The critical layer masks for 14 nm and 10 nm logic nodes are typically bright field, and the key features are opaque
structures on the mask. In order to meet the tight critical dimension (CD) requirements on these opaque features the use
of a high quality negative tone chemically amplified e-beam resist (NCAR) is required. Until very recently the only
negative tone e-beam resists available for use by the mask industry were the traditional cross linking type in which ebeam
exposure cross links the material and makes it insoluble in developer. In this paper we will describe the
performance of a new polarity switching type of NCAR resist that works by changing the solubility of the exposed resist
without cross linking. This has the advantage of significantly reduced swelling and scumming and resulted in major
improvements in the resolution of heavily nested features and small clear features on the mask. Additional detailed
characterization results will be described.
Resist materials rely on solubility differences between the exposed and unexposed areas to create the
desired image. Most negative-tone resists achieve the solubility difference by crosslinking the exposed area
causing it to be insoluble in developer. The negative tone resist studied here is a high sensitivity negativetone
resist that relies on polarity switching, similar to a positive-tone mechanism, but where the exposed
area is insoluble in aqueous developer resulting in a negative-tone image. During mask evaluation for 14nm
optical technology applications of the studied non-cross linking (polarity switching) resist, 1 - 5 μm size
blob-like defects were found in large numbers under certain exposure conditions. This paper will describe
the process and methodologies used to investigate these blob defects.
In order to meet the challenging patterning requirements of the 14 nm node, the semiconductor industry has
implemented use of negative tone develop (NTD) and other tone inversion techniques on wafer to enable use of bright field masks which provide an improved lithography process window.1,2,3 Due to e-beam write time and mask pattern fidelity requirements, the increased use of bright field masks means that mask makers must focus on improving the performance of their negative tone chemically amplified resist (NCAR) processes. In addition, the move to heavy use of bright field masks is introducing new challenges for mask makers. Bright field masks for 14 nm critical layers are required to have opaque sub-resolution assist features (SRAFs) as small as 50 nm while at the same time having across mask critical dimension uniformity (CDU) of less than 2 nm (3 sigma) to meet the 2014 ITRS targets.4 Achieving these specifications is particularly difficult for bright field contact and via level masks.
This paper will survey the performance requirements for NCAR resists for building 14 nm critical level masks. As part of this survey, the results of current commercially available and development NCAR resists will be compared. The study will focus on key elements of the resist process pertaining to line edge roughness, pattern fidelity, minimum feature size, and critical dimension control through density with differences in resist type, sensitivity, and thickness. In addition, use of a novel flow cell test apparatus for detailed study of the develop loading performance of the NCAR resists will be described. Data showing the current capability of these NCAR materials as well as remaining 14 nm node performance gaps and issues will be presented.
Electron beam resists develop a surface potential during exposure that can lead to image placement errors of up to several nanometers [1] and cause poor CD uniformity and image quality. To address this problem, we have formulated a conductive polymer that can be coated onto the resist. Our conductive discharge layer (CDL) is water soluble and it is easily removed during subsequent processing steps. We have established that our material has low enough resistance for full charge dissipation during e-beam exposure and have carried out extensive tests to evaluate the impact of the layer on lithographic performance. We will report these findings, which include measurements of the effect of the CDL application on resist resolution, contrast, speed, and roughness on both wafer and on mask.
Semiconductor manufacturing technology is currently undergoing a transformation from immersion
photolithography to double patterning or EUV technology. The resultant resist dimensional size and height shrinks will
require improved pattern transfer techniques and materials.
Underlayer (UL) processes which include chemical vapor deposition (CVD) and spin-on application play a very
important role in various chip manufacturing integration schemes. A pattern wiggling problem during substrate etch has
arisen as a critical issue when pattern dimensions shrink. CVD processes have shown better pattern transfer performance
than spin-on processes but at higher cost and process complexity along with difficulty in obtaining planarization and
good gap fill. Thus spin-on process development has received increased attention recently as an attractive alternative to
CVD processing.
In this work we focus on elucidating the mechanism of UL wiggling and have synthesized materials that address
several hypothesized mechanisms of failure: hydrogen content, modulus, film density, charge control unit type and
thermal resistance. UL materials with high thermal resistance additionally provide the ability to expand the applicability
of spin-on approaches. Material properties and wiggle failure test results will be discussed.
Electron beam resists develop a surface potential during exposure, which can lead to image placement
errors of up to several nanometers [1] and result in poor CD uniformity and image quality. To address this
problem, we have synthesized a conductive polymer that can be coated onto a resist. Our conductive
discharge layer (CDL) is water-soluble and is easily removed during subsequent processing steps.
Having established that our material has a low enough resistance for full charge dissipation, we have carried
out extensive tests to evaluate the impact of the layer on lithographic performance. We will report these
findings, which include measurements of the effect of the CDL on the resolution, roughness, and speed of
the resist.
Molecular glass resists have gained attention for the past decade as a potential platform
for high resolution lithography. Several molecular resist materials based on the
calix[4]resorcinarene system have been developed. Though this molecular system is very
versatile, there are several challenges with the synthesis and processing of these
materials. The difficulty to synthesize a monodipserse unit, the poor solubility in casting
solvents and incompatibility with conventional developer are some noted challenges. We
have addressed these issues by designing a new calix[4]resorcinarene resist material with
hexafluro alcohol (HFA) units. The resist platform has been evaluated with e-beam and
EUV lithography.
KEYWORDS: Dielectrics, Electron beam lithography, Lithography, Photomasks, Silicon, Scanning electron microscopy, Scanners, Copper, Back end of line, Optical lithography
Increasing complexity and manufacturing costs, along with the fundamental limits of planar CMOS devices, threaten to
slow down the historical pace of progress in the semiconductor industry. We have proposed and demonstrated proof-of-concept
of a simple and low-cost way to fabricate dual-damascene copper (Cu) on-chip interconnect or Back-End-Of-the-
Line (BEOL) structures using a novel multifunctional on-chip electrical insulator called a photo-patternable low
dielectric constant (low-κ) dielectric (PPLK) material [Q. Lin, et al, Proc. SPIE, 2010]. This demonstration was
accomplished with a silsesquioxane-based (SiCOH), κ=2.7 material which is compatible with 248 nm optical
lithography.
In this paper, we report on the extension of the photo-patternable low-κ concept to the ultra-low-κ (κ<2.5) regime and
resolution down well below 100 nm with 193 nm lithography as well as e-beam lithography. We have accomplished this
demonstration using the same silsesquioxane-based (SiCOH) material platform as that of the 248 nm photo-patternable
low-κ materials. The 193 nm photo-patternable low-κ materials possess dielectric constants below 2.5 and are able to
resolve 100 nm half-pith line/space features with dry 193 nm single exposure lithography. The resolution of photopatternable
low-κ materials can be pushed down to 40 nm half-pith line and space features with a line-edge-roughness
less than 3.0 nm with e-beam lithography.
Qinghuang Lin, S. Chen, A. Nelson, P. Brock, S. Cohen, B. Davis, N. Fuller, R. Kaplan, R. Kwong, E. Liniger, D. Neumayer, J. Patel, H. Shobha, R. Sooriyakumaran, S. Purushothaman, T. Spooner, R. Miller, R. Allen, R. Wisnieff
KEYWORDS: Back end of line, Copper, Dielectrics, Optical lithography, Scanning electron microscopy, Silicon, Manufacturing, Semiconducting wafers, Ultraviolet radiation, Polymers
In this paper, we wish to report, for the first time, on a simple, low-cost, novel way to form dual-damascene copper (Cu)
on-chip interconnect or Back-End-Of-the-Line (BEOL) structures using a patternable low dielectric constant (low-κ)
dielectric material concept. A patternable low-κ dielectric material combines the functions of a traditional resist and a
dielectric material into one single material. It acts as a traditional resist during patterning and is subsequently converted
to a low-κ dielectric material during a post-patterning curing process. No sacrificial materials (separate resists or
hardmasks) and their related deposition, pattern transfer (etch) and removal (strip) are required to form dual-damascene
BEOL patterns. We have successfully demonstrated multi-level dual-damascene integration of a novel patternable low-κ
dielectric material into advanced Cu BEOL. This κ=2.7 patternable low-κ material is based on the industry standard
SiCOH-based (silsesquioxane polymer) material platform and is compatible with 248 nm optical lithography. Multilevel
integration of this patternable low-κ material at 45 nm node Cu BEOL fatwire levels has been demonstrated with
very high electrical yields using the current manufacturing infrastructure.
We have developed a new silicon-containing resist for 193-nm immersion lithography. This resist is compatible with
topcoats used in the industry today for immersion lithography. Most of the current topcoats contain 4-methyl-2-
pentanol as a solvent. Our evaluations indicated that the previously developed silicon-containing resists are not
compatible with the current topcoats because of their solubility in 4-methyl-2-pentanol. In the new resist polymers,
we have incorporated high percentage (> 60 mol%) of lactone monomers to prevent them from dissolving in this
solvent. In order to increase the lactone content in a silicon polymer, we have incorporated lactone containing acidlabile
functionalities in addition to widely used acid-inert lactone monomers. Utilizing these polymers, we have
demonstrated a functional silicon-containing photoresist for immersion lithography.
We report here, new non-acetal containing low bake (PEB < 100° C ) resists that are suitable for immersion
lithography. These resists are based on novel low activation energy (low-Ea) tertiary ester protecting
groups. One major obstacle to imaging in the sub-50 nm regime using chemically amplified resists is the
diminished image integrity in the pattern ("image blur") due to photo-generated acid diffusion into
unexposed regions. Low processing temperatures are predicted to decrease the degree of photoacid
diffusion and, in turn, decrease the image blur. Even though many low bake resist compositions have
previously been reported, they are all based on acetal/ketal protecting groups. Unfortunately, these
materials require a stoichiometric amount of water for the photoacid-catalyzed deprotection reaction to
proceed. It is usually assumed that the water for the reaction comes from the environment in the bake
station. However, fluctuations in humidity could affect the performance of the resist. Furthermore,
acetal/ketal-based resists generally lack storage stability. For these reasons, acetal/ketal-based resists did
not receive widespread acceptance in the lithography community. With the introduction of water based
immersion lithography, acetal/ketal-based resists are expected to have further performance difficulties.
Therefore, we targeted the development of new "low blur" resists for 193nm lithography that do not
contain acetal/ketal protecting groups.
This paper will investigate the potential benefits and limitations of increasing the refractive index of the photoresist for water and high-index immersion based lithography. The primary potential benefits are increased exposure latitude due to restoration of the TM polarization component and improved depth of focus due to a delay in the onset of image-induced top-loss. After first understanding the physical origins of these effects, a series of simulation studies will probe the level of impact they may have for the 32nm and 22nm technology nodes. It is concluded that, although they may provide some process latitude relief, the benefits are minimal for 1.35NA water immersion, especially when weighed against the likely required development effort and cost. The benefits are slightly more compelling for high-index immersion (>1.5 NA), but a high index resist does not appear to be critical, provided the resist is at least as large as the immersion fluid index. A comparable benefit can be achieved with a conventional resist by using polarized illumination (a trend already happening for various reasons) and thinning the resist by ~9% for 1.35NA water immersion and ~15% for 1.55NA high-index immersion. Additionally, increasing the refractive index is typically accompanied by a corresponding increase in absorption. This will be addressed, concluding the limitations of absorption are likely chemical and not optical in nature. High absorption is likely tolerable, provided the chemistry can be engineered to account for exponential intensity decay. The level of difficulty in doing so is addressed.
Immersion lithography has placed a number of additional performance criteria on already stressed resist materials.
Much work over the past few years has shown that controlling the water-resist interface is critical to enabling high scan
rates (i.e. throughput) while minimizing film pulling and PAG extraction (i.e. defectivity). Protective topcoat polymers
were developed to control the aforementioned interfacial properties and emerged as key enablers of 193 nm immersion
lithography. Achieving the delicate balance between the low surface energies required for high water contact angles
(generally achieved via the incorporation of fluorinated groups) and the base solubility required for topcoat removal is
challenging. More recently, additional strategies using fluoropolymer materials to control the water-resist interface have
been developed to afford topcoat-free resist systems. In our explorations of fluoroalcohol-based topcoat materials, we
have discovered a number of structure-property relationships of which advantage can be taken to tailor the interfacial
properties of these fluorinated materials. This paper will address the effect of structure on immersion specific properties
such as water contact angle, aqueous base contact angle, and dissolution rate.
Surface properties of materials are an important, even vital, consideration in immersion lithography. Many
investigations have shown that sessile drop static contact angles are not entirely useful in the design of high performance
immersion lithography surfaces. We have synthesized and characterized a broad family of "hydrophobic" materials and
this paper will share information on the role of molecular structure on contact angles and hysteresis of these immersion
materials. Insight into the relationship between structure and contact angles for future immersion materials will be
presented.
UV curable resist formulations for nanoimprint must satisfy criteria for cure rate, volatility, viscosity, cohesion of the
cured material and release from the template in addition to being successfully imprintable. We describe an investigation
of the properties of a series of formulations comprising polyhedral oligomeric silsesquioxane and selected diluents as
candidates for imprintable dielectrics. Although all have low viscosity and volatility and are successfully imprinted,
significant variations in cure rate, mechanical and adhesion properties with resist composition are found. The trends
observed are not all predictable from the literature, indicating that formulation optimization for this application requires a
focus on the fundamentals of both materials and processes.
Exposure of photoresists to ultraviolet light results in outgassing of species that have the potential to contaminate surrounding optical surfaces. Of particular concern are silicon-containing products which cannot be cleaned and permanently detune optical coatings. Collection and identification of those species and quantification of the amounts formed is a difficult analytical problem because of the number and variety of products. We describe a general methodology for determining acidolytic decomposition pathways and absolute elemental composition changes induced in photoresists during exposure. Two silicon-containing 193 nm resists that differ in the mode of attachment of trimethylsilyl to the polymer have been investigated. Elemental abundances are measured in post-apply baked, exposed and post-expose baked films by secondary ion mass spectrometry (SIMS), thus probing volatile product formation from all photochemical and thermal decomposition pathways. Complementary data on primary thermal acidolytic deprotection pathways during post-exposure bake are obtained by mass spectrometry, enabling SIMS elemental abundance changes to be interpreted. The results show that decomposition of both the polymer protecting groups through room temperature acidolysis and the photoacid generator by photolysis lead to volatile product formation during exposure. Silicon bound through oxygen is acid labile while silicon bound through carbon is not, resulting in very low to no silicon outgassing from the latter polymer. Sulfur-containing products formed from PAGs outgas in significant amounts from the photoresists investigated, supporting recent mass spectrometric observations of sulfur outgassing by R. Kunz and coworkers.
Photoresist line edge roughness (LER) has been highlighted to have an adverse impact on device performance whereas post-etch LER is probably the more relevant metric. Post-etch LER can be reduced by migrating to thicker photoresist films or developing etch processes that are accompanied with lower energy ion bombardment. However, the photoresist and etching processes chosen might have desirable attributes and therefore cannot be changed, e.g. large process window or minimal nested-isolated feature etch bias. In this paper, we demonstrate the reduction of LER at the polysilicon gate level by an inexpensive treatment prior to etch. This HBr plasma treatment can be performed in the main etch chamber with minimal impact on wafer throughput. As a result, during the following etch steps, the photoresist mask is more homogeneous from an etch perspective which in turn helps lower the final LER. In addition, results from blanket etch studies on the various photoresist component films are shown. FTIR spectra of unetched and etched films are compared to demonstrate the preferential etching of certain photoresist/polymer components. The large differences observed in the unetched and etched film surface roughness values for certain photoresist components is postulated as an important source of final LER.
Polyhedral Oligomeric Silsesquioxane (POSS) derivatives have been investigated as potential candidates for high resolution resists. POSS materials are cage compounds with defined mono-disperse molecular weights. These materials are attractive candidates for molecular resist development because of their commercial availability and the ease with which they can be derivatized. These resists are more suited for bilayer resist applications because of their high silicon content. We have developed positive bilayer resists suitable for 193-nm and other emerging lithographic applications.
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.
Development of 193-nm negative resists that meet the stringent performance requirements of sub-100 nm resolution with conventional 0.26 N TMAH developer has proven to be a significant challenge. Most of the systems that are currently under development are based on cross-linking mechanisms. They commonly suffer from image distortion caused by micro-bridging. An alternative approach is to look at polarity switch mechanisms. We have investigated the acid-catalyzed elimination of polar molecules as one such mechanism which may provide a pathway to develop negative resists that do not suffer from micro-bridging.
As 193 nm resist moves into production with minimum feature sizes approaching 100nm, bilayer resist is being evaluated more closely for certain applications. Our polymer design has been evolving to meet tighter outgassing requirements. Optical density, etch resistance and dissolution behavior are other considerations. The protecting group used in our 248 nm bilayer is not useful for 193 nm lithography because of the high optical density contribution from Si-Si linkage. Silicon was incorporated into a COMA platform for the first generation polymer. Maleic anhydride is used to modulate dissolution characteristics. The first generation 193 nm bilayer was optimized to print 120 nm L/S patterns with an attenuated PSM on a 0.6 NA Nikon S302. We will describe next generation platforms that address silicon outgassing concern. The lithographic performance of these resists was evaluated on a 0.6 NA Nikon S302 with a dark field mask. Results for 280nm pitch (1:1 L/S) and 245 nm pitch (105 nm L, 140 nm S) lithography are presented. Also shown is result for a 245 nm pitch (1:1 L/S) and 210 nm pitch (1:1 L/S) on a 0.75 NA ASML PAS 5500/1100. Outgassing data generated at MIT Lincoln Laboratory will be discussed.
The greatly compressed resist development cycle and the explosion of the number of resists at a specific lithographic wavelength have necessitated a hastened pace in developing high-performance resists. Traditionally, high- performance chemically amplified resists have been developed by copolymerization of monomers with various functionalities to achieve the desired properties. This approach, while immensely successful, however suffers from long lead times to deliver successful products to the markplace. In this paper, we report a more rapid approach to developing high- performance chemically amplified resists by blending different polymers with complementary properties. As a model system, a 248nm negative-tone bilayer resist has been demonstrated based on acid catalyzed cross-linking of blends of silicon-containing polymers with a non-silicon-containing polymer. The silicon-containing polymers and the non- silicon-containing polymer used were poly(p- hydroxybenzylsilesquioxane-co-p-methoxybenzylsilsesquioxane) (PHBS/MBS), poly(p-hydroxyphenylethylsilesquioxane-co-t- butylsilsesquioxane)(PHPES/BS) and poly(p- hydroxystyrene)(PHS), respectively. The resist based on this simple polymer blend approach has achieved lithographic performance comparable to that based on more elaborate copolymers that require time-consuming synthetic optimization. Differential scanning calorimetry (DSC), quartz crystal microbalance (QCM), and atomic force microscopy (AFM) were employed to probe the properties of the polymer blends and the resist. DSC results suggested that PHBS/MSB and PHS are miscible throughout the entire composition range. Addition of the phenolic polymer into the silicon-containing polymer dramatically improves the lithographic performance of the bilayer resist. This improvement in lithographic performance is attributed to the enhancement of thermal properties (i.e. glass transition temperature), the modulation of dissolution properties, and more cross-linkable sites for the acid catalyzed cross-linking. O2 RIE etch selectivity of the blends vs. and organic underlayer increases with increasing concentration of the silicon-containing polymer in the blends. The present approach could also be applied to developing other high-performance resists more swiftly at other lithographic wavelengths.
193nm lithography will be the future technology for sub- 150nm resolution. As the dimensions get smaller, resist thickness is also needed to be reduced for better resolution and wider process window. Single layer 193nm resist, with thickness of less than 500nm, may not be able to satisfy some of the substrate etch requirement. With bilayer resist scheme, the thin resist offers the advantages of high resolution and good process window. The thick underlayer provides the etch resistance required for substrate etching. IBM has developed a silane substituted alternating copolymer based 193nm bilayer resist system and demonstrates sub-120nm resolution using Nikon 0.6NA stepper with Chrome on Glass (COG) mask. Lithographic performance and formulation optimizations of this 193nm bilayer resist as well as underlayer evaluation and some etch study will be discussed.
We have designed and developed an aqueous base soluble polymer system with a silsequioxane (SSQ) backbone for 157nm bilayer resist applications. These base resins have absorbances as low as 0.6micrometers -1 at 157nm. The imagable polymers which contain acid-labile ester functionalities have absorbances between 2.0 and 3.0micrometers -1. The silicon content of these polymers is around 15% by weight. Therefore, our polymers can be utilized in 157nm positive bilayer resist applications with a film thickness of around 150nm. We have evaluated several resist formulations based on these polymers. These resist formulations have shown high contrast and excellent resolution.
We have designed and developed a high resolution 193 nm bilayer resist system based on alternating copolymers of silane substituted norbornene and maleic anhydride. We have utilized a combination of acid labile silane functionalities and acid stable silicon groups in this resist development.
Material origin of resist line edge roughness (LER) in positive-tone chemically amplified resists has been investigated by designing experiments to mimic the composition and the morphology of the resists in the line edge regions where the resist consists of both the protected polymer and its de-protected counterparts. Blends of the protected and the de-protected base polymers for two silicon containing, positive-tone chemically amplified resists were prepared. Morphology and surface roughness of thin films of the polymer blends were probed with atomic force microscope (AFM). AFM results clearly showed that the protected polymer and its de- protected counterparts form distinct phase separated morphology after spin coating and baking. This phase separation leads to surface roughening of the blend films. Furthermore, the surface roughness of the blend films is enhanced after development with an aqueous TMAH developer. These results suggest that the material origin of resist LER in positive-tone chemically amplified resists stems from the compositional heterogeneity due to phase incompatibility of the protected base polymer and its de-protected counterparts in the line edge regions. The effects of blend composition, the extent of de-protection, and processing conditions on the morphology and surface roughness will be presented. The implications of these findings for high-resolution resist design will also be discussed.
Bilayer thin film imaging is one approach to extend 248 nm optical lithography to 150 nm regime and beyond. In this paper, we report our progress in the development of a positive-tone bilayer resist system consisting of a thin silicon containing imaging layer over a recently developed crosslinked polymeric underlayer. The chemically amplified imaging layer resist is based on a novel dual-functional silicon containing monomer, tris(trimethylsilyl)silylethyl methacrylate, which in addition to providing etch resistance, also functions as the acid sensitive functionality. The stabilization of (beta) -silyl carboncation by silicon allows this moiety to serve as an acid sensitive protecting group. Thus high silicon content and high resist contrast are achieved simultaneously. Lithographic evaluation of the bilayer resist with a 0.63 NA and a 0.68 NA 248 nm exposure tool has demonstrated resolution down to 125 nm equal line/space features with a dose latitude of 16 percent and depth of focus (DOF) of 0.6 um. The dose latitude and DOF for 150 nm equal line/space features are 22 percent and 1.2 um, respectively. Finally, residue-free, ultra-high aspect ratio resist features have been obtained by O2 or O2/SO2 reactive ion etching using a high-density plasma etch system. The resist design, deprotection chemistry, lithographic and etch characteristics of the top layer, as well as the design of the new underlay, will be discussed.
We have investigated three substantially different routes to 193nm single layer resists. This paper will attempt to shed light on the strengths and weaknesses of each approach. Design principles, polymer synthesis and properties, and resist properties will be discussed for the three main branches of 193nm resists.
The design of 193 nm photoresists with improved reactive ion etch (RIE) resistance has been a longstanding aim of both industrial and academic research and development programs. A variety of correlations between photoresist polymer structure and etch resistance have been developed, however, the universality of these approaches, and in particular, the practicality of marking comparisons across specific polymer families and specific RIE processes has recently been called in to question. In order to examine structure: RIE correlations in more detail, we have developed a new model based on the incremental structural parameters (ISP). This model makes use of a molecular fragment-based definition of polymer structure which incorporates and extends aspects of previous parameters such as the Ohnishi and Ring parameters. An initial study revealed that this model allowed quantitative correlations between polymer families and across etch processes to be made. Continuing studies which examine the use of the ISP model in integrating 193 nm photoresists in prototype production processes will be described. Various polymer families used in deep-UV and 193 nm photoresists including methacrylates, alternating copolymers, styrenes and cyclic olefins will be compared. We will present a more detailed description of the ISP a model and of the follow-on 'new' ISP method which has been developed base don insights gained from the original ISP model, and made extended comparisons between the tow ISP models.
Traditional I-line resists commonly use novolak as matrix resin and diazonaphthoquinone as photosensitizer. Novolak resins, however, can not be used in Deep-UV resist formulations because of their high optical absorption at 248 nm. When the lithography migrated to Deep-UV technology, polyvinylphenols (PVP), which has a low absorption at 248 nm, became the resin of choice. Styrene maleic anhydride polymers also have a low optical absorption at 248 nm and are commercially available with relatively lower cost than current polyvinylphenols. Therefore, we felt that styrene maleic anhydride polymers would be of interest for DUV resist applications. In our investigation, the styrene maleic anhydride copolymer was first reacted with methanol to form the half ester then was protected with tetrahydropyranyl and tetrahydrofuranyl groups using p- toluene sulfonic acid as catalyst. Since the protected polymers have no base soluble component, they exhibit high inhibition in TMAH developer. TGA analysis also shows these polymers having reasonable thermal stability with the onset of decomposition at temperature above 150 degree C. However the resists formulated with these polymers showed poor adhesion property. By blending PVP with these polymers in resist formulation, the adhesion problem was resolved and reasonable lithographic performance was obtained.
A negative-tone bilayer thin film imaged (TFI) resist has been developed for extension of 248 nm optical lithography to sub-150 nm regime. The bilayer TFI resist system consists of a thin (0.2 um) silicon containing top imaging layer and a thick (0.7 - 0.8 um) highly absorbing organic underlayer. The chemically amplified negative-tone top layer resist comprises of three major components: an aqueous base soluble silicon containing polymer, poly(hydroxybenzylsilsesquioxane); a crosslinking agent; and a photoacid generator. The highly absorptive underlayer is a hard baked novolak resist or a DUV ARC. Imaging of the top layer resist has shown resolutions down to 137.5 nm for line/space features and 130 nm for isolated features with 248 nm exposure tools and chrome on glass masks. The O2 reactive ion etch (RIE) selectively of the top layers versus a novolak underlayer is more than 25:1 as a result of the high silicon content in the silicon containing polymer. Furthermore, residue-free and nearly vertical wall profile image transfer to the underlayer has been achieved with RIE. Application of the negative-tone bilayer resist to 150 nm Gbit DRAM critical level lithography has been demonstrated. Resist line edge roughness is also discussed.
KEYWORDS: Etching, Polymers, Reactive ion etching, Oxides, Photoresist materials, Photoresist processing, Carbon, Resistance, Chemical reactions, Control systems
We have examined the reactive ion etch (RIE) resistance of two families of 193 nm photoresist candidates, poly(methacrylates) and vinyl-polymerized poly(cyclic olefins), in three RIE processes. Correlation of these measurements to polymer structure and composition using known methods (Ohnishi and Ring Parameter fits) was moderately successful in demonstrating global trends but proved generally inadequate for providing quantitative predictions. To address this shortcoming, we have developed a new empirical structural parameter which provides a much more precise model for predicting RIE rates within a given family of polymers. The model is applicable across polymer platforms, with two caveats: (1) The methacrylate and cyclic olefin families examined to date fall on essentially parallel, offset curves when examined with the new model, (2) The offset between polymer family curves is RIE tool- and process-dependent. While these caveats imply a setback to the idea of a truly `universal' model, they may in fact represent a powerful and unanticipated feature; the model appears to separate chemical RIE processes which affect individual functionalities within a polymer from predominantly polymer-family dependent processes such as global backbone degradation. In the course of conducting these studies, we have encountered several potential pitfalls in the measurement of etch rates. These illustrate the complex nature of plasma: resist interactions and highlight the careful experimental design and controls that are required if meaningful RIE rate comparisons between polymer and resist families are desired.
We have designed and developed new silicon containing methacrylate monomers that can be used in bilayer resist systems. New monomers were developed because the commercially available silicon monomers were found to be unsuitable for our applications. During the course of the investigation we determined that these monomers were acid labile. We have developed a high resolution DUV bilayer resist system based on these monomers. Although most of our work was concentrated on 248 nm lithography, we have demonstrated that this chemistry can be extended to 193 nm applications.
We describe a series of improvements to the `v2' etch- resistant methacrylate 193 nm photoresist platform. `V2' itself possesses many desirable characteristics, but requires weak developers and lacks ultimate etch resistance for production processes. Modifications to address these challenges include incorporation of polar modifier monomers which provide improved developer compatibility, and use of alternative etch-resistant monomers which ameliorate the excessive hydrophobicity of isobornyl methacrylate. Specifically, we explore the use of methacrylonitrile as a polar modifier which simultaneously imparts strong-developer compatibility and improves RIE performance. Integration of these improvements results in methacrylate resists displaying strong-developer compatibility, sub-0.15 micrometers resolution, and etch rates equivalent to current 248 nm photoresists in prototype materials.
Two versions of 193-nm single layer resists based on acrylic polymer chemistry have been described previously. The version 1 resist is a tool-testing version and is based on a methacrylate terpolymer structure. Its etch resistance analogue (version 2 resist) contains alicyclic compounds attached to the acrylic backbone. Key to enabling the performance of version 2 resist are the use of steroid additives which behave principally as thermomechanical modifiers to improve the mechanical properties of these rigid polymers through plasticization. We used the tertiary-butyl ester protecting group in these resists for thermal stability and other considerations. This paper describes an investigation of the impact of acid-cleavable protecting group structure on the properties of a series of model acrylic polymers. In this investigation, factors such as thermochemical stability, reactivity to photogenerated acid, and dissolution properties of exposed films as a function of dose were examined. A new highly reactive protecting group is introduced in this study, the tetrahydrofuranyl ester (THF) of methacrylic acid. Additionally, we introduce a new polymer family (polynorbornenes) with superior etch resistance, significantly broadening the polymer chemistry available for the construction of new 193-nm photoresists.
In previous papers, we described initial evaluations of CGR 248 negative resist using a variety of exposure tools. During subsequent studies, the emphasis has been placed on optimizing material and process for Micrascan and Micrascan II pilot line and manufacturing operations. The formulation is based on polyhydroxystyrene (PHS), tetramethoxymethyl glycoluril, and a sulfonate ester of an N-hydroxy compound. We will discuss image stability as a function of delay time between post apply bake (PA) and expose and as a function of delay time between expose and the post expose bake (PEB). Further, data will show that immersion or puddle development provides a larger process window than spray development for features in the 0.30 to 0.35 micrometers range. The thermal stability of the imaged resist will be discussed as well as the shelf life which is at least 6 months at 23 degree(s) C. Finally, additional data is available concerning image uniformity and how print bias and etch bias contribute to the overall nested-isolated line offset for positive tone (APEX-M) and negative tone (CGR) resists. Data obtained from Micrascan II exposures with test reticles will demonstrate an acceptable process latitude for 0.30 and 0.35 micrometers features and a wafer to wafer image uniformity similar to that observed for APEX.
This paper discusses a new negative tone aqueous base developable photoresist that has demonstrated excellent sub-half micron resolution with commercially available DUV (deep ultraviolet) exposure systems. This system which consists of a phenolic resin (pHOST), a glycoluril crosslinker (TMMGU), and a triflic acid generating material is currently in use for the manufacturing of 16 M b-DRAM and related CMOS logic technology. We provide supporting manufacturing data relating to our experiences with this program, along with the benefits realized by the implementation of a negative tone photoresist system.
A chemically amplified silicon-containing resist has been formulated and evaluated as a thin imaging layer in a positive tone deep UV (DUV) bilayer scheme. The key component is a silicon-containing polymer which has been characterized by GPC, UV, and dissolution rate studies. Dose and focus latitudes were determined for 0.4 and 0.5 micrometers patterns exposed on a SVGL Micrascan I step and scan system and on KrF excimer laser steppers. The dose latitude on a GCA (0.35 NA) excimer was found to be 20% for 0.4 micrometers features and about 30% for 0.5 micrometers features (+/- 10% CD variation). Focus latitude was at least 2 micrometers for 0.5 micrometers patterns. Wafer to wafer LW uniformity as well as within water uniformity is shown. Typical processing involves 5 - 10 mJ/cm2 exposure doses, employing a 90 degree(s)C post-expose bake (PEB) and a 60 sec 0.21 N TMAH develop. The dependence of linewidth upon PEB was found to be about 13 nm per degree C for 0.5 micrometers features. Pattern transfer into the hardbaked i-line resist underlayer was done in an MLR chamber on an AME 5000. A low pressure etch is preferred to eliminate residue but this can lead to a higher non-uniformity across the wafer. Sidewall roughness was prevalent and this could be partially attributed to `feet' on the silicon-containing imaging layer.
This paper describes the first logical approach to the design of chemical amplification resists that are stable toward airborne contamination. This molecular design is based on the observation that uptake of N-methylpyrrolidone (NMP) by thin polymer films is primarily governed by glass transition temperatures (Tg) of the polymers. This concept has led to the design of environmentally very robust chemical amplification resists that provide positive images upon development with aqueous base.
The increasing use of high density integrated circuits has created a need for development of new resist materials and lithographic schemes involving process simplification in semiconductor device fabrication to lower defect levels and improve product reliability. Towards that goal, we have developed a new negative working photoresist applicable to a bilayer resist scheme using optical and E-beam exposures. In this paper, we discuss the synthesis and lithographic applications of the silicon containing resist PHBS-AZIDE. The resist comprises a single component in which the photoactive group, an azide moiety, is chemically bonded to the base polymer, poly(4-hydroxybenzylsilsesquioxane) via an esterification reaction. The new polymer is easily synthesized and has the advantageous properties of aqueous base developability, excellent oxygen RIE resistance and high sensitivity to DUV, i-line and E-beam exposures. Sub-half micron images have been demonstrated using PHBS-AZIDE as a thin top imaging layer in a bilayer mode.
The reverse polarity change from a polar to a nonpolar state has been successfully incorporated in the design of chemical amplification resists. The imaging mechanism is based on the pinacol-pinacolone rearrangement, wherein vic-diols (pinacols) are converted to ketones or aldehydes with photochemically generated acid as a catalyst. In addition to a polymeric pinacol which undergoes the rearrangement very cleanly in the solid state, aqueous base developable three-component negative deep UV resist systems are described, which are based on phenolic resins, small pinacols, and triphenylsulfonium hexafluoroantimonate as the acid generator.
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