Developer-soluble bottom anti-reflective coating (DBARC) BSI.W09008 has provided promising lithography results
with five different 193-nm photoresists, with the accomplishments including 120-nm L/S (1:1) and 130-nm L/S
through-pitch (i.e., 1:1, 1:3, and isolated line). This DBARC is not inherently light sensitive and depends on diffusing
photoacid from the exposed photoresist for development. With undercutting being an issue for the PAG-less DBARC
with some resists, the shapes of 130-nm lines (both dense and isolated) were improved by either a) incorporating a small
amount of a base additive in the BSI.W09008 formulation or b) altering the structure of the DBARC's binder polymer.
With selected photoresist(s) and/or resist processing conditions, either photoacid diffusion or photoacid activity is
inadequate to give DBARC clearance and BSI.W09008 performs more as a dry BARC. The post-development residue
obtained from BSI.W09008 on a silicon substrate is much less dependent on the initial DBARC film thickness and the
exposure dose than for earlier-generation photosensitive (PS)-DBARC BSI.W07327A, using the same photoresist.
BSI.W09008 also gives less post-development residue than BSI.W07327A using the same resist on a silicon nitride
substrate at exposure doses of 14-25 mJ/cm2.
As the semiconductor industry approaches smaller and smaller features, applications that previously used top antireflective
coatings have now begun using developer-soluble bottom anti-reflective coatings (BARCs). However, there
are several drawbacks to a wholly developer-soluble system, mainly because many of these systems exhibit isotropic
development, which makes through-pitch and topography performance unsatisfactory. To solve this problem, we have
developed several photosensitive BARC (PS BARC) systems that achieve anisotropic development. One issue with the
PS BARC, as with traditional dry BARCs, is resist compatibility. This effect is compounded with the photosensitive
nature of our materials. The acid diffusion and quenching nature of the resists has been shown to have a significant
effect on the performance of the acid-sensitive PS BARC. Some resists contain a highly diffusive acid that travels to the
PS BARC during the post-exposure bake and aids in clearance. Others show the opposite effect, and the same PS BARC
formulation is not able to clear completely. To address the lack of compatibility and to further improve the PS BARC,
we have developed a solution that properly matches PS BARC and photoresist performance.
In a search for improved resolution and processing latitude for a family of light-sensitive developer-soluble bottom antireflective
coatings (BARCs), the structure of the binder terpolymer was altered by incorporating acid-cleavable
adamantyl methacrylates. Contrast curves and 193-nm microlithography were then used as tools in developing a novel
developer-soluble adamantyl BARC which does not include a photoacid generator (PAG) or quencher, but instead
depends on acid diffusing from the exposed resist for development. This formulation eliminates concern about PAG or
quencher leaching out of the BARC during application of the photoresist. Resolution for a resist A and the new BARC
was 150-nm L/S (1:1) for both 38-nm and 54- to 55-nm BARC thicknesses. Resolution and line shape were comparable
to that of the non-adamantyl control BARC with same resist at 55-nm BARC thickness, with both BARCs giving some
undercutting using an AmphibianTM XIS interferometer for the 193-nm exposures. Light-sensitive adamantyl BARCs
that do require inclusion of a PAG for optimum lithography with resist A are also described in this paper. The series of
developer-soluble adamantyl BARCs were solution and spin-bowl compatible. The 193-nm optical parameters (n and
k) for all adamantyl BARCs were 1.7 and 0.5-0.6, respectively.
A photosensitive developer-soluble bottom anti-reflective coating (DBARC) system is described for KrF and ArF lithographic applications. The system contains an acid-degradable branched polymer that is self-crosslinked into a polymeric film after spin coating and baking at high temperature, rendering a solvent-insoluble coating. The DBARC coating is tunable in terms having the appropriate light absorption (k value) and thickness for desirable reflection control. After the exposure of the resist, the DBARC layer decrosslinks into developer-soluble small molecules in the presence of photoacid generator (PAG). Thus the DBARC layer is removed simultaneously with the photoresist in the development process, instead of being etched away in a plasma-etching chamber in the case of traditional BARC layers. The etch budget is significantly improved so that a thin resist can be used for better resolution. Alternatively, the etch step can be omitted in the case of the formation of layers that may be damaged by exposure to plasma.
A family of dye-filled developer-soluble bottom anti-reflective coatings (BARCs) has been developed for use in 193-nm
microlithography. This new dye-filled chemical platform easily provides products covering a wide range of optical
properties. The light-sensitive and positive-working BARCs use a transparent polymeric binder and a polymeric dye in
a thermally crosslinking formulation, with the cured products then being photochemically decrosslinked prior to
development. The cured BARC films are imaged and removed with developer in the same steps as the covering
photoresist. Two dye-filled BARCs with differing optical properties were developed via a series of DOEs and then used
as a dual-layer BARC stack. Lithography with this BARC stack, using a 193-nm resist, gave 150-nm L/S (1:1). A
193-nm dual-layer BARC stack (gradient optical properties) from the well-established dye-attached family of light-sensitive
BARCs also gave 150-nm L/S (1:1) with the same resist. However, the latter provided much improved line
shape with no scumming. The targeted application for light-sensitive dual-layer BARCs is high-numerical aperture
(NA) immersion lithography where a single-layer BARC will not afford the requisite reflection control.
This paper describes the chemistry and performance of a new family of wet-developable (wet) bottom anti-reflective coatings (BARCs) that have been developed for 193-nm implant layer applications. These BARCs, which are light sensitive and positive working, are imaged and developed in the same steps as the covering 193-nm photoresist. The BARCs are spin coated from organic solvents and then insolubilized during a hot plate bake step. The resulting cured films exhibit minimal solubility in numerous organic solvents. Resolution of a photoresist A and light-sensitive BARC I at optimum exposure (Eop) on a silicon substrate was 150-nm L/S (1:1), with good sidewall angle and no scumming. These best-case results utilize a first reflectivity minimum BARC thickness and meet the desired resolution goals for noncritical implant layers. BARC optical parameters can easily be adjusted by altering the polymeric binder. PROLITHTM modeling shows that near zero reflectance can be achieved on a silicon substrate for both a first and a second reflectivity minimum BARC thickness. The light-sensitive, wet BARCs are both spin-bowl and solution compatible with most industry standard solvents. A selected BARC from this family of wet products was shown to be stable, providing reproducible film properties over several months of ambient storage conditions.
This paper presents our progress in developing spin-on, thermosetting hardmasks and bottom antireflective coatings (BARCs) for 193-nm trilayer usage. Binder materials that were used in preparing the silicon-containing hardmasks include polymers with pendant alkylsilane function and various polyhedral oligomeric silsesquioxane (POSS) substances, with the hardmasks being very transparent at both 193 and 248 nm. The second generation hardmasks (POSS-containing) offer significant improvements over earlier materials in oxygen (O2) plasma etching resistance. The etching selectivity (O2 plasma) for a trilayer BARC relative to the best-case hardmask is about 31.5:1 (15-second etch), with the selectivity numbers being much higher for longer etching times. The preferred hardmask is both spin-bowl and solution compatible. The new trilayer BARCs use binders that are rich in aromatic content for halogen plasma etching resistance, but the antireflective products also feature optical parameters that allow low reflectivity into the photoresist. The BARCs are very spin-bowl compatible. At about 500-nm film thickness, selected BARCs have provided 80-95% planarity over 200-nm topography. Combining the two thermosetting products (hardmask and BARC) with a thin 193-nm photoresist in a trilayer configuration has given excellent 80-nm L/S (1:1) after exposure and wet-development. A conventional resist has provided 100-nm L/S (1:1.4).
This paper highlights the performance of new materials that have been developed for use in 193-nm trilayer microlithography. The products are embedded etch masking layers (EMLs) and bottom antireflective coatings (BARCs). Both coatings are spin applied from organic solvent(s) and then thermoset during a hot plate bake. The EMLs (middle layers) are imaging compatible with JSR, Sumitomo, and TOK 193-nm photoresists. Best-case trilayer film stacks have given 100-nm dense and semi-dense L/S. Plasma etching, selectivities and solution compatibility performance of the EMLs meet or exceed proposed product targets. In addition, the EMLs exhibit both solution and plasma etching properties that should lead to successful rework processes for photoresists. The multiplayer BARCs offer good thick film coating quality and contribute to excellent images when used in trilayer applications. Combining the EMLs, which are nearly optically transparent (k=0.04) at 193-nm, with the new trilayer BARCs results in outstanding Prolith simulated reflectance control. In one modeling example, reflectance is a flat line at 0.5% on five different substrates for BARC thicknesses between 300 and 700-nm.
The need for constant reduction in critical dimensions (CD) of integrated circuits to make them faster has been the driving force for next generation lithography. Currently KrF (248nm) is the shortest wavelength of light being used by IC manufacturers to mass produce devices. If the semiconductor industry continues at the same pace of packing more information on a chip, shorter wavelength (193nm) (ArF Excimer laser) will soon be introduced in production. Shorter wavelengths mean larger swing ratios, CD variations, reflective notching and standing waves due to sharp increase in reflectivity. Therefore some mechanism to reduce reflectivity becomes increasingly important at shorter wavelengths. Bottom antireflective coatings (BARCs) will play an important role in this endeavor. This paper discusses the chemistry and performance of two new spin-on organic 193nm BARCs (ARC 27 and ARC 28) optimized for their use at 1st reflectivity minimum thickness (30-40nm). The optical values of ARC 27 (n= 1.7, k= 0.56) measured by ellipsometer at 193nm give 0% reflectivity at the 1st reflectivity minimum with the optimum thickness of the BARC being 30nm. Lithographic studies with 193nm photoresist show good performance down to 90nm with isolated line (PAR705) and 100nm with dense line photoresist (PAR710,718). The optical properties of ARC 28 are 1.53 and 0.54 and a nominal thickness of 40nm on silicon is recommended to achieve 0% reflectivity. It shows good resolution at 110nm L/S and broad photoresist compatibility.
The list of desired properties for a spin-on 193-nm BARC steadily increases. In response, crosslinkable polymers from different chemical families than the conventional acrylics and vinyls are being studied for applicability in preparing improved thermosetting BARCs. Alternate polymer platforms discussed in this paper include polyethers, polyesters, polyurethanes, and polysaccharides. A BARC that uses a blend or mixture of commercially-available polymers for the binder is highlighted and the product's performance is described. The BARC parameters that are discussed include film properties, flash point, optical data and reflectivity, solution and spin-bowl compatibility, plasma etching rate, resist profile, conformality, and metals content. Based on the test results outlined in this paper, the polymer blend BARC JM2218-56 is expected to advance towards commercialization.
Two organic, spin-on BARCs are in the small scale manufacturing phase -- with the goal being a 193-nm product optimized for commercialization. Chemistries of the BARCs are shown in this paper and performance of the two products relative to industry accepted needs is discussed. The thermoset BARCs, EXP98090B and EXP99001D, are prepared from hydroxy-functional, dye-attached acrylic polymers by adding an aminoplast and sulfonic acid catalyst. With select 193-nm resists, the BARCs give resolution of L/S pairs down to 0.12 micrometer. Plasma etch rates of both BARCs are comparable to those of 193-nm photoresists. Other BARC performance parameters that are discussed for the two products include: film and optical properties, conformality, simulated reflectance curves, spin-bowl compatibility, metals content, and defects.
This paper presents the chemistries and properties of organic, spin-on, bottom antireflective coatings (BARCs) that are designed for 193 nm lithography. All of the BARCs are thermosetting and use dye-attached/incorporated polymers. A first generation product, NEXT, will soon be commercialized. NEXT is built form i-line and deep-UV chemistries with the polymeric constituent being a substitute novolac. This product provide outstanding resolution of 0.16 micrometers L/S with several 193 nm photoresists. Second generation chemical platforms under study include acrylics, polyesters, and polyethers with the 193 nm absorbing chromophore being an aromatic function. The performance of selected BARCs from the four platforms is described, including: optical properties, 193 nm litho, plasma etch rates, Prolith modeling data, spin-bowl and waste line compatibility, and ambient stability.
A new bottom antireflective coating (BARC) for 248 nm lithography is described. The new coating has an optical density of approximately 10/micrometers (k equals 0.41 and n equals 1.482) and plasma etches at rates higher than that of DUV resists depending on the etch conditions. Coating conformality is superior to older generation BARCs, also contributing to improved etch dynamics. Excellent 0.25 micrometers features have been obtained with ESCAP, Acetal and t-BOC type photoresists. The new BARC is spin coated from safe solvents and is spin bowl compatible with EBR and photoresist solvents.
Preliminary studies with Brewer Science CD9 ARC have shown that high-intensity ultraviolet exposure results in significant changes in film properties, including thickness, plasma etch resistance, and develop rate. This process has been studied over a range of temperatures and exposure conditions, and their results are interpreted in terms of competing polymer main chain scission and crosslinking reactions. The process represents a path to improved etch performance, and the possibility exists for use of Brewer ARC in a bi-layer portable conformable mask resist scheme.
The properties of a new anti-reflective coating for 248 nm lithography are described. It is formed by thermally cross-linking a spin-on organic coating, and has an absorbance greater than 12/micrometers. It is compatible with UVIIHS and APEX-E photoresists. Thin films (less than 600 angstrom over silicon substrates) are found to completely suppress standing waves, to reduce EO swing curves to less than 3%, and to offer good CD control over typical field oxide topography. The etch rate was found to be comparable to that of the APEX-E photoresist.
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