PerformanceProfile. Initial Tests Demonstrate Improved Yield. Introduction

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1 PerformanceProfile Replacing Hydroxyl-amine-based Chemistries with Semi-aqueous-based Cleaning Formulations Generates Improved Yields in Post-etch Metal and Oxide Residue Removal by: Mustapha, Nik Senior Applications Engineer, Avantor Performance Materials Kim, Sang In R & D Manager Avantor Performance Materials Lim Huey Pin, Selinda Senior Etch Process Engineer, SSMC Inc. Teo Teck Seng, Steven Process Manager, SSMC Inc. Lili, Liu Process Engineer, SSMC Inc. The use of a semi-aqueous post-etch ash residue remover was compared with an industry-standard hydroxyl-amine (HA)-based residue removal chemistry. The semi-aqueousbased product was shown to reduce cost of ownership for manufacturing of low and high voltage logic devices. The use of this newer generation engineered product was also shown to increase yield when used to replace the existing residue removal chemistry in fabrication of 45 nm logic devices. Introduction SSMC Inc. is a manufacturer of advanced semiconductor wafers located in Singapore that is a joint venture of NXP B.V. and TSMC. It provides exclusive foundry services processing 200 mm wafers in the 0.14 to 0.25 µm technology node. SSMC features eight fab lines focused on producing deep sub-micron processes including complex logic chips and system-on-chip. SSMC chose to test BAKER ALEG -380 residue remover from Avantor Performance Materials ( to assess whether this change to the company s Process of Record (POR) could be accomplished without impacting yield, device quality, and with the desired cost savings. BAKER ALEG-380 residue remover is an engineered blend of organic solvents and semi-aqueous components suitable for bulk photoresist removal and post-etch ash residue and sidewall polymer removal. Designed to provide broad latitude in terms of processing times and temperatures, it is 100 percent water soluble and contains no HA or fluoride elements. Initial Tests Demonstrate Improved Yield One of the significant process challenges associated with using HA-based post-etch residue removal products is the chemistry s relatively limited process temperature range. The maximum recommended process temperature for the HA-based product in use at SSMC was 75 C for 20 minutes. However, process engineers require flexibility to use higher bath temperatures to enable better removal of excess photoresist and substrate residue that can result from certain metal and oxide etch processes. A wider bath process temperature range gives engineers a better process window in case of process drift prior to the cleaning step. In certain cases, etch processes prior to cleaning can generate excess polymer residues, requiring higher bath temperatures to ensure complete residue removal. Currently, the operating temperature recommended for ALEG-380 residue remover is 7 C but it can be increased to 85 C if needed without damaging the integrity of critical substrates. As shown in the scanning electron microscope (SEM) images (FIGURE 1), HA-based chemistries, when used at higher temperatures, will cause excessive etching pitting of metal layers, such as the etch results of the HA product used for 20 minutes at 85 C. In contrast, the ALEG-380 semi-aqueous product, which is HA-free, can be used at the higher temperatures to complete post-etch ash residue removal without etching barrier layers or sidewall structures including the ability to clean difficult-to-remove resides at the higher temperature.

2 HA PRODUCT 85 C 20 MIN ALEG-380 RESIDUE REMOVER 85 C 20 MIN METAL STACKS: TIN/SIO FIGURE 1: Evidence of excessive etching pitting of metal layers in vias treated with HA-based chemistry at higher temperatures (i.e. 85 C) with surfaces treated with ALEG-380 residue remover at the same temperature demonstrating virtually no barrier layer or sidewall etching. Significant improvements in yield were discovered using the ALEG-380 residue remover on the test wafers. As shown in the table (FIGURE 2) the HA-based wafers showed an percent yield, which was in line with yields SSMC experienced on its production lines. For the ALEG-380 treated wafers, metal line yields increased to percent, while via yields were raised to percent. Following standard SSMC testing protocol, two of the eight ALEG-380 wafers were removed at minus 10 percent run time (18 minutes), four followed the standard process (20 minutes) and two removed at plus 10 percent run time (22 minutes). The yield results for these ranged from percent to percent. SSMC reported two results from these tests: All test runs In early 2008, SSMC and Avantor teamed to test ALEG-380 of the ALEG-380 residue remover generated improved residue remover on one of the eight lines at the SSMC yield compared to the HA-based product, and that yield foundry in Singapore. Test wafers were sent through the improvement was significant: two to three percent standard manufacturing steps. consistently under test conditions. This equates to several million dollars in sellable die from a fifty-two thousand Eight wafers were tested using ALEG-380 residue remover; wafer start-per-month factory. The team decided to further five test wafers were cleaned with the HA-based product. investigate the process basis for this yield improvement. All wafers were subjected to residue removal baths at 70 C for 20 minutes. Wafer Area Tests (also referred to It was theorized that the improved yield from the ALEG-380 as full wafer testing or full loop testing) were conducted residue remover was related to lower etch rates compared to assess electrical performance on metal lines and vias to HA-based removal chemistries. Etch rates for a variety of to compare ALEG-380 residue remover and HA-based substrate materials and chemistry temperature ranges were performance. investigated and compared. FIGURE 2: Electrical performance test results conducted on eight wafers treated with ALEG-380 residue remover and five wafers treated with HA-based chemistry. Testing showed increases in yields on ALEG-380 residue remover tested wafers. P E R F O R M A N C E P R O F I L E

3 Etch rates for AlCu, titanium, tungsten and silicon oxide were measured in angstroms per minute (Å/m) on blanket films and coupon tests. The most significant differences were in the titanium etch rates for the HA-based product compared with ALEG-380 residue remover (FIGURE 3). At 65 C, the HA-based product showed an etch rate of 34.2 Å/m; at 75 C, the rate increased to 92.4 Å/m. In a standard 20 minute Substrates Supplier 65 C Supplier 75 C 85 C 85 C AL-Cu Ti <0.1 <0.1 W N/A N/A TEOS < 1 < FIGURE 3: Etch rates for AlCu, titanium, tungsten and silicon oxide were measured in angstroms per minute (Å/m) on blanket films and coupon tests. residue removal bath, this theoretically could cause loss of close to 1000 Å of barrier metal thickness. By comparison, the ALEG-380 residue remover shows a titanium etch rate of less than 0.1 Å/m at 85 C. Also, the ALEG-380 product displayed the minimal etch rates at 85 C, thus allowing ALEG-380 residue remover to be used at significantly higher temperatures to remove tough residues. Titanium Nitride (TiN) is used as a barrier metal in copperbased chips to prevent diffusion of the copper into surrounding materials while maintaining an electrical connection. In 45 nm nodes and below, maintaining the integrity of the TiN layer is crucial to yield and device performance. It should also be noted that exposing tungsten to hydroxylamine molecules can cause autocatalytic reactions which results in complete voids in via holes. In addition, hydroxylamine compatibility on titanium is not well-designed at high operating temperatures. At greater than 75 C, the titanium etch rate increases significantly for HA-based chemistries. It is not advisable to implement the HA-based chemistries at greater than 75 C due to incompatibility with titanium material. Since it was established that the ALEG-380 residue remover etch rates were much lower on both metal lines (Al and Cu) and on substrate materials, SEM studies were conducted on wafers to characterize various structures and clarify their condition. Further SEM studies were conducted on wafers treated with ALEG-380 residue remover at 70 C for 60 minutes three times longer than standard processing intervals. Crosssections of both wafer center and wafer edge metal via structures show no defects in the via tungsten plugs no voids, black lines or evidence of corrosion or degradation that could cause electrical performance issues such as changes in resistivity or noise. ALEG-380 residue remover has sufficient margin in processing time to prevent over-etch of the substrates. FIGURE 4: SEM images of cross-sections of both wafer center and wafer edge metal via structures show no defects in the via tungsten plugs after treatment with ALEG-380 residue remover.

4 FIGURE 5: SEM images of wafers treated with ALEG-380 residue remover at 70 C for twenty minutes show no residual polymer or sidewall etching on metal lines or substrate. SEM imaging was also used to characterize the wider performance window ALEG-380 residue remover offers (FIGURE 5). These images show metal lines on wafers treated with the product at 70 C for 20 minutes. This analysis showed no residual polymer particles, no sidewall etch or etching on either the top TiN or Al substrate. Nearly identical results were characterized in similar metal lines on wafers treated with ALEG-380 residue remover at 85 C for 20 minutes. Again, ALEG-380 residue remover gives process engineers the option of increasing residue removal chemistry to achieve desired cleaning performance, rather than repeating the wafer bath step, which would be required using the conventional 70 C HA-based processes. Both SSMC and Avantor teams concluded that the two to three percent improved yields exhibited on the ALEG-380 residue remover treated wafers could be related to the fact that ALEG-380 residue remover does not contain hydroxylamine, has a very low etch rate on metals such as TiN, tungsten and oxide substrates, thus reducing the incidence of metal line and via defects. Production-level Data Confirms Test Yield Results to assess whether the ALEG-380 residue remover yield advantage observed in the test wafers could be reproduced under production conditions. As shown (FIGURE 6), ALEG-380 residue remover offers a lower total defect count and variation performance profile, with offline particles of 0.2 microns or larger ranging from 1.0 to 4.0 particles detected at different measurement times, than did SSMC s HA-based chemistry. In the second comparison, aluminum etch rates for both chemistries were assessed during the same period as the offline particle comparison. At the start of each eight-hour shift, test aluminum wafers were passed through the post-etch ash The yield improvements demonstrated by the full wafer tests provided sufficient data to justify testing ALEG-380 residue remover under full production conditions. The goal of the test production run was to confirm compatibility of ALEG-380 residue remover with SSMC s tool set and processes, confirm that it offered comparable post-etch ash residue removal performance with the existing HA-based product, and FIGURE 6: SSMC production-level data for a 25-day run, assessing two critical dimensions: offline particle performance and etch rate after processing.

5 residue removal baths for 20 minutes at 70 C. After removal and rinse of the test wafers, the Al etch rate was measured in Å/m. ALEG-380 residue remover etch rate performance was comparable with the HA-based chemistry, exhibiting acceptably low etch levels. This demonstrated that the ALEG-380 residue remover is fully compatible with AlCu substrates, making it a technically feasible alternative to the more commonly used residue removal product. SSMC also assessed cleaning performance for both products. After post-metal etch, and prior to ash residue removal on test wafers, SEM studies were conducted of both metal lines and vias. The first four images in the series (FIGURE 7) show the top polymer residue ash. The final two images in each series show the metal structures after residue removal by the existing chemistry and the ALEG-380 residue remover. As shown in these images, both chemistries show comparable performance: virtually complete removal of top polymer residue, no sidewall polymer residue or sidewall etching. Detailed SEM studies demonstrate that the HA-based chemistry product generated pitting in via substrate layers. These side-by-side comparisons show the impact of using the HA-based product for 20 minutes at 85 C on TiN/SiO metal stacks. The outcome shows that HA-based cleaning results in less-complete polymer removal and pitting of the metal substrate. The ALEG-380 product run on the same structure under the same time/temperature conditions exhibited no pitting and complete residue removal. Cleaning performance of vias was also compared. SEM images were taken of cross-sections of test wafer vias filled with tungsten after post-etch ash residue removal by the HA-based chemistry product and the ALEG-380 residue remover, demonstrating comparable residue removal by both products. FIGURE 7: SEM studies of metal lines and vias from pilot line test wafers after treatment by both HA-based chemistry and ALEG-380 residue remover demonstrate comparable post-etch ash residue removal effectiveness.

6 demonstrated comparable particle removal, substrate etch and electrical performance while improving process yields. Conclusion FIGURE 8: WAT results of wafer yield after multi-pass treatment with ALEG-380 residue remover. SSMC also compared electrical performance results to assess yield impact of using ALEG-380 residue remover to replace the HA-based product. The devices being fabricated on the pilot line consisted of five metal layers, necessitating multi-pass residue removal after each metal etch step. WAT results for metal line and via electrical performance characteristics showed comparable performance to the HA-based chemistry for via resistance in VIA 1 through VIA 5 and M1 through M5 metal layers. Based on the results of the pilot production run with ALEG-380 residue remover, SSMC concluded that the ALEG-380 removed residues as well as the HA-based product, yet improved line yields. ALEG-380 residue remover Based on the results of the pilot production run with ALEG-380 residue remover, and the reduced cost compared to the HA-based product, SSMC determined that it could achieve a two to three point improvement in yield, and a corresponding 25 to 30 percent cost reduction in post-etch ash residue removal process using ALEG-380 residue remover. As a result, SSMC changed its Process of Record and replaced the HA-based product with ALEG-380 residue remover on all of its production lines. Avantor Performance Materials, Inc. Center Valley, PA (USA) AVANTOR ( ) Editorial Contact: Todd Walter Media Relations for Avantor Performance Materials c/o Godfrey Advertising twalter@godfrey.com Notes: 1. S.I. Kim, H.P Lim, L. Liu, N. Mustapha, T.T. Seng, Replacing Hydroxyl-Aminebased chemistries with semi-aqueous-based cleaning formulations generates improved yields in post-etch metal and oxide residue removal, Avantor Performance Materials, Inc., Phillipsburg, NJ 9001: 2008 & 14001: 2004 Paris, KY 9001: 2008 Mexico City, Mexico 9001: 2008 Deventer, the Netherlands 9001: 2008 & 14001: 2004 & 13485: 2003 Selangor, Malaysia 9001: 2008 About Avantor Performance Materials Avantor Performance Materials manufactures and markets high-performance chemistries and materials around the world under several respected brand names, including the J.T.Baker, Macron Fine Chemicals, Rankem, Diagnova, BeneSphera, and POCH brands. Avantor products are used in a wide range of industries. Our biomedical and life science solutions are used in academic, industry and quality control laboratories for research, pharmaceutical production and medical lab testing, while our electronics solutions are used in the manufacturing of semiconductors and flat panel displays. Based in Center Valley, Pennsylvania (USA), Avantor is owned by an affiliate of New Mountain Capital, LLC. For additional information please visit or follow Ordering Information and Assistance Customer Service and Technical Service toll free: AVANTOR ( ) outside of u.s. tel: fax: info@avantormaterials.com AskAvantor Our Web site features ASK Avantor, which includes live chat capabilities with customer service representatives. Lit Number: Avantor Performance Materials, Inc. All rights reserved. Trademarks are owned by Avantor Performance Materials, Inc. or its affiliates unless otherwise noted. Corporate Headquarters Avantor Performance Materials, Inc Corporate Parkway Suite #200 Center Valley, PA USA Worldwide Locations China Malaysia North America India Mexico Taiwan Korea The Netherlands For contact information at these locations, visit Us/Worldwide-Directory.aspx

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