Hydrogenated amorphous carbon nitride (a-CN x :H) films were formed on Al films deposited on Si or glass (SiO 2) substrates, using pulsed radio frequency (PRF) supermagnetron plasma (SMP) chemical vapor deposition (CVD) with N 2 /i-C 4 H 10 mixed gases. a-CN x :H films were grown under the upper and lower electrode RF powers (13.56 MHz) of continuous and pulsed conditions, respectively, which showed low band gap of about 0.7 eV. a-CN x :H films deposited on the Al/Si or Al/SiO 2 substrates showed same low threshold emission electric field (E TH) of 12 V/μm. Multiple layer of Al or ITO (anode)/50nm-SiO 2 /a-CN x :H/Al (cathode)/Si structures showed Fowler-Nordheim (FN) electron tunneling effect in both forward and reverse current directions. 12.5 nm a-CN x :H film on p-Si substrate showed a photoelectric conversion. Energy band structure and electron conduction models were proposed for the active states of both the field emission and FN tunneling devices and photovoltaic cells.