Hierarchical, branched carbon nanotube (CNT) forest assemblies were created by synthesizing a second generation of CNTs directly from the alumina-coated surface of a parent CNT forest. First, a parent CNT forest generation was synthesized using floating catalyst chemical vapor deposition (CVD) in which gaseous argon and hydrogen are flowed into a tube furnace, along with a controlled flow rate of ferrocene nanoparticles suspended in xylene solvent. Next, a thin alumina coating was applied to the parent CNT forest using atomic layer deposition (ALD). The ALD process pulses alternating gases of water vapor and trimethylaluminum (TMA) and is repeated for 100 cycles, yielding a 10nm coating. This coating adheres to the outer walls of the larger CNTs and serves as a supportive surface to enable the growth of a second CNT generation. Finally, a second CNT generation was synthesized from the parent CNT forest using a floating-catalyst CVD method similar to that used for the parent generation. The relatively low areal density of the parent CNT generation allows for gas-phase additive processing (i.e. ALD and floating catalyst CVD) to occur deep within the volume of the original parent CNT forest.

Transmission electron microscopy analysis of the hierarchical CNT forests shows that second-generation CNTs nucleate and grow from the alumina-coated walls of the parent generation rather than nucleating from the original growth substrate, as has been previously reported. Further, physical confinement of the second-generation catalyst particle on the external surface of the parent generation CNTs (28 nm average diameter) leads to small-diameter CNTs (8 nm average) for the second generation. Further, radial breathing modes are detected by Raman spectroscopy, indicating single-walled or few-walled CNTs are synthesized in the second generation.

The hierarchical forests exhibit many desirable properties compared to single generation forests. Because the second generation CNTs within the interstitial regions of the parent CNT forest, they increase the structural rigidity of the cellular CNT forest morphology, increasing in mechanical stiffness by ten-fold, relative to the parent CNT forest. Further, we demonstrate that electrical continuity between the CNT generations is retained. Because a thin alumina buffer layer exists between CNT generations, electrical continuity is not guaranteed. Cyclic voltammetry and electrochemical impedance spectroscopy are used to characterize the electrical resistance elements within the hierarchical forest. This hierarchical structure offers a new avenue to tailor the performance of CNT forests and offers performance enhancements for applications in thermal interfaces, electrical interconnects, dry adhesives and energy generation and storage.

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