Thesis (Ph. D.)--University of Hong Kong, 2006. / Title proper from title frame. Also available in printed format.

Ph.D. / Electrical Engineering / Nanometer-scale devices have attracted great attention as the ultimate evolution of silicon integrated circuit technology. However, fabrication of nanometer-scale silicon based devices has met great difficulty because it places severe constraints on process technology. This is especially true for SiGe/Si heterostructures because they are particularly sensitive to strain relaxation and/or process induced defects. Recently developed Pulsed Laser Induced Epitaxy (PLIE) offers a promising approach for the fabrication of nanometer- scale SiGe/Si devices. It possesses the advantage of ultra-short time, low thermal budget and full compatibility with current silicon technology. The selective nature of the process allows epitaxial growth of high quality, localized SiGe layers in silicon. In this thesis, a process to fabricate SiGe nanowires in silicon using PLIE is described. In particular, Ge nanowires with a cross-section of ~6 x 60 nm² are first formed using a lift-off process on the silicon substrate with e-beam lithography, followed by a thin low-temperature oxide deposition. Defect-free SiGe nanowires with a cross-section of ~25 x 95 nm² are then produced by impinging the laser beam on the sample. We thus demonstrate PLIE is a suitable fabrication technique for SiGe/Si nanostructures. Fabrication of Ge nanowires is also studied using Focused Ion Beam (FIB) micromachining techniques. Based on the SiGe nanowire process, we propose two advanced device structures, a quantum wire MOSFET and a lateral SiGe Heterojunction Bipolar Transistor (HBT). MEDICI simulation of the lateral SiGe HBT demonstrates high performance of the device. In order to characterize the SiGe nanowires using cross-sectional transmission electron microscopy, an advanced versatile focused ion beam assisted sample preparation technique using a multi-layer stack scheme for localized surface structures is developed and described in this thesis.

Vertical cavity lasers (VCLs) are of great interest aslow-cost, high-performance light sources for fiber-opticcommunication systems. They have a number of advantages overconventional edge-emitting lasers, including low powerconsumption, efficient fiber coupling and wafer scalemanufacturing/testing. For high-speed data transmission overdistances up to a few hundred meters, VCLs (or arrays of VCLs)operating at 850 nm wavelength is today the technology ofchoice. While multimode fibers are successfully used in theseapplications, higher transmission bandwidth and longerdistances require single-mode fibres and longer wavelengths(1.3-1.55 µm). However, long-wavelength VCLs are as yetnot commercially available since no traditional materialssystem offers the required combination of bothhigh-index-contrast distributed Bragg reflectors (DBRs) andhigh-gain active regions. Earlier work on long-wavelength VCLshas therefore focused on hybrid techniques, such as waferfusion between InP-based QWs and AlGaAs DBRs, but more recentlythe main interest in this field has shifted towardsall-epitaxial GaAs-based devices employing novel 1.3-µmactive materials. Among these, strained GaInNAs/GaAs QWs aregenerally considered one of the most promising approaches andhave received a great deal of interest. The aim of this thesis is to investigate monolithicGaAs-based long-wavelength (&gt;1.2 µm) VCLs with InGaAsor GaInNAs QW active regions. Laser structures - or partsthereof - have been grown by metal-organic vapor phase epitaxy(MOVPE) and characterized by various techniques, such ashigh-resolution x-ray diffraction (XRD), photoluminescence(PL), atomic force microscopy, and secondary ion massspectroscopy (SIMS). High accuracy reflectance measurementsrevealed that n-type doping is much more detrimental to theperformance of AlGaAs DBRs than previously anticipated. Asystematic investigation was also made of the deleteriouseffects of buried Al-containing layers, such as AlGaAs DBRs, onthe optical and structural properties of subsequently grownGaInNAs QWs. Both these problems, with their potential bearingon VCL fabrication, are reduced by lowering the DBR growthtemperature. Record-long emission wavelength InGaAs VCLs were fabricatedusing an extensive gain-cavity detuning. The cavity resonancecondition just below 1270 nm wavelength occurs at the farlong-wavelength side of the gain curve. Still, the gain is highenough to yield threshold currents in the low mA-regime and amaximum output power exceeding 1 mW, depending on devicediameter. Direct modulation experiments were performed on1260-nm devices at 10 Gb/s in a back-to-back configuration withopen, symmetric eye diagrams, indicating their potential foruse in high-speed transmission applications. These devices arein compliance with the wavelength requirements of emerging10-Gb/s Ethernet and SONET OC-192 standards and may turn out tobe a viable alternative to GaInNAs VCLs. <b>Keywords:</b>GaInNAs, InGaAs, quantum wells, MOVPE, MOCVD,vertical cavity laser, VCSEL, long-wavelength, epitaxy, XRD,DBR

Two types of photodetectors containing Ge/Si quantum dots have been fabricated based on materials grown by molecular beam epitaxy and characterized with several experimental techniques. The aim was to study new device architectures with the implementation of Ge nanostructures, in order to obtain high detection efficiency in the near infrared range at room temperature. Heterojunction bipolar phototransistors were fabricated with 10 Ge dot layers in the base-collector (b-c) junction. With the illumination of near infrared radiation at 1.31 to 1.55 µm, the incident light would excite the carriers. The applied field across the b-c junction caused hole transport into the base, leading to a reduced potential barrier between the emitter-base (e-b) junction. Subsequently, this resulted in enhanced injection of electrons across the base into the collector, i.e., forming an amplified photo-induced current. We have therefore obtained significantly enhanced photo-response for the Ge-dot based phototransistors, compared to corresponding quantum dot p-i-n photodiodes. Responsivity values up to 470 mA/W were measured at 1.31 µm using waveguide geometry, and ∼2.5 A/W at 850 nm, while the dark current was as low as 0.01 mA/cm2 at –2 V. Metal-oxide field-effect phototransistors were also studied. These lateral detectors were processed with three terminals for source, drain and gate contacts. The Ge quantum dot layers were sandwiched between pseudomorphically grown SiGe quantum wells. The detector devices were processed using a multi-finger comb structure with an isolated gate contact on top of each finger and patterned metal contacts on the side edges for source and drain. It was found that the photo-responsivity was increased by a factor of more than 20 when a proper gate bias was applied. With VG above threshold, the measured response was 350 and &gt;30 mA/W at 1.31 and 1.55 µm, respectively. Properties of Si/Si1-xGex nanostructures were examined, in order to facilitate proper design of the above mentioned transistor types of photodetectors. The carrier recombination processes were characterized by photoluminescence measurements, and the results revealed a gradual change from spatially indirect to direct transitions in type II Si1-xGex islands with increased measurement temperature. Energy dispersive X-ray spectrometry of buried Ge islands produced at different temperatures indicated a gradual decrease of the Ge concentration with temperature, which was due to the enhanced intermixing of Si and Ge atoms. At a deposition temperature of 730°C the Ge concentration was as low as around 40 %. Finally, the thermal stability of the Si/SiGe(110) material system, which is a promising candidate for future CMOS technology due to its high carrier mobility, was investigated by high resolution X-ray diffraction reciprocal space mapping. Anisotropic strain relaxation was observed with maximum in-plane lattice mismatch in the [001] direction. / On the day of the defence date the status of article IV was Manuscript and the title was "A three-terminal Ge dot/SiGe quantum well MOSFET photodetector for near infrared light detection"; the status of article VI was Submitted and the title was "Band alignment studies in Si/Ge quantum dots based on optical and structural investigations"; the status of article VII was Manuscript and the title was "Thermal stability of SiGe/Si(110) investigated by high-resolution X-ray diffraction reciprocal space mapping".

The strain introduced by lattice mismatch is a built-in characteristic in Si/SiGe heterostructures, which has significant influences on various material properties. Proper design and precise control of strain within Si/SiGe heterostructures, i.e. the so-called “strain engineering”, have become a very important way not only for substantial performance enhancement of conventional microelectronic devices, but also to allow novel device concepts to be integrated with Si chips for new functions, e.g. Si-based optoelectronics. This thesis thus describes studies on two subjects of such strain-engineered Si/SiGe heterostructures grown by molecular beam epitaxy (MBE). The first one focuses on the growth and characterizations of delicately strain-symmetrized Si/SiGe multi-quantum-well/superlattice structures on fully relaxed SiGe virtual substrates for light emission in the THz frequency range. The second one investigates the strain relaxation mechanism of thin SiGe layers during MBE growth and post-growth processes in non-conventional conditions. Two types of THz emitters, based on different quantum cascade (QC) intersubband transition schemes, were studied. The QC emitters using the diagonal transition between two adjacent wells were grown with Si/Si0.7Ge0.3 superlattices up to 100 periods. It was shown that nearly perfect strain symmetry in the superlattice with a high material quality was obtained. The layer parameters were precisely controlled with deviations of ≤ 2 Å in layer thickness and ≤ 1.5 at. % in Ge composition from the designed values. The fabricated emitter devices exhibited a dominating emission peak at ~13 meV (~3 THz), which was consistent with the design. An attempt to produce the first QC THz emitter based on the bound-to-continuum transition was made. The structures with a complicated design of 20 periods of active units were extremely challenging for the growth. Each unit contained 16 Si/Si0.724Ge0.276 superlattice layers, in which the thinnest one was only 8 Å. The growth parameters were carefully studied, and several samples with different boron δ-doping concentrations were grown at optimized conditions. Extensive material characterizations revealed a high crystalline quality of the grown structures with an excellent growth control, while the heavy δ-doping may introduce layer undulations as a result of the non-uniformity in the strain field. Moreover, carrier lifetime dynamics, which is crucial for the THz QC structure design, was also investigated. Strain-symmetrized Si/SiGe multi-quantum-well structures, designed for probing the carrier lifetime of intersubband transitions inside a well between heavy hole 1 (HH1) and light hole 1 (LH1) states with transition energies below the optical phonon energy, were grown on SiGe virtual substrates. The lifetime of the LH1 excited state was determined directly with pump-probe spectroscopy. The measurements indicated an increase of lifetime by a factor of ~2 due to the increasingly unconfined LH1 state, which agreed very well with the theory. It also showed a very long lifetime of several hundred picoseconds for the holes excited out of the well to transit back to the well through a diagonal process. Strained SiGe grown on Si (110) substrates has promising potentials for high-speed microelectronics devices due to the enhanced carrier mobility. Strain relaxation of SiGe/Si(110) subjected to different annealing treatments was studied by X-ray reciprocal space mapping. The in-plane lattice mismatch was found to be asymmetric with the major strain relaxation observed in the lateral [001] direction. It was concluded that this was associated to the formation and propagation of conventional a/2&lt;110&gt; dislocations oriented along [110]. This was different from the relaxation observed during growth, which was mainly along in-plane [110]. A novel MBE growth process to fabricate thin strain-relaxed Si0.6Ge0.4 virtual substrates involving low-temperature (LT) buffer layers was investigated. At a certain LT-buffer growth temperature, a dramatic increase in the strain relaxation accompanied with a decrease of surface roughness was observed in the top SiGe, together with a cross-hatch/cross-hatch-free transition in the surface morphology. It was explained by the association with a certain onset stage of the ordered/disordered transition during the growth of the LT-SiGe buffer. / Kisel(Si)-baserad mikroelektronik har utvecklats under en femtioårsperiod till att bli basen för vår nuvarande informationsteknologi. Förutom att integrera fler och mindre komponenter på varje kisel-chip så utvecklas metoder att modifiera och förbättra materialegenskaperna för att förbättra prestanda ytterligare. Ett sätt att göra detta är att kombinera kisel med germanium (Ge) bl.a. för att skapa kvantstrukturer av nanometer-storlek. Eftersom Ge-atomerna är större än Si-atomerna kan man skapa en töjning i materialet vilket kan förbättra egenskaperna, ex.vis hur snabbt laddningarna (elektronerna) rör sig i materialet. Genom att variera Gekoncentrationen i tunna skikt kan man skapa skikt som är antingen komprimerade eller expanderade och därmed ger möjlighet att göra strukturer för tillverkning av nya typer av komponenter för mikroelektronik eller optoelektronik. I detta avhandlingsarbete har Si/SiGe nanostrukturer tillverkats med molekylstråle-epitaxi-teknik (molecular beam epitaxy, MBE). Med denna teknik byggs materialet upp på ett substrat, atomlager för atomlager, med mycket god kontroll på sammansättningen av varje skikt. Samtidigt kan töjningen av materialet designas så att inga defekter skapas alternativt många defekter genereras på ett kontrollerat sätt. I denna avhandling beskrivs detaljerade studier av hur töjda i/SiGe-strukturer kan tillverkas och ge nya potentiella tillämpningar ex.vis som källa för infraröd strålning. Studierna av de olika töjda skikten har framför allt gjorts med avancerade röntgendiffraktionsmätningar och transmissionselektronmikroskopi.

Graduation date: 1993

The discovery of unique properties of graphene has led to the development of graphene for a variety of applications like integrated circuits, organic electronic devices, supercapacitors, sensors, and composite materials. Fluorination of graphene enables control of its physical, chemical, and electronic properties. Our initial studies demonstrated the viability of sulfur hexafluoride plasmas to fluorinate epitaxial graphene as a safer alternative to the commonly reported techniques of fluorination that include exposures to fluorine and xenon difluoride gas. Formation of carbon-fluorine bonds after SF6 plasma-treatment was confirmed by x-ray photoelectron spectroscopy. Raman spectroscopy and low-energy electron diffraction studies suggest that the framework of sp2-hybridized carbon atoms remains intact after the plasma-treatment. Increase in work function after the fluorination was determined by ultra-violet photoelectron spectroscopy. The findings of our subsequent investigation to controllably modify the work function of epitaxial graphene via plasma-fluorination indicate that the work function of fluorinated epitaxial graphene is controlled by the polarity of carbon-fluorine bonds. Further studies to investigate the effect of the surface topography of epitaxial graphene on the work function of plasma-fluorinated epitaxial graphene were performed using scanning Kelvin probe microscopy (SKPM). The results of SKPM characterization of plasma-fluorinated epitaxial graphene demonstrated that the increase in the work function of epitaxial graphene after plasma-treatment is independent of its surface topography, but non-uniform fluorination may result from non-uniformities in plasma density.

Solar photovoltaic has become one of the potential solutions for current energy needs and for combating greenhouse gas emissions. The photovoltaics (PV) industry is booming, with a yearly growth rate well in excess of 30% over the last decade. This explosive growth has been driven by market development programs to accelerate the deployment of sustainable energy options and rapidly increasing fossil fuel prices. Currently, the PV market is based on silicon wafer solar cells (thick cells of around 150–300 μm made of crystalline silicon). This technology, classified as the first-generation of photovoltaic cells. The second generation of photovoltaic materials is based on the introduction of thin film layers of semiconductor materials. Unfortunately, the conversion efficiency of the current PV systems is low despite the lower manufacturing costs. Nevertheless, to achieve highly efficient silicon solar cell devices, the development of new high quality materials in terms of structure and electrical properties is a must to overcome the issues related to amorphous silicon (a -Si:H) degradation. Meanwhile, to remain competitive with the conventional energy sources, cost must be taken into consideration. Moreover, novel approaches combined with conventional mature silicon solar cell technology can boost the conventional efficiency and break its maximum limits. In our approach, we set to achieve efficient, stable and affordable silicon solar cell devices by focusing on the development of a new device made of epitaxial films. This new device is developed using new epitaxial growth phosphorous and/or boron doped layers at low processing temperature using plasma enhanced chemical vapor deposition (PECVD). The junction between the phosphorous or boron-doped epitaxial film of the device is formed between the film and the p or n-type crystalline silicon (c-Si) substrate, giving rise to (n epi-Si/p c-Si device or p epi-Si/n c-Si device), respectively. Different processing conditions have been fully characterized and deployed for the fabrication of different silicon solar cells architectures. The high quality epitaxial film (up to 400 nm) was used as an emitter for an efficient stable homojunction solar cell. Extensive analysis of the developed fine structure material, using high resolution transmission electron microscope (HRTEM), showed that hydrogen played a crucial role in the epitaxial growth of highly phosphorous doped silicon films. The main processing parameters that influenced the quality of the structure were; radio frequency (RF) power density, the processing chamber pressure, the substrate temperature, the gas flow rate used for deposition of silicon films, and hydrogen dilution. The best result, in terms of structure and electrical properties, was achieved at intermediate hydrogen dilution (HD) regime between 91 and 92% under optimized deposition conditions of the rest of the processing parameters. The conductivity and the carrier mobility values are good indicators of the electrical quality of the silicon (Si) film and can be used to investigate the structural quality indirectly. The electrical conductivity analyses using spreading resistance profile (SRP), through the detection of active carriers inside the developed films, are presented in details for the developed epitaxial film under the optimized processing conditions. Measurements of the active phosphorous dopant revealed that, the film has a very high active carrier concentration of an average of 5.0 x1019 cm-3 with a maximum value of 6.9 x 1019 cm-3 at the interface between substrate and the epitaxial film. The observed higher concentration of electrically active P atoms compared to the total phosphorus concentration indicates that more than half of dopants become incorporated into substitutional positions. Highly doping efficiency ηd of more than 50 % was calculated from both secondary ion mass spectroscopy (SIMS) and SRP analysis. A variety of proposed structures were fabricated and characterized on planar, textured, and under different deposition temperatures. Detailed studies of the photovoltaic properties of the fabricated devices were carried out using epitaxial silicon films. The results of these studies confirmed that the measured open circuit voltage (Voc) of the device ranged between 575 and 580 mV with good fill factor (FF) values in the range of 74-76 %. We applied the rapid thermal process (RTP) for a very short time (60 s) at moderate temperature of 750oC to enhance the photovoltaic properties of the fabricated device. The following results were achieved, the values of Voc, and the short circuit current (Isc) were 598 mV and 27.5 mA respectively, with a fill factor value of up to 76 % leading to an efficiency of 12.5 %. Efficiency enhancement by 13.06 % was achieved over the reference cell which was prepared without using RTP. Another way to increase the efficiency of the fabricated device is to reduce the reflections from its polished substrate. This was achieved by utilizing the light trapping technique that transforms the reflective polished surface into a pyramidical texturing using alkaline solutions. Further enhancements of both Voc and Isc were achieved with values of 612 mV and 31mA respectively, and a fill factor of 76 % leading to an increase in the efficiency by up to 13.8 %. A noticeable efficiency enhancement by ~20 % over the reference cell is reported for the developed devices on the textured surfaces. Moreover, the efficiency of the fabricated epitaxial silicon solar cells can be boosted by the deployment of silicon nanocrystals (Si NCs) on the top surface of the fabricated devices. In the course of this PhD research we found a way to achieve this by depositing a thin layer of Si NCs, embedded in amorphous silicon matrix, on top of the epitaxial film. Structural analysis of the deposited Si NCs was performed. It is shown from the HRTEM analysis that the developed Si NCs, are randomly distributed, have a spherical shape with a radius of approximately 2.5 nm, and are 10-20 nm apart in the amorphous silicon matrix. Based on the size of the developed Si NCs, the optical band gap was found to be in the region of 1.8-2.2 eV. Due to the incorporation of Si NCs layer a noticeable enhancement in the Isc was reported.

In this thesis, we show that planar graphene ribbons have properties similar to those of nanotubes. Both exhibit semiconducting or metallic properties depending on crystal orientation. The band gap varies approximately as the inverse of the ribbon width. Both can be doped and gated. Due to these similarities, the patterned graphene also has nanotube like transport properties, which include coherent transport, ballistic transport, and high current capabilities. In essential contrast to nanotubes, graphene ribbons can be rationally patterned using standard electron beam lithography methods; functional graphene devices could be fabricated eliminating the need for metal interconnects on the wafer. This would remove many obstacles faced by carbon nanotubes, while retaining the benefits of high carrier mobility and quasi-1D transport. We have produced ultrathin epitaxial graphite films on single-crystal silicon carbide by vacuum graphitization, which show remarkable 2D electron gas (2DEG) behavior. The most highly ordered samples exhibit Shubnikov-de Haas oscillations that correspond to nonlinearities observed in the Hall resistance, indicating a potential new quantum Hall system. The transport properties, which are closely related to those of carbon nanotubes, are dominated by the single epitaxial graphene layer at the silicon carbide interface and reveal the Dirac nature of the charge carriers. Patterned structures show quantum confinement of electrons and phase coherence lengths beyond 1 micrometer at 4 kelvin, with mobilities exceeding 2.5 square meters per volt-second. We show that the high-mobility films can be patterned via conventional lithographic techniques, and we demonstrate modulation of the film conductance using a top-gate electrode. These key elements suggest electronic device applications based on nanopatterned epitaxial graphene (NPEG) with the potential for large-scale integration. The research created a foundation for graphene science and technology and established a path toward graphene-based nanoelectronics.

A wide variety of group III-Nitride-based photonic and electronic devices have opened a new era in the field of semiconductor research in the past ten years. The direct and large bandgap nature, intrinsic high carrier mobility, and the capability of forming heterostructures allow them to dominate photonic and electronic device market such as light emitters, photodiodes, or high-speed/high-power electronic devices. Avalanche photodiodes (APDs) based on group III-Nitrides materials are of interest due to potential capabilities for low dark current densities, high sensitivities and high optical gains in the ultraviolet (UV) spectral region. Wide-bandgap GaN-based APDs are excellent candidates for short-wavelength photodetectors because they have the capability for cut-off wavelengths in the UV spectral region (λ < 290 nm). These intrinsically solar-blind UV APDs will not require filters to operate in the solar-blind spectral regime of λ < 290 nm. For the growth of GaN-based heteroepitaxial layers on lattice-mismatched substrates, a high density of defects is usually introduced during the growth; thereby, causing a device failure by premature microplasma, which has been a major issue for GaN-based APDs. The extensive research on epitaxial growth and optimization of Al_x Ga _1-x N (0 ≤ x ≤ 1) grown on low dislocation density native bulk III-N substrates have brought UV APDs into realization. GaN and AlGaN UV <i> p-i-n </i> APDs demonstrated first and record-high true avalanche gain of > 10,000 and 50, respectively. The large stable optical gains are attributed to the improved crystalline quality of epitaxial layers grown on low dislocation density bulk substrates. GaN <i>p-i-n </i> rectifiers have brought much research interest due to its superior physical properties. The AIN-free full-vertical GaN<i> p-i-n </i> rectifiers on<i> n </i>- type 6H-SiC substrates by employing a conducting AIGaN:Si buffer layer provides the advantages of the reduction of sidewall damage from plasma etching and lower forward resistance due to the reduction of current crowding at the bottom<i> n </i> -type layer. The AlGaN:Si nucleation layer was proven to provide excellent electrical properties while also acting as a good buffer role for subsequent GaN growth. The reverse breakdown voltage for a relatively thin 2.5 μm-thick<i> i </i>-region was found to be over -400V.