Growth and process modeling studies of nickel-catalyzed metalorganic chemical vapor deposition of GaN nanowires

A combination of experimental and computational fluid dynamics-based reactor modeling studies were utilized to study the effects of process conditions on GaN nanowire growth by metalorganic chemical vapor deposition (MOCVD) in an isothermal tube reactor. The GaN nanowires were synthesized on (0 0 0 1) sapphire substrates using nickel thin films as a catalyst. GaN nanowire growth was observed over a furnace temperature range of 800–900 °C at V/III ratios ranging from 33 to 67 and was found to be strongly dependent on the position of the substrate relative to the group III inlet tube. The modeling studies revealed that nanowire growth consistently occurred in a region in the reactor where the GaN thin-film deposition rate was reduced and the gas phase consisted primarily of intermediate species produced by the reaction and decomposition of trimethylgallium–ammonia adduct compounds. The GaN nanowires exhibited a predominant [1 1 2¯ 0] growth direction. Photoluminescence measurements revealed an increase in the GaN near-band edge emission intensity and a reduction in the deep-level yellow luminescence with increasing growth temperature and V/III ratio.     

Zn掺杂Z形GaN纳米线的制备及表征

本文以氧化镓、氧化锌和氨气为原料,通过常压化学气相沉积法(APCVD)在Au/Si(100)衬底上成功生长出了Zn掺杂的"Z"形GaN纳米线。利用场发射扫描电镜(FESEM)、X-射线衍射仪(XRD)、透射电子显微镜(TEM)、光致发光谱(PL)等测试方法对样品的形貌、晶体结构及光学性质进行了表征。结果表明:在温度为950℃,氧化镓和氧化锌的质量比为8∶1的条件下,制备出的Zn掺杂Z形GaN单晶纳米线直径为70 nm、长度为数十个微米,生长机理遵循VLS机制。Zn元素的掺杂使GaN纳米线在420 nm处出现了光致发光峰,发光性能有所改善。     

A simple method to synthesize α-Si3N4, β-SiC and SiO2 nanowires by carbothermal route

α-Si₃N₄ nanowires, β-SiC nanowires and SiO₂ amorphous nanowires are synthesized via the direct current arc discharge method with a mixture of silicon, activated carbon and silicon dioxide as the precursor. The α-Si₃N₄ nanowires, β-SiC nanowires and SiO₂ amorphous nanowires are about 50–200 nm in stem diameter and 10–100 μm in length. α-Si₃N₄ nanowires and β-SiC nanowires consist of a solid single-crystalline core along the [0 0 1] and [1 1 1] directions, respectively, wrapped within an amorphous SiO_x layer. The direct current arc plasma-assisted self-catalytic vapor–solid and/or vapor–liquid–solid (VLS) growth processes are proposed as the growth mechanism of the nanowires.     

Mg segregation in a (1 1¯ 0 1) GaN grown on a 7° off-axis (0 0 1) Si substrate by MOVPE

Redistribution behavior of magnesium (Mg) in the N-terminated (1 1¯ 0 1) gallium nitride (GaN) has been investigated. A nominally undoped GaN layer was grown on a heavily Mg-doped GaN template by metalorganic vapor-phase epitaxy (MOVPE). Mg dopant profiles were measured by secondary ion mass spectrometry (SIMS) analysis. A slow decay of the Mg concentration was observed in the nominally undoped GaN layer due to the surface segregation. The calculated decay lengths of the (1 1¯ 0 1) GaN are ∼75–85 nm/decade. These values are shorter than the decay length determined in the sample grown on the Ga-terminated (0 0 0 1) GaN. This result indicates that Mg exhibited weak surface segregation in the (1 1¯ 0 1) GaN as compared to the (0 0 0 1) GaN. The weak surface segregation is in agreement with the high efficiency of Mg incorporation on the (1 1¯ 0 1) face. The high density of hydrogen was obtained in the (1 1¯ 0 1) GaN, which might enhance the Mg incorporation.     

Nature of luminescence and strain in gallium nitride nanowires

Photo- and cathodo-luminescence measurements of a variable-diameter ensemble of GaN nanowires revealed a diameter-dependent, spectral emission distribution between 350 nm and 850 nm. Spectral analysis indicated that wires with a diameter less than 400 nm were dominated by a yellow luminescence with a weaker near UV/violet emission also present. Examination of this ensemble showed that there was a general trend in the ratio of near-UV-to-yellow emission intensities with increasing nanowire diameter. Additionally, a broad green emission appears in the nanowires with a diameter above approximately 200 nm. A calculation based on the nanoheteroepitaxy model indicates that this diameter represents a transitional thickness where strain is relieved by defect formation mechanisms with a characteristic green emission.     

The influence of indium on the growth of GaN from solution under high pressure

The influence of significant fraction (10–50 mole%) indium in liquid gallium on GaN crystallization from a ternary Ga–In–N solution was analyzed. Crystallization experiments of GaN on GaN-sapphire templates from Ga–In solutions, at 1350–1450 °C, with prior to the growth seed wetting at 1500 °C, and 1.0 GPa N₂ pressure, without solid GaN source showed faster growth of GaN on the seed (by a factor of 1.5–2) than using pure gallium solvent. Nevertheless the new grown crystals were morphologically unstable. The instability was reduced by decrease of the wetting temperature down to 1100 °C or by omitting the wetting procedure entirely, which indicated that GaN dissolves much faster in Ga–In melt than in pure Ga and that the unstable growth was caused most likely by complete dissolution of GaN template before the growth. It was observed that the crystals grown on bulk GaN substrates did not show morphological instability observed for GaN-sapphire templates. The influence of indium on thermodynamic and thermal properties of the investigated system is discussed.     

Growth of hexagonal and cubic InN nanowires using MOCVD with different growth temperatures

We have performed a detailed investigation of the metal-organic chemical vapor deposition (MOCVD) growth and characterization of InN nanowires formed on Si(1 1 1) substrates under nitrogen rich conditions. The growth of InN nanowires has been demonstrated by using an ion beam sputtered (∼10 nm) Au seeding layer prior to the initiation of growth. We tried to vary the growth temperature and pressure in order to obtain an optimum growth condition for InN nanowires. The InN nanowires were grown on the Au+In solid solution droplets caused by annealing in a nitrogen ambient at 700 °C. By applying this technique, we have achieved the formation of InN nanowires that are relatively free of dislocations and stacking faults. Scanning electron microscopy (SEM) showed wires with diameters of 90–200 nm and lengths varying between 3 and 5 μm. Hexagonal and cubic structure is verified by high resolution X-ray diffraction (HR-XRD) spectrum. Raman measurements show that these wurtzite InN nanowires have sharp peaks E₂ (high) at 491 cm⁻¹ and A₁ (LO) at 591 cm⁻¹.     

Growth of GaN films on PLD-deposited TaC substrates

GaN films were grown by metal organic chemical vapor deposition on TaC substrates that were created by pulsed laser deposition of TaC onto (0 0 0 1) SiC substrates at ∼1000 °C. This was done to determine if good quality TaC films could be grown, and if good quality GaN films could be grown on this closely lattice matched to GaN, conductive material. This was done by depositing the TaC on on-axis and 3° or 8° off-axis (0 0 0 1) SiC at temperatures ranging from 950 to 1200 °C, and examining them using X-ray diffraction, scanning electron microscopy, atomic force microscopy, and transmission electron microscopy. The GaN films were grown on as-deposited TaC films, and films annealed at 1200, 1400, or 1600 °C, and examined using the same techniques. The TaC films were polycrystalline with a slight (1 1 1) texture, and the grains were ∼200 nm in diameter. Films grown on-axis were found to be of higher quality than those grown on off-axis substrates, but the latter could be improved to a comparable quality by annealing them at 1200–1600 °C for 30 min. TaC films deposited at temperatures above 1000 °C were found to react with the SiC. GaN films could be deposited onto the TaC when the surface was nitrided with NH₃ for 3 min at 1100 °C and the low temperature buffer layer was AlN. However, the GaN did not nucleate easily on the TaC film, and the crystallites did not have the desired (0 0 0 1) preferred orientation. They were ∼10 times larger than those typically seen in films grown on SiC or sapphire. Also the etch pit concentration in the GaN films grown on the TaC was more than 2 orders of magnitude less than it was for growth on the SiC.     

HRTEM investigation of high-reflectance AlN/GaN distributed Bragg-reflectors by inserting AlN/GaN superlattice

A high-quality AlN/GaN distributed Bragg-reflectors (DBR) was successfully grown on sapphire substrate by low-pressure metal-organic chemical vapor deposition using ultra-thin AlN/GaN superlattice insertion layers (SLILs). The reflectivity of AlN/GaN DBR with ultra-thin AlN/GaN SLIL was measured and achieved blue peak reflectivity of 99.4% at 462 nm. The effect of ultra-thin AlN/GaN superlattice insertion layer was examined in detail by transmission electron microscopy, and indicated that the crack of AlN/GaN DBR can be suppress by inserting AlN/GaN SLIL. For electronic properties, the turn on voltage is about 4.1 V and CW laser action of vertical-cavity surface-emitting laser (VCSEL) was achieved at a threshold injection current of 1.4 mA at 77 K, with an emission wavelength of 462 nm.     

Droplet epitaxy of zinc-blende GaN quantum dots

Zinc-blende GaN quantum dots were grown on 3C-AlN(0 0 1) by a vapor–liquid–solid process in a molecular beam epitaxy system. We were able to control the density of the quantum dots in a range of 5×10⁸–5×10¹² cm⁻². Photoluminescence spectroscopy confirmed the optical activity of the GaN quantum dots in a range of 10¹¹–5×10¹² cm⁻². The data obtained give an insight to the condensation mechanism of the vapor–liquid–solid process in general, because the GaN quantum dots condense in metastable zinc-blende crystal structure supplied by the substrate, and not in the wurtzite crystal structure expected from free condensation in the droplet.     

Hydrothermal synthesis of Bi2Te3 nanowires through the solid-state interdiffusion of Bi and Te atoms on the surface of Te nanowires

Polycrystalline Bi₂Te₃ nanowires were prepared by a hydrothermal method that involved inducing the nucleation of Bi atoms reduced from BiCl₃ on the surface of Te nanowires, which served as sacrificial templates. A Bi–Te alloy is formed by the interdiffusion of Bi and Te atoms at the boundary between the two metals. The Bi₂Te₃ nanowires synthesized in this study had a length of 3–5 μm, which is the same length as that of the Te nanowires, and a diameter of 300–500 nm, which is greater than that of the Te nanowires. The experimental results indicated that volume expansion of the Bi₂Te₃ nanowires was a result of the interdiffusion of Bi and Te atoms when Bi was alloyed on the surface of the Te nanowires. The morphologies of Bi₂Te₃ are strongly dependent on the reaction conditions such as the temperature and the type and concentration of the reducing agent. The morphologies, crystalline structure and physical properties of the product were analyzed by X-ray diffraction (XRD), field-emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), selected area electron diffraction (SAED) and X-ray photoelectron spectroscopy (XPS).     

Growth of high quality a-plane GaN epi-layer on r-plane sapphire substrates with optimization of multi-buffer layer

Nonpolar (1 1–2 0) a-plane GaN films have been grown using the multi-buffer layer technique on (1–1 0 2) r-plane sapphire substrates. In order to obtain epitaxial a-plane GaN films, optimized growth condition of the multi-buffer layer was investigated using atomic force microscopy, high resolution X-ray diffraction, and transmission electron microscopy measurements. The experimental results showed that the growth conditions of nucleation layer and three-dimensional growth layer significantly affect the crystal quality of subsequently grown a-plane GaN films. At the optimized growth conditions, omega full-width at half maximum values of (11–20) X-ray rocking curve along c- and m-axes were 430 and 530 arcsec, respectively. From the results of transmission electron microscopy, it was suggested that the high crystal quality of the a-plane GaN film can be obtained from dislocation bending and annihilation by controlling of the island growth mode.     

Effects of temperature and carrier gas flow amount on the formation of GaN nanorods by the HVPE method

We fabricated one-dimensional GaN nanorods on AlN/Si (1 1 1) substrates at various temperatures, and carrier gas flow amount, using the hydride vapor phase epitaxy (HVPE) method. An AlN buffer layer of 50 nm thickness was deposited by RF sputtering for 25 min. Stalagmite-like GaN nanorods formed at a growth temperature of 650 °C. The diameters and lengths of GaN nanorods increase with growth time, whereas the density of nanorods decreases. And we performed the experiments by changing the carrier gas flow amount at a growth temperature of 650 °C and HCl:NH₃ flow ratio of 1:40. GaN nanorods, with an average diameter of 50 nm, were obtained at a carrier gas flow amount of 1340 sccm. The shape, structures, and optical characteristics of the nanorods were investigated by field-emission scanning electron microscopy, X-ray diffraction, and photoluminescence.     

One-sidewall-seeded epitaxial lateral overgrowth of a-plane GaN by metalorganic vapor-phase epitaxy

The selective regrowth of GaN during sidewall-seeded epitaxial lateral overgrowth was performed. In addition to adjusting the V/III ratio, control of offset angle of the sidewall was found to be effective for realizing one-sidewall-seeded a-plane (1 1 2¯ 0) GaN on r-plane (1 1¯ 0 2) sapphire. The number of coalescence regions on the grooves was reduced, and threading-dislocation and stacking-fault densities as low as 10⁶–10⁷ cm⁻² and 10³–10⁴ cm⁻¹, respectively, were successfully realized.     

Hydride-assisted growth of GaN nanowires on Au/Si(0 0 1) via the reaction of Ga with NH3 and H2

High quality, straight GaN nanowires (NWs) with diameters of 50 nm and lengths up to 3 μm have been grown on Si(0 0 1) using Au as a catalyst and the direct reaction of Ga with NH₃ and N₂:H₂ at 900 °C. These exhibited intense, near band edge photoluminescence at 3.42 eV in comparison to GaN NWs with non-uniform diameters obtained under a flow of Ar:NH₃, which showed much weaker band edge emission due to strong non-radiative recombination. A significantly higher yield of β-Ga₂O₃ NWs with diameters of ≤50 nm and lengths up to 10 μm were obtained, however, via the reaction of Ga with residual O₂ under a flow of Ar alone. The growth of GaN NWs depends critically on the temperature, pressure and flows in decreasing order of importance but also the availability of reactive species of Ga and N. A growth mechanism is proposed whereby H₂ dissociates on the Au nanoparticles and reacts with Ga giving Ga_xH_y thereby promoting one-dimensional (1D) growth via its reaction with dissociated NH₃ near or at the top of the GaN NWs while suppressing at the same time the formation of an underlying amorphous layer. The higher yield and longer β-Ga₂O₃ NWs grow by the vapor liquid solid mechanism that occurs much more efficiently than nitridation.     

Hydride vapor phase epitaxy of GaN boules using high growth rates

The boule-like growth of GaN in a vertical AIXTRON HVPE reactor was studied. Extrinsic factors like properties of the starting substrate and fundamental growth parameters especially the vapor gas composition at the surface have crucial impact on the formation of inverse pyramidal defects. The partial pressure of GaCl strongly affects defect formation, in-plane strain, and crystalline quality. Optimized growth conditions resulted in growth rates of 300–500 μm/h. GaN layers with thicknesses of 2.6 and of 5.8 mm were grown at rates above 300 μm/h. The threading dislocation density reduces with an inverse proportionality to the GaN layer thickness. Thus, it is demonstrated that growth rates above 300 μm/h are promising for GaN boule growth.     

Characterizations of GaN film growth by ECR plasma chemical vapor deposition

The electron cyclotron resonance plasma-enhanced metalorganic chemical vapor deposition technology (ECR–MOPECVD) is adopted to grow GaN films on (0 0 0 1) α-Al₂O₃ substrate. The gas sources are pure N₂ and trimethylgallium (TMG). Optical emission spectroscopy (OES) and thermodynamic analysis of GaN growth are applied to understand the GaN growth process. The OES of ECR plasma shows that TMG is significantly dissociated in ECR plasma. Reactants N and Ga in the plasma, obtained easily under the self-heating condition, are essential for the GaN growth. They contribute to the realization of GaN film growth at a relatively low temperature. The thermodynamic study shows that the driving force for the GaN growth is high when N₂:TMG>1. Furthermore, higher N₂:TMG flow ratio makes the GaN growth easier. Finally, X-ray diffraction, photoluminescence, and atomic force microscope are applied to investigate crystal quality, morphology, and roughness of the GaN films. The results demonstrate that the ECR–MOPECVD technology is favorable for depositing GaN films at low temperatures.     

The effects of annealing on non-polar (1 1 2¯ 0) a-plane GaN films

Non-polar a-plane (1 1 2¯ 0) GaN films were grown on r-plane sapphire by metal–organic vapor phase epitaxy and were subsequently annealed for 90 min at 1070 °C. Most dislocations were partial dislocations, which terminated basal plane stacking faults. Prior to annealing, these dislocations were randomly distributed. After annealing, these dislocations moved into arrays oriented along the [0 0 0 1] direction and aligned perpendicular to the film–substrate interface throughout their length, although the total dislocation density remained unchanged. These changes were accompanied by broadening of the symmetric X-ray diffraction 1 1 2¯ 0 ω-scan widths. The mechanism of movement was identified as dislocation glide, occurring due to highly anisotropic stresses (confirmed by X-ray diffraction lattice parameter measurements) and evidenced by macroscopic slip bands observed on the sample surface. There was also an increase in the density of unintentionally n-type doped electrically conductive inclined features present at the film–substrate interface (as observed in cross-section using scanning capacitance microscopy), suggesting out-diffusion of impurities from the substrate along with prismatic stacking faults. These data suggest that annealing processes performed close to film growth temperatures can affect both the microstructure and the electrical properties of non-polar GaN films.     

Method for modulating the wafer bow of free-standing GaN substrates via inductively coupled plasma etching

The bowing curvature of the free-standing GaN substrate significantly decreased almost linearly from 0.67 to 0.056 m⁻¹ (i.e. the bowing radius increased from 1.5 to 17.8 m) with increase in inductively coupled plasma (ICP) etching time at the N-polar face, and eventually changed the bowing direction from convex to concave. Furthermore, the influences of the bowing curvature on the measured full width at half maximum (FWHM) of high-resolution X-ray diffraction (HRXRD) in (0 0 2) reflection were also deduced, which reduced from 176.8 to 88.8 arcsec with increase in ICP etching time. Decrease in the nonhomogeneous distribution of threading dislocations and point defects as well as V_Ga–O_N complex defects on removing the GaN layer from N-polar face, which removed large amount of defects, was one of the reasons that improved the bowing of the free-standing GaN substrate. Another reason was the high aspect ratio of needle-like GaN that appeared at the N-polar face after ICP etching, which released the compressive strain of the free-standing GaN substrate. By doing so, crack-free and extremely flat free-standing GaN substrates with a bowing radius of 17.8 m could be obtained.     

An ab initio-based approach to the stability of GaN(0 0 0 1) surfaces under Ga-rich conditions

Structural stability of GaN(0 0 0 1) under Ga-rich conditions is systematically investigated by using our ab initio-based approach. The surface phase diagram for GaN(0 0 0 1) including (2×2) and pseudo-(1×1) is obtained as functions of temperature and Ga beam equivalent pressure by comparing chemical potentials of Ga atom in the gas phase with that on the surface. The calculated results reveal that the pseudo-(1×1) appearing below 684–973 K changes its structure to the (2×2) with Ga adatom at higher temperatures beyond 767–1078 K via the newly found (1×1) with two adlayers of Ga. These results are consistent with the stable temperature range of both the pseudo-(1×1) and (2×2) with Ga adatom obtained experimentally. Furthermore, it should be noted that the structure with another coverage of Ga adatoms between the (1×1) and (2×2)-Ga does not appear as a stable structure of GaN(0 0 0 1). Furthermore, ghost island formation observed by scanning tunneling microscopy is discussed on the basis of the phase diagram.