Hot-wall Chemical Vapor Deposition Research Articles

Research on the Influence of Carbon Sources and Buffer Layers on the Homogeneous Epitaxial Growth of 4H-SiC.

In this study, a 4H-SiC homoepitaxial layer was grown on a 150 mm 4° off-axis substrate using a horizontal hot wall chemical vapor deposition reactor. Comparing C3H8 and C2H4 as C sources, the sample grown with C2H4 exhibited a slower growth rate and lower doping concentration, but superior uniformity and surface roughness compared to the C3H8-grown sample. Hence, C2H4 is deemed more suitable for commercial epitaxial wafer growth. Increasing growth pressure led to decreased growth rate, worsened thickness uniformity, reduced doping concentration, deteriorated uniformity, and initially improved and then worsened surface roughness. Optimal growth quality was observed at a lower growth pressure of 40 Torr. Furthermore, the impact of buffer layer growth on epitaxial quality varied significantly based on different C/Si ratios, emphasizing the importance of selecting the appropriate conditions for subsequent device manufacturing.

High crystalline quality homoepitaxial Si-doped β-Ga2O3(010) layers with reduced structural anisotropy grown by hot-wall MOCVD

A new growth approach, based on the hot-wall metalorganic chemical vapor deposition concept, is developed for high-quality homoepitaxial growth of Si-doped single-crystalline β-Ga2O3 layers on (010)-oriented native substrates. Substrate annealing in argon atmosphere for 1 min at temperatures below 600 °C is proposed for the formation of epi-ready surfaces as a cost-effective alternative to the traditionally employed annealing process in oxygen-containing atmosphere with a time duration of 1 h at about 1000 °C. It is shown that the on-axis rocking curve widths exhibit anisotropic dependence on the azimuth angle with minima for in-plane direction parallel to the [001] and maximum for the [100] for both substrate and layer. The homoepitaxial layers are demonstrated to have excellent structural properties with a β-Ga2O3(020) rocking curve full-widths at half-maximum as low as 11 arc sec, which is lower than the corresponding one for the substrates (19 arc sec), even for highly Si-doped (low 1019 cm−3 range) layers. Furthermore, the structural anisotropy in the layer is substantially reduced with respect to the substrate. Very smooth surface morphology of the epilayers with a root mean square roughness value of 0.6 nm over a 5 × 5 μm2 area is achieved along with a high electron mobility of 69 cm2 V−1 s−1 at a free carrier concentration n=1.9×1019 cm−3. These values compare well with state-of-the-art parameters reported in the literature for β-Ga2O3(010) homoepitaxial layers with respective Si doping levels. Thermal conductivity of 17.4 Wm−1K−1 is determined along the [010] direction for the homoepitaxial layers at 300 K, which approaches the respective value of bulk crystal (20.6 Wm−1K−1). This result is explained by a weak boundary effect and a low dislocation density in the homoepitaxial layers.

Low Al-content n-type Al[formula omitted]Ga[formula omitted]N layers with a high-electron-mobility grown by hot-wall metalorganic chemical vapor deposition

In this work, we demonstrate the capability of the hot-wall metalorganic chemical vapor deposition to deliver high-quality n-AlxGa1−xN (x = 0–0.12, [Si] = 1×1017 cm−3) epitaxial layers on 4H-SiC(0001). All layers are crack-free, with a very small root mean square roughness (0.13–0.25 nm), homogeneous distribution of Al over film thickness and a very low unintentional incorporation of oxygen at the detection limit of 5×1015 cm−3 and carbon of 2×1016 cm−3. Edge type dislocations in the layers gradually increase with increasing Al content while screw dislocations only raise for x above 0.077. The room temperature electron mobility of the n-AlxGa1−xN remain in the range of 400–470 cm2/(V.s) for Al contents between 0.05 and 0.077 resulting in comparable or higher Baliga figure of merit with respect to GaN, and hence demonstrating their suitability for implementation as drift layers in power device applications. Further increase in Al content is found to result in significant deterioration of the electrical properties.

1,4-Bis(trimethylsilyl)piperazine—Thermal Properties and Application as CVD Precursor

We report an investigation into 1,4-Bis-N,N-(trimethylsilyl)piperazine (BTMSP) as a novel precursor for the synthesis of silicon carbonitride films by chemical vapor deposition (CVD). The thermal stability, temperature dependence of vapor pressure and thermodynamic constants of the evaporation process of BTMSP were determined by static tensimetry with a glass membrane zero manometer. The transformation of the compound in low-power (25 W) plasma conditions was investigated by optical emission spectroscopy. It was shown that BTMSP undergoes destruction, accompanied by H and CH elimination and CN formation. SiCN(H) films were deposited in a hot-wall plasma-enhanced CVD reactor. The optical properties of the films were studied by spectral ellipsometry (refractive index: 1.5–2.2; absorption coefficient: 0–0.12) and UV–Vis spectroscopy (transmittance: up to 95%; optical bandgap: 1.6–4.9 eV). Information on the aging behavior of the films is also provided. The transformation of the films occurred through water adsorption and the formation of Si–O bonds with the degradation of Si–H, N–H and Si–CHx–Si bonds.

Impact of Doping on Cross-Sectional Stress Assessment of 3C-SiC/Si Heteroepitaxy.

In this paper, we used micro-Raman spectroscopy in cross-section to investigate the effect of different doping on the distribution of stress in the silicon substrate and the grown 3C-SiC film. The 3C-SiC films with a thickness up to 10 μm were grown on Si (100) substrates in a horizontal hot-wall chemical vapor deposition (CVD) reactor. To quantify the influence of doping on the stress distribution, samples were non-intentionally doped (NID, dopant incorporation below 1016 cm-3), strongly n-type doped ([N] > 1019 cm-3), or strongly p-type doped ([Al] > 1019 cm-3). Sample NID was also grown on Si (111). In silicon (100), we observed that the stress at the interface is always compressive. In 3C-SiC, instead, we observed that the stress at the interface is always tensile and remains so in the first 4 µm. In the remaining 6 µm, the type of stress varies according to the doping. In particular, for 10 μm thick samples, the presence of an n-doped layer at the interface maximizes the stress in the silicon (~700 MPa) and in the 3C-SiC film (~250 MPa). In the presence of films grown on Si(111), 3C-SiC shows a compressive stress at the interface and then immediately becomes tensile following an oscillating trend with an average value of 412 MPa.

Tuning composition in graded AlGaN channel HEMTs toward improved linearity for low-noise radio-frequency amplifiers

Compositionally graded channel AlGaN/GaN high electron mobility transistors (HEMTs) offer a promising route to improve device linearity, which is necessary for low-noise radio-frequency amplifiers. In this work, we demonstrate different grading profiles of a 10-nm-thick AlxGa1−xN channel from x = 0 to x = 0.1 using hot-wall metal-organic chemical vapor deposition (MOCVD). The growth process is developed by optimizing the channel grading and the channel-to-barrier transition. For this purpose, the Al-profiles and the interface sharpness, as determined from scanning transmission electron microscopy combined with energy-dispersive x-ray spectroscopy, are correlated with specific MOCVD process parameters. The results are linked to the channel properties (electron density, electron mobility, and sheet resistance) obtained by contactless Hall and terahertz optical Hall effect measurements coupled with simulations from solving self-consistently Poisson and Schrödinger equations. The impact of incorporating a thin AlN interlayer between the graded channel and the barrier layer on the HEMT properties is investigated and discussed. The optimized graded channel HEMT structure is found to have similarly high electron density (∼ 9 × 10 12 cm−2) as the non-graded conventional structure, though the mobility drops from ∼ 2360 cm2/V s in the conventional to ∼ 960 cm2/V s in the graded structure. The transconductance gm of the linearly graded channel HEMTs is shown to be flatter with smaller g m ′ and g m ″ as compared to the conventional non-graded channel HEMT implying improved device linearity.

Growth behavior of CVD Ti(C,N,O) coating on cemented carbide controlled by CO and the mechanism

In α-Al2O3-based chemical vapor deposition (CVD) coatings, Ti(C,N)- or Ti(C,N,O)-based layer exerts a significant influence on the crystal growth of α-Al2O3 and the performance of the coated cemented carbide cutting tools. To explore the reinforcement measures and the related mechanism of α-Al2O3-based coating, the effect of CO volume fraction from 0 to 8% on the growth behavior of Ti(C,N,O) on cemented carbide is systematically investigated. Both multilayer and monolayer Ti(C,N,O) coatings and Ti(C,O) intermediate were deposited at 830 °C in an industrial-scaled hot-wall CVD reactor. Experimental results show that CO reacts with TiCl4 in the H2 atmosphere, resulting in the formation of nanocrystalline Ti(C0.5,O0.5) with a slow growth rate. Thermodynamic calculation reveals that with the increase of CO fraction, the equilibrium partial pressure of HCN increases, which is a vital gas-phase for the formation of Ti(C,N,O). As a result, grain refinement and increase in the growth rate and oxygen content of Ti(C,N,O) coating are achieved by increasing the CO fraction and hence the amount of Ti(C0.5,O0.5) with strong reactivity. The growth mechanism of Ti(C,N,O) concerning the codeposition and their in situ reaction of Ti(C,N) and Ti(C,O) is proposed, and the related phenomena of preferential growth transformation and Cl residue in Ti(C,N,O) coating are discussed.

Polarity Control by Inversion Domain Suppression in N-Polar III-Nitride Heterostructures

Nitrogen-polar III-nitride heterostructures offer advantages over metal-polar structures in high frequency and high power applications. However, polarity control in III-nitrides is difficult to achieve as a result of unintentional polarity inversion domains (IDs). Herein, we present a comprehensive structural investigation with both atomic detail and thermodynamic analysis of the polarity evolution in low- and high-temperature AlN layers on on-axis and 4° off-axis carbon-face 4H-SiC (0001̅) grown by hot-wall metal organic chemical vapor deposition. A polarity control strategy has been developed by variation of thermodynamic Al supersaturation and substrate misorientation angle in order to achieve the desired growth mode and polarity. We demonstrate that IDs are completely suppressed for high-temperature AlN nucleation layers when a step-flow growth mode is achieved on the off-axis substrates. We employ this approach to demonstrate high quality N-polar epitaxial AlGaN/GaN/AlN heterostructures.

Influence of Temperature and Flow Ratio on the Morphology and Uniformity of 4H-SiC Epitaxial Layers Growth on 150 mm 4° Off-Axis Substrates

The homoepitaxial growth of 4H-SiC films was conducted on 4H-SiC 150 mm 4° off-axis substrates by using a home-made hot-wall chemical vapor deposition (CVD) reactor. Special attention was paid to the influence of the growth temperature on the surface morphology, growth rate, doping efficiency, and structural uniformity of the films. Among the above factors, growth temperature and flow ratio were shown to be the essential parameters to produce high-quality homoepitaxial layers. Furthermore, a two-side flow tunnel was introduced to control the growth temperature nonuniformity in the reactor. The influence of flow ratio on the epitaxial layer uniformity was also studied. It was found that the surface roughness increased with the increasing temperature, achieving its minimum value of 0.183 nm at 1610 °C. Besides that, the film growth rate decreased with the increase in growth temperature, whereas the degrees of thickness non-uniformity, N2 doping non-uniformity, and doping efficiency increased. Meanwhile, both the thickness and doping uniformity can be improved by adjusting H2 and N2 flow ratios, respectively. In particular, the use of the H2 ratio of 1.63 and N2 ratio of 0.92 enabled one to increase the degree of uniformity of thickness and doping by 0.79% (standard deviation/mean value) and 3.56% (standard deviation/mean value), respectively, at the growth temperature of 1630 °C.

Characterization of epitaxial layers grown on 4H-SiC (0 0 0 −1) substrates

SiC is an excellent semiconductor material that can be used in power semiconductor devices. It has the advantages of high thermal conductivity, stable chemical properties, and high critical breakdown field strength. The active region of a SiC device is usually in the SiC epitaxial layer, so the growth of high-quality SiC epitaxial layers is extremely valuable. In this paper, we investigate the epitaxial growth of SiC on n-type 4° off-axis SiC (0 0 0–1) substrates. We used a horizontal hot-wall chemical vapor deposition apparatus for rapid epitaxy on SiC substrates, using C2H4, and SiHCl3 as precursors and H2 as carrier gas, respectively, and growing at 1350 °C,1400 °C,1450 °C,1500 °C, 1550 °C, 1600 °C for half an hour to get epitaxial layer. The effect of growth temperature on the surface morphology of SiC (0 0 0 –1) epitaxial layer was analyzed and epitaxial layers is characterized by optical microscope, scanning electron microscope, atomic force microscope and Raman scattering instrument, and the growth rate of epitaxial layer was obtained. It is found that the higher growth temperature is helpful to obtain the epitaxial layer with smooth surface and higher content of 4H-SiC under certain pressure, C/Si molar ratio, and following rate of precursor and carrier gas.

Hot-Wall MOCVD for High-Quality Homoepitaxy of GaN: Understanding Nucleation and Design of Growth Strategies

Thick GaN layers with a low concentration of defects are the key to enable next-generation vertical power electronic devices. Here, we explore hot-wall metalorganic chemical vapor deposition (MOCVD) for the development of GaN homoepitaxy. We propose a new approach to grow high-quality homoepitaxial GaN in N2-rich carrier gas and at a higher supersaturation as compared to heteroepitaxy. We develop a low-temperature GaN as an optimum nucleation scheme based on the evolution and thermal stability of the GaN surface under different gas compositions and temperatures. Analysis in the framework of nucleation theory of homoepitaxial layers simultaneously grown on GaN templates on SiC and on hydride vapor phase epitaxy GaN substrates is presented. We show that residual strain and screw dislocation densities affect GaN nucleation and subsequent growth leading to distinctively different morphologies of GaN homoepitaxial layers grown on GaN templates and native substrates, respectively. The established comprehensive picture provides a guidance for designing strategies for growth conditions optimization in GaN homoepitaxy. GaN with atomically flat and smooth epilayer surfaces with a root-mean-square roughness value as low as 0.049 nm and low background carbon concentration of 5.3 × 1015 cm–3 has been achieved. It is also shown that there is no generation of additional dislocations during homoepitaxial growth. Thus, our results demonstrate the potential of the hot-wall MOCVD technique to deliver high-quality GaN material for vertical power devices.

GaN-based light-emitting materials prepared by hot-wall metal-organic chemical vapor deposition

GaN-based light-emitting materials prepared by hot-wall metal-organic chemical vapor deposition

Growth of vanadium doped semi-insulating 4H-SiC epilayer with ultrahigh-resistivity

4H-SiC epitaxial layers with ultrahigh resistivity of over 1010 Ω cm were successfully grown by using a hot wall chemical vapor deposition system with vanadium doping. The resistivity of the vanadium doped epilayer was found to be strongly dependent on the types of dopant impurities. The resistivity of n-type-based vanadium doped semi-insulating 4H-SiC epilayers showed stronger dependence on vanadium incorporation than that of p-type-based epilayers. This means that the carrier trap characteristics of vanadium atoms may differ with respect to electrons and holes. As the result, an ultrahigh resistivity of over 1010 Ω cm was realized on an n-type-based 4H-SiC epilayer with vanadium doping.

Mg-doping and free-hole properties of hot-wall MOCVD GaN

The hot-wall metal-organic chemical vapor deposition (MOCVD), previously shown to enable superior III-nitride material quality and high performance devices, has been explored for Mg doping of GaN. We have investigated the Mg incorporation in a wide doping range (2.45×1018 cm−3 up to 1.10×1020 cm−3) and demonstrate GaN:Mg with low background impurity concentrations under optimized growth conditions. Dopant and impurity levels are discussed in view of Ga supersaturation, which provides a unified concept to explain the complexity of growth conditions impact on Mg acceptor incorporation and compensation. The results are analyzed in relation to the extended defects, revealed by scanning transmission electron microscopy, x-ray diffraction, and surface morphology, and in correlation with the electrical properties obtained by Hall effect and capacitance–voltage (C–V) measurements. This allows to establish a comprehensive picture of GaN:Mg growth by hot-wall MOCVD providing guidance for growth parameters optimization depending on the targeted application. We show that substantially lower H concentration as compared to Mg acceptors can be achieved in GaN:Mg without any in situ or post-growth annealing resulting in p-type conductivity in as-grown material. State-of-the-art p-GaN layers with a low resistivity and a high free-hole density (0.77 Ω cm and 8.4×1017 cm−3, respectively) are obtained after post-growth annealing demonstrating the viability of hot-wall MOCVD for growth of power electronic device structures.

Epitaxial growth of β-Ga2O3 by hot-wall MOCVD

The hot-wall metalorganic chemical vapor deposition (MOCVD) concept, previously shown to enable superior material quality and high performance devices based on wide bandgap semiconductors, such as Ga(Al)N and SiC, has been applied to the epitaxial growth of β-Ga2O3. Epitaxial β-Ga2O3 layers at high growth rates (above 1 μm/h), at low reagent flows, and at reduced growth temperatures (740 °C) are demonstrated. A high crystalline quality epitaxial material on a c-plane sapphire substrate is attained as corroborated by a combination of x-ray diffraction, high-resolution scanning transmission electron microscopy, and spectroscopic ellipsometry measurements. The hot-wall MOCVD process is transferred to homoepitaxy, and single-crystalline homoepitaxial β-Ga2O3 layers are demonstrated with a 2̄01 rocking curve width of 118 arc sec, which is comparable to those of the edge-defined film-fed grown (2̄01) β-Ga2O3 substrates, indicative of similar dislocation densities for epilayers and substrates. Hence, hot-wall MOCVD is proposed as a prospective growth method to be further explored for the fabrication of β-Ga2O3.

Influence of carrier trapping on radiation detection properties in CVD grown 4H-SiC epitaxial layers with varying thickness up to 250 µm

Low doped n-type 4H-SiC epitaxial layers of thickness 50, 150, and 250 µm grown by hot wall chemical vapor deposition were used to fabricate Ni/4H-SiC Schottky radiation detectors. The epitaxial layers were grown on the (0001) face of highly conductive bulk 4H-SiC substrates 8° offcut towards the 〈112¯0〉 direction. The 50, 150, and 250 µm thick epilayer detectors, under optimized settings, showed energy resolutions of 2.0%, 0.78%, and 0.63%, respectively for 5.48 MeV alpha particles. Deep level transient spectroscopy studies showed that the observed variation in the detector resolution is linked to the defect parameters in the devices. Least-squares fitting of the bias dependence of the charge collection efficiency according to a drift-diffusion model, revealed minority carrier diffusion lengths of 16, 10, and 9.2 µm, respectively, implying that the detectors are not limited by minority carrier trapping. The detector performance was observed to be primarily dependent on the concentration and capture cross-sections of the lifetime killing electron traps Z1/2 and EH6/7.

Temperature Dependence of Ultrathin Mixed-Phase Ga2O3 Films Grown on the α-Al2O3 Substrate via Mist-CVD.

Alpha (α)- and beta (β)-phase gallium oxide (Ga2O3), emerging as ultrawide-band gap semiconductors, have been paid a great deal of attention in optoelectronics and high-performance power semiconductor devices owing to their ultrawide band gap ranging from 4.4 to 5.3 eV. The hot-wall mist chemical vapor deposition (mist-CVD) method has been shown to be effective for the growth of pure α- and β-phase Ga2O3 thin films on the α-Al2O3 substrate. However, challenges to preserve their intrinsic properties at a critical growth temperature for robust applications still remain a concern. Here, we report a convenient route to grow a mixed α- and β-phase Ga2O3 ultrathin film on the α-Al2O3 substrate via mist-CVD using a mixture of the gallium precursor and oxygen gas at growth temperatures, ranging from 470 to 700 °C. The influence of growth temperature on the film characteristics was systematically investigated. The results revealed that the as-grown Ga2O3 film possesses a mixed α- and β-phase with an average value of dislocation density of 1010 cm–2 for all growth temperatures, indicating a high lattice mismatch between the film and the substrate. At 600 °C, the ultrathin and smooth Ga2O3 film exhibited a good surface roughness of 1.84 nm and an excellent optical band gap of 5.2 eV. The results here suggest that the mixed α- and β-phase Ga2O3 ultrathin film can have great potential in developing future high-power electronic devices.

Effect of Nitrogen and Aluminum Doping on 3C-SiC Heteroepitaxial Layers Grown on 4° Off-Axis Si (100).

This work provides a comprehensive investigation of nitrogen and aluminum doping and its consequences for the physical properties of 3C-SiC. Free-standing 3C-SiC heteroepitaxial layers, intentionally doped with nitrogen or aluminum, were grown on Si (100) substrate with different 4° off-axis in a horizontal hot-wall chemical vapor deposition (CVD) reactor. The Si substrate was melted inside the CVD chamber, followed by the growth process. Micro-Raman, photoluminescence (PL) and stacking fault evaluation through molten KOH etching were performed on different doped samples. Then, the role of the doping and of the cut angle on the quality, density and length distribution of the stacking faults was studied, in order to estimate the influence of N and Al incorporation on the morphological and optical properties of the material. In particular, for both types of doping, it was observed that as the dopant concentration increased, the average length of the stacking faults (SFs) increased and their density decreased.

Predicting Graphene Growth on Cu: Universal Kinetic Growth Model and Its Experimental Verification.

The kinetics of the chemical vapor deposition (CVD) of graphene on Cu in CH4 + H2 were investigated by monitoring the graphene flake size as a function of CVD growth time. A growth model was set up which relates the CVD parameters to the mass action constant Qexp of the methane decomposition reaction toward graphene at a given temperature T. Graphene growth was shown to proceed from pre-equilibrated adsorbed carbon (Cad) within a wide CVD parameter range. The model not only leads to the correct scaling relation of the growth kinetics but quantitatively determines how far the CVD parameters deviate from thermal equilibrium and correctly predicts the absolute flake size increase per time. Fitting experimental data delivers the energy barrier for carbon detachment from the graphene island edge (Edet = 4.7 ± 0.3 eV) and the methane decomposition entropy toward Cad on Cu (ΔdecS° = 260 ± 20 J mol-1 K-1). The latter value is used to estimate the vanishingly small Cad equilibrium concentration of 3 × 10-10 monolayers at 1045 °C. The universal validity of the model is proven by comparison with literature data providing the correct order of magnitude growth velocities up to 1000 μm/h. The performed reactor experiments deliver data that match the predicted flake growth velocity with a precision of about 50%. The obtained results can be used to calibrate any hot wall CVD reactor setup for the methane decomposition reaction toward graphene on Cu. The description can be directly applied for any hydrocarbon in the gas feed, and the technique can be easily applied for other catalytic support surfaces.

GaN-based pyramidal quantum structures for micro-size light-emitting diode applications

GaN-based pyramidal quantum structures, InGaN nanostructures located on top of micro-sized GaN pyramids, were fabricated by selective-area growth on SiC substrates by means of hot-wall metal-organic chemical vapor deposition. Arrays of GaN-based pyramidal structures exhibit micro-size pyramids possessing high uniformity, precise hexagonal bases, and InGaN/GaN quantum-well layers with well-defined interfaces. Each pyramid comprises a p-i-n InGaN/GaN structure, which is separated from that of other pyramids by a dielectric layer, serving as a building block for micro-emitters. Moreover, interconnected micro-size light-emitting diodes (microLEDs) built on the GaN-based pyramidal quantum structures were demonstrated, resulting in well-determined electroluminescence in the near-ultraviolet regime with negligible spectral shifts at high current levels. The results elucidated the rewards for development of these light-emitting designs and their potential for microLED applications.