Traditional implant layers are becoming increasingly complex in design and continuously pushing
resolution limits lower. In response, developer-soluble bottom anti-reflective coatings (DBARCs) were
introduced to meet these more challenging requirements. These DBARCs excelled over the traditional
combination of single-layer resist and dyed resist/top anti-reflective coating (TARC). DBARCs offered the
resolution and critical dimension (CD) control needed for the increasingly critical implant layers.
Lithographic performance, focusing on CD control over topography and through-pitch behavior,
demonstrated the inherent benefit of the DBARCs over the alternative solutions. Small-space residue
testing showed the benefit of photosensitive (PS) DBARCs for cleanout of sub-100 nm trenches. A study
of improved post-develop residue in various ion-implantation processes validated the use of new DBARC
materials in implant layers.
Lithographic scaling beyond the 22 nm node requires double patterning techniques to achieve
pitch values below 80nm. The semiconductor industry is focusing on the development of several process
techniques including track-only lithographic processing methods in order to reduce cost, cycle time and
defects. Initial efforts for track-only double expose processes have relied on the use of chemical freeze
materials to prevent inter-mixing of resists, and also by means of thermal curable materials. These two
techniques may be complementary, in the sense that a chemical freeze may be very robust for protection of
exposed regions, while thermal cure systems may provide strong protection of large unexposed areas.
We will describe our results with mainly the thermal-cure double patterning resist materials, and
the application of these materials to the fabrication of sub-80 nm pitch semiconductor structures. We will summarize the process window and defect capability of these materials, for both line/space and via applications.
Over a period of last several years 193 nm immersion lithography from a remote and unlikely possibility
gradually became a reality in many fabrication facilities across the globe and solid candidate for high volume
manufacturing for the next generation technology node. It is being widely understood in the industry that top-coatless
resist approach is a desirable final stage of the immersion process development. However creating low-defect high
performance top-coatless resist materials requires understanding of the fundamental material properties of the top layer,
responsible for leaching suppression, immersion fluid meniscus stability, and in this way enabling high speed low-defect
scanning.
While a lot of progress has been made in implementing specific top coat materials into the process flow, clear
understanding effects of the top coat properties on the lithographic conditions and printing capability is still lacking. This
paper will discuss top coat materials design, properties and functional characteristics in application to novel
fluoroalcohol polymer-based immersion top coat.
We have used our fluoroalcohol based-series designs (titled MVP top coat materials further on in the paper) as a
test vehicle for establishing correlations between top coat performance and its physical and chemical properties including
hydrophobicity, molecular weight/dispersity etc. Effects of polymer-solvent interactions on the contact angle and
characteristics of the top coat material are explored, providing valuable understanding transferable to design of new
generation top coats and top-coatless materials. Our resultant new designs demonstrated excellent lithographic
performance, profiles and low leaching levels with commercially available resist and high receding contact angles,
comparable to the commercial top coat materials.
The combination of immersion lithography and reticle enhancement techniques (RETs) has extended 193nm
lithography into the 45nm node and possibly beyond. In order to fulfill the tight pitch and small critical dimension
requirements of these future technology nodes, the performance of 193nm resist materials needs to further improve. In
this paper, a high performance 193nm photoresist system based on fluorosulfonamide (FSM) is designed and
developed. The FSM group has good transparency at 193nm. Compared to the commonly used hexafluoroalcohol
(HFA) group, the trifluoromethyl sulfonamide (TFSM) functionality has a lower pKa value and contains less fluorine
atoms. Polymers containing the TFSM functionality have exhibited improved dissolution properties and better etch
resistance than their HFA counterparts. Resists based on the FSM-containing polymers have shown superior
lithographic performance for line, trench and contact hole levels under the 45nm node exposure conditions. In
addition, FSM resists have also demonstrated excellent bright field and dark field compatibility and thereby make it
possible to use one resist for both bright field and dark field level applications. The structure, property and lithographic
performance of the FSM resist system are reported.
The focus of this paper is to utilize the acidity of hexafluoroalcohol (HFA) in addressing performance deficiencies associated with current 193nm methacrylate resist materials. In this study, we have designed and developed a variety of HFA pendant methacrylate monomers and the corresponding imaging polymers for ArF lithography. It was shown that typical swelling behavior observed in methacrylate resists can be substantially reduced or eliminated by replacing commonly used multicylcic lactone polar functionalities with acidic HFA side chains. The incorporation of aliphatic spacers between HFA and polymer backbone were found to be more effective than cyclic hindered moieties, in achieving linear dissolution characteristics. The typical poor etch stability associated with fluorine atoms in HFA can be substantially minimized by designing side chains with a combination of appropriate cyclic and aliphatic moieties and fine-tuning the corresponding polymer compositions. PEB sensitivity of high activation energy protecting group (e.g., methyladamentyl group) based methacrylate resists can be substantially improved through the incorporation of acidic HFA side chains (6nm/C to <1 nm/C). The key application space for HFA-methacrylate resists appears to be trench level lithography. It was also demonstrated that these HFA materials are compatible with immersion lithography and result in dramatically improved process windows for iso trench features, in addition to other lines/space features.
To make immersion lithography a reality in manufacturing, several challenges related to materials and defects must be addressed. Two such challenges include the development of water immersion compatible materials, and the vigorous pursuit of defect reduction with respect to both the films and the processes. Suitable resists and topcoats must be developed to be compatible with the water-soaked environment during exposure. Going beyond the requisite studies of component leaching from films into the water, and absorption of water into the films, application-specific optimization of photoresists and top coats will be required. This would involve an understanding of how a wide array of resist chemistry and formulations behave under immersion conditions. The intent of this paper is to compare lithographic performance under immersion and dry conditions of resists containing different polymer platforms, protecting groups, and formulations. The compatibility of several developer-soluble top-coat materials with a variety of resists is also studied with emphasis on profile control issues. With respect to defects, the sources are numerous. Bubbles and particles created during the imaging process, material remnants from incomplete removal of topcoats, and image collapse as related to resist swelling from water infusion are all sources of yield-limiting defects. Parallel efforts are required in the material development cycle focusing both on meeting the lithographic requirements, and on understanding and eliminating sources of defects. In this paper, efforts in the characterization and reduction of defects as related to materials chemistry and processing effects will be presented.
Fluorinated dissolution inhibitors (DIs) for 157 nm lithography were designed and synthesized as part of an ongoing study on the structure/property relationships of photoresist additives. The problem of volatilization of small DI candidates was observed from matrices such as poly(methyl methacrylate) (PMMA) and poly(hexafluorohydroxy-isopropyl styrene) (PHFHIPS) during post-apply bake cycles using Fourier Transform Infrared Spectroscopy (FT-IR). To avoid this problem, low volatility fluorinated inhibitors were designed and synthesized. Three fluorinated DIs, perfluorosuberic acid bis-(2,2,2,-trifluoro-1-phenyl-1-trifluoromethyl-ethyl) ester (PFSE1), perfluorosuberic acid bis-[1-(4-trifluoromethyl-phenyl)-ethyl] ester (PFSE2) and a fluorinated phenylmethanediol diester (FPMD1), largely remained in a PHFHIPS film during the post-apply bake. The dissolution behavior of the two fluorinated diesters was studied and found to slow down the dissolution rate of PHFHIPS with inhibition factors of 1.9 and 1.6, respectively. The absorbance of PHFHIPS films containing 10 wt% of the diester inhibitors is 3.6 AU/micron compared with an absorbance of 3.3 AU/micron for the polymer itself. The absorbance of 10% FPMD1 in PHFHIPS was measured as 3.5 AU/micron compared with an absorbance of 3.4 AU/micron for the polymer itself. Thus, the non-volatility and transparency of the fluorinated inhibitors at 157 nm as well as their ability to reduce the development rate of fluorinated polymers make them suitable for use in a 157 nm resist system.
We report on a lithographic study of the behavior of non- cholate tert-butylcarboxylate dissolution inhibitor (DI's) formulated in a poly(norbornene/maleic anhydride/acrylic acid/tert-butyl acrylate) 193 nm single layer resin. A comparision is made between formulations containing non- cholate DI's, cholate based DI's and formulations containing blends of the two different types of DI's. It was found that formulations containing the non-cholate materials tended to give T-topped profiles while the formulations containing cholate based materials and blends containing as little as 1% cholate based DI did not.
Post exposure bake (PEB) models in the STORM program have been extended to study pattern formation in 193 nm chemically amplified resists. Applications to resists formulated with cycloolefin-maleic anhydride copolymers, cholate based dissolution inhibitor, nonaflate photoacid generator and base quencher are presented. The PEB modeling is based on the chemical and physical mechanisms including the thermally induced deprotection reaction, acid loss due to base neutralization and protected-sites-enhanced acid diffusion. Simplifying assumptions are made to derive analytical expressions for PEB. The model parameters are extracted from the following experiments. UV-visible spectroscopy is used to extract the resist absorbance parameters. The generation of acid is monitored using the method of 'base additions.' The extent of deprotection that occurs during the bake is determined by monitoring the characteristic FTIR absorbance band around 1170 cm-1 over a range of exposure doses and bake temperatures. Diffusion parameters are extracted from line end shortening (LES) measurements. These parameters are optimized using the Method of Feasible Directions algorithm. Application results show good agreement with experimental data for different LES features.
The fundamental nature of the interactions between poly (norbornene-alt-maleic anhydride) based resins and cholate based dissolution inhibitors (DIs) were studied by FT-IR and NMR spectroscopy. We also studied the role that photo-acid generators (PAGs) play in the dissolution of these polymer resins. We attempted to disentangle the hydrophobic effects of the DIs and PAGs from the specific interactions (Van der Waal's, hydrogen bonding or ionic) that these materials have within the polymer system. We employed solubility studies of DIs and PAGs using cloud point determinations and dissolution inhibition experiments on spun films to determine the extent that hydrophobicity and polymer interactions play in development. We found that for simple cholate derivatives the interactions with maleic anhydride repeating units parallel the dissolution inhibition sequence (t-butyllithocholate > t-butyldeoxycholate > t-butylcholate). For a wider range of cholate derivatives, the cloud point in water is a useful predictive tool, in that it takes into account both the hydrophobicity and the propensity to interact with other moieties. Thus for these materials, dissolution inhibition is governed by both interactions between the DI and the polymer, and the hydrophobic nature of the DIs. In contrast, for the PAGs, the cloud point is not a good predictive tool for dissolution inhibition. We found for onium salt materials, that the extent of dissolution inhibition is predicated by the size of the anion. For example, large sterically hindered anions which give rise to PAGs that exhibit poor solubility in water, paradoxically also show poor dissolution inhibition. This may be because the steric hinderance disfavors interactions with the polymer matrix.
We have found that the progress of developer base into films of terpolymers of norbornene (NB)-maleic anhydride (MA) and acrylic acid (AA) is a percolation process with a critical site concentration of x(c) equals 0.084 which suggests that every acrylic acid site in the terpolymer of norbornene-maleic anhydride-acrylic acid can make 12 monomer units of the polymer water compatible. In practice these systems are being used with various tert-butyl esters of cholic acid as dissolution inhibitors. The cholates differ very much in their dissolution inhibition factors (lowest t-butyl cholate (1.3) to highest t-butyl lithocholate glutarate dimer (7.4). The change in these factors corrected for molarity follow the hydrophobic character of the dissolution as measured by log(p). A quick screening method has also been established to evaluate dissolution inhibitors based on our observation that the cloud point (the volume % acetone in a water/acetone which gives persistent cloudiness) parallels the dissolution inhibiting power as measured by the dissolution inhibition factor. For dissolution promotion, optimal results are obtained with t-butyl 1,3,5-cyclohexanetricarboxylate (f equals -6.3) and poorest results with t-butyl lithocholate (f equals -2.8); this appears to track with the number of carboxyl groups and the hydrophobicity of the carboxylic acids. The Rmax found for resist formulations tracks well with these findings. Another factor in determining the ultimate achievable contrast is the degree of acidolytic deprotection achieved by the material. It appears that acidolyticaly cleaveable carboxylate esters with a higher concentration of electron withdrawing groups such as t-butyl 1,3,5-cyclohexanetricarboxylate are more effective.
The fundamental nature of the interaction between the polymer matrix and the cholate based dissolution inhibitors are being studied by Fourier Transform-IR (FTIR) spectroscopy. It was found that the simple cholate derivatives undergo, in a blend with poly(norbornene-alt- maleic anhydride) and in a blend with the terpolymers poly(norbornene-alt-maleic anhydride-co-t-butylacrylate) and poly(norbornene-alt-maleic anhydride-co-acrylic acid), stronger interaction as seen by shifts in the OH region of the spectra than do blends with dimeric or oligomeric cholates.
Through a series of statistical design experiments we optimized the lithographic performance of a 193 nm single layer resists based on a norbornene-maleic anhydride matrix resin. Several interesting findings were found including that having the PEB temperature improved the performance of the resist. The polymer composition was found to strongly influence the lithographic performance of the resist. Variables that we examined included acrylate loading and blocking level. By optimizing the composition of the polymer, we have obtained resist with high etch resistance, square profiles and 0.130 micron dense line ultimate resolution in 0.5 micron thick films. The resist formulations are compatible with industry standard 0.262 N TMAH. During exposure the resists does not suffer from the outgassing of volatile species.
Plasma polymerized methylsilane (PPMS) films exposed to UV light in the presence of air undergo photo-oxidation to produce a glass-like material, PPMSO, which can be selectively removed using aqueous HF based chemistries. We find that PPMS, used in such positive tone imaging processes, suffers from several drawbacks which make it an unattractive candidate for use as an imaging layer in positive tone resist schemes. We have used infrared and X- ray photoelectron spectroscopy to characterize the PPMS films. We have found evidence for the presence of bridging methylene groups in the Si-Si backbone of the PPMS polymer at the PPMS/Substrate interface. This thin underlayer of a polycarbosilane material is initially deposited in the PPMS CVD process and is insoluble in aqueous or vapor HF contributing to residue after the development. The limitation as to how rapidly PPMS films can be photo- oxidized in the presence of air using high-fluence laser steppers is determined by the rate of oxygen diffusion into the PPMS films during exposure. This reciprocity failure exhibited by PPMS films may limit positive tone PPMS processing from consideration in high-throughput UV based lithography.
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