Materials Science and Engineering Commons^™

Effect Of Fabrication Parameters On The Ferroelectricity Of Hafnium Zirconium Oxide Films: A Statistical Study, Guillermo A. Salcedo, Ahmad E. Islam, Elizabeth Reichley, Michael Dietz, Christine M. Schubert Kabban, Kevin D. Leedy, Tyson C. Back, Weison Wang, Andrew Green, Timothy S. Wolfe, James M. Sattler

Faculty Publications

Ferroelectricity in hafnium zirconium oxide (Hf_1−xZr_xO₂) and the factors that impact it have been a popular research topic since its discovery in 2011. Although the general trends are known, the interactions between fabrication parameters and their effect on the ferroelectricity of Hf_1−xZr_xO₂ require further investigation. In this paper, we present a statistical study and a model that relates Zr concentration (x), film thickness (t_f), and annealing temperature (T_a) with the remanent polarization (P_r) in tungsten (W)-capped Hf_1−xZr_xO₂. …

Intrinsic And Atomic Layer Etching Enhanced Area-Selective Atomic Layer Deposition Of Molybdenum Disulfide Thin Films, Jake Soares, Wesley Jen, John D. Hues, Drew Lysne, Jesse Wensel, Steven M. Hues, Elton Graugnard

Materials Science and Engineering Faculty Publications and Presentations

For continual scaling in microelectronics, new processes for precise high volume fabrication are required. Area-selective atomic layer deposition (ASALD) can provide an avenue for self-aligned material patterning and offers an approach to correct edge placement errors commonly found in top-down patterning processes. Two-dimensional transition metal dichalcogenides also offer great potential in scaled microelectronic devices due to their high mobilities and few-atom thickness. In this work, we report ASALD of MoS₂ thin films by deposition with MoF₆ and H₂S precursor reactants. The inherent selectivity of the MoS₂ atomic layer deposition (ALD) process is demonstrated by growth …

Thermal Atomic Layer Etching Of Mos2 Using Mof6 And H2O, Jake Soares, Anil U. Mane, Devika Choudhury, Steven Letourneau, Steven M. Hues, Jeffrey W. Elam, Elton Graugnard

Materials Science and Engineering Faculty Publications and Presentations

Two-dimensional (2D) layered materials offer unique properties that make them attractive for continued scaling in electronic and optoelectronic device applications. Successful integration of 2D materials into semiconductor manufacturing requires high-volume and high-precision processes for deposition and etching. Several promising large-scale deposition approaches have been reported for a range of 2D materials, but fewer studies have reported removal processes. Thermal atomic layer etching (ALE) is a scalable processing technique that offers precise control over isotropic material removal. In this work, we report a thermal ALE process for molybdenum disulfide (MoS₂). We show that MoF₆ can be used as …

Hierarchically Structured Photoelectrodes Via Atomic Layer Deposition, Justin Rowan Reed Demoulpied

Graduate Theses and Dissertations

In the search for a sustainable method to meet increasing energy needs, solar energy emerges as an underutilized, plentiful resource. Solar intermittency and requirements for transportation necessitate storing solar energy in the form of chemical bonds via artificial photosynthesis. Photoelectrochemical (PEC) water splitting generates hydrogen fuel from solar energy and water. A semiconducting material that successfully meets the complex requirements for building an industrially scalable PEC device has yet to emerge. This is leading to a reevaluation of materials previously overlooked within PEC research, mainly materials with limitations such as minimal charge carrier mobility and propensity to corrosion under illumination …

Application Of In Situ And Ex Situ Characterization Of Atomic Layer Deposition Processes For Gallium Phosphide And Sodium Fluoride, Sara Rose Kuraitis

Boise State University Theses and Dissertations

Atomic layer deposition (ALD) is a vapor deposition technique for synthesizing thin films with nanometer thickness control. ALD films are deposited on a substrate surface in a cyclic layer-by-layer fashion utilizing alternating doses of highly reactive chemical precursors. Precursors are selected to undergo self-limiting chemical reactions with the surface, and desired film thickness is achieved by varying the number of ALD cycles accordingly. Optimization of ALD process parameters and precursor chemistry enables conformal coating of arbitrary substrate geometries, including high aspect ratio features such as trenches. In the decades since its introduction, ALD has been used for applications across many …

Atomic Layer Deposition Of Sodium Fluoride Thin Films, Sara Kuraitis, Donghyeon Kang, Anil U. Mane, Hua Zhou, Jake Soares, Jeffrey W. Elam, Elton Graugnard

Materials Science and Engineering Faculty Publications and Presentations

The need for advanced energy conversion and storage devices remains a critical challenge amid the growing worldwide demand for renewable energy. Metal fluoride thin films are of great interest for applications in lithium-ion and emerging rechargeable battery technologies, particularly for enhancing the stability of the electrode-electrolyte interface and thereby extending battery cyclability and lifetime. Reported within, sodium fluoride (NaF) thin films were synthesized via atomic layer deposition (ALD). NaF growth experiments were carried out at reactor temperatures between 175 and 250 °C using sodium tert-butoxide and HF-pyridine solution. The optimal deposition temperature range was 175–200 °C, and the resulting …

First-Principles Studies Of Nucleation Of Atomic-Layered Molybdenum Disulfide By Atomic Layer Deposition, Matthew Lawson

Boise State University Theses and Dissertations

This dissertation implements first-principles calculations to understand the nucleation mechanisms for atomic layer deposition (ALD) of molybdenum disulfide (MoS₂) using MoF₆ and H₂S precursors. ALD is a self-limiting process that can deposit a range of materials at the nanoscale, while maintaining chemical stoichiometry, atomic scale thickness control, and can conform to high-aspect ratio substrate designs. ALD is extremely sensitive to surface chemistry and morphology; therefore, it is critical to understand how these factors control deposition.

Density functional theory (DFT) was used to understand what factors can control the nucleation for ALD of MoS₂ using …

First-Principles Studies Of Mof Absorption On Hydroxylated And Non-Hydroxylated Metal Oxide Surfaces And Implications For Atomic Layer Deposition Of Mos2, Matthew Lawson, Elton Graugnard, Lan Li

Materials Science and Engineering Faculty Publications and Presentations

Significant interest in two-dimensional transition metal dichalcogenides has led to numerous experimental studies of their synthesis using scalable vapor phase methods, such as chemical vapor deposition (CVD) and atomic layer deposition (ALD). ALD typically allows lower deposition temperatures, and nucleation of chemical precursors requires reactions with surface functional groups. A common first-principles method used to study ALD modeling is the calculation of activation energy for a proposed reaction pathway. In this work we calculated the partial charge densities, local density of states (LDoS), Bader charge analysis, adsorption energies, and charge density difference using density functional theory (DFT) to investigate the …

Multi-Level Analysis Of Atomic Layer Deposition Barrier Coatings On Additively Manufactured Plastics For High Vacuum Applications, Nupur Bihari

Dissertations, Master's Theses and Master's Reports

While hardware innovations in micro/nano electronics and photonics are heavily patented, the rise of the open-source movement has significantly shifted focus to the importance of obtaining low-cost, functional and easily modifiable research equipment. This thesis provides a foundation of open source development of equipment to aid in the micro/nano electronics and photonics fields.

First, the massive acceptance of the open source Arduino microcontroller has aided in the development of control systems with a wide variety of uses. Here it is used for the development of an open-source dual axis gimbal system. This system is used to characterize optoelectronic properties of …

Kinetic Monte Carlo Investigations Involving Atomic Layer Deposition Of Metal-Oxide Thinfilms, David Tyler Magness

MSU Graduate Theses

Atomic Layer Deposition is a method of manufacturing thin film materials. Metal-oxides such as zinc-oxide and aluminum-oxide are particularly interesting candidates for use in microelectronic devices such as tunnel junction barriers, transistors, Schottky diodes, and more. By adopting a 3D Kinetic Monte Carlo model capable of simulating ZnO deposition, the effect of parameters including deposition temperature, chamber pressure, and composition of the initial substrate at the beginning of deposition can be investigated. This code generates two random numbers: One is used to select a chemical reaction to occur from a list of all possible reactions and the second is used …

Rational Interface Design For High-Performance All-Solid-State Lithium Batteries, Changhong Wang

Electronic Thesis and Dissertation Repository

All-solid-state lithium batteries (ASSLBs) have gained substantial attention owing to their excellent safety and high energy density. However, the development of ASSLBs has been hindered by large interfacial resistance originating from the detrimental interfacial reactions, poor solid-solid contact, and lithium dendrite growth. The research in this thesis aims at achieving high-performance ASSLBs via rational interface design and understanding the interfacial reaction mechanisms.

At the cathode interface, an ideal dual core-shell nanostructure was first designed. Moreover, single-crystal LiNi_0.5Mn_0.3Co_0.2O₂ (SC-NMC532) cathode was compared with polycrystalline NMC532, the former exhibits much enhanced Li⁺ diffusion kinetics …

Enhanced Sensing Performance Of Novel Nanostructured Zno Gas Sensors In Ethanol Vapor Concentration Detection Applications, Pengtao Lin

Electrical & Computer Engineering Theses & Dissertations

Sensors are devices which have been commonly used to measure the functional dependence and the variability of physical parameters like temperature, pressure, pH, voltage, current, concentration, and others. Among the numerous kinds of sensors in different areas, gas sensors have been widely used and investigated for gas monitoring. Gas sensors are of crucial importance for the detection of hazardous atmospheres, because toxic gases are frequently odorless, colorless, invisible, rapidly evaporating, and flammable, and would otherwise go unnoticed. Gas sensors have been used in a variety of applications among others for the detection of specific gas species and the detection of …

Permeability Of Oxygen And Carbon Dioxide Through Pinholes In Barrier Coatings, Petri Johansson, Johanna Lahti, Jorma Vihinen, Jurkka Kuusipalo

Journal of Applied Packaging Research

Abstract

Packaging materials are typically made of multilayer structures combining polymers, metals and inorganic materials. Multilayer structures are selected in order to optimize the thickness and performance in packaging applications. Atomic layer deposited (ALD) aluminium oxide (Al₂O₃) layer provides good barrier properties against oxygen and carbon dioxide gases i.e. permeation of gases through ALD coated polymer films will reduce remarkably. The target was to study the effect of pinholes on the oxygen and carbon dioxide permeability of ALD coated extrusion-coated packaging paper. Pinholes were artificially generated by ultra violet (UV) laser drilling through the polymer layer …

Strategies For The Stabilization Of Metal Anodes For Li And Na Metal Batteries, Yang Zhao

Electronic Thesis and Dissertation Repository

Li-metal batteries (LMBs) and Na-metal batteries (NMBs) are considered as the promising candidates to replace the conventional Li-ion batteries (LIBs) due to their high theoretical energy density. For LMBs and NMBs, Li metal and Na metal are the ultimate choices to achieve their high energy density due to the high specific capacity, low electrochemical potential and lightweight. However, as alkali metals, both Li and Na metal anodes suffer from serious challenges including 1) Li/Na dendrite formations and short circuits; 2) Low Coulombic efficiency (CE) and poor cycling performance; and 3) Infinite volume changes. This thesis mainly focuses on the design …

Improved Gas Sensing Performance Of Ald Azo 3-D Coated Zno Nanorods, P. Lin, X. Chen, K. Zhang, H. Baumgart

Electrical & Computer Engineering Faculty Publications

This paper reports an enhancement on the sensing performance of ZnO nanorod ethanol sensors with a new approach by utilizing nested coatings of Aluminum doped ZnO (AZO) thin films by Atomic Layer Deposition (ALD) technology. ZnO nanorods were grown by the hydrothermal method with the ZnO seed layer synthesized on Silicon wafers by ALD. To enhance the sensing performance of ZnO nanorod ethanol sensors, multiple coated AZO thin film 3-D coatings were deposited on the surface of the intrinsic ZnO nanorods by ALD.To investigate the sensing performance of the ZnO nanorods sensor for the detection of ethanol vapor, a gas …

Structural Evolution Of Molybdenum Disulfide Prepared By Atomic Layer Deposition For Realization Of Large Scale Films In Microelectronic Applications, Steven Letourneau, Elton Graugnard

Materials Science and Engineering Faculty Publications and Presentations

Molybdenum disulfide (MoS₂) films are attractive materials for electronic and optoelectronic devices, but the temperatures used in the chemical vapor deposition (CVD) of these materials are too high for device integration. Recently, a low-temperature atomic layer deposition (ALD) process was demonstrated for growth of MoS₂ films at 200 °C using MoF₆ and H₂S. However, the as-deposited films were amorphous and required annealing to obtain the desired layered structure. The MoS₂ films were sulfur-deficient; however, after annealing the crystallinity improved. To study the structure of these films and the process by which they crystallize, …

Molybdenum Sulfide Prepared By Atomic Layer Deposition: Synthesis And Characterization, Steven Payonk Letourneau

Boise State University Theses and Dissertations

Molybdenum disulfide (MoS₂) is the prototypical two-dimensional (2D) semiconductor. Like graphite, it has a layered structure containing weak van der Waals bonding between layers, while exhibiting strong covalent bonding within layers. The weak secondary bonding allows for isolation of these 2D materials to single layers, like graphene. While bulk MoS₂ is an indirect band gap semiconductor with a band gap of ~1.3 eV, monolayer MoS₂ exhibits a direct band gap of ~1.8 eV, which is an attractive property for many opto-electronic applications. Atomic layer deposition (ALD) has been used to grow amorphous films of MoS_{2 …}

Synthesis Of Volatile And Thermally Stable Aluminum Hydride Complexes And Their Use In Atomic Layer Deposition Of Metal Thin Films, Kyle Blakeney

Wayne State University Dissertations

The research discussed in this dissertation spans both synthetic inorganic and nanomaterials chemistry. Aluminum hydride complexes have been synthesized and characterized which are highly volatile and thermally stable and their potential as reducing agents for ALD of electropositive metal and metal-containing films was evaluated. A major discovery has been the deposition of aluminum metal films by thermal ALD using an aluminum dihydride complex supported by a simple amido-amine ligand (Chapters 2). Aluminum is the most electropositive element deposited by purely thermal ALD to date and represents a significant breakthrough for this field. This process may have important industrial applications and …

Atomic Layer Deposition Of Molybdenum Disulfide Films Using Mof6 And H2S, Steven Letourneau, Elton Graugnard

Materials Science and Engineering Faculty Publications and Presentations

Molybdenum sulfide films were grown by atomic layer deposition on silicon and fused silica substrates using molybdenum hexafluoride (MoF₆) and hydrogen sulfide at 200 °C. In situ quartz crystal microbalance (QCM) measurements confirmed linear growth at 0.46 Å/cycle and self-limiting chemistry for both precursors. Analysis of the QCM step shapes indicated that MoS₂ is the reaction product, and this finding is supported by x-ray photoelectron spectroscopy measurements showing that Mo is predominantly in the Mo(IV) state. However, Raman spectroscopy and x-ray diffraction measurements failed to identify crystalline MoS₂ in the as-deposited films, and this might result …

Development Of Nanomaterials For Lithium-Ion Batteries By Atomic Layer Deposition, Biqiong Wang

Electronic Thesis and Dissertation Repository

Lithium ion batteries (LIBs) have been the dominant candidate in the field of energy storage. The ever-growing demand of high energy and power density, longer battery life, and more assured safety level has geared the development of LIBs towards all-solid-state batteries (ASSBs). The solid-state nature allows more flexibility in battery design and higher area capacity to be obtained within limited space. Moreover, replacing liquid electrolytes with solid-state electrolytes (SSEs) is a most effective approach to achieve safer battery system. In addition, ASSBs hold great promise in the actual fabrication of microbatteries for microelectronics. Therefore, a technique which can synthesize materials …

Chemically Stable Artificial Sei For Li-Ion Battery Electrodes, Qinglin Zhang, Lei Han, Jie Pan, Zhi Chen, Yang-Tse Cheng

Chemical and Materials Engineering Faculty Publications

The importance of coating's chemical stability in lithium-ion batteries has been demonstrated by this study. It is well known that the mechanical properties determine the cycle life, and chemical stability or chemical degradation rate determines the calendar life. In this study, we used HfO₂ coatings prepared by atomic layer deposition as an example to show the chemical stability of the coatings for lithium ion battery electrodes.

Surface Modification Of Electrode Materials For Lithium-Ion Batteries, Biwei Xiao

Electronic Thesis and Dissertation Repository

The development of lithium-ion batteries (LIBs) has been hampered by the intrinsic limitations of the electrode materials. High-performance LIBs demand electrode materials with fast lithium/electron diffusion rate, stable surface chemistry and high specific capacity. Surface modification by atomic layer deposition (ALD) is an essential method to optimize the performance of the electrode materials. The research in this thesis aims at achieving high-performance LIBs via surface modification and understanding the mechanisms via synchrotron radiation.

Firstly, by applying ALD FePO₄ on LiNi_0.5Mn_1.5O₄ (LNMO), we successfully alleviated the electrolyte decomposition under high voltage by using the electrochemically …

Doping Plasmon-Enhanced Tio2 With Zirconia To Improve Solar Energy Harvesting In Dye-Sensitized Solar Cells, Anastasia Pasche

Electronic Thesis and Dissertation Repository

Solar energy is a promising solution towards meeting the world’s ever-growing energy demand. Dye-sensitized solar cells (DSSCs) are hybrid organic-inorganic solar cells with potential for commercial application, but are plagued by inefficiency due to their poor sunlight absorption. Silver nanoparticles have been shown to enhance the absorptive properties of DSSCs, but their plasmonic resonance causes local hot spots, resulting in cell deterioration. This thesis studies the mitigation of thermal energy loss of plasmon-enhanced DSSCs by the co-incorporation of zirconia, a well-known thermostabilizer, into the cell’s photoactive material. TiO2 was also synthesized using green bio-sourced solvents in supercritical CO2 to compare …

A Non-Destructive Method For Measuring The Mechanical Properties Of Ultrathin Films Prepared By Atomic Layer Deposition, Qinglin Zhang, Xingcheng Xiao, Yang-Tse Cheng, Mark W. Verbrugge

Chemical and Materials Engineering Faculty Publications

The mechanical properties of ultrathin films synthesized by atomic layer deposition (ALD) are critical for the liability of their coated devices. However, it has been a challenge to reliably measure critical properties of ALD films due to the influence from the substrate. In this work, we use the laser acoustic wave (LAW) technique, a non-destructive method, to measure the elastic properties of ultrathin Al₂O₃ films by ALD. The measured properties are consistent with previous work using other approaches. The LAW method can be easily applied to measure the mechanical properties of various ALD thin films for multiple …

In Situ Study Of The Role Of Substrate Temperature During Atomic Layer Deposition Of Hfo2 On Inp, H. Dong, Santosh Kc, X. Qin, B. Brennan, S. Mcdonnell, D. Zhernokletov, C. Hinkle, J. Kim, K. Cho, R. Wallace

Faculty Publications

The dependence of the “self cleaning” effect of the substrate oxides on substrate temperature during atomic layer deposition (ALD) of HfO2 on various chemically treated and native oxide InP (100) substrates is investigated using in situ X-ray photoelectron spectroscopy. The removal of In-oxide is found to be more efficient at higher ALD temperatures. The P oxidation states on native oxide and acid etched samples are seen to change, with the total P-oxide concentration remaining constant, after 10 cycles of ALD HfO2 at different temperatures. An (NH4)2 S treatment is seen to effectively remove native oxides and passivate the InP surfaces …

Indium Diffusion Through High-K Dielectrics In High-K/Inp Stacks, H. Dong, W. Cabrera, R. Galatage, Santosh Kc, B. Brennan, X. Qin, S. Mcdonnell, D. Zhernokletov, C. Hinkle, K. Cho, Y. Chabal, R. Wallace

Faculty Publications

Evidence of indium diffusion through high-k dielectric (Al2O3 and HfO2) films grown on InP (100) by atomic layer deposition is observed by angle resolved X-ray photoelectron spectroscopy and low energy ion scattering spectroscopy. The analysis establishes that In-out diffusion occurs and results in the formation of a POx rich interface.High mobility III-V channel materials are contenders to replace Si in semiconductor devices like metal oxide semiconductor filed effect transistors (MOSFETs) for the sub 22 nm technology node.1 Extensive research is being carried out to determine the validity of these III-V materials for use as the channel, in a variety of …

High Performance Membrane Electrode Assembly With Low Platinum Loadings Prepared By Atomic Layer Deposition For Pemfc Application, Ting Shu, Shi-Jun Liao, Chien-Te Hsieh, Ay Su

Journal of Electrochemistry

A high performance membrane electrode assembly (MEA) with low platinum loadings was successfully prepared with atomic layer deposition (ALD) technique. The anode of the MEA was prepared by depositing platinum on the carbon paper substrate, which was prepared by coating the slurry of carbon black (XC-72R) and Teflon, followed by drying and calcining at 350 °C. The MEAs consisted of the ALD anode or commercial catalyst anode, pretreated Nafion membrane (Nafion-117) and commercial cathode. Performances of MEAs were measured by single cell testing, and the anodes and MEAs were characterized by CV, SEM, TEM and XRD. The results revealed that …

Plasma Enhanced Atomic Layer Deposition Of Cu Seed Layers At Low Process Temperatures, Jiajun Mao

Legacy Theses & Dissertations (2009 - 2024)

In conventional Cu interconnect fabrication, a sputtered copper seed layer is deposited before the electrochemically deposited (ECD) copper plating step. However, as interconnect dimensions scale down, non-conformal seed layer growth and subsequent voiding of metallized structures is becoming a critical issue. With its established excellent thickness controllability and film conformality, atomic layer deposition (ALD) is becoming an attractive deposition approach for the sub-24nm fabrication regime. However, in order to achieve a smooth and continuous seed layer deposition, a low process temperature (below 100oC) is needed, given the tendency of Cu agglomeration at elevated temperature. In this research, plasma enhanced ALD …

On Developing Novel Energy-Relates Nanostructured Materials By Atomic Layer Deposition, Xiangbo Meng

Electronic Thesis and Dissertation Repository

ABSTRACT

This thesis presents the fabrication of a series of novel nanostructured materials using atomic layer deposition (ALD). In contrast to traditional methods including chemical vapor deposition (CVD), physical vapor deposition (PVD), and solution-based processes, ALD benefits the synthesis processes of nanostructures with many unrivalled advantages such as atomic-scale control, low temperature, excellent uniformity and conformality. Depending on the employed precursors, substrates, and temperatures, the ALD processes exhibited different characteristics. In particular, ALD has capabilities in fine-tuning compositions and structural phases. In return, the synthesis and the resultant nanostructured materials show many novelties.

This thesis covers ALD processes of four …

Photonic Band Tuning In 2d Photonic Crystals By Atomic Layer Deposition, Elton Graugnard, Davy P. Gaillot, Simon N. Dunham, Curtis W. Neff, Tsuyoshi Yamashita, Christopher J. Summers

Materials Science and Engineering Faculty Publications and Presentations

Atomic layer deposition (ALD) has become a powerful tool for the fabrication of high quality 3-dimentional photonic crystals (PCs) from both inorganic (opal) and organic (holographically patterned polymer) templates [1,2]. With ALD, highly conformal films can be grown with a precision of 0.05 nm, which, when combined with the availability of a wide range of low temperature film growth protocols, enables a high degree of control over material and structural properties to precisely tune optical properties [3]. Two-dimensional photonic crystals have been developed extensively for applications in optical interconnects, beam steering, and sensor devices; and are predominantly fabricated by electron-beam …