{"id":64152,"date":"2022-04-20T10:43:37","date_gmt":"2022-04-20T14:43:37","guid":{"rendered":"https:\/\/www.hajim.rochester.edu\/senior-design-day\/?p=64152"},"modified":"2022-09-12T10:57:20","modified_gmt":"2022-09-12T14:57:20","slug":"nmp-replacement-investigation","status":"publish","type":"post","link":"https:\/\/www.hajim.rochester.edu\/senior-design-day\/nmp-replacement-investigation\/","title":{"rendered":"NMP Replacement Investigation"},"content":{"rendered":"\n<h2 class=\"wp-block-heading\">Team<\/h2>\n\n\n\n<ul class=\"wp-block-list\"><li>Kudzai Mbinda <\/li><li>Joseph Frye <\/li><li>Brittany Pitt<\/li><li>Akram Ismail&nbsp;<\/li><\/ul>\n\n\n\n<h2 class=\"wp-block-heading\">Mentor<\/h2>\n\n\n\n<p>Alexander A. Shestopalov, Assistant Professor of Chemical Engineering, University of Rochester <\/p>\n\n\n\n<h2 class=\"wp-block-heading\">Sponsor<\/h2>\n\n\n\n<p>Michaela Wentz, Process Development Engineer, Meta Reality Labs (Cork, Ireland)<\/p>\n\n\n\n<h2 class=\"wp-block-heading\">Abstract<\/h2>\n\n\n\n<p>N-methyl-2-pyrrolidone (NMP) solvent is used to strip photoresist residues from coated silicon wafers in the post-etch stages of \u00b5LED Manufacture by Meta Reality Labs. The relation between NMP stripping rate and the concentrations of water and photoresistor are studied. It is concluded&nbsp;that&nbsp;the effect of concentration on stripping rate can be fit to mathematical models. Additionally, the concentration models using refractive index and UV-Vis&nbsp;spectroscopy are developed.<\/p>\n\n\n\n<h2 class=\"wp-block-heading\">Introduction<\/h2>\n\n\n\n<div class=\"wp-block-columns is-layout-flex wp-container-core-columns-is-layout-9d6595d7 wp-block-columns-is-layout-flex\">\n<div class=\"wp-block-column is-layout-flow wp-block-column-is-layout-flow\" style=\"flex-basis:100%\">\n<div class=\"wp-block-group\"><div class=\"wp-block-group__inner-container is-layout-flow wp-block-group-is-layout-flow\">\n<div class=\"wp-block-columns is-layout-flex wp-container-core-columns-is-layout-9d6595d7 wp-block-columns-is-layout-flex\">\n<div class=\"wp-block-column is-vertically-aligned-top is-layout-flow wp-block-column-is-layout-flow\" style=\"flex-basis:100%\">\n<div class=\"wp-block-image\"><figure class=\"alignleft size-full is-resized\"><img loading=\"lazy\" decoding=\"async\" src=\"https:\/\/www.hajim.rochester.edu\/senior-design-day\/wp-content\/uploads\/2022\/04\/image-97.png\" alt=\"\" class=\"wp-image-82952\" width=\"240\" height=\"201\" srcset=\"https:\/\/www.hajim.rochester.edu\/senior-design-day\/wp-content\/uploads\/2022\/04\/image-97.png 530w, https:\/\/www.hajim.rochester.edu\/senior-design-day\/wp-content\/uploads\/2022\/04\/image-97-300x250.png 300w\" sizes=\"auto, (max-width: 240px) 100vw, 240px\" \/><figcaption><strong>Fig 1.<\/strong> Meta Reality Labs headsets<\/figcaption><\/figure><\/div>\n\n\n\n<div class=\"wp-block-image\"><figure class=\"alignleft size-full is-resized\"><img loading=\"lazy\" decoding=\"async\" src=\"https:\/\/www.hajim.rochester.edu\/senior-design-day\/wp-content\/uploads\/2022\/04\/image-98.png\" alt=\"\" class=\"wp-image-82962\" width=\"177\" height=\"36\" srcset=\"https:\/\/www.hajim.rochester.edu\/senior-design-day\/wp-content\/uploads\/2022\/04\/image-98.png 480w, https:\/\/www.hajim.rochester.edu\/senior-design-day\/wp-content\/uploads\/2022\/04\/image-98-300x61.png 300w\" sizes=\"auto, (max-width: 177px) 100vw, 177px\" \/><\/figure><\/div>\n\n\n\n<figure class=\"wp-block-image size-full is-resized\"><img loading=\"lazy\" decoding=\"async\" src=\"https:\/\/www.hajim.rochester.edu\/senior-design-day\/wp-content\/uploads\/2022\/04\/image-99.png\" alt=\"\" class=\"wp-image-82972\" width=\"204\" height=\"184\" srcset=\"https:\/\/www.hajim.rochester.edu\/senior-design-day\/wp-content\/uploads\/2022\/04\/image-99.png 424w, https:\/\/www.hajim.rochester.edu\/senior-design-day\/wp-content\/uploads\/2022\/04\/image-99-300x272.png 300w\" sizes=\"auto, (max-width: 204px) 100vw, 204px\" \/><\/figure>\n<\/div>\n<\/div>\n<\/div><\/div>\n<\/div>\n<\/div>\n\n\n\n<p><strong>Augmented Reality\/Virtual&nbsp;<\/strong><strong>Reality Devices<\/strong><strong>:<\/strong><\/p>\n\n\n\n<p>Augmented reality (AR) is the practice of superimposing computer-generated graphics onto real images and\/or footage. Virtual reality (VR) is the practice of spatially simulating 3-d computer generated graphics. AR and VR simulation is typically done with the use of headsets which have displays projecting onto the users&#8217; field of vision. AR\/VR has applications in medicine, education, and entertainment.<\/p>\n\n\n\n<p>An important parameter in the design of AR\/VR headsets is the image resolution of the headset\u2019s display measured in pixels. Meta Reality labs uses \u00b5LED arrays in the manufacture of certain headset products. \u00b5LED\u2019s are diodes derived from semiconductor materials, and they are manufactured using photolithography.<\/p>\n\n\n\n<p><strong>Photolithography and Stripping:<\/strong><\/p>\n\n\n\n<div class=\"wp-block-image\"><figure class=\"aligncenter size-full is-resized\"><img loading=\"lazy\" decoding=\"async\" src=\"https:\/\/www.hajim.rochester.edu\/senior-design-day\/wp-content\/uploads\/2022\/04\/image-100.png\" alt=\"\" class=\"wp-image-82982\" width=\"192\" height=\"195\" srcset=\"https:\/\/www.hajim.rochester.edu\/senior-design-day\/wp-content\/uploads\/2022\/04\/image-100.png 362w, https:\/\/www.hajim.rochester.edu\/senior-design-day\/wp-content\/uploads\/2022\/04\/image-100-295x300.png 295w\" sizes=\"auto, (max-width: 192px) 100vw, 192px\" \/><figcaption><strong>Fig 2.<\/strong> Chip microstructure<\/figcaption><\/figure><\/div>\n\n\n\n<p>Photolithography is a multistep process that ultimately shapes semiconductor chips. This process is also used to shape \u00b5LED\u2019s. The process is typically done using light to etch specific regions of the wafer.&nbsp;Photoresist is a chemical used in the etching process. All photoresist must be removed in the post-etch stage of the process. The photoresist is typically dissolved using organic solvents such as acetone, NMP, and THF. The stripping rate (photoresist dissolution rate) is related to the amount of contaminants present.<\/p>\n\n\n\n<h2 class=\"wp-block-heading\">Project Objectives<\/h2>\n\n\n\n<ol class=\"is-style-default wp-block-list\"><li>Determine how NMP stripping performance degrades as a function of water content.<\/li><li>Determine how NMP stripping performance degrades as a function of dissolved photoresist.<\/li><li>Devise a method for the Meta Reality Labs plant to monitor NMP degradation over time.<\/li><\/ol>\n\n\n\n<h2 class=\"wp-block-heading\">Experimental Setup<\/h2>\n\n\n\n<div class=\"wp-block-image\"><figure class=\"aligncenter size-large is-resized\"><img loading=\"lazy\" decoding=\"async\" src=\"https:\/\/www.hajim.rochester.edu\/senior-design-day\/wp-content\/uploads\/2022\/04\/image-101-1024x553.png\" alt=\"\" class=\"wp-image-82992\" width=\"586\" height=\"316\" srcset=\"https:\/\/www.hajim.rochester.edu\/senior-design-day\/wp-content\/uploads\/2022\/04\/image-101-1024x553.png 1024w, https:\/\/www.hajim.rochester.edu\/senior-design-day\/wp-content\/uploads\/2022\/04\/image-101-300x162.png 300w, https:\/\/www.hajim.rochester.edu\/senior-design-day\/wp-content\/uploads\/2022\/04\/image-101-768x415.png 768w, https:\/\/www.hajim.rochester.edu\/senior-design-day\/wp-content\/uploads\/2022\/04\/image-101-1536x830.png 1536w, https:\/\/www.hajim.rochester.edu\/senior-design-day\/wp-content\/uploads\/2022\/04\/image-101-1200x648.png 1200w, https:\/\/www.hajim.rochester.edu\/senior-design-day\/wp-content\/uploads\/2022\/04\/image-101.png 1636w\" sizes=\"auto, (max-width: 586px) 100vw, 586px\" \/><figcaption><strong>Fig 3.<\/strong> Process flow diagram for partial stripping<\/figcaption><\/figure><\/div>\n\n\n\n<div class=\"wp-block-image\"><figure class=\"aligncenter size-large is-resized\"><img loading=\"lazy\" decoding=\"async\" src=\"https:\/\/www.hajim.rochester.edu\/senior-design-day\/wp-content\/uploads\/2022\/04\/image-102-1024x306.png\" alt=\"\" class=\"wp-image-83002\" width=\"594\" height=\"177\" srcset=\"https:\/\/www.hajim.rochester.edu\/senior-design-day\/wp-content\/uploads\/2022\/04\/image-102-1024x306.png 1024w, https:\/\/www.hajim.rochester.edu\/senior-design-day\/wp-content\/uploads\/2022\/04\/image-102-300x90.png 300w, https:\/\/www.hajim.rochester.edu\/senior-design-day\/wp-content\/uploads\/2022\/04\/image-102-768x229.png 768w, https:\/\/www.hajim.rochester.edu\/senior-design-day\/wp-content\/uploads\/2022\/04\/image-102-1536x458.png 1536w, https:\/\/www.hajim.rochester.edu\/senior-design-day\/wp-content\/uploads\/2022\/04\/image-102-1200x358.png 1200w, https:\/\/www.hajim.rochester.edu\/senior-design-day\/wp-content\/uploads\/2022\/04\/image-102.png 1642w\" sizes=\"auto, (max-width: 594px) 100vw, 594px\" \/><figcaption><strong>Fig 4.<\/strong> Process flow diagram for complete stripping<\/figcaption><\/figure><\/div>\n\n\n\n<div class=\"wp-block-image\"><figure class=\"aligncenter size-full is-resized\"><img loading=\"lazy\" decoding=\"async\" src=\"https:\/\/www.hajim.rochester.edu\/senior-design-day\/wp-content\/uploads\/2022\/04\/image-103.png\" alt=\"\" class=\"wp-image-83012\" width=\"302\" height=\"252\" srcset=\"https:\/\/www.hajim.rochester.edu\/senior-design-day\/wp-content\/uploads\/2022\/04\/image-103.png 542w, https:\/\/www.hajim.rochester.edu\/senior-design-day\/wp-content\/uploads\/2022\/04\/image-103-300x250.png 300w\" sizes=\"auto, (max-width: 302px) 100vw, 302px\" \/><figcaption><strong>Fig 5<\/strong>. Ellipsometry thickness map<\/figcaption><\/figure><\/div>\n\n\n\n<div class=\"wp-block-image\"><figure class=\"aligncenter size-full is-resized\"><img loading=\"lazy\" decoding=\"async\" src=\"https:\/\/www.hajim.rochester.edu\/senior-design-day\/wp-content\/uploads\/2022\/04\/image-8.jpeg\" alt=\"\" class=\"wp-image-83022\" width=\"298\" height=\"225\" srcset=\"https:\/\/www.hajim.rochester.edu\/senior-design-day\/wp-content\/uploads\/2022\/04\/image-8.jpeg 516w, https:\/\/www.hajim.rochester.edu\/senior-design-day\/wp-content\/uploads\/2022\/04\/image-8-300x227.jpeg 300w\" sizes=\"auto, (max-width: 298px) 100vw, 298px\" \/><figcaption><strong>Fig 6.<\/strong> NMP-photoresist solutions with 2% incremental contamination level<\/figcaption><\/figure><\/div>\n\n\n\n<div class=\"wp-block-image\"><figure class=\"aligncenter size-full is-resized\"><img loading=\"lazy\" decoding=\"async\" src=\"https:\/\/www.hajim.rochester.edu\/senior-design-day\/wp-content\/uploads\/2022\/04\/image-9.jpeg\" alt=\"\" class=\"wp-image-83032\" width=\"306\" height=\"230\" srcset=\"https:\/\/www.hajim.rochester.edu\/senior-design-day\/wp-content\/uploads\/2022\/04\/image-9.jpeg 526w, https:\/\/www.hajim.rochester.edu\/senior-design-day\/wp-content\/uploads\/2022\/04\/image-9-300x226.jpeg 300w\" sizes=\"auto, (max-width: 306px) 100vw, 306px\" \/><figcaption><strong>Fig 7.<\/strong> Post-strip NMP solutions <\/figcaption><\/figure><\/div>\n\n\n\n<h2 class=\"wp-block-heading\">Results and Discussions<\/h2>\n\n\n\n<div class=\"wp-block-image\"><figure class=\"aligncenter size-large\"><img loading=\"lazy\" decoding=\"async\" width=\"1024\" height=\"732\" src=\"https:\/\/www.hajim.rochester.edu\/senior-design-day\/wp-content\/uploads\/2022\/04\/Screen-Shot-2022-04-27-at-11.30.51-AM-1024x732.png\" alt=\"\" class=\"wp-image-83822\" srcset=\"https:\/\/www.hajim.rochester.edu\/senior-design-day\/wp-content\/uploads\/2022\/04\/Screen-Shot-2022-04-27-at-11.30.51-AM-1024x732.png 1024w, https:\/\/www.hajim.rochester.edu\/senior-design-day\/wp-content\/uploads\/2022\/04\/Screen-Shot-2022-04-27-at-11.30.51-AM-300x215.png 300w, https:\/\/www.hajim.rochester.edu\/senior-design-day\/wp-content\/uploads\/2022\/04\/Screen-Shot-2022-04-27-at-11.30.51-AM-768x549.png 768w, https:\/\/www.hajim.rochester.edu\/senior-design-day\/wp-content\/uploads\/2022\/04\/Screen-Shot-2022-04-27-at-11.30.51-AM-1200x858.png 1200w, https:\/\/www.hajim.rochester.edu\/senior-design-day\/wp-content\/uploads\/2022\/04\/Screen-Shot-2022-04-27-at-11.30.51-AM.png 1345w\" sizes=\"auto, (max-width: 1024px) 100vw, 1024px\" \/><figcaption><strong>Fig 8.<\/strong> Strip rate vs contamination levels for complete stripping<\/figcaption><\/figure><\/div>\n\n\n\n<div class=\"wp-block-group\"><div class=\"wp-block-group__inner-container is-layout-flow wp-block-group-is-layout-flow\">\n<p>\u2022 Expected contamination levels are 0.64% by mass for photoresist annually and 1% by volume for water from ambient moisture.<\/p>\n\n\n\n<p>\u2022 At these contamination levels, the desired stripping performance is exceeded.\u00a0<\/p>\n\n\n\n<p>\u2022 Independently, photoresist contamination has a slightly greater impact on the stripping rate of NMP.\u00a0\u2022The target stripping rate of 17.5 nm\/s at 80\u2103 is exceeded at the expected contamination levels at ~ 23 \u2103.<\/p>\n<\/div><\/div>\n\n\n\n<div class=\"wp-block-image\"><figure class=\"aligncenter size-large is-resized\"><img loading=\"lazy\" decoding=\"async\" src=\"https:\/\/www.hajim.rochester.edu\/senior-design-day\/wp-content\/uploads\/2022\/04\/image-105-1024x740.png\" alt=\"\" class=\"wp-image-83052\" width=\"488\" height=\"352\" srcset=\"https:\/\/www.hajim.rochester.edu\/senior-design-day\/wp-content\/uploads\/2022\/04\/image-105-1024x740.png 1024w, https:\/\/www.hajim.rochester.edu\/senior-design-day\/wp-content\/uploads\/2022\/04\/image-105-300x217.png 300w, https:\/\/www.hajim.rochester.edu\/senior-design-day\/wp-content\/uploads\/2022\/04\/image-105-768x555.png 768w, https:\/\/www.hajim.rochester.edu\/senior-design-day\/wp-content\/uploads\/2022\/04\/image-105-1200x867.png 1200w, https:\/\/www.hajim.rochester.edu\/senior-design-day\/wp-content\/uploads\/2022\/04\/image-105.png 1354w\" sizes=\"auto, (max-width: 488px) 100vw, 488px\" \/><figcaption><strong>Fig 9.<\/strong> Absorbance vs contamination level for partial stripping<\/figcaption><\/figure><\/div>\n\n\n\n<p>\u2022 Wafers were partially stripped for 10 seconds in different solutions and the stripping was completed using pure NMP.<\/p>\n\n\n\n<p>\u2022 As both contamination levels increased, the amount of photoresist remaining on the wafers after 10 seconds of stripping increased as shown by increasing absorbances of the solutions.\u00a0<\/p>\n\n\n\n<p>\u2022 Validates the trend shown with the increasing time it takes complete stripping to occur as the contamination level increases<\/p>\n\n\n\n<div class=\"wp-block-image\"><figure class=\"aligncenter size-large is-resized\"><img loading=\"lazy\" decoding=\"async\" src=\"https:\/\/www.hajim.rochester.edu\/senior-design-day\/wp-content\/uploads\/2022\/04\/image-106-1024x669.png\" alt=\"\" class=\"wp-image-83062\" width=\"499\" height=\"325\" srcset=\"https:\/\/www.hajim.rochester.edu\/senior-design-day\/wp-content\/uploads\/2022\/04\/image-106-1024x669.png 1024w, https:\/\/www.hajim.rochester.edu\/senior-design-day\/wp-content\/uploads\/2022\/04\/image-106-300x196.png 300w, https:\/\/www.hajim.rochester.edu\/senior-design-day\/wp-content\/uploads\/2022\/04\/image-106-768x502.png 768w, https:\/\/www.hajim.rochester.edu\/senior-design-day\/wp-content\/uploads\/2022\/04\/image-106-1200x784.png 1200w, https:\/\/www.hajim.rochester.edu\/senior-design-day\/wp-content\/uploads\/2022\/04\/image-106.png 1390w\" sizes=\"auto, (max-width: 499px) 100vw, 499px\" \/><figcaption><strong>Fig 10. <\/strong>Refractive index vs contamination level<\/figcaption><\/figure><\/div>\n\n\n\n<p>\u2022 As expected, the refractive index of NMP decreases with increased water concentration.<\/p>\n\n\n\n<p>\u2022 Also, the refractive index of NMP increases with photoresist concentration.<\/p>\n\n\n\n<p>\u2022 The models are statistically significant and can be used to predict concentration given refractive index.<\/p>\n\n\n\n<h2 class=\"wp-block-heading\">Conclusions<\/h2>\n\n\n\n<ol class=\"is-style-default wp-block-list\"><li>The stripping rate of NMP decreases with increased contamination of both NMP and water.&nbsp;<\/li><li>Stripping rate can be quantified using:&nbsp;<ul><li>The time required for a wafer to completely strip.&nbsp;<\/li><li>The mass remaining on a wafer after stripping for 10 seconds.<\/li><\/ul><\/li><li>Stripping rate is high at room temperature, consequently the NMP bath does not need to be heated to 80\u00b0C<strong>.<\/strong><\/li><li>Refractive index of NMP\/water decreases as the contamination level increases, the inverse is true for NMP\/photoresist, and can consequently be used as an in-line method to monitor contamination levels.&nbsp;<\/li><\/ol>\n\n\n\n<h2 class=\"wp-block-heading\">Future Work<\/h2>\n\n\n\n<ol class=\"is-style-default wp-block-list\"><li>Repeat&nbsp;study using room equipped with only yellow light to reduce possibility of white\/natural light exposure.<\/li><li>Quantitively determine how the joint interaction of water and photoresist alter stripping rates.<\/li><li>Explore the effects of other contaminations, such as trace metals and natural light.<\/li><li>Explore the effect of operating conditions, such as pressure and temperature.<\/li><li>Determine what compounds are formed that reduce the effectiveness of stripping and propose a degradation pathway for NMP.<\/li><\/ol>\n\n\n\n<h2 class=\"wp-block-heading\">Acknowledgements<\/h2>\n\n\n\n<p>We would like to thank and acknowledge:<\/p>\n\n\n\n<ol class=\"is-style-default wp-block-list\"><li>Our sponsor Michaela Wentz and the staff of Meta Reality Labs.<\/li><li>Our professor, instructors and advisors Dr. Lawton, Dr. Shestopalov, Dr. Kelley, Dr. Yates,&nbsp;Professor&nbsp;Juba, Clair Cunningham , Mason Garlatti , Dr. Tenhaeff, Dr. Mack, Dr. Madejski, Jeffery Lefler.<\/li><li>The graduate students who assisted us: Jorge Medina Andrade, Nan Liu, Ben Carlson, Xiao Li, Ni Huo, Zhengfu Huang.<\/li><\/ol>\n\n\n\n<h2 class=\"wp-block-heading\">References<\/h2>\n\n\n\n<ol class=\"is-style-default wp-block-list\"><li>John C. Moore. Proc. SPIE 4690, <em>Advances in Resist Technology and Processing XIX<\/em>, (2002).<\/li><li>Hugger, Alexander, et al.&nbsp;<em>IEEE Transactions on Semiconductor Manufacturing<\/em>&nbsp;33.4 (2020): 552-556.<\/li><li>Le, Q. T., et al.&nbsp;<em>Microelectronic engineering<\/em>&nbsp;86.2 (2009): 181-185.<\/li><li>Lennon, Gavin, et al.&nbsp;&nbsp;<em>Journal of analytical methods in chemistry<\/em>&nbsp;(2020).<\/li><li>Spuller, M. T., et al.&nbsp;<em>Journal of the Electrochemical Society<\/em>&nbsp;152.1 (2004): G40.&nbsp;<\/li><\/ol>\n","protected":false},"excerpt":{"rendered":"<p>One or two sentence description of the project.<\/p>\n","protected":false},"author":6242,"featured_media":39542,"comment_status":"closed","ping_status":"closed","sticky":false,"template":"","format":"standard","meta":{"_coblocks_attr":"","_coblocks_dimensions":"","_coblocks_responsive_height":"","_coblocks_accordion_ie_support":"","_monsterinsights_skip_tracking":false,"_monsterinsights_sitenote_active":false,"_monsterinsights_sitenote_note":"","_monsterinsights_sitenote_category":0,"footnotes":""},"categories":[76],"tags":[],"coauthors":[8612],"class_list":["post-64152","post","type-post","status-publish","format-standard","has-post-thumbnail","hentry","category-che-archive"],"acf":[],"yoast_head":"<!-- This site is optimized with the Yoast SEO plugin v27.5 - https:\/\/yoast.com\/product\/yoast-seo-wordpress\/ -->\n<title>NMP Replacement Investigation - 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