MOVPE growth and characterization of Al(Ga)N and InAlN/AlGaN quantum wells for UV LED applications

The study of III-nitride materials (InN, GaN and AlN) gained huge research momentum after breakthroughs in the production light emitting diodes (LEDs) and laser diodes (LDs) over the past two decades. Last year, the Nobel Prize in Physics was awarded jointly to Isamu Akasaki, Hiroshi Amano and Shuji Nakamura for inventing a new energy efficient and environmental friendly light source: blue light-emitting diode (LED) from III-nitride semiconductors in the early 1990s. Nowadays, III-nitride materials not only play an increasingly important role in the lighting technology, but also become prospective candidates in other areas, for example, the high frequency (RF) high electron mobility transistor (HEMT) and photovoltaics. These devices require the growth of high quality III-nitride films, which can be prepared using metal organic vapour phase epitaxy (MOVPE). The main aim of my thesis is to study and develop the growth of III-nitride films, including AlN, u-AlGaN, Si-doped AlGaN, and InAlN, serving as sample wafers for fabrication of ultraviolet (UV) LEDs, in order to replace the conventional bulky, expensive and environmentally harmful mercury lamp as new UV light sources. For application to UV LEDs, reducing the threading dislocation density (TDD) in AlN epilayers on sapphire substrates is a key parameter for achieving high-efficiency AlGaNbased UV emitters. In Chapter 4, after careful and systematic optimisation， a working set of conditions, the screw and edge type dislocation density in the AlN were reduced to around 2.2×108 cm-2 and 1.3×109 cm-2 , respectively, using an optimized three-step process, as estimated by TEM. An atomically smooth surface with an RMS roughness of around 0.3 nm achieved over 5×5 µm 2 AFM scale. Furthermore, the motion of the steps in a one dimension model has been proposed to describe surface morphology evolution, especially the step bunching feature found under non-optimal conditions. In Chapter 5, control of alloy composition and the maintenance of compositional uniformity across a growing epilayer surface were demonstrated for the development of u-AlGaN epilayers. Optimized conditions (i.e. a high growth temperature of 1245 °C) produced uniform and smooth film with a low RMS roughness of around 2 nm achieved in 20×20 µm 2 AFM scan. The dopant that is most commonly used to obtain n-type conductivity in AlxGa1-xN is Si. However, the incorporation of Si has been found to increase the strain relaxation and promote unintentional incorporation of other impurities (O and C) during Si-doped AlGaN growth. In Chapter 6, reducing edge-type TDs is observed to be an effective appoach to improve the electric and optical properties of Si-doped AlGaN epilayers. In addition, the maximum electron concentration of 1.3×1019 cm-3 and 6.4×1018 cm-3 were achieved in Si-doped Al0.48Ga0.52N and Al0.6Ga0.4N epilayers as measured using Hall effect. Finally, in Chapter 7, studies on the growth of InAlN/AlGaN multiple quantum well (MQW) structures were performed, and exposing InAlN QW to a higher temperature during the ramp to the growth temperature of AlGaN barrier (around 1100 °C) will suffer a significant indium (In) desorption. To overcome this issue, quasi-two-tempeature (Q2T) technique was applied to protect InAlN QW. After optimization, an intense UV emission from MQWs has been observed in the UV spectral range from 320 to 350 nm measured by room temperature photoluminescence.

Efficiency measurement of GaN-based quantum well and light-emitting diode structures grown on silicon substrates

The optical efficiency of GaN-based multiple quantum well (MQW) and light emitting diode (LED) structures grown on Si(111) substrates by metal-organic vapor phase epitaxy was measured and compared with equivalent structures on sapphire. The crystalline quality of the LED structures was comprehensively characterized using x-ray diffraction, atomic force microscopy, and plan-view transmission electron microscopy. A room temperature photoluminescence (PL) internal quantum efficiency (IQE) as high as 58% has been achieved in an InGaN/GaN MQW on Si, emitting at 460 nm. This is the highest reported PL-IQE of a c-plane GaN-based MQW on Si, and the radiative efficiency of this sample compares well with similar structures grown on sapphire. Processed LED devices on Si also show good electroluminescence (EL) performance, including a forward bias voltage of ∼3.5 V at 20 mA and a light output power of 1 mW at 45 mA from a 500 ×500 μm2 planar device without the use of any additional techniques to enhance the output coupling. The extraction efficiency of the LED devices was calculated, and the EL-IQE was then estimated to have a maximum value of 33% at a current density of 4 A cm-2, dropping to 30% at a current density of 40 A cm-2 for a planar LED device on Si emitting at 455 nm. The EL-IQE was clearly observed to increase as the structural quality of the material increased for devices on both sapphire and Si substrates. © 2011 American Institute of Physics.

Epitaxial growth of ZnO films on (100) and (001) gamma-LiAlO2 substrates by pulsed laser deposition

Structural and optical properties were investigated for ZnO films grown on (100) and (001) gamma-LiAlO2 (LAO) substrates by pulsed laser deposition method. According XRD results, it is intuitionistic that (100) LAO is suitable for fabricating high quality ZnO film, while (001) LAO is unsuitable. The FWHM of XRD, stress in film and FWHM of UV PL spectra for ZnO films on (100) LAO show a decreasing with increasing substrate temperature from 300 to 600 degrees C. ZnO film fabricated at 600 degrees C has the greatest grain size, the smallest stress (0.47 Gpa) and PL FWHM value (similar to 85 meV). This means that the substrate temperature of 600 degrees C is optimum for ZnO film deposited on (100) LAO. Moreover, it was found that the UV PL spectra intensity of ZnO film is not only related to the grain size and stoichiometric, but also depends on the stress in the film.

Preparation of crystalline beta barium borate thin films on Sr2+-doped alpha barium borate substrates by liquid phase epitaxy

Thin films of beta barium borate have been prepared by liquid phase epitaxy on Si2+-doped alpha-BaB2O4 (alpha-BBO, the high temperature phase of barium berate) (001) and (110) substrates. The results of X-ray diffraction indicate that the films show highly (001) preferred orientation on (001)-oriented substrates while the films grown on (110) substrates are textured with (140) orientation. The crystallinity of these films was found to depend on growth temperature, rotation rate, dip time and orientation of substrate. Growth conditions were optimized to grow films with (001) orientation on (001) substrates reproducibly. The films show second harmonic generation of 400 nm light upon irradiation with 800 nm Ti: Sapphire femtosecond laser light. (c) 2005 Elsevier B.V. All rights reserved.

Noncatalytic chemical vapor deposition of graphene on high-temperature substrates for transparent electrodes

A noncatalytic chemical vapor deposition mechanism is proposed, where high precursor concentration, long deposition time, high temperature, and flat substrate are needed to grow large-area nanocrystalline graphene using hydrocarbon pyrolysis. The graphene is scalable, uniform, and with controlled thickness. It can be deposited on virtually any nonmetallic substrate that withstands ∼1000 °C. For typical examples, graphene grown directly on quartz and sapphire shows transmittance and conductivity similar to exfoliated or metal-catalyzed graphene, as evidenced by transmission spectroscopy and transport measurements. Raman spectroscopy confirms the sp 2-C structure. The model and results demonstrate a promising transfer-free technique for transparent electrode production. © 2012 American Institute of Physics.

Structural and optical properties of ZnO films on SrTiO3 substrates by MOCVD

ZnO films have been fabricated on (0 0 1), (0 1 1) and (1 1 1) SrTiO3 (STO) substrates by metal-organic chemical vapour deposition (MOCVD). It is interesting that the ZnO films on (0 0 1) and (0 1 1) STO substrates show polar and semipolar orientations, which are different from previous reports, while the same growing direction of polar ZnO with previous results is found on (1 1 1) STO. For the atomic arrangements, two orthogonal domains and a single domain are observed on (0 0 1) and (1 1 1) STO, respectively. Photoluminescence spectra show that every sample has a sharp near-band-edge emission peak at about 3.28 eV without any deep-level emission band between 1.5 and 2.8 eV, implying a high optical quality. A violet emission around 3.0 eV is observed only in ZnO films on (0 0 1) and (0 1 1) STO substrates grown at 600 degrees C, which is discussed briefly. Additionally, the semipolar ZnO does not weaken the emission efficiency along with the reduction in the polarization effect compared with polar ZnO. These results show that high-quality polar and semipolar ZnO films can be grown on STO substrates by MOCVD.

Structural and optical properties of ZnO films on Si substrates using a gamma-Al2O3 buffer layer

High quality ZnO films have been successfully grown on a Si (100) substrate by metal organic chemical vapour deposition with a gamma-Al2O3 buffer. The crystal structure, surface morphology and optical properties of the ZnO films were characterized by x-ray diffraction, Raman spectroscopy, atomic force microscopy and photoluminescence (PL) spectroscopy. The propel-ties of the films with the Al2O3 buffer were improved in comparison with those of as-grown ZnO films. It is shown that the ZnO films with the gamma-Al2O3 buffer grown on Si (100) substrates have a highly-preferential c-axis (0002) orientation, a narrow (0002) peak, smooth surface morphology and better PL spectral properties. This demonstrates that the use of gamma-Al2O3/Si as a ZnO substrate is beneficial for reducing the residual stress for further growth of ZnO films, compared with the growth on bulk Si substrates.

Stress and its effect on optical properties of GaN epilayers grown on Si(111), 6H-SiC(0001), and c-plane sapphire

The stress states in unintentionally doped GaN epilayers grown on Si(111), 6H-SiC(0001), and c-plane sapphire, and their effects on optical properties of GaN films were investigated by means of room-temperature confocal micro-Raman scattering and photoluminescence techniques. Relatively large tensile stress exists in GaN epilayers grown on Si and 6H-SiC while a small compressive stress appears in the film grown on sapphire. The latter indicates effective strain relaxation in the GaN buffer layer inserted in the GaN/sapphire sample, while the 50-nm-thick AlN buffer adopted in the GaN/Si sample remains highly strained. The analysis shows that the thermal mismatch between the epilayers and the substrates plays a major role in determining the residual strain in the films. Finally, a linear coefficient of 21.1+/-3.2 meV/GPa characterizing the relationship between the luminescent bandgap and the biaxial stress of the GaN films is obtained. (C) 2003 American Institute of Physics.

Structural characteristic of cubic GaN nucleation layers on GaAs(001) substrates by MOCVD

The structural characteristic of cubic GaN (C-GaN) nucleation layers on GaAs(0 0 1) substrates by metalorganic chemical vapor deposition was in detail investigated first by X-ray diffraction (XRD) measurements, using a Huber five-circle diffractometer and an intense synchrotron X-ray source. The XRD results indicate that the C-GaN nucleation layers are highly crystallized. Phi scans and pole figures of the (1 1 1) reflections give a convincing proof that the GaN nucleation layers show exactly cubic symmetrical structure. The GaN(1 1 1) reflections at 54.74degrees in chi are a measurable component, however (002) components parallel to the substrate surface are not detected. Possible explanations are suggested. The pole figures of {1 0 (1) over bar 0} reflections from H-GaN inclusions show that the parasitic H-GaN originates from the C-GaN nucleation layers. The coherence lengths along the close-packed [1 1 1] directions estimated from the (1 1 1) peaks are nanometer order of magnitude. (C) 2002 Elsevier Science B.V. All rights reserved.

Effect of buffer layer growth conditions on the secondary hexagonal phase content in cubic GaN films on GaAs(001) substrates

In this letter, we investigated the effect of the buffer layer growth conditions on the secondary hexagonal phase content in cubic GaN films on GaAs(0 0 1) substrate. The reflection high-energy electron diffraction (RHEED) pattern of the low-temperature GaN buffer layers shows that both the deposition temperature and time are important in obtaining a smooth surface. Four-circle X-ray double-crystal diffraction (XRDCD) reciprocal space mapping was used to study the hexagonal phase inclusions in the cubic GaN (c-GaN) films grown on the buffer layers. The calculation of the volume contents of the hexagonal phase shows that higher temperature and longer time deposition of the buffer layer is not preferable for growing pure c-GaN film. Under optimized condition, 47 meV FWHM of near band gap emission of the c-GaN film was achieved. (C) 2000 Elsevier Science B.V. All rights reserved.

Rapid thermal annealing processing of GaN epilayer on sapphire(0 0 0 1)

The effect of rapid thermal annealing (RTA) in a Nz ambient up to 900 degrees C has been investigated for GaN films grown on sapphire(0 0 0 1) substrates. Raman spectra, X-ray diffractometry and Hall-effect studies were performed for this purpose. The Raman spectra show the presence of the E-2 (high) mode and a shift in the wave number of this mode with respect to the annealing processing. This result suggests the presence and relaxation of residual stress due to thermal expansion misfit in the films which are confirmed by X-ray measurements and the structure quality of GaN epilayer was improved. Furthermore, the electron mobility increased at room temperature with respect to decrease of background electron concentration after RTA. (C) 1998 Elsevier Science B.V. All rights reserved.

Structural identification of a cubic phase in hexagonal GaN films grown on sapphire by gas-source molecular beam epitaxy

The structural characteristics of gallium nitride (GaN) films grown on sapphire(0001) substrates by gas source molecular beam epitaxy (GSMBE) have been investigated using high-resolution synchrotron irradiation X-ray diffraction and cathodoluminescence with a variable energy electron beam. Besides the well-known GaN hexagonal structure, a small portion of cubic phase GaN was observed. The X-ray measurements provide an essential means for the structural identification of the GaN layers. Arising from the variable penetration depth of the electron beam in the cathodoluminescence measurements, it was found that the fraction of the GaN cubic-phase typically increased as the probing depth was increased. The results suggest that the GaN cubic phase is mostly located near the interface between the substrate and GaN layer due to the initial nucleation.

Raman Investigatins of 3C-SiC Films Grown on Si (100) and Sapphire (0001) by LPCVD

The Raman measurements have been performed with the back-scattering geometry on the SiC films grown on Si(100) and sapphire (0001) by LPCVD. Typical TO and LO phonon peaks of 3C-SiC were observed for all the samples grown on Si and apphire substrates, indicating the epilayers are 3C-SiC polytype. Using a free-standing 3C-SiC film removed from Si(100) as a free-stress sample, the stresses of 3C-SiC on Si(100) and sapphire (0001) were estimated according to the shift of TO and LO phonons.

(Invited) Germanium on Sapphire Technology

Silicon-on-sapphire (SOS) substrates have been proven to offer significant advantages in the integration of passive and active devices in RF circuits. Germanium on insulator technology is a candidate for future higher performance circuits. Thus the advantages of employing a low loss dielectric substrate other than a silicon-dioxide layer on silicon will be even greater. This paper covers the production of germanium on sapphire (GeOS) substrates by wafer bonding. The quality of the germanium back interface is studied and a tungsten self-aligned gate process MOST process has been developed. High low field mobilities of 450-500 cm2/V-s have been achieved for p-channel MOSTs produced on GeOS substrates. Thick germanium on alumina (GOAL) substrates have also been produced.

Self-assembled MgxZn1−xO quantum dots (0 ≤ x ≤ 1) on different substrates using spray pyrolysis methodology

By using the spray pyrolysis methodology in its classical configuration we have grown self-assembled MgxZn1−xO quantum dots (size [similar]4–6 nm) in the overall range of compositions 0 ≤ x ≤ 1 on c-sapphire, Si (100) and quartz substrates. Composition of the quantum dots was determined by means of transmission electron microscopy-energy dispersive X-ray analysis (TEM-EDAX) and X-ray photoelectron spectroscopy. Selected area electron diffraction reveals the growth of single phase hexagonal MgxZn1−xO quantum dots with composition 0 ≤ x ≤ 0.32 by using a nominal concentration of Mg in the range 0 to 45%. Onset of Mg concentration about 50% (nominal) forces the hexagonal lattice to undergo a phase transition from hexagonal to a cubic structure which resulted in the growth of hexagonal and cubic phases of MgxZn1−xO in the intermediate range of Mg concentrations 50 to 85% (0.39 ≤ x ≤ 0.77), whereas higher nominal concentration of Mg ≥ 90% (0.81 ≤ x ≤ 1) leads to the growth of single phase cubic MgxZn1−xO quantum dots. High resolution transmission electron microscopy and fast Fourier transform confirm the results and show clearly distinguishable hexagonal and cubic crystal structures of the respective quantum dots. A difference of 0.24 eV was detected between the core levels (Zn 2p and Mg 1s) measured in quantum dots with hexagonal and cubic structures by X-ray photoemission. The shift of these core levels can be explained in the frame of the different coordination of cations in the hexagonal and cubic configurations. Finally, the optical absorption measurements performed on single phase hexagonal MgxZn1−xO QDs exhibited a clear shift in optical energy gap on increasing the Mg concentration from 0 to 40%, which is explained as an effect of substitution of Zn2+ by Mg2+ in the ZnO lattice.