Lead-free perovskite layers may provide a good alternative to the commonly used lead-halide-based perovskite absorber layers in photovoltaics. Energy level alignment of the active semiconductor with contact layers is a key factor in device performance. Kelvin probe force microscopy was used during vapor deposition of C60 onto formamidinium tin iodide to investigate contact formation with detailed local resolution of these materials that are significant for photovoltaic cells. Significant differences dependent on the growth rate of C60 were detected. Sufficiently high deposition rates were essential to reach compact C60 films needed for good contact. A space charge layer larger than 90 nm within the C60 layer was established without indication of interfacial dipoles. The present analysis gives a clear indication of a well-functioning contact of fullerenes to formamidinium tin iodide that is suitable for the use in photovoltaic devices provided that thin compact fullerene films are formed.

The energy level alignment that occurs at the interfaces in planar-hetero structured perovskite photovoltaic devices strongly influences the charge transport across the interface, and thus plays a crucial role in overall device performance. To directly observe the energy level alignment requires pristine homogeneous surfaces that are free of contamination including adventitious carbon. Co-evaporation offers the ability to grow perovskite thin films in-situ, and the method involves thermally evaporating the perovskite precursors such as PbI2 and CH3NH3I. Early reports have shown that the perovskite film formation and stoichiometry are problematic at ultralow coverages. In particular, it was reported that there was excessive PbI2 and a deficiency in CH3NH3I. Using photoemission spectroscopy, we investigated the perovskite precursor PbI2 on gold and highly oriented pyrolytic graphite (HOPG) surfaces. Results show that the nature of the surface and the deposition conditions can strongly influence the film formation. Excessive iodine observed in the initial evaporation stages appears to be substrate dependent, and this may influence the overall energy level alignment.

Highly oriented VO2 (M1) thin films are difficult to produce using non-crystalline substrates. For example, to produce such films on glass has required post-annealing or the use of a ZnO transparent layer. Here, we overcome this challenge and report highly oriented VO2 (M1) in the (100) plane directly on the glass substrate by pulsed laser deposition (PLD). We study the influence of the laser wavelengths (1064, 532, 355 and 266 nm) on the orientation of VO2 (M1) deposited on Corning glass. We find that the laser wavelength of 532 nm leads the most highly a-axis textured VO2 (M1) demonstrating the highest reversible metal-to-insulator at about 62 °C with a lowest hysteresis width of approximately 9 °C. One of the conditions is to select the green 532 nm wavelength laser in PLD as this particular laser wavelength also produces films with highest roughness value (of more than 60 nm) when compared to other wavelengths which produce films of roughness values less than 40 nm.

The phase evolution of reactive radio frequency (RF) magnetron sputtered Cr0.28Zr0.10O0.61 coatings has been studied by in situ synchrotron X-ray diffraction during annealing under air atmosphere and vacuum. The annealing in vacuum shows t-ZrO2 formation starting at ∼750–800 °C, followed by decomposition of the α-Cr2O3 structure in conjunction with bcc-Cr formation, starting at ∼950 °C. The resulting coating after annealing to 1140 °C is a mixture of t-ZrO2, m-ZrO2, and bcc-Cr. The air-annealed sample shows t-ZrO2 formation starting at ∼750 °C. The resulting coating after annealing to 975 °C is a mixture of t-ZrO2 and α-Cr2O3 (with dissolved Zr). The microstructure coarsened slightly during annealing, but the mechanical properties are maintained, with no detectable bcc-Cr formation. A larger t-ZrO2 fraction compared with α-Cr2O3 is observed in the vacuum-annealed coating compared with the air-annealed coating at 975 °C. The results indicate that the studied pseudo-binary oxide is more stable in air atmosphere than in vacuum.

In this paper, the effect of TiN metal gate deposition conditions on the crystal orientation and size of TiN grains has been investigated. We have focused on process conditions that reduce the grain size or provide a unique orientation, which might impact CMOS threshold voltage variability. We have shown that the grain size can be significantly modulated by the RF power and pressure, with grain size as low as 5.2 nm. Further it has been shown that for a few optimized conditions, a unique grain orientation can be obtained. Then, the impact of these process conditions on TiN gate mechanical stress and electrical properties has been investigated. Mechanical stress and sheet resistance are modulated by pressure and RF power and have been correlated to the deposition rate and TiN grain size respectively. The effect of TiN process conditions on MOS capacitor effective workfunction (WFeff) has been investigated, and the trend is opposite to the expected modulation of the intrinsic TiN metal gate workfunction with grain orientation. On the contrary, WFeff variation is well correlated to the Ti/N ratio, suggesting an effect related to dipole at the SiO2/high-k interface.

The electrical properties of Radio Frequency Sputtered NiFeO and NiO films deposited on n and p-type Silicon is investigated for two different oxygen flows. Rectifying properties for Ni0.8Fe0.2O1+ α on n-Si showed Iforward/Ireverse >10,000 for α>0 and Iforward/Ireverse >50 for α<0. Both types of devices have opposite forward biases. Results suggest that NiFeO sputtered at high oxygen flow is p-type. For NiO and NiFeO on p-Si no strong rectifying properties were observed. The specific contact resistivity of Pt/Ni0.9Fe0.1O1+ α (α>0) was estimated from the difference between the two and four-point probe resistances (0.0007 ± 0.0003 Ω cm2). Using density functional theory calculations, density of state and charge density plots were obtained for systems modelled after experiment, showing that states introduced by O vacancies in NiFeO are localized and prefer locations near Ni explaining the observed hysteresis effects in the IV curves of devices sputtered at low oxygen flow.

The patterning of gold and silver micro and nanostructures on rigid and flexible substrates is investigated by microcontact printed thiol based self-assembled monolayers. The aspect ratio of the noble metal micro and nanostructures is determined by interaction of the -SH head group of the CH3(CH2)19SH molecules and the surface of the noble metal. Silver micro and nanostructures with >10 times higher aspect ratios can be realized in comparison to commonly realized gold micro and nanostructures. The printing process is described, and the etching process is characterized in terms of etching window and etching selectivity. Potential electronic and photonic applications of the micro and nanostructures are discussed taking the boundary conditions of the printing process and the selected material system into consideration.

Selective solar absorbers comprised of plasmonic materials offer great flexibility in design along with a highly promising optical performance. However, the nanopattern generation, typically done with electron beam writing, is a very time-intensive process. In this work, we present a fast, scalable, and flexible method for the fabrication of plasmonic materials by the combination of a deposition mask prepared by nanoimprint lithography and thin film deposition by magnetron sputtering. The fabrication process was first performed on silicon wafer substrates using AFM and SEM measurements to calibrate the deposition time, determine maximal deposition height, and characterize samples. Afterwards, the process was transferred to polished Inconel NiCr-alloy substrates used in high temperature solar absorbers. To investigate the adhesion properties of the nanostructure on the substrate, two different deposition methods were investigated: DC magnetron sputtering and High Power Impulse Magnetron Sputtering (HiPIMS).

Optical isolators, devices that only allow unidirectional light propagation, constitute an essential building block for photonic integrated circuits. For near-infrared communications wavelengths, most current isolator designs rely on the incorporation of magneto-optical (MO) materials to break time-reversal symmetry, such as iron garnets or magnetically substituted semiconductors. MO garnets form the backbone of traditional bulk isolators, but suffer from large lattice and thermal mismatch with common semiconductor substrates, which has significantly impeded their integration into on-chip optical isolators. Materials innovations over the past few years have overcome these barriers and enabled monolithic deposition of MO oxide thin films on silicon using techniques such as pulsed laser deposition and magnetron sputtering. On-chip optical isolator devices with polarization diversity in the telecommunication band have been demonstrated based on these materials. This article reviews the latest technological breakthroughs in MO oxide material growth as well as device design and integration strategies toward practical implementation of on-chip optical isolation.

Typical electron transport (2,2′,2″-(1,3,5-benzinetriyl)-tris(1-phenyl-1-H-benzimidazole) (TPBi)) and injection (Cs2CO3) materials are successfully replaced by zirconium tetrakis(8-hydroxyquinolinolate) (Zrq4) and lithium 2-((o-tolylimino)methyl)-phenolate (EI-111) in simplified OLED (organic light-emitting diodes) processed by organic vapor phase deposition (OVPD). The performance of combining Zrq4 and EI-111 is analyzed in unipolar devices and compared to devices with configurations of Zrq4/Cs2CO3, TPBi/EI-111 and TPBi/Cs2CO3. Current density-voltage (J-V) measurements are performed and correlated to different carrier injection and transport properties. The investigated material combinations are implemented in the simplified OLED structures and compared to each other. To account for the high HOMO level of Zrq4, 5 nm of TPBi are added to confine holes and excitons in the emissive layer (EML) and to improve device performance. After tailoring the organic stack for OLED with Zrq4, a remarkable boost in device efficiency is observed. The luminous efficacy increased from 3.0 to 21.9 lm/W and the EQE from 2.1 to 11.0 % for a device with Zrq4/EI-111. Furthermore, OLED having Zrq4/Cs2CO3 show an even greater enhancement to 26.3 lm/W and 11.7 %.

Thermal evaporation is a simple method to fabricate a BaSi2 film, a new solar cell material consisting of earth-abundant elements. In this study, we optimized the evaporation process and suppressed near-interface oxidation in evaporated BaSi2 films on Si(100) substrates, which has been detected in previous studies. Composition depth profiles determined by Auger electron spectroscopy show the decrease of oxygen concentration near the interface to the background level by optimizing the source pre-melting condition. By reducing oxygen concentration, the BaSi2 film becomes more preferentially oriented toward [100] as long as the deposition rate is not changed, as evidenced by X-ray diffraction. It is also shown that the rectification behavior of n-BaSi2/p+-Si diodes improves by suppressing the near-interface oxidation.

Bismuth triiodide (BiI3) is a potential candidate for application in solar cell due to its good optoelectronic properties and because it is free of toxic elements. It can be used as the absorber material in solar cells or converted into the perovskite-like material MA3Bi2I9, suitable also for photovoltaic applications. Bismuth triiodide has been prepared by physical vapour transport (PVT) and by solution process through spin coating. In this work we present optical and structural/topological properties of BiI3 deposited by thermal evaporation under high vacuum. The films are slightly tensile, polycrystalline, homogenously distributed and with good adherence on several substrates, with an indirect bandgap of 1.81 eV, index of refraction of 3.3 (630 nm), photoluminescence centered at 1.74 eV and a Raman peak at 118cm-1 associated with the Ag mode.

Ternary sulfides and selenides in the distorted-perovskite structure (“chalcogenide perovskites”) are predicted by theory to be semiconductors with band gap in the visible-to-infrared and may be useful for optical, electronic, and energy conversion technologies. Density functional theory can be used in combination with computational thermodynamics to predict the pressure-temperature phase diagrams for chalcogenide perovskites. We report results using the Strongly Constrained and Appropriately Normed (SCAN) and the rVV10 density functionals, and compare to previously-published results using the PBEsol functional. We highlight the windows of thermodynamic equilibrium between solid chalcogenide perovskites and the vapor phase at high temperature and very low pressure. These phase diagrams can guide adsorption-limited growth of ternary chalcogenides by molecular beam epitaxy (MBE).

ZnO1-xTex thin films were deposited by DC reactive magnetron co-sputtering using pure Zn and Te targets. Te atomic concentration in the films ranged from x=0 to 0.33 by adjusting the applied power on the targets or varying the cathode-substrate distance. Chemical composition and crystalline structure were determined by RBS experiments and X-ray Diffraction, respectively. For low Te atomic concentrations (x≤0.04) the deposited ZnO1-xTex films showed a crystalline structure ZnO wurtzite type however, for increasing Te concentration significant broadening and decreasing intensities of the main peaks belonging to pure ZnO films together with some weak peaks characteristic of crystalline Trizinc Tellurate salt have appeared. For the highest x values some non-identified weak peaks beside to some others peaks corresponding to the crystalline phases mentioned above as well as, a broad band probably associated to amorphous TeO2 phase were observed. A preliminary optical characterization of the samples point out the possibility of different electronic transitions within the ZnO band gap.

Chromium doped II-VI semiconductors (such as ZnSe and ZnS) feature broad mid-IR emission in the 2-3 μm spectral range due to intershell transitions of the Cr2+ ions. These materials show much promise for development of a tunable, electrically-pumped, mid-IR laser source. For integration into a mid-IR active multilayered structure, the ternary alloy ZnSxSe1-x is an attractive waveguiding material due to its lattice-matching ability and lower index of refraction with respect to the Cr2+:ZnSe active material. Epitaxial growth of each layer is desired to achieve the electronic and optical properties necessary for successful integration into a lasing device, so a study was conducted on the effects of sulfur content and growth temperature on the crystal quality of the resulting thin films. Several films of ZnSxSe1-x were deposited by pulsed laser deposition (PLD) using a 248 nm KrF excimer laser source at varying growth temperatures and with various compositional parameters onto (100) GaAs substrates. The samples were analyzed via x-ray diffraction (XRD) and energy dispersive x-rays (EDX) to investigate the crystal quality and elemental content of the films for device integration. Film-substrate epitaxy was achieved and upper bounds to the defect density were calculated for several regimes of compositional parameter and growth temperature. From all samples produced, the lowest defect density of 2.2 x 1010 cm-2 was observed for the x=0.06 film grown at 450°C, while the lowest lattice mismatch between the substrate and epilayer of 0.059% was observed for the x=0.02 film grown at 450°C.

The radiation environment of space poses a challenge for electronic systems, in particular flash memory, which contains multiple radiation-sensitive parts. Resistive memory (RRAM) devices have the potential to replace flash memory, functioning as an inherently radiation resistant memory device. Several studies indicate significant radiation resistance in RRAM devices to a broad range of radiation types and doses. In this study, we focus on the effect of displacement damage on tantalum oxide-based RRAM devices, as this form of damage is likely a worst-case scenario. An Ar+ (170 keV) ion beam was used to minimize any contribution from ionization damage, maximizing the effect of displacement damage. Fluence levels were chosen to generate enough oxygen vacancies such that devices in the high resistance state (HRS) would likely switch to the low resistance state (LRS). More than half of devices tested at the highest fluence level (1.43E13 ions/cm2) switched from HRS to LRS. The devices were then switched for 50 set/reset cycles, after which the radiation-induced resistance shift disappeared. These results suggest that device switching may mitigate radiation damage by accelerating oxygen vacancy-interstitial recombination.

Carbon films were energetically deposited onto copper foil using the physical vapor deposition technique filtered cathodic vacuum arc. Raman spectroscopy and x-ray absorption spectroscopy showed that high quality graphene films of uniform thickness can be deposited onto copper foil at temperatures of 850 °C. The films can be prepared at high deposition rates (∼1 nm/min) and were comparable to graphene films grown at 1050 °C using chemical vapor deposition. This lower growth temperature was made possible by the energetic carbon flux which assisted the arrangement of carbon atoms into graphene layers on the Cu growth surface. Floating substrate potential was found to produce the highest quality graphene and the addition of hydrogen gas during film growth resulted in more defective films.

Applications such as batteries, fuel cells, solar cells, and sensors, can benefit from high surface-to-volume ratio core/shell arrays of nanorods. The fabrication of the conformal shell layers on nanorod arrays has been a formidable task. In order to assess the deposition conditions for the production of conformal shell coatings by physical vapor deposition (PVD) techniques, we employed Monte Carlo (MC) simulations that involved shell depositions under different flux distributions and angles on arrays of rods. We investigated the conformality of PVD shell layers on nanorod arrays of different aspect ratios, which is defined to be the ratio of rod height to the gaps between nearest-neighbor rods. MC simulated core/shell structures were analyzed for the thickness uniformity of the shell layer across the sidewalls of rods. Our results show that a small angle deposition approach involving a uniform oblique flux (U-SAD) with a small incidence angle ≤ 30o can generate a fairly conformal shell coating around small aspect-ratio rods. However, normal angle deposition with an angular flux distribution (A-NAD) achieves superior conformality both on small and high-aspect-ratio structures compared to U-SAD, conventional uniform normal angle deposition (U-NAD), and SAD with an angular flux distribution (A-SAD). A-NAD can be realized in a PVD system such as by high pressure sputter deposition; while U-SAD can be achieved in thermal evaporation system with a small angle incident flux. In addition, U-NAD and A-SAD can correspond to film growth by normal incidence thermal evaporation and SAD-high pressure sputter deposition, respectively.

Photolithographically patterned thin films often possess unwanted spikes along the side edges. These spikes are a significant issue for the development of spinvalve memory, tunnel junction based molecular devices, and micro-electromechanical systems. Here, we report a very simple, economical, and fast way of creating an optimum photoresist profile for the production of spike-free patterned films. This approach is based on performing a soaking step in the positive-photoresist’s developer solution before the UV exposure. However, the success of this method depends on multiple photolithography factors: photoresist thickness (governed by spin speed), soft baking temperature, soaking time in developer, and exposure time. In this paper, we report our systematic experiments to study the effect of these factors by following the L9 experimental scheme of the Taguchi Design of experiment (TDOE) approach. The L9 experiment scheme effectively accommodated the study of four photolithography factors, each with three levels. After performing photolithography as per L9 TDOE scheme, we sputter deposited 20 nm Tantalum to check the side edge profile of the patterned film by atomic force microscope (AFM). We measured the heights of the spikes along the thin film edges. We utilized spike height as the desired property and chose “smaller the better” criteria for the TDOE analysis. TDOE enabled us to understand the relative importance of the parameters, relationship among the parameters, and impact of the various levels of the parameters on the thin film edge profile. TDOE analysis yielded an optimum combination of levels for the four photolithography factors. The optimum combination of photolithography factors included spin speed 4000 rpm, 100 °C soft baking temperature, 60 sec pre-soaking in the developer solution, and 15 sec UV exposure. We validated the TDOE by AFM and observed spike free patterned films. We also made complete tunnel junction devices by utilizing the optimized photolithography factors for the bottom electrode and obtained excellent tunneling behavior. In summary, this study provides a very simple, economical, and fast photolithography approach for creating optimum photoresist profile for the micro-nano scale devices and electromechanical structures.

Growth of unexpected phases from a composite target of BiFeO3:BiMnO3 and/or BiFeO3:BiCrO3 has been explored using pulsed laser deposition. The Bi2FeMnO6 tetragonal phase can be grown directly on SrTiO3 (STO) substrate, while two phases (S1 and S2) were found to grow on LaAlO3 (LAO) substrates with narrow growth windows. However, introducing a thin CeO2 buffer layer effectively broadens the growth window for the pure S1 phase, regardless of the substrate. Moreover, we discovered two new phases (X1 and X2) when growing on STO substrates using a BiFeO3:BiCrO3 target. Pure X2 phase can be obtained on CeO2-buffered STO and LAO substrates. This work demonstrates that some unexpected phases can be stabilized in a thin film form by using composite perovskite BiRO3 (R = Cr, Mn, Fe, Co, Ni) targets. Furthermore, it also indicates that CeO2 can serve as a general template for the growth of bismuth compounds with potential room-temperature multiferroicity.