Showing papers by "Joshua E. Goldberger published in 2003"

Low-temperature wafer-scale production of ZnO nanowire arrays.

Abstract: Since the first report of ultraviolet lasing from ZnO nanowires, substantial effort has been devoted to the development of synthetic methodologies for one-dimensional ZnO nanostructures. Among the various techniques described in the literature, evaporation and condensation processes are favored for their simplicity and high-quality products, but these gas-phase approaches generally require economically prohibitive temperatures of 800–900 8C. Despite recent MOCVD schemes that reduced the deposition temperature to 450 8C by using organometallic zinc precursors, the commercial potential of gas-phase-grown ZnO nanowires remains constrained by the expensive and/or insulating (for example, Al2O3) substrates required for oriented growth, as well as the size and cost of the vapor deposition systems. A low-temperature, large-scale, and versatile synthetic process is needed before ZnO nanowire arrays find realistic applications in solar energy conversion, light emission, and other promising areas. Solution approaches to ZnO nanowires are appealing because of their low growth temperatures and good potential for scale-up. In this regard, Vayssieres et al. developed a hydrothermal process for producing arrays of ZnO microrods and nanorods on conducting glass substrates at 95 8C. Recently, a seeded growth process was used to make helical ZnO rods and columns at a similar temperature. Here we expand on these synthetic methods to produce homogeneous and dense arrays of ZnO nanowires that can be grown on arbitrary substrates under mild aqueous conditions. We present data for arrays on four-inch (ca. 10 cm) silicon wafers and two-inch plastic substrates, which demonstrate the ease of commercial scale-up. The simple two-step procedure yields oriented nanowire films with the largest surface area yet reported for nanowire arrays. The growth process ensures that a majority of the nanowires in the array are in direct contact with the substrate and provide a continuous pathway for carrier transport, an important feature for future electronic devices based on these materials. Well-aligned ZnO nanowire arrays were grown using a simple two-step process. In the first step, ZnO nanocrystals (5–10 nm in diameter) were spin-cast several times onto a four-inch Si(100) wafer to form a 50–200-nm thick film of crystal seeds. Between coatings, the wafer was annealed at 150 8C to ensure particle adhesion to the wafer surface. The ZnO nanocrystals were prepared according to the method of Pacholski. A NaOH solution in methanol (0.03m) was added slowly to a solution of zinc acetate dihydrate (0.01m) in methanol at 60 8C and stirred for two hours. The resulting nanoparticles are spherical and stable for at least two weeks in solution. After uniformly coating the silicon wafer with ZnO nanocrystals, hydrothermal ZnO growth was carried out by suspending the wafer upside-down in an open crystallizing dish filled with an aqueous solution of zinc nitrate hydrate (0.025m) and methenamine or diethylenetriamine (0.025m) at 90 8C. Reaction times spanned from 0.5 to 6 h. The wafer was then removed from solution, rinsed with deionized water, and dried. A field-emission scanning electron microscope (FESEM) was used to examine the morphology of the nanowire array across the entire wafer, while single nanowires were characterized by transmission electron microscopy (TEM). Nanowire crystallinity and growth direction were analyzed by X-ray diffraction and electron diffraction techniques. SEM images taken of several four-inch samples showed that the entire wafer was coated with a highly uniform and densely packed array of ZnO nanowires (Figure 1). X-ray diffraction (not shown) gave a wurtzite ZnO pattern with an enhanced (002) peak resulting from the vertical orientation of the nanowires. A typical synthesis (1.5 h) yielded wires with diameters ranging between 40–80 nm and lengths of 1.5–2 mm.

Langmuir-Blodgett Silver Nanowire Monolayers for Molecular Sensing Using Surface-Enhanced Raman Spectroscopy

Abstract: Langmuir−Blodgett technique was used to assemble monolayers (with areas over 20 cm2) of aligned silver nanowires that are ∼50 nm in diameter and 2−3 μm in length. These nanowires possess pentagonal cross-sections and pyramidal tips. They are close-packed and are aligned parallel to each other. The resulting nanowire monolayers serve as excellent substrates for surface-enhanced Raman spectroscopy (SERS) with large electromagnetic field enhancement factors (2 × 105 for thiol and 2,4-dinitrotoluene, and 2 × 109 for Rhodamine 6G) and can readily be used in ultrasensitive, molecule-specific sensing utilizing vibrational signatures.

Single-crystal gallium nitride nanotubes.

Abstract: Since the discovery of carbon nanotubes in 1991 (ref. 1), there have been significant research efforts to synthesize nanometre-scale tubular forms of various solids. The formation of tubular nanostructure generally requires a layered or anisotropic crystal structure. There are reports of nanotubes made from silica, alumina, silicon and metals that do not have a layered crystal structure; they are synthesized by using carbon nanotubes and porous membranes as templates, or by thin-film rolling. These nanotubes, however, are either amorphous, polycrystalline or exist only in ultrahigh vacuum. The growth of single-crystal semiconductor hollow nanotubes would be advantageous in potential nanoscale electronics, optoelectronics and biochemical-sensing applications. Here we report an 'epitaxial casting' approach for the synthesis of single-crystal GaN nanotubes with inner diameters of 30-200 nm and wall thicknesses of 5-50 nm. Hexagonal ZnO nanowires were used as templates for the epitaxial overgrowth of thin GaN layers in a chemical vapour deposition system. The ZnO nanowire templates were subsequently removed by thermal reduction and evaporation, resulting in ordered arrays of GaN nanotubes on the substrates. This templating process should be applicable to many other semiconductor systems.

Metalorganic Chemical Vapor Deposition Route to GaN Nanowires with Triangular Cross Sections

Abstract: High-quality gallium nitride nanowires have been synthesized via metal-initiated metalorganic chemical vapor deposition for the first time. Excellent substrate coverage was observed for wires prepared on silicon, c-plane, and a-plane sapphire substrates. The wires were formed via the vapor−liquid−solid mechanism with gold, iron, or nickel as growth initiators and were found to have widths of 15-200 nm. Transmission electron microscopy confirmed that the wires were single-crystalline and were oriented predominantly along the [210] or [110] direction. Wires growing along the [210] orientation were found to have triangular cross-sections. Transport measurements confirmed that the wires were n-type and had electron mobilities of ∼65 cm2/V·s. Photoluminescence measurements showed band edge emission at 3.35 eV (at 5 K), with a marked absence of low-energy emission from impurity defects.

Self-Organized GaN Quantum Wire UV Lasers

Abstract: Quantum wire lasers are generally fabricated through complex overgrowth processes with molecular beam epitaxy. The material systems of such overgrown quantum wires have been limited to Al−Ga−As−P, which leads to emission largely in the visible region. We describe a simple, one-step chemical vapor deposition process for making quantum wire lasers based on the Al−Ga−N system. A novel quantum-wire-in-optical-fiber (Qwof) nanostructure was obtained as a result of spontaneous Al−Ga−N phase separation at the nanometer scale in one dimension. The simultaneous excitonic and photonic confinement within these coaxial Qwof nanostructures leads to the first GaN-based quantum wire UV lasers with a relatively low threshold.

Watching GaN Nanowires Grow

Abstract: We report real-time high temperature transmission electron microscopy observations of the growth of GaN nanowires via a self-catalytic vapor-liquid-solid (VLS) mechanism. High temperature thermal decomposition of GaN in a vacuum yields nanoscale Ga liquid droplets and gallium/nitrogen vapor species for the subsequent GaN nanowire nucleation and growth. This is the first direct observation of self-catalytic growth of nanowires via the VLS mechanism and suggests new strategies for synthesizing electronically pure single-crystalline semiconductor nanowires.

Low‐Temperature Wafer‐Scale Production of ZnO Nanowire Arrays.

Abstract: Since the first report of ultraviolet lasing from ZnO nanowires, substantial effort has been devoted to the development of synthetic methodologies for one-dimensional ZnO nanostructures. Among the various techniques described in the literature, evaporation and condensation processes are favored for their simplicity and high-quality products, but these gas-phase approaches generally require economically prohibitive temperatures of 800–900 8C. Despite recent MOCVD schemes that reduced the deposition temperature to 450 8C by using organometallic zinc precursors, the commercial potential of gas-phase-grown ZnO nanowires remains constrained by the expensive and/or insulating (for example, Al2O3) substrates required for oriented growth, as well as the size and cost of the vapor deposition systems. A low-temperature, large-scale, and versatile synthetic process is needed before ZnO nanowire arrays find realistic applications in solar energy conversion, light emission, and other promising areas. Solution approaches to ZnO nanowires are appealing because of their low growth temperatures and good potential for scale-up. In this regard, Vayssieres et al. developed a hydrothermal process for producing arrays of ZnO microrods and nanorods on conducting glass substrates at 95 8C. Recently, a seeded growth process was used to make helical ZnO rods and columns at a similar temperature. Here we expand on these synthetic methods to produce homogeneous and dense arrays of ZnO nanowires that can be grown on arbitrary substrates under mild aqueous conditions. We present data for arrays on four-inch (ca. 10 cm) silicon wafers and two-inch plastic substrates, which demonstrate the ease of commercial scale-up. The simple two-step procedure yields oriented nanowire films with the largest surface area yet reported for nanowire arrays. The growth process ensures that a majority of the nanowires in the array are in direct contact with the substrate and provide a continuous pathway for carrier transport, an important feature for future electronic devices based on these materials. Well-aligned ZnO nanowire arrays were grown using a simple two-step process. In the first step, ZnO nanocrystals (5–10 nm in diameter) were spin-cast several times onto a four-inch Si(100) wafer to form a 50–200-nm thick film of crystal seeds. Between coatings, the wafer was annealed at 150 8C to ensure particle adhesion to the wafer surface. The ZnO nanocrystals were prepared according to the method of Pacholski. A NaOH solution in methanol (0.03m) was added slowly to a solution of zinc acetate dihydrate (0.01m) in methanol at 60 8C and stirred for two hours. The resulting nanoparticles are spherical and stable for at least two weeks in solution. After uniformly coating the silicon wafer with ZnO nanocrystals, hydrothermal ZnO growth was carried out by suspending the wafer upside-down in an open crystallizing dish filled with an aqueous solution of zinc nitrate hydrate (0.025m) and methenamine or diethylenetriamine (0.025m) at 90 8C. Reaction times spanned from 0.5 to 6 h. The wafer was then removed from solution, rinsed with deionized water, and dried. A field-emission scanning electron microscope (FESEM) was used to examine the morphology of the nanowire array across the entire wafer, while single nanowires were characterized by transmission electron microscopy (TEM). Nanowire crystallinity and growth direction were analyzed by X-ray diffraction and electron diffraction techniques. SEM images taken of several four-inch samples showed that the entire wafer was coated with a highly uniform and densely packed array of ZnO nanowires (Figure 1). X-ray diffraction (not shown) gave a wurtzite ZnO pattern with an enhanced (002) peak resulting from the vertical orientation of the nanowires. A typical synthesis (1.5 h) yielded wires with diameters ranging between 40–80 nm and lengths of 1.5–2 mm.

Sacrificial template method of fabricating a nanotube

Abstract: Methods of fabricating uniform nanotubes are described in which nanotubes were synthesized as sheaths over nanowire templates, such as using a chemical vapor deposition process. For example, single-crystalline zinc oxide (ZnO) nanowires are utilized as templates over which gallium nitride (GaN) is epitaxially grown. The ZnO templates are then removed, such as by thermal reduction and evaporation. The completed single-crystalline GaN nanotubes preferably have inner diameters ranging from 30 nm to 200 nm, and wall thicknesses between 5 and 50 nm. Transmission electron microscopy studies show that the resultant nanotubes are single-crystalline with a wurtzite structure, and are oriented along the direction. The present invention exemplifies single-crystalline nanotubes of materials with a non-layered crystal structure. Similar “epitaxial-casting” approaches could be used to produce arrays and single-crystalline nanotubes of other solid materials and semiconductors. Furthermore, the fabrication of multi-sheath nanotubes are described as well as nanotubes having multiple longitudinal segments.

Nonaqueous, Molecular Precursor Route to Hybrid Inorganic/Organic Zirconia−Silica Materials Containing Covalently Linked Organic Bridges

Abstract: New hybrid inorganic/organic materials possessing zirconium in the inorganic framework have been synthesized. Co-thermolyses in sealed reactors (toluene, AlCl3 catalyst, 155 °C) of Zr[OSi(OtBu)3]4 in the presence of (EtO)3Si(CH2)nSi(OEt)3 (n = 1, 2) or (EtO)3Si(C6H4)nSi(OEt)3 (n = 1, 2; C6H4 = 1,4-phenylene) monomers rapidly yielded monolithic, transparent gels. The resulting xerogels were amorphous and exhibited high surface areas and high surface coverages of OH functionalities. Solid-state 29Si and 13C CP MAS NMR spectroscopies were used to establish the presence of intact, organic bridging groups and to verify the presence of unreacted ethoxy groups. Energy-dispersive X-ray spectroscopy was used to elucidate the elemental composition and distribution throughout the material, and atomic force microscopy was used to probe surface adhesive properties.

Single‐Crystal Gallium Nitride Nanotubes.

Abstract: Since the discovery of carbon nanotubes in 1991 (ref. 1), there have been significant research efforts to synthesize nanometre-scale tubular forms of various solids. The formation of tubular nanostructure generally requires a layered or anisotropic crystal structure. There are reports of nanotubes made from silica, alumina, silicon and metals that do not have a layered crystal structure; they are synthesized by using carbon nanotubes and porous membranes as templates, or by thin-film rolling. These nanotubes, however, are either amorphous, polycrystalline or exist only in ultrahigh vacuum. The growth of single-crystal semiconductor hollow nanotubes would be advantageous in potential nanoscale electronics, optoelectronics and biochemical-sensing applications. Here we report an 'epitaxial casting' approach for the synthesis of single-crystal GaN nanotubes with inner diameters of 30-200 nm and wall thicknesses of 5-50 nm. Hexagonal ZnO nanowires were used as templates for the epitaxial overgrowth of thin GaN layers in a chemical vapour deposition system. The ZnO nanowire templates were subsequently removed by thermal reduction and evaporation, resulting in ordered arrays of GaN nanotubes on the substrates. This templating process should be applicable to many other semiconductor systems.