A number of unconventional micromachining technologies are emerging that are of potential interest for microelectromechanical systems (MEMS) manufacturing. Such micromachining processes include sequential processes in which devices on a substrate are formed one at a time, which is in contrast to conventional parallel semiconductor manufacturing processes. Nevertheless, many of the serial micromachining processes, including inkjet printing technologies and laser-based processes can be highly efficient and cost competitive, especially for low- and medium-sized manufacturing volumes as well as for prototyping purposes. The technologies presented in this chapter can be categorized as additive micromachining approaches (e.g., inkjet printing) and subtractive micromachining approaches (e.g., laser ablation). This chapter discusses the more mature technologies that are already being developed in a commercial context and a number of new and emerging micromachining approaches that are still in the early research and development stage. 

Graphene's unparalleled strength, chemical stability, ultimate surface-to-volume ratio and excellent electronic properties make it an ideal candidate as a material for membranes in micro- and nanoelectromechanical systems (MEMS and NEMS). However, the integration of graphene into MEMS or NEMS devices and suspended structures such as proof masses on graphene membranes raises several technological challenges, including collapse and rupture of the graphene. We have developed a robust route for realizing membranes made of double-layer CVD graphene and suspending large silicon proof masses on membranes with high yields. We have demonstrated the manufacture of square graphene membranes with side lengths from 7 mu m to 110 mu m, and suspended proof masses consisting of solid silicon cubes that are from 5 mu mx5 mu mx16.4 mu m to 100 mu mx100 mu mx16.4 mu m in size. Our approach is compatible with wafer-scale MEMS and semiconductor manufacturing technologies, and the manufacturing yields of the graphene membranes with suspended proof masses were >90%, with >70% of the graphene membranes having >90% graphene area without visible defects. The measured resonance frequencies of the realized structures ranged from tens to hundreds of kHz, with quality factors ranging from 63 to 148. The graphene membranes with suspended proof masses were extremely robust, and were able to withstand indentation forces from an atomic force microscope (AFM) tip of up to 7000nN. The proposed approach for the reliable and large-scale manufacture of graphene membranes with suspended proof masses will enable the development and study of innovative NEMS devices with new functionalities and improved performances.

Nanoelectromechanical system (NEMS) sensors and actuators could be of use in the development of next-generation mobile, wearable and implantable devices. However, these NEMS devices require transducers that are ultra-small, sensitive and can be fabricated at low cost. Here, we show that suspended double-layer graphene ribbons with attached silicon proof masses can be used as combined spring–mass and piezoresistive transducers. The transducers, which are created using processes that are compatible with large-scale semiconductor manufacturing technologies, can yield NEMS accelerometers that occupy at least two orders of magnitude smaller die area than conventional state-of-the-art silicon accelerometers. With our devices, we also extract the Young’s modulus values of double-layer graphene and show that the graphene ribbons have significant built-in stresses.

The preparation, characterization, and evaluation of a cobalt(III) complex [CO{(OC)2(o,o'-NC6H4NCO)2CMe2}(OH2)]- with 13-membered tetraamide macrocyclic ligand (TAML) is described. This is a square-planar (X-ray) S=1 paramagnetic (H-1 NMR) compound, which becomes an S=0 diamagnetic octahedral species in excess d(5)-pyridine. Its one-electron oxidation at an electrode is fully reversible with the lowest E-1/2 value (0.66V vs SCE) among all investigated Co-III TAML complexes. The oxidation results in a neutral blue species which is consistent with a Co-III/radical-cation ligand. The ease of oxidation is likely due to the two benzene rings incorporated in the ligand structure (whereas there is just one in many other Co-III TAMLs). The oxidized neutral species are unexpectedly EPR silent, presumably due to the -stacking aggregation. However, they display eight-line hyperfine patterns in the presence of excess of 4-tert-butylpyridine or 4-tert-butyl isonitrile. The EPR spectra are more consistent with the Co-III/radical-cation ligand formulation rather than with a Co-IV complex. Attempts to synthesize a similar vanadium complex under the same conditions as for cobalt using [(VO)-O-V(OCHMe2)(3)] were not successful. TAML-free decavanadate was isolated instead. [GRAPHICS] .

A through-glass via (TGV) provides a vertical electrical connection through a glass substrate. TGVs are used in advanced packaging solutions, such as glass interposers and wafer-level packaging of microelectromechanical systems (MEMS). However, TGVs are challenging to realize because via holes in glass typically do not have a sufficiently high-quality sidewall profile for super-conformal electroplating of metal into the via holes. To overcome this problem, we demonstrate here that the via holes can instead be filled by magnetically assembling metal wires into them. This method was used to produce TGVs with a typical resistance of 64 m Omega, which is comparable with other metal TGV types reported in the literature. In contrast to many TGV designs with a hollow center, the proposed TGVs can be more area efficient by allowing solder bump placement directly on top of the TGVs, which was demonstrated here using solder-paste jetting. The magnetic assembly process can be parallelized using an assembly robot, which was found to provide an opportunity for increased wafer-scale assembly speed. The aforementioned qualities of the magnetically assembled TGVs allow the realization of glass interposers and MEMS packages in different thicknesses without the drawbacks associated with the current TGV fabrication methods.

Novelty / Progress Claims We have developed a new method for fabrication of through-glass vias (TGVs). The method allows rapid filling of via holes with metal rods both in thin and thick glass substrates.

Background Vertical electrical feedthroughs in glass substrates, i.e. TGVs, are often required in wafer-scale packaging of MEMS that utilizes glass lids. The current methods of making TGVs have drawbacks that prevent the full utilization of the excellent properties of glass as a package material, e.g. low RF losses. Magnetic assembly has been used earlier to fabricate through-silicon vias (TSVs), and in this work we extend this method to realize TGVs [1].

Methods The entire TGV fabrication process is maskless, and the processes used include: direct patterning of wafer metallization using femtosecond laser ablation, magnetic-fieldassisted self-assembly of metal wires into via holes, and solder-paste jetting of bump bonds on TGVs.

Results We demonstrate that: (1) the magnetically assembled TGVs have a low resistance, which makes them suitable even for low-loss and high-current applications; (2) the magneticassembly process can be parallelized in order to increase the wafer-scale fabrication speed; (3) the magnetic assembly produces void-free metal filling for TGVs, which allows solder placement directly on top of the TGV for the purpose of high integration density; and (4) good thermal-expansion compatibility between TGV metals and glass substrates is possible with the right choice of materials, and several suitable metals-glass pairs are identified for possible improvement of package reliability [2].

[1] M. Laakso et al., IEEE 30th Int. Conf. on MEMS, 2017. DOI:10.1109/MEMSYS.2017.7863517

[2] M. Laakso et al., “Through-Glass Vias for Glass Interposers and MEMS Packaging Utilizing Magnetic Assembly of Microscale Metal Wires,” manuscript in preparatio

The precipitation of solid compounds from model electrolytes for liquid dye-sensitized solar cells has a story to tell regarding decomposition processes to be expected in such systems. Of course, the crystal lattice energy for a specific crystalline compounds plays a role in what compound that will eventually precipitate, but the compounds nevertheless serve as indicators for what type of processes that take place in the solar cell electrolytes upon ageing. From the compounds isolated in this study we learn that both ligand exchange processes, double-salt precipitation and oxidation are degradation processes that should not be overlooked when formulating efficient and stable electrolytes for this type of electrochemical system.

We present graphene-based CO2 sensing and analyze its cross-sensitivity with humidity. In order to assess the selectivity of graphene-based gas sensing to various gases, measurements are performed in argon (Ar), nitrogen (N2), oxygen (O2), carbon dioxide (CO2), and air by selectively venting the desired gas from compressed gas bottles into an evacuated vacuum chamber. The sensors provide a direct electrical readout in response to changes in high concentrations, from these bottles, of CO2, O2, nitrogen and argon, as well as changes in humidity from venting atmospheric air. From the signal response to each gas species, the relative graphene sensitivity to each gas is extracted as a relationship between the percentage-change in graphene's resistance response to changes in vacuum chamber pressure. Although there is virtually no response from O2, N2 and Ar, there is a sizeable cross-sensitivity between CO2 and humidity occurring at high CO2 concentrations. However, under atmospheric concentrations of CO2, this cross-sensitivity effect is negligible – allowing for the use of graphene-based humidity sensing in atmospheric environments. Finally, charge density difference calculations, computed using density functional theory (DFT) are presented in order to illustrate the bonding of CO2 and water molecules on graphene and the alterations of the graphene electronic structure due to the interactions with the substrate and the molecules.

Through glass vias (TGVs) are a key component in glass-based interposers and microelectromechanical-system lid wafers. Magnetic-field-assisted self-assembly has been demonstrated earlier in fabrication of through silicon vias. Here we present an entirely maskless TGV fabrication process utilizing magnetic assembly. Femtosecond laser is used for ablative direct patterning of surface metal layers and for exposing the TGV conductors after wafer thinning. The proposed TGV structure is shown to be electrically functional by measuring the TGV resistance values.

Through silicon vias (TSVs) are key enablers of 3-D integration technologies which, by vertically stacking andinterconnecting multiple chips, achieve higher performances,lower power, and a smaller footprint. Copper is the mostcommonly used conductor to fill TSVs; however, copper hasa high thermal expansion mismatch in relation to the siliconsubstrate. This mismatch results in a large accumulation ofthermomechanical stress when TSVs are exposed to high temperaturesand/or temperature cycles, potentially resulting in devicefailure. In this paper, we demonstrate 300 μm long, 7:1 aspectratio TSVs with Invar as a conductive material. The entireTSV structure can withstand at least 100 thermal cycles from −50 °C to 190 °C and at least 1 h at 365 °C, limited bythe experimental setup. This is possible thanks to matchingcoefficients of thermal expansion of the Invar via conductor andof silicon substrate. This results in thermomechanical stressesthat are one order of magnitude smaller compared to copperTSV structures with identical geometries, according to finiteelement modeling. Our TSV structures are thus a promisingapproach enabling 2.5-D and 3-D integration platforms for hightemperatureand harsh-environment applications.