Kestutis Grigoras

Conformal titanium nitride in a porous silicon matrix: A nanomaterial for in-chip supercapacitors

Abstract Todays supercapacitor energy storages are typically discrete devices aimed for printed boards and power applications. The development of autonomous sensor networks and wearable electronics and the miniaturization of mobile devices would benefit substantially from solutions in which the energy storage is integrated with the active device. Nanostructures based on porous silicon (PS) provide a route towards integration due to the very high inherent surface area to volume ratio and compatibility with microelectronics fabrication processes. Unfortunately, pristine PS has limited wettability and poor chemical stability in electrolytes and the high resistance of the PS matrix severely limits the power efficiency. In this work, we demonstrate that excellent wettability and electro-chemical properties in aqueous and organic electrolytes can be obtained by coating the PS matrix with an ultra-thin layer of titanium nitride by atomic layer deposition. Our approach leads to very high specific capacitance (15xa0Fxa0cm−3), energy density (1.3xa0mWhxa0cm−3), power density (up to 214xa0Wxa0cm−3) and excellent stability (more than 13,000 cycles). Furthermore, we show that the PS–TiN nanomaterial can be integrated inside a silicon chip monolithically by combining MEMS and nanofabrication techniques. This leads to realization of in-chip supercapacitor, i.e., it opens a new way to exploit the otherwise inactive volume of a silicon chip to store energy.

Review Article: Recommended reading list of early publications on atomic layer deposition—Outcome of the “Virtual Project on the History of ALD”

Atomic layer deposition (ALD), a gas-phase thin film deposition technique based on repeated, self-terminating gas-solid reactions, has become the method of choice in semiconductor manufacturing and many other technological areas for depositing thin conformal inorganic material layers for various applications. ALD has been discovered and developed independently, at least twice, under different names: atomic layer epitaxy (ALE) and molecular layering. ALE, dating back to 1974 in Finland, has been commonly known as the origin of ALD, while work done since the 1960s in the Soviet Union under the name molecular layering (and sometimes other names) has remained much less known. The virtual project on the history of ALD (VPHA) is a volunteer-based effort with open participation, set up to make the early days of ALD more transparent. In VPHA, started in July 2013, the target is to list, read and comment on all early ALD academic and patent literature up to 1986. VPHA has resulted in two essays and several presentations at international conferences. This paper, based on a poster presentation at the 16th International Conference on Atomic Layer Deposition in Dublin, Ireland, 2016, presents a recommended reading list of early ALD publications, created collectively by the VPHA participants through voting. The list contains 22 publications from Finland, Japan, Soviet Union, United Kingdom, and United States. Up to now, a balanced overview regarding the early history of ALD has been missing; the current list is an attempt to remedy this deficiency.

Aluminum oxide mask fabrication by focused ion beam implantation combined with wet etching

A novel aluminum oxide (Al2O3) hard mask fabrication process with nanoscale resolution is introduced. The Al2O3 mask can be used for various purposes, but in this work it was utilized for silicon patterning using cryogenic deep reactive ion etching (DRIE). The patterning of Al2O3 is a two-step process utilizing focused ion beam (FIB) irradiation combined with wet chemical etching. Gallium (Ga(+)) FIB maskless patterning confers wet etch selectivity between the irradiated region and the non-irradiated one on the Al2O3 layer, and mask patterns can easily be revealed by wet etching. This method is a modification of Ga(+) FIB mask patterning for the silicon etch stop, which eliminates the detrimental lattice damage and doping of the silicon substrate in critical devices. The shallow surface gallium FIB irradiated Al2O3 mask protects the underlying silicon from Ga(+) ions. The performance of the masking capacity was tested by drawing pairs consisting of a line and an empty space with varying width. The best result was seven such pairs for 1xa0μm. The smallest half pitch was 59xa0nm. This method is capable of arbitrary pattern generation. The fabrication of a freestanding single-ended tuning fork resonator utilizing the introduced masking method is demonstrated.

Porous silicon electrodes for high performance integrated supercapacitors

We demonstrate high performance porous Si based supercapacitor electrodes that can be utilized in integrated micro supercapacitors. The key enabler here is ultra-thin TiN coating of the porous Si matrix leading to high power and stability. The TiN layer is deposited by atomic layer deposition (ALD), which provides sufficient conformality to reach the bottom of the high aspect ratio pores. Our porous Si supercapacitor devices exhibit almost ideal double layer capacitor characteristic with electrode volumetric capacitance of 7.3 F/cm. Several orders of magnitude increase in power and energy density is obtained comparing to uncoated porous silicon electrodes. Good stability of devices is confirmed performing over 5 000 charge/discharge cycles.

Microfabricated sensor platform with through-glass vias for bidirectional 3-omega thermal characterization of solid and liquid samples

Abstract A novel microfabricated, all-electrical measurement platform is presented for a direct, accurate and rapid determination of the thermal conductivity and diffusivity of liquid and solid materials. The measurement approach is based on the bidirectional 3-omega method. The platform is composed of glass substrates on which sensor structures and a very thin dielectric nanolaminate passivation layer are fabricated. Using through-glass vias for contacting the sensors from the chip back side leaves the top side of the platform free for deposition, manipulation and optical inspection of the sample during 3-omega measurements. The thin passivation layer, which is deposited by atomic layer deposition on the platform surface, provides superior chemical resistance and allows for the measurement of electrically conductive samples, while maintaining the conditions for a simple thermal analysis. We demonstrate the measurement of thermal conductivities of borosilicate glass, pure water, glycerol, 2-propanol, PDMS, cured epoxy, and heat-sink compounds. The results compare well with both literature values and values obtained with the steady-state divided bar method. Small sample volumes (∼0.02 mm³) suffice for accurate measurements using the platform, allowing rapid temperature-dependent measurements of thermal properties, which can be useful for the development, optimization and quality testing of many materials, such as liquids, gels, pastes and solids.

Silicon grass based nano functional electrodes for MEMS supercapacitors of improved energy density

Nano-structure functional electrodes for high energy density MEMS supercapacitors have been fabricated by combining atomic layer deposition (ALD) and cyclic deep reactive ion etch (C-DRIE) in MEMS technology. The electrodes were structured with C-DRIE organized silicon grass (Si-g) as the scaffold for conformal coating with ALD nano-layer TiN as the current collector, and electrochemical loading pseudo-capacitive active material. As obtained Si-g/TiN/MnOx on-chip electrode results in 1) large surface gain scaffold with one dimensional ionic diffusion, 2) high conductivity and electrochemical stability current collector, 3) high effective number of redox centers per volume, which enable largely improved energy density.