Acceptor incorporation in SiC epilayers grown at high growth rate with chloride-based CVD

A systematic p-type doping study has been performed on 4H- and 6H-silicon carbide (SiC) epilayers grown at high growth rate using chloride-based chemical vapor deposition. The effect of temperature, pressure, growth rate, C/Si-, Cl/Si-ratios and dopant flow on the incorporation of the acceptor atoms aluminum and boron has been studied. The C/Si-ratio on the aluminum incorporation has similar behavior to what has been reported for the standard non-chlorinated low growth rate process, while no clear effect of C/Si-ratio was observed for the boron incorporation. A higher Cl/Si-ratio seems to lead to lower the aluminum and boron incorporation either due to more effective silicon supply at high Cl/Si-ratio or due to removal of dopant atoms from the surface by chlorine. The doping concentration is stable to the variations in silicon molar fraction, growth pressure and growth temperature for the aluminum-doped layers. Also p-type doping with gallium was tested.     

LPE growth of DH laser structures with the double source method

For the reproducible processing of double heterojunction injection laser structures to stripe geometry laser diodes, e.g. by proton bombardment, the thickness of the p-Ga_0.7Al_0.3As confining layer and of the p-GaAs top layer are of great importance. It is shown that the thickness control of these layers grown by liquid phase epitaxy can be improved considerably by introducing two source crystals into the growth system. Both source crystals are brought into contact with the solutions consecutively and prior to the seed. If this method is combined with the use of relatively thin melts (about 2 mm), a growth scheme may be chosen such that the growth rates of the p-GaAlAs and of the p-GaAs layers have reached a practically constant value on the seed crystal, independent of the initial degree of supersaturation. This behaviour is found to be in accordance with the diffusion-limited growth model applied for thin solutions, including a temperature dependence for both the diffusion constant and the slope of the liquidus curve. The results indicate that a second solid phase may appear in the p-GaAlAs solutions at a supersaturation as small as 4°C, which reduces the growth rate on the substrates by a factor of about 2. This situation is different from that of GaAs solutions, where a second phase appears only at a much higher degree of supersaturation. For the p-GaAlAs and the p-GaAs layers a thickness control of ⁺_-0.2 μm is thus achieved with this growth method, without the necessity of very precise temperature control and weighing so as to keep the total supersaturation less than 0.2°C.     

Current-controlled growth,segregation and amphoteric behavior of Si IN GaAs from Si-doped solutions

An unusual behavior of the growth kinetics and the segregation of Si during current-controlled LPE of GaAs is reported. The growth velocity (for a fiven current density) decreased by about two orders of magnitude from a value higher to a value smaller than that found in undoped solutions as the growth temperature decreased from 975 to 850°C; at 825°C dissolution of the substrate took place and a reversed current polarity was required for growth. At the same temperature range the growth velocity from undoped solutions decreased by a factor of only 3. Similarly, a two orders of magnitude decrease of the silicon segregation coefficient was observed for the same temperature change compared to changes by a factor or two in the thermally grown layers. For a given growth temperature (900°C) a change in conductivity from p- to n-type took place in the grown layers as the current density was increased. These findings were accounted for with a qualitative model based on the presence in the solution of different charged complexes containing silicon with different electromigrating characteristics. According to this model, the behavior of Si as p- and as n-type dopant (amphoteric dopant) in GaAs is related to the existence in the solution of the different charged complexes containing silicon.     

Investigations on the HCl gas-phase etching of differently doped and oriented gaas crystals

The influence of the orientation and dopant on the dissolution of GaAs surfaces in H₂–HCl gas mixtures has been investigated. For this purpose the etch rates, temperature regions of different etching behaviour and the corresponding activation energies were determined for temperatures ranging from 540 °C to 945 °C. The etch rate anisotropy is correlated with the three existing temperature regions of different dissolution mechanisms. The orientation-dependent transition temperatures are influenced by the dopant and can be related to the thermodynamic data of the dopant.     

Nucleation and growth kinetics for the crystallization of ice from dextrose solutions in a continuous stirred tank crystallizer with supercooled feed

The crystallization of ice in aqueous dextrose solutions is studied in an adiabatic continuous stirred tank crystallizer with a supercooled feed stream. The effective diameter of the ice crystals was determined for various values of mean crystal residence time, feed supercooling, magma density, stirring rate, and dextrose concentration. For all process conditions the supercooling was measured at 9-12 different locations in the crystallizer. These local supercoolings were averaged algebraically to yield the bulksupercooling. From the experimental results growth and nucleation rates have been calculated. By comparing the experimental growth rates to growth rates calculated by means of a mathematical model kinetics for the inbuilding of water molecules into the ice lattice have been determined. The growth rate appears to be directly proportional to the interface supercooling. The rate constant decreases exponentially with increasing weight percentage of dextrose in the solution. The nucleation rate was found to be directly proportional to total crystal surface per unit volume of suspension and proportional to the bulksupercooling to the power 2.1. Nucleation is believed to occur by breakage of dendrites from the surface of parent crystals.     

In-process monitoring and control of doping gas concentration during vapor phase silicon epitaxial growth by using a flame photometric detector

An in-process monitoring and control method of the doping gas concentration during epitaxial growth of Si was developed. A flame photometric detector (FPD) can be used as a monitor for the PH₃ and B₂H₆ dopant concentrations in the injected doping gases. A combination of this dopant monitor with an automatic control system of the silicon source (SiHCl₃) gas concentration using an infrared spectrophotometer as a monitor, makes possible an automatic in-process control of the concentrations of dopant and of silicon source gas supplied to the reactor. The present system provides an accurate and reproducible control of impurity concentrations in Si epitaxial layers. Good correlation between the monitored signal (or the doping gas concentration) and the impurity concentration incorporated into the growth layers was confirmed for PH₃ (n-type) and B₂H₆ (p-type) doping. For the B₂H₆ doping, a divergence from the linear relationship between the doping gas concentration and the impurity concentration in the layers was observed in the level of acceptor concentration below about 10¹⁵ atoms/cm³. The transient response of the present system was measured by growing epitaxial layers with increasing and decreasing step-changes in the dopant gas flow during continuous deposition of the layers. Some interesting, but complicated, transient responses of impurity concentration in the growth layer were observed. The responses are different between the PH₃ doping and the B₂H₆ doping, and also different between increasing and decreasing steps especially for the B₂H₆ doping.     

Analysis of ambient gas influence on silicon layers crystallized by means of LPE

Epitaxial growth of thin layers from the liquid phase can occur with the use of solutions saturated under different ambient gases. Most often this process takes place in a vacuum or gaseous atmosphere of hydrogen or argon. As the experimental data show, the morphology of crystallized layers is determined by the ambient type in which the process occurs.The cohesion energy responsible for epitaxial lateral deposition processes on the substrate surface depends on the surface free energy which is a measure of attraction of the solution atoms by substrate atoms. In the case of crystallization of an epitaxial lateral layer of Si on a substrate partially masked with dielectric, the chemical potentials of atoms in the neighboring phases (determining the interface evolution) are not without influence on the relaxation velocity of the saturated liquid phase, and on the horizontal and vertical growth rate.The aim of the investigation was to analyze experimentally the influence of the ambient gases used during the LPE growth on the cohesion of the Sn–Si solution with substrates applied for the lateral epitaxial growth of Si layers. This work presents comparative temperature analysis of the wetting angle of such surfaces as Si, SiO₂ and SiN_x by the Sn–Si solution.     

Influence of phosphine flow rate on Si growth rate in gas source molecular beam epitaxy

As reported by other authors, we have also observed that the Si growth rate decreases with increasing phosphine (PH₃) flow rate in gas source Si molecular beam epitaxy using phosphorous (P) as a n-type dopant. Why small quantity PH₃ can affect Si growth rate? Up to now, the quantitative characterization of PH₃ flow influence on Si growth rate is little known. In this letter, the PH₃ influence will be analyzed in detail and a model considering strong P surface segregation and its absorption of hydrogen will be proposed to characterize the effect.     

多次热氧化削减硅通孔内壁扇贝纹

硅通孔(TSV)在三维集成系统中扮演着非常重要的角色.BOSCH刻蚀技术是当前主流的硅通孔刻蚀方法,因为刻蚀和钝化交替进行,这种干法刻蚀工艺不可避免地会在硅通孔的内部形成扇贝纹,其尺度一般在几十纳米到几百纳米不等.扇贝纹会导致后续填充的各层材料以及它们之间的界面不平滑,从而严重影响TSV的性能以及三维集成系统的可靠性....     

Growth of Zn‐doped Germanium under Microgravity

The doping of germanium with zinc from a remote, temperature‐stabilized source was studied under microgravity. A nominally undoped Ge‐crystal was grown by the Gradient‐Freeze technique with the melt surface being in permanent contact with a gaseous atmosphere of zinc. The dopant and carrier concentrations in the solidified Germanium were measured by SIMS, Hall and resistance measurements and compared with the results of a terrestrial reference experiment as well as with concentration profiles calculated on the basis of the thermodynamics of the growth system. The results prove the possibility of vapour phase doping under microgravity. Moreover, the Zn‐concentration at the initial phase boundary even agrees well with the equilibrium value, strongly indicating a nearly homogeneous distribution of the dopant within the melt before the crystallization.     

Confinement of δ Be at the one monolayer level in GaAs

We investigate growth dependences to the planar confinement of Be near the 1 monolayer, ML, level when δ doped in GaAs. We examine concentration dependences on the rates of segregation and diffusion, as well as the effect of As₂, As₂ and AsH₃ overpressure on Be confinement during growth. Evidence from both chemical profiling and surface electron diffraction point to a Be surface dimerization process that drives dopant segregation.     

Tin and tellurium doping of InAs using SnTe in molecular beam epitaxy (MBE)

Tin telluride (SnTe) was utilized as an n-type dopant in the MBE growth of InAs epitaxial layers on GaAs substrates. The highest carrier concentration obtained was 2.9 × 10¹⁹ cm^-3 and the carrier density could be varied over three orders of magnitude by changing the SnTe source temperature. The highest mobilities obtained were 16,900 and 23,300 cm²/V … s at 300 and 77 K, respectively, for carrier concentration of 5 × 10¹⁶ cm^-3. Both Sn and Te were incorporated in the layers as determined by secondary ion mass spectroscopy (SIMS) analysis and the total concentration of Sn and Te were the same as the carrier density in the layer.     

Low temperature growth of AlGaAs by MOMBE (CBE) using trimethylamine alane

In order to gain further insight into the surface chemistry of AlGaAs growth by metalorganic molecular beam epitaxy, we have investigated the deposition behavior and material quality of AlGaAs grown at temperatures from 350 to 500°C using trimethylamine alane (TMAA), triethylgallium (TEG) and arsine (AsH₃). Though the Al incorporation rate decreases with decreasing temperature, Ga-alkyl pyrolysis, and hence Ga incorporation rate, declines more rapidly. Thus the Al content increases from X_AlAs = 0.25 at 500°C to X_AlAs = 0.57 at 350°C. Below 450°C, the Ga incorporation rate appears to be determined by the desorption of diethylgallium species, rather than interaction with adsorbed AlH₃. Similarly, carbon incorporation is enhanced by 2 orders of magnitude over this temperature range due to the increasingly inefficient pyrolysis of the Ga-C bond in TEG. Additionally, active hydrogen from the TMAA1, which normally is thought to getter the surface alkyls, is possibly less kinetically active at lower growth temperatures. Contrary to what has been observed in other growth methods, low growth temperatures produced a slight decrease in oxygen concentration. This effect is likely due to reduced interaction between Ga alkoxides (inherent in the TEG) and the atomic hydrogen blocked Al species on the growth surface. This reduction in oxygen content and increase in carbon concentration causes the room temperature PL intensity to actually increase as the temperature is reduced from 500 to 450°C. Surprisingly, the crystalline perfection as measured by ion channeling analysis is quite good, χ_min≤5%, even at growth temperatures as low as 400°C. At 350°C, the AlGaAs layers exhibit severe disorder. This disorder is indicative of insufficient Group III surface mobility, resulting in lattice site defects. The disorder also supports our conclusions of kinetically limited surface mobility of all active surface components.     

Growth and annealing effect of high-quality ZnSe:N/ZnSe by MOCVD

The ZnSe : N epitaxial layers were grown on (1 1 0) ZnSe substrates in a low-pressure metalorganic chemical vapor deposition (MOCVD) system using hydrogen as a carrier gas, and using ammonia as a dopant source. In order to obtain highly doped ZnSe : N epitaxial layers, the optimum growth and doping conditions were determined by studying the photoluminescence (PL) spectra from the ZnSe epitaxial layers grown at different ammonia flux and VI/II flux ratio. Furthermore, in order to enhance the concentration of active nitrogen in ZnSe epitaxial layer, a rapid thermal anneal technique was used for post-heat-treating. The results show that the annealing temperature of over 1023 K is necessary. Beside, a novel treatment method to obtain a smooth substrate surface for growing high quality ZnSe epitaxial layers is also described.     

Autodoping of Epitaxial Silicon Layers (III). Theoretical Treatment of Lateral Autodoping

Solving dopants from the silicon surface into the volume during epitaxial layer growth is commonly described as a solution equilibrium, which forms an essential part of modelling intentional silicon doping. Above buried layers a so-called redistribution autodoping causes the inversely directed process within an initial layer growth period. When the layer begins to grow, the dopants are not totally buried by the silicon deposited, but are partially swept towards the surface to develop the redistribution equilibrium. Above that part of the layer surface located above buried layers, simultaneously a certain dopant partial pressure is established. It gives rise to a vertical and lateral dopant transport by means of gas diffusion. The flow in lateral direction is considered the source of lateral autodoping. In the present paper a theoretical model of autodoping is developed and the layer deposition parameters are discussed with regard to minimizing autodoping effects.     

Kinetic aspects in the vapour phase epitaxy of III–V compounds

Successful exploitation of the unique properties of III–V compound semiconductors has resulted in development of several new devices for optoelectronic and solid state microwave applications. These achievements, however, would not have been possible without major advances in the technology for epitaxial growth of such materials. Further improvements in device performances together with new applications of III–V compounds must be closely coupled with even more progress toward achievement of material with properties approaching the theoretical values. Chemical vapour deposition has emerged as the most common technique for epitaxial growth. Although significant improvements can be obtained through empirical methods of investigation of such processes, it is recognized that in the long run a firm fundamental understanding is essential. This realization provides the motivation for detailed, basic studies of the kinetics and thermodynamics of epitaxial growth by chemical vapour deposition. This review will examine the progress, both past and projected, in measurement and interpretation of the kinetics of vapour phase deposition of III–V epitaxial layers. The scope will be limited to near-atmospheric pressure, open flow epitaxial systems utilizing chemical transport. To date, most of the studies have concerned GaAs, GaP, InAs, InP, and their alloys. It has been demonstrated for GaAs, and for some of the other compounds as well, that, depending on the growth conditions, epitaxial deposition may proceed in two fundamentally different rate-limiting regimes. At low temperatures the rate is limited by a surface process; while at higher temperatures mass transport limitations appear to prevail. For mass-transport-limited deposition the sensitivity of the growth rate to various operating parameters can, in many cases, be predicted from theoretical considerations. Investigation of kinetically limited growth offers a path toward a fundamental understanding of the atomistic surface events that result in epitaxial growth. The progress in these areas will be discussed; in addition, experimental and theoretical tasks for future studies will be recommended.     

Extended defects in bulk GaN and III-nitrides grown on this substrate

A short review of the structural perfection of high-pressure grown bulk crystals is given. As-grown undoped and Mg-doped crystals are described. The dependence of defect arrangement and quality of the surface on growth polarity is described. A high perfection of homoepitaxial layers grown on these substrates is shown. However, growth of thick layers by HVPE may lead to the formation of differently arranged dislocations and the formation of low angle grain boundaries associated with cracks. It is shown that the introduction of dopant or growth of mismatched layers on undoped high-pressure substrates may lead to the formation of additional defects.     

Effect of electrical field on growth of gallium arsenide layers from vapour phase

The effect of electrical fields on the growth rate and morphology of gallium arsenide layers in the GaAs AsCl₃ H₂ system is investigated. The fields both parallel and perpendicular to the substrate surface are used. It is found that application of the parallel field results n increase of growth rate of (111)A face but does not change that of 2° (001). The morphology of layers grown in such a field is better than that grown without any. The application of perpendicular field results in decrease of growth rate for both crystallographic orientations, the layer morphology worthening. In both cases the effect is greater when the substrate has a negative potential. Possible mechanisms of the field influence on the growth rates of gallium arsenide layers are discussed such as: supersaturation decrease because of nucleation in vapour phase and the change in the rates of surface processes.     

The effects of varying metal precursor fluxes on the growth of InAlN by metal organic vapour phase epitaxy

InAlN is a relatively new addition to the palette of nitride semiconductor alloys, with potential applications in distributed Bragg reflectors and high electron mobility transistors. However relatively little is known about the effects of different growth conditions on InAlN’s structure and properties and more importantly what these effects can tell us about the surface processes of growth. Here we have investigated the effects of varying various metal fluxes. First, we varied the total fluxes of all the precursors while maintaining their ratios. This led to an increase in growth rate, of itself very desirable, but at the considerable cost of significantly roughened surfaces. Analysis of these surfaces using power spectral density functions suggests that they were all produced by a combination of stochastic roughening and smoothing by surface diffusion, suggesting that at a given temperature increasing the growth rate will always lead to roughening. In addition, we examined the effect of varying just the trimethylindium flux (and therefore varying the indium to gallium ratio). As this flux was increased the indium incorporation initially increased but then levelled off, and for further increases the amount of indium on the surface as droplets increases significantly, suggesting that there is a limit to the indium incorporation that than be achieved at a given temperature and pressure. This suggests that there are practical limits to simultaneously achieving high growth rates, high indium contents and low surface roughnesses.