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Tungsten disulfide (WS2) films were grown on c-plane sapphire in a cold-wall gas-source chemical vapor deposition system to ascertain the effect of the chalcogen precursor on the film growth and properties. Tungsten hexacarbonyl (W(CO)6) was used as the tungsten source, and hydrogen sulfide (H2S) and diethyl sulfide (DES-(C2H5)2S) were the chalcogen sources. The film deposition was studied at different temperatures and chalcogen-to-metal ratios to understand the effect of each chalcogen precursor on the film growth rate, thickness, coverage, photoluminescence, and stoichiometry. Larger lateral growth was observed in films grown with H2S than DES. The reduced lateral growth with DES can be attributed to carbon contamination, which also quenches the photoluminescence. Thermodynamic calculations agreed well with the experimental observations, suggesting formation of WS2 with both sulfur precursors and additional formation of carbon when deposition is done using DES.

Germanium telluride (GeTe) is a phase change material (PCM) that has gained recent attention because of its incorporation as an active material for radio frequency (RF) switches, as well as memory and novel optoelectronic devices. Considering PCM-based RF switches, parasitic resistances from Ohmic contacts can be a limiting factor in device performance. Reduction of the contact resistance ( Rc) is therefore critical for reducing the on-state resistance to meet the requirements of high-frequency RF applications. To engineer the Schottky barrier between the metal contact and GeTe, Sn was tested as an interesting candidate to alter the composition of the semiconductor near its surface, potentially forming a narrow band gap (0.2 eV) SnTe or a graded alloy with SnTe in GeTe. For this purpose, a novel contact stack of Sn/Fe/Au was employed and compared to a conventional Ti/Pt/Au stack. Two different premetallization surface treatments of HCl and deionized (DI) H2O were employed to make a Te-rich and Ge-rich interface, respectively. Contact resistance values were extracted using the refined transfer length method. The best results were obtained with DI H2O for the Sn-based contacts but HCl treatment for the Ti/Pt/Au contacts. The as-deposited contacts had the Rc (ρc) of 0.006 Ω·mm (8 × 10-9 Ω·cm2) for Sn/Fe/Au and 0.010 Ω·mm (3 × 10-8 Ω·cm2) for Ti/Pt/Au. However, the Sn/Fe/Au contacts were thermally stable, and their resistance decreased further to 0.004 Ω·mm (4 × 10-9 Ω·cm2) after annealing at 200 °C. In contrast, the contact resistance of the Ti/Pt/Au stack increased to 0.012 Ω·mm (4 × 10-8 Ω·cm2). Transmission electron microscopy was used to characterize the interfacial reactions between the metals and GeTe. It was found that formation of SnTe at the interface, in addition to Fe diffusion (doping) into GeTe, is likely responsible for the superior performance of Sn/Fe/Au contacts, resulting in one of the lowest reported contact resistances on GeTe.

Sulfidation of selected transition metal thin films (Mo, W, Re, Nb, Ta) was combined with thermodynamic calculations to study the synthesis of transition metal dichalcogenides (TMDCs) and understand variations among the metals as well as processing atmosphere. Metal seed layers were prepared by DC magnetron sputtering and sulfidized using sulfur vapor and H2S. Surface chemistry, structure, and morphology of the films were investigated using X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and atomic force microscopy (AFM), respectively. XPS analysis revealed that after treatment with sulfur vapor (p (S2) = 1–10 Torr), Mo, W, and Re films were transformed into MoS2, WS2, and ReS2, respectively. However, Nb and Ta films changed little, and Nb2O5 and Ta2O5 remained the predominant components. Alternatively, conversion of Nb and Ta films to NbS2 and TaS2 was feasible under H2S. Raman spectroscopy also revealed improved crystallinity for Mo, W, and Re sulfidized under H2S. Isobaric and isothermal stability diagrams were calculated to identify feasible processing conditions (sulfur partial pressure and temperatures) for the sulfidation of all of the metals, and our findings were in good agreement with the XPS and Raman results. It was found that for Mo, W, and Re a p (S2) = 10−5 bar is sufficient for the metals to be converted to sulfide phases at 750 °C. On the other hand, due to very high stability of Nb2O5 and Ta2O5, even at very low p (O2), a sulfur partial pressure of 103–104 bar is required to make NbS2 and TaS2, respectively. Nevertheless, thermodynamic calculations confirmed that Nb and Ta could be transformed to NbS2 and TaS2 under 760 Torr H2S. AFM analysis revealed very smooth films for MoS2, WS2, and NbS2 films, but dewetting of TaS2, and ribbons for ReS2. These results provide guidance for designing new processes for synthesizing 2D TMDCs.

Surfaces of polycrystalline α-GeTe films were studied by X-ray photoelectron spectroscopy (XPS) after different treatments in an effort to understand the effect of premetallization surface treatments on the resistance of Ni-based contacts to GeTe. UV–O3 is often used to remove organic contaminants after lithography and prior to metallization; therefore, UV–O3 treatment was used first for 10 min prior to ex situ treatments, which led to oxidation of both Ge and Te to GeOx (x < 2) and TeO2, respectively. Then the oxides were removed by deionized (DI) H2O, (NH4)2S, and HCl treatments. Additionally, in situ Ar+ ion etching was used to clean the GeTe surface without prior UV–O3 treatment. Ar+ ion etching, H2O, and (NH4)2S treatments create a surface richer in Ge compared to the HCl treatment, after which the surface is Te-rich. However, (NH4)2S also oxidizes Ge and gradually etches the GeTe film. All treated surfaces showed poor stability upon prolonged exposure to air, revealing that even (NH4)2S does not pas...

A novel method to prepare anodes for water electrolysis cells has been developed, which starts from layers of elemental manganese deposited by physical vapour deposition (PVD) on indium-doped tin oxide (ITO). Oxidation in dry air at 300 °C transforms this metallic Mn layer into a manganese(II)-rich MnOx coating (x = 1–1.3), which also contains a buried layer of an In–Sn alloy originating from reactions with the ITO support. The MnOx films are well connected to the underlying substrate and act as efficient catalysts for water-oxidation catalysis (WOC) at neutral pH. Detailed post-operando analyses using XRD, SEM, TEM and XAS revealed that the dense MnO/Mn3O4 film is virtually not affected by 2 h of electrochemical WOC at E ≈ +1.8 V vs. RHE, corresponding well to the observed good stability of catalytic currents, which is unusual for such thin layers of a MnOx catalyst. The current densities during electrolyses are so far low (i ≈ 50–100 μA cm−2 at pH 7), but optimization of the preparation process may allow for significant improvements. This new, rather easy, and adaptable preparation method for stable, thin-layer MnOx water-oxidation anodes could thus prove to be very useful for a variety of applications.

Calcium manganese oxide films were prepared by cosputter deposition from Mn and CaMnO3 targets and evaluated for their suitability as catalysts for the oxygen evolution reaction (OER). Scanning electron microscopy (SEM) revealed a compact morphology for the as-deposited films and the formation of nanorodlike features on the surfaces after annealing at 600 °C. X-ray-photoelectron-spectroscopy analysis showed that the surface oxidation state is close to +III (as in Mn2O3) for the as-deposited films and increases slightly to a mixture of III and IV after annealing occurs in dry air at 400–600 °C. Glancing-incidence X-ray diffraction (GIXRD) suggested that the CaMnxOy films are amorphous even when heated to 600 °C. However, transmission electron microscopy (TEM) showed that there is actually a polycrystalline component of the film, which best matches Mn3O4 (hausmannite with the average Mn oxidation state of ∼+2.7) but may have a slightly expanded unit cell because of the incorporation of Ca. Electrochemical a...

Molybdenum oxide (MoO3) and tungsten oxide (WO3) are considered as transparent back contacts for (Ag,Cu)(In,Ga)Se-2 thin film solar cells. MoO3 and WO3 films were deposited by reactive RF sputtering at room temperature in an Ar/O-2 ambient on (Ag,Cu)(In,Ga) Se-2 absorber layers with various Ga/(Ga + In) and Ag/(Ag + Cu) ratios. Determination of the valence band offsets by XPS showed that Ag-alloying of absorber layer changes the energy band alignment at the absorber-back contact interface with MoO3 and WO3 contacts. This produces a primary contact with lower valence band offset compared with Cu(In,Ga) Se-2 counterparts. The effect is less significant in films with Ga > 0.5 and Ag > 0.5 (corresponding to E-g > 1.4 eV) probably due to the different nature of ordered vacancy compounds forming near the surface phases.

Transparent back contacts can be used in thin film solar cells facilitating their potential application in tandem cells, bifacial devices and solar windows. In this study, tungsten oxide (WO3) thin films were deposited by Radio Frequency (RF) reactive sputtering in Ar + O2 ambient. The effects of post deposition anneals in air on the structural, optical, and surface properties of the deposited films were investigated using X-ray diffraction, UV/Vis/NIR spectrophotometry, and X-ray photoelectron spectroscopy, respectively. As-deposited films exhibited amorphous structures with no change after annealing at 300 °C. Samples annealed at 400 and 500 °C were crystallized and identified as pure monoclinic WO3 phase with (2 0 0) and (0 0 2) preferred orientation, respectively, determined by XRD fiber texture analysis. Scherrer analysis of excess broadening indicated a coherency length of 50 and 65 nm for the 400 and 500 °C annealed films, respectively. High resolution XPS studies showed the presence of W6+ (WO3) oxidation states at the surface of the as-deposited and the 300 °C annealed films. Annealing at 400–500 °C led to an oxygen deficient surface with a sub-stoichiometric WO3−x phase. UV/Vis/NIR spectrophotometry revealed that post processing decreased the optical bandgap from 3.30 eV for the as-deposited films to 3.17 eV for the 500 °C annealed films. Results are compared with MoO3 films deposited by a similar technique.

A backwall superstrate device structure that outperforms conventional substrate Cu(In,Ga)Se 2 devices for thin absorbers is described. The backwall structure of glass/ITO/MoO 3 /Cu(In,Ga)Se 2 /CdS/i-ZnO/Ag utilizes a MoO 3 transparent back contact to allow illumination of the device from the back. The device performance has been improved by modifying the Cu(In,Ga)Se 2 , including alloying with Ag to form (AgCu)(InGa)Se 2 absorber layers. In addition, sulfized back contacts including ITO-S and MoS 2 are compared. Interface properties are discussed based on the XPS analysis and thermodynamics of reactions.

(Ag w Cu 1 − w )(In 1 − x Ga x )Se 2 alloy absorber layers with w ≈ 0.8 and x ≈ 0.78 ratios were deposited using multi-source elemental evaporation and analyzed by glancing incidence X-ray diffraction, scanning electron microscopy combined with energy dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy. The effect of Rapid Thermal Processing (RTP) on the structure and composition of the near-surface layers was investigated. It was found that the RTP doesn't have a noticeable effect on the grain size and roughness of the film surface. On the other hand, additional reflections of the films with 0.5 ≤ Ga/(Ga + In) 0.5, due to an ordered defect phase which is confined to the near-surface region of the film, are completely diminished after RTP with excess Se present. X-ray photoelectron spectroscopy results show that RTP with excess Se present altered the distribution of elements, rendering the film surface less group I deficient after that process. Consequently, atomic ratios were changed from the composition of I 1 III 5 VI 8 compound to the composition close to that of I 1 III 3 VI 5 ordered defect phase. Additionally, the RTP treatment, especially with excess Se, significantly enhanced solar cell efficiency performance due to an improvement in the open circuit voltage.

MoO3 films with a high work function (5.5 eV), high transparency, and a wide bandgap (3.0 - 3.4 eV) are a potential candidate for the primary back contact of Cu(InGa)Se2 thin film solar cells. This may be advantageous to form ohmic contact in superstrate devices where the back contact will be deposited after the Cu(InGa)Se2 layer and MoSe2 layer doesn’t form during Cu(InGa)Se2 deposition. In addition, the MoO3 may be incorporated in a transparent back contact in tandem or bifacial cells. In this study, MoO3 films for use as a back contact for Cu(In,Ga)Se2 thin film solar cells were prepared by reactive rf sputtering with O2/(O2+Ar) = 35%. The effect of post processing on the structural properties of the deposited films were investigated using x-ray diffraction and scanning electron microscopy. Annealing resulted in crystallization of the films to the α-MoO3 phases at 400°C. Increasing the oxygen partial pressure had no significant effect on optical transmittance of the films, and bandgaps in the range of 2.6-2.9 eV and 3.1-3.4 eV were obtained for the as deposited and annealed films, respectively. Cu(In,Ga)Se2 thin film solar cells prepared using an as-deposited Mo-MoO3 back contact yielded an efficiency of >14% with VOC = 647 (mV), JSC = 28.4 (mA), and FF. = 78.1%. Cells with ITO-MoO3 back contact showed an efficiency of ∼12% with VOC = 642 (mV), JSC = 26.8 (mA), and FF. = 69.2%. The efficiency of cells with an annealed MoO3 back contact was limited to 4%, showing a blocking diode behavior in the forward bias J-V curve. This may be caused by the presence of a barrier between the valence bands of the Cu(In,Ga)Se2 and MoO3, due to the higher bandgap of the annealed MoO3 films. SEM cross section studies showed uniform coverage of the as-deposited MoO3 layer and formation of voids for the annealed MoO3 film. Structural orientation of the Cu(In,Ga)Se2 absorber layer was also altered by the MoO3 film and less-oriented films were observed for either cases.

(Ag,Cu)(In,Ga)Se2 alloy absorber layers with various Ga/(Ga+In) and Ag/(Ag+Cu) ratios were deposited using multisource elemental evaporation and analyzed by glancing incidence X-ray diffraction and energy dispersive X-ray spectroscopy. All films exhibit chalcopyrite reflections in the X-ray diffraction pattern and films with 0.5 ≤ Ga/(Ga+In) ; 0.5 have additional reflections consistent with an ordered defect phase which is limited to the near-surface region of the film. X-ray photoelectron spectroscopy measurements show that all films studied have low (Ag+Cu)/Se and (Ag+Cu)/(Ga+In) ratios near the surface relative to the bulk composition, consistent with an ordered defect compound identified as (Ag,Cu)(In,Ga)5Se8. Additionally, the near-surface region of (Ag,Cu)(In,Ga)Se2 films contains a higher Ag/(Ag+Cu) ratio than the bulk and the Ag(In,Ga)Se2 film contains excess Ag near the surface.

The effect of particle size, lattice strain and crystallite size on the hydrogen desorption properties of nanocrystalline magnesium hydride powder was investigated. Commercial MgH2 powder was milled in a Spex 8000M up to 16 h and its structural evolution and desorption characteristics at different time intervals were examined using various analytical techniques. At the early stage of milling, the formation of metastable γ-MgH2 phase was noticed. While the crystallite size gradually decreased to 12 nm with increasing the milling time, the accumulated lattice strain gained a maximum value of 0·9% after 4 h milling. The highest drop in the desorption temperature (∼100°C) was attained at the peak strain with the average grain size of 20 nm. The particle size of MgH2 varied in the range of 20–50 μm without profound effect of the desorption properties.

Nanostructured MgH 2 -Ni/Nb 2 O 5 nanocomposite was synthesized by high-energymechanical alloying. The effect of MgH 2 structure, i.e. crystallite size and lattice strain, andthe presence of 0.5 mol% Ni and Nb 2 O 5 on the hydrogen-desorption kinetics was investi-gated. It is shown that the dehydrogenation temperature of MgH 2 decreases from 426 Cto327 C after 4 h mechanical alloying. Here, the average crystallite size and accumulatedlattice strain are 20 nm and 0.9%, respectively. Further improvement in the hydrogendesorption is attained in the presence of Ni and Nb 2 O 5 , i.e. the dehydrogenation temper-ature of MgH 2 /Ni and MgH 2 /Nb 2 O 5 is measured to be 230 C and 220 C, respectively.Meanwhile, the dehydrogenation starts at 200 C in MgH 2 –Ni/Nb 2 O 5 system, revealingsynergetic effect of Ni and Nb 2 O 5 . The mechanism of the catalytic effect is presented.a 2009 Professor T. Nejat Veziroglu. Published by Elsevier Ltd. All rights reserved. 1. Introduction Due to a series of special characteristics of hydrogen storagein metals such as high capacity, light weight, low environ-mental impact, low cost and high natural abundance, manymetal–hydrogen systems have been studied for mobilehydrogen storage application. Critical reviews on metalhydridesforsolidhydrogenstoragecanbe foundinreferences[1,2]. Among various metals, magnesium is considered as oneof the most promising candidate, mainly due to its highstorage capacity (7.6 wt% in MgH

Work carried out in Iran seems to indicate that nanostructured materials may hold a key to fuel storage in a future hydrogen economy…

Alumina dispersion-strengthened copper was produced by an internal oxidation process and hot powder extrusion method. The microstructure of the composite consisted of fine-grained region with an average grain size of 1.1 ± 0.1 μm, coarse-grained region with an average grain size of 5.6 ± 0.1 μm, nanometric alumina particles (γ-type) with an average diameter of 30 nm, and coarse alumina particles (350 nm) at the boundaries of the large grains. The tensile and fatigue fracture of the composite was studied in the extruded condition and after 11% cold working. The low cycle fatigue behavior was examined in strain control mode ( ɛ = 0.5%) under fully reverse tension-compression cycle at 1 Hz up to 1000 cycles. High cycle fatigue was conducted using rotate-bending test up to 10 7 cycles. To reveal the role of alumina particles and the bimodal grain size structure, the tensile and fatigue fracture of extruded copper with normal grain structure was examined. It is shown that: (1) the strength and hardness of the nanocomposite are about three folders of the magnitude of the unreinforced copper; (2) fatigue strength of the nanocomposite at 10 7 cycles is about 40% higher than that of the copper; (3) both extruded copper and the nanocomposite exhibit cyclic hardening during the early stages of low cycle fatigue test which eventually approaches to a saturation stress; (4) dimple-type fracture is realized on the fracture surface of the tensile tests where dimple size decreases in the presence of the alumina particles; (5) the fatigue fracture mechanism is locally ductile deformation, microscopic void formation and coalescence.

Low-resistance and thermally stable Ohmic contacts are essential for radio frequency switches based on the unique phase change properties of GeTe. Herein, Mo-based Ohmic contacts to p-type GeTe are reported, including the effect of pre-metallization surface preparation and annealing on Mo/Ti/Pt/Au contacts. In-situ Ar+ plasma treatment resulted in a very low contact resistance of 0.004 ± 0.002 Ω mm (5 ± 3 × 10−9 Ω cm2), which could not be achieved using ex-situ surface treatments, highlighting the need for oxide-free interfaces to obtain very low contact resistance using Mo-based contacts. Experiments aimed at creating a more Ge- or Te-rich interface yielded higher contact resistances in both cases. The contact resistance increased for short-term annealing (30 min) above 200 °C and for long-term annealing (1 week) at 200 °C. No solid-state reaction between Mo and GeTe was observed using transmission electron microscopy with energy dispersive spectroscopy. However, Te migrated from GeTe after annealing at ...

Understanding oxidation of layered chalcogenide semiconductors is important for device processing, as oxidation can be both an intentional and unintentional result of processing steps. Here, the authors investigate chemical and morphological changes in mechanically exfoliated few-layer MoS2 in oxidizing and inert environments using different microscopies (optical, scanning electron, and atomic force) and spectroscopy (Raman, x-ray photoelectron, and Auger electron) techniques. The environments studied were oxygen, oxygen and water vapor, argon, argon and water vapor, and ultraviolet-generated ozone at temperatures from 25 to 550 °C. Oxidation at low temperatures resulted in the formation of a condensed molybdenum oxide phase and sulfur trioxide gas. At sufficiently elevated temperatures, all the products of oxidation volatilize, resulting in a vapor-phase etch. The kinetics of oxidation and etching depended upon the annealing gas, temperature, time, and the number of layers of MoS2. Conditions can be sele...

The addition of Ag to Cu-Ga-In precursors for reaction to form (AgCu)(InGa)Se 2 has shown benefits including improved adhesion, greater process tolerance and potential for improved device performance. In this study, sequential layer sputtering of Ag-Ga, Cu-Ga, and In targets with different layer sequences is characterized. Ag/(Cu+Ag) and (Ag+Cu)/(Ga+In) ratios were fixed at 0.25 and 0.9, respectively. The most uniform morphology is achieved in Ag-Ga/Cu-In-Ga co-sputtered precursors. No metallic In phase was found in this case, and only the Ag(In,Ga) 2 phase was detected. Varying the sputtering sequence for stacked layers results in dissimilar morphologies and structural phases. X-ray diffraction (XRD) analyses reveal that the Ag-Ga and In layers intermix when they are in contact, forming a Ag(In,Ga) 2 phase. Incorporating a Cu-Ga layer between the Ag-Ga and In layers prevents the formation of such a phase. Finally, solar cells fabricated from the Cu-Ga/In/Ag-Ga metal precursor sequence showed the highest overall performance.

Molybdenum oxide (MoO3) is considered as a possible primary back contact for Cu(InGa)Se2 thin film solar cells for its potential as a transparent back contact for superstrate and bifacial devices. MoO3 films were deposited on Mo or ITO-coated soda lime glass substrates by reactive rf sputtering in an ambient of Ar + O2 with O2/(O2 + Ar) = 35% on which Cu(In0.7Ga0.3)Se2 alloy absorber layers were deposited using multi-source elemental evaporation. Scanning Electron Microscopy studies showed uniform coverage of the as-deposited MoO3 layer and good adhesion was obtained in all cases. X-ray Photoelectron Spectroscopy depth profile analysis showed that MoSe2 was not formed at the Cu(InGa)Se2 interface with either the Mo-MoO3 or ITO-MoO3 back contacts. Determination of the valence band offsets showed that the MoO3 layer at the interface changes the energy band alignment with Cu(InGa)Se2, producing a primary contact with lower valence band offset than ITO. Cu(In,Ga)Se2 thin film solar cells prepared using an as-deposited Mo-MoO3 back contact yielded a best conversion efficiency of 14%, with VOC = 647 mV, JSC = 28.4 mA/cm2, and FF = 78.1%. Cells with ITO-MoO3 back contact showed a best efficiency of 12%, with VOC = 642 mV, JSC = 26.8 mA/cm2, and FF = 69.2%.

A backwall superstrate device structure that outperforms conventional substrate Cu(In,Ga)Se2 devices for thin absorbers is demonstrated. The backwall structure (glass/In2O3-SnO2/MoO3-x/Cu(In,Ga)Se2/CdS/i-ZnO/Ag) utilizes a MoO3−x transparent back contact to allow illumination of the device from the back. In combination with a silver front reflector this cell structure is tailored to enhance performance of devices with submicron thick absorbers. It was found that devices with the backwall configuration outperform substrate devices in the absorber thickness range dCIGS = 0.1-0.5 μm. The advantage of the backwall configuration is mainly through superior JSC, achieved by application of a front reflector and elimination of parasitic absorption in CdS.

Molybdenum oxide (MoO3) thin films were prepared via Radio Frequency (RF) sputtering at different ambient composition and post-deposition annealing. The effects on the structural, optical, and surface properties of the deposited films were investigated. The ambient oxygen concentration O2/(O2 + Ar) was varied from 10% to 100% at 10 mTorr. Post deposition anneals were performed in Ar at 300–500 °C. The films were analyzed using glancing incidence x-ray diffraction (GIXRD), UV/Vis/NIR spectrophotometry, and x-ray photoelectron spectroscopy (XPS). As-deposited films have amorphous structures, independent of the oxygen partial pressure. Annealing at 300 °C in air resulted in crystallization of the molybdenum oxide films to the monoclinic β-MoO3 phase. Samples annealed at 400 and 500 °C were identified as pure orthorhombic α-MoO3 phase with (020) preferred orientation. High resolution XPS studies showed the presence of Mo6+ (MoO3) and Mo5+ (Mo4O11) oxidation states at the surface of as deposited and low temper...