Joseph S. Gordon

Novel hydrofluorocarbon polymers for use as pellicles in 157 nm semiconductor photolithography: fundamentals of transparency

With the advent of 157 nm as the next photolithographic wavelength, there has been a need to find transparent and radiation durable polymers for use as soft pellicles. Pellicles are � 1 mm thick polymer membranes used in the photolithographic reproduction of semiconductor integrated circuits to prevent dust particles on the surface of the photomask from imaging into the photoresist coated wafer. Practical pellicle films must transmit at least 98% of incident light and have sufficient radiation durability to withstand kilojoules of optical irradiation at the lithographic wavelength. As exposure wavelengths have become shorter the electronics industry has been able to achieve adequate transparency only by moving from nitrocellulose polymers to perfluorinated polymers as, for example, Teflon 1 AF 1600 and Cytop TM for use in 193 nm photolithography. Unfortunately, the transparency advantages of perfluorinated polymers fail spectacularly at 157 nm; 1 mm thick films of Teflon 1 AF 1600 and Cytop TM have 157 nm transparency of no more than 38 and 2%, respectively, with 157 nm pellicle lifetimes measured in millijoules. Polymers such as ‐[(CH2CHF)xC(CF3)2CH2]y‐, or ‐(CH2CF2)x[2,2-bis(trifluoromethyl)-4,5-difluoro-1,3-dioxole]y‐ with chains that alternate fluorocarbon segments with either oxygen or hydrocarbon segments frequently show >98% transparency at 157 nm, if amorphous. These polymers are made from monomers, such as vinylidene fluoride (VF2) and hexafluoroisobutylene, which themselves exhibit good alternation of CH2 and CF2 in their structures. In addition, we find that ether linkages also can serve to force alternation. In addition, we find that fluorocarbon segments shorter than six carbons, and hydrocarbon segments less than two carbons or less than three carbons if partially fluorinated also promote 157 nm transparency. We also find that even with these design principles, it is advantageous to avoid small rings, as arise in the cyclobutanes. These results suggest a steric component to transparency in addition to the importance of alternation. Upon irradiation these polymers undergo photochemical darkening and therefore none has demonstrated the kilojoule radiation durability lifetimes required to be commercially attractive. This is likely because these exposure lifetimes require every bond to absorb � 10 photons, each photon having an energy roughly twice common bond energies. We have studied intrinsic (composition, molecular weight) and extrinsic (trace metals, impurities, environmental contaminants, oxygen, water) contributions to optical absorption and photochemical darkening in these polymers. Studies of photochemical darkening in model molecules illustrate the dynamics of photochemical darkening and that appreciable lifetimes can be achieved in fluorocarbons. To a first approximation the polymers that have lower 157 nm optical absorbance also tend to show the longest lifetimes. These results imply that quantum yield, or the extent to which the polymer structure can harmlessly dissipate the energy, can be important as well. # 2003 Elsevier Science B.V. All rights reserved.

Materials design and development of fluoropolymers for use as pellicles in 157-nm photolithography

The introduction of 157 nm as the next optical lithography wavelength has created a need for new soft (polymeric) or hard (quartz) pellicle materials optimized for this wavelength. Materials design and development of ultra transparent fluoropolymers suitable for 157 nm soft pellicle applications has produced a number of promising candidate materials with absorbances below 0.03/micrometer as is necessary to achieve pellicle transmissions above 95%. We have developed 12 families of experimental TeflonAFR (TAFx) materials which have sufficient transparency to produce transmissions above 95%. For the successful fabrication of 157 nm pellicles from these materials, the fluoropolymers must have appropriate physical properties to permit the spin coating of thin polymer films and their lifting and adhesive mounting to pellicle frames, the processes which produce free standing pellicle membranes of micron scale thickness. Relevant physical properties include molecular weight, glass transition temperature, and mechanical strength and toughness. We have successfully developed various of the ultra transparent TAFx polymer families with these physical properties. Upon irradiation these 157 nm pellicle polymers undergo photochemical darkening, which reduces the 157 nm transmission of the material. Measurements of the photochemical darkening rate allow the estimation of the pellicle lifetime corresponding to a 10% drop in 157 nm transmission. Increasing the 157 nm lifetime of fluoropolymers involves simultaneous optimization of the materials, the pellicle and the end use. Similar optimization was essential to achieve the desired radiation durability lifetimes for pellicles successfully developed for use with KrF (248 nm) and ArF (193 nm) lithography.

Influence of environmental components on haze growth

With the use of 193nm lithography, haze growth has increasingly become a critical issue for photomask suppliers and wafer fabs. Recent photomask industry surveys indicate the occurrence rate of haze is 10 times higher on 193nm masks compared to 248nm masks. Additionally, work has been presented that shows strong relationship between environmental conditions around the photomask and the occurrence of haze at 193nm. This underscores the need to better understand the basic mechanisms of haze and the measures such as environmental airborne molecular contamination (AMC) control which can be employed to reduce the occurrence of haze in use. A custom excimer laser test system capable of 193nm and 248nm wavelengths was built to accelerate haze growth and to better understand haze formation mechanisms. Work on materials impact on haze growth, such as pellicles and reticle compacts, as well as preliminary findings on environmental impacts have been presented previously. Results indicate even on pristine surfaces haze can grow when contaminants are present in the storage and use environment. The test system has been upgraded to include tight control on the concentration of specific airborne contaminants of concern. The impact of these contaminants and their relative concentrations will be examined in this paper and are presented to aid the industry in determining the level of environmental control needed over the life of a reticle.

Optical issues of thin organic pellicles in 45-nm and 32-nm immersion lithography

The semiconductor industry will soon be putting >=1.07NA 193nm immersion lithography systems into production for the 45nm device node and in about three years will be putting >=1.30NA systems into production for the 32nm device node. For these very high NA systems, the maximum angle of light incident on a 4X reticle will reach ~16 degrees and ~20 degrees for the 45nm and 32nm nodes respectively. These angles can no longer be accurately approximated by an assumption of normal incidence. The optical diffraction and thin film effects of high incident angles on the wafer and on the photomask have been studied by many different authors. Extensive previous work has also investigated the impact of high angles upon hard (e.g., F-doped silica) thick (>700μm) pellicles for 157nm lithography, e.g.,. However, the interaction of these high incident angles with traditional thin (< 1μm) organic pellicles has not been widely discussed in the literature. In this paper we analyze the impact of traditional thin organic pellicles in the imaging plane for hyper-NA immersion lithography at the 45nm and 32nm nodes. The use of existing pellicles with hyper-NA imaging is shown to have a definite negative impact upon lithographic CD control and optical proximity correction (OPC) model accuracy. This is due to the traditional method of setting organic pellicle thickness to optimize normally incident light transmission intensity. Due to thin film interference effects with hyper-NA angles, this traditional pellicle optimization method will induce a loss of high spatial frequency (i.e., high transmitted angle) intensity which is similar in negative impact to a strong lens apodization effect. Therefore, using simulation we investigate different pellicle manufacturing options (e.g., multi-layer pellicle films) and OPC modeling options to reduce the high spatial frequency loss and its impact.

Pellicles designed for high-performance lithographic processes

The semiconductor industry continues to push the resolution capability of lithographic processes in order to produce increasingly smaller device geometry at higher densities. To achieve these advances corresponding changes are occurring in the lithography equipment used to manufacture these devices. The wavelengths used for exposure are decreasing, numerical apertures are increasing and new off axis illumination systems are being introduced. These all have ramifications on the performance, effect and proper use of pellicles in the lithography system. At the same time the available process budgets are decreasing thereby increasing the relative effect of the pellicle contribution towards those budgets. Many of the traditional pellicle designs are no longer the optimum choice for use in high performance lithography. This study examines the effects of pellicles in high performance lithography systems.

Study of time dependent 193 nm reticle haze

While significant progress has been made in reducing the occurrence rate of progressive defect growth on photomasks used at 193nm, the issue continues to be a problem for many semiconductor fabs. Increasing evidence from multiple sources indicates that further reduction in haze risk involves closely controlling the storage and exposure environment of the photomask. Further controlled testing is necessary to characterize the impact of environment and individual components on growth. In this way, photomask users, equipment and material providers may be better prepared to ensure the proper storage and use of photomasks in order to reduce the risk of haze growth. In continuation of work previously reported by Toppan Photomasks, advanced test apparatus, recently designed and built, now enables researchers to generate and maintain stable and controlled levels of multiple impurities which potentially effect haze growth. Supported by on-line and off-line analytical methods and instrumentation, new experimental set-up enables accuracy in the testing and validation of the impacts of environmental variables. Different classes of pollutants in multiple combinations have been studied to more precisely characterize environmental sensitivity of varying types of 193 nm reticles. Authors report further on the study of the effect of environmental conditions on severity and rate of haze formation to provide insight into the requirements for reducing or even preventing such conditions.

Contamination control for ArF photo masks

Advanced photolithography tools use 193 nanometer wavelength light for conventional and immersion printing. The increased energy of 193 nm (ArF) light coupled with the higher absorption cross section of most materials has lead to a dramatic increase in the rate of haze formation as compared to previously used lithographic wavelengths (248 KrF and 365 nm i-line systems). It is well known that at this short wavelength photochemical reactions are enhanced leading to progressive defect formation, or haze, on optical surfaces within microlithography tools. Therefore, strict contamination control of the optics environment is needed to avoid cumulative effects. Such measures have been implemented in lithography tools both for the optics and for the reticle during exposure. However, the patterned side of the photomask is the most sensitive element in the litho optical path for haze growth, because it is in focus and small defects will show up as printing defects. Moreover, the reticle life time depends both on rigorous contamination control for expose and transport/storage conditions (both inside and outside of the lithography tool). The litho operating cost depends directly on reticle life time. It is imperative that the industry takes the required measures to improve the airborne molecular contamination levels both in the storage part of the photolithography tool and in devices used to transport reticles outside of the tool to slow down reticle haze Past studies have shown the large effects of humidity and AMC on haze growth during storage and exposure. Therefore, significant improvements in storage and exposure environment have been implemented by many fabs to reduce the frequency of haze failures. It has also been shown that outgassing from materials surrounding the mask can influence or cause haze. It is clear that the reticle must be adequately protected from contamination sources throughout the life cycle of the reticle (both inside and outside of the lithography tool). In this paper we examine improvements in the storage conditions of reticles inside the lithography tool as well as improvements in commercial SMIF pods used in fab storage and automated handling of reticles.