Surface gradients of chemistry or morphology represent powerful tools for the high-throughput investigation of interfacial phenomena in the areas of physics, chemistry, materials science and biology. A wide variety of methods for the fabrication of such gradients has been developed in recent years, relying on principles ranging from diffusion to time-dependent irradiation in order to achieve a gradual change of a particular parameter across a surface. In this review we have endeavoured to cover the principal fabrication approaches for surface-chemical and surface-morphological gradients that have been described in the literature, and to provide examples of their applications in a variety of different fields.

We demonstrate a very simple and reproducible preparative approach for the fabrication of surface-chemical gradients. A surface concentration gradient of adsorbed methyl- or hydroxyl-terminated thiolates was achieved upon gradually immersing a gold-coated substrate into a very dilute thiol solution (0.0033 mM) by means of a linear-motion drive. Subsequent immersion of the substrate into the complementary thiol solution provided a hydrophobicity gradient with a large range (50° of the water-contact angle) and over a significant distance (35 mm). The self-assembled monolayer gradient produced in this way also displayed a high packing density, as demonstrated by dynamic contact-angle and X-ray photoelectron spectroscopy measurements.

Lateral force microscopy and microdroplet density measurements have been used to examine the microstructure of surface-chemical gradients of thiols on gold, prepared by a two-step immersion method. A single-component coverage gradient, generated by gradual immersion of a gold surface into a solution of a single thiol, yielded islands of approximately 25 nm in diameter at the end that had only been briefly immersed, whereas an increasingly continuous film was formed along the gradient. After saturation with a second thiol with a different end group, the structure generated during the initial immersion step was found to persist.