Flexible hardware concept of pulsed laser deposition for large areas and combinatorial composition spreads.

Pulsed laser deposition (PLD) is one of the most flexible physical growth techniques for thin films of functional materials at the research and demonstrator level. We describe here a relatively simple and reliable concept of the PLD hardware that allows both deposition on large areas up to 4 in. diameter and deposition of tailored lateral and vertical composition spreads without time-consuming hardware changes. Different PLD approaches have been implemented in various chambers via specific and correlated computer-controlled movements of the target, substrate, and masks in conjunction with an appropriate target phase composition. The design of the chambers benefits from our long-term experience to find the most reliable solutions for the critical mechanical and high-temperature parts.

Growth of κ-([Al,In]xGa1-x)2O3 Quantum Wells and Their Potential for Quantum-Well Infrared Photodetectors.

The wide band gap semiconductor κ-Ga2O3 and its aluminum and indium alloys have been proposed as promising materials for many applications. One of them is the use of inter-sub-band transitions in quantum-well (QW) systems for infrared detectors. Our simulations show that the detection wavelength range of nowadays state of the art GaAs/AlxGa1-xAs quantum-well infrared photodetectors (QWIPs) could be substantially excelled with about 1-100 µm using κ-([Al,In]xGa1-x)2O3, while at the same time being transparent to visible light and therefore insensitive to photon noise due to its wide band gap, demonstrating the application potential of this material system. Our simulations further show that the QWIPs efficiency critically depends on the QW thickness, making a precise control over the thickness during growth and a reliable thickness determination essential. We demonstrate that pulsed laser deposition yields the needed accuracy, by analyzing a series of (InxGa1-x)2O3 QWs with (AlyGa1-y)2O3 barriers with high-resolution X-ray diffraction, X-ray photoelectron spectroscopy (XPS) depth profiling, and transmission electron microscopy (TEM). While the superlattice fringes of high-resolution X-ray diffraction only yield an average combined thickness of the QWs and the barrier and X-ray spectroscopy depth profiling requires elaborated modeling of the XPS signal to accurately determine the thickness of such QWs, TEM is the method of choice when it comes to the determination of QW thicknesses.

Amorphous Transparent Cu(S,I) Thin Films with Very High Hole Conductivity.

Amorphous transparent conductors (a-TCs) are key materials for flexible and transparent electronics but still suffer from poor p-type conductivity. By developing an amorphous Cu(S,I) material system, record high hole conductivities of 103-104 S cm-1 have been achieved in p-type a-TCs. These high conductivities are comparable with commercial n-type TCs made of indium tin oxide and are 100 times greater than any previously reported p-type a-TCs. Responsible for the high hole conduction is the overlap of large p-orbitals of I- and S2- anions, which provide a hole transport pathway insensitive to structural disorder. In addition, the bandgap of amorphous Cu(S,I) can be modulated from 2.6 to 2.9 eV by increasing the iodine content. These unique properties demonstrate that the Cu(S,I) system holds great potential as a promising p-type amorphous transparent electrode material for optoelectronics.

Suppression of Rotational Domains of CuI Employing Sodium Halide Buffer Layers.

The occurrence of rotational domains is a well-known issue for copper iodide (CuI) that naturally occurs for growth on popular substrates like sapphire. However, this has detrimental effects on the thin film quality like increasing surface roughness or deteriorated transport characteristics due to grain boundary scattering. Utilizing pulsed laser deposition and the in situ growth of sodium chloride (NaCl) and sodium bromide (NaBr) template layers, studies were performed on their potential on suppressing the formation of rotational domains of CuI on c-plane sapphire and SrF2(111) substrates. Corresponding samples were investigated concerning their epitaxial properties and further characterized regarding (volume) crystalline, morphological, and electrical properties. Particularly for NaBr template layers, fully single-crystalline growth of CuI thin films was obtained and resulted in significantly reduced surface roughness of the CuI layer.

Mid- and far-infrared localized surface plasmon resonances in chalcogen-hyperdoped silicon.

Plasmonic sensing in the infrared region employs the direct interaction of the vibrational fingerprints of molecules with the plasmonic resonances, creating surface-enhanced sensing platforms that are superior to traditional spectroscopy. However, the standard noble metals used for plasmonic resonances suffer from high radiative losses as well as fabrication challenges, such as tuning the spectral resonance positions into mid- to far-infrared regions, and the compatibility issue with the existing complementary metal-oxide-semiconductor (CMOS) manufacturing platform. Here, we demonstrate the occurrence of mid-infrared localized surface plasmon resonances (LSPR) in thin Si films hyperdoped with the known deep-level impurity tellurium. We show that the mid-infrared LSPR can be further enhanced and spectrally extended to the far-infrared range by fabricating two-dimensional arrays of micrometer-sized antennas in a Te-hyperdoped Si chip. Since Te-hyperdoped Si can also work as an infrared photodetector, we believe that our results will unlock the route toward the direct integration of plasmonic sensors with the on-chip CMOS platform, greatly advancing the possibility of mass manufacturing of high-performance plasmonic sensing systems.

Indium Gallium Oxide Alloys: Electronic Structure, Optical Gap, Surface Space Charge, and Chemical Trends within Common-Cation Semiconductors.

The electronic and optical properties of (InxGa1-x)2O3 alloys are highly tunable, giving rise to a myriad of applications including transparent conductors, transparent electronics, and solar-blind ultraviolet photodetectors. Here, we investigate these properties for a high quality pulsed laser deposited film which possesses a lateral cation composition gradient (0.01 ≤ x ≤ 0.82) and three crystallographic phases (monoclinic, hexagonal, and bixbyite). The optical gaps over this composition range are determined, and only a weak optical gap bowing is found (b = 0.36 eV). The valence band edge evolution along with the change in the fundamental band gap over the composition gradient enables the surface space-charge properties to be probed. This is an important property when considering metal contact formation and heterojunctions for devices. A transition from surface electron accumulation to depletion occurs at x ∼ 0.35 as the film goes from the bixbyite In2O3 phase to the monoclinic ß-Ga2O3 phase. The electronic structure of the different phases is investigated by using density functional theory calculations and compared to the valence band X-ray photoemission spectra. Finally, the properties of these alloys, such as the n-type dopability of In2O3 and use of Ga2O3 as a solar-blind UV detector, are understood with respect to other common-cation compound semiconductors in terms of simple chemical trends of the band edge positions and the hydrostatic volume deformation potential.

The principal axes systems for the elastic properties of monoclinic gallia.

We discuss the principal axes systems of monoclinic and triclinic crystals regarding their elastic properties. Explicit formulas are presented for the orientation of these coordinate systems for monoclinic crystals. In this context, theoretical results from literature on the elastic properties of monoclinic (space group C2/m) gallia and alumina are critically discussed.

Toward three-dimensional hybrid inorganic/organic optoelectronics based on GaN/oCVD-PEDOT structures.

The combination of inorganic semiconductors with organic thin films promises new strategies for the realization of complex hybrid optoelectronic devices. Oxidative chemical vapor deposition (oCVD) of conductive polymers offers a flexible and scalable path towards high-quality three-dimensional inorganic/organic optoelectronic structures. Here, hole-conductive poly(3,4-ethylenedioxythiophene) (PEDOT) grown by oxidative chemical vapor deposition is used to fabricate transparent and conformal wrap-around p-type contacts on three-dimensional microLEDs with large aspect ratios, a yet unsolved challenge in three-dimensional gallium nitride technology. The electrical characteristics of two-dimensional reference structures confirm the quasi-metallic state of the polymer, show high rectification ratios, and exhibit excellent thermal and temporal stability. We analyze the electroluminescence from a three-dimensional hybrid microrod/polymer LED array and demonstrate its improved optical properties compared with a purely inorganic microrod LED. The findings highlight a way towards the fabrication of hybrid three-dimensional optoelectronics on the sub-micron scale.

Band Offsets at κ-([Al,In]xGa1-x)2O3/MgO Interfaces.

Conduction and valence band offsets are among the most crucial material parameters for semiconductor heterostructure device design, such as for high-electron mobility transistors or quantum well infrared photodetectors (QWIP). Because of its expected high spontaneous electrical polarization and the possibility of polarization doping at heterointerfaces similar to the AlGaN/InGaN/GaN system, the metastable orthorhombic κ-phase of Ga2O3 and its indium and aluminum alloy systems are a promising alternative for such device applications. However, respective band offsets to any dielectric are unknown, as well as the evolution of the bands within the alloy systems. We report on the valence and conduction band offsets of orthorhombic κ-(AlxGa1-x)2O3 and κ-(InxGa1-x)2O3 thin films to MgO as reference dielectric by X-ray photoelectron spectroscopy. The thin films with compositions xIn ≤ 0.27 and xAl ≤ 0.55 were grown by pulsed laser deposition utilizing tin-doped and radially segmented targets. The determined band alignments reveal the formation of a type I heterojunction to MgO for all compositions with conduction band offsets of at least 1.4 eV, providing excellent electron confinement. Only low valence band offsets with a maximum of ∼300 meV were observed. Nevertheless, this renders MgO as a promising gate dielectric for metal-oxide-semiconductor transistors in the orthorhombic modification. We further found that the conduction band offsets in the alloy systems are mainly determined by the evolution of the band gaps, which can be tuned by the composition in a wide range between 4.1 and 6.2 eV, because the energy position of the valence band maximum remains almost constant over the complete composition range investigated. Therefore, tunable conduction band offsets of up to 1.1 eV within the alloy systems allow for subniveau transition energies in (AlxGa1-x)2O3/(InxGa1-x)2O3/(AlxGa1-x)2O3 quantum wells from the infrared to the visible regime, which are promising for application in QWIPs.

Enhanced Magnetoelectric Coupling in BaTiO3-BiFeO3 Multilayers-An Interface Effect.

Combining various (multi-)ferroic materials into heterostructures is a promising route to enhance their inherent properties, such as the magnetoelectric coupling in BiFeO3 thin films. We have previously reported on the up-to-tenfold increase of the magnetoelectric voltage coefficient α ME in BaTiO3-BiFeO3 multilayers relative to BiFeO3 single layers. Unraveling the origin and mechanism of this enhanced effect is a prerequisite to designing new materials for the application of magnetoelectric devices. By careful variations in the multilayer design we now present an evaluation of the influences of the BaTiO3-BiFeO3 thickness ratio, oxygen pressure during deposition, and double layer thickness. Our findings suggest an interface driven effect at the core of the magnetoelectric coupling effect in our multilayers superimposed on the inherent magnetoelectric coupling of BiFeO3 thin films, which leads to a giant α ME coefficient of 480 V c m -1 Oe-1 for a 16 × (BaTiO3-BiFeO3) superlattice with a 4 . 8 nm double layer periodicity.

Voigt Exceptional Points in an Anisotropic ZnO-Based Planar Microcavity: Square-Root Topology, Polarization Vortices, and Circularity.

Voigt points represent propagation directions in anisotropic crystals along which optical modes degenerate, leading to a single circularly polarized eigenmode. They are a particular class of exceptional points. Here, we report the fabrication and characterization of a dielectric, anisotropic optical microcavity based on nonpolar ZnO that implements a non-Hermitian system and mimics the behavior of Voigt points in natural crystals. We prove the exceptional-point nature by monitoring the complex-square-root topology of the mode eigenenergies (real and imaginary parts) around the Voigt points. Polarization state analysis shows that these artificially engineered Voigt points behave as vortex cores for the linear polarization and sustain chiral modes. Our findings apply to any planar microcavity with broken cylindrical symmetry and, thus, pave the way for exploiting exceptional points in widespread optoelectronic devices such as vertical cavity surface emitting lasers and resonant cavity light emitting diodes.

Processing Strategies for High-Performance Schottky Contacts on n-Type Oxide Semiconductors: Insights from In2O3.

Preparation of rectifying Schottky contacts on n-type oxide semiconductors, such as indium oxide (In2O3), is often challenged by the presence of a distinct surface electron accumulation layer. We investigated the material properties and electrical transport characteristics of platinum contact/indium oxide heterojunctions to define routines for the preparation of high-performance Schottky diodes on n-type oxide semiconductors. Combining the evaluation of different Pt deposition methods, such as electron-beam evaporation and (reactive) sputtering in an (O and) Ar atmosphere, with oxygen plasma interface treatments, we identify key parameters to obtain Schottky-type contacts with high electronic barrier height and high rectification ratio. Different photoelectron spectroscopy approaches are compared to characterize the chemical properties of the contact layers and the interface region toward In2O3, to analyze charge transfer and plasma oxidation processes as well as to evaluate the precision and limits of different methodologies to determine heterointerface energy barriers. An oxygen-plasma-induced passivation of the semiconductor surface, which induces electron depletion and generates an intrinsic interface energy barrier, is found to be not sufficient to generate rectifying platinum contacts. The dissolution of the functional interface oxide layer within the Pt film results in an energy barrier of ∼0.5 eV, which is too low for an In2O3 electron concentration of ∼1018 cm-3. A reactive sputter process in an Ar and O atmosphere is required to fabricate rectifying contacts that are composed of platinum oxide (PtOx). Combining oxygen plasma interface oxidation of the semiconductor surface with reactive sputtering of PtOx layers results in the generation of a high Schottky barrier of ∼0.9 eV and a rectification ratio of up to 106. An additional oxygen plasma treatment after contact deposition further reduced the reverse leakage current, likely by eliminating a surface conduction path between the coplanar Ohmic and Schottky contacts. We conclude that processes that allow us to increase the oxygen content in the interface and contact region are essential for fabrication of device-quality-rectifying contacts on various oxide semiconductors.

Native Point Defect Measurement and Manipulation in ZnO Nanostructures.

This review presents recent research advances in measuring native point defects in ZnO nanostructures, establishing how these defects affect nanoscale electronic properties, and developing new techniques to manipulate these defects to control nano- and micro- wire electronic properties. From spatially-resolved cathodoluminescence spectroscopy, we now know that electrically-active native point defects are present inside, as well as at the surfaces of, ZnO and other semiconductor nanostructures. These defects within nanowires and at their metal interfaces can dominate electrical contact properties, yet they are sensitive to manipulation by chemical interactions, energy beams, as well as applied electrical fields. Non-uniform defect distributions are common among semiconductors, and their effects are magnified in semiconductor nanostructures so that their electronic effects are significant. The ability to measure native point defects directly on a nanoscale and manipulate their spatial distributions by multiple techniques presents exciting possibilities for future ZnO nanoscale electronics.

Applicability of the constitutive equations for the determination of the material properties of optically active materials.

For the description of the optical response of optically active media, different constitutive equations have been proposed and are still used in literature. Here, we demonstrate on potassium titanyl phosphate (KTiOPO4) by means of ellipsometry that only the symmetric constitutive equation describes the observed spectra properly and allows the unique determination of the gyration tensor.

Defect Manipulation To Control ZnO Micro-/Nanowire-Metal Contacts.

Surface states that induce depletion regions are commonly believed to control the transport of charged carriers through semiconductor nanowires. However, direct, localized optical, and electrical measurements of ZnO nanowires show that native point defects inside the nanowire bulk and created at metal-semiconductor interfaces are electrically active and play a dominant role electronically, altering the semiconductor doping, the carrier density along the wire length, and the injection of charge into the wire. We used depth-resolved cathodoluminescence spectroscopy to measure the densities of multiple point defects inside ZnO nanowires, substitutional Cu on Zn sites, zinc vacancy, and oxygen vacancy defects, showing that their densities varied strongly both radially and lengthwise for tapered wires. These defect profiles and their variation with wire diameter produce trap-assisted tunneling and acceptor trapping of free carriers, the balance of which determines the low contact resistivity (2.6 × 10-3 Ω·cm-2) ohmic, Schottky (Φ ≥ 0.35 eV) or blocking nature of Pt contacts to a single nano/microwire. We show how these defects can now be manipulated by ion beam methods and nanowire design, opening new avenues to control nanowire charge injection and transport.

Combinatorial Material Science and Strain Engineering Enabled by Pulsed Laser Deposition Using Radially Segmented Targets.

Vertical composition gradients of ternary alloy thin films find applications in numerous device structures. Up to now such gradients along the growth direction have not been realized by standard pulsed laser deposition (PLD) systems. In this study, we propose an approach based on a single elliptically segmented PLD target suited for the epitaxial growth of vertically graded layers. The composition of the thin films can be varied by a simple adjustment of the position of the PLD laser spot on the target surface. We demonstrate this principle for the Mg xZn1- xO alloy system. Such vertically composition-graded Mg xZn1- xO thin films exhibit high optical quality and a well-defined Mg-content for each layer. No signs of interdiffusion of Mg-atoms between the layers have been found. Further, this method is capable to deposit homogeneous thin films with any desired, well-defined cation composition having the same high optical and structural quality as films grown by conventional PLD.

Spatiotemporal Evolution of Coherent Polariton Modes in ZnO Microwire Cavities at Room Temperature.

Tunable waveguides for propagating coherent quantum states are demanded for future applications in quantum information technology and optical data processing. We present coherent whispering gallery mode polariton states in ZnO-based hexagonal microwires at room temperature. We observed their propagation over the field of view of about 20 µm by picosecond time-resolved real space imaging using a streak camera. Spatial coherence was proven by time integrated Michelson interferometry superimposing the inverted spatial emission pattern with its original one. We furthermore show that the real and momentum space evolution of the coherent states can not only be described by the commonly used model developed for ballistically propagating Bose-Einstein condensates based on the Gross-Pitaevskii equation but equivalently by classical ray optics considering a spatially varying particle density dependent refractive index of the cavity material, not yet considered in literature so far. By changing the excitation spot size, the refractive index gradient and thus the propagation velocity is changed.

Impact of magnetization and hyperfine field distribution on high magnetoelectric coupling strength in BaTiO3-BiFeO3 multilayers.

Correlations were established between the hyperfine field distribution around the Fe atoms, the multiferroic properties, and the high magnetoelectric coefficient in BaTiO3-BiFeO3 multilayer stacks with variable BiFeO3 single layer thickness, down to 5 nm. Of key importance in this study was the deposition of 57Fe - enriched BiFeO3, which enhances the sensitivity of conversion electron Mössbauer spectroscopy by orders of magnitude. The magnetoelectric coefficient αME reaches a maximum of 60.2 V cm-1 Oe-1 at 300 K and at a DC bias field of 2 Tesla for a sample of 15 × (10 nm BaTiO3-5 nm BiFeO3) and is one of the highest values reported so far. Interestingly, the highest αME is connected to a high asymmetry of the hyperfine field distribution of the multilayer composite samples. The possible mechanisms responsible for the strong magnetoelectric coupling are discussed.

Dynamical Tuning of Nanowire Lasing Spectra.

Realizing visionary concepts of integrated photonic circuits, nanospectroscopy, and nanosensing will tremendously benefit from dynamically tunable coherent light sources with lateral dimensions on the subwavelength scale. Therefore, we demonstrate an individual nanowire laser based device which can be gradually tuned by reversible length changes of the nanowire such that uniaxial tensile stress is applied to the respective semiconductor gain material. By straining the device, the spontaneous excitonic emission of the nanowire shifts to lower energies caused by the bandgap reduction of the semiconductor. Moreover, the optical gain spectrum of the nanolaser can be precisely strain-tuned in the high excitation regime. The tuning of the emission does not affect the laser threshold of the device, which is very beneficial for practical applications. The applied length change furthermore adjusts the laser resonances inducing a redshift of the longitudinal modes. Thus, this concept of gradually and dynamically tunable nanolasers enables controlling and modulating the coherent emission on the nanoscale without changing macroscopic ambient conditions. This concept holds therefore huge impact on nanophotonic switches and photonic circuit technology.

Vital Role of Oxygen for the Formation of Highly Rectifying Schottky Barrier Diodes on Amorphous Zinc-Tin-Oxide with Various Cation Compositions.

We present electrical properties of Schottky barrier diodes on room-temperature deposited amorphous zinc-tin-oxide (ZTO) with Zn/(Zn + Sn) contents between 0.12 and 0.72. A combinatorial approach with continuous composition spread pulsed laser deposition is used to achieve the wide range of compositions with four samples each on 50 × 50 mm2 glass substrates. The Schottky barrier contacts were fabricated by the reactive direct-current sputtering of platinum. Best diode properties (rectification ratio SV = 2.7 × 107, ideality factor η = 1.05, and effective barrier height ϕB,eff = 1.25 eV) are obtained for a composition of 0.63 Zn/(Zn + Sn). Aging on the timescale of days and months is observed that leads to improved device properties (higher rectifications and lower ideality factors). In particular, the diodes with the lowest performance in the as-prepared state show the biggest improvements. The best diode properties after the aging process (SV = 3.9 × 107, η = 1.12, and ϕB,eff = 1.31 eV) were also observed for 0.63 Zn/(Zn + Sn).