Lithography
A typical integrated circuit consists of various patterned thin films of metals, dielectrics and semiconductors on various substrates such as silicon, gallium arsenide, or germanium. Such a device is fabricated by a technology known as lithography, in which radiation sensitive polymeric materials called resists are used to produce circuit patterns in the substrates. Figure 1 depicts the lithographic process sequence.
Figure 1: Schematic representation of the lithographic process.
The resist material is applied as a thin coating, typically by spin coating over the substrate (wafer) and then heated to remove the casting solvent (post-apply bake, pre-exposure bake, or pre-bake). The resist film is subsequently exposed in an image-wise fashion through a mask (in photo- and X-ray lithography) or directly with finely focused electron beams. The exposed resist film is then developed typically by immersion in a developer solvent to generate three-dimensional relief images. The exposure may render the resist film more soluble in the developer, thereby producing a positive-tone image of the mask. Conversely, it may become less soluble upon exposure, resulting in generation of a negative-tone image. When the resist image is transferred into the substrate by etching and related processes, the resist film that remains after the development functions as a protective mask. The resist film must “resist” the etchant and protect the underlying substrate while the bared areas are being etched. The remaining resist film is finally stripped, leaving an image of the desired circuit in the substrate. The process is repeated many times to fabricate complex semiconductor devices.
For a resist material to be useful in device fabrication:
- it must be capable of spin casting from solution into a thin and uniform film that adheres to various substrates such as metals, semiconductors, and insulators
- possess high radiation sensitivity
- possess high resolution capability, dictated by solubility/insolubility characteristics
- withstand extremely harsh environments, for example, high temperature, strong corrosive acids, and plasmas such as used in subsequent etching, doping and sputtering operations.
In earlier generations of resists (often based on novolok phenolformaldehyde polymers), each absorbed quantum of radiation induced on average less than one chemical reaction within the material. “Photosolubilizable compositions” for photographic and photoresist applications with overall quantum yields greater than one were described by Smith as early as 1973. The idea was limited in practice, however, until thermostable yet photosensitive onium salts of strong acids were developed by Crivello as PAGs for cationic photopolymerization. The first CA resist for microlithography was reported by the university industry team of Fréchet (University of Ottawa) and Willson and Ito (IBM Inc.), who combined onium salts with the acid-deprotectable poly(4-[t-butyloxycarbonyloxy]styrene) (poly-TBOCST), and coined the term chemical amplification. Over 200 articles and several reviews have appeared on this topic between January 1992 and June 1994 alone.
In chemical amplification (CA) resists, the primary photochemical event produces a mobile catalyst that, typically during later postexposure baking (PEB), goes on to induce a cascade of material transforming secondary catalytic events within a 5-25 nm radius. Such chemical amplification thus makes possible an overall quantum yield (the number of material reactions divided by number of absorbed photons) of up to several hundred. Thus, a CA resist must contain:
- a small amount (ca. 1-5 wt%) of radiation-sensitive catalyst precursor, generally a photoacid generator (PAG);
- many chemical groups that can react by elimination, addition, or rearrangement only in the presence of catalyst;
- a polymer matrix able to disperse all other components in a smooth clear film; and
- optional additives to improve performance or processability; e.g., surfactants, photosensitizers, and etch resistors.
Although in most reported compositions the catalyst-sensitive groups are polymer-bound and the catalyst precursors are free (i.e., i + ii~iii), components i-iii or iv can in principle be interconnected in any combination, as small molecules, homopolymers, copolymers or blends (e.g., i + ii + iii, i~ii + iii, i~ii~iii). Along with their higher sensitivity and contrast in forming images, CA are also better than earlier resists in being more flexible in design and formulation, versatile in radiation source (electromagnetic or particle beams), and compatible with dry (plasma), multilayer, and other advanced pattern transfer techniques. In general, resist systems can be classified on the basis of their design, namely, one-, two-, or multi-component systems. One-component resist systems consist of pure polymers that must combine all the necessary attributes such as substrate protection, radiation sensitivity, and film-forming characteristics. The most popular resist designs in modern lithography are based on two-component systems in which resist functions are provided by two separate components.
Resist systems can also be divided into three groups on the basis of the radiation source: UV or photoresists, electron-beam resists, and X-ray resists. Photolithography that utilizes UV light has been the predominant technology in semiconductor manufacture and will continue to be so in the foreseeable future. X-ray lithography is capable of producing high-resolution, high-aspect-ratio (height-width) images and is considered to be the technology of the future, whereas elctron-beam lithography is used in photomask fabrication. Photolithography can be further subdivided into near-UV (350-450 nm), mid-UV (300-350 nm), and deep-UV (< 300 nm) technologies, depending on the wavelength of the exposure. The resolution is proportional to the exposing wavelength and inversely proportional to the numerical aperture (NA) of the lens. Thus the i-line (365 nm) with a high-NA lens shifting from the g-line (436 nm), has been regarded as the dominant technology in the manufacture of 16-megabit (Mbit) dynamic random access memory (DRAM) devices with a minimum feature size of 0.5 mm. Krypton fluoride (KrF, 248 nm), argon fluoride (ArF, 193 nm), and F2 (157nm) excimer laser technologies are emerging as the minimum feature size continues to shrink far below 0.5 mm down to 80 nm.
The breakthrough that ultimately led to the adoption of 248 nm lithography as the technology of choice for advanced device fabrication was the development of CA resists. The consensus candidate for the next generation of optical lithography tools has been photolithograpy using 193 nm light. At this wavelength, the opacity of traditional aromatic-based materials precludes their use. Alternate resist materials based on aliphatic polymers and dissolution inhibitors have been examined. The introduction of monomers bearing cyclic side groups such as adamantyl or norbornyl significantly improves the etch resistance over that of simple acrylic polymers. Alternately alicyclic structures have been incorporated directly into the polymer backbone offering a second route to 193 nm single layer resists.
The next generation of optical lithography at 157 nm has necessitated new developments in resist technology. Due to their high optical absorbance at 157 nm, single-layer 248 nm and 193 nm photoresists are not a viable alternative. The incorporation of fluorine into polymers have led the way to suitable resist materials.