Although gold is the subject of one of the most ancient themes of investigation in science, its renaissance now leads to an exponentially increasing number of publications, especially in the context of emerging nanoscience and nanotechnology with nanoparticles and self-assembled monolayers (SAMs). We will limit the present review to gold nanoparticles (AuNPs), also called gold colloids. AuNPs are the most stable metal nanoparticles, and they present fascinating aspects such as their assembly of multiple types involving materials science, the behavior of the individual particles, size-related electronic, magnetic and optical properties (quantum size effect), and their applications to catalysis and biology. Their promises are in these fields as well as in the bottom-up approach of nanotechnology, and they will be key materials and building block in the 21st century. Whereas the extraction of gold started in the 5th millennium B.C. near Varna (Bulgaria) and reached 10 tons per year in Egypt around 1200-1300 B.C. when the marvelous statue of Touthankamon was constructed, it is probable that “soluble” gold appeared around the 5th or 4th century B.C. in Egypt and China. In antiquity, materials were used in an ecological sense for both aesthetic and curative purposes. Colloidal gold was used to make ruby glass 293 Chem. Rev. 2004, 104, 293−346

Gold nanoparticles: assembly, supramolecular chemistry, quantum-size-related properties, and applications toward biology, catalysis, and nanotechnology.

Surface plasmons (SPs) are coherent oscillations of conduction electrons on a metal surface excited by electromagnetic radiation at a metal -dielectric interface. The growing field of research on such light -metal interactions is known as ‘plasmonics’. 1-3 This branch of research has attracted much attention due to its potential applications in miniaturized optical devices, sensors, and photonic circuits as well as in medical diagnostics and therapeutics. 4-8

Nanostructured plasmonic sensors.

During the past decade, enormous progress has been made in growing ultrathin organic films and multilayer structures with a wide range of exciting optoelectronic properties. This progress has been made possible by several important advances in our understanding of organic films and their modes of growth. Perhaps the single most important advance has been the use of ultrahigh vacuum (UHV) as a means to achieve, for the first time, monolayer control over the growth of organic thin films with extremely high chemical purity and structural precision.1-3 Such monolayer control has been possible for many years using well-known techniques such as Langmuir-Blodgett film deposition,4 and more recently, self-assembled monolayers from solution have also been achieved.5 However, ultrahighvacuum growth, sometimes referred to as organic molecular beam deposition (OMBD) or organic molecular beam epitaxy (OMBE), has the advantage of providing both layer thickness control and an atomically clean environment and substrate. When combined with the ability to perform in situ highresolution structural diagnostics of the films as they are being deposited, techniques such as OMBD have provided an entirely new prospect for understanding many of the fundamental structural and optoelectronic properties of ultrathin organic film systems. Since such systems are both of intrinsic as well as practical interest, substantial effort worldwide has been invested in attempting to grow and investigate the properties of such thin-film systems. This paper is a review of recent progress made in organic thin films grown in ultrahigh vacuum or using other vapor-phase deposition methods. We will describe the most important work which has been published in this field since the emergence of OMBD in the mid-1980s. Both the nature of thin-film growth and structural ordering will be discussed, as well as some of the more interesting consequences to the physical properties of such organic thin-film systems will be considered both from a theoretical as well as an experimental viewpoint. Indeed, it will 1793 Chem. Rev. 1997, 97, 1793−1896

Ultrathin Organic Films Grown by Organic Molecular Beam Deposition and Related Techniques.

Nanoporous anodic aluminium oxide has been widely used for the development of various functional nanostructures. So far these self-organized pore structures could only be prepared within narrow processing conditions. Here we report a new oxalic-acid-based anodization process for long-range ordered alumina membranes. This process is a new generation of the so-called "hard anodization" approach that has been widely used in industry for high-speed fabrication of mechanically robust, very thick (>100 microm) and low-porosity alumina films since the 1960s. This hard anodization approach establishes a new self-ordering regime with interpore distances, (D(int))=200-300 nm, which have not been achieved by mild anodization processes so far. It offers substantial advantages over conventional anodization processes in terms of processing time, allowing 2,500-3,500% faster oxide growth with improved ordering of the nanopores. Perfectly ordered alumina membranes with high aspect ratios (>1,000) of uniform nanopores with periodically modulated diameters have been realized.

/pdf/fast-fabrication-of-long-range-ordered-porous-alumina-1bigpxis0y.pdf

Fast fabrication of long-range ordered porous alumina membranes by hard anodization

Chemistries that Facilitate Nanotechnology Kim E. Sapsford,† W. Russ Algar, Lorenzo Berti, Kelly Boeneman Gemmill,‡ Brendan J. Casey,† Eunkeu Oh, Michael H. Stewart, and Igor L. Medintz*,‡ †Division of Biology, Department of Chemistry and Materials Science, Office of Science and Engineering Laboratories, U.S. Food and Drug Administration, Silver Spring, Maryland 20993, United States ‡Center for Bio/Molecular Science and Engineering Code 6900 and Division of Optical Sciences Code 5611, U.S. Naval Research Laboratory, Washington, D.C. 20375, United States College of Science, George Mason University, 4400 University Drive, Fairfax, Virginia 22030, United States Department of Biochemistry and Molecular Medicine, University of California, Davis, School of Medicine, Sacramento, California 95817, United States Sotera Defense Solutions, Crofton, Maryland 21114, United States

Functionalizing nanoparticles with biological molecules: developing chemistries that facilitate nanotechnology.

We have tried to develop a new procedure to prepare the clean surface of a silicon single crystal. We successfully prepared the contamination free bare silicon surface with ultraviolet cleaning followed by HF dipping with low concentration HF obtained by dilution by organic free ultrapure water, at room temperature under the atmospheric condition. X‐ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, and ultraviolet photoelectron spectroscopy measurements proved thus prepared surface has a hydrogen monoatomic layer terminating the dangling bonds of silicon. The hydrogen termination was found to have remarkable passivation effect against surface oxidation reaction. A silicon thin‐film epitaxially grown on the prepared surface was confirmed to have perfect crystal structure and high‐purity level by scanning electron microscopy, reflection high‐energy electron diffraction, Raman spectroscopy and secondary ion mass spectroscopy.

The formation of hydrogen passivated silicon single‐crystal surfaces using ultraviolet cleaning and HF etching

Self-organization of a two-dimensional array of nanoholes which were formed by anodic oxidation of aluminum was investigated quantitatively using fast Fourier transformation (FFT) analysis of scanning electron microscopy (SEM) images. The highly ordered array of nanoholes with diameters of 26 nm was obtained by two-step anodization at anodic voltage around 40 V, and oxalic acid concentration of 0.5 M. A two-dimensional ordered array of Au free standing nanowires was successfully fabricated by the deposition of Au using DC electroplating in nanoholes of aluminum oxide, by removal of the aluminum oxide barrier layer using wet chemical etching. The present method has a high efficiency to fabricate ordered nanowire array of a variety of conductive materials in a large area, and wide applications for fabricating quantum effect devices and materials would be expected.

https://iopscience.iop.org/article/10.1143/JJAP.36.7791/pdf

Ordered Two-Dimensional Nanowire Array Formation Using Self-Organized Nanoholes of Anodically Oxidized Aluminum

Gas phase chemical modification (GCM) is found to be more preferable as a pretreatment for the XPS surface analysis of polymer materials than the conventional liquid phase treatment because it can circumvent problems such as solvent contamination and swelling. We have tried the quantification of the surface composition successfully by estimating the yield of the reaction from model samples. GCM was then applied to correlate the surface composition of NH3 plasma-treated polystyrene films with their cell-affinity. The amount of primary-amine and that of carboxylic acid were directly determined by GCM. Although the amount of primary-amine, 15–20% of total nitrogen, did not depend on the treatment intensity, the total amine content for the treated samples increased with the plasma treatment intensity. The quantity of carboxylic acid generated was found to be very small. All treated samples had better cell-affinity than the control. The sample N2 (of medium treatment) showed the best cell-affinity. The most strongly treated sample N3, with larger amine content than N2, showed worse cell-affinity because of the interference by the sputtered SiO2 on the surface.

XPS analysis of NH3 plasma‐treated polystyrene films utilizing gas phase chemical modification

The possibility of fabricating a highly regular nanohole array using different acid mixtures for the anodic oxidation of aluminum was investigated. The regularity of a nanohole array formed using a 1:1 sulfuric/oxalic acid mixture was quantified. Excellent regularity was obtained at around an anode voltage of 32 to 36 V. Cell pitch of the nanohole array at 36 V was 73 nm, which falls between those obtained using sulfuric acid (65 nm at 28 V) and oxalic acid (95 nm at 40 V). The present results strongly suggest that the pitch of the regular nanohole array can be varied by changing the ratio of the different acids.

Self-organization of a porous alumina nanohole array using a sulfuric/oxalic acid mixture as electrolyte

Bottom-up fill of Cu in deep submicrometer via holes was achieved through electroless plating alone for the first time. We investigated the effect of addition of inhibitor molecules to electroless Cu plating solution, and found that sulfopropyl sulfonate ~SPS! was highly effective in promoting the bottom-up fill. The tendency for bottom-up filling was enhanced by shrinkage of the hole diameter. This suggests that the diffusion flux of SPS molecules to the bottom of holes was more suppressed for smaller holes.

https://www.webpages.uidaho.edu/nanomaterials/research/Papers/Barriers/Ta/ECSSL%20Bottom%20up%20fill%20of%20copper%207(6)%20C78-C80%20(2004).pdf

Takayuki Takahagi

Papers

The formation of hydrogen passivated silicon single‐crystal surfaces using ultraviolet cleaning and HF etching

Ordered Two-Dimensional Nanowire Array Formation Using Self-Organized Nanoholes of Anodically Oxidized Aluminum

XPS analysis of NH3 plasma‐treated polystyrene films utilizing gas phase chemical modification

Self-organization of a porous alumina nanohole array using a sulfuric/oxalic acid mixture as electrolyte

Bottom-Up Fill of Copper in Deep Submicrometer Holes by Electroless Plating