A method for manufacturing a semiconducting, organic, covalent polymer network thin film is disclosed, said method comprising the steps of deposing a solution comprising azide- containing monomers and electron-deficient alkyne-containing monomers onto a receiving substrate to prepare a film of monomers, and subsequently providing a thermal trigger to the deposed film of monomers to allow a 1,3-dipolar cycloaddition polymerization reaction to occur between azide-containing monomers and alkyne-containing monomers, thereby forming said covalent polymer network thin film on said receiving substrate. The obtainable thin film has optoelectronic and/or semiconductor properties and can be used for the manufacturing of e.g. solar cells, transistors, light-emitting diodes or organic electronic devices.