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The Colloidal Chemistry Synthesis and Electron Microscopy Characterization of Shape-controlled Metal and Semiconductor Nanocrystals

The Colloidal Chemistry Synthesis and Electron Microscopy Characterization of Shape-controlled Metal and Semiconductor Nanocrystals PDF Author: Adam Biacchi
Publisher:
ISBN:
Category :
Languages : en
Pages :

Book Description
Solution methods of materials synthesis have found application in a variety of fields due to the diversity of products accessible, facility of process scalability, and the ease of tuning their properties through prudent selection of reaction conditions. Control of experimental variables during the formation of colloidally stable nanoscale solids within a liquid matrix allows for tailoring of the particles' characteristics, including shape, size, composition, and surface chemistry. In this dissertation, I will discuss how the manipulation of reaction chemistries can be used to synthesize shape-controlled metal and semiconductor colloidal nanocrystals. Further, I will elaborate on the mechanisms by which these particles form from molecular precursors and describe how their properties can differ from their bulk analogues through extensive characterization, especially using transmission electron microscopy. These studies contribute to the continued development of chemical routes to nanocrystals and their application as functional materials.First, I will review recent advances in the synthesis and characterization of shape-controlled nanocrystals, as well as highlight their promising applicability in a number of emerging technologies. These principles will then be leveraged to the specific case of catalytically-active rhodium nanocrystals, which can be synthesized with morphological and dimensional control using a polyol solution-mediated strategy. I describe an innovative shape-controlled synthesis to monodisperse colloidal rhodium icosahedra, cubes, triangular plates, and octahedra using this route. Additionally, new insights into the important role of the polyol reducing solvent on the synthesis of these nanocrystals are revealed, and how these might be exploited to engender superior reaction control and novel products.Next, I will describe how a crystallization mechanism was established for the synthesis of numerous morphologies of noble metal nanocrystals. I present a thorough analysis of the synthesis of shape-controlled rhodium nanocrystals, using extensive transmission electron microscopy characterization, and relate these findings to one of the primary synthetic levers available in the polyol synthesis: the anionic ligands present. Further, I show that the crystallization process proceeds by a nonclassical mechanism in which cluster particles serve as a stable intermediate between molecular precursors and the final product. I then apply these principles to the shape-controlled synthesis of other noble metal nanocrystals before expounding a generalized formation mechanism in the polyol synthesis of colloidal metal nanocrystals. Finally, I will highlight my efforts in the designed synthesis and characterization of colloidal tin(II) sulfide (SnS) semiconducting "quantum dot" nanocrystals. I describe a route for the solution synthesis of monodisperse colloidal SnS nanosheets, nanocubes, and nanospherical polyhedra in high yield. Further, detailed crystallographic characterization of these nanocrystals using transmission electron microscopy indicates that their atomic structure possesses a previously-unreported nanoscale deviation from the bulk phase. Additionally, I show that their electronic and photocatalytic properties of these quantum dots are both shape-dependent and distinct from bulk SnS.

The Colloidal Chemistry Synthesis and Electron Microscopy Characterization of Shape-controlled Metal and Semiconductor Nanocrystals

The Colloidal Chemistry Synthesis and Electron Microscopy Characterization of Shape-controlled Metal and Semiconductor Nanocrystals PDF Author: Adam Biacchi
Publisher:
ISBN:
Category :
Languages : en
Pages :

Book Description
Solution methods of materials synthesis have found application in a variety of fields due to the diversity of products accessible, facility of process scalability, and the ease of tuning their properties through prudent selection of reaction conditions. Control of experimental variables during the formation of colloidally stable nanoscale solids within a liquid matrix allows for tailoring of the particles' characteristics, including shape, size, composition, and surface chemistry. In this dissertation, I will discuss how the manipulation of reaction chemistries can be used to synthesize shape-controlled metal and semiconductor colloidal nanocrystals. Further, I will elaborate on the mechanisms by which these particles form from molecular precursors and describe how their properties can differ from their bulk analogues through extensive characterization, especially using transmission electron microscopy. These studies contribute to the continued development of chemical routes to nanocrystals and their application as functional materials.First, I will review recent advances in the synthesis and characterization of shape-controlled nanocrystals, as well as highlight their promising applicability in a number of emerging technologies. These principles will then be leveraged to the specific case of catalytically-active rhodium nanocrystals, which can be synthesized with morphological and dimensional control using a polyol solution-mediated strategy. I describe an innovative shape-controlled synthesis to monodisperse colloidal rhodium icosahedra, cubes, triangular plates, and octahedra using this route. Additionally, new insights into the important role of the polyol reducing solvent on the synthesis of these nanocrystals are revealed, and how these might be exploited to engender superior reaction control and novel products.Next, I will describe how a crystallization mechanism was established for the synthesis of numerous morphologies of noble metal nanocrystals. I present a thorough analysis of the synthesis of shape-controlled rhodium nanocrystals, using extensive transmission electron microscopy characterization, and relate these findings to one of the primary synthetic levers available in the polyol synthesis: the anionic ligands present. Further, I show that the crystallization process proceeds by a nonclassical mechanism in which cluster particles serve as a stable intermediate between molecular precursors and the final product. I then apply these principles to the shape-controlled synthesis of other noble metal nanocrystals before expounding a generalized formation mechanism in the polyol synthesis of colloidal metal nanocrystals. Finally, I will highlight my efforts in the designed synthesis and characterization of colloidal tin(II) sulfide (SnS) semiconducting "quantum dot" nanocrystals. I describe a route for the solution synthesis of monodisperse colloidal SnS nanosheets, nanocubes, and nanospherical polyhedra in high yield. Further, detailed crystallographic characterization of these nanocrystals using transmission electron microscopy indicates that their atomic structure possesses a previously-unreported nanoscale deviation from the bulk phase. Additionally, I show that their electronic and photocatalytic properties of these quantum dots are both shape-dependent and distinct from bulk SnS.

Metal Nanocrystals

Metal Nanocrystals PDF Author: Kallum M. Koczkur
Publisher: American Chemical Society
ISBN: 0841299013
Category : Science
Languages : en
Pages : 164

Book Description
Our society depends heavily on metals. They are ubiquitous construction materials, critical interconnects in integrated circuits, common coinage materials, and more. Excitingly, new uses for metals are emerging with the advent of nanoscience, as metal crystals with nanoscale dimensions can display new and tunable properties. The optical and photothermal properties of metal nanocrystals have led to cancer diagnosis and treatment platforms now in clinical trials, while, at the same time, the ability to tune the surface features of metal nanocrystals is giving rise to designer catalysts that enable more sustainable use of precious resources. These are just two examples of how metal nanocrystals are addressing important social needs.

Nanoparticles

Nanoparticles PDF Author: Celso de Mello Donegá
Publisher: Springer
ISBN: 3662448238
Category : Technology & Engineering
Languages : en
Pages : 303

Book Description
This book can be roughly divided into three parts: fundamental physico-chemical and physical principles of Nanoscience, chemistry and synthesis of nanoparticles, and techniques to study nanoparticles. The first chapter is concerned with the origin of the size dependence of the properties of nanomaterials, explaining it in terms of two fundamental nanoscale effects. This chapter also serves as a general introduction to the book, briefly addressing the definition and classification of nanomaterials and the techniques used to fabricate and study them. Chapter 2 lays out the theoretical framework within which to understand size effects on the properties of semiconductor nanocrystals, with particular emphasis on the quantum confinement effect. The optical properties of metal nanoparticles and metal nanostructures (periodic lattices) are discussed in Chapter 3. Chapter 4 is devoted to nanoporous materials, treating in detail their synthesis, structure and functional properties, as well as the physical properties of liquids confined in nanopores. The preparation methods, characterization techniques, and applications of supported nanoparticles are covered in Chapter 5. The sixth Chapter presents the essential physical-chemical concepts needed to understand the preparation of colloidal inorganic nanoparticles, and the remarkable degree of control that has been achieved over their composition, size, shape and surface. The last four Chapters are dedicated to a few selected characterization techniques that are very valuable tools to study nanoparticles. Chapter 7 concentrates on electron microscopy techniques, while Chapter 8 focuses on scanning probe microscopy and spectroscopy. Electron paramagnetic resonance (EPR) based spectroscopic techniques and their application to nanoparticles are explored in Chapter 9. Finally, Chapter 10 shows how solution Nuclear Magnetic Resonance (NMR) spectroscopic techniques can be used to unravel the surface chemistry of colloidal nanoparticles.

Metal and Semiconductor Nanocrystals

Metal and Semiconductor Nanocrystals PDF Author: Jing Zhao
Publisher: Frontiers Media SA
ISBN: 2889633624
Category :
Languages : en
Pages : 91

Book Description


Colloidal Synthesis and Photophysical Characterization of Group IV Alloy and Group IV-V Semiconductors

Colloidal Synthesis and Photophysical Characterization of Group IV Alloy and Group IV-V Semiconductors PDF Author: Venkatesham Tallapally
Publisher:
ISBN:
Category : Alloys
Languages : en
Pages :

Book Description
Nanomaterials, typically less than 100 nm size in any direction have gained noteworthy interest from scientific community owing to their significantly different and often improved physical properties compared to their bulk counterparts. Semiconductor nanoparticles (NPs) are of great interest to study their tunable optical properties, primarily as a function of size and shape. Accordingly, there has been a lot of attention paid to synthesize discrete semiconducting nanoparticles, of where Group III-V and II-VI materials have been studied extensively. In contrast, Group IV and Group IV-V based nanocrystals as earth abundant and less-non-toxic semiconductors have not been studied thoroughly. From the class of Group IV, Ge1-xSnxalloys are prime candidates for the fabrication of Si-compatible applications in the field of electronic and photonic devices, transistors, and charge storage devices. In addition, Ge1-xSnx alloys are potentials candidates for bio-sensing applications as alternative to toxic materials. Tin phosphides, a class of Group IV-V materials with their promising applications in thermoelectric, photocatalytic, and charge storage devices. However, both aforementioned semiconductors have not been studied thoroughly for their full potential in visible (Vis) to near infrared (NIR) optoelectronic applications. In this dissertation research, we have successfully developed unique synthetic strategies to produce Ge1-xSnxalloy quantum dots (QDs) and tin phosphide (Sn3P4, SnP, and Sn4P3) nanoparticles with tunable physical properties and crystal structures for potential applications in IR technologies. Low-cost, less-non-toxic, and abundantly-produced Ge1-xSnxalloys are an interesting class of narrow energy-gap semiconductors that received noteworthy interest in optical technologies. Admixing of Îł-Sn into Ge results in an indirect-to-direct bandgap crossover significantly improving light absorption and emission relative to indirect-gap Ge. However, the narrow energy-gaps reported for bulk Ge1-xSnxalloys have become a major impediment for their widespread application in optoelectronics. Herein, we report the first colloidal synthesis of Ge1-xSnxalloy quantum dots (QDs) with narrow size dispersity (3.3±0.5 -- 5.9±0.8 nm), wide range of Sn compositions (0--20.6%), and composition-tunable energy-gaps and near infrared (IR) photoluminescence (PL). The structural analysis of alloy QDs indicates linear expansion of cubic Ge lattice with increasing Sn, suggesting the formation of strain-free nanoalloys. The successful incorporation of Îł-Sn into crystalline Ge has been confirmed by electron microscopy, which suggests the homogeneous solid solution behavior of QDs. The quantum confinement effects have resulted in energy gaps that are significantly blue-shifted from bulk Ge for Ge1-xSnxalloy QDs with composition-tunable absorption onsets (1.72±0.84 eV for x=1.5--20.6%) and PL peaks (1.62--1.31 eV for x=1.5--5.6%). Time-resolved PL (TRPL) spectroscopy revealed microsecond and nanosecond timescale decays at 15 K and 295 K, respectively owing to radiative recombination of dark and bright excitons as well as the interplay of surface traps and core electronic states. Realization of low-to-non-toxic and silicon-compatible Ge1-xSnxQDs with composition-tunable near IR PL allows the unprecedented expansion of direct-gap Group IV semiconductors to a wide range of biomedical and advanced technological studies. Tin phosphides are a class of materials that received noteworthy interest in photocatalysis, charge storage and thermoelectric devices. Dual stable oxidation states of tin (Sn2+ and Sn4+) enable tin phosphides to exhibit different stoichiometries and crystal phases. However, the synthesis of such nanostructures with control over morphology and crystal structure has proven a challenging task. Herein, we report the first colloidal synthesis of size, shape, and phase controlled, narrowly disperse rhombohedral Sn4P3, hexagonal SnP, and amorphous tin phosphide nanoparticles (NPs) displaying tunable morphologies and size dependent physical properties. The control over NP morphology and crystal phase was achieved by tuning the nucleation/growth temperature, molar ratio of Sn/P, and incorporation of additional coordinating solvents (alkylphosphines). The absorption spectra of smaller NPs exhibit size-dependent blue shifts in energy gaps (0.88--1.38 eV) compared to the theoretical value of bulk Sn3P4 (0.83 eV), consistent with quantum confinement effects. The amorphous NPs adopt rhombohedral Sn4P3 and hexagonal SnP crystal structures at 180 and 250 ̊C, respectively. Structural and surface analysis indicates consistent bond energies for phosphorus across different crystal phases, whereas the rhombohedral Sn4P3 NPs demonstrate Sn oxidation states distinctive from those of the hexagonal and amorphous NPs owing to complex chemical structure. All phases exhibit N(1s) and ʋ(N-H) energies suggestive of alkylamine surface functionalization and are devoid of tetragonal Sn impurities.

Semiconductor and Metal Nanocrystals

Semiconductor and Metal Nanocrystals PDF Author: Victor I. Klimov
Publisher: CRC Press
ISBN: 0203913264
Category : Science
Languages : en
Pages : 505

Book Description
The vast technological potential of nanocrystalline materials, as well as current intense interest in the physics and chemistry of nanoscale phenomena, has led to explosive growth in research on semiconductor nanocrystals, also known as nanocrystal quantum dots, and metal nanoparticles. Semiconductor and Metal Nanocrystals addresses current topics impacting the field including synthesis and assembly of nanocrystals, theory and spectroscopy of interband and intraband optical transitions, single-nanocrystal optical and tunneling spectroscopies, electrical transport in nanocrystal assemblies, and physical and engineering aspects of nanocrystal-based devices. Written by experts who have contributed pioneering research, this reference comprises key advances in the field of semiconductor nanocrystal quantum dots and metal nanoparticles over the past several years. Focusing specifically on nanocrystals generated through chemical techniques, Semiconductor and Metal Nanocrystals Merges investigative frontiers in physics, chemistry, and engineering Documents advances in nanocrystal synthesis and assembly Explores the theory of electronic excitations in nanoscale particles Presents comprehensive information on optical spectroscopy of interband and intraband optical transitions Reviews data on single-nanocrystal optical and tunneling spectroscopies Weighs controversies related to carrier relaxation dynamics in ultrasmall nanoparticles Discusses charge carrier transport in nanocrystal assemblies Provides examples of lasing and photovoltaic nanocrystal-based devices Semiconductor and Metal Nanocrystals is a must read for scientists, engineers, and upper-level undergraduate and graduate students interested in the physics and chemistry of nanoscale semiconductor and metal particles, as well as general nanoscale science.

Silver Nanoparticles

Silver Nanoparticles PDF Author: Khan Maaz
Publisher: Intechopen
ISBN: 1789234786
Category : Technology & Engineering
Languages : en
Pages : 290

Book Description
Silver nanoparticles are the subject of immense interest because of their distinct chemical and physical properties that are different from their bulk counterpart. This makes these nanoparticles very important in many fields including antimicrobial applications, biosensor materials, composite fibers, cryogenic superconducting materials, cosmetic products, and electronic components. This book aims to provide in-depth study and analysis of various fabrication, characterization, and application techniques of silver nanoparticles that lead these nanoparticles very important in the recent technology. This book presents deep understanding of the new techniques from basic to the advanced level. This book addresses scientists, engineers, doctoral and postdoctoral fellows, and technical professionals working in specialized fields.

Transmission Electron Microscopy Characterization of Nanomaterials

Transmission Electron Microscopy Characterization of Nanomaterials PDF Author: Challa S.S.R. Kumar
Publisher: Springer Science & Business Media
ISBN: 3642389341
Category : Science
Languages : en
Pages : 718

Book Description
Third volume of a 40volume series on nanoscience and nanotechnology, edited by the renowned scientist Challa S.S.R. Kumar. This handbook gives a comprehensive overview about Transmission electron microscopy characterization of nanomaterials. Modern applications and state-of-the-art techniques are covered and make this volume an essential reading for research scientists in academia and industry.

Comprehensive Nanoscience and Technology

Comprehensive Nanoscience and Technology PDF Author:
Publisher: Academic Press
ISBN: 0123743966
Category : Science
Languages : en
Pages : 2785

Book Description
From the Introduction: Nanotechnology and its underpinning sciences are progressing with unprecedented rapidity. With technical advances in a variety of nanoscale fabrication and manipulation technologies, the whole topical area is maturing into a vibrant field that is generating new scientific research and a burgeoning range of commercial applications, with an annual market already at the trillion dollar threshold. The means of fabricating and controlling matter on the nanoscale afford striking and unprecedented opportunities to exploit a variety of exotic phenomena such as quantum, nanophotonic and nanoelectromechanical effects. Moreover, researchers are elucidating new perspectives on the electronic and optical properties of matter because of the way that nanoscale materials bridge the disparate theories describing molecules and bulk matter. Surface phenomena also gain a greatly increased significance; even the well-known link between chemical reactivity and surface-to-volume ratio becomes a major determinant of physical properties, when it operates over nanoscale dimensions. Against this background, this comprehensive work is designed to address the need for a dynamic, authoritative and readily accessible source of information, capturing the full breadth of the subject. Its six volumes, covering a broad spectrum of disciplines including material sciences, chemistry, physics and life sciences, have been written and edited by an outstanding team of international experts. Addressing an extensive, cross-disciplinary audience, each chapter aims to cover key developments in a scholarly, readable and critical style, providing an indispensible first point of entry to the literature for scientists and technologists from interdisciplinary fields. The work focuses on the major classes of nanomaterials in terms of their synthesis, structure and applications, reviewing nanomaterials and their respective technologies in well-structured and comprehensive articles with extensive cross-references. It has been a constant surprise and delight to have found, amongst the rapidly escalating number who work in nanoscience and technology, so many highly esteemed authors willing to contribute. Sharing our anticipation of a major addition to the literature, they have also captured the excitement of the field itself in each carefully crafted chapter. Along with our painstaking and meticulous volume editors, full credit for the success of this enterprise must go to these individuals, together with our thanks for (largely) adhering to the given deadlines. Lastly, we record our sincere thanks and appreciation for the skills and professionalism of the numerous Elsevier staff who have been involved in this project, notably Fiona Geraghty, Megan Palmer and Greg Harris, and especially Donna De Weerd-Wilson who has steered it through from its inception. We have greatly enjoyed working with them all, as we have with each other.

Nanoparticulate Materials

Nanoparticulate Materials PDF Author: Kathy Lu
Publisher: John Wiley & Sons
ISBN: 1118408950
Category : Technology & Engineering
Languages : en
Pages : 379

Book Description
Serving as the only systematic and comprehensive treatment on the topic of nanoparticle-based materials, this book covers synthesis, characterization, assembly, shaping and sintering of all types of nanoparticles including metals, ceramics, and semiconductors. A single-authored work, it is suitable as a graduate-level text in nanomaterials courses.