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Description
Wide bandgap semiconductors are of much current interest due to their superior electrical properties. This dissertation describes electron microscopy characterization of GaN-on-GaN structures for high-power vertical device applications. Unintentionally-doped (UID) GaN layers grown homoepitaxially via metal-organic chemical vapor deposition on freestanding GaN substrates, were subjected to dry etching, and layers

Wide bandgap semiconductors are of much current interest due to their superior electrical properties. This dissertation describes electron microscopy characterization of GaN-on-GaN structures for high-power vertical device applications. Unintentionally-doped (UID) GaN layers grown homoepitaxially via metal-organic chemical vapor deposition on freestanding GaN substrates, were subjected to dry etching, and layers of UID-GaN/p-GaN were over-grown. The as-grown and regrown heterostructures were examined in cross-section using transmission electron microscopy (TEM). Two different etching treatments, fast-etch-only and multiple etches with decreasing power, were employed. The fast-etch-only devices showed GaN-on-GaN interface at etched location, and low device breakdown voltages were measured (~ 45-95V). In comparison, no interfaces were visible after multiple etching steps, and the corresponding breakdown voltages were much higher (~1200-1270V). These results emphasized importance of optimizing surface etching techniques for avoiding degraded device performance. The morphology of GaN-on-GaN devices after reverse-bias electrical stressing to breakdown was investigated. All failed devices had irreversible structural damage, showing large surface craters (~15-35 microns deep) with lengthy surface cracks. Cross-sectional TEM of failed devices showed high densities of threading dislocations (TDs) around the cracks and near crater surfaces. Progressive ion-milling across damaged devices revealed high densities of TDs and the presence of voids beneath cracks: these features were not observed in unstressed devices. The morphology of GaN substrates grown by hydride vapor-phase epitaxy (HVPE) and by ammonothermal methods were correlated with reverse-bias results. HVPE substrates showed arrays of surface features when observed by X-ray topography (XRT). All fabricated devices that overlapped with these features had typical reverse-bias voltages less than 100V at a leakage current limit of 10-6 A. In contrast, devices not overlapping with such features reached voltages greater than 300V. After etching, HVPE substrate surfaces showed defect clusters and macro-pits, whereas XRT images of ammonothermal substrate revealed no visible features. However, some devices fabricated on ammonothermal substrate failed at low voltages. Devices on HVPE and ammonothermal substrates with low breakdown voltages showed crater-like surface damage and revealed TDs (~25µm deep) and voids; such features were not observed in devices reaching higher voltages. These results should assist in developing protocols to fabricate reliable high-voltage devices.
ContributorsPeri, Prudhvi Ram (Author) / Smith, David J. (Thesis advisor) / Alford, Terry (Committee member) / Mccartney, Martha R (Committee member) / Nemanich, Robert (Committee member) / Zhao, Yuji (Committee member) / Arizona State University (Publisher)
Created2021
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Description
Physical vapor deposition (PVD) of phase-separating multicomponent alloy films generates a rich variety of unique self-organized nanoscale morphologies. However, an understanding of how the different material and process parameters influence the formation of these nanostructures is limited. My dissertation aims to bridge this gap by developing phase-field models that can

Physical vapor deposition (PVD) of phase-separating multicomponent alloy films generates a rich variety of unique self-organized nanoscale morphologies. However, an understanding of how the different material and process parameters influence the formation of these nanostructures is limited. My dissertation aims to bridge this gap by developing phase-field models that can predict an entire spectrum of nanostructures as a function of processing conditions and composition in multicomponent alloys under a set of material-specific constraints. Firstly, I developed a numerical model to simulate nanoscale phase separation in codeposited immiscible binary alloy films. An investigation on the influence of deposition rates, phase-fraction, and temperature, on the evolution of self-assembled nanostructures yielded many characteristic patterns, including well-known morphologies such as the lateral and vertical concentration modulations, as well as some previously undocumented variants. I also simulated phase-separation in ternary alloyed PVD films, and studied the influence of deposition rate and composition on the evolution of self-assembled nanostructures, and recorded many novel nanoscale morphologies. I then sought to understand the role of material properties such as elastic misfit due to lattice mismatch between phases, grain boundaries formed in polycrystalline films, and the interplay of interphase and surface boundaries at the film surface. To this end, I developed phase-field models of binary PVD film deposition that incorporated these constraints and studied their role in altering the temporal and spatial characteristics of the evolving morphologies. I also investigated the formation of surface hillocks and the role of surface and interfacial energies in their evolution. By studying the change in total free energy across the different deposition models, I established that, in addition to influencing the temporal and spatial characteristics of nanoscale structures in the films, this quantity is also responsible for driving morphological transitions as the rate of deposition is increased. Insights gained from this computational study will demonstrate the viability of these models in predicting experimentally observed morphologies and form a basis for understanding the various factors involved in driving phase-separation and morphological transitions. In addition, morphology maps will serve as templates for developing new pathways for morphology control in the manufacturing of PVD alloy films.
ContributorsRaghavan, Rahul (Author) / Ankit, Kumar (Thesis advisor) / Rajagopalan, Jagannathan (Committee member) / Mushongera, Leslie T (Committee member) / Arizona State University (Publisher)
Created2021
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Description
This dissertation focuses on the structure-function relationships of nanomaterials (NMs) and some of their applications in environmental engineering. The aim is to investigate NMs of different surface chemistries and assess their interactions with biological models, evaluate the weathering impact and degradation parameters to improve polymer coatings, test their efficiency for

This dissertation focuses on the structure-function relationships of nanomaterials (NMs) and some of their applications in environmental engineering. The aim is to investigate NMs of different surface chemistries and assess their interactions with biological models, evaluate the weathering impact and degradation parameters to improve polymer coatings, test their efficiency for contaminant removal and provide further understanding in the safe design of nanomaterials. Nanoecotoxicological risk assessment currently suffers from a lack of testing procedures adapted to nanomaterials. Graphene oxide (GO) is a carbon nanomaterial (CNM) that consists of a single layer of carbon atoms arranged in a hexagonal network. It is decorated with a high density of oxygen functional groups including epoxide and hydroxyl moieties on the basal planes and carboxylic and carbonyl groups at the edges. The changes in surface chemistry give GO unique properties that can be tailored for a function. Additionally, because of its simple synthesis and flexible chemistry, GO has been a popular building block of many composite CNMs. In environmental engineering, specifically, water treatment, GO has been studied by itself or as a composite for pollutant removal, biofouling reduction, and as an antimicrobial agent, just to name a few. Like GO, silver (Ag) is another NM widely used in water treatment for its biocidal properties. Despite the recent growth in this field, a fundamental understanding of the function-structure relationships in NMs is still progressing. Through a systematic set of experiments, the structure-properties-function and structure-properties-hazard relationships were investigated. These relationships can be used to establish guidelines to engineer “safe-by-design” functional nanomaterials, where materials are tailored to enhance their function while minimizing their inherent biological or environmental hazard.
ContributorsBarrios, Ana Cecilia (Author) / Perreault, Francois (Thesis advisor) / Abbaszadegan, Morteza (Committee member) / Conroy-Ben, Otakuye (Committee member) / Hua-Wang, Qing (Committee member) / Arizona State University (Publisher)
Created2021
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Description
The evolution of defects at different stages of strain relaxation in low-mismatched GaAs/GaAs1-xSbx/GaAs(001) (x ~ 0.08) heterostructures, and the underlying relaxation mechanisms, have been comprehensively studied primarily using transmission electron microscopy (TEM). Aberration-corrected scanning transmission electron microscopy (STEM) has been used for atomic-scale study of interfacial defects in low-mismatched GaAs(001)-based

The evolution of defects at different stages of strain relaxation in low-mismatched GaAs/GaAs1-xSbx/GaAs(001) (x ~ 0.08) heterostructures, and the underlying relaxation mechanisms, have been comprehensively studied primarily using transmission electron microscopy (TEM). Aberration-corrected scanning transmission electron microscopy (STEM) has been used for atomic-scale study of interfacial defects in low-mismatched GaAs(001)-based and high-mismatched GaSb/GaAs(001) heterostructures.Three distinct stages of strain relaxation were identified in GaAs/GaAs1-xSbx/GaAs(001) (x ~ 0.08) heterostructures with GaAsSb film thicknesses in the range of 50 to 4000 nm capped with 50-nm-thick GaAs layers. Diffraction contrast analysis with conventional TEM revealed that although 60° dislocations were primarily formed during the initial sluggish Stage-I relaxation, 90° dislocations were also created. Many curved dislocations, the majority of which extended into the substrate, were formed during Stage-II and Stage-III relaxation. The capping layers of heterostructures with larger film thickness (500 nm onwards) exhibited only Stage-I relaxation. A decrease in dislocation density was observed at the cap/film interface of the heterostructure with 4000-nm-thick film compared to that with 2000-nm-thick film, which correlated with smoothening of surface cross-hatch morphology. Detailed consideration of plausible dislocation sources for the capping layer led to the conclusion that dislocation half-loops nucleated at surface troughs were the main source of threading dislocations in these heterostructures. Aberration-corrected STEM imaging revealed that interfacial 60° dislocations in GaAs/GaAsSb/GaAs(001) and GaAs/GaAsP/GaAs(001) heterostructures were dissociated to form intrinsic stacking faults bounded by 90° and 30° Shockley partial dislocations. The cores of the 30° partials contained single atomic columns indicating that these dislocations primarily belonged to glide set. Apart from isolated dissociated 60° dislocations, Lomer-Cottrell locks, Lomer dislocations and a novel type of dissociated 90° dislocation were observed in GaAs/GaAsSb/GaAs heterostructures. The core structure of interfacial defects in GaSb/GaAs(001) heterostructure was also investigated using aberration-corrected STEM. 90° Lomer dislocations were primarily formed; however, glide-set perfect 60° and dissociated 60° dislocations were also observed. The 5-7 atomic-ring shuffle-set dislocation, the left-displaced 6-8 atomic-ring glide-set and the right-displaced 6-8 atomic-ring glide-set dislocations were three types of Lomer dislocations that were identified, among which the shuffle-set type was most common.
ContributorsGangopadhyay, Abhinandan (Author) / Smith, David J. (Thesis advisor) / Bertoni, Mariana (Committee member) / Crozier, Peter A. (Committee member) / King, Richard R. (Committee member) / McCartney, Martha R. (Committee member) / Arizona State University (Publisher)
Created2021
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Description
How to effectively and accurately describe, character and quantify the microstructure of the heterogeneous material and its 4D evolution process with time suffered from external stimuli or provocations is very difficult and challenging, but it’s significant and crucial for its performance prediction, processing, optimization and design. The goal of this

How to effectively and accurately describe, character and quantify the microstructure of the heterogeneous material and its 4D evolution process with time suffered from external stimuli or provocations is very difficult and challenging, but it’s significant and crucial for its performance prediction, processing, optimization and design. The goal of this research is to overcome these challenges by developing a series of novel hierarchical statistical microstructure descriptors called “n-point polytope functions” which is as known as Pn functions to quantify heterogeneous material’s microstructure and creating Pn functions related quantification methods which are Omega Metric and Differential Omega Metric to analyze its 4D processing.In this dissertation, a series of powerful programming tools are used to demonstrate that Pn functions can be used up to n=8 for chaotically scattered images which can hardly be distinguished by our naked eyes in chapter 3 to find or compare the potential configuration feature of structure such as symmetry or polygon geometry relation between the different targets when target’s multi-modal imaging is provided. These n-point statistic results calculated from Pn functions for features of interest in the microstructure can efficiently decompose the structural hidden features into a set of “polytope basis” to provide a concise, explainable, expressive, universal and efficient quantifying manner. In Chapter 4, the Pn functions can also be incorporated into material reconstruction algorithms readily for fast virtualizing 3D microstructure regeneration and also allowing instant material property prediction via analytical structure-property mappings for material design. In Chapter 5, Omega Metric and Differential Omega Metric are further created and used to provide a time-dependent reduced-dimension metric to analyze the 4D evaluation processing instead of using Pn functions directly because these 2 simplified methods can provide undistorted results to be easily compared. The real case of vapor-deposition alloy films analysis are implemented in this dissertation to demonstrate that One can use these methods to predict or optimize the design for 4D evolution of heterogeneous material. The advantages of the all quantification methods in this dissertation can let us economically and efficiently quantify, design, predict the microstructure and 4D evolution of the heterogeneous material in various fields.
ContributorsCHEN, PEI-EN (Author) / Jiao, Yang (Thesis advisor) / Ren, Yi (Thesis advisor) / Liu, Yongming (Committee member) / Zhuang, Houlong (Committee member) / Nian, Qiong (Committee member) / Arizona State University (Publisher)
Created2021
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Description
Lithium conducting garnets in the family of Li7La3Zr2O12 (LLZO) are promising lithium conductors for solid-state batteries, due to their high ionic conductivity, thermal stability, and electrochemical stability with metallic lithium. Despite these advantages, LLZO requires a large energy input to synthesize and process. Generally, LLZO is synthesized using solid-state reaction

Lithium conducting garnets in the family of Li7La3Zr2O12 (LLZO) are promising lithium conductors for solid-state batteries, due to their high ionic conductivity, thermal stability, and electrochemical stability with metallic lithium. Despite these advantages, LLZO requires a large energy input to synthesize and process. Generally, LLZO is synthesized using solid-state reaction (SSR) from oxide precursors, requiring high reaction temperatures (900-1000 °C) and producing powder with large particle sizes, necessitating high energy milling to improve sinterability. In this dissertation, two classes of advanced synthesis methods – sol-gel polymer-combustion and molten salt synthesis (MSS) – are employed to obtain LLZO submicron powders at lower temperatures. In the first case, nanopowders of LLZO are obtained in a few hours at 700 °C via a novel polymer combustion process, which can be sintered to dense electrolytes possessing ionic conductivity up to 0.67 mS cm-1 at room temperature. However, the limited throughput of this combustion process motivated the use of molten salt synthesis, wherein a salt mixture is used as a high temperature solvent, allowing faster interdiffusion of atomic species than solid-state reactions. A eutectic mixture of LiCl-KCl allows formation of submicrometer undoped, Al-doped, Ga-doped, and Ta-doped LLZO at 900 °C in 4 h, with total ionic conductivities between 0.23-0.46 mS cm-1. By using a highly basic molten salt medium, Ta-doped LLZO (LLZTO) can be obtained at temperatures as low as 550 °C, with an ionic conductivity of 0.61 mS cm-1. The formation temperature can be further reduced by using Ta-doped, La-excess pyrochlore-type lanthanum zirconate (La2Zr2O7, LZO) as a quasi-single-source precursor, which convert to LLZTO as low as 400 °C upon addition of a Li-source. Further, doped pyrochlores can be blended with a Li-source and directly sintered to a relative density up to 94.7% with high conductivity (0.53 mS cm-1). Finally, a propensity for compositional variation in LLZTO powders and sintered ceramics was observed and for the first time explored in detail. By comparing LLZTO obtained from combustion, MSS, and SSR, a correlation between increased elemental inhomogeneity and reduced ionic conductivity is observed. Implications for garnet-based solid-state batteries and strategies to mitigate elemental inhomogeneity are discussed.
ContributorsWeller, Jon Mark (Author) / Chan, Candace K (Thesis advisor) / Crozier, Peter (Committee member) / Sieradzki, Karl (Committee member) / Arizona State University (Publisher)
Created2021
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Description
Two-dimensional (2D) materials have nanometer-scale thickness in one dimension but macroscopic sizes in the other two dimensions and have unique physical and chemical properties that arise from this dimensionality. For example, atomically thin forms of semiconducting materials like transition metal dichalcogenides (TMDs) have attracted significant attention for electric and optical

Two-dimensional (2D) materials have nanometer-scale thickness in one dimension but macroscopic sizes in the other two dimensions and have unique physical and chemical properties that arise from this dimensionality. For example, atomically thin forms of semiconducting materials like transition metal dichalcogenides (TMDs) have attracted significant attention for electric and optical device applications due to their tunable bandgaps. Most 2D materials are derived from layered materials with weak van der Waals (vdW) bonds between layers, but more recently, non-vdW materials with stronger bonds and non-layered structures have also been formed into nanosheets. Because of their aspect ratios, surface chemistry plays a substantial role in both vdW- and non-vdW-derived 2D materials, and involves intercalation and exfoliation, surface modification and functionalization, which contribute to their use in diverse applications. In this thesis, the materials chemistry of nanosheets from both vdW and non-vdW materials has been studied. First, this work demonstrates the covalent functionalization of a new rising 2D material in the TMDs family, palladium diselenide (PdSe2), which has a layer-dependent bandgap and is much more stable in air than many other 2D materials. Aryl diazonium salts were used to functionalize monolayer PdSe2 nanosheets, and the reaction kinetics were studied as a function of reaction time and concentrations. Raman spectroscopy suggests the structure of PdSe2 is undisturbed after functionalization, which will expand its future applications in areas like electronics, sensors, and energy storage. Next, liquid-phase exfoliation (LPE), an economical, scalable, and efficient method, was used to produce nanosheets of two types of non-vdW materials: metal diborides (MB2) which are a family of ceramic materials with a layered structure, and boron carbide (B4C), a non-layered material with covalent bonding. Quasi-2D nanosheets were formed from eight different metal diborides, with sizes and thicknesses that were found to correlate with the hardness of the bulk compounds. CrB2 nanosheets incorporated into polyvinyl alcohol (PVA) thin films showed enhanced mechanical properties that exceed the specific performance of additives from other 2D materials. Boron carbide, the third hardest known material, has also been successfully exfoliated into ultrathin by LPE. Combined theory and experiment show the rich surface structures of B4C nanosheets.
ContributorsGuo, Yuqi (Author) / Wang, Qing Hua QW (Thesis advisor) / Green, Alexander AG (Committee member) / Jiao, Yang YJ (Committee member) / Arizona State University (Publisher)
Created2021
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Description
There is a high demand for customized designs of various types of cement-based materials in order to address specific purposes in the construction field. These demands stem from the need to optimize the cementitious matrix properties and reinforcement choices, especially in high reliability, durability, and performance applications that include infrastructure,

There is a high demand for customized designs of various types of cement-based materials in order to address specific purposes in the construction field. These demands stem from the need to optimize the cementitious matrix properties and reinforcement choices, especially in high reliability, durability, and performance applications that include infrastructure, energy production, commercial buildings, and may ultimately be extended to low risk/high volume applications such as residential applications. The typical tools required to guide practicing engineers should be based on optimization algorithms that require highly efficient capacity and design alternatives and optimal computational tools. The general case of flexural design of members is an important aspect of design of structural members which can be extended to a variety of applications that include various cross-sections such as rectangular, W-sections, channels, angles, and T sections. The model utilized the simplified linear constitutive response of cement-based composite in compression and tension and extends into a two-segment elastic-plastic, strain softening, hardening, tension-stiffening, and a multi-segment system. The generalized parametric model proposed uses a dimensionless system in the stress-strain materials diagram to formulate piecewise equations for an equilibrium of internal stresses and obtains strain distributions for the closed-form solution of neutral axis location. This would allow for the computation of piecewise moment-curvature response. The number of linear residual stress implemented is flexible to a user to maintain a robust response. In the present approach bilinear, trilinear, and quad-linear models are addressed and a procedure for incorporating additional segments is presented. Moreover, a closed-form solution of moment-curvature can be solved and employed in calculating load-deflection response. The model is adaptable for various types of fiber-reinforced and textile reinforced concrete (FRC, TRC, UHPC, AAC, and Reinforced Concrete). The extensions to cover continuous fiber reinforcement such as textile reinforced concrete (TRC, FRCM) strengthening and repair are addressed. The theoretical model is extended to incorporate the hybrid design (HRC) with continuous rebar with FRC to increase the ductility and ultimate moment capacity. HRC extends the performance of the fiber system to incorporate residual capacity into a serviceability-based design that reduced the reliance on the design based on the limit state. The design chart for HRC and as well as conventional RC has been generated for practicing engineering applications. Results are compared to a large array of data from experimental results conducted at the ASU structural lab facilities and other published literature.
Contributorspleesudjai, chidchanok (Author) / Mobasher, Barzin (Thesis advisor) / Neithalath, Narayanan (Committee member) / Rajan, Subramaniam (Committee member) / Arizona State University (Publisher)
Created2021
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Description
Nanoholes on the basal plane of graphene can provide abundant mass transport channels and chemically active sites for enhancing the electrochemical performance, making this material highly promising in applications such as supercapacitors, batteries, desalination, molecule or ion detection, and biosensing. However, the current solution-based chemical etching processes to manufacture these

Nanoholes on the basal plane of graphene can provide abundant mass transport channels and chemically active sites for enhancing the electrochemical performance, making this material highly promising in applications such as supercapacitors, batteries, desalination, molecule or ion detection, and biosensing. However, the current solution-based chemical etching processes to manufacture these nanoholes commonly suffer from low process efficiency, scalability, and controllability, because conventional bulk heating cannot promote the etching reactions. Herein, a novel manufacturing method is developed to address this issue using microwave irradiation to facilitate and control the chemical etching of graphene. In this process, microwave irradiation induces selective heating of graphene in the aqueous solution due to an energy dissipation mechanism coupled with the dielectric and conduction losses. This strategy brings a remarkable reduction of processing time from hour-scale to minute-scale compared to the conventional approaches. By further incorporating microwave pretreatment, it is possible to control the population and area percentage of the in-plane nanoholes on graphene. Theoretical calculations reveal that the nanoholes emerge and grow by a repeating reduction–oxidation process occurring at the edge-sites atoms around vacancy defects on the graphene basal plane. The reduced holey graphene oxide sheets obtained via the microwave-assisted chemical etching method exhibit great potentials in supercapacitors and electrocatalysis. Excellent capacitive performance and electrocatalytic activity are observed in electrochemical measurements. The improvements against the non-holey counterpart are attributed to the enhanced kinetics involving ion diffusion and heterogeneous charge transfer.
ContributorsWang, Dini (Author) / Nian, Qiong (Thesis advisor) / Alford, Terry (Committee member) / Wang, Qing Hua (Committee member) / Zhuang, Houlong (Committee member) / Arizona State University (Publisher)
Created2021
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Description
In this dissertation, far UV spectroscopy is applied to investigate the optical properties of dielectric thin films grown by atomic layer deposition. The far UV (120 – 200 nm) reflectance for several dielectric oxides and fluorides, including AlF3, Al2O3, Ga2O3, HfO2, and SiO2, was measured at variable angles and thicknesses.

In this dissertation, far UV spectroscopy is applied to investigate the optical properties of dielectric thin films grown by atomic layer deposition. The far UV (120 – 200 nm) reflectance for several dielectric oxides and fluorides, including AlF3, Al2O3, Ga2O3, HfO2, and SiO2, was measured at variable angles and thicknesses. Multiple optical calculation methods were developed for the accurate determination of the optical constants from the reflectance. The deduced optical constants were used for optical designs, such as high-reflectivity coatings, and Fabry-Perot bandpass interference filters. Three filters were designed for use at 157 nm, 212 nm, and 248 nm wavelengths, based on multilayer structures consisting of SiO2, Al2O3, HfO2, and AlF3. A thorough error analysis was made to quantify the non-idealities of the optical performance for the designed filters. Far UV spectroscopy was also applied to analyze material mixtures, such as AlF3/Al and h-BN/c-BN mixtures. Using far UV spectroscopy, different phases in the composite can be distinguished, and the volume concentration of each constituent can be determined. A middle UV reflective coating based on A2O3 and AlF3 was fabricated and characterized. The reflective coating has a smooth surface (?? < 1 nm), and a peak reflectance of 25 – 30 % at a wavelength of 196 nm. The peak reflectance deviated from the design, and an analysis of the AlF3 layer prepared by plasma-enhanced atomic layer deposition (PEALD) indicated the presence of Al-rich clusters, which were associated with the UV absorption. Complementary techniques, such as spectroscopic ellipsometry, and X-ray photoelectron spectroscopy, were used to verify the results from far UV spectroscopy. In conclusion, this Dissertation demonstrated the use of in-situ far UV spectroscopy to investigate the optical properties of thin films at short wavelengths. This work extends the application of far UV spectroscopy to ultrawide bandgap semiconductors and insulators. This work supports a path forward for far UV optical filters and devices. Various errors have been discussed with solutions proposed for future research of methods and materials for UV optics.
ContributorsHuang, Zhiyu (Author) / Nemanich, Robert (Thesis advisor) / Ponce, Fernando (Committee member) / Menéndez, Jose (Committee member) / Holman, Zachary (Committee member) / Arizona State University (Publisher)
Created2021