Effect of the substrate temperature on the crystallization of TiO2 films prepared by DC reactive magnetron sputtering

Titanium oxide (TiO₂) films were deposited on silicon substrates at the temperature in the range 50–600 °C by DC reactive magnetron sputtering. It was found that the anatase and rutile phases co-existed in the TiO₂ films deposited at 450–500 °C, while only the anatase phase existed in those deposited at other temperatures. The mechanism of such a crystallization behavior of TiO₂ films is preliminarily explained.     

Epitaxial growth of ZnO thin films on Si substrates by PLD technique

Epitaxial ZnO thin films have been grown on Si(1 1 1) substrates at temperatures between 550 and 700 °C with an oxygen pressure of 60 Pa by pulsed laser deposition (PLD). A ZnO thin film deposited at 500 °C in no-oxygen ambient was used as a buffer layer for the ZnO growth. In situ reflection high-energy electron diffraction (RHEED) observations show that ZnO thin films directly deposited on Si are of a polycrystalline structure, and the crystallinity is deteriorated with an increase of substrate temperature as reflected by the evolution of RHEED patterns from the mixture of spots and rings to single rings. In contrast, the ZnO films grown on a homo-buffer layer exhibit aligned spotty patterns indicating an epitaxial growth. Among the ZnO thin films with a buffer layer, the film grown at 650 °C shows the best structural quality and the strongest ultraviolet (UV) emission with a full-width at half-maximum (FWHM) of 86 meV. It is found that the ZnO film with a buffer layer has better crystallinity than the film without the buffer layer at the same substrate temperature, while the film without the buffer layer shows a more intense UV emission. Possible reasons and preventive methods are suggested to obtain highly optical quality films.     

Effect of NH3 on the growth characterization of TiN films at low temperature

Titanium nitride (TiN) films were obtained by the atmospheric pressure chemical vapor deposition method of the TiCl₄–N₂–H₂ system with various flow rates of NH₃ at 600°C. The growth characteristics, morphology and microstructure of the TiN films deposited were analyzed by X-ray diffraction, scanning electron microscopy and transmission electron microscopy. Without NH₃ addition, no TiN was deposited at 600°C as shown in the X-ray diffraction curve. However, by adding NH₃ into the TiCl₄–N₂–H₂ system, the crystalline TiN was obtained. The growth rate of TiN films increased with the increase of the NH₃ flow rate. The lattice constant of TiN films decreased with the increase of the NH₃ flow rate. At a low NH₃ flow rate, the TiN (2 2 0) with the highest texture coefficient was found. At a high NH₃ flow rate, the texture coefficient of TiN (2 0 0) increased with the increase of the NH₃ flow rate. In morphology observation, thicker plate-like TiN was obtained when the NH₃ flow rate was increased. When the flow rate of NH₃ was 15 sccm, Moiré fringes were observed in the TiN film as determined by TEM analysis. The intrinsic strain was found in the TiN film as deposited with 60 sccm NH₃.     

Effects of growth temperature on the properties of ZnO/GaAs prepared by metalorganic chemical vapor deposition

A series of ZnO films were grown on GaAs(0 0 1) substrates at different growth temperatures in the range 250–720°C by metalorganic chemical vapor depostion. Field emission scanning electron microscopy was utilized to investigate the surface morphology of ZnO films. The crystallinity of ZnO films was investigated by the double-crystal X-ray diffractometry. The optical and electrical properties of ZnO films were also investigated using room-temperature photoluminescence and Hall measurements. Arrhenius plots of the growth rate versus reciprocal temperature revealed the kinetically limited growth behavior depending on the growth temperature. It was found that the surface morphology, structural, optical and electrical properties of the films were improved with increasing growth temperature to 650°C. All the properties of the film grown at 720°C were degraded due to the decomposition of ZnO film.     

Characteristic crystal growth from amorphous WO3 film by vacuum heating

Selective growth of WO₂, W and WO_3−x crystals from amorphous WO₃ film by vacuum heating at 400–900°C was clarified. The grown WO_3−x crystals were incommensurate structure based on crystallographic share structure. The growth process of WO₂ crystal in the amorphous film was directly observed at high temperature in the electron microscope. The growth front of the WO₂ crystal consumes WO₃ microcrystallites with various orientations. The growth speed of the WO₂ depended on WO₃ microcrystallites orientation. The origin of the wavy growth front of WO₂ was due to an orientation dependence of the WO₃ microcrystallites.     

Impedance spectroscopy analysis of AlGaN/GaN HFET structures

For HFET application a series of samples with 30 nm Al_xGa_1−xN (x=0.02–0.4) layers deposited at 1040°C onto optimised 2 μm thick undoped GaN buffers were fabricated. The Al_xGa_1−xN/GaN heterostructures were grown on c-plane sapphire in an atmospheric pressure, single wafer, vertical flow MOVPE system. Electrical properties of the Al_xGa_1−xN/GaN heterostructures and thick undoped GaN layers were evaluated by impedance spectroscopy method performed in the range of 80 Hz–10 MHz with an HP 4192A impedance meter using a mercury probe. The carrier concentration distribution through the layer thickness and the sheet carrier concentration were evaluated. A non-destructive, characterisation technique for verification of device heterostucture quality from the measured C–V and G–V versus frequency characteristics of the heterostructure is proposed.     

Agglomeration control during the selective epitaxial growth of Si raised sources and drains on ultra-thin silicon-on-insulator substrates

We have studied the impact of several Si selective epitaxial growth (SEG) process on the agglomeration of ultra-thin, patterned silicon-on-insulator (SOI) layers. Through a careful analysis of the effects of the in situ H₂ bake temperature (that followed an ex situ “HF-last” wet cleaning) and of the silicon growth temperature on the SOI film quality, we have been able to develop a low-temperature SEG process that allows the growth of Si on patterned SOI layers as thin as 3.4 nm without any agglomeration or Si moat recess at the Si window/shallow trench isolation edges. This process consists of an in situ H₂ bake at 650 °C for 2 min, followed by a ramping-up of the temperature to 750 °C, then some SEG of Si at 750 °C using a chlorinated chemistry (i.e. SiH₂Cl₂+HCl).     

Selective epitaxial growth of Si1−xGex by cold-wall ultrahigh vacuum chemical vapor deposition using disilane and germane

Selective epitaxial growth of Si_1−xGe_x alloys in a cold-wall-type ultrahigh vacuum chamber using pure disilane and pure germane was studied at a constant temperature 550°C. The germanium content in the grown layer was increased as the germane flow rate increased. In all cases, the germanium content in the solid is less than the germane content in the gaseous source. The growth rate was enhanced by germane addition. It is conceivable that the growth rate enhancement is due to increasing the germanium content in the solid. Selectivity was constant at high disilane flow rate and increased at low disilane flow rate by germane addition. Selective epitaxial growth of Si_1−xGe_x was successfully achieved with high growth rate.     

Ambient-condition growth of superconducting YBa2Cu4O8 single crystals using KOH flux

YBa₂Cu₄O₈ is a stoichiometric oxide superconductor of T_c80 K. Unlike YBa₂Cu₃O_7−δ, this compound is free from oxygen vacancy or twin formation and does not have any microscopic disorder in the crystal. Doping with Ca raises its T_c to 90 K. The compound is a promising superconductor for technological application. Up to now, single crystals have not been grown without using specialized apparatus with extremely high oxygen pressure up to 3000 bar and at over 1100 °C due to the limited range of reaction kinetics of the compound. This fact has delayed the progress in the study of its physical properties and potential applications. We present here a simple growth method using KOH as flux that acts effectively for obtaining high-quality single crystals in air/oxygen at the temperature as low as 550 °C. As-grown crystals can readily be separated from the flux and exhibit a perfect orthorhombic morphology with sizes up to 0.7×0.4×0.2 mm³. Our results are reproducible and suggest that the crystals can be grown using a conventional flux method under ambient condition.     

Correlation between interfacial structure and c-axis-orientation of LiNbO3 films grown on Si and SiO2 by electron cyclotron resonance plasma sputtering

Thin films of crystalline lithium niobate (LN) grown on Si(1 0 0) and SiO₂ substrates by electron cyclotron resonance plasma sputtering exhibit distinct interfacial structures that strongly affect the orientation of respective films. Growth at 460–600 °C on the Si(1 0 0) surface produced columnar domains of LiNbO₃ with well-oriented c-axes, i.e., normal to the surface. When the SiO₂ substrate was similarly exposed to plasma at temperatures above 500 °C, however, increased diffusion of Li and Nb atoms into the SiO₂ film was seen and this led to an LN–SiO₂ alloy interface in which crystal-axis orientations were randomized. This problem was solved by solid-phase crystallization of the deposited film of amorphous LN; the degree of c-axis orientation was then immune to the choice of substrate material.     

XPS and electroluminescence studies on SrS1−xSex and ZnS1−xSex thin films deposited by atomic layer deposition technique

SrS_1−xSe_x and ZnS_1−xSe_x thin films were deposited by the atomic layer deposition (ALD) technique using elemental selenium as the Se source, thus avoiding use of H₂Se or organometallic selenium compounds. X-ray diffraction (XRD) analysis showed that the films were solid solutions and X-ray photoelectron spectroscopy (XPS) data showed that the surface of both ZnS_1−xSe_x and SrS_1−xSe_x were covered with an oxide and carbon-containing contaminants from exposure to air. The oxidation of SrS_1−xSe_x extended into the film and peak shifts from sulfate were found on the surface. Luminance measurements showed that emission intensity of the ZnS_1−xSe_x:Mn alternating current thin film electroluminescent (ACTFEL) devices at fixed voltage was almost the same as that of the ZnS:Mn device, while emission intensity of the SrS_1−xSe_x:Ce devices decreased markedly as compared to the SrS:Ce device. Emission colors of the devices were altered only slightly due to selenium addition.     

Epitaxial growth of the CoFe2O4 film on SrTiO3 and its characterization

Cobalt ferrite (CoFe₂O₄) thin film is epitaxially grown on (0 0 1) SrTiO₃ (STO) by laser molecular beam epitaxy (LMBE). The growth modes of CoFe₂O₄ (CFO) film are found to be sensitive to laser repetition, the transitions from layer-by-layer mode to Stranski–Krastanov (SK) mode and then to island mode occur at the laser repetition of 3 and 5 Hz at 700 °C, respectively. The X-ray diffraction (XRD) results show that the CFO film on (0 0 1) SrTiO₃ is compressively strained by the underlying substrate and exhibits high crystallinity with a full-width at half-maximum of 0.86°. Microstructural studies indicate that the as-deposited CFO film is c-oriented island structure with rough surface morphology and the magnetic measurements reveal that the compressive strained CoFe₂O₄ film exhibits an enhanced out-of-plane magnetization (190 emu/cm³) with a large coercivity (3.8 kOe).     

The effect of oxygen pressure on the microstructures of Co-doped rutile TiO2 thin films grown by pulsed laser deposition

Comprehensive microstructures of 7% cobalt-doped rutile TiO₂ thin films grown on c-plane sapphire by pulsed laser deposition were characterized using transmission electron microscopy (TEM). The effects of oxygen pressure during growth on the Co distribution inside the films were investigated, and the detailed growth mechanism of both TiO₂ and TiO₂+Co was discussed. The similar oxygen sublattices and low mismatch between (1 0 0) rutile and c-plane sapphire favors the rutile phase. However, the three-fold symmetry of the substrate surface resulted in three rutile domain orientation variants, and they grow adjacent to each other. Cobalt was found to precipitate out as nanocrystals inside the TiO₂ matrix as the growth pressure of oxygen was decreased. At 0.05 mTorr oxygen pressure, almost all of the Co segregates into crystallographically aligned nanocrystals with a particle size of 4.4±0.15 nm. All the samples have magnetic coercivity at room temperature. The magnetic moment per Co atom increased with decreased oxygen pressure, suggesting that the Co that replaced the Ti²⁺ in the TiO₂ lattice does not have a large magnetic moment.     

CrO2 (1 0 0) and TiO2 (1 0 0) film heteroepitaxy on a BaF2 (1 1 1)/Si (1 0 0) substrate

Multi-domained heteroepitaxial rutile-phase TiO₂ (1 0 0)-oriented films were grown on Si (1 0 0) substrates by using a 30-nm-thick BaF₂ (1 1 1) buffer layer at the TiO₂–Si interface. The 50 nm TiO₂ films were grown by electron cyclotron resonance oxygen plasma-assisted electron beam evaporation of a titanium source, and the growth temperature was varied from 300 to 600 °C. At an optimal temperature of 500 °C, X-ray diffraction measurements show that rutile phase TiO₂ films are produced. Pole figure analysis indicates that the TiO₂ layer follows the symmetry of the BaF₂ surface mesh, and consists of six (1 0 0)-oriented domains separated by 30° in-plane rotations about the TiO₂ [1 0 0] axis. The in-plane alignment between the TiO₂ and BaF₂ films is oriented as [0 0 1] TiO₂ || BaF₂ or [0 0 1] TiO₂ || BaF₂ . Rocking curve and STM analyses suggest that the TiO₂ films are more finely grained than the BaF₂ film. STM imaging also reveals that the TiO₂ surface has morphological features consistent with the BaF₂ surface mesh symmetry. One of the optimally grown TiO₂ (1 0 0) films was used to template a CrO₂ (1 0 0) film which was grown via chemical vapor deposition. Point contact Andreev reflection measurements indicate that the CrO₂ film was approximately 70% spin polarized.     

Step annealing effects on the structural and optical properties of InAs quantum dots grown on GaAs

The effects of multi-step rapid thermal annealing (RTA) for the self-assembled InAs quantum dots (QDs), which were grown by a molecular beam epitaxy (MBE), were investigated through photoluminescence (PL) and transmission electron microscopy (TEM). Postgrowth multi-step RTA was used to modify the structural and optical properties of the self-assembled InAs QDs. Postgrowth multi-step RTAs are as follows: one step (20 s at 750 °C); two step (20 s at 650 °C, 20 s at 750 °C); three step (30 s at 450 °C, 20 s at 650 °C, 20 s at 750 °C). It is found that significant narrowing of the luminescence linewidth (from 132 to 31 meV) from the InAs QDs occurs together with about 150 meV blueshift by two-step annealing, compared to as-grown InAs QDs. Observation of transmission electron microscopy (TEM) shows the existence of the dots under one- and two-step annealing but the disappearance of the dots by three-step annealing. Comparing with the samples under only one-step annealing, we demonstrate a significant enhancement of the interdiffusion in the dot layer under multi-step annealing.     

Metalorganic vapor-phase epitaxy of III/V phosphides with tertiarybutylphosphine and tertiarybutylarsine

Indium phosphide, gallium arsenide phosphide, and aluminum indium phosphide have been deposited by metalorganic vapor-phase epitaxy using tertiarybutylphosphine and tertiarybutylarsine. The effects of growth temperature and V/III ratio on the amount of silicon, sulfur, carbon, and oxygen in InP have been determined. Minimum incorporation was observed at 565 °C and a V/III ratio of 32. In this case, the material contained a background carrier concentration of 2.7×10¹⁴ cm⁻³, and the Hall mobilities were 4970 and 135,000 cm²/V s at 300 and 77 K. The oxygen contamination in AlInP was found to be only 9.0×10¹⁵ cm⁻³ for deposition at 650 °C and a V/III ratio of 35. The relative distribution of arsenic to phosphorus in GaAs_yP_1−y was determined at temperatures between 525 and 575 °C. The distribution coefficient [(N_As/N_P)_film/(P_TBAs/P_TBP)_gas] ranged from 25.4 to 8.4, and exhibited an Arrhenius relationship with an apparent activation energy of 1.2 eV.     

Solubility of YBa2Cu3O7−δ and Nd1+xBa2−xCu3O7±δ in the BaO/CuO flux

The knowledge of the phase relations and solubilities in the Y–Ba–Cu–O and Nd–Ba–Cu–O systems are of fundamental importance for crystal growth and liquid-phase epitaxy of YBa₂Cu₃O_7−δ (YBCO) and Nd_1+xBa_2−xCu₃O_7±δ (NdBCO). The determination of the solubility curve of YBCO and NdBCO in a BaO/CuO flux containing 31 mol% BaO was done by observation of the formation and dissolution of crystals on the surface of the high-temperature solution. The heat of the solution of YBCO at 1000°C was found to be 34.7 kcal/mol, and for NdBCO at 1060°C, it was found to be 28.1 kcal/mol. The determination of the solubility curves requires special care, and the problems of the time-dependent shift of the solution composition due to the corrosion of the crucible is discussed. The scatter of the solubility data published by different authors could be due to the use of solutions with different Ba : Cu ratios, different determination methods, i.e. different crystallization mechanisms, different crucibles and starting chemicals.     

MBE growth of cubic AlyGa1−yN/GaN heterostructures—structural, vibrational and optical properties

Cubic Al_yGa_1−yN/GaN heterostructures on GaAs(0 0 1) substrates were grown by radio-frequency plasma-assisted molecular beam epitaxy. High resolution X-ray diffraction, micro-Raman, spectroscopic ellipsometry, and cathodoluminescence measurements were used to characterize the structural, optical and vibrational properties of the Al_yGa_1−yN epilayers. The AlN mole fraction y of the alloy was varied between 0.07<y<0.20. X-ray diffraction reciprocal space maps demonstrate the good crystal quality of the cubic Al_yGa_1−yN films. The measured Raman shift of the phonon modes of the Al_yGa_1−yN alloy was in excellent agreement with theoretical calculations. Both SE and CL of the Al_yGa_1−yN epilayer showed a linear increase of the band gap with increasing Al-content.     

Photocurrent measurements on GaAs1−xNx epilayers grown by metalorganic chemical vapor deposition

GaAs_1−xN_x epilayers were grown on a GaAs(0 0 1) substrate by metalorganic chemical vapor deposition. Composition was determined by high resolution X-ray diffraction. Band gap was measured from 77 to 400 K by using photocurrent measurements. The photocurrent spectra show clear near-band-edge peak and their peak energies drastically decrease with increasing nitrogen composition due to band gap bowing in the GaAs_1−xN_x epilayers. Those red shifts were particularly notable for low nitrogen compositions. However, the shifts tended to saturate when the nitrogen composition become higher than 0.98%. When the nitrogen composition is in the range 1.68–3.11%, the measured temperature dependence of the energy band gap was nicely fitted. However, the properties for the nitrogen composition range 0.31–0.98% could not be fitted with a single fitting model. This result indicates that the bowing parameter reaches 25.39 eV for low nitrogen incorporation (x=0.31%), and decreases with increasing nitrogen composition.     

Growth behavior and microstructure of Ge self-assembled islands on nanometer-scale patterned Si substrate

We investigate the growth behavior and microstructure of Ge self-assembled islands of nanometer dimension on Si (0 0 1) substrate patterned with hexagonally ordered holes of 25 nm depth, 30 nm diameter, and 7×10¹⁰ cm⁻² density. At 9 Å Ge coverage and 650 °C growth temperature, Ge islands preferentially nucleate inside the holes, starting at the bottom perimeter. Approximately 14% of the holes are filled by Ge islands. Moiré fringe analysis reveals partial strain relaxation of about 72% on average, which is not uniform even within a single island. Crystalline defects such as dislocation are observed from islands smaller than 30 nm. Increased Ge coverage to 70 Å forms larger aggregates of many interconnected islands with slightly increased filling factor of about 17% of the holes. Reducing the growth temperature to 280 °C results in much higher density of islands with a filling factor of about 80% and with some aggregates. The results described in this report represent a potential approach for fabricating semiconductor quantum dots via epitaxy with higher than 10¹⁰ cm⁻² density.