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Network-based biocomputation (NBC) relies on accurate guiding of biological agents through nanofabricated channels produced by lithographic patterning techniques. Here, we report on the large-scale, wafer-level fabrication of optimized microfluidic channel networks (NBC networks) using electron-beam lithography as the central method. To confirm the functionality of these NBC networks, we solve an instance of a classical non-deterministic-polynomial-time complete (“NP-complete”) problem, the subset-sum problem. The propagation of cytoskeletal filaments, e.g., molecular motor-propelled microtubules or actin filaments, relies on a combination of physical and chemical guiding along the channels of an NBC network. Therefore, the nanofabricated channels have to fulfill specific requirements with respect to the biochemical treatment as well as the geometrical confienement, with walls surrounding the floors where functional molecular motors attach. We show how the material stack used for the NBC network can be optimized so that the motor-proteins attach themselves in functional form only to the floor of the channels. Further optimizations in the nanolithographic fabrication processes greatly improve the smoothness of the channel walls and floors, while optimizations in motor-protein expression and purification improve the activity of the motor proteins, and therefore, the motility of the filaments. Together, these optimizations provide us with the opportunity to increase the reliability of our NBC devices. In the future, we expect that these nanolithographic fabrication technologies will enable production of large-scale NBC networks intended to solve substantially larger combinatorial problems that are currently outside the capabilities of conventional software-based solvers. more...

The synthesis of 1‐Fc‐ (3), 1‐Br‐6‐Fc‐ (5 a), 2‐Br‐7‐Fc‐ (7 a), 1,6‐Fc2‐ (5 b), 2,7‐Fc2‐pyrene (7 b), 3,6‐Fc2‐9,10‐phenanthrenedione (10), and 3,6‐Fc2‐9,10‐dimethoxyphenanthrene (12; Fc=Fe(η5‐C5H4)(η5‐C5H5)) is discussed. Of these compounds, 10 and 12 form 1D or 2D coordination polymers in the solid state. (Spectro)Electrochemical studies confirmed reversible Fc/Fc+ redox events between −130 and 160 mV. 1,6‐ and 2,7‐Substitution in 5 a (E°′=−130 mV) and 7 a (E°′=50 mV) influences the redox potentials, whereas the ones of 5 b and 7 b (E°′=20 mV) are independent. Compounds 5 b, 7 b, 10, and 12 show single Fc oxidation processes with redox splittings between 70 and 100 mV. UV/Vis/NIR spectroelectrochemistry confirmed a weak electron transfer between FeII/FeIII in mixed‐valent [5 b]+ and [12]+. DFT calculations showed that 5 b non‐covalently interacts with the single‐walled carbon nanotube (SWCNT) sidewalls as proven by, for example, disentangling experiments. In addition, CV studies of the as‐obtained dispersions confirmed exohedral attachment of 5 b at the SWCNTs., Ferrocene complexes: The synthesis of 1‐Fc‐, 1‐Br‐6‐Fc‐, 2‐Br‐7‐Fc‐, 1,6‐Fc2‐, 2,7‐Fc2‐pyrene, 3,6‐Fc2‐9,10‐phenanthrenedione, and 3,6‐Fc2‐9,10‐dimethoxyphenanthrene (Fc=Fe(η5‐C5H4)(η5‐C5H5)) is discussed. Two of these compounds form 1D or 2D coordination polymers in the solid state. (Spectro)electrochemical studies confirmed reversible Fc/Fc+ redox events between −130 and 160 mV. more...

The adsorption of chiral molecules was recently shown to trigger a change in the magnetisation of mesoscopic magnetic domains in a ferromagnetic underlayer. In this work, we investigated the macroscopic (magneto-)optical response of chemisorbed α-helical polyalanine self-assembled monolayers (SAMs) on a gold and gold-capped-cobalt thin film on Au substrates using spectroscopic ellipsometry and magneto-optical Kerr effect spectroscopy and microscopy. The optical and magneto-optical spectra reveal selective chemisorption of the α-helical polyalanine molecules depending on the orientation of the substrate remanent magnetisation during the SAMs process. Moreover, a sign change of the magneto-optical response was observed in some of the magnetic substrates after the chiral SAMs formation. more...

The ¦-ketoiminato complex [Pd(OAc)L] (3) can be synthesized by the reaction of bis(benzoylacetone)diethylenetriamine (1, = LH) with [Pd(OAc)2] (2). The structure of 3 in the solid state has been determined by single X-ray diffraction analysis. Complex 3 crystallizes as a dimer (3 2), which is formed by hydrogen bonds between NH and OOAc functionalities of two adjacent ligands. Each of the Pd atoms is complexed by one ON2 donor unit of the polydentate ligand L − and an acetate group. Pd–Pd interactions and hydrogen bond formation between a NH and the C=O acetate moiety lead to a [4 + 2] coordination at Pd. The non-coordinated part of L exists in its ¦-keto-enamine form. The thermal decomposition behavior of 3 2 was studied by TG (thermogravimetry) and TG-MS showing that 3 2 decomposes between 200 and 500°C independent of the applied atmosphere. Under oxygen PdO is produced, while under argon Pd is formed as confirmed by PXRD measurements. Complex 3 2 was applied as a spin-coating precursor (conc. 0.1 mol L−1, volume 1.5 mL, 3000 rpm, deposition time 6 min, heating rate 50 K min−1, holding time 60 min (Ar) and 120 min (air) at T = 800°C). The as-obtained samples are characterized by granulated particles of Pd/PdO on the substrate surface. EDX (energy-dispersive X-ray spectroscopy) and XPS (X-ray photoelectron spectroscopy) measurements confirmed the formation of Pd (Ar) or PdO (O2) with up to 12 mol% C impurity. more...

Macroscopic materials made of two-dimensional components such as flakes of graphene or transition metal dichalcogenides represent a material class with great potential for large-scale applications. Depending on the structure, they can inherit the exceptional properties of the nanoscale building blocks while developing new features on the macroscopic scale. Supported by theoretical considerations and finite element analysis, we developed a network simulation method to model 2D-based electrical conductors. Here, we systematically explain the technical and methodological details of our approach, using the example of graphene-based conductor materials. Apart from the raw material properties, we discuss the importance of homogeneity and internal structure of the material. Our findings are supported by finite element analysis. We demonstrate the application of our method by studying the intricate interaction of several material parameters and the resulting effect on the macroscopic network. Finally, we provide guidelines for adapting our method to different physical situations. more...

Complexes [Fe(β-diketonate)3] (β-diketonate = 2-acetylcyclopentanoate (3a), = 2-acetylcyclohexanoate (3b), = 4,4-dimethyl-1-phenyl pentanedionate (3c)) were synthesized by the reaction of FeCl3 with the respective β-diketones in presence of NaOH. The molecular structures of 3a and 3c in the solid state are discussed, confirming an octahedral coordination sphere at Fe(III) setup by the three bidentate-bonded β-diketonato ligands. Variation of the β-diketonato ligands allowed to influence the thermal behavior and vapor pressure of the complexes. TG-MS ( = Thermo Gravimetry-Mass Spectrometry) studies, exemplarily carried out on 3a, confirmed the release of the β-diketonate ligands. Complexes 3a–c were applied as MOCVD (=Metal-Organic Chemical Vapor Deposition) precursors for the deposition of Fe2O3 thin films on silicon substrates. It was found that with 3a,b, conformal and dense carbon-free γ- and α-Fe2O3 layers were produced at 450 °C, which was verified by scanning electron microscopy, energy dispersive X-ray spectroscopy and X-ray photon spectroscopy. more...

The performance of CoFeB/MgO tunnel junctions is strongly dependent on an annealing step at the end of the fabrication process to first, set a reference magnetization through the exchange bias effect and second, to crystallize the MgO/CoFe layers while boron diffuses out, in order to maximize the magnetoresistance ratio. In this regard, a laser-induced annealing process presents several advantages against traditional oven annealing techniques, providing a scalable approach with no limitations regarding the defined reference magnetization that can be aligned in different directions on a wafer. This paper concentrates on the mechanisms and dependences of laser annealing on the magnetic properties in comparison to the standard vacuum oven annealing, providing a first insight for the applicability of laser annealing for CoFeB-/MgO-based magnetic tunnel junctions with all concomitant needs. more...

Wafer-level catalytic chemical vapour deposition (CCVD) of semiconducting enriched single-walled carbon nanotubes (sc-SWCNTs) with high quality is of high interest for industrial realization of SWCNT-based sensor and electronic applications. While bimetallic catalysts systems are known to favor type-enriched growth of SWCNTs, surface morphological evolution of different bimetallic catalyst stacks during catalyst conditioning as well as its impact on SWCNTs growth is not clearly understood. Here, we present a systematic study on the effect of bimetallic catalyst composition, layer stack thickness configuration as well as CCVD process parameters on the composition of grown SWCNTs. Besides the well-known Co and Co-Mo system, the Co-Ru system was investigated. We found that in case of Co-Mo bimetallic system, highest degree of sc-SWCNTs content is achieved using bilayer configuration Co-Mo:0.2–0.1 nm processed at 810 °C and 20 kPa total pressure. In case of Co-Ru bimetallic system, highest degree of sc-SWCNTs content is achieved using Co-Ru:0.1–0.1 nm processed at 840 °C and 10 kPa total pressure. more...

The synthesis of well-aligned and type-enriched semiconducting single-walled carbon nanotubes (sc-SWCNTs) with high quality by means of catalytic chemical vapour deposition (CCVD) on wafer-level are essential prerequisites for the implementation of nanodevices for sensor and electronic applications. In particular, the Co-Mo bilayer catalyst system is promising due to its ability to grow semiconducting enriched SWCNTs by CCVD. However, there is still a gap in understanding how to adjust catalyst properties aiming further improvements in SWCNTs film composition and morphology. In particular, surface morphological evolution during catalyst conditioning as well as its impact on SWCNT growth are not clearly understood. Here we present a systematic investigation on effects of catalyst support layer, catalyst preparation conditions, catalyst type and composition as well as gas composition for catalyst treatments on the size of catalyst nanoparticles (NPs) and the properties of CCVD grown SWCNTs. We show that H2 treatment favors the formation of small catalyst NPs with narrow size distribution in the case of Al2O3 support layer. Moreover, we correlate the growth rates, quality of SWCNTs structures and sc-SWCNTs content with the Co-Mo catalyst morphological evolution. Evolution of quality, height and sc-SWCNTs content with respect to the different catalyst configurations and catalyst deposition conditions.Display Omitted Using Al2O3 support layer with certain morphology and annealing under H2, catalyst NP with small size and narrow size distribution can be formed.Differentiated study on the effect of different bilayer CoźMo catalyst configuration on the properties of grown SWCNTs.Lowering catalyst deposition rate is a straightforward approach to fabricate catalyst layer with low surface roughness and small NP size.Bilayer CoźMo:0.5ź0.1nm prepared by low catalyst deposition rate shows a high potential for future applications. more...

Cobalt oxides are a promising anode material for lightweight rechargeable lithium-ion batteries. Thus, the low temperature deposition of cobalt oxide is a key-technology for the production of flexible energy storage systems enabling novel application opportunities such as wearables. To satisfy the emerging process requirements the dicobaltatetrahedrane precursor [Co2(CO)6(η2-H–CC–nC5H11)] was investigated for the low-temperature chemical vapor deposition of cobalt oxides. Oxygen, water vapor and a combination of both were examined as possible co-reactants. In particular, wet oxygen proves to be an appropriate oxidizing agent providing dense and high purity cobalt oxide films within the examined temperature range from 130 °C to 250 °C. Film growth occurred at temperatures as low as 100 °C making this process suitable for the coating of temperature-sensitive and flexible substrates. more...

The synthesis of compounds [Mn(η5–C5H4SiMe3)(CO)3] (1), [Mn(η5–C5H3-1-SiMe3-3-Me)(CO)3] (2), [Mn(η5–C5H4tBu)(CO)3] (3), [Mn(η5–C5Me5)(CO)3] (4) and [Mn(η5–C5H7)(CO)3] (5) and their potential use as metal-organic chemical vapor deposition (MOCVD) precursors for the deposition of manganese-based layers is reported. The thermal behavior of 1–5 was studied by thermogravimetry showing that these compounds evaporate in the temperature range of 363–498 K depending on the cyclopentadienyl substituents and the type of pentadienyl used. Vapor pressure measurements indicate that all compounds possess vapor pressures between 60 and 630 Pa at 353 K. Compounds 1–5 could be successfully applied in manganese-based film deposition without activation steps prior to the MOCVD experiments. The as-deposited thin layers were characterized by scanning electron microscopy, energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy and X-ray powder diffraction. Under comparatively mild conditions, whereas 5 possesses the lowest deposition temperature (553 K), dense and conformal layers with growth rates up to 7.0 nm min− 1 (5) could be deposited. Metal carbonyls 1 and 2 featuring a SiMe3 group produced Si-containing manganese-based films. The as-deposited layers from 1, 2, 4 and 5 contain carbon impurities (5–8.9 mol-%), while the films from 3 are carbon-free. The layers from 1 and 2 consist of mainly manganese silicate and manganese oxide, whereas those obtained from 3 to 5 are composed of manganese oxides. more...

Direct synthesis of poly (sodium 4-styrenesulfonate) (P(NaSS)) inside the channel of single-walled carbon nanotube (SWCNT) field-effect transistors (FETs), is shown to be highly beneficial in improving the device parameters. Starting with monomeric compounds, the FET-channel was in-situ polymerized, using the self-initiated photografting and photopolymerization process. Upon formation of the P(NaSS) polymer matrix, we report improved device-to-device consistency, lower variability in the threshold voltage, higher drain currents and higher on/off ratios. Annealing in vacuum was shown to further improve the device performance and induce an ambipolar behavior. Moreover, those FET devices showed a long-term stability even under ambient environment. more...

Organosilicate-glass films with a varying ratio of terminal methyl and bridging ethylene groups are synthesized using 1,2-bis(trimethoxysilyl)ethane/methyltrimethoxysilane mixtures and sol-gel technology. The films are characterized by Fourier Transform Infrared spectroscopy, Ellipsometric Porosimetry and Positron Annihilation Spectroscopy. The hard bake at 400 °C generates the final pore structure, which depends on the curing environment. It is shown that ethylene bridge is destructed during the hard bake in the air via formation of peroxide radicals that form ≡SiOH during the transformation. Continuous hard bake leads to condensation of silanol groups and form a structure similar to the ordinary silica. The pore size of highly porous materials (>30%) is larger in air cured films. Destruction of the ethylene bridge makes the films matrix soft and micropores collapse due to the capillary forces during the template evaporation. It leads to the film shrinkage, increases the size of internal voids. The air cured samples showed better mechanical properties than N2 cured ones although in the last case ethylene bridging groups were preserved. The reason is that the collapse of micropores increase the internal density and creates more favorable condition for condensation of silanol groups. more...

The synthesis of complexes [M(OCHMeCH

We report about the inkjet printing of multi-walled carbon nanotubes (MWCNTs) for conductive tracks. The MWCNTs were grown by chemical vapor deposition allowing a defined length and diameter. An inkjet-printable ink formulation was prepared by dispersing the MWCNTs in water. Inkjet-printed high resolution patterns were obtained by printing the prepared ink formulation on silicon wafers utilizing evaporation-driven self-assembly processes. After the deposition of the ink, the solvent evaporation induces material flows within the liquid moving the MWCNTs preferably to the edges of the printed patterns as well as to the print starting position where they assemble. Atomic force microscopy (AFM) reveals a preferential orientation of the deposited MWCNTs. The resulting deposit pattern is well-known as coffee-ring effect which is used here to enable high resolution printing and self-ordering of the MWCNTs. Depending on different print parameters such as drop spacing or substrate temperature, conductive track widths in the range of 5–15 μm were achieved with a electrical resistivity of about 3.9·10−3 to 5.6·10−3 Ω·m measured by current-sensitive AFM. more...

Single-walled carbon nanotubes (SWCNTs) were decorated with metal nanoparticles. Using a complementary analysis with spatially resolved micro-Raman spectroscopy, high resolution transmission electron microscopy, electron diffraction, and tip-enhanced Raman spectroscopy, we show that the SWCNTs form bundles in which smaller diameter SWCNTs are the ones preferentially affected by the presence of Au and Ag nanoparticles. This result is exploited to evaluate the structural organization of SWCNTs with mixed chiralities in bundles, leading us to postulate that smaller diameter SWCNTs surround larger ones. We found that this effect occurs for very distinct scenarios including SWCNTs both in nanometer thin films and in field effect transistor configurations at the wafer-level, suggesting a universal phenomenon for SWCNTs deposited from dispersions. more...

Here we present a holistic wafer-level approach for the fabrication of highly sensitive electromechanical transducers, using the intrinsic piezoresistive effect of enriched semiconducting single-walled carbon nanotubes (SWCNTs). Therefore membrane based demonstrators were fabricated on 150 mm wafers using MEMS compatible micromachining. Carbon nanotube field-effect transistors were positioned at membrane sites with the highest strain upon pressure driven actuation. The giant piezoresistive effect of SWCNTs was proved and quantified. We derived the gauge factor to be more than 600, which is significantly higher than for common silicon strain gauges. more...

The interactions between carbon nanotubes (CNTs) and metal adatoms as well as metal contacts are studied by means of ab initio electronic structure calculations. We show that the electronic properties of a semiconducting (8,4) CNT can be modified by small amounts of Pd adatoms. Such a decoration conserves the piezoelectric properties of the CNT. Besides the electronic influence, the stability of a single adatom, which is of big importance for future technology applications, is investigated as well. We find only small energy barriers for the diffusion of a Pd adatom on the CNT surface. Thus, single Pd adatoms will be mobile at room temperature. Finally we present results for the interaction between a metallic (6,0) CNT and metal surfaces. Binding energies and distances for Al, Cu, Pd, Ag, Pt, and Au are discussed and compared, showing remarkable agreement between the interaction of single metal atoms and metal surfaces with CNTs., Comment: 6 pages, 7 figures more...

The synthesis and characterization of bis(ketoiminato)magnesium(ii) complexes of composition [Mg(OCR

A series of cobalt half-sandwich complexes of type [Co( η 5 -C 5 H 5 )(L)(L′)] ( 1 : L, L′ = 1,5-hexadiene; 2 : L = P(OEt) 3 , L′ = H 2 C CHSiMe 3 ; 3 : L = L′ = P(OEt) 3 ) has been studied regarding their physical properties such as the vapor pressure, decomposition temperature and applicability within the metal-organic chemical vapor deposition (MOCVD) process, with a focus of the influence of the phosphite ligands. It could be shown that an increasing number of P(OEt) 3 ligands increases the vapor pressure and thermal stability of the respective organometallic compound. Complex 3 appeared to be a promising MOCVD precursor with a high vapor pressure and hence was deposited onto Si/SiO 2 (100 nm) substrates. The resulting reflective layer is closed, dense and homogeneous, with a slightly granulated surface morphology. X-ray photoelectron spectroscopy (XPS) studies demonstrated the formation of metallic cobalt, cobalt phosphate, cobalt oxide and cobalt carbide. more...

The continuous scaling of transistor size towards deep submicron level demands an inevitable replacement of SiO 2 with a low-k dielectric material. Doping of methyl groups in SiO 2 network reduces the dielectric constant by replacing oxygen atoms bonded with silicon and creating a lower polarizable silicon methyl bond in the network. Further reduction in dielectric constant is possible by introducing porosity in the dense low-k network. The detailed knowledge about atomic structure of such low-k materials is a must for understanding their electronic and optical properties. In this study, electron diffraction and (density functional based tight binding) DFTB calculations are used to investigate the structure of dense and porous low-k dielectric materials. The radial distribution function (RDF) obtained from electron diffraction technique contains information about the short-range order present in the material. Bond lengths and bond angles determined from RDF indicate a significant modification occurring in the SiO 2 network after doping with methyl groups. The local density of the materials is also derived from radial distribution function. It depends on the number and distances of nearest neighbors and was found to be decreased in these low-k materials compared with amorphous SiO 2 . more...

Porous ultra low constant materials (ULK) for isolation within the interconnect system of integrated circuits are a promising approach to reduce crosstalk and RC-delays due to shrinking feature sizes [1]. Due to their porosity and the integration of carbon rich species like methyl groups into the Si-O-Si backbone of currently fabricated PECVD SiCOH dielectrics those materials are highly sensible towards plasma processing, e.g. dry etching or resist stripping [2]. Metal hard mask approaches, e.g. using TiN hard masks are widely used to prevent the resist stripping plasma directly attacking the low-k material [3]. To reduce further plasma damage like carbon depletion and formation of polar silanol groups the development of less aggressive etching processes is in the focus of research and development activities. Nevertheless dry etching will attack the sidewalls and cause a material degradation. That is why repair processes, mainly based on silylation, are considered to follow the patterning step to reintegrate carbon rich species and to recover the dielectric’s properties [3]. Subsequently to dry etching and repairing the dielectric the wet chemical plasma etch residue removal process is performed. Besides material compatibility and effectiveness in residue removal the wetting behavior of the applied cleaning solutions towards the surface which has to be cleaned is crucial, especially looking on wetting issues like the incomplete wetting of very small via holes or pattern collapse. In this study we investigate in which way different silylation based repair processing regimes are affecting the wettability of the dielectric by water based cleaning solutions using contact angle based surface energy calculations. more...

In this study, the dielectric response of low-k dielectric materials has been characterized by electron energy loss spectroscopy. A widely accepted fast Fourier transform based Kramers–Kronig method (Johnson, 1975) [3] has been used to derive the high-frequency response of these materials. We used three different low-k dielectric materials to find out the effect of porosity and carbon content on the dielectric response of materials. Amorphous SiO 2 and SiC:H samples are used for comparison. All samples were deposited by plasma-enhanced chemical vapor deposition technique. A Lorentzian-based oscillator model has been used to determine the eigen-energy of excitations by fitting the measured loss function. The model is specially designed to let all oscillator parameters move freely and find their most probable position by using a least square fitting analysis procedure. The band gap for amorphous SiO 2 which corresponds to the first absorption peak in the imaginary part of dielectric function is found to be at around 9 eV. We observed that in the case of dense low-k material, there appears a finite density of states (DOS) inside the band gap of SiO 2 , whereas the inclusion of porosity into dense low-k network diminishes the in-gap DOS and widens the band gap to around 10 eV. more...

Single-walled carbon nanotubes (SWCNTs) as the colloid in a colloidal solution can be polarized in a non-uniform electric field and experience a net force that is the so-called dielectrophoresis (DEP) force, due to the interaction between the induced dipoles and the electric field. The positive DEP force can be used to position and assemble arrays of SWCNTs. Inversely, the negative DEP force can be utilized to separate SWCNTs in terms of their electronic properties. Moreover, Joule heating generated by the electric field can lead to other electrokinetics forces in the colloidal solution, which give rise to fluidic motion of the solution. Additionally, at low frequencies, the electrical double layer also induces a steady fluidic motion, a phenomenon known as AC electroosmotic flow. These fluidic motion in turn exerts a drag force on the nanotubes. Hence, to controllably assemble SWCNTs using DEP force is a non-trivial task. In this article, the mechanisms of electrokinetics and electrohydrodynamics are systematically analyzed through numerical simulations for a set of parameters that are typically used for assembling SWCNTs between metal electrodes. Finally, experimental results from the frequency-dependent assembly of SWCNTs using this set of parameters are described and discussed. These results show that the density of SWCNTs assembled between electrodes can be varied by controlling the electrokinetics parameters. more...

This paper investigates the influence of CH"4, NH"3, H"2 and He plasma on properties of porous low-k film and its effects on resisting moisture absorption during CMP and ions penetration from sputtering. It is found that the H"2, He, NH"3 plasma can cause aggressive carbon depletion in the porous low-k films and change the low-k surface from hydrophobic to hydrophilic, which will induce moisture uptake into the low-k material during the CMP process, and result in increase of the k value and leakage current density. The CH"4 plasma can make low-k material more resist against moisture uptake and keep the k value stable and a good electrical property of the low-k films. more...

Non-covalent functionalization based on surfactants has become one of the most common methods for dispersing of single-walled carbon nanotubes (SWCNTs). Previously, efforts have mainly been focused on experimenting with different surfactant systems, varying their concentrations and solvents. However sonication plays a very important role during the surfactant-based dispersion process for SWCNTs. The sonication treatment enables the surfactant molecules to adsorb onto the surface of SWCNTs by overcoming the interactions induced by the hydrophobic, electrostatic and van der Waals forces. This work describes a systematic study of the influence of the sonication power and time on the dispersion of SWCNTs. UV–vis-NIR absorption spectra is used to analyze and to evaluate the dispersion of SWCNTs in an aqueous solution of 1 w/v% sodium deoxycholate (DOC) showing that the resonant and nonresonant background absorption strongly depends on the sonication conditions. Furthermore, the diameter and length of SWCNTs under different sonication parameters are investigated using atomic force microscopy (AFM). more...

Consecutive synthesis methodologies for the preparation of a series of trimethylsilyl and tert-butyl-substituted ruthenocenes of the type Ru(η5-C5H3R1R2)(η5-C5H3R3R4) (2, R1 = SiMe3, R2 = R3 = R4 = H; 3, R1 = R3 = SiMe3, R2 = R4 = H; 4, R1 = R2 = R3 = SiMe3, R4 = H; 5, R1 = R2 = R3 = R4 = SiMe3; 6, R1 = R3 = tBu, R2 = R4 = H; 7, R1 = R3 = tBu, R2 = SiMe3, R4 = H; 8, R1 = R3 = tBu, R2 = R4 = SiMe3) and Ru(η5-2,3-Me2C5H5)(η5-C5H4R) (10, R = tBu; 12, R = SiMe3) are discussed and their use as a MOCVD precursor for the deposition of ruthenium is reported. The molecular structures of 3, 5–8, 10, and 12 in the solid state are reported. The half-open ruthenocenes 10 and 12, which are liquids at ambient temperature, exhibit significantly shorter Ru–centroid (η5-2,3-Me2C5H5) bond lengths in contrast to ruthenocenes 3 and 5–8. The thermal behavior of all ruthenocenes was studied by thermogravimetric analysis showing that they evaporate without decomposition at atmospheric pressure. In addition, vapor pressure measurements were carried out to obtain profound information about the volatility of the synthesized sandwich compounds. The highest vapor pressures were found for 10 and 12. It was observed that the higher the number of SiMe3 groups, the higher the deposition temperature. All compounds were applied as precursors in MOCVD. The depositions on Si/SiO2 targets were carried out in a vertical cold-wall CVD reactor between 633 and 688 K with a flow rate of 50 mL min–1 using nitrogen as the carrier gas and oxygen as the coreactant (50 mL min–1). With the tBu-functionalized ruthenocenes 6 and 10 ruthenium thin films were obtained, while mixed ruthenium/SiO2 layers were formed with 2, 7, 8, and 12. The appropriate layers possess thicknesses between 75–135 nm and are conformal and dense as proven by SEM, EDX spectroscopy, and XPS studies. more...

The integration of porous ultra low-k (ULK) materials within the interconnect system of integrated circuits is one of the most promising approaches to reduce RC-delay or crosstalk. The application of plasma processes for patterning, cleaning and photoresist removal is known to degrade the electrical parameters of the ULK by carbon depletion, densification and introduction of silanol species. In this study we investigate the influence of different thermally assisted immersion processes on the effectiveness of a silylation based k-restore process of plasma damaged porous low-k dielectrics. The results show that network recovery effects like methyl incorporation are different at the surface and in the depth of the damaged area addicted to precursor temperature and curing conditions. The most promising process sequence was shown to consist of an immersion at temperatures of 100-150 °C with subsequent UV anneal depending on the precursor used for recovery process. more...

Due to the shrinking of the device size in integrated circuits together with the use of novel, less stable low-k back-end-of-line dielectrics more attention has to be paid to the time dependent dielectric breakdown (TDDB) effect. In this work the TDDB mechanisms are investigated and modeled based on constant-voltage bias-temperature stress (BTS) experiments from the 90 nm and 45 nm technology nodes. The modeling of the I-t dependencies is based on the numerical model of Haase in which it is assumed that the degradation of the dielectric is caused just by the electronic leakage current itself. By two simple modifications of the model and an adjustment of several model parameters it was possible to achieve a very good agreement between the model and the experiment for single constant-voltage BTS dependencies. For two different experimental data sets from the 45 nm technology node the TDDB behavior in dependence on the bias voltage and temperature is analyzed and compared with the results of the modified Haase model and the Poole-Frenkel lifetime model. more...

To realize fast and efficient integrated circuits the interconnect system gains an increasing importance. In particular, this is the case for logic and processor circuits with up to 12 metallization layers. In order to optimize this technology and the according processes it is desirable to generate flexible test structures in small lot production. In opposition to standard optical lithography using masks, Electron Beam Direct Write (EBDW) lithography can rapidly deliver special test structures at low cost. Furthermore, critical dimensions of future technology nodes which are not yet manufacturable by standard optical lithography tools can be produced. In this paper we demonstrate the potential of the 50kV variable shaped EBDW cluster for patterning of future back-end-of-line (BEOL) structures on full 200mm wafers. The patterned wafers have been used to develop next generation copper damascene interconnect processes for critical dimensions down to 50nm. more...

A method to evaluate the surface free energy in pattern structure, of chemical vapor deposited dense and ultra low-κ (ULK) SiOCH dielectric films, is presented. Therefore dense and ultra low-κ films were treated by different post ash plasma processes. This films were characterized using Auger electron spectroscopy, atomic force microscopy and contact angle measurements. For both material systems a correlation between the amount of surface near carbon and the surface free energy was found, independent on the plasma chemistry used. The range of the surface roughness is very small and does not have a strong impact on the surface free energy. The correlation model can be applied for pattern structures. After measuring the carbon concentration at the side walls by methods like TEM-EELS or XPS the model provides the polar and dispersive part of the surface free energy. Having the surface free energy, contact angle of different liquids on or in pattern structures can be calculated. Hence, the wetting behavior and the probability of pattern collapse can be predicted, which is essential to select an appropriate chemical for cleaning and other wet chemical based processes. more...

Reactive ion etch processes for modern interlevel dielectrics become more and more complex, especially for further scaling of interconnect dimensions. The materials will be damaged within such processes with the result of an increase in their dielectric constants. The capability of selected additives to minimize the low-k sidewall damage during reactive ion etching (RIE) of SiCOH materials in fluorocarbon plasmas was shown in different works in the past. Most of the investigated additive gases alter the fluorine to carbon ratio as well as the dissociation of the parent gas inside the etch plasma. The result is a changed etch rate, a modified polymerization behavior and other characteristics of the process induced SiCOH damage. Heavy inert ions like argon will be accelerated to the sample surface in the cathode dark space and enhance therewith the sputter yield on the SiCOH network [1]. In this paper the additives Ar, O"2, C"4F"8, H"2, N"2 and CO were added to a conventional CF"4 etch plasma. We try to provoke different changes in the plasma conditions and therewith in the process results. Contact angle measurements, spectroscopic ellipsometry, Hg-probe analysis, FTIR measurements and SEM cross-sections were used to overview the additive induced modifications. To understand the influences of the additives gases more exactly, changes in the physical and chemical plasma behavior must be analyzed. Therefore quadrupole mass spectrometry (QMS) and quantum cascade laser absorption spectroscopy (QCLAS) were used. more...

In this contribution we show experimental investigations regarding Periodic Pulse Reverse (PPR) plating for the filling of Through Silicon Vias that are aimed for the use in 3D integration applications. The purpose of this method is to prevent the use of plating additives that induce high process complexity in terms of process control and high process costs due to the high consumption of those additives. We therefore compare the effect of PPR plating without additives to that effect of PPR plating with additives. In first results with non-optimized PPR plating we already show the large gain in step coverage during TSV filling compared to standard DC plating. more...

In this work we demonstrate a new approach for ultra fine flip chip interconnections based on carbon nanotubes as a wiring material. In contrast to other works we show patterned growth of multi walled CNTs on substrates with pre-structured bond pads including a complete metallization system for electrical characterization. Furthermore, we succeeded achieving a reliable flip chip connection between CNT-covered contact pads and metal pads at temperatures lower than 200^oC. Our goal is a reversible electrical and mechanical chip assembly with CNT bumps. For bonding experiments and electrical characterization a test structure with a damascene metallization including a layer stack of TiN/Cu/TiN was prepared. For CNT growth a thin nickel catalyst layer was selectively deposited with sputtering and a lift-off technique on the contact pads. The CNTs were grown by thermal CVD with ethylene as carbon source. CNT growth parameters like catalyst thickness, gas composition, growth time and temperature were optimized to get dense CNT growth. The metal bumps of the counter chip consist of electroless deposited Ni. With the selected layout we can obtain daisy chain and four-point measurements for lossless determination of single contact resistance. We have obtained reliable electrical contacts with relatively small resistance reaching values as low as 2.2@W. As CNT-quality is strongly dependent on the growth temperature we observed a strong change in resistivity of the flip chip connection as the growth temperature was varied. Reliability tests showed long time stability under thermal stress proving a reliable electrical contact between the contact pads. There is an appropriate potential for further optimization of the CNT bump resistance and applying this technology for IC-devices. more...

The focus of this paper is the impact of CF"4 based plasma etch processes with the additives argon and C"4F"8 on material properties and geometrical parameters of etched trenches using dense and porous SiCOH. Argon and C"4F"8 were added to change the radical to ion composition and to shift the carbon to fluorine ratio, respectively. With several techniques, FTIR, spectral ellipsometry and contact angle measurements, modifications in the structure of the materials and their surface conditions were analyzed. To understand the influences of the additives on the plasma conditions, optical emission spectroscopy (OES) and quadrupole mass spectrometry (QMS) were used to estimate the composition of the plasma insitu. For the additive argon, a slightly enhanced etch rate and an increased refractive index due to serious plasma damage for porous SiCOH was observed. At higher Ar flow rates peaks of Si"2O"4H"x clusters in the QMS spectra and increased CO and O lines, measured with OES, indicate a higher sputter yield on the SiCOH network. SEM cross-sections show, that argon has no effect on the sidewall geometry of etched trenches. A higher CH/CN line in the OES spectra indicates an enhanced sputter effect of the SiCN films in via bottoms. For C"4F"8 addition results of spectral ellipsometry show a decreased etch rate and refractive index. Using FTIR the formation of a polymer film on the surface was observed. Higher C"2 lines in the OES spectra are indications of enhanced polymerization efficiency. Finally, the addition of C"4F"8 decreases the etch rate in the trench sidewalls and therewith assumedly the sidewall damage. more...

The physical and chemical property changes of chemical vapor deposited ultra low-@k (ULK) SiOCH dielectric films due to different post ash treatments were studied by Auger electron spectroscopy, ellipsometric porosimetry and surface free energy evaluation. Structural changes in the ULK layer with respect to the carbon content were analyzed. Using a downstream and a reactive ion etch process for photo resist removal a reduction of carbon was observed. For different plasma gas chemistries the pore size reduction depends first on the process condition (downstream or reactive ion etch) and then on the gas. Differences in the pore size then also influence the amount of carbon depletion besides the influence of the gases used for photo resist processes. The damage at the surfaces was characterized by contact angle measurements providing both the polar and dispersive part of the surface free energy. The wettability of different solvents and repair chemicals was classified calculating their surface free energies and comparing those energies with the surface free energies of modified ULK surface. It is shown that especially reducing gases provide a surface free energy with a higher dispersive part compared to oxidative plasma treatments. Furthermore it was found that the wettability of repair chemicals and solvents strongly changes for reductive based strip processes with plasma exposure time, since a high variation of the surface free energy occur. more...