As the semiconductor chip size continues to decrease, extreme ultra violet lithography (EUVL) is becoming a vital technology to achieve the high resolution patterning required for sub-7 nm node technologies. The patterning resolution of EUVL is highly dependent on the performance of EUV photoresists (PR) which can lead to variations in the patterning process and affects the overall quality of the semiconductor. Although there are several traditional methods to determine a patterning performance of PR, it becomes more challenging as scale tighten. To this end, we develop a new analysis method, named ‘W-curve’, defining EUV PR resolution using ADI SEM images, that visualizes micro-bridge and -break defect cliffs and local CD uniformity at the same time. Using W-curve method, 3 different PR performance at 36 nm-pitch line/space pattern was clearly distinguished. Also, the obtained result was well correlated with time-series trend data and electric test data. Therefore, we believe that W-curve method could provide a new insight for understanding EUV PR performance and improve patterning performance in a facile and versatile manner.
Initial readiness of EUV (extreme ultraviolet) patterning was demonstrated in 2016 with IBM Alliance's 7nm device technology. The focus has now shifted to driving the 'effective' k1 factor and enabling the second generation of EUV patterning. With the substantial cost of EUV exposure there is significant interest in extending the capability to do single exposure patterning with EUV. To enable this, emphasis must be placed on the aspect ratios, adhesion, defectivity reduction, etch selectivity, and imaging control of the whole patterning process. Innovations in resist materials and processes must be included to realize the full entitlement of EUV lithography at 0.33NA. In addition, enhancements in the patterning process to enable good defectivity, lithographic process window, and post etch pattern fidelity are also required. Through this work, the fundamental material challenges in driving down the effective k1 factor will be highlighted.
One of the most prospective alternative lithography ways prior to EUV implementation is the reverse imaging by means of a negative tone development (NTD) process with solvent-based developer. Contact and trench patterns can be printed in CAR (Chemically amplified resist) using a bright field mask through NTD development, and can give much better image contrast (NILS) than PTD process. Not only for contact or trench masks, but also pattering of IIP (Ion Implantation) layers whose mask opening ratio is less than 20% may get the benefit of NTD process, not only in the point of aerial imaging, but also in achievement of vertical resist profile, especially for post gate layers which have complex sub_topologies and nitride substrate. In this paper, we present applications for the NTD technique to IIP (Ion Implantation) layer lithography patterning, via KrF exposure, comparing the performance to that of the PTD process. Especially, to extend 248nm IIP litho to sub-20nm logic device, optimization of negative tone imaging (NTI) with KrF exposure is the main focus in this paper. With the special resin system designed for KrF NTD process, even sub 100nm half-pitch trench pattern can be defined with enough process margin and vertical resist profiles can be also obtained on the nitride substrate with KrF exposure.
In hyper NA immersion lithography which has over 1.0 numerical aperture (NA) exposure system, reflectivity control
between PR and substrate is key technique to overcome resolution limit. Trilayer resist process, which has two layers of
spin-on hard mask (SOH) composed of silicon and carbon, was introduced and applied to various generation of ArF
lithography from dry to immersion process. However, lack of adhesion between PR (hydrophobic) and Si-SOH
(hydrophilic) can cause pattern collapse problem. Moreover, PR profile was not easily adjusted to optimum shape
because some side reaction may be occurred at the interfacial layer between PR and Si-SOH. Herein, we studied how to
control interfacial side reaction between PR and Si-SOH layer in Trilayer process. We approached three conceptual
items: acidity control to PR, uniformity control of Si-SOH itself, and intermixing control of Si-SOH with PR. First, we
checked PR lifting margin with line and space pattern. Although vertical profile was obtained in contact pattern, it was
useless if line pattern was collapsed. With first screening tests, we made a conclusion that a major factor for side reaction
at interfacial layer was penetration of proton into Si-SOH layer produced exposed region. To solve that problem,
intermixing control of Si-SOH with PR was the best solution. We introduced network structure formation with Si-O-Si
bond by cross-linking catalyst. AFM and contact angle data showed improved surface morphology. We could obtain improved pattern profiles with several PR samples. This result can be optimized to various generations of ArF immersion lithography and further more.
With the aid of ArF immersion lithography, semiconductor device node was extended sub-40nm and numerical aperture
(NA) of litho process was exceeded to unity. In this high NA (over 1.0) lithography, however, it is very hard to control
reflectivity between resist and substrate because of total reflection of light. To overcome this problem, the necessities of
dual bottom antireflective coating (BARC) which have different refractivity became to realize. Trilayer resist process,
which has two layers of spin-on hard mask (SOH) composed of silicon and carbon, was introduced and applied to various
generation of ArF lithography from dry to immersion process. However, Lack of adhesion between photoresist
(hydrophobic) and Si-SOH (hydrophilic) layer can cause pattern collapse problem, especially during process of line and
space pattern. Herein we studied modified trilayer resist process. We introduced Alkyldisilazane(ADS) treatment after Si-
SOH coating in trilayer resist process. Silazane functional groups in ADS react with silanols on the Si-SOH surface and
silanols are converted to alkyl siloxane groups. Alkyl siloxane groups are more hydrophobic than silanols, so they can act
as adhesion promoter during lithography process. And the hydrophobicity was increased when more hydrocarbons were
inserted in ADS. We could improve pattern collapse in trilayer resist process and CD uniformity. This process can be
optimized to various generations of ArF immersion lithography and further more.
Negative working nanomolecular resists based on fully epoxy-protected tetra-Cmethylcalix[4]resorcinarene (epoxy C-4-R) and oxetanyl-protected tetra-methylcalix[4]resocinarene (oxetanyl C-4-R) have been developed. They were prepared by the reaction of C-4-R with epichlorohydrin or in the presence of trimethylamine. They can be coated on the silicon wafer by spin-coating method. A clear film cast from a 20 wt% epoxy C-4-R solution in chloroform showed high transparency to UV above 300 nm. A fine negative image featuring 0.8 μm of minimum line and space patterns was observed on the film of the photoresist exposed to 40 mJ/ cm2 of Near UV-light by the contact mode.
A novel nanomolecular resist based on POSS substituted with diazodiketo-functionalized cholate derivatives was successfully synthesized as a candidate for 193-nm lithography. The diazodiketo group was introduced into the cholate derivatives to provide the solubility change and to eliminate the problems of chemically amplified resists. The decomposition temperature of the resist was found to be 130°C. The initial lithographic studies showed the feasibility of the resist to be used as a candidate for 193-nm lithography.
To satisfy the upcoming demand of next generation lithography, new chemically amplified resist materials should be developed that can perform at the limit where the image feature size is on the order of molecular dimensions. Amorphous low-molecular-weight materials have several advantages over conventional polymeric systems. First, the limit of resolution can be enhanced since the building block of the image feature shrinks to the small molecule. Second, nanomolecular materials do not have chain entanglement due to the short chain length. Third, resist molecules that are free of intermolecular chain entanglement may decrease line edge roughness at very small feature sizes. Fourth, they can be coated on the silicon substrate by spin coating method because of their amorphous properties. Herein we studied several nanomolecular resists for 193-nm lithography. Adamantane was used as a core and two cholate derivatives were attached to adamantane.
Outgassing from the resist causes volume shrinkage of the resist film and extensive damage to optical lenses of exposure tools. Image distortion and throughput loss can take place due to the outgassing. In this study, we designed and synthesized a new acid labile group, 7,7-dimethyloxepan-2-one, which was introduced into the matrix polymers for ArF chemically amplified resists. The 7,7-dimethyloxepan-2-one group was readily cleaved and the carboxylic acid functionality was formed by acid-catalyzed ring-opening reaction in the exposed region after post-exposure bake. The resist patterns of 0.22 μm feature size were obtained with a conventional developer using an ArF exposure tool.
Several molecular resist materials were synthesized for 193 nm photoresists. They include cholate derivatives as dendrimer cores and ester groups as peripheral parts. Cholate derivatives provide etch resistance and peripheral parts give coatability and acid-labile polarity change. They were synthesized using an acetal-protected anhydride derivative of 2,2-bis(hydroxymethyl)proponic acid as an acylating reagent. These dendrimer materials were grown to the 1st generation. t-Butoxy esters are attached to the end of peripheral parts for positive-tone resists. These molecular resist materials were coated well to the silicon wafer and show good sensitivity and etch resistance.
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