward improving the efficiency of CZTS thin film devices.

We report an efficient one-step method to achieve highly reduced graphene oxide (rGO) hydrogel doped with nitrogen where the rGO sheets are interconnected forming a porous structure by means of hyd ...

Surface sulfurization of Cu(In,Ga)Se2 (CIGSe) absorbers is a commonly applied technique to improve the conversion efficiency of the corresponding solar cells, via increasing the bandgap towards the heterojunction. However, the resulting device performance is understood to be highly dependent on the thermodynamic stability of the chalcogenide structure at the upper region of the absorber. The present investigation provides a high-resolution chemical analysis, using energy dispersive X-ray spectrometry and laser-pulsed atom probe tomography, to determine the sulfur incorporation and chemical re-distribution in the absorber material. The post-sulfurization treatment was performed by exposing the CIGSe surface to elemental sulfur vapor for 20 min at 500°C. Two distinct sulfur-rich phases were found at the surface of the absorber exhibiting a layered structure showing In-rich and Ga-rich zones, respectively. Furthermore, sulfur atoms were found to segregate at the absorber grain boundaries showing concentrations up to ~7 at% with traces of diffusion outwards into the grain interior.

Li- and Mn-rich layered oxides show significant promise as electrode materials for future Li-ion batteries. However, an accurate description of its crystallography remains elusive, with both single-phase solid solution and multiphase structures being proposed for high performing materials such as Li1.2Mn0.54Ni0.13Co0.13O2. Herein, we report the synthesis of single- and multiphase variants of this material through sol-gel and solid-state methods, respectively, and demonstrate that its crystallography is a direct consequence of the synthetic route and not necessarily an inherent property of the composition, as previously argued. This was accomplished via complementary techniques that probe the bulk and local structure followed by in situ methods to map the synthetic progression. As the electrochemical performance and anionic redox behavior are often rationalized on the basis of the presumed crystal structure, clarifying the structural ambiguities is an important step toward harnessing its potential as an electrode material.

This study explores carbon addition as a materials design approach for simultaneously improving the hardness, crack resistance, and corrosion resistance of high entropy thin films. CoCrFeMnNi was selected as a starting point, due to its high concentration of weak carbide formers. The suppression of carbides is crucial to the approach, as carbide formation can decrease both ductility and corrosion resistance. Films with 0, 6, and 11 at.% C were deposited by magnetron co-sputtering, using a graphite target and a sintered compound target. The samples with 0 at.% C crystallized with a mixture of a cubic closed packed (ccp) phase and the intermetallic χ-phase. With 6 and 11 at.% C, the films were amorphous and homogenous down to the nm-scale. The hardness of the films increased from 8 GPa in the carbon-free film to 16 GPa in the film with 11 at.% C. Furthermore, the carbon significantly improved the crack resistance as shown in fragmentation tests, where the crack density was strongly reduced. The changes in mechanical properties were primarily attributed to the shift from crystalline to amorphous. Lastly, the carbon improved the corrosion resistance by a progressive lowering of the corrosion current and the passive current with increasing carbon concentration.

Li- and Mn-rich layered oxides show significant promise as electrode materials for future Li-ion batteries. However, accurate descriptions of its crystallography remain elusive, with both single-phase solid solution and multi-phase structures being proposed for high performing materials such as Li1.2Mn0.54Ni0.13Co0.13O2. Herein, we report the synthesis of single- and multi-phase variants of this material through sol-gel and solid-state methods, respectively, and conclusively demonstrate that its crystallography is a direct consequence of the synthetic route and not an inherent property of the composition, as previously argued. This was accomplished via complementary techniques that probe the bulk and local structure followed by in situ methods to map the synthetic progression. As the electrochemical performance and anionic redox behaviour is often rationalised on the basis of the presumed crystal structure, clarifying the structural ambiguities is an important step towards harnessing its potential as an electrode material.

Materials and design 196, 109070 (2020). doi:10.1016/j.matdes.2020.109070, Published by Elsevier Science, Amsterdam [u.a.]

The microstructure and distribution of the elements have been studied in thin films of a near-equimolar CrNbTaTiW high entropy alloy (HEA) and films with 8 at.% carbon added to the alloy. The films were deposited by magnetron sputtering at 300°C. X-ray diffraction shows that the near-equimolar metallic film crystallizes in a single-phase body centered cubic (bcc) structure with a strong (110) texture. However, more detailed analyses with transmission electron microscopy (TEM) and atom probe tomography (APT) show a strong segregation of Ti to the grain boundaries forming a very thin Ti–Cr rich interfacial layer. The effect can be explained by the large negative formation enthalpy of Ti–Cr compounds and shows that CrNbTaTiW is not a true HEA at lower temperatures. The addition of 8 at.% carbon leads to the formation of an amorphous structure, which can be explained by the limited solubility of carbon in bcc alloys. TEM energy-dispersive X-ray spectroscopy indicated that all metallic elements are randomly distributed in the film. The APT investigation, however, revealed that carbide-like clusters are present in the amorphous film.

Multicomponent nitride coatings of the Hf-Nb-Ti-V-Zr system with different Hf content (0-18 at.%) were deposited using reactive dc magnetron sputtering. Coatings with lower Hf content (0-7 at.%) we ...

Hydrogen‐doped In2O3 (IOH) films are used as a transparent back contact in bifacial Cu(In,Ga)Se2 (CIGS) solar cells. The effect of the IOH thickness and the impact of the sodium incorporation techn ...

In this study, the crystal structure and phase stability of gas atomized equiatomic AlCoCrFeNi powder was investigated. This alloy is usually described as a high entropy alloy forming a solid solution phase stabilized by a high mixing entropy. However, thermodynamic calculations show that the high entropy phase is stable only at very high temperatures close to the melting point and that a mixture of several phases are the most stable state at lower temperatures. This suggest that kinetic effects may influence the phase composition of atomized powder. The unique features of X-ray diffraction, neutron diffraction as well as transmission electron microscopy were used to study the atomic structure of the atomized powder in detail. The results show that the powder crystallises in an ordered B2 (CsCl-type) structure with a preferred site occupation of Al and Fe on the (½ ½ ½) position and Co and Ni on the (0 0 0) position. During heat-treatment of the powder, the B2 phase decomposes into fcc and σ phases and the final phase composition is highly dependent on the heating rate. The effect of heat-treatment on the atomized powder was also investigated and revealed a significant phase transformation with e.g. the formation of σ phase preferably at the surface of the powder particles. The phase content was also dependent on the size fraction of the powder particles. Sintering of green bodies made with different heat cycles showed that the phase composition of the starting material had a significant impact on the final phase composition and microstructure of the sintered components. The results illustrate the importance of well-defined powder materials for powder consolidation, especially additive manufacturing (binder jetting) of high entropy alloys.

This study evaluates the potential of hydrogen‐doped In2O3 (IOH) as a transparent back contact material in (Agy,Cu1‐y)(In1‐x,Gax)Se2 solar cells. It is found that the presence of Na promotes the cr ...

This contribution studies the impact of the KF-induced Cu(In,Ga)Se2 (CIGSe) absorber modification on the suitability of different transparent conductive oxide (TCO) layers in solar cells. The TCO m ...

This paper focuses on the development of 2-terminal CIGS-perovskite tandem solar cells by exploring a range of stack sequences and synthetic procedures for depositing the associated layers. In the end, we converged at a stack sequence composed of SLG/Mo/CIGS/CdS/i-ZnO/ZnO:Al/NiO/PTAA/Perovskite/LiF/PCBM/SnO2/ITO. With this architecture, we reached performances only about 1% lower than the corresponding 4-terminal tandem cells, thus demonstrating functional interconnects between the two sub-cells while grown monolithically on top of each other. We go through the stack, layer-by-layer, discussing their deposition and the results, from which we can conclude what works, what does not work, and what potentially could work after additional modifications. The challenges for a successful 2-terminal tandem device include: how to deal with, or decrease, the surface roughness of the CIGS-stack, how to obtain uniform coverage of the layers between the CIGS and the perovskite while also obtaining a benign interface chemistry, and how to tune the band gaps of both the CIGS and the perovskite to obtain good optical matching. The investigation was based on CIGS with a power conversion efficiency around 14%, and perovskites with an efficiency around 12%, resulting in 2-terminal tandem cells with efficiencies of 15–16%. The results indicate that by using higher performing CIGS and perovskite sub-cells, it should be possible to manufacture highly efficient 2-terminal CIGS-perovskite tandem devices by using the protocols, principles, and procedures developed and discussed in this paper. (Less)

Despite intensive studies on the complex perovskite Pb(Fe2/3W1/3)O3 (PFWO) relaxor, understanding the exact nature of its multifunctional properties has remained a challenge for decades. In this work we report a comprehensive structural study of the PFWO single crystals using a combination of synchrotron X-ray diffraction and high-resolution electron microscopy. The set of {h + ½, k + ½, l + ½} superlattice reflections was observed for the first time based on single-crystal synchrotron X-ray experiments (100–450 K) and transmission electron microscopy investigations, which indicates some kind of B-cation ordering in PFWO which had been thought to be totally disordered. It was found that (1) the crystal structure of PFWO should be described by a partly ordered cubic perovskite (i.e. Fm − 3m), (2) the weak ferromagnetic properties and excess magnetic moment of PFWO can be understood based on non-random distribution of Fe cations between the 4a and 4b sites, and (3) the Pb displacement disorder is present in this material and the cations are probably displaced along the directions. The X-ray diffraction results of this investigation show that partial cation ordering indeed exists in PFWO, which makes it necessary to revisit the generally accepted interpretations of the results obtained up to date. In agreement with X-ray diffraction study the main results of TEM study include: (1) a long range order that can be described with the Fm − 3m symmetry is reliably detected, (2) the coherence length of that long range order is in the order of 1–2 nm and (3) no remarkable chemical inhomogeneity is found in the tested PFWO crystal, excluding the possibility of a compositional ordering arising from substitutional defects in the perovskite structure.

International audience

Thin films of the CrMnFeCoNi high entropy alloy were deposited by magnetron sputtering from a sintered equimolar target. The substrate temperature and bias were varied during deposition, and the structure, morphology and elemental distribution were studied in detail. All films formed phase mixtures of multiple crystal structures. This contrasts with studies on the bulk alloy, where it typically forms a single phase with a simple cubic closed packed (ccp) structure, with other phases precipitating only after long annealing times. For higher substrate temperatures, we observed a mixture of phases with ccp and bcc (body centered cubic) structures, and the intermetallic phases σ-phase and L10, the first three being the predicted equilibrium phases at the deposition temperature. For room temperature depositions, we found evidence of very limited diffusion of metal atoms during the deposition. These films formed a mixture of a ccp and the intermetallic χ-phase. Two mechanisms can be distinguished that govern the phase formation at lower and higher temperatures. From the present results and comparisons with the literature, we also discuss why the small grain size, the low process temperature, and the fast surface diffusion during synthesis causes magnetron sputtering to yield different results compared to bulk synthesis from the melt. These principles explain why it is easier to form the equilibrium phases by sputtering, and why a single ccp phase should not be expected as a rule for this deposition method. Following the thermodynamic principles of high entropy alloys, this may also be the case in other high entropy alloy systems.

Tandem solar cells based on hybrid organic-inorganic metal halide perovskites have reached efficiencies up to 28%, but major concerns for long-term stability and the presence of Pb have raised interest in searching for fully earth-abundant, intrinsic chemically stable, and nontoxic alternatives. With a direct band gap around 1.8 eV and stability in air up to at least 500 degrees C, BaZrS3 is a promising candidate. This work presents the first approach of synthesizing a thin film of such compound by sputtering at ambient temperature with a subsequent rapid thermal process. Despite the short fabrication time, the width of the XRD diffraction peaks and the energy and distribution of the photoluminescence response show comparable crystalline quality to that from bulk synthesis methods. Good crystallization required around 900 degrees C. Such a high temperature could be incompatible with fabrication of tandem solar cells.

This contribution evaluates the effect of absorber off‐stoichiometry in wide‐gap (Ag,Cu)(In,Ga)Se2 (ACIGS) solar cells. It is found that ACIGS films show an increased tendency to form ordered vacancy compounds (OVCs) with increasing Ga and Ag contents. Very little tolerance to off‐stoichiometry is detected for absorber compositions giving the desired properties of 1) an optimum bandgap (EG) for a top cell in tandem devices (EG = 1.6–1.7 eV) and at the same time 2) a favorable band alignment with a CdS buffer layer. Herein, massive formation of either In‐ or Ga‐enriched OVC patches is found for group I‐poor ACIGS. As a consequence, carrier transport and charge collection are significantly impeded in corresponding solar cells. The transport barrier appears to be increasing with storage time, questioning the long‐term stability of wide‐gap ACIGS solar cells. Furthermore, the efficiency of samples with very high Ga and Ag contents depends on the voltage sweep direction. It is proposed that the hysteresis behavior is caused by a redistribution of mobile Na ions in the 1:1:2 absorber lattice upon voltage bias. Finally, a broader perspective on OVC formation in the ACIGS system is provided and fundamental limitations for wide‐gap ACIGS solar cells are discussed.

Ge nanoparticles embedded in thin films have attracted a lot of attention due to their promising optical and electronic properties that can be tuned by varying the particle size and choice of matrix material. In this study, Ge nanoparticle formation was investigated for Al-Ge-N based thin films by simultaneous measurements of HAXPES and grazing incidence XRD during in situ annealing in vacuum conditions. As-deposited Al-Ge-N thin films, synthesized by reactive dc magnetron sputtering, consisted of a nanocrystalline (Al1-xGex)Ny solid solution and an amorphous tissue phase of Ge3Ny. Upon annealing to 750 °C, elemental Ge was formed shown by both HAXPES and XRD measurements, and N2 gas was released as measured by a mass spectrometer. Postannealed ex situ analysis by SEM and TEM showed that the elemental Ge phase formed spherical nanoparticles on the surface of the film, with an average size of 210 nm. As the annealing temperature increased further to 850 °C, the Ge particles on the film surface evaporated, while the phase segregation of Ge still could be observed within the film. Thus, these results show the possibility for a controlled synthesis of Ge nanoparticles through annealing of Al-Ge-N thin films to produce materials suitable for use in electronic or optoelectronic devices.

This contribution evaluates a sequential post‐deposition treatment of Cu(In,Ga)Se2 (CIGS) films, consisting of 1) a post‐sulfurization in elemental S‐atmosphere and 2) a subsequent treatment by heavy alkali fluorides (Alk‐PDT). First, the effect of the sulfurization step on the corresponding solar cell performance is investigated and optimum process parameters, leading to an efficiency improvement, are identified. Losses in carrier collection observed after S‐incorporation are attributed to an increased grain boundary (GB) recombination. It is found that the corresponding reduction in short‐circuit current density can be mitigated by a RbF‐ or KF‐PDT, supposedly by depleting GBs in Cu. However, in strong contrast to non‐sulfurized CIGS, the Alk‐PDT results in a lower open‐circuit voltage and distortions in the current–voltage (I –V ) characteristics for sulfurized absorbers. Possible explanations are the absence of a wide‐gap surface phase and/or air exposure between the post‐treatment steps. It is further proposed that a back contact barrier may be responsible for the distortions in I–V.

Two different Li-rich nickel–cobalt–manganese-oxide (Li-rich NCM) active materials with the same nominal composition 0.5Li2MnO3:0.5Li(Ni1/3Co1/3Mn1/3)O2 but different pristine nano structure have been analyzed structurally and electrochemically in different cycling states. For structural characterization, transmission electron microscopy (TEM) and high resolution synchrotron powder diffraction (S-XRD) experiments were conducted. The changes in structure with increasing cycle number are correlated with characteristic features in the corresponding electrochemical dQ/dV-profiles that were obtained by galvanostatically cycling the two different active materials. The presented data demonstrates that structural changes upon cycling, e.g. LiMnO2 and spinel formation, strongly depend on the degree oxygen is involved in the reversible charge compensation for delithiation/lithiation. According to our data, firstly a twin-like environment with nanometer dimensions is formed within the R-3m matrix during the initial cycle, which then gradually transforms into a spinel-like structure with increasing cycle number. As another result, we can show that Li2MnO3 to LiMnO2 transformation is not directly dependent in the irreversible oxygen loss in the first cycle but more importantly on transition metal migration. A model is presented explaining the dependency of LiMnO2 and spinel formation on the ability of Li-rich active materials to include oxygen in the charge compensation process.

Al-Cr-Nb-Y-Zr-N films have been deposited with reactive dc magnetron sputtering at various N2 flow ratios to achieve films with different nitrogen content, from purely metallic to fully nitrided films. The structure evolved from mainly amorphous with a minor crystalline intermetallic phase for the film without nitrogen, to nanocomposites with a cubic crystalline phase in an amorphous matrix for intermediate nitrogen content (15–41 at.% N), and at higher nitrogen content (46–51 at.% N) to crystalline solid solution nitrides with a NaCl-type structure. Partial elemental segregation on the nanoscale was found in all studied samples and the films exhibited different segregation behaviour depending on the nitrogen content, implying that the structural evolution on the nanoscale of films in this material system complex and highly composition-dependent. The hardness increased with increasing nitrogen content, reaching a maximum at about 30 GPa at for the nitride films with 50 at.% N. Deformation behaviour, studied by indentation measurements, of the nitride films was found to be ductile, where no sign of crack formation could be observed. This can be attributed to a metallic phase in the columnar boundaries caused by partial elemental segregation of mainly yttrium. Hence, films within in this material system, although the nanostructure is found to be relatively complex, show very promising mechanical properties and the structural complexity can be used as a guide for designing nitride materials that combine high hardness with ductility.

A wide range of applications benefit from transparent semiconducting oxides with tunable electronic properties, for example, electron transport layers in solar cell devices, where the electron affinity is a key parameter. Presently, a few different ternary oxides are used for this purpose, but the attainable electron affinity range is typically limited. In this study, the authors develop a low-temperature atomic layer deposition (ALD) process to grow amorphous Sn1-xGaxOy thin films from dimethylamino-metal complexes and water. This oxide is predicted to provide a wide selection of possible electron affinity values, from around 3 eV for pure Ga2O3 to 4.5 eV for pure SnO2. The ALD process is evaluated for deposition temperatures in the range of 105-195 degrees C by in situ quartz crystal microbalance and with ex situ film characterization. The growth exhibits an ideal-like behavior at 175 degrees C, where the film composition can be predicted by a simple rule of mixture. Depending on film composition, the growth per cycle varies in the range of 0.6-0.8 angstrom at this temperature. Furthermore, the film composition for a given process appears insensitive to the deposition temperature. From material characterization, it is shown that the deposited films are highly resistive, fully amorphous, and homogeneous, with moderate levels of impurities (carbon, nitrogen, and hydrogen). By tailoring the metal cation ratio in films grown at 175 degrees C, the optical bandgap can be varied in the range from 2.7 eV for SnO2 to above 4.2 eV for Ga2O3. The bandgap also varies significantly as a function of deposition temperature. This control of properties indicates that Sn1-xGaxOy is a promising candidate for an electron transport layer material in a wide electron affinity range. Published by the AVS.

Cu2ZnSnS4(CZTS) thin-film solar cell absorbers with different bandgaps can be produced by parameter variation during thermal treatments. Here, the effects of varied annealing time in a sulfur atmosphere and an ordering treatment of the absorber are compared. Chemical changes in the surface due to ordering are examined, and a downshift of the valence band edge is observed. With the goal to obtain different band alignments, these CZTS absorbers are combined with Zn1−xSnxOy (ZTO) or CdS buffer layers to produce complete devices. A high open circuit voltage of 809 mV is obtained for an ordered CZTS absorber with CdS buffer layer, while a 9.7% device is obtained utilizing a Cd free ZTO buffer layer. The best performing devices are produced with a very rapid 1 min sulfurization, resulting in very small grains.

Structural and electrochemical (EC) data of five different xLi 2 MnO 3 :(1-x)Li(Ni 1/3 Co 1/3 Mn 1/3 )O 2 cathode ceramics are presented. The aim of this work is to highlight the nano structure of this material class, next to the choice of right composition, as the key to anomalously high discharge capacities > 250 mAhg −1 . Therefore, the pristine nano composite structure of five different samples has been analyzed extensively by transition electron microscopy with respect to Li 2 MnO 3 domain size, shape and dispersion. DIFFaX simulations and Rietveld refinements to synchrotron X-Ray diffraction patterns are used to confirm the TEM results with a statistically reliable bulk method. The EC characteristics of the first cycle have been evaluated with respect to an EC active Li 2 MnO 3 component. By comparing the EC features of materials with x = 0.3, x = 0.5 and x = 0.7, it is evident that a composition of x = 0.5 is the most promising. To point out the impact of the pristine nano structure on the EC performance, three samples with x = 0.5 but considerable different nano domain arrangement, are compared. A strong influence has been found, with the highest discharge capacities for nano composites with small and evenly dispersed Li 2 MnO 3 domains.

SnP2O7 was prepared by a sol-gel route. The structural changes of tin pyrophosphate during the electrochemical lithiation were followed by using in situ XRD measurements that reveal the existence of a crystalline phase at the beginning of the discharge process. Nevertheless, it becomes amorphous after the full discharge as a result of a conversion reaction leading to the formation of LixSny alloys. The electrochemical tests show a high capacity with high retention upon cycling. To better understand the reaction mechanism of SnP2O7 with Li, several techniques were applied, such as ex situ(119)Sn Mossbauer and ex situ(7)Li and (31)P NMR spectroscopies with which we can follow the changes in the local environment of each element during cycling.

It is investigated if the performance of Cu(In,Ga)Se-2 (CIGSe) solar cells produced by co-evaporation can be improved by surface sulfurization in a postdeposition treatment. The expected benefit would be the formation of a sulfur/selenium gradient resulting in reduced interface recombination and increased open-circuit voltage. In the conditions used here it was, however, found that the reaction of the CIGSe layer in a sulfur environment results in the formation of a CuInS2 (CIS) surface phase containing no or very little selenium and gallium. At the same time, a significant pile up of gallium was observed at the CIGSe/CIS boundary. This surface structure was formed for a wide range of annealing conditions investigated in this paper. Increasing the temperature or extending the time of the dwell stage had a similar effect on the material. The gallium enrichment and CIS surface layer widens the surface bandgap and therefore increases the open-circuit voltage. At the same time, the fill factor is reduced, since the interface layer acts as an electron barrier. Due to the balance of these effects, the conversion efficiency could not be improved.

Ultrathin Co films deposited on SiO2 with conductivities exceeding that of Cu are demonstrated. Ionized deposition implemented by high-power impulse magnetron sputtering (HiPIMS) is shown to result in smooth films with large grains and low resistivities, namely, 14 mu Omega cm at a thickness of 40 nm, which is close to the bulk value of Co. Even at a thickness of only 6 nm, a resistivity of 35 mu Omega cm is obtained. The improved film quality is attributed to a higher nucleation density in the Co-ion dominated plasma in HiPIMS. In particular, the pulsed nature of the Co flux as well as shallow ion implantation of Co into SiO2 can increase the nucleation density. Adatom diffusion is further enhanced in the ionized process, resulting in a dense microstructure. These results are in contrast to Co deposited by conventional direct current magnetron sputtering where the conductivity is reduced due to smaller grains, voids, rougher interfaces, and Ar incorporation. The resistivity of the HiPIMS films is shown to be in accordance with models by Mayadas-Shatzkes and Sondheimer which consider grain-boundary and surface-scattering.

Multi-component nitride thin films in the Al-Cr-Nb-Y-Zr system with non-equimolar composition have been deposited by reactive dc magnetron sputtering. The substrate temperature and substrate bias h ...

Herein, the effect of the initial copper content of co‐evaporated Cu(In1−x,Gax)Se2 (CIGS) absorber films on the impact of a post‐annealing step in elemental sulfur atmosphere is studied. The Cu con ...

SnP2O7 was prepared by a sol-gel route. The structural changes of tin pyrophosphate during the electrochemical lithiation were followed by using in situ XRD measurements that reveal the existence of a crystalline phase at the beginning of the discharge process. Nevertheless, it becomes amorphous after the full discharge as a result of a conversion reaction leading to the formation of LixSny alloys. The electrochemical tests show a high capacity with high retention upon cycling. To better understand the reaction mechanism of SnP2O7 with Li, several techniques were applied, such as ex situ(119)Sn Mössbauer and ex situ(7)Li and (31)P NMR spectroscopies with which we can follow the changes in the local environment of each element during cycling.