Andrew Romano

Resist component leaching in 193 nm immersion lithography

The leaching of ionic PAGs from model resist films into a static water volume is shown to follow first order kinetics. From the saturation concentration and the leaching time constant, the leaching rate at time zero is obtained which is a highly relevant parameter for evaluating lens contamination potential. The levels of leaching seen in the model resists generally exceed both static and rate-based dynamic leaching specifications. The dependence of leaching on anion structure shows that more hydrophobic anions have lower saturation concentration; however, the time constant of leaching increases with anion chain length. Thus in our model system, the initial leaching rates of nonaflate and PFOS anions are identical. Investigation of a water pre-rinse process unexpectedly showed that some PAG can still be leached from the surface although the pre-rinse times greatly exceeded the times required for saturation of the leaching phenomenon, which are expected to correspond to complete depletion of leachable PAG from the surface. A model is proposed to explain this phenomenon through re-organization of the surface as the surface energy changes during the air/water/air contact sequence of the pre-rinse process.

Understanding the photoresist surface-liquid interface for ArF immersion lithography

Extraction of small molecule components into water from photoresist materials designed for 193 nm immersion lithography has been observed. Leaching of photoacid generator (PAG) has been monitored using three techniques: liquid scintillation counting (LSC); liquid chromatography mass spectrometry (LCMS); and scanning electrochemical microscopy (SECM). LSC was also used to detect leaching of residual casting solvent (RCS) and base. The amount of PAG leaching from the resist films, 30 - 50 ng/cm2, was quantified using LSC. Both LSC and LCMS results suggest that PAG and photoacid leach from the film only upon initial contact with water (within 10 seconds) and minimal leaching occurs thereafter for immersion times up to 30 minutes. Exposed films show an increase in the amount of photoacid anion leaching by upwards of 20% relative to unexposed films. Films pre-rinsed with water for 30 seconds showed no further PAG leaching as determined by LSC. No statistically significant amount of residual casting solvent was extracted after 30 minutes of immersion. Base extraction was quantified at 2 ng/cm2 after 30 seconds. The leaching process is qualitatively described by a model based on the stratigraphy of resist films.

Surface roughness investigation of 157- and 193-nm polymer platforms using different etch conditions

A series of different fluorinated polymer platforms used for early and current 157-nm photoresists is investigated with regard to blanket etch properties and surface roughness. Besides methacrylic-based polymers applied for 193-nm lithography, fluorine containing norbornene homopolymers, fluorinated cycloolefines, and tetrafluoroethylene (TFE) norbornene copolymers are chosen. Etch rates in different plasmas used for several applications, such as poly, SiN mask open, and selective/nonselective SiO2 etch, are determined and compared to standard 193-nm platforms currently used for DRAM manufacturing. Looking at various base resins, significant differences can be found using HBr- or Cl2-based poly etch conditions and various fluorocarbon-based oxide etch chemistries. Up to 2.4 times higher etch rates in Cl2 and the different CxFy oxide etch recipes are observed for the highly fluorinated cycloolefines and the TFE norbornenes, showing a strong correlation between fluorine content and etch rate. After stress by different etch conditions, the polymer surfaces are characterized using atomic force microscopy (AFM) and scanning electron microscopy (SEM). Surprisingly, the surface roughness of the methacrylic platforms and the norbornene base resin (determined by AFM) are found to be substantially higher than that of the highly fluorinated platforms. These results can directly be correlated to pictures obtained by optical methods (SEM).

193nm dual layer organic BARCs for high NA immersion lithography

Extending the resolution capability of 193nm lithography through the implementation of immersion has created new challenges for ArF B.A.R.C.s. The biggest of which will be controlling reflectivity over a wider range of incident angles of the incoming imaging rays. An optimum B.A.R.C. thickness will depend on the angle of incidence of the light in the B.A.R.C. and will increase as the angle increases. At high angles different polarization have different optimum thicknesses. These confounding effects will make it increasingly difficult to control reflectivity over a range of angles through interference effects within a single homogenous B.A.R.C. Unlike single layer B.A.R.C.s, multilayer B.A.R.C.s are capable of suppressing reflectivity through a wide range of incident angles. In fact, remarkable improvements in antireflective properties can be achieved with respect to CD control and through angle performance with the simplest form of a multilayer B.A.R.C., a dual layer. Here we discuss the attributes of an all organic dual layer B.A.R.C. through simulations and preliminary experiments. One attribute of an organic over inorganic B.A.R.C. in high-NA lithography is its ability to planarize topography. ArF scanners designed to meet the needs of the 45nm node will have a very small depth-of-focus (DOF) which will require planar surfaces.

Second-generation radiation sensitive developable bottom anti-reflective coatings (DBARC) and implant resists approaches for 193-nm lithography

We will discuss our approach towards a second generation radiation sensitive developable bottom antireflective coating (DBARCs) for 193 nm. We will show imaging results (1:1 L/S features down to 140 nm) for some first generation implant resist material based upon a fluorinated resins and also show relative implant resistance of these first generation fluorinated resists towards As implantation (15 KeV at 5x1015 dose with 20 x 10-4 amp). Also, discussed will be a second generation of implant resists based on a non-fluorinated resins. Surprisingly, we found that the nonfluorinated materials gave better implant resistance (~2-3 X1011 atoms/cm2) despite the higher atomic number of fluorine compared to hydrogen in the fluorinated implant materials (~2-5X1012 atoms/cm2). Finally, we will give an update on the lithographic performance of this second generation of implant resists.

Study of barrier coats for application in immersion 193-nm lithography

We will describe our barrier coat approach for use in immersion 193 nm lithography. These barrier coats may act as either simple barriers providing protection against loss of resist components into water or in the case of one type of these formulations which have a refractive index at 193 nm which is the geometric mean between that of the resist and water provide, also top antireflective properties. Either type of barrier coat can be applied with a simple spinning process compatible with PGMEA based resin employing standard solvents such as alcohols and be removed during the usual resist development process with aqueous 0.26 N TMAH. We will discuss both imaging results with these materials on acrylate type 193 nm resists and also show some fundamental studies we have done to understand the function of the barrier coat and the role of differing spinning solvents and resins. We will show LS (55 nm) and Contact Hole (80 nm) resolved with a 193 nm resist exposed with the interferometric tool at the University of New Mexico (213 nm) with and without the use of a barrier coat.

Study of barrier coats for protection against airborne contamination in 157-nm lithography

We summarize our work on devising protective barrier coats for use against airborne contamination when using tert-butoxycarbonylmethyl (BOCME) capped fluoroalcohol resist resins as part of our strategy to develop a 157 nm resist platform. We will describe how a barrier coat (AZ EXP FX Coating 145) consisting of a fluoro-cyclopolymer formulation, soluble in aqueous developer, can improve the post-exposure delay (PED) latitude of 157 nm resist resists exposed under conditions or airborne contamination. Specifically, a 20 nm thick coating of AZ EXP FX Coating 145 gives a PED latitude for L/S features of at least 10 min under condition of airborne amine contamination (10 ppb amine contamination). The barrier coat, AZ EXP FX coating 145 is formulated in a solvent which is compatible with resist film coated from typical 193 nm resist spin casting solvents. Moreover, it can be easily removed as part of the normal aqueous base development scheme, no extra post-apply bake or stripping step is required.

Study of the Effect of Amine Additives on LWR and LER

We will give an account of our investigation on structure property relationships of amines with regards to line width roughness (LWR) and line edge roughness (LER) of a 193 nm alicyclic-acrylate resist. Specifically, we have looked at basicity, molar volume and logD as factors which may have an influence of roughness of 80 nm 1:1 L/S features. For relatively hydrophobic amines (Log D > -1), the lower the hydrophilicity at acidic pH the greater the LER and LWR becomes. Specifically, in this range of Log D, more hydrophobic larger amines, with higher basicity, tend to give worse L/S feature roughness. For amines which are more hydrophilic, the relationship becomes more complex with some amines giving a lower LER while others do not. This appears to be predicated on a delicate balance between basicity, hydrophilicy and size.

Performance of a dry 193nm resist under wet conditions

193 nm immersion lithography is rapidly moving towards industrial application, and an increasing number of tools are being installed worldwide, all of which will require immersion-capable photoresists to be available. At the same time, existing 193 nm processes are being ramped up using dry lithography. In this situation, it would be highly advantageous to have a single 193 nm resist that can be used under both dry and wet conditions, at least in the initial stages of 45nm node process development. It has been shown by a number of studies that the dominant (meth)acrylate platform of 193 nm dry lithography is in principle capable of being ported to immersion lithography, however, it has been an open question whether a single resist formulation can be optimized for dry and wet exposures simultaneously. For such a dry/wet crossover resist to be successful, it will need to make very few compromises in terms of performance. In particular, the resist should have similar LER/LWR, acceptable process window and controlled defects under wet and dry exposure conditions. Additionally, leaching should be at or below specifications, preferably without but at very least with the use of a top protective coat. In this paper, we will present the performance of resists under wet and dry conditions and report on the feasibility of such crossover resists. Available results so far indicate that it is possible to design such resists at least for L/S applications. Detailed data on lithographic performance under wet and dry conditions will be presented for a prototype dry/wet crossover L/S resist.

Study of 157 nm resists with full field exposure tools

A detailed account will be given of work done on the Micrascan VII (NA 0.75) at INVENT in Albany with AZ EXP X20 and AZ EXP X25 resist systems based upon BOCME protected fluoroalcohol resins. These resins were examined either with a high or low level of formulated photoacid generator (PAG). Our evaluations done both with binary and alternating phase shift mask exposures. It was found in our initial studies done at relatively high amine levels (1-2 ppb) that AZ EXP X25 X with low PAG gave the best performance.