A comprehensivesystematic method for chemical vapour deposition modelling consisting of sevenwell defined steps is presented. The method is general in the sense that it isnot adapted to a certain type of chemistry or reactor configuration. The methodis demonstrated using silicon carbide (SiC) as model system, with accuratematching to measured data without tuning of the model. We investigate the causeof several experimental observations for which previous research only have hadspeculative explanations. In contrast to previous assumptions, we can show thatSiCl2 does not contribute to SiC deposition. We can confirm thepresence of larger molecules at both low and high C/Si ratios, which have beenthought to cause so-called step-bunching. We can also show that highconcentrations of Si lead to other Si molecules than the ones contributing togrowth, which also explains why the C/Si ratio needs to be lower at theseconditions to maintain high material quality as well as the observed saturationin deposition rates. Due to its independence of chemical system and reactorconfiguration, the method paves the way for a general predictive CVD modellingtool.

The deposition rate of silicon carbide (SiC) in chemical vapor deposition (CVD) can be boosted by addition of chlorine. This has been explored and applied for hard coatings and electronic grade SiC. We briefly summarize the recent research done in the field of SiC CVD and discuss the understanding of the CVD chemistry with addition of halides. We seek to improve a previous statement that SiCl(2)is the main silicon species for growth of SiC. Recent experiments and modeling suggest that SiCl2, and its fluorinated and brominated analogues, are inactive and that SiF/SiCl/SiBr are the main halogenated species for growth.

The chemical vapour deposition (CVD) process, used to produce high quality, large area thin film coatings, is in many aspects a black box, where input parameters are adjusted to control the final deposition output, but where the underlying mechanisms are largely unknown. Modelling and simulations are sometimes used to unveil these mechanisms, but surprisingly few studies on CVD modelling use a systematic approach to ensure the model is adequate for its purpose. This leads to models that are useful only for certain experimental setups, or simulations resulting in already known data. Here, we present a comprehensive method for CVD modelling that certifies robustness and correct handling in all parts. The method is demonstrated using silicon carbide (SiC) as model system, explaining several experimental observations and accurately matching measured data without tuning of the model. The method thus paves the way for a general predictive CVD modelling tool for future materials and processes.

Highly resistive homoepitaxial layers of 4H-SiC have been grown on the Si-face of nominally on-axis, n-type substrates using chemical vapor deposition. Vanadium tetrachloride has been used as the V-dopant which is responsible for the high resistivity of the epilayers. 100% 4H-polytype was reproduced in the epilayers using the optimized on-axis growth process. The upper limit of vanadium tetrachloride flow rate was also established to achieve high resistivity epilayers free of 3C polytype inclusion. A resistivity of more than 1 × 105 Ω cm has been achieved in epilayers with a very low concentration of V (1 × 1015 cm−3). Owing to the low concentration of V, superior epilayer structural quality was achieved compared to V-doped and standard high purity semi-insulating bulk grown material of similar resistivity. Epitaxial layers with varying vanadium tetrachloride flow have also been grown to study the influence of V concentration on the polytype stability, structural quality, and optical and electrical properties of epilayers. A clear correspondence has been observed in the flow-rates of vanadium tetrachloride, the atomic concentration of V, and electrical, optical, and structural properties of epilayers.

Understanding the chemistry in CVD of SiC is important to be able to control, improve and scale up the process to become industrially competitive. A thorough understanding have so far been difficult to achieve due to the complex nature of the process. Through modeling tools, and a systematic approach when constructing the chemical models, new insights to the SiC CVD chemistry can be obtained. Using a general model that is independent on the choice of precursors and reactor configuration, and by coupling modeling results to experimental findings, we here show that SiCl2 and SiH2 previously suggested as the main silicon bearing growth species in the chlorinated and standard chemistries, respectively, does not contribute significantly to the SiC growth, and that the main active species are C2H2, CH3, Si, and SiCl.

Silicon carbide is a wide bandgap semiconductor with unique characteristics suitable for high temperature and high power applications. Fabrication of SiC epitaxial layers is usually performed using chemical vapor deposition (CVD). In this work, we use quantum chemical density functional theory (B3LYP and M06-2X) and transition state theory to study etching reactions occurring on the surface of SiC during CVD in order to combine etching effects to the surface kinetic model for SiC CVD. H2, H atoms and HCl gases are chosen in the study as the most likely etchants responsible for surface etching. We consider etchings of four surface sites, namely CH3(ads), SiH3CH2(ads), SiH2(CH2)2(ads), and SiH(CH2)3(ads), which represent four subsequent snapshots of the surface as the growth proceeds. We find that H atoms are the most effective etchant on CH3(ads) and SiH3CH2(ads), which represent the first and second steps of the growth. HCl and H2 are shown to be much less effective than H atoms and produce the etching rate constants which are ∼104 and ∼107 times slower. In comparison to CH3(ads), SiH3CH2(ads) is shown to be less stable and more susceptible to etchings. Unlike the first and second steps of the growth, the third and fourth steps (i.e., SiH2(CH2)2(ads) and SiH(CH2)3(ads)) are stable and much less susceptible to any of the three etchants considered. This implies that the growth species become more stable via forming Si-C bonds with another surface species. The formation of a larger surface cluster thus helps stabilizing the growth against etchings.

Silicon carbide is a wide bandgap semiconductor ideally suitable for high temperature and high power applications. An active SiC layer is usually fabricated using halide-assisted chemical vapor deposition (CVD). In this work, we use quantum chemical density functional theory (B3LYP and M06-2X) and transition state theory to study adsorptions of active Si species in the CVD process on both the Si face and the C face of 4H-SiC. We show that adsorptions of SiCl, SiCl2, SiHCl, SiH, and SiH2 on the Si face likely occur on a methylene site, CH2(ads), but the processes are thermodynamically less favorable than their reverse or desorptions. Nevertheless, the adsorbed products become stabilized with the help of subsequent surface reactions to form a larger cluster. These cluster formation reactions happen with rates that are fast enough to compete with the desorption processes. On the C face, the adsorptions likely occur on a surface site terminated by a dangling bond, *(ads), and produce the products which are thermodynamically stable. Lastly, we present the Gibbs free energies of adsorptions of Si atoms, SiX, SiX2, and SiHX, for X being F and Br. Adsorptions of Si atoms are shown to be the most thermodynamically favorable among all the species in the study. Among the halide-containing species, the Gibbs free energies (ARG) from smallest to largest are observed in the adsorptions of SiX, SiHX, and SiX2, for X being the halides. The results in this study suggest that the major Si contributors in the SiC CVD process are Si atoms, SiX (for X being the halide) and SiH.

Silicon carbide is a semiconductor material with ideal properties for high-temperature and high-power applications. The epitaxial layer fabrication Is usually performed using chemical vapor deposition (CVD) under a hydrogen rich atmosphere and high temperature. At such conditions the surface of the growing layer is expected to be passivatecl,by the abundantly present hydrogen. In this work, we use quantum chemical density functional theory (B3LYP and M06-2X) and transition state theory to study surface reactions related to the deposition of carbon on the (0001) surface of 4H-SiC. We show that it is unlikely for an adsorption to occur on a passivated, site unless the hydrogen termination is removed. We propose that unterminated sites can be effectively created during the CVD by an abstraction process. We provide details of the adsorption process of active carbon species, namely CH3, CH4, C2H2, and C2H4 gases, and their subsequent surface reactions such as desorption, abstraction of neighboring surface, hydrogens and dinner formation. The reaction rates and sticking coefficients are provided for the temperature range of 298-2500 K. Finally, entire reaction paths from adsorptions to stable surface products are presented and discussed.

We show by a combination of experiments and gas phase kinetics modeling that the combinations of precursors with the most well-matched gas phase chemistry kinetics gives the largest area of homoepitaxial growth of SiC.

The use of chlorinated chemical vapor deposition (CVD) chemistry for growth of homoepitaxial layers of silicon carbide (SiC) has diminished the problem of homogeneous gas-phase nucleation, mainly the formation of Si droplets, in CVD of SiC by replacing Si–Si bonds with stronger Si–Cl bonds. Employing the even stronger Si–F bond could potentially lead to an even more efficient CVD chemistry; however, fluorinated chemistry is very poorly understood for SiC CVD. Here, we present studies of the poorly understood fluorinated CVD chemistry for homoepitaxial SiC layers using SiF4 as Si precursor. We use a combination of experimental growth studies, thermal equilibrium calculations of gas-phase composition, and quantum chemical computations (i.e., hybrid density functional theory) of the surface chemistry to probe the silicon chemistry in the CVD process. We show that although growth rates on the order of 35 μm/h can be achieved with a fluorinated chemistry, the deposition chemistry is very sensitive to the mass ...

Carbon doping during CVD of GaN semiconductor materials is modeled using ab initio quantum chemical calculations and computational fluid dynamics.

AlGaN/GaN high electron mobility transistors (HEMTs) fabricated on a heterostructure grown by metalorganic chemical vapor deposition using an alternative method of carbon (C) doping the buffer are characterized. C-doping is achieved by using propane as precursor, as compared to tuning the growth process parameters to control C-incorporation from the gallium precursor. This approach allows for optimization of the GaN growth conditions without compromising material quality to achieve semi-insulating properties. The HEMTs are evaluated in terms of isolation and dispersion. Good isolation with OFF-state currents of 2 × 10 −6 A/mm, breakdown fields of 70 V/µm, and low drain induced barrier lowering of 0.13 mV/V are found. Dispersive effects are examined using pulsed current–voltage measurements. Current collapse and knee walkout effects limit the maximum output power to 1.3 W/mm. With further optimization of the C-doping profile and GaN material quality this method should offer a versatile approach to decrease dispersive effects in GaN HEMTs.

Atomization energies, enthalpies of formation, entropies as well as heat capacities of the SiHnXm and CHnXm systems, with X being F, Cl and Br, have been studied using quantum chemical calculations. The Gaussian-4 theory (G4) and Weizman-1 theory as modified by Barnes et al. 2009 (W1RO) have been applied in the calculations of the electronic, zero point and thermal energies. The effects of low-lying electronically excited states due to spin orbit coupling were included for all atoms and diatomic species by mean of the electronic partition functions derived from the experimental or computational energy splittings. The atomization energies, enthalpies of formation, entropies and heat capacities derived from both methods were observed to be reliable. The thermochemical properties in the temperature range of 298-2500 K are provided in the form of 7-coefficient NASA polynomials. (C) The Author(s) 2015. Published by ECS. All rights reserved.

Methane (CH4), ethylene (C2H4), acetylene (C2H2), propane (C3H8), iso-butane (i-C4H10), and trimethylamine [N(CH3)3] have been investigated as precursors for intentional carbon doping of (0001) GaN in chemical vapor deposition. The carbon precursors were studied by comparing the efficiency of carbon incorporation in GaN together with their influence on morphology and structural quality of carbon doped GaN. The unsaturated hydrocarbons C2H4 and C2H2 were found to be more suitable for carbon doping than the saturated ones, with higher carbon incorporation efficiency and a reduced effect on the quality of the GaN epitaxial layers. The results indicate that the C2H2 molecule as a direct precursor, or formed by the gas phase chemistry, is a key species for carbon doping without degrading the GaN quality; however, the CH3 species should be avoided in the carbon doping chemistry.

The creation of a semi insulating (SI) buffer layer in AlGaN/GaN High Electron Mobility Transistor (HEMT) devices is crucial for preventing a current path beneath the two-dimensional electron gas (2DEG). In this investigation, we evaluate the use of a gaseous carbon gas precursor, propane, for creating a SI GaN buffer layer in a HEMT structure. The carbon doped profile, using propane gas, is a two stepped profile with a high carbon doping (1.5 × 1018 cm−3) epitaxial layer closest to the substrate and a lower doped layer (3 × 1016 cm−3) closest to the 2DEG channel. Secondary Ion Mass Spectrometry measurement shows a uniform incorporation versus depth, and no memory effect from carbon doping can be seen. The high carbon doping (1.5 × 1018 cm−3) does not influence the surface morphology, and a roughness root-mean-square value of 0.43 nm is obtained from Atomic Force Microscopy. High resolution X-ray diffraction measurements show very sharp peaks and no structural degradation can be seen related to the heavy carbon doped layer. HEMTs are fabricated and show an extremely low drain induced barrier lowering value of 0.1 mV/V, demonstrating an excellent buffer isolation. The carbon doped GaN buffer layer using propane gas is compared to samples using carbon from the trimethylgallium molecule, showing equally low leakage currents, demonstrating the capability of growing highly resistive buffer layers using a gaseous carbon source.

Chlorinated chemical vapor deposition (CVD) chemistry for growth of homoepitaxial layers of silicon carbide (SiC) has paved the way for very thick epitaxial layers in short deposition time as well as novel crystal growth processes for SiC. Here, we explore the possibility to use a brominated chemistry for SiC CVD by using HBr as additive to the standard SiC CVD precursors. We find that brominated chemistry leads to the same high material quality and control of material properties during deposition as chlorinated chemistry and that the growth rate is on average 10% higher for a brominated chemistry compared to chlorinated chemistry. Brominated and chlorinated SiC CVD also show very similar gas-phase chemistries in thermochemical modeling. This study thus argues that brominated chemistry is a strong alternative for SiC CVD because the deposition rate can be increased with preserved material quality. The thermochemical modeling also suggest that the currently used chemical mechanism for halogenated SiC CVD might need to be revised.

4H-SiC epilayers grown by standard and chlorinated chemistry were analyzed for their minority carrier lifetime and deep level recombination centers using time-resolved photoluminescence (TRPL) and standard deep level transient spectroscopy (DLTS). Next to the well-known Z(1/2) deep level a second effective lifetime killer, RB1 (activation energy 1.05 eV, electron capture cross section 2 x 10(-16) cm(2), suggested hole capture cross section (5 +/- 2) x 10(-15) cm(2)), is detected in chloride chemistry grown epilayers. Junction-DLTS and bulk recombination simulations are used to confirm the lifetime killing properties of this level. The measured RB1 concentration appears to be a function of the iron-related Fe1 level concentration, which is unintentionally introduced via the corrosion of reactor steel parts by the chlorinated chemistry. Reactor design and the growth zone temperature profile are thought to enable the formation of RB1 in the presence of iron contamination under conditions otherwise optimal for growth of material with very low Z(1/2) concentrations. The RB1 defect is either an intrinsic defect similar to RD1/2 or EH5 or a complex involving iron. Control of these corrosion issues allows the growth of material at a high growth rate and with high minority carrier lifetime based on Z(1/2) as the only bulk recombination center.

Chemical vapor deposition of silicon carbide with a chloride-based chemistry can be done using several different silicon and carbon precursors. Here, we present a comparative study of SiCl4, SiHCl3, SiH4+HCl, C3H8, C2H4 and CH4 in an attempt to find the optimal precursor combination. We find that while the chlorinated silanes SiCl4 and especially SiHCl3 give higher growth rate than natural silane and HCl, SiH4+HCl gives better morphology at C/Si around 1 and SiCl4 gives the best morphology at low C/Si. Our study shows no effect on doping incorporation with precursor chemistry. We suggest that these results can be explained by the number of reaction steps in the gas phase chemical reaction mechanisms for producing SiCl2, which is the most important Si species, and by formation of organosilicons in the gas phase. As carbon precursor, C3H8 or C2H4 are more or less equal in performance with a slight advantage for C3H8, CH4 is however not a carbon precursor that should be used unless extraordinary growth conditions are needed. (C) The Author(s) 2014. Published by ECS.