This paper describes the fabrication and use of thin polycrystalline films in matrix-assisted laser desorption experiments. These films consist of microcrystals of protein-doped matrix (crystal dimensions ⩽ 1 μm). The films produce intense protein-ion currents and can be grown in the presence of high concentrations of involatile solvents (e.g., glycerol, 6 M urea) without any purification. They strongly adhere to the substrate, allowing easier washing of the film, compared to dried-droplet deposits. The films are also more uniform than dried-droplet deposits, with respect to ion production. It is suggested that matrix-assisted laser desorption/ionization samples are composed of nonlinear optical devices that function as polymer ion-current sources. These devices (protein-doped matrix crystals) can be designed and fabricated in many forms to serve the special functions required by the analytical scientist.