ABSTRACT
Although graphene has considerable potential as a next-generation transparent conducting electrode (TCE) material owing to its excellent optical transparency and flexibility, its electrical properties require further improvement for industrial application. This study reports a pathway of doping graphene by selective atomic layer deposition (ALD) of metals to elevate the electrical conductivity of graphene. Introduction of a novel Pt precursor [dimethyl(N,N-dimethyl-3-butene-1-amine-N)platinum(II); C8H19NPt; DDAP] facilitates a low-temperature (165 °C) process. The sheet resistance (Rs) of graphene is reduced significantly from 471 to 86.8 Ω sq-1 after 200 cycles of Pt ALD, while the optical transmittance at 550 nm (T) is maintained above 90% up to 200 cycles due to the selective growth of Pt on the defects of graphene. Furthermore, comprehensive analysis, including metal (Ru, Pt, and Ni) ALD on graphene, metal (Ru, Pt, Ni, Au, and Co) evaporation on graphene, and change in the ALD chemicals, demonstrates that ALD allows efficient graphene doping and the oxygen affinity of the metal is one of the key properties for efficient graphene doping. Finally, Pt ALD is applied to a multilayer graphene to further reduce Rs down to 75.8 Ω sq-1 yet to be highly transparent (T: 87.3%) after 200 cycles. In summary, the selective ALD of metals opens a way of improving the electrical properties of graphene to a level required for the industrial TCE application and has the potential to promote development of other types of functional metal-graphene composites.
ABSTRACT
Atomic layer deposition (ALD) of Ni was demonstrated by introducing a novel oxygen-free heteroleptic Ni precursor, (η3-cyclohexenyl)(η5-cyclopentadienyl)nickel(II) [Ni(Chex)(Cp)]. For this process, non-oxygen-containing reactants (NH3 and H2 molecules) were used within a deposition temperature range of 320-340 °C. Typical ALD growth behavior was confirmed at 340 °C with a self-limiting growth rate of 1.1 Å/cycle. Furthermore, a postannealing process was carried out in a H2 ambient environment to improve the quality of the as-deposited Ni film. As a result, a high-quality Ni film with a substantially low resistivity (44.9 µΩcm) was obtained, owing to the high purity and excellent crystallinity. Finally, this Ni ALD process was also performed on a graphene surface. Selective deposition of Ni on defects of graphene was confirmed by transmission electron microscopy and atomic force microscopy analyses with a low growth rate (â¼0.27 Å/cycle). This unique method can be further used to fabricate two-dimensional functional materials for several potential applications.
ABSTRACT
Ruthenium (Ru) thin films were grown on thermally-grown SiO2 substrates by plasma enhanced atomic layer deposition (PEALD) using a sequential supply of a new betadiketonate Ru metallorganic precursor, dicarbonyl-bis(5-methyl-2,4-hexanediketonato) Ru(II) (C16H22O6Ru) with a high vapor pressure and NH3 plasma as a reactant at the substrate temperature ranging from 175 and 310 degrees C. A self-limited film growth was confirmed at the deposition temperature of 225 degrees C and the growth rate was 0.063 nm/cycle on the SiO2 substrate with very short number of incubation cycles (approximately 10 cycles). The resistivity of PEALD-Ru films was dependent on the microstructural features characterized by grain size and crystallinity, which could be controlled by varying the deposition temperature. Ru film with the resistivity of -20 µΩ-cm and high density of 11.5 g/cm3 was obtained at the deposition temperature as low as 225 degrees C. It formed polycrystalline structure with hexagonal-close-packed phase that was confirmed by X-ray diffractometry and transmission electronic microscopy analysis. Step coverage of PEALD-Ru film deposited with the optimum condition was good (-75%) at the very small-sized trench (aspect ratio: -4.5 and the top opening size of 25 nm).
