We will discuss our approach towards a second generation radiation sensitive developable bottom antireflective
coating (DBARC's) 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.
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.
KEYWORDS: Line edge roughness, Line width roughness, Polymers, Semiconducting wafers, Lithography, Transistors, Diffusion, Photoresist processing, Critical dimension metrology, Control systems
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.
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).
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.
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.
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.
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.
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.
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.
Liquid immersion lithography (LIL) can extend the resolution of optical lithography well beyond today’s capabilities. The half-pitch limit is given by the well-known formula P=λ/(4/NA), where λ is the optical wavelength and NA=nsin(θ) is the numerical aperture of the exposure device with n the refractive index of the exposure medium. Through the use of exposure media such as purified water (n of 1.44 at 193 nm), it is possible to reduce minimum pitches by a factor of as much as 44% - a full technology node. Beyond this simple observation, there is a good deal of work necessary to fully understand the impact of LIL on a lithography processes. This paper will address issues con-cerning resist chemistry and the impact of water immersion on the imaging capabilities of different resist formulations. All resists were evaluated by imaging dense line-space structures at a 65-nm half-pitch both in air and with water im-mersion. Studies of dense 65-nm lines made by immersion imaging in HPLC grade water with controlled variations in resist components were performed. Significant differences were observed and will be discussed.
This paper is part of our continuing work on a new generation of more transparent, 157 nm resist platforms, which are based upon capping of fluoroalcohol-substituted, transparent perfluorinated resins (TFR) with a tert-butoxycarbonylmethyl (BOCME) moiety. Recent results indicate that by optimizing both resin structure and loading of photoacid generator and base additive a good compromise can be achieved between resolution power, dark erosion resistance, sensitivity and transparency at 157 nm. Specifically, it was found that a decrease in PAG (50% nominal loading) and base loading (75% nominal loading), coupled with optimization of the TFR resins to achieve higher transparency, gives the best compromise of properties. In this manner, resist systems with a transparency as low as 0.87 AU/micron were designed capable of resolving 60 nm 1:1 features, at a dose of 92 mJ/cm2 (non corrected for sigma), using a strong phase shift mask, and a sigma of 0.3 on a Exitech 157 nm small field mini-stepper. This type of resist material has also been imaged with a larger field tool (DUV30 Micrascan VII) to give 80 nm 1.1.5 L/S features at a dose of 135 mJ/cm2 employing using a Binary mask (σ=0.85). Finally, it was found that our BOCME-TFR based resist system can be used to transfer a 120 nm L/S pattern (imaged by 193 nm lithography) into a hardmask stack on top of silicon.
A statistical design of experiments for the post-applied bake and post-exposure bake temperatures for two types of resists, the commercial formulation AZ FX 1000P and an experimental resist AZ EXP 20 X, was carried out using contrast, clearing dose and dark erosion as response variables examined. It was found that for AZ FX 1000P dark erosion could be suppressed entirely and contrast improved by employing a lower PEB without significant impact on the contrast. In this manner, a substantial improvement in the image quality for AZ FX 1000P was obtained. AZ EXP 20X was not susceptible to dark erosion at higher post-applied bakes as was AZ FX 1000P. Both resists gave better imaging at lower post-exposure bake temperatures in the range of ~110°C, presumably because of excessive acid diffusion at higher temperatures, such as 150°C. Generally, the contrast achievable with AZ EXP 20 X (>16) is much higher than that possible for AZ FX 1000P (~6).
As part of a new generation of more transparent 157 nm resist platforms we are developing, a novel resist system is described that has higher transparency and contrast than AZ FX 1000P. Using a new protecting group strategy, encouraging results have been obtained with both poly(α,α-bis(trifluoromethyl)bicyclo(2.2.1)hept-5-ene-2-ethanol) and a more transparent perfluorinated resin (TFR). These new resist systems show absorbance values as low as 1 μm-1 at 157 nm, have twice the contrast (i.e., 12 instead of 7) of AZ FX 1000P, and have neither significant dark erosion nor do they switch to negative tone behavior within the dose range studied. The dry etch resistance of the TPR platform is found to be superior to APEX-E DUV resist for polysilicon but somewhat lower for oxide etches. Features as small as 50 nm lines and spaces were resolved for slightly relaxed pitches (1:1.5 micron). By adjusting the base level it is possible to improve the photospeed by a factor of more than 10 while still maintaining a resolution of 70 nm L/S features.
We have studied 193 nm contact hole resists in view of resist components, process conditions and optical settings. Sidewall roughness was improved by optimizing photoacid generators. Side lobes were eliminated by applying higher post exposure bake temperature or modification of polymers. The influence of optical settings, types of masks and mask bias was discussed with simulation and lithographic results and guidelines for better resolution and iso-dense bias were proposed. The optimized formulation, AZAX1050P has a high resolution combined with a large depth of focus and an iso- dense overlap window (130 nm(NA=0.63) DOF 0.38micrometers Exposure latitude 10%).
The design of 157 nm photoresists is a daunting task since air, water, and most organic compounds are opaque at this wavelength. Spectroscopic studies1 led to the observation that fluorinated hydrocarbons and siloxanes offer the best hope for the transparency that is necessary for the design of an effective 157nm photoresist, and these classes of materials have quickly become the prominent platforms for a variety of research activities in this field. There have been a number of authors that have suggested that negative resists have unique attributes for specific device applications. Numerous authors have discussed negative photoresists over the years. There are many uses for such materials at various levels in a semiconductor device. One such use is with complementary phase shift mask thus eliminating the need for a second exposure step. This paper reports our recent progress toward developing a negative 157nm resist materials based on fluoropolymers with crosslinkers that are transparent at 157nm. The authors will report on the synthesis of the polymers used in this work along with the crosslinkers and other additives used in the formulation of the photoresist. Imaging experiments at practical film thicknesses at 157nm with binary and strong phase shifting masks will be shown demonstrating imaging capabilities. Spectroscopic data demonstrating chemical mechanisms and material absorbance will be shown along with other process related information.
The copolymerization reaction between methyl cyanoacrylate (MCA) and a variety of cycloolefins (CO) was investigated. Cycololefin/cyanoacrylate (COCA) copolymers were obtained in good yields and with lithographically interesting molecular weights for all cycoolefins studied. Anionic MCA homopolymerization could be largely suppressed using acetic acid. Based on NMR data, the copolymerization may tend to a 1:1 CO:MCA incorporation ratio but further work with better suppression of the anionic component is needed to confirm this. Lithographic tests on copolymers of appropriately substituted norbornenes and MCA showed semi-dense and isolated line performance down to 90 nm.
Fluorocarbon based polymers have been identified as promising resist candidates for 157nm material design because of their relatively high transparency at this wavelength. This paper reports our recent progress toward developing 157nm resist materials based on transparent dissolution inhibitors. These 2 component resist systems have been prepared and preliminary imaging studies at 157nm are described. Several new approaches to incorporating these transparent monomers into functional polymers have been investigated and are described. The lithographic performance of some of these polymers is discussed.
In our previous experiment for sub-0.15micrometers contact hole, we used water-soluble organic over-coating material (for short: WASOOM) as a barrier layer to distribute thermal stress evenly from top to bottom of contact hole resist. It is assumed that WASOOM inside a contact hole will be acting as a barrier layer (or buffer) so that overhang can be reduced. In this paper we will describe a 0.1micrometers contact hole process with well controlled DICD and good etch profile. In order to get a good WASOOM for this study, lots of water soluble polymers have been evaluated. Our methods for resist flow technique use WASOOM's property that it should not react with photoresist at high temperature. The criteria and chemistry of good WASOOM materials will be described for further study. In addition to WASOOM material, we will also explain the results of top flare by using PVP based WASOOM and appropriate etch processes. For etching characterization, we used C5F8 chemistry for the initial study and then later on it is found that there is some etch stop issue which appears related to surface carbon contamination of the etch front coming from C5F8. This surface contamination issue will be also investigated. Mixed C5F9/CF4 chemistry was introduced to make a more robust etching process. This uses the carbon polymerization of C5F8 for good etching profile and adds a small portion of CF4 to generate radical CF species which will prevent etch stop.
The development of sufficiently transparent resin systems is one of the key elements required for a successful and timely introduction for 157 nm lithography. This paper reports on the Simple Transmission Understanding and Prediction by Incremental Dilution (STUPID) model, a quick back-of-the-envelope increment scheme to estimate the absorption of polymers at 157 nm. A number of promising candidate resins based on norbornenes are discussed, and results with a first 157 nm resin system developed at the University of Austin are presented. The new system is based on copolymers of norbornene-5-methylenehexafluoroisopropanol (NMHFA) and t-butyl norbornene carboxylate (BNC), formulated with an acetal additive obtained by copolymerization of t-butyl norbornene-5-trifluoromethyl-5-carboxylate (BNTC) with carbon monoxide. Lithographic performance of this system extends to 110 nm dense features using standard illumination and a binary mask, or 80 nm semi-dense and 60 nm isolated features with a strong phase shift mask. The dry etch resistance of this resist is found to be slightly lower than APEX-E DUV resist for polysilicon but superior to it for oxide etches.
KEYWORDS: Scanning electron microscopy, Electron beams, Lithography, 3D metrology, Line edge roughness, Polymers, 3D image processing, Imaging technologies, Semiconducting wafers, Photoresist materials
In addition to stability and collapse issues facing 193 nm resists, a new concern is rising regarding line width decrease when exposed to an electron beam (e-beam) during CD measurements using scanning electron microscope (SEM). Such an interaction between the measurement system and sample materials poses a great challenge in process development for 193 nm lithography which is believed to be next lithography node. This paper reports the investigation results of 193 nm resist line width slimming under e-beam. We have observed vertical, as well as lateral 193 nm resist shrinkage under e-beam exposure using VeraSEM 3D's unique sidewall imaging technology. We have observed different CD changing behaviors for lines and spaces, as expected. Repeated SEM CD measurements on space magnify the CD changing effect due to 3-5 times more resist exposed to the d-beam than a line. Hence, the influence of other competing effects form line edge roughness, carbonization etc. are reduced. By measuring a space or an edge width at a tilted view, the severity of resist shrinkage of different resist types can be compared directly with a high level of confidence.
KEYWORDS: Data modeling, Chemically amplified resists, Photoresist processing, Systems modeling, Polymers, Process modeling, Lithography, Molecules, Interfaces, Computing systems
Improvements in the modeling of chemically amplified resist systems are necessary to extract maximum possible information form limited experimentation. Previous post- exposure bake models have neglected volume shrinkage, thus violating the continuity equations used to model the process. This work aims at describing the kinetics of the post-exposure bake process by tracking the volume shrinkage observed in both low and high activation energy resists. Both static and dynamic models are derived and corroborated with experimental results for Shipley UV5 and AZ 2549 resists. A global simulation technique is then used in conjunction with the models to extract the lithography parameters for these resists.
Chemically Amplified Resists (CARs) are much less observable than their i-line counterparts due to the absence of photoresist actinic absorbency. CARs however, exhibit resist thinning during the Post-Exposure Bake process (PEB). A Design of Experiments (DOE) technique was employed around the exposure and the PEB temperature for a commercial DUV photoresist. A Fourier Transform Infrared (FTIR) technique was used to measure the deprotection of the CARs after the PEB step while standard interferometry techniques were used for exposed area thickness loss measurements after the PEB step. Our analysis indicates that exposed area thickness loss is strongly correlated to the deprotection of the photoresist, so that thickness loss can serve as a reliable deprotection indicator and can hence be possibly used as an observable for control of the photolithography sequence.
Access to the requested content is limited to institutions that have purchased or subscribe to SPIE eBooks.
You are receiving this notice because your organization may not have SPIE eBooks access.*
*Shibboleth/Open Athens users─please
sign in
to access your institution's subscriptions.
To obtain this item, you may purchase the complete book in print or electronic format on
SPIE.org.
INSTITUTIONAL Select your institution to access the SPIE Digital Library.
PERSONAL Sign in with your SPIE account to access your personal subscriptions or to use specific features such as save to my library, sign up for alerts, save searches, etc.