| Challenges are encountered during atomic layer deposition (ALD) on large quantities of nanoparticles. The particles must be agitated or vigorously mixed to perform the ALD surface reactions in reasonable times and to prevent the particles from being agglomerated by the ALD film. The high surface area of nanoparticles also demands efficient reactant usage because large quantities of reactant are required for the surface reactions to reach completion.; To address these challenges, a novel rotary reactor was developed to achieve constant particle agitation during static ALD reactant exposures. In the design of this new reactor, a cylindrical drum with porous metal walls was positioned inside a vacuum chamber. The porous cylindrical drum was rotated by a magnetically coupled rotary feedthrough. By rotating the cylindrical drum to obtain a centrifugal force of less than one gravitational force, the particles were agitated by a continuous "avalanche" of particles.; The effectiveness of this rotary reactor was demonstrated by Al 2O3 ALD on ZrO2 particles. A number of techniques including transmission electron microscopy, Fourier transform infrared spectroscopy, scanning Auger spectroscopy and x-ray photoelectron spectroscopy confirmed that the Al2O3 ALD film conformally coats the ZrO 2 particles.; Combining static reactant exposures with a very high surface area sample in the rotary reactor also provides unique opportunities for studying the surface chemistry during ALD. Sequential, subsaturating doses can be used to examine the self-limiting behavior of the ALD reactions in the rotary reactor. This dosing method is the first demonstration of self-limiting ALD on bulk quantities of nanoparticles.; By combining these sequential, subsaturating doses with quadrupole mass spectrometry, ALD reactions can be analyzed from the gas phase using full mass spectrum analysis. The reaction products are present in a high enough concentration to discern a gas phase mechanism for reactions which previously only had surface studies as mechanism determination and characterization. |
