Removal of JSR THB-S375N Photoresist Using a Photoresist Stripper with an Improved EHS Profile Abstract Key words

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1 Removal of JSR THB-S375N Photoresist Using a Photoresist Stripper with an Improved EHS Profile Yuanmei Cao, Kimberly Pollard, Travis Acra, Nichelle Gilbert, Richie Peters, Donald Pfettscher Abstract Negative liquid photoresist (resist) has been used broadly in wafer bumping for fine pitch bump pitch formation. One of the major challenges in using these resists is effective removal of the resist without leaving organic residue or re-depositing the polymer on the surface during the photoresist strip process. Failure to completely remove photoresist on the device can cause device performance problems and create reliability issues, lowering the die yield and increasing the cost. Therefore, wafer cleanliness becomes increasingly important yet, as advances continue and pitch sizes decrease, cleaning difficulties increase. Meanwhile, new concerns in environmental health and safety (EHS) locally, nationally, and worldwide, have pushed fabs to evaluate, select and introduce green chemistries to reduce the impact on worker health and the environment. Conventional photoresist strippers for thick negative photoresists often contain tetramethylammonium hydroxide, (TMAH), and they are highly effective in removing photoresist in immersion processes in wafer level packaging applications. However, they have shown some drawbacks including short bath life at elevated temperatures and a major concern of toxicity, requiring more extensive EHS oversight. These issues create a demand and thus an opportunity for TMAH-free photoresist strippers to (1) increase the stability of the stripper during storage and in use and (2) to reduce the potential toxicity while maintaining the effectiveness of photoresist stripper to remove the photoresist. This paper will focus on the cleaning capabilities of TMAH-free formulations for removal of JSR THB-S375N spin-on negative photoresist in an immersion process. Optical images and scanning electron microscopy analysis will be used to illustrate the cleaning results. Key words: TMAH-free, photoresist stripper, JSR THB-S375N removal

2 Introduction Negative acrylic-based photoresists are commonly coated on surfaces, patterned and used as molds for plating solder bumps in back-end semiconductor packaging applications. The films can be applied as a dry film in a laminating process or as a liquid that is spun onto the wafer surface to form a wet film. The photoresist THB-S375N, made by Japan Synthetic Rubber (JSR) is an example of a negative liquid photoresist which is widely employed in wafer bumping processes throughout the world. Photoresist stripping has traditionally been considered a low technology process step, but due to the number of cleaning steps on a wafer and the increasing complexity of integrated circuit manufacturing, it has become more challenging. There is no end to the increase in complexity in sight with the dimensions of circuit features continuing to shrink and new 3-D processing schemes with more cleaning challenges coming into mass production. Removing negative acrylic-type photoresist poses serious challenges due to their cross linking nature. Commercial strippers are commonly based upon formulated blends of organic solvents and bases, including tetramethylammonium hydroxide, (TMAH) which has been shown to cause metal corrosion, solder attack especially on tin-based lead-free solder and other irregularities. More recently, additional concerns have been raised over health-related problems with acute exposure 1,2,3. According to the 2009 ITRS, Environmental Health and Safety (EHS), strategies include the reduction of chemical exposure, usage, and waste 4, and soon may consider building certification 5. The difficult photoresist removal step, which has required the harsh formulations to be implemented for successful removal of the negative photoresist, continues to burden EHS concerns and cost. Therefore, there is a considerable opportunity to find innovative solutions which incorporate EHS improvements while maintaining effective cleaning processes in a platform that can be integrated into current manufacturing processes. This paper describes a TMAH-free photoresist remover that offers complete photoresist removal while maintaining

3 good bath lifetime, good materials compatibility, and the additional advantages of reduced toxicity resulting in a better EHS profile. Experimental Multiple 300mm wafers were patterned with negative liquid photoresist, JSR THB-S375N, and plated with lead-free solder bumps. The details of the wafer are listed in Table 1. Table 1 Details of JSR THB-S375N patterned wafers Resist Thickness/μm Bump Size/μm Bump Height/μm Bump Pitch/μm Wafers were cleaved into coupons and used in bench-scale immersion testing. Coupons were cleaned using a TMAH-free photoresist stripper, XP02018GG, which was heated in a beaker at 70 C for 60 min. The coupons were rinsed with DI water and dried prior to optical microscope (OM) and scanning electron microscope (SEM) inspection. Metal etch rates of Al and Cu were measured at 70 C for 30 min. Results & Discussion Inspection of the wafer surface for cleaning and compatibility after processing with XP02018GG at 70 C for 60 minutes was done using optical microscopy (OM) and scanning electron microscopy (SEM). No resist residue, organic particles or resist stringers were observed from the optical images (a-c). SEM images further confirmed the cleanliness of the sample (d-f). a b c

4 d e f Figure 1 Optical Images of wafer surface after removal of JSR THB375N. (a) 50x magnification, (b) 200x magnification. SEM images of coupon surface after removal of JSR THB375N. (c) 1000x magnification, (d) 200x magnification, (e) 800x magnification, (f) 3000x magnification. Coupons were cleaned using a TMAH-free formulation, XP02018GG at 70 C for 60 min in an immersion-type process. The smoothness of sidewall of solder bumps and field metal indicated good compatibility with lead-free solder and Cu field metal. The metal etch rate was performed and results are tabulated in Table 2 below. Low metal etch rates of Cu and Al were achieved, which were consistent with good compatibility found using SEM observation. Table 2 Metal etch rate of Al and Cu in formula XP02018GG processed at 70 C for 30 min Metal Etch Rate (Å/min) Al 6.9 Cu <3.0 The bath lifetime experiment comparing a TMAH-free formulation and a commercialized TMAH-based formulation was performed with continuous heating at 70 C for 24 hours. The results were plotted in Figure 2. This study showed comparable bath lifetime of the TMAH-free formulation and commercialized TMAH-containing formulation.

5 Time/Hours TMAH-free formulation TMAH-based formulation Figure 2 Bath lifetime of TMAH-free formulation and commercialized TMAH-based formulation Conclusions A TMAH-free photoresist stripper, XP02018GG, was successfully developed to completely remove JSR THB-S375N negative liquid photoresist in an immersion process, providing good bath lifetime, good metal compatibility and reduced health concerns. References 1. Lee, C.-H., et al., Toxicology and Industrial Health, v27, p (2011). 2. Wu, C.-L., et al., J. Occup. Health, v50, p (2008) 3. Chun-Chi Lin et al., Clinical Toxicology, v48, p (2010) 4. International Technology Roadmap for Semiconductors, 2009 ed., Environment, Safety, and Health, 5. Leadership in Energy and Environmental Design (LEED), Green Building Rating SystemTM, U.S. Green Building Council,

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