Martin Tschinkl

Naphthalene derivatives peri-substituted by Group 13 elements

Abstract This review focuses on the chemistry of naphthalene derivatives substituted by Group 13 moieties at the peri-positions. Depending on the nature of the Group 13 elements, different synthetic approaches have been considered. 1,8-Diborylated naphthalene complexes are conveniently prepared by metathesis of boron halides or alkoxides with 1,8-dilithionaphthalene. Such complexes can also be obtained by ring opening reaction of 1,8-boron bridged naphthalene species. Owing to the proximity of the boryl moieties, these derivatives are often sterically congested. Gallium and indium derivatives have also been prepared. In this case, however, alternative synthetic approaches have been used. These derivatives can be obtained by reaction of GaCl3 or InCl3 with 1,8-bis(trimethylstannyl)naphthalene. The transmetalation reaction of indium(I) halides with 1,8-bis(halomercurio)naphthalene has also proved useful for the synthesis of naphthalenediylindium complexes. While the development of various applications is still being explored, the 1,8-diborylated naphthalene complexes serve as bidendate Lewis acidic hosts for neutral and anionic guests. Recently, such complexes have also served to provide a scaffold for the formation of radicals that feature intramolecular one-electron σ-bonds.

Micropore Decoration with Bidentate Lewis Acids: Spontaneous Assembly of 1,2-Bis(chloromercurio)tetrafluorobenzene.

Dimethyl sulfoxide templates the assembly of 1,2-bis(chloromercurio)tetrafluorobenzene (1) into an internally Lewis acidic microporous solid of composition 1 small middle dot(DMSO)(3) (2). The channels of 2 contain both chelated and solvate DMSO molecules (omitted in the drawing for clarity), which can be partly exchanged with water molecules. The hydration-dehydration of the resulting compound is reversible.

Alumination of resorcinol and hydroquinone. An easy access to bifunctional Lewis acids

Abstract The reaction of trimethylaluminum with hydrochinone and resorcinol produces [(1,4-(Me2AlO)2C6H4)—THF]2 (1) and [(1,3-(Me2AlO)2C6H4)—THF]2 (3) respectively. Compounds 1 and 3 are poorly soluble in common solvents but readily dissolve in pyridine to give the corresponding adducts (1,4-(Me2AlO)2C6H4)—(Py)2 (2) and (1,3-(Me2AIO)2C6H4)—(Py)2 (4). The reaction of 4,6-dichlorore-sorcinol with trimethylaluminum produces the soluble chlorinated analog of compound 3 [(1,3-(Me2AlO)2-4,6-Cl2C6H2)—THF]2 (5). As indicated by NMR, the dimeric structure of 5 is fluxional in solution. Upon addition of chloride or t-butoxide anions to solution of 5 in THF, 27Al NMR monitoring indicates that there is formation of anionic complexes but that the chelation of the anionic hosts by the two aluminum centers present in the [1,3-(Me2AlO)2-4,6-Cl2C6H2] unit does not occur.

Preparation of mercury–anthracene derivatives: π–π-stacking, Hg⋯Cl and Hg⋯π interactions in the X-ray crystal structure of polymeric 9-chloromercurioanthracene

Abstract 9-Lithio-anthracene and 9,10-dilithioanthracene react with mercury(II)chloride in THF to afford 9-chloromercurio-anthracene ( 1 ) and 9,10-bis(chloromercurio)-anthracene ( 2 ), respectively. Compounds 1 and 2 have been characterized by 1 H-, 13 C- and 199 Hg-NMR spectroscopy as well as by elemental analysis and CI mass spectrometry. The structure of 1 has been determined by X-ray crystallography. In the solid state, 1 forms polymeric chains that are cemented by concomitant π–π-stacking, Hg⋯Cl and Hg⋯π-system interactions.

Synthesis and structure of fluorinated dialacycles

Addition of THF to a solution of dimeric 1,2-bis(chloromethylalumino) tetrafluorobenzene ( 1 ) induces a ring contraction process that results in the formation of a mixture of three dialacycles as shown by 1 H- and 19 F-NMR. The three diaalacycles have been identified as 9-methyl-10-chloro-9,10-dihydro-9,10-diala-octafluoroanthracene bis(THF) adduct ( 2a ), 9,10-dichloro-9,10-dihydro-9,10-diala-octafluoroanthracene bis(THF) adduct ( 2b ) and 9,10-dimethyl-9,10-dihydro-9,10-diala-octafluoroanthracene bis(THF) adduct ( 2c ). A co-crystal of these three compounds was examined by X-ray crystallography, confirming the structure of the dialacycle and revealing that the central six-membered ring is in a chair conformation. In 2 , each aluminum center is four-coordinate with a slightly distorted tetrahedral geometry. The coordination sites of the aluminum are occupied by the ipso -carbon atoms of the tetrafluorophenylene units, the oxygen atom of a coordinated THF molecule, and either a methyl group (50%) or a chloride ion (50%).

Comparison of new film nozzle with standard nozzle for aqueous puddle developing of photomasks

With shrinking feature sizes there is a growing demand for improved uniformity values and defect levels especially for aqueous develop during photomask processing. Standard nozzle systems with discrete dispense channels for applying the developer medium onto the photomask surface may cause non-uniformities. This results in characteristic imprints in CD-uniformity reflecting the nozzle design used during the develop process step. These can lead on the one hand to an increased number and various types of defects and on the other hand to variations in CD-uniformity. A new puddle nozzle design for the STEAG HamaTechs ASP5500 has been developed to address this issue. Instead of discrete dispense holes the developer medium is applied onto the substrate surface by a full-width film. This media film is applied uniform across the substrate and has low impact onto the photomask surface. By combining the new nozzle design with gas-less high volume dispense pumps a very uniform and defect-free dispense can be achieved. The uniformity and defect performance of the new film nozzle will be presented and compared to a standard dispense nozzle system. The study has been done on masks with Chemically Amplified Resist (CAR).

Investigation of e-beam sensitive negative-tone chemically amplified resists for binary mask making

Negative-tone chemically amplified resists MES-EN1G (JSR), FEN-270 (Fujifilm ARCH), EN-024M (TOK) and NEB-22 (Sumitomo) were evaluated for binary mask making. The investigations were performed on an advanced tool set comprising a 50kV e-beam writer Leica SB350, a Steag Hamatech hot/cool plate module APB5000, a Steag Hamatech developer ASP5000, an UNAXIS MASK ETCHER III and a SEM LEO1560 with integrated CD measurement option. We investigated and compared the evaluated resists in terms of resolution, e-beam sensitivity, resist profile, post exposure bake sensitivity, CD-uniformity, line edge roughness, pattern fidelity and etch resistance. Furthermore, the influence of post coating delay and post exposure delay in vacuum and air was determined.

1,2-Bis(chloromethylalumino)tetrafluorobenzene, an aluminium-based bifunctional Lewis acid with a perfluorinated backbone

1,2-Bis(trimethylstannyl)tetrafluorobenzene reacts with chlorodimethylaluminium(III) to afford dimeric 1,2-bis(chloromethylalumino)tetrafluorobenzene the structure of which has been determined by X-ray analysis.

Application of a wafer development process to mask making

Recently, the design of integrated circuits has become more and more complicated due to higher circuit densities. In particular for logic applications, the design is no longer uniform but combines different kinds of circuits into one mask layout resulting in stringent criteria for both wafer and photomask manufacturing. Photomask CD uniformity control and defectivity are two key criteria in manufacturing today’s high-end reticles, and they are both strongly impacted by the mask developing process. A new photomask develop tool (ACT-M) designed by Tokyo Electron Limited (TEL) has been installed at the Advanced Mask Technology Center (AMTC) in Dresden, Germany. This ACT-M develop tool is equipped with a standard NLD nozzle as well as an SH nozzle which are both widely used in wafer developing applications. The AMTC and TEL used the ACT-M develop tool to adapt wafer puddle develop technology to photomask manufacturing, in an attempt to capture the same optimum CD control enjoyed by the wafer industry. In this study we used the ACT-M develop tool to examine CD uniformity, local loading and defect control on P-CAR and N-CAR photomasks exposed with 50keV e-beam pattern generators. Results with both nozzle types are reported. CD uniformity, loading, and defectivity results were sufficient to meet 65-nm technology node requirements with these nozzles and tailored made develop recipes for photomask processing.

Templated assembly of 1,2-bis(chloromercurio) tetrafluorobenzene in the presence of THF

Slow evaporation of a THF solution containing the bidentate Lewis acid 1,2-bis(chloromercurio) tetrafluorobenzene (1) , yields colorless crystals of the complex 1⋅μ2-THF (2) as indicated by elemental analysis, thermal gravimetric analysis and 13C CPMAS solid-state NMR spectroscopy. As shown by X-ray analysis, the oxygen atom of the THF molecules bridges the two mercury center of the bidentate Lewis acid. Compound 2 forms an extended structure that features channels filled with THF molecules. In this structure, the individual molecules of the organomercurial are held together by π-π and Hg ⋅⋅⋅ Cl interactions. Immersion of 2 in water results in THF loss to afford 1,2-bis(chloromercurio) tetrafluorobenzene in a pure form. Exposure to THF vapor results in a stoichiometric uptake and formation of a solid whose composition corresponds to that of 2.