Atomic layer deposition on porous powders with in situ gravimetric monitoring in a modular fixed bed reactor setup

A modular setup for Atomic Layer Deposition (ALD) on high-surface powder substrates in fixed bed reactors with a gravimetric in situ monitoring was developed. The design and operation are described in detail. An integrated magnetically suspended balance records mass changes during ALD. The highly versatile setup consists of three modular main units: a dosing unit, a reactor unit, and a downstream unit. The reactor unit includes the balance, a large fixed bed reactor, and a quartz crystal microbalance. The dosing unit is equipped with a complex manifold to deliver gases and gaseous reagents including three different ALD precursors, five oxidizing or reducing agents, and two purge gas lines. The system employs reactor temperatures and pressures in the range of 25-600 °C and 10−3 to 1 bar, respectively. Typically, powder batches between 100 mg and 50 g can be coated. The capabilities of the setup are demonstrated by coating mesoporous SiO2 powder with a thin AlOx (submono) layer using three cycles with trimethylaluminium and H2O. The self-limiting nature of the deposition has been verified with the in situ gravimetric monitoring and full saturation curves are presented. The process parameters were used for a scale-up in a large fixed bed reactor. The samples were analyzed with established analytics such as X-ray diffraction, N2 adsorption, transmission electron microscopy, and inductively coupled plasma optical emission spectrometry.