Geometric modeling of homoepitaxial CVD diamond growth: I. The {1 0 0}{1 1 1}{1 1 0}{1 1 3} system

Plasma-assisted CVD homoepitaxial diamond growth is a process that must satisfy many stringent requirements to meet industrial applications, particularly in high-power electronics. Purity control and crystalline quality of the obtained samples are of paramount importance and their optimization is a subject of active research. In the process of such studies, we have obtained high purity CVD diamond monocrystals with unusual morphologies, namely with apparent {1 1 3} stable faces. This phenomenon has led us to examine the process of CVD diamond growth and build up a 3D geometrical model, presented here, describing the film growth as a function of time. The model has been able to successfully describe the morphology of our obtained crystals and can be used as a predictive tool to predetermine the shape and size of a diamond crystal grown in a given process configuration. This renders accessible control of desirable properties such as largest usable diamond surface area and/or film thickness, before the cutting and polishing manufacture steps take place. The two latter steps are more sensitive to the geometry of the growth sectors, which will be addressed in a companion paper.Our model, applicable to the growth of any cubic lattice material, establishes a complete mapping of the final morphology state of growing diamond, as a function of the growth rates of the crystalline planes considered, namely {1 0 0}, {1 1 1}, {1 1 0}, and {1 1 3} planes, all of which have been observed experimentally in diamond films. The model makes no claim as to the stability of the obtained faces, such as the occurrence of non-epitaxial crystallites or twinning. It is also possible to deduce transient behavior of the crystal morphology as growth time is increased. The model conclusions are presented in the form of a series of diagrams, which trace the existence (and dominance) boundaries of each face type, in presence of the others, and where each boundary crossing represent a topology change in terms of number of faces, edges and vertices. We validate the model by matching it against crystals published in the literature and illustrate its predictive value by suggesting ways to increase usable surface area of the diamond film.     

High-quality diamond films grown at high deposition rates using high-power-density MWPCVD method with conventional quartz-type chamber

Undoped and boron-doped homoepitaxial diamond films with high quality have been successfully grown on high-pressure/high-temperature-synthesized type-Ib single-crystalline diamond (1 0 0) substrates. In the growth process, a conventional microwave-plasma (MWP) chemical-vapor-deposition (CVD) system with an easily-exchangeable 36-mm-inner-diameter quartz-tube growth chamber was employed under a condition of high MW power densities while a rather high methane concentration (4%) and high substrate temperatures (>1000 °C) were used. The growth conditions applied to the undoped and B-doped diamond thin films were separately optimized by controlling the MW plasma density and substrate temperatures. The homoepitaxial films thus grown yielded strong exciton-related luminescence even at room temperature, meaning that their crystalline quality was good and roughly comparable with that of homoepitaxial films deposited using a high-power MWPCVD system with a stainless steel chamber having a rather large diameter. This indicates that by using such a conventional deposition system with inexpensive and easily-exchangeable exclusive-use quartz-tube chambers, various growth experiments can be performed under different process conditions without any severe interference among the different experiments.     

ZnO microtube ultraviolet detectors

ZnO stands a good chance of being a candidate material for solar-blind UV detection because of its direct band-gap of 3.37 eV and high photoresponse. In this work, we present the UV photodetection properties of ZnO single crystal microtubes synthesized using a microwave-heating growth method. The ZnO microtubes exhibited relatively fast UV photoresponse with a cut-off wavelength ～370 nm, indicating their potential application as UV detectors with high efficiency and low cost.     

Effects of vicinal angles from (0 0 1) surface on the Boron-doping features of high-quality homoepitaxial diamond films grown by the high-power microwave plasma chemical-vapor-deposition method

Vicinal surface effects on homoepitaxial growth and boron-doping processes have been studied in case of single-crystalline diamond (0 0 1) surfaces grown using the high-power microwave plasma chemical-vapor-deposition (MWPCVD) method. The off-angles inclined from the on-orientation (0 0 1) surfaces ranged to 5° along the [1 1 0] or [1 0 0] direction, while the concentration of doping B(CH₃)₃ gas was kept constant with a B/C ratio of 50 ppm. Although a number of square-like growth hillocks often appeared, depending substantially on the crystalline quality of the high-pressure/high-temperature-synthesized (HPHT) Ib diamond substrates employed, the number and shape of the hillocks changed significantly with the increasing off-angle. For the vicinal surfaces with off-angles of ≈3° inclined along the [1 1 0] direction, macroscopically flat surfaces were obtained, compared with the other off-angle cases examined. Furthermore, the growth rate and acceptor density of substitutional boron atoms in the homoepitaxial layers were found to substantially increase with the increasing off-angle. These indicate that the step density can play important roles not only in the homoepitaxial growth but also in the boron-incorporation process during the high-power MWPCVD growth.     

VUV and IR absorption spectra induced in H2-loaded and UV hyper-sensitized standard germanosilicate preform plates through exposure to ArF laser light

H₂-loaded Ge-doped preform plates have been UV hyper-sensitized and subsequently post-exposed by means of UV ArF laser pulses at 193 nm. Both Fourier Transform Infrared (FTIR) and Vacuum Ultraviolet (VUV) absorption spectroscopy has been carried out at each step of the sensitization process with a view to get a better understanding of the UV hyper-sensitization process at 193 nm. Exposing the H₂-loaded samples firstly triggers a partial bleaching of the 5 eV absorption band, followed by a new growth of the band for longer exposure time. As it has already been reported for exposure at 248 nm, the exposure at 193 nm firstly yields an increase in the absorption ascribed to hydroxyl (≈3600 cm⁻¹), hydride species (≈2140–2185 cm⁻¹) and GeE′ defects (≈6.3 eV). The evolution of the absorption related to the GeH₂ species is not monotonous but rather the absorption reaches a peak (N_pre = 2000) and then slightly decreases for further exposure time. Post-exposing the hyper-sensitized samples (N_pre = 2000) lead to a partial bleaching of the absorption ascribed to hydride species and to increases in the intensity of the GeE′ defect-related absorption and in the absorption ascribed to hydroxyl species. The accurate determination of the species concentration from the absorption spectra proved to be rather tricky due to the problem of accurately measuring the depth of the UV beam penetration at each time of the exposure. Nevertheless, a correlation could be established between the growth of the UV-induced UV excess loss ascribed to GeE′ species and the UV-induced decrease in the intensity of the IR bands related to hydride species. These observations are discussed within the frame-work of the two step model.     

Laser heated pedestal growth of potassium lithium niobate for UV generation

Potassium lithium niobate (KLN) is a nonlinear optical material with a high nonlinearity. It has the potential to improve the performance and reduce the cost of blue and UV lasers. KLN crystals are not commercially viable because growth by traditional techniques is not possible. In an effort to develop commercially viable KLN, single crystals of the material were grown by the laser heated pedestal growth method (LHPG) with compositions of x=0.02, 0.06 and 0.2 following K₃Li_2?xNb_5+xO_15+2x. Noncritical phase matching at 20 °C for previously unreported compositions of x=0.02 and 0.06 was measured at 795 nm and 805 nm, respectively. Overall, the results suggest that single crystal KLN can be used for SHG into the UV region of the spectrum and can be developed into a commercially viable nonlinear optical material.     

Growth of pure ZnO thin films prepared by chemical spray pyrolysis on silicon

Structural, morphological, optical and electrical properties of ZnO thin films prepared by chemical spray pyrolysis from zinc acetate (Zn(CH₃COO)₂ 2H₂O) aqueous solutions, on polished Si(1 0 0), and fused silica substrates for optical characterization, have been studied in terms of deposition time and substrate temperature. The growth of the films present three regimes depending on the substrate temperature, with increasing, constant and decreasing growth rates at lower, middle, and higher-temperature ranges, respectively. Growth rate higher than 15 nm min⁻¹ can be achieved at T_s=543 K. ZnO film morphological and electrical properties have been related to these growth regimes. The films have been characterized by X-ray diffraction, scanning electron microscopy and X-ray photoelectron spectroscopy.     

High quality MOCVD GaN film grown on sapphire substrates using HT-AlN buffer layer

In this work we report on the growth and characterization of high quality MOCVD GaN film grown on Al₂O₃ substrates by using a HT (>1150 °C)-AlN buffer layer. We have investigated the most favorable growth conditions in terms of temperature, thickness and growth rate of AlN buffer layer in order to optimize the high temperature GaN layer. The improved morphological and structural properties of GaN layer were verified by AFM and XRD measurements. The optimized GaN layer presents a smooth surface with a rms value of 1.4 Å. The full width at half maximum (FWHM) for 800 nm thick GaN films is 144″. Furthermore PL measurements and C–V analysis confirm that in GaN layer grown on HT-AlN buffer layer defect density is drastically reduced.     

FTIR and UV–VIS optical absorption spectra of gamma-irradiated MoO3-doped lead borate glasses

Structure and optical properties of MoO₃-doped lead borate glasses which contain high PbO content (60, 70 and 80%) have been studied using Fourier transform infrared (FTIR) and ultraviolet–visible (UV–VIS) spectroscopic tools. FTIR spectra reveal absorption bands which are characteristic for various structural units of borate network, mainly BO₃ triangles and BO₄ tetrahedra, in addition to the PbO_n (where n = 3 and/or 4) structural units. UV–VIS optical absorption spectra reveal broad intense charge transfer UV bands due to Pb^2 + ions in the range 320–385 nm. Within this range, molybdenum ions, preferably Mo^3 + and Mo^5 +, can interfere at about 360–385 nm. Additionally, molybdenum ions give a weak visible band at about 850–860 nm. The optical absorption spectra of the studied glasses show marked resistance to successive gamma irradiation up to 5 Mrad. This shielding behavior can be related to the present high content of the high atomic mass Pb^2 + ions. Changes in the atomic structure before and after gamma irradiation are described and explained.     

Thermal decomposition and new luminescence bands in wet,dry, and additional oxygen implanted silica layers

Wet and dry silica oxide layers have been treated thermally up to T_a = 1300 °C and were investigated by cathodoluminescence (CL) spectroscopy. Whereas the dry oxides after high temperature treatment show an increase of the yellow–red spectra region, contrary, in wet oxides the UV–blue region is enhanced. Even a new strong band in the near-UV region (NV) at 330 nm (3.76 eV) is found for wet oxides at liquid nitrogen temperature (LNT), but much broader and with lower intensity for room temperature (RT) in a triple band structure UV: 290 nm, NV: 330 nm, and V: 400 nm. These violet bands should be associated with a thermally decomposed and rapidly cooled-down silica network in presence of OH groups or even dissociated oxygen. Additional oxygen implantation into dry silica with high doses up to 10¹⁷ ions/cm² and high thermal treatment T > 1100 °C leads as well to enhanced UV–NV–V luminescence emission bands supporting the fact that oxygen and structural decomposition play a decisive role in formation of near-UV luminescent defects in silica.     

A narrow process window for the preparation of polytypes of microcrystalline silicon carbide thin films by hot-wire CVD method

Effects of deposition conditions on the structure of microcrystalline silicon carbide (μc-SiC) films prepared by hot-wire chemical vapor deposition (hot-wire CVD) method have been investigated. It is found from X-ray diffraction patterns of the film that a diffraction peak from crystallites from hexagonal polytypes of SiC is observed in addition to those of 3 C-SiC crystallites. This result is obtained in the film under a narrow deposition conditions of SiH₃CH₃ gas pressure of 8 Pa, the H₂ gas pressure of 80–300 Pa and the total gas pressure of 40–300 Pa under fixed substrate and filament temperatures employed in this study. Furthermore, the grain size of hexagonal crystallites (about 20 nm) on c-Si substrates becomes larger than that of 3 C-SiC crystallites (about 10 nm) for the films deposited under the total gas pressure of 36–88 Pa. The fact that microcrystalline hexagonal SiC can be deposited under limited deposition conditions could be interpreted in the context of a result for c-SiC polytypes prepared by thermal CVD method.     

GeO2 based high k dielectric material synthesized by sol–gel process

Recently, there has been lot of research on new high dielectric constant (high k) materials for use in future generations of ultra-large scale integrated circuits (ULSI). There are number of requirements for the new high k materials, such as high dielectric constant, thermal stability (400 °C or higher), high mechanical strength, and good adhesion to neighboring layers. Keeping in view the properties required for the replacement of existing SiO₂ dielectrics, new high k dielectric material based on GeO₂ has been synthesized. Polycrystalline GeO₂ thin films have been deposited by simple, and cost effective sol–gel spin coating process. The obtained xerogel films of germanium oxide have been annealed at 400 °C, 600 °C and 800 °C for 3 h in argon atmosphere. Elemental composition, morphology, and phase analysis have been measured by employing X-ray photoelectron spectroscopy, scanning electron microscopy, and X-ray diffraction techniques, respectively. The formation of the hexagonal GeO₂ phase at and above 400 °C has been reported. The composition of the annealed films have been measured and found to be 68 at.% of O, 32 at.% of Ge for GeO₂, which are close to the stoichiometry of the GeO₂.     

Simulation of temperature and gas density field distribution in diamond films growth on silicon wafer by hot filament CVD

In the present study, the temperature and gas density field inside the hot filament chemical vapor deposition (HFCVD) reactor, which play a determinate role on the growth rate and quality of as-deposited diamond films, are simulated using the finite volume method, and the influence of the size and arrangement of filaments and inlets are investigated. Firstly, the correctness of the simulation model is verified by comparing the temperature data obtained from the simulation with that measured in an actual depositing process, and the results show that the error between them is less than 3%. Thereafter, the deposition parameters are optimized using this model as N(filament number)=6, r(filament radius)=0.4 mm, D(filament separation)=16–18 mm, H(substrate–filament distance)=8–9 mm, and 25 inlets. Finally, diamond films are deposited on silicon (100) wafers using above parameters and the results of characterization by SEM and Raman spectrum exhibit that the deposited diamond films appear homogeneous surface with fine-faceted crystals.     

Nonlinear optical studies of lead lanthanum borate glass doped with Au nanoparticles

Synthesis, characterization and optical nonlinearity of lead lanthanum borate glass embedded with gold nanoparticles have been investigated. DSC thermogram shows characteristics glass transition temperature at T_g = 775 K. Glasses doped with Au were subjected to heat treatment at 823 K with different annealing time and then, slowly cooled to room temperature show striking ruby color. SAED and TEM analyses have confirmed that f.c.c. Au nanoparticles of ~ 40 nm size are present in these glasses. An absorption peak centered on 563 nm has been observed in heat treated samples, which is attributed to surface plasmon resonance of gold nanoparticles. Nonlinear optical studies with open aperture Z-Scan technique show saturable absorption for heat treated samples at low intensity and reverse saturable absorption in samples without heat treatment at high intensity.     

Preparation and characterization of CdGeAs2 crystal by modified vertical Bridgman method

A large, crack-free CdGeAs₂ single crystal measuring 15 mm in diameter and 45 mm in length was grown in a vertical three-zone tubular furnace by a modified vertical Bridgman method, i.e. quasi-seed technique with small temperature gradient and descending quartz ampoule. High-purity, single phase CdGeAs₂ polycrystallite for crystal growth was synthesized using a rocking furnace with temperature oscillation techniques. Various measuring means, including X-ray diffractometer(XRD), Fourier transform infrared spectroscopy(FTIR), and Field emission scanning electron microscope(FE-SEM) were adopted to characterize the as-grown crystal. It is found that the cleavage plane of the as-grown crystal is {1 0 1} face; the crystal is integrated in structure and crystallized well; etch pits in the shape of pentagon on (1 1 2) face have been observed for the first time using the new preferential etchant we prepared. All these results encouragingly indicate that the modified vertical Bridgman method is a convenient and effective way for high quality CdGeAs₂ crystal growth.     

Mechanisms controlling primary crystallisation of Ga20Te80 glasses

The kinetic study of the crystallisation process of Ga₂₀Te₈₀ glass from isothermal and continuous heating calorimetric data have been performed applying a recently developed procedure. The kinetic information was complemented with X-ray diffraction measurements. With this scope, three crystallisation patterns, with three-dimensional isotropic growth have been analysed: (i) site saturation and interface controlled growth. (ii) homogeneous nucleation with interface controlled growth and (iii) homogeneous nucleation with two simultaneous modes of crystal growth (interface- and diffusion-controlled). A complex model with two simultaneous modes of three-dimensional isotropic crystal growth with decreasing homogeneous nucleation and soft impingement has been applied for modelling primary crystallisation of the Ga₂₀Te₈₀ glass. The model goes beyond the isokinetic hypothesis when coupling isothermal and continuous heating kinetic data. The apparent activation energy E_a = (2.06 ± 0.03) eV/at obtained for the primary crystallisation of the phase Te is shown to correspond to an activation energy for nucleation E_I = (2.85 ± 0.03) eV/at and an interface controlled activation energy for growth E_u = (1.90 ± 0.03) eV/at at the crystallisation onset.     

A facile route for the fabrication of CeO2 nanosheets via controlling the morphology of CeOHCO3 precursors

The morphology and size of the functional oxide rare earth material CeO₂ are crucial for its efficient applications. CeO₂ nanosheets, which are 30–50 nm in thickness and about 300 nm in the lateral direction, have been synthesized via controlling the morphology of CeOHCO₃ precursors by a facile hydrothermal technique. The dependences of morphologies and phase transitions of CeOHCO₃ precursors on reaction time, chemical compositions are investigated in detail. Results show that the precursors exhibit changes both in morphology and phase structure as reaction time elongated. One-dimensional nanowire morphology with an orthorhombic phase structure is obtained when the reaction time is less than 3 h, while two-dimensional nanosheet with a hexagonal phase structure is formed when the reaction time is more than 9 h. The detailed transition process is recorded by snapshots of products between 3 and 9 h. Experimental results reveal that the amount of acetic acid is a key parameter for the nucleation and crystal growth of CeOHCO₃ nanosheets. A defect driven dissolving and recrystallization mechanism is proposed for the phase and morphology transition behavior of the precursors. The CeO₂ nanosheets are obtained after thermal decomposition of the precursors. Compared to the nanodisk, the CeO₂ nanosheets show a blue shift in the UV–Vis absorption spectra due to the quantum confinement effect.     

Device grade hydrogenated polymorphous silicon deposited at high rates

Hydrogenated polymorphous silicon (pm-Si:H) thin films have been deposited by plasma-enhanced chemical vapor deposition at high rate (8–10 Å/s), and a set of complementary techniques have been used to study transport, localized state distribution, and optical properties of these films, as well as the stability of these properties during light-soaking. We demonstrate that these high deposition rate pm-Si:H films have outstanding electronic properties, with, for example, ambipolar diffusion length (L_d) values up to 290 nm, and density of states at the Fermi level well below 10¹⁵ cm^?3 eV^?1. Consistent with these material studies, results on pm-Si:H PIN modules show no dependence of their initial efficiency on the increase of the deposition rate from 1 to 10 Å/s. Although there is some degradation after light-soaking, the electronic quality of the films is better than for degraded standard hydrogenated amorphous silicon (values of L_d up to 200 nm). This result is reflected in the light-soaked device characteristics.     

Growth and characterization of InxBi2−xTe3 single crystals

The V–VI group narrow band gap compounds are known to have important photoconductivity and thermoelectric properties. Among these, Bi₂Te₃ is the most potential material for thermoelectric devices having a direct band gap of 0.16 eV. There has been ample study reported on crystal growth and polycrystalline thin films of both pure and indium doped Bi₂Te₃ pertaining to its basic semiconducting, optoelectronic and thermoelectric properties. It has been shown that on exceeding certain limiting concentration of indium in Bi₂Te₃, the conductivity changes from p-type to n-type. However, there is hardly any work reported in literature on crystal growth, dislocation etching and optical band gap of In_xBi_2?xTe₃ (x=0.1, 0.2, 0.5) single crystals. The authors have grown their single crystals using the zone melting method. The freezing interface temperature gradient of 70 °C/ cm^?1 has been found to yield the best quality crystals obtainable at the growth rate of 0.4 cm/h. The as-grown crystals have been observed to exhibit certain typical features on their top free surfaces. The crystals have been characterized using XRD technique. A chemical dislocation etchant has been used for estimating perfection in terms of dislocation density in the crystals. The optical absorption was measured in the wave number range 500 to 4000 cm^?1. The transitions in all the cases were observed to be allowed direct type. The detailed results are reported in the paper.     

Amorphous silicon diamond based heterojunctions with high rectification ratio

We have fabricated and characterized diamond based heterojunctions composed of homoepitaxial diamond (B-doped film: p type) and hydrogenated amorphous silicon (a-Si:H film: n-type). All devices include an intrinsic amorphous silicon interface (i-a-Si:H). (J–V) characteristics of a-Si:H heterojunctions measured from 300 K to 460 K present a very high rectification ratio (in the range 10⁸–10⁹) and a current density of 10 mA/cm² under 2 V of forward bias. The reverse current up to ? 4 V is below the detection limit in the whole temperature range. The devices present two regimes of operation indicating that more than one mechanism governs the carrier transport. These characteristics are compared with a Schottky barrier diode (SBD) using a tungsten carbide metal on top of the p-type diamond as a Schottky contact. The SBD device exhibits J–V characteristic with an ideality factor n close to one and the heterojunction follows this trend for low bias voltages whereas for bias voltage above 1 V a second regime with larger ideality factors n ~ 3.6 is observed. These results point out the prominent role of transport mechanisms at heterointerface between the a-Si:H layers and the p-type doped diamond which degrades the current injection. The breakdown voltage reached ? 160 V indicating the good quality of the deposited layers.