An etchant of PSG (14) or BPSG with high selectivity to substantially undoped oxide (12) includes a fluorine-liberating compound and a fluorine-scavenging compound. The fluorine-liberating compound is preferably a perfluorinated inorganic compound, and the fluorine-scavenging compound is preferably a hydrogen-liberating compound such as hydrogen. A particularly preferred inorganic fluorine-liberating compound is nitrogen trifluoride. In an exemplary embodiment, etch rate ratios of PSG to undoped oxide as high as 11 to 1 were obtained.

A method has been developed for the removal of silicon nitride and silicon dioxide, or other semiconductor materials from a surface of a wafer or CVD reactor. The method uses NF.sub.3, mixed with an electropositive diluent, preferably argon, at a given range of concentration, pressure, flowrate, and power to obtain the fastest possible etch rates. The etch rates of the film being processed can be caused to increase even as the concentration of NF.sub.3 in the diluent is decreased by choosing the proper diluent and operating conditions. Not only does this method increase the etch rate, thereby increasing the throughput of the reactor using this process, it also accomplishes this task at low concentrations of NF3 resulting in a lower cost.

A method for etching of sub-quarter micron openings in insulative layers for contacts and vias is described. The method uses high resolution DUV photolithography. By using a thin layer of photoresist to pattern a hardmask, full advantage of the high resolution can be attained. The hardmask in turn, is sufficiently durable to withstand subsequent etching of the insulative layer. The methods taught by this invention are of particular value for the formation of contacts to semiconductive devices although they are also applied to forming via openings. DUV photoresists having thicknesses of less than 500 nm are used with a DUV stepper. The hardmask materials include Ti/TiN and amorphous silicon. Etching selectivities of these materials with respect to typical insulative materials used in integrated circuit manufacture are of the order of 50:1.

A method of etching an oxide layer is disclosed. First, a resist layer is formed on an oxide layer on a substrate. Next, a photosensitive layer is formed on the oxide layer and patterned to expose regions of the oxide layer to be removed. The exposed regions may overlie a nitride layer, and may overlie a structure such as a polysilicon gate. The etch is performed such that polymer deposits on the photosensitive layer, thus eliminating interactions between the photosensitive layer and the plasma. In this way, a simple etch process allows for good control of the etch, resulting in reduced aspect ratio dependent etch effects, high oxide:nitride selectivity, and good wall angle profile control.

According to this invention, a semiconductor wafer on which an oxide or nitride film is formed is loaded in a processing vessel, and when the oxide or nitride film of the semiconductor wafer is to be etched by a plasma of CHF.sub.3 gas in the processing vessel, CO gas is present in the plasma atmosphere.