Chemical Bath Deposition of ZnO Nanowires Using Copper Nitrate as an Additive for Compensating Doping.

The controlled incorporation of dopants like copper into ZnO nanowires (NWs) grown by chemical bath deposition (CBD) is still challenging despite its critical importance for the development of piezoelectric devices. In this context, the effects of the addition of copper nitrate during the CBD of ZnO NWs grown on Au seed layers are investigated in detail, where zinc nitrate and hexamethylenetetramine are used as standard chemical precursors and ammonia as an additive to tune the pH. By combining thermodynamic simulations with chemical and structural analyses, we show that copper oxide nanocrystals simultaneously form with ZnO NWs during the CBD process in the low-pH region associated with large supersaturation of Cu species. The Cu(II) and Zn(II) speciation diagrams reveal that both species show very similar behaviors, as they predominantly form either X2+ ions (with X = Cu or Zn) or X(NH3)42+ ion complexes, depending on the pH value. Owing to their similar ionic structures, Cu2+ and Cu(NH3)42+ ions preferentially formed in the low- and high-pH regions, respectively, are able to compete with the corresponding Zn2+ and Zn(NH3)42+ ions to adsorb on the c-plane top facets of ZnO NWs despite repulsive electrostatic interactions, yielding the significant incorporation of Cu. At the highest pH value, additional attractive electrostatic interactions between the Cu(NH3)42+ ion complexes and negatively charged c-plane top facets further enhance the incorporation of Cu into ZnO NWs. The present findings provide a deep insight into the physicochemical processes at work during the CBD of ZnO NWs following the addition of copper nitrate, as well as a detailed analysis of the incorporation mechanisms of Cu into ZnO NWs, which are considered beyond the only electrostatic forces usually driving the incorporation of dopants such as Al and Ga.

Improvement of AlN Film Quality Using Plasma Enhanced Atomic Layer Deposition with Substrate Biasing.

In recent years, plasma enhanced atomic layer deposition (PEALD) has emerged as a key method for the growth of conformal and homogeneous aluminum nitride (AlN) films at the nanoscale. In this work, the utilized PEALD reactor was equipped not only with a traditional remote Inductively Coupled Plasma source but also with an innovative additional power supply connected to the substrate holder. Thus, we investigate here the substrate biasing effect on AlN film quality deposited on (100) silicon. We report that by adjusting the ion energy via substrate biasing, the AlN film quality can be significantly improved. Indeed, compared to films commonly deposited without bias, AlN deposited with a platen power of 5 W displays a 14% increase in the number of N-Al bonds according to X-ray spectroscopy analysis. Moreover, after having integrated them into Metal-AlN-Si capacitors, the 5 W AlN film exhibits a permittivity increase from 4.5 to 7.0 along with a drastic drop of leakage current density of more than 5 orders of magnitude. The use of substrate biasing during PEALD is thereby a promising strategy for the improvement of AlN film quality.

Use of optical spacers to enhance infrared Mueller ellipsometry sensitivity: application to the characterization of organic thin films.

Mueller ellipsometry in the mid-infrared (IR) spectral range can be used to obtain information about chemical composition through the vibrational spectra of samples. In the case of very thin films (<100 nm), the ellipsometric spectral features due to vibrational absorption are in general quite weak, and sometimes they are hidden by the noise in the measured data. In this work, we present one method based on the use of optical spacers as a tool to enhance the sensitivity of IR Mueller ellipsometry. An optical spacer is a thin film made of a known material which is between the substrate and the layer of interest. We show that, when the thickness of the two layers fulfills a given condition, the spectral features due to vibrational absorptions are enhanced. We explain the enhancement effect in terms of the Airy formula. The theoretical discussion is illustrated with two examples. We analyzed polystyrene thin films deposited on silicon wafers. Some of the wafers were covered by a thin film of thermal silicon dioxide (SiO2), which was used as a spacer. The results show the suitability of the proposed technique to overcome the lack of sensitivity in ellipsometric measurements when it comes to working with either very thin films or materials with low absorption.

Plastid transformation in soybean.

The biotechnological potential of plastid genetic engineering has been illustrated in a limited number of higher plant species. We have developed a reproducible method to generate plastid transformants in soybean (Glycine max), a crop of major agronomic importance. The transformation vectors are delivered to embryogenic cultures by the particle gun method and selection performed using the aadA antibiotic resistance gene. Homoplasmy is established rapidly in the selected events without the need for further selection or regeneration cycles, and genes of interest can be expressed at a high level in green tissues. This is a significant step toward the commercial application of this technology.

Preparation and characterization of silver substrates coated with antimony-doped SnO2 thin films for surface plasmon resonance studies.

This paper reports on the preparation of silver/antimony-doped tin oxide (Ag/SnO(2):Sb) hybrid interfaces using magnetron sputtering and their characterization. The influence of the Sn target composition (doping with 2 or 5% Sb) on the electrochemical and electrical characteristics of the hybrid interface was investigated using X-ray photoelectron spectroscopy (XPS), sheet resistance measurements, cyclic voltammetry, scanning tunneling microscopy (STM) and surface plasmon resonance (SPR). The best interface in terms of electrical conductivity and SPR signal is a hybrid interface with a 8.5 +/- 0.3 nm thick SnO(2):Sb layer obtained from a Sn target with 2% Sb deposited on 38 nm thick silver film. Different strategies to link functional groups onto the Ag/SnO(2):Sb interface are also presented.

Generation and characterization of soybean and marker-free tobacco plastid transformants over-expressing a bacterial 4-hydroxyphenylpyruvate dioxygenase which provides strong herbicide tolerance.

Plant 4-hydroxyphenylpyruvate dioxygenase (HPPD) is part of the biosynthetic pathway leading to plastoquinone and vitamin E. This enzyme is also the molecular target of various new bleaching herbicides for which genetically engineered tolerant crops are being developed. We have expressed a sensitive bacterial hppd gene from Pseudomonas fluorescens in plastid transformants of tobacco and soybean and characterized in detail the recombinant lines. HPPD accumulates to approximately 5% of total soluble protein in transgenic chloroplasts of both species. As a result, the soybean and tobacco plastid transformants acquire a strong herbicide tolerance, performing better than nuclear transformants. In contrast, the over-expression of HPPD has no significant impact on the vitamin E content of leaves or seeds, quantitatively or qualitatively. A new strategy is presented and exemplified in tobacco which allows the rapid generation of antibiotic marker-free plastid transformants containing the herbicide tolerance gene only. This work reports, for the first time, the plastome engineering for herbicide tolerance in a major agronomic crop, and a technology leading to marker-free lines for this trait.

Stability of soybean recombinant plastome over six generations.

The stability of a plastid transgene has been evaluated in soybean transformants over six generations. These transformants had integrated the aadA selection cassette in the intergenic region between the rps12/7 and trnV genes. Three independent homoplasmic T0 transformation events were selected and ten plants from each event propagated to generation T5 in the absence of selection pressure. No transgene rearrangement nor wild-type plastome were detected in generation T5 by Southern blot analysis. All tested progenies were uniformly resistant to spectinomycin. Therefore, soybean transformants of generations T0 and T5 appear to be genetically and phenotypically identical.

p-Hydroxyphenylpyruvate dioxygenase inhibitor-resistant plants.

The enzyme p-hydroxyphenylpyruvate dioxygenase (HPPD) catalyzes the formation of homogentisic acid, the aromatic precursor of plastoquinone and vitamin E. HPPD is the specific target of several herbicide families: isoxazoles, triketones and pyroxazoles. Its inhibition results in the depletion of the plant plastoquinone and vitamin E pools, leading to bleaching symptoms. These herbicides are very potent for the selective pre- and in some cases post-emergence control of a wide range of broadleaf and grass weeds in maize and rice. Their herbicidal potential raised interest in the development of highly resistant transgenic crops. This goal was first achieved by over-expression of a bacterial HPPD in crop plants, and an increased level of resistance was obtained by using a mutant enzyme. A second strategy based on bypassing HPPD in the production of homogentisate was then developed. Recently, a third strategy of resistance based on the increase of p-hydroxyphenylpyruvate substrate flux has been developed. This was achieved by the introduction of the yeast prephenate dehydrogenase gene (PDH) into transgenic plants already overexpressing HPPD. In addition to a high level of herbicide resistance, a massive accumulation of vitamin E, mainly tocotrienols, was observed in leaves of the transgenic HPPD-PDH plants.

Generation of fertile transplastomic soybean.

We describe here the development of a plastid transformation method for soybean, a leguminous plant of major agronomic interest. Chloroplasts from embryogenic tissue of Glycine max have been successfully transformed by bombardment. The transforming DNA carries a spectinomycin resistance gene (aadA) under the control of tobacco plastid regulatory expression elements, flanked by two adjacent soybean plastome sequences allowing its targeted insertion between the trnV gene and the rps12/7 operon. All generated spectinomycin resistant plants were transplastomic and no remaining wild type plastome copies were detected. No spontaneous mutants were obtained. The transformation efficiency is similar to that of tobacco plastids. All transplastomic T0 plants were fertile and T1 progeny was uniformly spectinomycin resistant, showing the stability of the plastid transgene. This is the first report on the generation of fertile transplastomic soybean.