7CVD diamond fi lms are currently prepared with high purity, and these materials resist electrical breakdown in high electric fi elds and exhibit electron and hole mobilities that are the highest among wide bandgap semiconductors. Dopants Diamond is a unique material that often exhibits extreme properties compared to other materials. Discovered about 30 years ago, the use of hydrogen in plasma-enhanced chemical vapor deposition (CVD) has enabled the growth and coating of diamond in fi lm form on various substrate materials. CVD diamond research has been actively continued subsequently to develop new understanding and approaches for the growth and processing of this fascinating material. Currently, the study and development of diamond fi lms has enabled a wide range of applications based on the combination of unique and extreme properties of diamond and the variety of fi lm properties obtainable through tuning the microstructure, morphology, impurities, and surfaces. This issue of MRS Bulletin introduces the latest research, recent applications, and the challenges ahead for CVD diamond fi lms.
Diamond-like carbon (DLC) films have been extensively applied in industries owing to their excellent characteristics such as high hardness. In particular, there is a growing demand for their use as protective films for mechanical parts owing to their excellent wear resistance and low friction coefficient. DLC films have been deposited by various methods and many deviate from the DLC regions present in the ternary diagrams proposed for sp3 covalent carbon, sp2 covalent carbon, and hydrogen. Consequently, redefining the DLC region on ternary diagrams using DLC coatings for mechanical and electrical components is urgently required. Therefore, we investigate the sp3 ratio, hydrogen content, and other properties of 74 types of amorphous carbon films and present the classification of amorphous carbon films, including DLC. We measured the sp3 ratios and hydrogen content using near-edge X-ray absorption fine structure and Rutherford backscattering-elastic recoil detection analysis under unified conditions. Amorphous carbon films were widely found with nonuniform distribution. The number of carbon atoms in the sp3 covalent carbon without bonding with hydrogen and the logarithm of the hydrogen content were inversely proportional. Further, we elucidated the DLC regions on the ternary diagram, classified the amorphous carbon films, and summarized the characteristics and applications of each type of DLC.
The utility of various kinds of acid salts of azole derivatives as promoters for the condensation of a nucleoside phosphoramidite and a nucleoside is investigated. Among the salts, N-(phenyl)imidazolium triflate, N-(p-acetylphenyl)imidazolium triflate, N-(methyl)benzimidazolium triflate, benzimidazolium triflate, and N-(phenyl)imidazolium perchlorate have shown extremely high reactivity in a liquid phase. These reagents serve as powerful activators of deoxyribonucleoside 3'-(allyl N,N-diisopropylphosphoramidite)s or 3'-(2-cyanoethyl N,N-diisopropylphosphoramidite)s employed in the preparation of deoxyribonucleotides, and 3'-O-(tert-butyldimethylsilyl)ribonucleoside 2'-(N,N-diisopropylphosphoramidite)s or 2'-O-(tert-butyldimethylsilyl)ribonucleoside 3'-(N,N-diisopropylphosphoramidite)s used for the formation of 2'-5' and 3'-5' internucleotide linkages between ribonucleosides, respectively. The azolium salt has allowed smooth and high-yield condensation of the nucleoside phosphoramidite and a 5'-O-free nucleoside, in which equimolar amounts of the reactants and the promoter are employed in the presence of powdery molecular sieves 3A in acetonitrile. It has been shown that some azolium salts serve as excellent promoters in the solid-phase synthesis of oligodeoxyribonucleotides and oligoribonucleotides. For example, benzimidazolium triflate and N-(phenyl)imidazolium triflate can be used as effective promoters in the synthesis of an oligodeoxyribonucleotide, (5')CGACACCCAATTCTGAAAAT(3') (20mer), via a method using O-allyl/N-allyloxycarbonyl-protected deoxyribonucleoside 3'-phosphoramidites or O-(2-cyanoethyl)/N-phenoxyacetyl-protected deoxyribonucleotide 3'-phosphoramidite as building blocks, respectively, on high-cross-linked polystyrene resins. Further, N-(phenyl)imidazolium triflate is useful for the solid-phase synthesis of oligoribonucleotides, such as (5')AGCUACGUGACUACUACUUU(3') (20mer), according to an allyl/allyloxycarbonyl-protected strategy. The utility of the azolium promoter has been also demonstrated in the liquid-phase synthesis of some biologically important substances, such as cytidine-5'-monophosphono-N-acetylneuraminic acid (CMP-Neu5Ac) and adenylyl(2'-5')adenylyl(2'-5')adenosine (2-5A core).
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