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Sarah H Tolbert

Publications and source records attributed to Sarah H Tolbert.

14 recordsLinked to original sources
PubMed2006

Synthesis and self-assembly of an amphiphilic poly(phenylene ethynylene) ionomer.

We have synthesized a conjugated amphiphilic polyelectrolyte, a poly(phenylene ethynylene) (PPE), and the structurally analogous neutral polymer. The solution-phase aggregation of the uncharged PPE can be reversibly controlled by varying the solvent polarity and concentration, while the charged polymer appears to self-assemble at any concentration in compatible solvents. These conclusions are based on a combination of absorption and photoluminescence spectroscopy and dynamic light scattering. Photoinduced absorption spectroscopy was also employed to investigate interchain electronic communication and the photoinduced production of free charge carriers. The uncharged PPE had a relatively high polaron yield, indicating pi-stacking of adjacent PPE chains and efficient exciton splitting, while the charged polymer did not produce polarons, indicating that the polymers are not pi-stacked despite their tendency to form aggregates. This is most likely due to the presence of the cationic trimethylammonium side chains which force neighboring polymer chains too far apart to achieve effective pi-orbital overlap. Polarons were observed in both polymers after chemical doping with iodine. The ability to control aggregation and interchain electronic communication could be a useful tool in designing nanostructured electronic materials.

Journal Article↗
PubMed2006

Hexagonal nanoporous germanium through surfactant-driven self-assembly of Zintl clusters.

Surfactant templating is a method that has successfully been used to produce nanoporous inorganic structures from a wide range of oxide-based material. Co-assembly of inorganic precursor molecules with amphiphilic organic molecules is followed first by inorganic condensation to produce rigid amorphous frameworks and then, by template removal, to produce mesoporous solids. A range of periodic surfactant/semiconductor and surfactant/metal composites have also been produced by similar methods, but for virtually all the non-oxide semiconducting phases, the surfactant unfortunately cannot be removed to generate porous materials. Here we show that it is possible to use surfactant-driven self-organization of soluble Zintl clusters to produce periodic, nanoporous versions of classic semiconductors such as amorphous Ge or Ge/Si alloys. Specifically, we use derivatives of the anionic Ge9(4-) cluster, a compound whose use in the synthesis of nanoscale materials is established. Moreover, because of the small size, high surface area, and flexible chemistry of these materials, we can tune optical properties in these nanoporous semiconductors through quantum confinement, by adsorption of surface species, or by altering the elemental composition of the inorganic framework. Because the semiconductor surface is exposed and accessible in these materials, they have the potential to interact with a range of species in ways that could eventually lead to new types of sensors or other novel nanostructured devices.

Journal Article↗
PubMed2005

Controlling optical properties and interchain interactions in semiconducting polymers by encapsulation in periodic nanoporous silicas with different pore sizes.

The photophysics of MEH-PPV incorporated into the pores of periodic silica hosts has been investigated in an effort to understand the role played by interchain aggregation and chain morphology in polaron production. In this work, guest/host interactions were used to incorporate MEH-PPV into the straight, homogeneous pores of hexagonal surfactant- or polymer-templated mesoporous silicas of varying pore diameters. Polarized photoluminescence and photoluminescence excitation spectroscopy were then used to investigate the polymers' environment within the silica pores. Experiments exploiting luminescence peak shifts and depolarization indicate that depending on the pore size and preparation conditions, the alignment and packing of the polymer chains within the pores could be controlled. Samples could be produced with isolated chains, interacting straight chains, and coiled interacting chains. The sub-bandgap absorption by polarons was then measured with photoinduced absorption as a function of pore size. Small-diameter pores that allowed single polymer chains to reside within the pore showed little evidence of interchain contact and had a low polaron yield. Increasing the number of polymer chains within the pore increased the polaron yield. Finally, when the pores were large enough that the chains could coil, strong polaron absorption was observed, indicative of a further increase in polaron yield or an increase in polaron lifetime. The polaron absorption spectra also sharpen and red shift with increasing pore diameter, suggesting that excitons may migrate to lower energy polymer segments in samples where polymer chains are both coiled and interacting.

Journal Article↗
PubMed2005

Chemical tuning of the electronic properties in a periodic surfactant-templated nanostructured semiconductor.

In this work, we report the synthesis and characterization of a series of hexagonal nanostructured platinum/tin/tellurium inorganic/surfactant composites. The composites are formed through solution-phase self-assembly of SnTe4(4-) Zintl clusters, which are cross-linked with platinum salts in the presence of a cetyltriethylammonium cationic structure directing agent. The cross-linking utilizes various combinations of Pt(II) and Pt(IV) salts. Low-angle X-ray diffraction indicates that all composites form hexagonal honeycomb (p6mm) structures. A combination of elemental analysis and XANES is used to describe the composition and oxidation states within the composites. We find that the extent of tin telluride self-oligomerization and the platinum:tin telluride ratio both vary, indicating that the composite compensates for different platinum oxidation states by tuning the inorganic composition. Near-IR/visible reflectance spectroscopy and UPS can be used to measure both band gaps and absolute band energies. The results show that while moving from all Pt(II) to all Pt(IV) increases the band gap from 0.6 to 0.8 eV, it increases the absolute valence and conduction band energies by almost a full electronvolt. AC impedance spectroscopy further reveals that the conductivities of the materials can be tuned from 0.009 to 0.003 Omega(-1).cm(-1). Additionally, a capacitance arising from the periodic nanoscale organic domains was observed. The conductivity and band gap were used to estimate carrier mobilities in these composites. Chemical tuning of the electronic properties within related nanostructured composites is a useful tool for designing applications that exploit the properties of nanostructured semiconductors.

Electrons↗
PubMed2005

Osmium diboride, an ultra-incompressible, hard material.

The need for wear- and scratch-resistant materials drives the quest for new superhard materials. In this work, we apply two design parameters to identify ultra-incompressible, superhard materials-high valence electron density and high bond covalency. Our first example of such a material is OsB2. The bulk modulus of OsB2 was measured using in situ high-pressure X-ray diffraction and was determined to be in the range of 365-395 GPa. While this value is slightly less than that of the bulk modulus of diamond, due to the anisotropic crystal structure of OsB2, the axis compressibility in the orthorhombic c-direction is less than the axis compressibility found in diamond. OsB2 also scratches the surface of a sapphire window, indicating that the hardness of OsB2 exceeds 2000 kg/mm2.

Journal Article↗
PubMed2005

Tantalum(V) nitride inverse opals as photonic structures for visible wavelengths.

The development of materials with a complete photonic band gap at visible wavelengths is believed to have the potential to lead to new control over long-lived emissive excited states, single molecule lasers, and nearly lossless nanoscale waveguides. In this work we move toward that goal with the synthesis of an inverse opal thin film of Ta3N5 produced through atomic layer deposition. The highly regular architecture achievable by atomic layer deposition is combined with an unusually high refractive index and transparency in at least part of the visible spectrum. The result is a material that represents the closest example to date of a photonic crystal with a band gap at optical wavelengths.

Journal Article↗
PubMed2005

Examining the role of surfactant packing in phase transformations of periodic templated silica/surfactant composites.

In this work, we examine the role of curvature and surfactant packing in controlling the structure of periodic silica/surfactant composites by driving such materials through a transformation from a hexagonal to a lamellar phase. We focus on how the interplay of desired packing and volume constraints dictates the resulting structures. In general, surfactants expand in a complex way upon heating, and this can cause a change in the optimal packing geometry. However, the presence of a rigid silica framework may prevent surfactants from reaching this preferred volume and/or curvature. Real-time in situ X-ray diffraction is used to monitor the structural evolution of these materials heated under hydrothermal treatments. Because the thermal-driven disorder of the surfactant tails drives the phase transition, we examine four types of composites with varying tail density. Ordinarily, composites consist of surfactants with one 20-carbon tail and one positively charged ammonium headgroup. Tail density is varied by replacing a small amount (0-16%) of these single-tail, single-head surfactants with single-tail, double-head 'gemini' surfactants. A greater head--tail ratio indeed produces different results, causing the phase transition to occur at higher temperatures. Using simple geometric models to gain better understanding of our experimental results, we find that, while both unfavorable curvature and limited volume may exist for the surfactants in these composites, the constrained curvature appears to be the dominant effect in driving structural rearrangement.

Journal Article↗
PubMed2005

An amphiphilic poly(phenylene ethynylene) as the structure-directing agent for periodic nanoscale silica composite materials.

We have synthesized optically active nanostructured composite materials by using an amphiphilic semiconducting polymer, a poly(phenylene ethynylene) (PPE), and a conventional ammonium surfactant as the structure-directing agents. The PPE consists of phenylene units para-substituted with an octyloxy chain and a charged trimethylammoniumethoxy group, resulting in a surfactant-like structure that can assemble into cylindrical micelles. The resulting silica/organic composite material has a hexagonal honeycomb structure with a repeat distance of 45.3 A, as confirmed by low-angle X-ray diffraction and transmission electron microscopy. Scanning electron microscopy indicates that the larger scale particle size is on the order of micrometers. The incorporation of the polymer into the composite was confirmed by elemental analysis, photoluminescence spectroscopy, and fluorescence microscopy. The polymer retains its photophysical properties in the composite, showing luminescence similar to polymers in the solution phase. The polymer displays a high degree of luminescence polarization anisotropy, indicating that the polymer chains are straight and isolated from each other in the composite.

Journal Article↗
PubMed2004

Probing the effects of interfacial chemistry on the kinetics of phase transitions in amorphous and tetragonal zirconia nanocrystals.

In this work, we examine the phase stability of both uncoated and alumina-coated zirconia nanoparticles using in-situ X-ray diffraction. By tracking structural changes in these particles, we seek to understand how changing interfacial bonding affects the kinetics of amorphous zirconia crystallization and the kinetics of grain growth in both initially amorphous and initially crystalline zirconia nanocrystals. Activation energies associated with crystallization are calculated using nonisothermal kinetic methods. The crystallization of the uncoated amorphous zirconia colloids has an activation energy of 117 +/- 13 kJ/mol, while that for the alumina-coated amorphous colloids is 185 +/- 28 kJ/mol. This increase in activation energy is attributed to inhibition of atomic rearrangement imparted by the alumina coating. The kinetics of grain growth are also studied with nonisothermal kinetic methods. The alumina coating again dramatically affects the activation energies. For colloids that were coated with alumina when they were in an amorphous structure, the coating imparts a 5x increase in the activation energy for grain growth (33 +/- 8 versus 150 +/- 30 kJ/mol). This increase shows that the alumina coating inhibits zirconia cores from coarsening. When the colloids are synthesized in the tetragonal phase and then coated with alumina, the effect of surface coating on coarsening kinetics is even more dramatic. In this case, a 10x increase in activation energies, from 28 +/- 3 kJ/mol for the uncoated particles to 300 +/- 25 kJ/mol for the alumina-coated crystallites, is found. The results show that one can alter phase stability in colloidal systems by using surface coatings and interfacial energy to dramatically change the kinetic barriers to structural rearrangement.

Chemical Phenomena↗
PubMed2004

Highly polarized luminescence from optical quality films of a semiconducting polymer aligned within oriented mesoporous silica.

In this Communication, we show that nanometer scale control of semiconducting polymer chain conformation is possible using host/guest chemistry in highly ordered and macroscopically oriented thin films of mesoporous silica. This control leads to a thin film composite material that is optically transparent, densely filled with polymer, and has highly polarized optical properties. Calculations of absorption and emission anisotropies further indicate full incorporation of the polymer into the nanoscale pore spaces. Such materials could serve as a useful tool for further investigations of polymer photophysics, as well as for device applications.

Journal Article↗
PubMed2003

Synthesis of periodic hexagonal surfactant templated platinum tin tellurides: narrow band gap inorganic/organic composites.

In this work we report the synthesis and characterization of a new nanostructured platinum/tin/telluride inorganic/surfactant composite. The material is synthesized from soluble SnTe(4)(4-) clusters and is shown to have well-defined nanometer scale periodicity along with unique optical properties. Small-angle X-ray scattering indicates that the material forms with a 2D hexagonal honeycomb structure, which is size tunable based on surfactant tail length. Multinuclear EXAFS is used as a probe of local order in these materials. The results indicate that the tetrahedral SnTe(4) unit dimerizes during assembly, and these clusters are coordinated to square planar platinum ions. Near-IR/visible reflectance spectroscopy indicates that the material is a narrow band gap semiconductor with a band gap of 0.8 eV. The extension of the ideas of surfactant templating to a narrow band gap semiconductor opens up the exciting potential for future optoelectronic applications.

Journal Article↗
PubMed2002

Chemical control of phase transformation kinetics in periodic silica/surfactant composites.

Control of phase stability is investigated through control of silica chemistry in ordered silica/surfactant composites under hydrothermal conditions. The composites were hydrothermally treated in pH 9 through pH 11 buffers while using in situ real time X-ray diffraction to follow a p6mm hexagonal-to-lamellar structural transition. The data were analyzed using both isothermal and nonisothermal (temperature-ramped) kinetics to determine activation energies. It was found that the most mildly basic conditions utilized (pH 9), which favor silica condensation, best inhibit the phase transition and thus produce the most kinetically stable composites. High-pH treatment, conversely, allows for the most facile rearrangements. Condensation occurring during composite synthesis rather than during hydrothermal treatment has a much smaller effect on phase stability, probably because much of the condensation that occurs during synthesis is random and not optimally coupled to the nanoscale architecture. Materials that start out poorly condensed, by contrast, can be extensively hydrothermally modified so that the final material has an inorganic framework with a highly uniform silica density; this provides the maximum resistance to transformation and the highest kinetic stability. In all cases, very good agreement is found between the results of isothermal and nonisothermal kinetic methods. The trends across pHs indicate that both isothermal and nonisothermal measurements are accurate and that differences between them are meaningful and represent physical differences in the transforming materials resulting from the different heating processes.

Journal Article↗