The effects of air, oxygen and water exposure on the sub-bandgap absorption, the electronic conductivity and the ambipolar diffusion length in highly crystalline microcrystalline silicon films for photovoltaic applications

Reversible and irreversible changes due to long term air and short term de-ionized water (DIW) or pure oxygen exposure were investigated in about 1 µm thick hydrogenated microcrystalline silicon (µc-Si:H) films deposited on rough glass substrates, thereby comparing highly crystalline with compact material. Time and temperature dependent dark conductivity, steady-state photoconductivity, the steady-state photocarrier grating and dual-beam photoconductivity methods have been used to study the effects. Standard measurement procedures defined previously have been carefully applied to record the changes after different treatments using the steady-state methods under light. After long term air exposure of highly crystalline µc-Si:H films, a thermal annealing step leads to an increase in dark conductivity (σ_D) and steady-state photoconductivity (σ_ph) as well as to a significant increase in the sub-bandgap absorption. These effects are likely due to a reversible recovery from surface adsorbents in a porous microstructure after air exposure resulting in surface charge and Fermi level shifts in agreement with earlier results. Compact µc-Si:H films showed only marginal effects upon an annealing after long term air exposure suggesting much reduced susceptibility to surface adsorbent induced by Fermi level shifts. Five hours exposure to de-ionized water at 80 °C caused more than an order of magnitude increase in σ_D and σ_ph and a substantial decrease in the sub-bandgap absorption spectrum in highly crystalline as well as in compact µc-Si:H films. In addition, minority carrier diffusion lengths measured by the steady-state photocarrier grating method improved significantly. The changes after exposure to water were not reversible upon our standard annealing procedure. Exposure to high purity oxygen gas at 150 °C resulted in similar effects like the exposure to DIW. Also here the changes in material properties were not reversible upon annealing. Results are discussed in terms of adsorption and chemical reactions on surfaces in the porous highly crystalline material versus the materials with more compact structures. Results are compared to earlier observations and consequences for device application will be indicated.