The current state of thin film heterojunction solar cells based on cuprous oxide (Cu2O), cupric oxide (CuO) and copper (III) oxide (Cu4O3) is reviewed. These p-type semiconducting oxides prepared by Cu oxidation, sputtering or electrochemical deposition are non-toxic, sustainable photovoltaic materials with application potential for solar electricity. However, defects at the copper oxide heterojunction and film quality are still major constraining factors for achieving high power conversion efficiency, η. Amongst the Cu2O heterojunction devices, a maximum η of 6.1% has been obtained by using pulsed laser deposition (PLD) of AlxGa1−xO onto thermal Cu2O doped with Na. The performance of CuO-Si heterojunction solar cells formed by magnetron sputtering of CuO is presently limited by both native oxide and Cu rich copper oxide layers at the heterointerface. These interfacial layers can be reduced by using a two-step sputtering process. A high η of 2.88% for CuO heterojunction solar cells has been achieved by incorporation of mixed phase CuO/Cu2O nanopowder. CuO/Cu2O heterojunction solar cells fabricated by electrodeposition and electrochemical doping has a maximum efficiency of 0.64% after surface defect passivation and annealing. Finally, early stage study of Cu4O3/GaN deposited on sapphire substrate has shown a photovoltaic effect and an η of ~10−2%.
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