Browsing by Subject "Plasma-Enhanced Atomic Layer Deposition"
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Item Open Access Atomic layer deposition of III-nitrides and metal oxides : their application in area selective ALD(Bilkent University, 2017-07) Haider, AliIII-nitride compound semiconductor materials (GaN, AlN, and InN) and their alloys have generated significant interest in both basic research and commercial applications mainly in the field of photonics, energy storage, nano-sensors, and nano-(opto)electronics. Wurtzite type III-nitrides exhibit direct band gaps, which extend from the ultra-violet (UV) to the mid-IR spectrum with values of 6.2, 3.4 and 0.64 eV for AlN, GaN, and InN, respectively. This feature allows the band gap of III-nitride alloys to be conveniently tuned by precisely controlling the composition for a particular application. Metalorganic chemical vapor deposition (MOCVD) and molecular beam epitaxy (MBE) are the most common successful techniques for achieving high-quality epitaxial III-nitride layers with low impurity concentrations and decent electrical properties. However, both of these methods employ high growth temperatures, which is neither compatible with the existing CMOS technology nor suitable for temperature-sensitive device layers (e.g. In-rich InxGa1-xN) and substrates (e.g. glass, flexible polymers, etc.). These limitations are the main driving source for a continuous exploration of alternative low temperature processes for the growth of III-nitride layers and their alloys. High aspect ratio III-nitride nanostructures in the form of nanowires and nanorods have been synthesized using different techniques including vapor-liquid-solid crystal growth, electrospinning, template based synthesis, and etching. Critical breakthroughs in fabrication of III-nitrides nanostructures have been achieved by above mentioned techniques but suffer from limited control over properties of nanostructures (shape, orientation, and size) and in some cases high growth-temperature requirement. A recent flurry of interest in developing high quality I-D III-nitride nanostructures derives from the desire to obtain flexible optoelectronic devices having wider applications. Template-assisted growth technique is one of the most promising approach to fabricate III-nitride nanostructures with precise control over shape, size, position, and distribution. In the first part of thesis, we have deposited InN and III-nitride alloys using hollow-cathode plasma assisted atomic layer deposition (HCPA-ALD) at low growth temperatures. The aim was to deposit III-nitride materials at lowest growth temperatures with decent crystalline quality and minimum impurity content. Depositions were carried out using group III organometallic precursors along with N2/H2 or N2 plasma as metal and nitrogen source, respectively. Process parameters including precursor pulse time, plasma flow duration, purge time, and deposition temperature are investigated and correlations were developed between process parameters and material properties. Refractive index of the InN film deposited at 200 C was found to be 2.66 at 650 nm. 48 nm-thick InN films exhibited relatively smooth surfaces with RMS surface roughness values of 0.98 nm, while the film density was extracted as 6.30 g/cm3. The effect of In content on structural, optical, and morphological properties of InxGa1-xN thin films was investigated. Grazing incidence X-ray diffraction (GIXRD) and transmission electron microscope (TEM) showed that InN and InxGa1-xN thin films were polycrystalline with hexagonal wurtzite structure. Spectral absorption measurements exhibited an optical band edge of InN around 1.9 eV. X-ray photoelectron spectroscopy (XPS) confirmed the deposition of InN and alloy thin films and revealed the presence of low impurity contents. Higher In concentrations resulted in an increase of refractive indices of InxGa1-xN ternary alloys from 2.28 to 2.42 at a wavelength of 650 nm. Optical band edge of InxGa1-xN films red-shifted with increasing In content, confirming the tunability of the band edge with alloy composition. Photoluminescence measurements of InxGa1-xN exhibited broad spectral features with an In concentration dependent wavelength shift. We have also studied the compositional dependence of structural, optical, and morphological properties of BxGa1-xN and BxIn1-xN ternary thin film alloys grown using sequential pulsed CVD. GIXRD measurements showed that boron incorporation in wurtzite lattice of GaN and InN diminishes the crystallinity of BxGa1-xN and BxIn1-xN sample. Refractive index decreased from 2.24 to 1.65 as the B concentration of BxGa1-xN increased from 35 to 88 %. Similarly, refractive index of BxIn1-xN changed from 1.98 to 1.74 for increase in B concentration value from 32 to 87 %, respectively. Optical transmission band edge values of the BxGa1-xN and BxIn1-xN films shifted to lower wavelengths with increasing boron content, indicating the tunability of energy band gap with alloy composition. Atomic force microscopy measurements revealed an increase in surface roughness with boron concentration of BxGa1-xN, while an opposite trend was observed for BxIn1-xN thin films. Moreover, we demonstrate vertical GaN, AlN, and InN hollow nano-cylindrical arrays (HNCs) integrated to Si(100) substrates using anodized aluminum oxide (AAO) membrane templated PA-ALD. Our fabrication and Si-integration strategy consists of the following process steps: (i) reactive ion etching (RIE) of Si using AAO membrane as hard mask material to achieve nanoporous Si substrate, (ii) conformal growth of III-nitride films on nanoporous Si via low-temperature PA-ALD, (iii) removal of PA-ALD coated III-nitride material from top surface of Si via plasma etching, and (iv) isotropic dry etching of surrounding Si to attain long-range ordered vertical III-nitride HNCs. The material properties of nanostructured III-nitride materials have been compared with the thin-film counterparts which were also grown using low-temperature PA-ALD. SEM images revealed that long-range ordered arrays of III nitride HNCs were successfully integrated in Si(100) substrates. TEM, GIXRD, and selected area electron diffraction (SAED) cumulatively confirmed that III-nitride HNCs possess hexagonal wurtzite crystalline structure. XPS survey and high-resolution scans detected presence of different elements and peaks at specific binding energies which confirmed the formation of III-nitride HNCs. The second part of the thesis deals with self-aligned thin film patterning of metal oxides using area selective atomic layer deposition (AS-ALD). Nanoscale process integration demands novel nano-patterning techniques in compliance with the requirements of next generation devices. Conventionally, top-down subtractive (etch) or additive (deposition/lift-off) processes in conjunction with various lithography techniques is employed to achieve film patterning, which become increasingly challenging due to the ever-shrinking misalignment requirements. To reduce the complexity burden of lithographic alignment in critical fabrication steps, self-aligned processes such as selective deposition and selective etching might provide attractive solutions. We demonstrate a methodology to achieve AS-ALD by using inductively couple plasma (ICP) grown fluorocarbon polymer film as growth inhibition layer. The fluorocarbon layer was grown using C4F8 feed gas in a conventional ICP-etch reactor. Our approach has been tested for metal-oxides including ZnO, Al2O3, TiO2, and HfO2. Additionally, we investigate the poly(methyl methacrylate) (PMMA) and polyvinylpyrrolidone (PVP) as growth inhibition layers for AS-ALD of TiO2. Contact angle, XPS, spectroscopic ellipsometer, energy dispersive X-ray spectroscopy (EDX), and scanning electron microscopy (SEM) measurements were performed to investigate the blocking ability of polymer layers against ALD-grown films. Characterizations carried out revealed that effective blocking on fluorocarbon layer is achieved for ZnO film upto 136 growth cycles. On the other hand, a rather slow nucleation has been observed for HfO2 growth on fluorocarbon coated surfaces, while TiO2 and Al2O3 growth showed almost no delay with a growth rate equal to the ones on conventional substrate surfaces. For TiO2, PMMA revealed successful growth inhibition upto the maximum inspected growth cycles while PVP was able to block TiO2 growth upto 300 growth cycles. By exploiting this inhibition feature, thin film patterning has been demonstrated by growing ZnO films on photo lithographically patterned fluorocarbon/Si samples. We also demonstrate nanoscale patterned deposition of TiO2 using a PMMA masking layer that has been patterned using e-beam lithography.Item Open Access Atomic layer deposition of metal oxide thin films and nanostructures(Bilkent University, 2013) Dönmez, İnciWith the continuing scaling down of microelectronic integrated circuits and increasing need for three-dimensional stacking of functional layers, novel or improved growth techniques are required to deposit thin films with high conformality and atomic level thickness control. As being different from other thin film deposition techniques, atomic layer deposition (ALD) is based on selflimiting surface reactions. The self-limiting film growth mechanism of ALD ensures excellent conformality and large area uniformity of deposited films. Additionally, film thickness can be accurately controlled by the number of sequential surface reactions. Gallium oxide (Ga2O3) thin films were deposited by plasma-enhanced ALD (PEALD) using trimethylgallium as the gallium precursor and oxygen plasma as the oxidant. A wide ALD temperature window was observed from 100 to 400 °C, where the deposition rate was constant at ~0.53 Å/cycle. The deposition parameters, composition, crystallinity, surface morphology, optical and electrical properties were studied for as-deposited and annealed Ga2O3 films. In order to investigate the electrical properties of the deposited films, metal-oxide-semiconductor capacitor structures were fabricated for a variety of film thicknesses and annealing temperatures. Ga2O3 films exhibited decent dielectric properties after crystallization upon annealing. Dielectric constant was increased with film thickness and decreased slightly with increasing annealing temperature. As an additional PEALD experiment, deposition parameters of In2O3 thin films were studied as well, using the precursors of cyclopentadienyl indium and O2 plasma. Initial results of this experiment effort are also presented. Accurate thickness control, along with high uniformity and conformality offered by ALD makes this technique quite promising for the deposition of conformal coatings on nanostructures. This thesis also deals with the synthesis of metal oxide nanotubes using organic nanofiber templates. Combination of electrospinning and ALD processes provided an opportunity to precisely control both diameter and wall thickness of the synthesized nanotubes. As a proof-ofconcept, hafnia (HfO2) nanotubes were synthesized using three-step approach: (i) preparation of the nylon 6,6 nanofiber template by electrospinning, (ii) conformal deposition of HfO2 on the electrospun polymer template via ALD using the precursors of tetrakis(dimethylamido)hafnium and water at 200 °C, and (iii) removal of the organic template by calculation to obtain freestanding HfO2 nanotubes (hollow nanofibers). When the same deposition procedure was applied on nanofibers with different average fiber diameters, thinner HfO2 wall thicknesses were obtained for the templates having smaller diameters due to insufficient exposure of precursor molecules to saturate their extremely large surface area. Thus, “exposure mode” was applied to obtain the desired wall thickness while coating high-surface area nanofibers. We present the experimental efforts including film deposition parameters, structural, elemental, and morphological properties of HfO2 nanotubes.Item Open Access Growth and characterization of boron nitride thin films and nanostructures using atomic layer deposition = Bor nitrür ince filmlerin ve nanoyapıların atomik katman biriktirme yöntemi ile büyütülmesi ve karakterizasyonu(Bilkent University, 2014) Haider, AliBeing a member of III-nitride family, boron nitride (BN) and its nanostructures have recently attracted a lot of attention, mainly due to their distinctive and superior material properties, including wide band gap, high-temperature stability, high oxidation and corrosion resistance, as well as high thermal conductivity. This versatile material has found applications in UV emission, lubrication, composite reinforcement, gas adsorption, cosmetics, and thermal management. For modern electronic applications, it is imperative to obtain high quality BN films on large area substrates with a controlled thickness in order to fulfill the entire spectrum of hBN applications. Also, a facile method such as atomic layer deposition (ALD) using non halide precursors is necessary to obtain BN films at low temperatures compliant with the standards in terms of having nontoxic byproducts. ALD is a special case of chemical vapor deposition (CVD), in which two or more precursors are sequentially exposed to substrate surface separated by purging periods. In comparison with other thin film growth methods, hall mark of ALD is self limiting growth mechanism which enables deposition of highly uniform and conformal thin films with sub-angstrom thickness control. The precise and conformal layer by layer growth of ALD can be exploited to achieve growth of BN hollow nanofibers (HNFs) on high aspect ratio electrospun polymer nanofibrous templates. BN HNFs fabricated by combination of ALD and electrospinning can be utilized to address and solve important constraints associated with previous methods of fabrication such as severe preparation conditions, limited control over morphology, and low purity of the resulting BN HNFs. In this thesis, we report on the controlled deposition of BN films and its nanostructures with the use of a hollow-cathode plasma source integrated (HCPA-ALD) reactor and present detailed materials characterization results of deposited thin films and fabricated nanostructures. Depositions are carried out at low substrate temperatures (less than 450 °C) using sequential injection of nonhalide triethylboron (TEB) and N2/H2 plasma as boron and nitrogen precursors, respectively. The deposition process parameters such as pulse length of TEB and substrate temperature, as well as the influence of post-deposition annealing are studied. Moreover, another nonhalide alternative precursor named tris(dimethyl)amidoboron (TDMAB) was studied for deposition of BN films. Initial experiments were performed using TDMAB and N2/H2 plasma as boron and nitrogen precursor. In addition to BN thin film growth studies, we report on electrospun polymeric nanofibrous template-based fabrication and characterization of AlN/BN bishell HNFs. Synthesized AlN/BN bishell HNFs were found to be polycrystalline with a hexagonal structure along with lowimpurity content.