We fabricated nanostructured Ge and GeSn films using He radio-frequency magnetron plasma sputtering deposition. Monodisperse amorphous Ge and GeSn nanoparticles of 30–40 nm size were arranged without aggregation by off-axis sputtering deposition in the high He-gas-pressure range of 0.1 Torr. The Ge film porosity was over 30%. We tested the charge/discharge cycle performance of Li-ion batteries with nanostructured Ge and GeSn anodes. The Ge anode with a dispersed arrangement of nanoparticles showed a Li-storage capacity of 565 mAh/g after the 60th cycle. The capacity retention was markedly improved by the addition of 3 at% Sn in Ge anode. The GeSn anode (3 at% Sn) achieved a higher capacity of 1128 mAh/g after 60 cycles with 92% capacity retention. Precise control of the nano-morphology and electrical characteristics by a single step procedure using low temperature plasma is effective for stable cycling of high-capacity Ge anodes.

We present a study on morphological control of nanostructured Ge films by the Ar gas pressure in plasma sputtering deposition. In the low Ar-gas-pressure range, aggregated islands of amorphous grains are formed on the film surface, while in the high-pressure range of 500 mTorr monodisperse nano-grains of about 30 nm in size are orderly arranged without aggregation. The film porosity shows a high value of over 10%. We tested the charge/discharge cycle performance of Li-ion batteries with nanostructured Ge films as anodes. The battery cell with an ordered arrangement structure maintained a high capacity of 434 mAh g−1 after 40 charge/discharge cycles, while that with an aggregated structure exhibited a rapid degradation of capacity to 5.08–183 mAh g−1. An ordered arrangement of Ge nano-grains with a high porosity, which is realized in a simple one-step procedure using high Ar-gas-pressure plasma sputtering, is effective for the stable cycling of high-capacity metal anodes.

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We fabricated nanocrystalline Ge films using radio-frequency (RF) magnetron plasma sputtering deposition under a high Ar-gas pressure. The Ge nanograins changed from amorphous to crystalline when the distance between the Ge sputtering target and the substrate was decreased to 5 mm and the RF input power was 11.8 W/cm 2 (60 W), where the deposition rate was as high as 660 nm/min. In addition, the size of the nanocrystalline grains increased from 100 to 307 nm when the RF input power for plasma production was increased from 11.8 W/cm 2 (60 W) to 17.7 W/cm 2 (90 W). In the developed narrow-gap plasma process at sub-Torr pressures, nanocrystalline Ge films were successfully fabricated on Cu substrates at low temperatures, without the substrate being heated. However, when annealing was conducted under an N2 atmosphere, which is the conventional method to induce solid-phase crystallization, the amorphous Ge layer on a Cu substrate changed to a Cu3Ge crystal layer through interdiffusion of Ge and Cu atoms at 400-500 °C.

Plasma-sputtered amorphous films for all-solid-state Li+-ion batteries are investigated. In LiPON electrolyte films, the amount of N incorporated into LiPO films is controlled by the sputtering discharge gas. Ionic conductivity increases with increasing N2 gas proportion in Ar/N2 discharge, reaching a maximum of 2.7 × 10−6 S/cm at Li2.39PO3.71N0.13. In amorphous LiAlGePO electrolyte films, the amounts of Al and Ge incorporated into LiPO films are controlled in a combinatorial approach using two-source co-sputtering. The P/Ge ratio varies over a wide range from 23.3 to 1.61 at the radial substrate positions, and the highest ionic conductivity of 4.32 × 10−5 S/cm is achieved at Li4.80Al0.80Ge1.16P3O13.1. We evaluate all-solid-state Li+-ion batteries fabricated using the developed amorphous LiPON electrolyte and GeSn anode films, where GeSn films with about 50 nm nanograins are fabricated by high-gas-pressure sputtering at 500 mTorr. A maximum capacity of 2.86 µAh/cm2 is attained for all-solid state Li+-ion battery.