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Low-temperature ALD/MLD growth of alucone and zincone thin films from non-pyrophoric precursors.

Anish PhilipLukas MaiRamin GhiyasiAnjana DeviMaarit Karppinen
Published in: Dalton transactions (Cambridge, England : 2003) (2022)
The combined atomic/molecular layer deposition (ALD/MLD) technique is emerging as a state-of-the-art synthesis route for new metal-organic thin-film materials with a multitude of properties by combining those of the inorganic and the organic material. A major part of the studies so far reported have focused on aluminum or zinc alkyls, so-called alucone and zincone films, typically grown from trimethyl aluminum (TMA) or diethyl zinc (DEZ) as the metal-bearing precursor, and a simple aliphatic bi-functional alcohol molecule such as ethylene glycol (EG) as the organic precursor. However, these common precursors possess certain disadvantages: both TMA and DEZ are pyrophoric, DEZ being additionally thermally unstable, while EG has a strong tendency for various unideal reaction modes. Here we report novel ALD/MLD processes for alucone and zincone films based on non-pyrophoric bis-diisopropylamido-[3-( N , N -dimethylamino)propyl] aluminum(III) [Al(NiPr 2 ) 2 (DMP)] and bis-3-( N , N -dimethylamino)propyl zinc(II) [Zn(DMP) 2 ] precursors in combination with hydroquinone (HQ) as the organic precursor. We demonstrate that the [Al(NiPr 2 ) 2 (DMP)] + HQ and [Zn(DMP) 2 ] + HQ ALD/MLD processes work even at record low deposition temperatures (140 °C and 60 °C, respectively) yielding high-quality and relatively stable Al-HQ and Zn-HQ thin films with appreciably high growth rates (2.8 Å / cycle and 3.2 Å / cycle, respectively). Moreover, these ALD/MLD processes are compatible with the corresponding ALD processes, i.e. [Al(NiPr 2 ) 2 (DMP)] + H 2 O and [Zn(DMP) 2 ] + H 2 O, for the Al 2 O 3 and ZnO films, thus opening up new horizons for the fabrication of novel metal-oxide : organic superlattice structures for e.g. flexible gas-barrier coatings or wearable thermoelectrics.
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