PolySi-SiO 2 -ZrO 2 -SiO 2 -Si Flash Memory Incorporating a Sol-Gel-Derived ZrO 2 Charge Trapping Layer

In this paper, we propose a method for depositing the charge trapping layer of a high-k polySi-SiO 2 -ZrO 2 -SiO 2 -Si ͑SOZOS͒ memory device. In this approach, the trapping layer was formed through simple two steps: ͑i͒ spin-coating of the ZrCl 4 precursor and ͑ii͒ rapid thermal annealing for 1 min at 900°C under an oxygen atmosphere. The morphology of the ZrO 2 charge trapping layer was confirmed through X-ray photoemission spectroscopy analysis. The sol-gel-derived layer exhibited improved charge trapping in the SOZOS memory device, resulting in a threshold voltage shift of 2.7 V in the I d -V g curve, P/E ͑program/erase͒ speeds as fast as 0.1 ms, good data retention up to 10 4 s ͑only a 5% charge loss due to deep trapping in the ZrO 2 layer͒, and good endurance ͑no memory window narrowing after 10 5 P/E cycles͒. © 2006 The Electrochemical Society. ͓DOI: 10.1149/1.2337846͔ All rights reserved. The first floating-gate ͑FG͒ nonvolatile semiconductor memory was invented by Sze and Kahng in 1967. 1 Conventional FG memory uses polysilicon as a charge-storage layer surrounded by the dielectric. 2 Although floating-gate structures can achieve high densities and good program/erase ͑P/E͒ speeds and exhibit good reliability in portable flash memory devices, there are concerns regarding the ability to scale up their production. 3 When the tunneling oxide thickness is below 10 nm, the storage charge in the FG leaks readily because defects form in the tunneling oxide after repeated write-erase cycles or through direct tunneling of the current. PolySi-oxide-nitride-oxide-silicon ͑SONOS͒ memory devices have been studied recently as an approach to solving the issue of scaling FG memory. 3 Because of their spatially isolated deep-level traps, SONOS memories exhibit better charge retention than do FG memories that have a bitcell tunneling oxide layer thinner than 10 nm. As a result, a single defect in the tunneling oxide will not cause the discharge of the memory cell. 3 SONOS memory devices use silicon nitride as a charge trapping layer; the conduction band offset between the tunneling oxide and nitride is 1.05 eV. When a positive voltage is applied on the gate, the band bends downward so that the electrons in the Si subconduction band will tunnel through the tunneling oxide and a portion of the nitride will become trapped in the charge trapping layer. Before they become trapped in the nitride, the electrons must tunnel through a portion of the nitride, which degrades the program speed. In addition, because the conduction band offset of the nitride is only 1.05 eV, back tunneling of the trapped electron may also occur. To solve these problems, high-k materials are potential candidates to replace the traditional silicon nitride as the charge trapping layer. The advantages of using high-k materials are the larger band offset with the tunneling oxide and the greater number of trapping sites than those found in silicon nitride. For an HfO 2 high-k material, the conduction band offset between the tunneling oxide and HfO 2 is 1.6 eV. When programming, the electron will tunnel through a shorter distance in HfO 2 than in the nitride to become trapped. This feature can be exploited to achieve high P/E speeds. Thus, it will be beneficial to use a high-k material as the charge trapping layer in a SONOS-type memory device, provided that there are many deep-level trapping sites in the high-k material. Many technologies have been developed recently for the deposition of high-k layers onto tunneling oxides, 7-10 including atomic layer deposition ͑ALD͒, metallorganic chemical vapor deposition ͑MOCVD͒, and physical vapor deposition ͑PVD͒. In the ALD method, ZrCl 4 and H 2 O are used to prepare the ZrO 2 films. For the PVD process, a zirconium metal target is used for sputtering under ambient oxygen to deposit the ZrO 2 films. In the CVD method, ZrCl 4 is used as a precursor to deposit ZrO 2 films. Recently, we proposed the first so-called sol-gel spin-coating method for the deposition of the thin film. 11 Sol-gel spin-coating methods use metal halides hydrolyzed in organic or colloidal solvents to form precursor compounds that undergo hydrolysis, condensation, and polymerization to form metal-oxide networks. The advantages of using sol-gel methods to fabricate high-k films are that they are cheaper than ALD, PVD, and MOCVD approaches, and that various types of thin films can be synthesized. To the best of our knowledge, sol-gel spin-coating of a high-k film has yet to be reported for the preparation of charge trapping layers for flash memory devices. In this paper, we describe the fabrication of a polySi-SiO 2 -ZrO 2 -SiO 2 -Si ͑SOZOS͒ flash memory device prepared through the deposition of ZrCl 4 using the sol-gel spin-coating method and subsequent rapid thermal annealing ͑RTA͒. We performed physical and electrical analyses, including X-ray photoemission spectroscopy ͑XPS͒, I d -V g , retention, and P/E speed measurements, to evaluate the performance of the sol-gel ZrO 2 films for their potential use as charge trapping layers in SOZOS memory devices. Experimental ZrCl 4 ͑99.5%, Aldrich, USA͒ was used as the synthetic precursor of the zirconia. A mother sol solution was first prepared by dissolving ZrCl 4 in isopropanol ͑IPA; Fluka; water content Ͻ0.1%͒ under vigorous stirring in an ice bath. The sol solution was obtained by fully hydrolyzing ZrCl 4 with a stoichiometric quantity of water in IPA to yield a Zr:IPA molar ratio of 1:1000. The fabrication of the sol-gel spin-coated SOZOS memory began with LOCOS isolation process on p-type 150 mm silicon ͑100͒ substrate. At first, a 4 nm tunneling oxide layer was grown thermally at 925°C through furnace oxidation. The Zr:IPA solution ͑molar ratio: 1:1000͒ was coated using a spin-coater at 3000 rpm for 60 s at 25°C. A TEL Clean Track model-MK8 ͑Japan͒ spin-coater was used. The as-deposited thin film was initially baked at 200°C for 10 min to perform densification, followed by high-k RTA for 1 min in an O 2 atmosphere to form the ZrO 2 charge trapping layer. The film thickness, measured using an ellipsometer, was 10 nm. A 30 nm thick blocking oxide was deposited using high-density-plasmaenhanced chemical vapor deposition ͑HDPCVD͒, followed by deposition of a poly-Si gate ͑200 nm͒. After gate deposition, the following processes were applied to fabricate the SOZOS memory: * Electrochemical Society Active Member.

Star Poly( N

New star poly(N-isopropylacrylamide)-b-polyhedral oligomeric silsesquioxane (PNIPAm-b-POSS) copolymers were synthesized from octa-azido functionalized POSS (N3-POSS) and alkyne-PNIPAm, which was prepared using an alkyne-functionalized atom transfer radical polymerization (ATRP) initiator (propargyl 2-bromo-2-methylpropionamide), via click chemistry. These star PNIPAm-b-POSS copolymers undergo a sharp coil-globule transition in water at above 32°C changing from a hydrophilic state below this temperature to a hydrophobic state above it, which is similar to linear PNIPAm homopolymers. More interestingly, we found that these star polymers exhibited strong blue photoluminescence in water above a lower critical solution temperature (LCST). This photoluminescence was likely due to the constrained geometric freedom and relatively rigid structure caused by intramolecular hydrogen bonding within the star PNIPAm polymers, which exhibit an intrinsic fluorescent behavior

A Nanodot Array Modulates Cell Adhesion and Induces an Apoptosis-Like Abnormality in NIH-3T3 Cells

Micro-structures that mimic the extracellular substratum promote cell growth and differentiation, while the cellular reaction to a nanostructure is poorly defined. To evaluate the cellular response to a nanoscaled surface, NIH 3T3 cells were grown on nanodot arrays with dot diameters ranging from 10 to 200 nm. The nanodot arrays were fabricated by AAO processing on TaN-coated wafers. A thin layer of platinum, 5 nm in thickness, was sputtered onto the structure to improve biocompatibility. The cells grew normally on the 10-nm array and on flat surfaces. However, 50-nm, 100-nm, and 200-nm nanodot arrays induced apoptosis-like events. Abnormality was triggered after as few as 24 h of incubation on a 200-nm dot array. For cells grown on the 50-nm array, the abnormality started after 72 h of incubation. The number of filopodia extended from the cell bodies was lower for the abnormal cells. Immunostaining using antibodies against vinculin and actin filament was performed. Both the number of focal adhesions and the amount of cytoskeleton were decreased in cells grown on the 100-nm and 200-nm arrays. Pre-coatings of fibronectin (FN) or type I collagen promoted cellular anchorage and prevented the nanotopography-induced programed cell death. In summary, nanotopography, in the form of nanodot arrays, induced an apoptosis-like abnormality for cultured NIH 3T3 cells. The occurrence of the abnormality was mediated by the formation of focal adhesions

Plasma-made silicon nanograss and related nanostructures

Plasma-made nanostructures show outstanding potential for applications in nanotechnology. This paper provides a concise overview on the progress of plasma-based synthesis and applications of silicon nanograss and related nanostructures. The materials described here include black silicon, Si nanotips produced using a self-masking technique as well as self-organized silicon nanocones and nanograss. The distinctive features of the Si nanograss, two-tier hierarchical and tilted nanograss structures are discussed. Specific applications based on the unique features of the silicon nanograss are also presented

Bio-Inspired Supramolecular Chemistry Provides Highly Concentrated Dispersions of Carbon Nanotubes in Polythiophene

In this paper we report the first observation, through X-ray diffraction, of noncovalent uracil–uracil (U–U) dimeric π-stacking interactions in carbon nanotube (CNT)–based supramolecular assemblies. The directionally oriented morphology determined using atomic force microscopy revealed highly organized behavior through π-stacking of U moieties in a U-functionalized CNT derivative (CNT–U). We developed a dispersion system to investigate the bio-inspired interactions between an adenine (A)-terminated poly(3-adeninehexyl thiophene) (PAT) and CNT–U. These hybrid CNT–U/PAT materials interacted through π-stacking and multiple hydrogen bonding between the U moieties of CNT–U and the A moieties of PAT. Most importantly, the U···A multiple hydrogen bonding interactions between CNT–U and PAT enhanced the dispersion of CNT–U in a high-polarity solvent (DMSO). The morphology of these hybrids, determined using transmission electron microscopy, featured grape-like PAT bundles wrapped around the CNT–U surface; this tight connection was responsible for the enhanced dispersion of CNT–U in DMSO

Au@CdS Nanocomposites as a Visible-Light Photocatalyst for Hydrogen Generation from Tap Water

The Au@CdS nanocomposites have been synthesized using a combination of wet chemical and hydrothermal approaches at lower reaction temperatures. The concentrations of CdS precursors and reaction temperature can be essential in influencing photocatalytic water splitting under blue-LED light excitation. The optimized Au@CdS nanocomposites (5 mM CdS precursors and 100 °C) exhibited the highest hydrogen evolution rate of 1.041 mmolh−1 g−1, which is 175.3 times higher than CdS nanoparticles for de-ionized water under blue-LED light excitation. This result is ascribed to separate photogenerated charge carriers and increased light absorption by the Au core. The Au@CdS nanocomposites (1.204 mmolh−1 g−1) revealed significant applications in photocatalytic tap water splitting under blue-LED light excitation, which is 512.3 times higher than CdS nanoparticles. In addition, reusability experiments demonstrate that Au@CdS nanocomposites exhibit excellent stability for the long-term photocatalytic tap water splitting process. Furthermore, this research shows that Au nanoparticles decorated with CdS shells effectively achieve high-efficiency conversion from light to hydrogen energy

Weathering-Resistant Replicas Fabricated by a Three-Dimensional Printing Robotic Platform Induce Shoaling Behavior in Zebrafish

In recent decades, zebrafish have become an increasingly popular laboratory organism in several fields of research due to their ease of reproduction and rapid maturation. In particular, shoaling behavior has attracted the attention of many researchers. This article presents a fully printed robotic model used to sense and stimulate shoaling behavior in zebrafish (Danio rerio). Specifically, we exposed laboratory-fabricated replicated materials to critical acid/base/salt environments and evaluated the mechanical, optical, and surface properties after a three-month immersion period. Focusing on weatherability, these test samples maintained high tensile strength (~45 MPa) and relatively similar transmission (>85%T in the visible region), as determined by UV–vis/FTIR spectroscopy. Three-dimensional (3D) printing technology allowed printing of models with different sizes and appearances. We describe the sense of zebrafish responses to replicas of different sizes and reveal that replicas approximating the true zebrafish size (3 cm) are more attractive than larger replicas (5 cm). This observation suggests that larger replicas appear as predators to the zebrafish and cause fleeing behavior. In this study, we determined the weatherability of a high-transparency resin and used it to fabricate a fully printed driving device to induce shoaling by zebrafish. Finally, we demonstrate a weathering-resistant (for three months) 3D-printed decoy model with potential utility for future studies of outdoor shoaling behavior, and the result has the potential to replace the traditional metal frame devices used in outdoor experiments

The Multifunctionally Graded System for a Controlled Size Effect on Iron Oxide–Gold Based Core-Shell Nanoparticles

We report that Fe3O4@Au core-shell nanoparticles (NPs) serve as a multifunctional molecule delivery platform. This platform is also suitable for sensing the doxorubicin (DOX) through DNA hybridization, and the amount of carried DOX molecules was determined by size-dependent Fe3O4@Au NPs. The limits of detection (LODs) for DOX was found to be 1.839 nM. In our approach, an Au nano-shell coating was coupled with a specially designed DNA sequence using thiol bonding. By means of a high-frequency magnetic field (HFMF), a high release percentage of such a molecule could be efficiently achieved in a relatively short period of time. Furthermore, the thickness increase of the Au nano-shell affords Fe3O4@Au NPs with a larger surface area and a smaller temperature increment due to shielding effects from magnetic field. The change of magnetic property may enable the developed Fe3O4@Au-dsDNA/DOX NPs to be used as future nanocarrier material. More importantly, the core-shell NP structures were demonstrated to act as a controllable and efficient factor for molecule delivery