Nano-needle structured, ambipolar high electrical conductivity SnO_x (x ≤ 1) thin films for infrared optoelectronics

摘要

SnO has become an important earth-abundant transparent conductive oxide (TCO) with applications not only in photovoltaics but also in electrodes for energy storage. For optoelectronic applications, low fabrication temperature, high electrical conductivity, and low optical losses are highly desirable. This study presents self-assembled, ambipolar (i.e., n and p-type) nano-needle structured SnO_x (x ≤ 1) thin films with high electrical conductivity, low infrared (IR) optical losses, and potentials for effective light trapping. These nano-needle structured SnO_x films are fabricated through non-reactive co-sputtering of Sn and SnO_2 followed by crystallization annealing at low temperatures ＜250℃. The crystallization of SnO_x thin films occurred rapidly above 210 ℃, resulting in SnO nano-needles with average dimensions of 1 μm long, 0.1 μm wide, and 0.15 μm thick that are interspersed with Sn nanocrystals. The optical scattering from these nanostructures can be utilized for light trapping in thin film absorbers. We also found that laser pre-patterning enabled control over nano-needle crystal size and growth directions. The electrical conductivity of 1500-2000 S/cm is comparable to state-of-the-art SnO_2:F TCOs while the fabrication temperature is reduced by ～200℃, enabling a broader range of applications, such as optoelectronics on flexible substrates. Hall effect measurements show an intriguing ambipolar behavior depending on the annealing ambient. Especially, a strong p-type conductivity with a hole concentration of p ～ 5 × 10~(21) cm~(-3) and mobility μ_p～2cm~2 V~(-1) s~(-1) is obtained in a weak oxidizing ambient. Such a high p-type conductivity is particularly rare in TCOs, and it offers potential applications in bipolar oxide semiconductor devices. Optical measurements showed a low absorption loss of ＜3% in a broad IR wavelength regime of λ = 1100-2500 nm for p-type SnO_x, suggesting that these nano-needle structured SnO_x TCOs can be engineered to enhance low-loss optical scattering/light trapping in thin film thermophotovoltaic cells and IR photodetectors.