Post-growth Annealing Treatments Research Articles

XMCD study of magnetism and valence state in iron-substituted strontium titanate

Room temperature ferromagnetism was characterized for thin films of SrTi$_{0.6}$Fe$_{0.4}$O$_{3-{\delta}}$ grown by pulsed laser deposition on SrTiO$_{3}$ and Si substrates under different oxygen pressures and after annealing under oxygen and vacuum conditions. X-ray magnetic circular dichroism demonstrated that the magnetization originated from Fe$^{2+}$ cations, whereas Fe$^{3+}$ and Ti$^{4+}$ did not contribute. Films with the highest magnetic moment (0.8 {\mu}B per Fe) had the highest measured Fe$^{2+}$:Fe${^3+}$ ratio of 0.1 corresponding to the largest concentration of oxygen vacancies ({\delta} = 0.19). Post-growth annealing treatments under oxidizing and reducing conditions demonstrated quenching and partial recovery of magnetism respectively, and a change in Fe valence states. The study elucidates the microscopic origin of magnetism in highly Fe-substituted SrTi$_{1-x}$Fe$_x$O$_{3-{\delta}}$ perovskite oxides and demonstrates that the magnetic moment, which correlates with the relative content of Fe$^{2+}$ and Fe$^{3+}$, can be controlled via the oxygen content, either during growth or by post-growth annealing.

Understanding arsenic incorporation in CdTe with atom probe tomography

Overcoming the open circuit voltage deficiency in Cadmium Telluride (CdTe) photovoltaics may be achieved by increasing p-type doping while maintaining or increasing minority carrier lifetimes. Here, routes to higher doping efficiency using arsenic are explored through an atomic scale understanding of dopant incorporation limits and activation in molecular beam epitaxy grown CdTe layers. Atom probe tomography reveals spatial segregation into nanometer scale clusters containing > 60 at% As for samples with arsenic incorporation levels greater than 7–8 × 1017 cm−3. The presence of arsenic clusters was accompanied by crystal quality degradation, particularly the introduction of arsenic-enriched extended defects. Post-growth annealing treatments are shown to increase the size of the As precipitates and the amount of As within the precipitates.

Effect of annealing on the compositional modulation of InAlAsSb

The effect of a post-growth thermal treatment in two different heterostructures with InAlAsSb as the top layer grown by molecular beam epitaxy lattice-matched to InP, have been studied by diffraction contrast transmission electron microscopy (TEM).11TEM: transmission electron microscopy This novel top cell layer material with application in ultra-high efficiency solar cells were grown on (001) InP substrate with or without an InGaAs buffer layer. Initial photoluminescence (PL)22PL: photoluminescence measurements revealed deviations from their predicted bandgap, suggesting non-random atomic distribution of the quaternary layer. Then, a thermal annealing was performed at different temperatures and times. The effect on the structure of the InAlAsSb active layer caused by the new arrangement of layers and the post-growth annealing treatments has been reported. Our results show that the small compositional fluctuations of the as-grown heterostructures disappear after being annealed, and the bandgap energy correspondingly increases towards the predicted value.

Effect of post-growth annealing treatment on interfacial misfit GaSb/GaAs heterostructures

Post-growth annealing treatments in the range 400–600°C are performed on GaSb/GaAs Interfacial Misfit grown samples. Current density–voltage (J–V), Capacitance–voltage (C–V), capacitance–frequency (C–F) and Deep Level Transient Spectroscopy (DLTS) measurements are performed on as-grown and annealed samples. Our studies show that possible defect compensation is observed with the annealing treatments, resulting in a significant improvement in the performances of the devices.

Luminescence studies on green emitting InGaN/GaN MQWs implanted with nitrogen.

We studied the optical properties of metalorganic chemical vapour deposited (MOCVD) InGaN/GaN multiple quantum wells (MQW) subjected to nitrogen (N) implantation and post-growth annealing treatments. The optical characterization was carried out by means of temperature and excitation density-dependent steady state photoluminescence (PL) spectroscopy, supplemented by room temperature PL excitation (PLE) and PL lifetime (PLL) measurements. The as-grown and as-implanted samples were found to exhibit a single green emission band attributed to localized excitons in the QW, although the N implantation leads to a strong reduction of the PL intensity. The green band was found to be surprisingly stable on annealing up to 1400°C. A broad blue band dominates the low temperature PL after thermal annealing in both samples. This band is more intense for the implanted sample, suggesting that defects generated by N implantation, likely related to the diffusion/segregation of indium (In), have been optically activated by the thermal treatment.

Tunable electronic structure in dilute magnetic semiconductor Sr3SnO/c-YSZ/Si (001) epitaxial heterostructures

We report a systematic study of the structural, physical, and chemical properties of epitaxial thin films of emerging dilute magnetic semiconductor (DMS) Sr3SnO (SSO) integrated with Si (100) prepared by various post-growth annealing treatments. The transport properties of these films are primarily governed by oxygen vacancies and the results are explained with the variable-range hopping model. The increased oxygen vacancy concentration generated by post-growth vacuum annealing results in a shorter hopping distance and reduced hopping energy and Coulomb gap, leading to lower resistivity; oxygen annealing shows the opposite effects. The work function ranges from 4.54 to 4.02 eV and shows a negative linear relationship with oxygen vacancy concentration, accompanied by a 0.42 eV shift in the surface Fermi level. The transport and ultraviolet photoelectron spectroscopy probes agree quantitatively on measurement of the resistivity and surface electronic structure. The results provide a direct and consistent explanation that the property changes in the bulk and at the surface are primarily attributed to oxygen vacancies, which are believed to be the carriers in the SSO thin films. The ability to manipulate the work function and oxygen vacancy concentration in epitaxial DMS SSO thin films offers great potential for the development of spintronic devices.

Tuning of deep level emission in highly oriented electrodeposited ZnO nanorods by post growth annealing treatments

Highly dense and c-axis oriented zinc oxide (ZnO) nanorods with hexagonal wurtzite facets were deposited on fluorine doped tin oxide coated glass substrates by a simple and cost-effective electrodeposition method at low bath temperature (80 °C). The as-grown samples were then annealed at various temperatures (TA = 100–500 °C) in different environments (e.g., zinc, oxygen, air, and vacuum) to understand their photoluminescence (PL) behavior in the ultra-violet (UV) and the visible regions. The PL results revealed that the as-deposited ZnO nanorods consisted of oxygen vacancy (VO), zinc interstitial (Zni), and oxygen interstitial (Oi) defects and these can be reduced significantly by annealing in different environments at optimal annealing temperatures. However, the intensity of deep level emission increased for TA greater than the optimized values for the respective environments due to the introduction of various defect centers. For example, for TA ≥ 450 °C in the oxygen and air environments, the density of Oi defects increased, whereas, the green emission associated with VO is dominant in the vacuum annealed (TA = 500 °C) ZnO nanorods. The UV peak red shifted after the post-growth annealing treatments in all the environments and the vacuum annealed sample exhibited highest UV peak intensity. The observations from the PL data are supported by the micro-Raman spectroscopy. The present study gives new insight into the origin of different defects that exist in the electrodeposited ZnO nanorods and how these defects can be precisely controlled in order to get the desired emissions for the opto-electronic applications.

Oxygen vacancy enhanced room-temperature ferromagnetism in Sr3SnO/c-YSZ/Si (001) heterostructures

Abstract

Annealing control of magnetic anisotropy and phase separation in CoFe2O4-BaTiO3 nanocomposite films

Multiferroic heteroepitaxial nanocomposite films of BaTiO3 and CoFe2O4 (CFO) have been grown by pulsed laser deposition employing alternating ablation of two ceramic targets. Films grown at temperatures between 650 °C and 710 °C contain columnar CFO grains about 10–20 nm in diameter embedded in a BaTiO3 matrix. The very strong vertical compression of these grains causes large perpendicular magnetic anisotropy. Post-growth annealing treatments above the growth temperature gradually release the compression. This allows one to tune the stress-induced magnetic anisotropy. Additionally, annealing leads to substantial enhancement of the saturation magnetization MS. Since MS of a pure CFO film remains unchanged by a similar annealing procedure, MS is proposed to depend on the volume fraction of the obtained CFO phase. We suggest that MS can be utilized to monitor the degree of phase separation in nanocomposite films.

Optimization of InGaAsN(Sb)/GaAs quantum dots for optical emission at 1.55 μm with low optical degradation

Low optical degradation in GaInAsN(Sb)/GaAs quantum dots (QDs) p–i–n structures emitting up to 1.55μm is presented in this paper. We obtain emission at different energies by means of varying N content from 1 to 4%. The samples show a low photoluminescence (PL) intensity degradation of only 1 order of magnitude when they are compared with pure InGaAs QD structures, even for an emission wavelength as large as 1.55μm. The optimization studies of these structures for emission at 1.55μm are reported in this work. High surface density and homogeneity in the QD layers are achieved for 50% In content by rapid decrease in the growth temperature after the formation of the nanostructures. Besides, the effect of N and Sb incorporation in the redshift and PL intensity of the samples is studied by post-growth rapid thermal annealing treatments. As a general conclusion, we observe that the addition of Sb to QD with low N mole fraction is more efficient to reach 1.55μm and high PL intensity than using high N incorporation in the QD. Also, the growth temperature is determined to be an important parameter to obtain good emission characteristics. Finally, we report room temperature PL emission of InGaAsN(Sb)/GaAs at 1.4μm.

Optical properties of the InAs/InAlGaAs quantum dots subjected to thermal treatments

The inter-diffusion kinetics of group-III elements at the interface between self-assembled InAs quantum dots (QDs) and InAlGaAs barriers were investigated indirectly by post-growth annealing treatments and photoluminescence (PL) spectroscopy. The emission wavelength of the InAs/InAlGaAs QDs subjected to thermal annealing at 550 °C was 1444 nm at 10 K, which indicated a 57 nm red shift compared to the as-grown sample (1387 nm). The emission wavelength was blue-shifted with further increases in annealing temperature to 650 °C. Although there was a blue shift in the emission wavelength at an annealing temperature of 600 and 650 °C, the emission peak was still longer than that of the as-grown sample. These results were explained by the difference in inter-diffusion probability between group-III elements at the interface between the InAs QDs and InAlGaAs barrier.

Effects of annealing on properties of ZnO thin films prepared by electrochemical deposition in chloride medium

The development of cost-effective and low-temperature synthesis techniques for the growth of high-quality zinc oxide thin films is paramount for fabrication of ZnO-based optoelectronic devices, especially ultraviolet (UV)-light-emitting diodes, lasers and detectors. We demonstrate that the properties, especially UV emission, observed at room temperature, of electrodeposited ZnO thin films from chloride medium (at 70 °C) on fluor-doped tin oxide (FTO) substrates is strongly influenced by the post-growth thermal annealing treatments. X-ray diffraction (XRD) measurements show that the films have preferably grown along (0 0 2) direction. Thermal annealing in the temperature range of 150–400 °C in air has been carried out for these ZnO thin films. The as-grown films contain chlorine which is partially removed after annealing at 400 °C. Morphological changes upon annealing are discussed in the light of compositional changes observed in the ZnO crystals that constitute the film. The optical quality of ZnO thin films was improved after post-deposition thermal treatment at 150 °C and 400 °C in our experiments due to the reducing of defects levels and of chlorine content. The transmission and absorption spectra become steeper and the optical bandgap red shifted to the single-crystal value. These findings demonstrate that electrodeposition have potential for the growth of high-quality ZnO thin films with reduced defects for device applications.

Near band-edge luminescence and evidence of the weakening of the N-conduction-band coupling for partially relaxed and high nitrogen composition GaAs1−xNx epilayers

Photoluminescence and absorption spectroscopy experiments are implemented on as-grown and thermally annealed GaAs1−xNx epilayers grown on GaAs(001) having a nitrogen content in the range of 0.4%–7.1%. At low temperature, photoluminescence spectra exhibit two sets of features: (i) a relatively broad peak at low energy in the vicinity of the band gap predicted by the band anticrossing model (BAC) and (ii) sharp excitonic features at higher energy (over 100meV above the band gap for x>4%). An enhancement of the photoluminescence response of excitonic emissions and a notable intensity reduction of the deeper luminescence were systematically observed for samples subjected to high-temperature postgrowth annealing treatments. For pseudomorphically strained low nitrogen-containing epilayers (x<2%), and by taking into account the strain magnitude and the average substitutional nitrogen concentration (as extracted from x-ray analysis), excitonic energies and corresponding band gaps (as determined by absorption spectroscopy) are well described within the framework of the BAC model. The extracted binding energies of split heavy- and light-hole excitons are found to be consistent with the expected increase of electron effective masses. For thick partially relaxed epilayers (1%<x<2%) and relaxed epilayers with high nitrogen content (x>4%), the fundamental band gap of GaAsN is found at significantly higher energies than those predicted by the BAC model using the commonly accepted nitrogen coupling parameter CNM=2.7eV. To account, within the BAC framework, for the apparent deceleration in the band-gap reduction rate requires the use of a smaller coupling constant (CNM=2.0eV), which suggests a weakening of the strength of the interaction between the localized nitrogen state and the conduction band of the host matrix. This observation seems to be associated with the increasing population of N-related defects.

Crystal Growth and Characterization of CdTe and Cd0.9Zn0.1Te for Nuclear Radiation Detectors

AbstractCdTe and Cd0.9Zn0.1Te (CZT) crystals have been studied extensively at EIC Laboratories, Inc. for various applications including x- and γ-ray imaging and high energy radiation detectors. The crystals were grown from in-house zone refined ultra pure precursor materials using a vertical Bridgman furnace. The growth process has been monitored, controlled and optimized by a computer simulation and modeling program (MASTRAPP). The grown crystals were thoroughly characterized after sequential surface passivations and post-growth annealing treatments with and without component overpressures. The infrared (IR) transmission images of the post-treated CdTe and CZT crystals showed average Te inclusion size of ∼10 μm for CdTe crystal and ∼8 μm for CZT crystal. The etch pit density was ≤ 5×104 cm−2 for CdTe and ≤ 3×104 cm−2 for CZT. Various planar and Frisch collar detectors were fabricated and evaluated. From the current-voltage measurements, the electrical resistivity was estimated to be ∼1.5×1010 Ω·cm for CdTe and 2-5×1011 Ω·cm for CZT. The Hecht analysis of electron and hole mobility-lifetime products (μτe and μτh) showed μτe=2×10−3 cm2/V (μτh=8×10−5 cm2/V) and μτ3-6×10−3 cm2/V (μτh=4-6×10−5 cm2/V) for CdTe and CZT, respectively. Final assessments of the detector performance have been carried out using 241Am (60 keV) and 137Cs (662 keV) energy sources and the results are presented in this paper.

Point defects in thermal SiO2 layers: Thermally stimulated luminescence and corona oxide electrical characterization

Point defects in thin (≈100 Å) SiO2 layers thermally grown on silicon were investigated by thermally stimulated luminescence (TSL) and corona oxide characterization of semiconductor measurements. A comparison is proposed between layers grown by steam and N2 diluted steam processes. The effects of post-growth annealing treatments in N2O, NO, and N2 atmospheres and of ion irradiation (As or P) have been investigated. A good correlation between the results obtained by the two different techniques has been found, suggesting a common structural origin of defects responsible for TSL active traps and total oxide charge.

GaAsN/AlAs/AlGaAs double barrier quantum wells grown by molecular beam epitaxy as an alternative to infrared absorption below 4 μm

In this work, we report on the design, growth and characterization of GaAsN/AlAs/AlGaAs double barrier quantum well infrared detectors to achieve intraband absorption below 4 μm. Due to the high effective mass of N-dilute alloys, it is common for these N-containing double barrier quantum well structures to have more than one bound state within the quantum well, enabling the possibility of achieving multispectral absorption from these confined levels to the quasi-bound. Based on a transfer matrix calculation we will study the influence of the potential parameters, in particular the well width and the introduction of a GaAs spacer layer in between the N-well and the AlAs barriers. We will compare the case in which there are two confined levels with the case in which only one level is bound, like in the conventional AlGaAs/AlAs/GaAs structures. On the basis of the simulation, we have grown and characterized some N-containing double barrier detectors. Moreover, an optimization of the post-growth annealing treatments of the GaAsN quantum well structures has also been performed. Finally, room temperature absorption measurements of both as-grown and annealed samples are presented and analyzed.

Magnetic resonance studies on ZnO nanocrystals

ZnO nanocrystals with diameters ranging from 4 to 50 nm were prepared via a wet chemical method and post-growth annealing treatments. The electron paramagnetic resonance (EPR) spectra of the nanocrystals show the resonance of electron centers with g-value close to that of the shallow donors in bulk ZnO. The temperature dependence of the resonance, which can be measured in the nanocrystals up to room temperature, shows the behavior expected from K· P theory for shallow donors, i.e. it decreases with increasing temperature due to the shrinkage of the bandgap. With decreasing diameter of the nanocrystals, we observe an increase of the g-values which is explained in terms of the quantum size effect.

Optical study of APCVD-grown Si 1− xGe x/Si quantum well structures under different post-growth annealing conditions

Single and double Si 1− x Ge x /Si quantum well (QW) structures, which were grown by atmospheric pressure chemical vapor deposition (APCVD), are characterized by photoluminescence and secondary-ion mass spectrometry. Systematic post-growth annealing treatments are carried out at temperatures between 600 and 1100°C in pure N 2 ambient. The interdiffusion between the Si layer and the Si 1− x Ge x well layers occurs at the annealing temperature around 900°C. From SIMS measurements for single QW structures we have estimated the activation energy which is about 3.9 eV in the temperature range between 950°C and 1100°C. The double QW structures show a similar value. The intensity of the exciton recombination related to carriers confined in the double QW structures decreases with increasing annealing temperatures and becomes strongly suppressed at 750°C. When the annealing temperature is increased further, the intensity of the QW emission recovers in the QW structures.

Radiation damage measurements of undoped lead tungstate crystals for the CMS electromagnetic calorimeter at LHC

A measurement method is described which allows to accurately track the scintillation light yield changes of lead tungstate crystals. The method has been used to study crystals to which post-growth high-temperature annealing treatments in various atmospheres were applied; it has allowed to select the most radiation resistant crystals and thus to optimize the annealing process. We describe the irradiation facility, irradiation procedure and results obtained. This work has led to the production of radiation resistant 50 mm long crystals and the process is now being extended to 230 mm long crystals.

Thermal Stability Of SiGe/Si Quantum Well Structures Grown By APCVD

AbstractSingle and double Si1-xGexx/Si quantum well (QW) structures, which were grown by atmospheric pressure chemical vapor deposition (APCVD), are characterized by photoluminescence and secondary ion mass spectrometry. Systematic post-growth annealing treatments were carried out at temperatures between 600°C and 1100°C in pure N2 ambient. The interdiffusion between the Si layer and the Si1-xGex, well layers occurs at the annealing temperature around 900°C. The diffusion coefficient is deduced at different temperatures from SIMS measurements for single QW structures. The activation energy is about 3.9 eV in the temperature range between 950°C and 1100°C. The double QW structures show a similar value, but the accurate value is more difficult to obtain because it is more complicated to analyze the SIMS profile of the double QW structures. The intensity of the exciton recombination related to carriers confined in the double QW structures decreases with increasing annealing temperatures and becomes strongly suppressed at 750°C. When the annealing temperature is increased further, the intensity of the QW emission recovers. The results indicate that nonradiative centers were generated at annealing temperature of about 750°C