Post-growth Annealing Research Articles

193 nm laser annealing on p-GaN with enhanced hole concentration and wall-plug-efficiency in deep ultraviolet LED

The high acceptor ionization energy and, thus, low carrier concentration in p-type III-nitride have widely been recognized as the bottleneck preventing the development of high-efficiency light-emitting-diodes (LEDs). In this contribution, the influences of 193 nm pulsed laser annealing on the structure, electrical, and optical properties of p-type GaN were systematically analyzed. The hole concentration of p-GaN first increases and then decreases with increasing laser fluence, regardless of post-growth thermal annealing. The effective dopant activation due to laser annealing can be attributed to the dissociation of Mg–H complexes during the treatment. Laser-annealed p-GaN was utilized in a 280 nm deep ultraviolet LED. A maximum of 1.47 times higher wall-plug-efficiency enhancement factor was obtained compared to that without laser annealing, demonstrating that 193 nm laser annealing plays a decisive role in the boosting of quantum efficiency of optoelectronic devices.

Influence of Bi doping on the electronic structure of (Ga,Mn)As epitaxial layers

The influence of the addition of Bi to the dilute ferromagnetic semiconductor (Ga,Mn)As on its electronic structure as well as on its magnetic and structural properties has been studied. Epitaxial (Ga,Mn)(Bi,As) layers of high structural perfection have been grown using low-temperature molecular-beam epitaxy. Post-growth annealing of the samples improves their structural and magnetic properties and increases the hole concentration in the layers. Hard X-ray angle-resolved photoemission spectroscopy reveals a strongly dispersing band in the Mn-doped layers, which crosses the Fermi energy and is caused by the high concentration of Mn-induced itinerant holes located in the valence band. An increased density of states near the Fermi level is attributed to additional localized Mn states. In addition to a decrease in the chemical potential with increasing Mn doping, we find significant changes in the valence band caused by the incorporation of a small atomic fraction of Bi atoms. The spin–orbit split-off band is shifted to higher binding energies, which is inconsistent with the impurity band model of the band structure in (Ga,Mn)As. Spectroscopic ellipsometry and modulation photoreflectance spectroscopy results confirm the valence band modifications in the investigated layers.

High performance germanium on silicon photodiodes for back-end-of-line photonic integration

Integration of near-infrared photodetectors in the back-end-of-line requires low temperature growth of Ge (<450 °C). We have fabricated high performance, vertical incidence Ge-on-Si photodiodes under thermal budget constraints with as-grown diodes achieving an internal quantum efficiency (IQE) of 38% and a dark current density of Jd = 272 μA/cm2 at a reverse bias of Vr = 5 V and a wavelength of λ = 1310 nm. The photodiode design incorporates a remote heterointerface, demonstrating that Ge material quality is sufficiently high for minority carriers to diffuse to the Ge/Si interface. Post-growth annealing improves device performance, including 500 °C 3 h exposure that improves IQE to 57% and Jd = 165 μA/cm2. Low-temperature grown Ge-on-Si photodiodes give comparable performance to diodes processed at high temperatures despite thermal budget constraints.

Degradation mechanisms of annealed GaAsPBi films grown by molecular beam epitaxy

GaAsPBi is a novel semiconductor that can broaden the bandgap range of III−V compounds, but its growth on GaAs(001) by molecular beam epitaxy is complicated by the presence of Bi. To avoid the nucleation of Bi droplets, the growth temperature must be low (<400°C), resulting in GaAsPBi films with poor photoluminescent yields. It is shown here that while post-growth annealing of GaAsPBi improves its optical quality, the GaAsPBi surface and the underlying GaAsPBi/GaAs interface undergo structural and chemical changes that limit the usefulness of annealing. Using synchrotron radiation-based spectromicroscopy, morphological and chemical changes on the surface are followed in situ, allowing the temperature limit to be estimated at ∼510°C. Beyond this, the GaAsPBi film degrades, first by the nucleation of interfacial dislocations at ∼520°C, then by the desorption of surface oxides at ∼580°C, and by congruent sublimation of the film itself at ∼670°C. The damages are spatially correlated and inhomogeneous, with areas above the dislocations being the preferential damage sites. These in situ observed events provide critical insights to the mechanisms and chronology of surface and interfacial degradation during high-temperature processing of GaAsPBi/GaAs structure, with implications for the process and device designs of heteroepitaxial III−V films prevalence in optoelectronics.

Si–Sn codoped n-GaN film sputtering grown on an amorphous glass substrate

DC-pulse magnetron sputtering was utilized to deposit a 300 nm-thick n-type GaN thin film that was co-doped with Si–Sn onto an amorphous glass substrate with a ZnO buffer layer. The deposited thin films were then subjected to post-growth thermal annealing at temperatures of 300 °C, 400 °C, or 500 °C to enhance their crystal quality. Hall measurements revealed that the film annealed at 500 °C had the lowest thin-film resistance of 0.82 Ω cm and the highest carrier concentration of 3.84 × 1019 cm−3. The thin film surface was studied using atomic force microscopy; the film annealed at 500 °C had an average grain size and surface roughness of 25.3 and 2.37 nm, respectively. Furthermore, the x-ray diffraction measurements revealed a preferential (002) crystal orientation and hexagonal wurtzite crystal structure at 2θ ≈ 34.5°. The thin film had a full width at half maximum value of 0.387°, it was also found to be very narrow. Compositional analysis of the films was conducted with x-ray photoelectron spectroscopy and verified that both Si and Sn were doped into the GaN film utilizing covalent bonding with N atoms. Finally, the film annealed at 500 °C had a high optical transmittance of 82.9% at 400–800 nm, a high figure of merit factor of 490.3 × 10−3 Ω−1, and low contact resistance of 567 Ω; these excellent optoelectronic properties were attributed to the film’s high electron concentration and indicate that the material is feasible for application in transparent optoelectronic devices.

Growth of nanostructured molybdenum disulfide (MoS2) thin films on a nanohole-patterned substrate using plasma-enhanced atomic layer deposition (ALD)

Nanostructured molybdenum disulfide (MoS2) thin films were grown on a nanohole-patterned silicon substrate using plasma-enhanced atomic layer deposition. A nanoscale hole-patterned silicon substrate was fabricated for the growth of MoS2 film using the self-assembly-based nanofabrication method. The nanoscale holes can significantly increase the surface area of the substrate while the formation and growth of nanostructures normally start at the surface of the substrate. Hydrogen sulfide (H2S) gas was used as the S source in the growth of molybdenum disulfide (MoS2) while molybdenum (V) chloride (MoCl5) powder was used as the Mo source. The MoS2 film had a stoichiometric ratio of 1 (Mo) to 2 (S), and had peaks of E12g and A1g, which represent the in-plane and out-plane vibration modes of the Mo–S bond, respectively. It was found that the MoS2 film grown in the nanoscale hole, especially at the wall of the hole, has more hexagonal-like structures due to the effects of nanoscale space confinement and the nanoscale interface although the film shows an amorphous structure. Post-growth high-temperature annealing ranging from 800 to 900 °C produced local crystalline structures in the film, which are compatible with those reported by other researchers.

Conversion of p-type SnO to n-type SnO2 via oxidation and the band offset and rectification of an all-Tin oxide p-n junction structure

p-Type Tin monoxide (SnO) is a metastable phase and can be oxidized into n-type SnO2 in an O2 environment during growth and post-growth annealing. Here we first grow SnO thin films by RF magnetron sputtering with different oxygen partial pressure in the sputtering gas followed by rapid thermal annealing (RTA) in O2 to obtain n-type conducting SnO2 films. We found that while after RTA in N2 stoichiometric SnO film is p-type conducting, films sputtered with excess O and RTA in O2 crystallize in rutile SnO2 structure and exhibit n-type conductivity. Exploiting the transformation of p-SnO to n-SnO2 through oxidation, we fabricate an all-Tin Oxide transparent p-n quasi-homojunction (p-SnO/n-SnO2) and compare it to a p-SnO/n-ZnO heterojunction structure in term of their rectification behavior. XPS measurements reveal that both SnO2 and ZnO at the Γ point exhibit a type II band offset with SnO with their respective valence band (conduction band) offset of 2.8 eV (1.9 eV) and 2.4 eV (1.33 eV). On the other hand, the indirect conduction band minimum of SnO shows a type I band offset in both junctions with a small conduction band offset of ∼0.1–0.17 eV. The SnO/SnO2 p-n structure shows a reasonable rectification with an ideality factor of ∼12.3, which can be potentially useful in many transparent p-n junction based devices.

Effect of postgrowth annealing in an oxygen-containing atmosphere on the microhardness of single-crystal calcium molybdate CaMoO4

Effect of postgrowth annealing in an oxygen-containing atmosphere on the microhardness of single-crystal calcium molybdate CaMoO4

The effect of annealing treatment on the structural and optical properties of nanostructured CuxO films obtained by 3D printing

This work studies the effect of post-growth annealing on the structural and optical properties of copper oxide films. Thin films were obtained by 3D printing on glass substrates using ink based on a suspension of CuO nanoparticles. To optimize their structural characteristics and optical quality, the samples were subjected to thermal annealing for 30 min in an argon environment at different temperatures from 250 °C to 500 °C. The obtained samples were studied by scanning electron microscopy, X-ray diffraction, energy dispersive X-Ray, Raman, optical and photoelectric spectroscopy. Based on the obtained results, the main structural and substructural characteristics of the films were established, such as lattice parameters, unit cell volume, texture, sizes of coherent scattering regions, and the level of microdeformation, as well as their dependence on the annealing temperature. In addition, the nature of optical absorption, band gap energies for various types of electronic transitions, and the optical quality of the studied nanostructured copper oxide films were determined. It was shown that CuO films annealed at 350 °C have the best crystalline and optical quality. It was established that at an annealing temperature above 400 °C, a phase transition from the tenorite phase to the cuprite phase is observed. At the same time, a change in the films' substructural characteristics is already observed at Ta = 400 °C. Optimal thermal annealing conditions of CuxO films for effective control of their phase composition have been established.

Effect of post-growth anneals in oxygen-containing atmosphere on the microhardness of single crystal calcium molybdate CaMoO4

Single crystal calcium molybdate CaMoO4 is a well-known material. However the interest to CaMoO4 has recently grown due to a number of its important applications including as a working material in cryogenic scintillation bolometers. CaMoO4 single crystals acquire blue color during growth due to the presence of color-center type defect centers which are unacceptable for optical applications. Color can be eliminated through annealing in an oxygen containing atmosphere, following which required optical components can be produced from the single crystals by mechanical treatment (cutting, polishing etc.). Therefore assessment of the mechanical properties of these single crystal materials is an important task for the optimal solution of issues occurring in the fabrication of optical components and their further practical application. There are but scarce data on the mechanical properties of CaMoO4, and the available ones have been reported without allowance for anisotropy. There is a significant scatter of data on the Mohs hardness of the single crystals, ranging from 3.3 to 6 in different publications. In this work we present data on calcium molybdate single crystals in the initial state and after high-temperature anneals of different durations in an oxygen containing atmosphere. We show that long-term annealing leads to decolorization of the crystals. Calcium molybdate single crystals prove to be quite brittle: the brittleness index Zp of the crystals in the initial state is the highest and equals 5, while annealing reduces the brittleness index to 4. The Palmqvist toughness factors S have been calculated The limit indentation destruction loads Flim have been determined and annealing in an oxygen containing atmosphere has been shown to increase Flim by 2.5 times for the Z cut and by 10 times for the X cut. The microhardness of the crystals has been shown to exhibit a II type anisotropy: the microhardness of all the specimens was higher for the Z cut than for the X cut. The microhardness anisotropy coefficients KH of the specimens have been evaluated. The bond ionicity degree I has been calculated on the basis of the experimentally measured microhardness.

Low-threshold visible InP quantum dot and InGaP quantum well lasers grown by molecular beam epitaxy

III-V lasers based on self-assembled quantum dots (QDs) have attracted widespread interest due to their unique characteristics, including low threshold current density (Jth), low sensitivity to backreflections, and resistance to threading dislocations. While most work to date has focused on 1.3 μm InAs/GaAs QDs, InP QDs have also aroused interest in lasers emitting at visible wavelengths. Molecular beam epitaxy (MBE) enables the growth of high-density InP/AlGaInP QDs on exact (001)-oriented GaAs substrates but requires a relatively low substrate temperature of &amp;lt;500 °C. The low substrate temperature used for phosphide growth in MBE leads to degraded optical properties and makes post-growth annealing a crucial step to improve the optical quality. Here, we report the exceptional thermal stability of InP/AlGaInP QDs grown using MBE, with up to 50× improvement in room temperature photoluminescence intensity with the optimization of annealing temperature and time. We also demonstrate the room temperature pulsed operation of InP multiple quantum dot (MQD) lasers on GaAs (001) emitting close to 735 nm with Jth values of 499 A/cm2 after annealing, a factor of 6 lower than their as-grown counterparts and comparable to such devices grown by MOCVD. In0.6Ga0.4P single quantum well (SQW) lasers on GaAs (001) also exhibit a substantial reduction in Jth from 340 A/cm2 as-grown to 200 A/cm2 after annealing, emitting at 680 nm under pulsed operation conditions. This work shows that post-growth annealing is essential for realizing record-performance phosphide lasers on GaAs grown by MBE for applications in visible photonics.

Dislocation Density Reduction in MOVPE-Grown (211) CdTe/Si by Post-Growth Patterning and Annealing

Dislocation Density Reduction in MOVPE-Grown (211) CdTe/Si by Post-Growth Patterning and Annealing

Engineering Pt/Co/AlO x heterostructures to enhance the Dzyaloshinskii–Moriya interaction

The study of interfacial Dzyaloshinskii–Moriya interaction (DMI) in perpendicularly magnetized structurally asymmetric heavy metal/ferromagnet multilayer systems is of high importance due to the formation of chiral magnetic textures in the presence of DMI. Here, we report the impact of cobalt oxidation at the Co/AlO x interface in Pt/Co/AlO x trilayer structures on the DMI by varying the post-growth annealing time, Al thickness and substrate. To quantify DMI we employed magneto-optical imaging of the asymmetric domain wall expansion, hysteresis loop shift, and spin-wave spectroscopy techniques. We further correlated the Co oxidation with low-temperature Hall effect measurements and x-ray photoelectron spectroscopy. Our results emphasize the importance of full characterization of the magnetic films that could be used for magnetic random access memory technologies when subjected to the semiconductor temperature processing conditions, as the magnetic interactions are critical for device performance and can be highly sensitive to oxidation and other effects.

In Situ Study of the Interface-Mediated Solid-State Reactions during Growth and Postgrowth Annealing of Pd/a-Ge Bilayers.

Ohmic or Schottky contacts in micro- and nanoelectronic devices are formed by metal-semiconductor bilayer systems, based on elemental metals or thermally more stable metallic compounds (germanides, silicides). The control of their electronic properties remains challenging as their structure formation is not yet fully understood. We have studied the phase and microstructure evolution during sputter deposition and postgrowth annealing of Pd/a-Ge bilayer systems with different Pd/Ge ratios (Pd:Ge, 2Pd:Ge, and 4Pd:Ge). The room-temperature deposition of up to 30 nm Pd was monitored by simultaneous, in situ synchrotron X-ray diffraction, X-ray reflectivity, and optical stress measurements. With this portfolio of complementary real-time methods, we could identify the microstructural origins of the resistivity evolution during contact formation: Real-time X-ray diffraction measurements indicate a coherent, epitaxial growth of Pd(111) on the individual crystallites of the initially forming, polycrystalline Pd2Ge[111] layer. The crystallization of the Pd2Ge interfacial layer causes a characteristic change in the real-time wafer curvature (tensile peak), and a significant drop of the resistivity after 1.5 nm Pd deposition. In addition, we could confirm the isostructural interface formation of Pd/a-Ge and Pd/a-Si. Subtle differences between both interfaces originate from the lattice mismatch at the interface between compound and metal. The solid-state reaction during subsequent annealing was studied by real-time X-ray diffraction and complementary UHV surface analysis. We could establish the link between phase and microstructure formation during deposition and annealing-induced solid-state reaction: The thermally induced reaction between Pd and a-Ge proceeds via diffusion-controlled growth of the Pd2Ge seed crystallites. The second-phase (PdGe) formation is nucleation-controlled and takes place only when a sufficient Ge reservoir exists. The real-time access to structure and electronic properties on the nanoscale opens new paths for the knowledge-based formation of ultrathin metal/semiconductor contacts.

Effective substrate for the growth of multilayer h-BN on sapphire—substrate off-cut, pre-growth, and post-growth conditions in metal-organic vapor phase epitaxy

The substrate is one of the key components that determines the quality of the epitaxial layers. However, the implications of growing two-dimensional layers on three-dimensional bulk substrates have not yet been fully understood, and these implications need to be studied for different combinations of materials and substrates. Here, we present a study that addresses the influence of the sapphire substrate off-cut angle on the final growth of two-dimensional layers of hexagonal boron nitride (h-BN) by metal-organic vapor phase epitaxy (MOVPE). A two-step wafer-scale process was used in one epitaxial MOVPE procedure. The main process starts with a self-limiting continuous growth of a BN buffer followed by flow-modulated epitaxy in the second step, and is used to study substrates with different off-cuts angles, pre-growth nitridation steps, and post-growth annealing. An initial nitridation step at the growth temperature allowed for the growth of an AlN sublayer. This layer is shown to smooth out the underlying sapphire and establishes an ‘effective’ sapphire/AlN substrate. This step is also responsible for enforcing a specific growth of the BN layer in a crystallographic orientation, which is shown to strongly deviate from the substrate for off-cut angles larger than 0.3°. A substrate with off-cut angle of 1° clearly yields the highest quality of h-BN layers as evidenced by the lowest amount of debris on the surface, most intense x-ray diffraction signal, minimal Raman phonon line width and thinnest amorphous BN (a-BN) at the interface with the effective substrate. Our study shows that the off-cut angles of sapphire substrates strongly influence the final epitaxial h-BN, clearly indicating the importance of optimal substrate preparation for the growth of two-dimensional BN layers. Post-growth annealing in N2 atmosphere at 800 °C improves the top surface morphology of the final stack, as well as suppresses further the presence of a-BN.

Optimization of La2−xSrxCuO4 Single Crystal Film Growth via Molecular Beam Epitaxy

Atomic layer-by-layer molecular beam epitaxy (ALL-MBE) combined with ozone is one of the best methods to fabricate single-crystal thin films of complex oxides. Cuprate such as La2−xSrxCuO4 (LSCO) is a representative complex-oxide high-temperature superconductor (HTS) material. Our group utilizes this method to produce high-quality single-crystal HTS films with atomically smooth surfaces and interfaces. In addition, ALL-MBE enables us to engineer multilayer heterostructures with atomic precision. This allows the fabrication of tunnel junctions, various nanostructures, and other HTS devices of interest for superconducting electronics. We have synthesized over three thousand LSCO thin films in the past two decades. These films’ structural and electronic properties have been studied and characterized by various methods. Here, we distill the extensive experience we accumulated into a step-by-step protocol to fabricate atomically perfect LSCO films. The recipe includes substrate preparation, ozone generation and distillation, source calibration, the in situ monitoring of the film synthesis, post-growth annealing, and ex situ characterization. It discloses a reproducible way to fabricate single-crystal LSCO films for basic research and HTS electronic applications.

Enhanced light output of Eu, O-codoped GaN caused by reconfiguration of luminescent sites during post-growth thermal annealing

Luminescence efficiency of Eu-related emission from Eu, O-codoped GaN (GaN:Eu, O) strongly depends on the local structure of Eu ions. Growth at relatively low temperature (∼960 °C) not only enables high Eu doping concentration but also elevates Eu-clustering due to its low diffusion coefficient, which results in formation of a large number of inefficient luminescent sites. We have studied the impact of post-growth thermal annealing at high temperatures on elimination of Eu clusters by photoluminescence measurements. These clarify that thermal annealing at high temperatures induces changes in the structural conformation and converts inefficient luminescent sites to efficient ones. As a result, the sample annealed at 1100 °C shows increased luminescence efficiency with a maximum of 5.1 times that of the as-grown sample. Post-growth thermal annealing offers a way to improve the efficiency of GaN:Eu, O further for practical application in III-nitride-based monolithic three-primary colors' light-emitting diodes.

Dynamics of Vacancy Formation and Distribution in Semiconductor Heterostructures: Effect of Thermally Generated Intrinsic Electrons.

The effect of thermally generated equilibrium carrier distribution on the vacancy generation, recombination, and mobility in a semiconductor heterostructure with an undoped quantum well is studied. A different rate of thermally generated equilibrium carriers in layers with different band gaps at annealing temperatures forms a charge-carrier density gradient along a heterostructure. The nonuniform spatial distribution of charged vacancy concentration that appears as a result of strong dependence in the vacancy formation rate on the local charge-carrier density is revealed. A model of vacancy-mediated diffusion at high temperatures typical for post-growth annealing that takes into account this effect and dynamics of nonequilibrium vacancy concentration is developed. The change of atomic diffusivity rate in time that follows on the of spatial vacancy distribution dynamics in a model heterostructure with quantum wells during a high-temperature annealing at fixed temperatures is demonstrated by computational modeling.

Spinodal decomposition introduces strain-enhanced thermochromism in polycrystalline V1-xTixO2 thin films.

Processes of self-organization play a key role in the development of innovative functional nanocomposites, allowing, in particular, the transformation of metastable solid solutions into multilayers by activating spinodal decomposition instead of layer-by-layer film growth. We report the formation of strained layered (V,Ti)O2 nanocomposites in thin polycrystalline films using a spinodal decomposition. Already during the growth of V0.65Ti0.35O2 films, spinodal decomposition was detected while producing atomic-scale disordered V- and Ti-rich phases. Post-growth annealing enhances compositional modulation, arranges the local atomic structures of the phases, and yields periodically layered nanostructures that resemble superlattices. The coherent interfacing of the V- and Ti-rich layers results in the compression of the V-rich phase along the c-axis of the rutile structure and enables strain-enhanced thermochromism. The latter is characterized by a simultaneous decrease in the temperature and width of the metal-insulator transition in the V-rich phase. Our results provide proof-of-concept for an alternative strategy to develop VO2-based thermochromic coatings by introducing strain-enhanced thermochromism into polycrystalline thin films.

Energy Storage Properties of Sol-Gel-Processed SrTiO3 Films.

Dielectric films with a high energy storage density and a large breakdown strength are promising material candidates for pulsed power electrical and electronic applications. Perovskite-type dielectric SrTiO3 (STO) has demonstrated interesting properties desirable for capacitive energy storage, including a high dielectric constant, a wide bandgap and a size-induced paraelectric-to-ferroelectric transition. To pave a way toward large-scale production, STO film capacitors were deposited on Pt(111)/Ti/SiO2/Si(100) substrates by the sol-gel method in this paper, and their electrical properties including the energy storage performance were studied as a function of the annealing temperature in the postgrowth rapid thermal annealing (RTA) process. The appearance of a ferroelectric phase at a high annealing temperature of 750 °C was revealed by X-ray diffraction and electrical characterizations (ferroelectric P-E loop). However, this high dielectric constant phase came at the cost of a low breakdown strength and a large hysteresis loss, which are not desirable for the energy storage application. On the other hand, when the RTA process was performed at a low temperature of 550 °C, a poorly crystallized perovskite phase together with a substantial amount of impurity phases appeared, resulting in a low breakdown strength as well as a very low dielectric constant. It is revealed that the best energy storage performance, which corresponds to a large breakdown strength and a medium dielectric constant, is achieved in STO films annealed at 650 °C, which showed a large energy density of 55 J/cm3 and an outstanding energy efficiency of 94.7% (@ 6.5 MV/cm). These findings lay out the foundation for processing high-quality STO film capacitors via the manufacturing-friendly sol-gel method.