As a wide band gap semiconductor, ZnO have attracted much attention due to their opportunity of combining band gap engineering, with large excitonic binding energies in the UV-visible range. While many wonderful fundamental results (LED, polariton lasers, etc) have been obtained with this material platform thanks a huge improvement of the growth methods, the development has always been limited in terms of applications by a lack of reliable p-type doping. In this presentation I will address new opportunities of this material platform in a radically different range which does not require p-type doping: from IR to THz. After a deep optimization of the designs and the growth processes, quantum cascade detectors and emitters have been processed and characterized in the Mid-IR and the THz range demonstrating the huge potential of oxides to address the issue of efficient emitters in the THz range. In addition, new opportunities of these heterostructures in even more emerging fields such as hyperbolic metamaterials and multisubband plasmons will be explored.
We studied polarization-resolved photoluminescence originating from a ZnO-(Mg,Zn)O quantum well heterostucture embedded within an atom probe tip, i.e. a nanoscale needle-shaped sample with apex radius of several tens of nm, prepared by focused ion beam. The study was carried out within a photonic atom probe before the atom probe analysis of the sample. This setup allows for the analysis of the polarization of the photoluminescence emitted by the tip and for its orientation around its axis. While the photoluminescence emitted by bulk ZnO and by the (Mg,Zn)O alloy is strongly polarized along the tip axis, coinciding with the crystal [1-100] axis, the ZnO/(Mg,Zn)O quantum well luminescence appears to be strongly polarized along its in-plane direction, perpendicular to the crystal [1-100] axis. Finite-difference time domain calculations provide a key for the interpretation of these results in terms of selection rules and of effects related to the waveguide effect of the tip.
Zincoxide is a rather new material system and promising candidate for mid-infrared (mir) and THz optoelectronic devices like quantum cascade lasers (QCLs) and detectors (QCDs) due to its twice as high LO-phonon energy as GaAs. The non-polar m-plane orientation allows designing and realizing such complex devices without internal electrical fields.
We present the full fabrication scheme of such QCL/QCD devices including novel optimized etching techniques, surface leakage current suppression by multiple orders of magnitude and low resistance Ohmic contacts (~10^(-5) Ohm x cm^2). Optimized fabrication schemes resulted in fabrication yielding up to more than 80% of operational devices.
Recently Zinc Oxide has received a renewed attention for the realization of intersubband devices such as quantum cascade lasers (QCLs). Indeed this material is predicted to be able to tackle the main limitation of current terahertz (THz) QCLs: the limited operation temperature. We report the observation of electronic coupling within ZnO/(Zn, Mg)O asymmetric quantum wells (QWs), first step towards this goal. Samples were grown by molecular beam epitaxy (MBE) with surfaces down to 0.4 nm. X-ray reflectivity (XRR) was used for thickness measurements checking and for the investigation of the interface quality. Atomic resolution scanning transmission electron microscopy (STEM) images reveals that we are able to grow 2 monolayers (MLs) thin (Zn, Mg)O barriers in a reproducible way while keeping abrupt interfaces. Room temperature (RT) photoluminescence (PL) spectra show that QWs are still coupled when separated by a 1.0 nm thick barrier. On the contrary, a 4.0 nm thick barrier allows no coupling. Doped samples were investigated by absorption experiment. Absorption spectra were successfully fitted by a theoretical model, proving a clear electronic coupling in our heterostructures. This demonstration allows us to seriously envision the realization of ZnO based intersubband devices.
Intersubband absorption at normal incidence is forbidden by the selection rules and requires oblique incidence operation or texturing of the surface of intersubband-based devices such as focal plane arrays, adding additional processing steps to their fabrication and therefore increasing complexity and costs. Here we demonstrate normal-incidence, polarization sensitive intersubband absorption by wurtzite ZnO/MgZnO quantum wells grown on an m-plane orientation. When grown in this non-polar plane, the ZnO/MgZnO quantum wells spontaneously assemble forming a V-groove profile in the direction perpendicular to the c-axis, i.e. along the a-direction. A stack of quantum wells featuring this morphology acts as a metamaterial that allows for intersubband absorption at normal incidence whenever the electric field of the light is polarized in the direction perpendicular to the c axis. This phenomenon occurs because when the electric field is perpendicular to the c-axis it is no longer contained in the plane of the quantum wells therefore allowing for a small intersubband absorption. On the contrary, if the electric field is parallel to the c-axis, the usual normal-incidence conditions are recovered and no absorption is observed.
We report on the first demonstration of quantum cascade detectors based on ZnO/ZnMgO quantum wells grown by molecular beam epitaxy on an m-plane ZnO substrate. The sample is processed in the form of square mesas with special attention paid to the passivation of the side facets. Photocurrent spectroscopy reveals a resonance at 2.8 μm wavelength slightly blue-shifted with respect to the intersubband absorption peak at 3 μm wavelength. The photocurrent persists up to room temperature. The peak responsivity amounts to 0.15 mA/W under irradiation at Brewster’s angle of incidence of the top surface of the mesas.
In this work we show the potential of the ZnO/ZnMgO material system for intersubband (ISB)-based devices. This family of alloys presents a unique set of properties that makes it highly attractive for THz emission as well as strong coupling regimes: it has a very large longitudinal optical phonon energy of 72 meV, it can be doped up to ~1021 cm-3, it is very ionic with a large difference between the static and high frequency dielectric constants, and it can be grown homoepitaxially on native substrates with low defect densities. The films analyzed here are grown by molecular beam epitaxy (MBE) on a non-polar orientation, the m-plane, with varying QW thicknesses and 30% Mg concentrations in the barrier, and are examined with polarization-dependent IR absorption spectroscopy. The QW band structure and the intersubband transitions energies are modeled considering many body effects, which are key to predict correctly the measured values.
Although ZnO and its related heterostructures are really attractive for their potential application in optoelectronics, their developments have been limited by the p-type doping issue. Here, we will show why ZnO properties are also very attractive for unipolar structures, only dealing with electrons, and how the material quality has been improved to reach these devices requirements.
First, the benefit of homoepitaxy through material quality improvement is presented. We will show that molecular beam epitaxy allows getting defect density, surface roughness, and residual doping, comparable to the state-of-the-art of GaAs. Moreover, (Zn,Mg)O alloy could be used to fabricate heterostructures with very good optical and transport properties.
In the second part, we will give a brief overview of the main transport results, especially bidimensional electron gas, reported in the literature. Few examples of possible applications will also be addressed. Then, we will focus on the potentialities of nonpolar ZnO heterostructures for unipolar devices based on intersubband transitions. Once the advantages of using ZnO for TeraHertz quantum cascade laser discussed, we will show that the structural properties of the ZnO/(Zn,Mg)O heterostructures fulfill the requirements of these devices operation. Moreover, we will finish with absorption measurements clearly showing intersubband transitions in agreement with the light polarization selection rule. The strong influence of physical parameters, like doping level, on the energy of these kind of transitions will also be discussed.
This work was funded by EU commission under the H2020 FET-OPEN program; project “ZOTERAC” FET-OPEN 6655107.
We address the electronic, phononic, and thermal properties of oxide based superlattices and multi quantum well heterostructures. In the first part, we review the present understanding of phonon coupling and phonon propagation in superlattices and elucidate current research aspects of phonon coherence in these structure. Subsequently, we focus on the experimental study of MBE grown ZnO/ZnMgO multi quantum well heterostructures with varying Mg content, barrier thickness, quantum well thickness, and number of periods. In particular, we discuss how the controlled variation of these parameters affect the phonon dispersion relation and phonon propagation and their impact on the thermal properties.
The development of Zinc Oxide (ZnO)-based applications have been strongly limited due to the lack of reproducible p-type doping. Here we present novel opportunities in the field of unipolar oxide wide band gap semiconductors. First we have developed the growth of nonpolar ZnO/ZnMgO multiple quantum wells (MQWs) and then we demonstrate that the structural and optical properties of the MQWs are reaching the required level for intersubband devices in terms of defects, surface and interface roughness and doping. We will show and discuss the most recent results as, for instance, intersubband transitions which have been observed in such structures.
This "Zoterac" project has received funding from the European Union’s Horizon 2020 research and
innovation programme under grant agreement No 665107
The terahertz (THz) spectral range (lambda ~ 30µm – 300µm) is also known as the “THz-gap” because of the lack of compact semiconductor devices. Various real-world applications would strongly benefit from such sources like trace-gas spectroscopy or security-screening. A crucial step is the operation of THz-emitting lasers at room temperature. But this seems out of reach with current devices, of which GaAs-based quantum cascade lasers (QCLs) seem to be the most promising ones. They are limited by the parasitic, non-optical LO-phonon transitions (36meV in GaAs), being on the same order as the thermal energy at room temperature (kT = 26meV). This can be solved by using larger LO-phonon materials like ZnO (E_LO = 72meV). But to master the fabrication of ZnO-based QC structures, a high quality epitaxial growth is crucial followed by a well-controlled fabrication process including ZnO/ZnMgO etching.
We use devices grown on m-plane ZnO-substrate by molecular beam epitaxy. They are patterned by reactive ion etching in a CH4-based chemistry (CH4:H2:Ar/30:3:3 sccm) into 50μm to 150μm square mesas. Resonant tunneling diode structures are investigated in this geometry and are presented including different barrier- and well-configurations. We extract contact resistances of 8e-5 Omega cm^2 for un-annealed Ti/Au contacts and an electron mobility of above 130cm^2/Vs, both in good agreement with literature. Proving that resonant electron tunneling can be achieved in ZnO is one of the crucial building blocks of a QCL.
This project has received funding from the European Union’s Horizon 2020 research and innovation programme under grant agreement No 665107.
Quantum cascade (QC) lasers opens new prospects for powerful sources operating at THz frequencies. Up to now the best THz QC lasers are based on intersubband emission in GaAs/AlGaAs quantum well (QW) heterostructures. The maximum operating temperature is 200 K, which is too low for wide-spread applications. This is due to the rather low LO-phonon energy (36 meV) of GaAs-based materials. Indeed, thermal activation allows non-radiative path through electron-phonon interaction which destroys the population inversion. Wide band gap materials such as ZnO have been predicted to provide much higher operating temperatures because of the high value of their LO-phonon energy. However, despite some observations of intersubband absorption in c-plane ZnO/ZnMgO quantum wells, little is known on the fundamental parameters such as the conduction band offset in such heterostructures. In addition the internal field inherent to c-plane grown heterostuctures is an handicap for the design of QC lasers and detectors.
In this talk, we will review a systematic investigation of ZnO/ZnMgO QW heterostructures with various Mg content and QW thicknesses grown by plasma molecular beam epitaxy on low-defect m-plane ZnO substrates. We will show that most samples exhibit TM-polarized intersubband absorption at room temperature linked either to bound-to-quasi bound inter-miniband absorption or to bound-to bound intersubband absorption depending on the Mg content of the barrier material. This systematic study allows for the first time to estimate the conduction band offset of ZnO/ZnMgO heterostructures, opening prospects for the design of QC devices operating at THz frequencies.
This was supported by the European Union’s Horizon 2020 research and
innovation programme under grant agreement #665107.
ZnO has great potential for devices in the mid IR and the THz range through the use of intersubband (ISB) transitions in multiple quantum wells (MQWs), although exploiting these transitions requires great control of the epitaxial layers as well as of the physics involved. In this work we present an analysis of non-polar ZnO grown homoepitaxially by molecular beam epitaxy on m-plane ZnO substrates as an ISB optical absorber. The MQWs were characterized under a 45°-bevelled multi-pass waveguide configuration allowing the observation at room temperature of an ISB transition in the 4-6 μm region for p-polarized incident light.
Detecting the UV part of the spectrum is fundamental for a wide range of applications where ZnMgO has the potential to play a central role. The shortest achievable wavelength is a function of the Mg content in the films, which in turn is dependent on the growth technique. Moreover, increasing Mg contents lead to an electrical compensation of the films, which directly affects the responsivity of the photodetectors. In addition, the metal-semiconductor interface and the presence of grain boundaries have a direct impact on the responsivity through different gain mechanisms. In this work, we review the development of ZnMgO UV Schottky photodiodes using molecular beam epitaxy and spray pyrolysis, and we analyze and compare the physical mechanisms underlying the photodetector behavior.
We review in this paper the application of ZnO/(Zn,Mg)O quantum wells to the photodetection of the polarization state of UV light. This photodetection is achieved by using the natural anisotropy that exists in non-polar ZnO/(Zn,Mg)O quantum wells, which separates the excitonic absorption from the three valence bands to the conduction band depending on the incident light polarization. The device structures covered here consist of Schottky photodiodes on a- and m-plane orientations, grown by molecular beam epitaxy on ZnO or sapphire substrates, and are analyzed as a function of the incident light polarization.
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