Electrical and Optical Characteristics of Si-Nanoparticle Films Deposited onto Substrates by High-Voltage Electrospraying from Ethanol Sols

The optical and electrical characteristics of films consisting of nanocrystalline silicon (nc-Si) deposited onto substrates by the high-voltage electrospraying of nc-Si sols in ethanol are investigated. It is found that the interaction of ethanol droplets carrying Si nanoparticles with a corona-discharge electric field leads to the polymerization of ethanol and the formation of a polymer layer on the Si-nanoparticle surface. A high-voltage facility for depositing the films using an additional focusing electrode allows one to change the geometry of the electric field and intensity in the region of the ethanol droplet flow. As a result, nc-Si films with qualitatively different properties of the polymer on the nanoparticle surface are formed, specifically, nc-Si_A and nc-Si_B, obtained without a focusing electrode and with it, respectively. Upon annealing at temperatures of up to 400°С, the optical band gap E_g of the nc-Si_A films increases from ~1.9 to ~2.2 eV, while the E_g value of the nc-Si_B films remains constant and amounts to 1.85 eV. The constant E_g value of the nc-Si_B films is explained by the properties of the polymer on the Si-nanoparticle surface and the more effective blocking of oxygen penetration from the surrounding environment upon annealing at temperatures of up to 400°C than in the case of a polymer in nc-Si_A films. The temperature dependences of the dark and photoinduced conductivity of nc-Si_A films are approximated with good accuracy by two activation-type exponential functions and the dark activation energies are ~0.75 and 0.1 eV, respectively. The conductivity of the nc-Si_A films noticeably decreases under irradiation of the samples at wavelengths of 460–470 nm. The temperature dependences of the conductivity of the nc-Si_B films are approximated with good accuracy by exponential functions with activation energies of 0.73 (in the dark) and 0.59 eV (under photoexcitation). In contrast to the case of nc-Si_A films, the photoconductivity of nc-Si_B films grows more than fourfold relative to the dark conductivity under analogous illumination. The nc-Si_B films are photoactive and sandwich-like Al/nc-Si_B/Al structures can generate a voltage. The dark conductivity and photoconductivity of the nc-Si_A films in the voltage range of V > 2 V are determined by the two-center Poole–Frenkel effect; the concentration of the centers affecting the Poole–Frenkel conductivity is ~3 × 10¹⁷ cm^–3. In nc-Si_B films in the voltage range of 2–5 V, electron transport is determined by space-charge-limited currents and, at high voltages, by the two-center Poole–Frenkel effect. The concentration of traps contributing to the space-charge-limited currents is ~4 × 10¹⁶ cm^–3. The concentration of Poole–Frenkel centers affecting the conductivity decreases according to the activation law with an activation energy of 0.7 eV from 3 × 10¹⁶ to 2 × 10¹⁴ cm^–3 with a decrease in temperature from 120°C to 40°C.