P. R. Meyer, Ji Yeon Kim, Nathaniel A. Lynd, C. Willson
This project, “Pitch Division Photolithography at I-line,” seeks to accomplish pitch multiplication by using a traditional 248 nm photoresist polymer in conjunction with a photo-acid generator (PAG) and a photo-base generator (PBG). This formulation can achieve a two-fold improvement in resolution without the need for new equipment or significant changes in processing conditions. The photoresist matrix used in this work is poly[4-[(tert-butoxycarbonyl)oxy] styrene] (PTBOC), which is employed in combination with a PAG in 248 nm resists. When exposed to light, the PAG decomposes to form acid which, upon post-exposure baking, deprotects multiple pendant groups on the PTBOC to produce hydroxyl groups, thereby changing its solubility. This polymer exhibits another key feature: the dissolution rate with respect to dose has a threshold-like response, meaning that below a threshold dose, the polymer will not appreciably dissolve in a developer containing tetramethyl ammonium hydroxide (TMAH), but above this dose, the dissolution rate increases several orders of magnitude. This behavior becomes vital at feature sizes that approach theoretical resolution limits where the aerial image near the photoresist becomes more sinusoidal. Because the dissolution rate is controlled by the acid content within the polymer matrix, it is possible to cross this dissolution threshold twice with increasing dose if the acid is somehow quenched at higher doses. A PBG is an easy way to achieve this goal. If a PBG is chosen such that it is decomposes more slowly than the PAG and is incorporated with a stochiometric excess, then this dissolution threshold may be crossed twice. The addition of a PBG generates three different regimes with respect to dose: At low doses, neither the PAG nor PBG will have appreciably decomposed and the resist remains insoluble in aqueous base. At medium doses, enough acid will be generated by the PAG to cross the threshold, with too little PBG decomposition to effectively quench said acid. At high doses, both the PAG and PBG have mostly decomposed and the net acid concentration will be below the dissolution threshold. If the relative rates of the PAG and PBG can be tuned such that these two dissolution thresholds properly match the sinusoid intensity profile, the resolution of patterns can be improved by a factor of two. Dr. Xinyu Gu previously demonstrated the feasibility of such a system for 193 nm tools [1]. In this work, we report several combinations of PAGs and PBGs that meet the above criteria and show promise for exhibiting pitch-division. In some cases, a photosensitizer was needed to enable the decomposition of the PAG. These combinations were tested by exposing a film to a given dose and then developing in an aqueous solution of TMAH. It was found that the relative dissolution rates closely match the ideals as described above. These combinations are ready for testing with an exposure tool to verify and optimize their function as a pit
{"title":"Pitch division photolithography at I-line (Conference Presentation)","authors":"P. R. Meyer, Ji Yeon Kim, Nathaniel A. Lynd, C. Willson","doi":"10.1117/12.2514762","DOIUrl":"https://doi.org/10.1117/12.2514762","url":null,"abstract":"This project, “Pitch Division Photolithography at I-line,” seeks to accomplish pitch multiplication by using a traditional 248 nm photoresist polymer in conjunction with a photo-acid generator (PAG) and a photo-base generator (PBG). This formulation can achieve a two-fold improvement in resolution without the need for new equipment or significant changes in processing conditions. \u0000\u0000The photoresist matrix used in this work is poly[4-[(tert-butoxycarbonyl)oxy] styrene] (PTBOC), which is employed in combination with a PAG in 248 nm resists. When exposed to light, the PAG decomposes to form acid which, upon post-exposure baking, deprotects multiple pendant groups on the PTBOC to produce hydroxyl groups, thereby changing its solubility. This polymer exhibits another key feature: the dissolution rate with respect to dose has a threshold-like response, meaning that below a threshold dose, the polymer will not appreciably dissolve in a developer containing tetramethyl ammonium hydroxide (TMAH), but above this dose, the dissolution rate increases several orders of magnitude. This behavior becomes vital at feature sizes that approach theoretical resolution limits where the aerial image near the photoresist becomes more sinusoidal.\u0000\u0000Because the dissolution rate is controlled by the acid content within the polymer matrix, it is possible to cross this dissolution threshold twice with increasing dose if the acid is somehow quenched at higher doses. A PBG is an easy way to achieve this goal. If a PBG is chosen such that it is decomposes more slowly than the PAG and is incorporated with a stochiometric excess, then this dissolution threshold may be crossed twice. The addition of a PBG generates three different regimes with respect to dose: At low doses, neither the PAG nor PBG will have appreciably decomposed and the resist remains insoluble in aqueous base. At medium doses, enough acid will be generated by the PAG to cross the threshold, with too little PBG decomposition to effectively quench said acid. At high doses, both the PAG and PBG have mostly decomposed and the net acid concentration will be below the dissolution threshold. If the relative rates of the PAG and PBG can be tuned such that these two dissolution thresholds properly match the sinusoid intensity profile, the resolution of patterns can be improved by a factor of two. Dr. Xinyu Gu previously demonstrated the feasibility of such a system for 193 nm tools [1]. \u0000\u0000In this work, we report several combinations of PAGs and PBGs that meet the above criteria and show promise for exhibiting pitch-division. In some cases, a photosensitizer was needed to enable the decomposition of the PAG. These combinations were tested by exposing a film to a given dose and then developing in an aqueous solution of TMAH. It was found that the relative dissolution rates closely match the ideals as described above. These combinations are ready for testing with an exposure tool to verify and optimize their function as a pit","PeriodicalId":437977,"journal":{"name":"Advances in Patterning Materials and Processes XXXVI","volume":"28 1","pages":"0"},"PeriodicalIF":0.0,"publicationDate":"2019-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"117030753","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Metal-Containing Resists for EUV Lithography Robert L. Brainard State University of New York Polytechnic Institute - CNSE, 257 Fuller Rd. Albany, NY 12203 Since 2009, the photoresist community has shown a great deal of interest in EUV photoresists containing metallic elements. This interest was initiated by two events: (1) Publication of the pioneering work of OSU1 and Cornell;2 (2) The realization that increasing the EUV optical density of resists will improve stochastics.3 Since these two events, photoresist chemists all over the world have begun investigating the possibility of creating photoresists containing metals that strongly absorb EUV photons. Figure 1 shows the periodic table that is color-coded to indicate the relative EUV optical density of the elements.4 This table also shows all of the elements for which EUV resists have been published. This keynote presentation will attempt to review the most successful EUV resist platforms containing metals. In particular, the work of Inpria,5 Cornell, SUNY Poly6 and ARCNL7 will be described and discussed. The presentation will also describe some of the critical issues facing the industry as it evaluates the merits and challenges of using resists containing metals.
EUV光刻用含金属光刻胶robert L. brainardnew York state University Polytechnic Institute - CNSE, 257 Fuller Rd. Albany, NY 12203自2009年以来，光刻胶界对含金属元素的EUV光刻胶表现出了极大的兴趣。这一兴趣是由两个事件引起的:(1)OSU1和Cornell的开创性工作的发表;(2)认识到增加电阻的EUV光密度将改善随机性自从这两件事之后，世界各地的光刻胶化学家开始研究制造含有金属的光刻胶的可能性，这种金属能强烈吸收EUV光子。图1显示了元素周期表，用颜色表示元素的相对EUV光密度该表还显示了已发表的EUV电阻的所有元素。本主题演讲将尝试回顾最成功的含金属的EUV抗蚀剂平台。特别是Inpria,5 Cornell, SUNY Poly6和ARCNL7的工作将被描述和讨论。该演讲还将描述该行业在评估使用含金属抗蚀剂的优点和挑战时面临的一些关键问题。
{"title":"Metal-containing resists for EUV lithography (Conference Presentation)","authors":"R. Brainard","doi":"10.1117/12.2516012","DOIUrl":"https://doi.org/10.1117/12.2516012","url":null,"abstract":"Metal-Containing Resists for EUV Lithography\u0000Robert L. Brainard\u0000\u0000State University of New York Polytechnic Institute - CNSE, 257 Fuller Rd. Albany, NY 12203\u0000\u0000 Since 2009, the photoresist community has shown a great deal of interest in EUV photoresists containing metallic elements. This interest was initiated by two events: (1) Publication of the pioneering work of OSU1 and Cornell;2 (2) The realization that increasing the EUV optical density of resists will improve stochastics.3 Since these two events, photoresist chemists all over the world have begun investigating the possibility of creating photoresists containing metals that strongly absorb EUV photons. Figure 1 shows the periodic table that is color-coded to indicate the relative EUV optical density of the elements.4 This table also shows all of the elements for which EUV resists have been published.\u0000 This keynote presentation will attempt to review the most successful EUV resist platforms containing metals. In particular, the work of Inpria,5 Cornell, SUNY Poly6 and ARCNL7 will be described and discussed. The presentation will also describe some of the critical issues facing the industry as it evaluates the merits and challenges of using resists containing metals.","PeriodicalId":437977,"journal":{"name":"Advances in Patterning Materials and Processes XXXVI","volume":"11 1","pages":"0"},"PeriodicalIF":0.0,"publicationDate":"2019-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"115197205","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
G. Wallraff, H. Truong, M. Sanchez, Noel Arellno, A. Friz, Wyatt A. Thornley, O. Kostko, D. Slaughter, F. Ogletree
As EUV approaches its insertion point into high volume manufacturing the semiconductor industry is increasingly focusing on photoresist performance. Recently metal containing resists have been proposed as alternatives to standard Chemically Amplified (CA) systems. Both approaches suffer from an incomplete knowledge of the EUV imaging mechanism. In particular the origin, number and fate of the secondary electrons believed to be active in the resist reactions is poorly understood. In this contribution we describe a study designed to try and characterize these processes and quantify the reactions that determine resist performances. We will describe experiments on a series of model CA systems doped with inorganic salts. Photoacid yields and relative rates of deprotection will be reported for metal salts that can be incorporated into polymer films at concentrations as high as 10 molal. In addition to comparing the relative performance at EUV we will also be characterizing the response at 248 nm and 100 KeV e beam. The results of these studies will be discussed in terms of the metal ion crossection, ionization potential and redox potential. In addition we will describe some unanticipated EUV reactivity of standard acid indicators that may impact the accepted electron yield/photospeed measurements that have been reported for EUV CA resists.
{"title":"Model studies on the metal salt sensitization of chemically amplified photoresists (Conference Presentation)","authors":"G. Wallraff, H. Truong, M. Sanchez, Noel Arellno, A. Friz, Wyatt A. Thornley, O. Kostko, D. Slaughter, F. Ogletree","doi":"10.1117/12.2514610","DOIUrl":"https://doi.org/10.1117/12.2514610","url":null,"abstract":"As EUV approaches its insertion point into high volume manufacturing the semiconductor industry is increasingly focusing on photoresist performance. Recently metal containing resists have been proposed as alternatives to standard Chemically Amplified (CA) systems. Both approaches suffer from an incomplete knowledge of the EUV imaging mechanism. In particular the origin, number and fate of the secondary electrons believed to be active in the resist reactions is poorly understood. In this contribution we describe a study designed to try and characterize these processes and quantify the reactions that determine resist performances. \u0000We will describe experiments on a series of model CA systems doped with inorganic salts. Photoacid yields and relative rates of deprotection will be reported for metal salts that can be incorporated into polymer films at concentrations as high as 10 molal. In addition to comparing the relative performance at EUV we will also be characterizing the response at 248 nm and 100 KeV e beam. The results of these studies will be discussed in terms of the metal ion crossection, ionization potential and redox potential. In addition we will describe some unanticipated EUV reactivity of standard acid indicators that may impact the accepted electron yield/photospeed measurements that have been reported for EUV CA resists.","PeriodicalId":437977,"journal":{"name":"Advances in Patterning Materials and Processes XXXVI","volume":"254 1","pages":"0"},"PeriodicalIF":0.0,"publicationDate":"2019-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"121531050","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
EMD Performance Materials provides a broad material portfolio for photolithography, Chemical Shrink and EUV Rinse materials are two categories of aqueous materials enabling advanced patterning. Chemical Shrink materials generate an additional layer on the surface of photoresist pattern through chemical/physical interactions, resulting in finer trench or hole structures. The technique helps IC manufacturers improve process margin and reduce cost of ownership by relaxing the requirements for lithography. EMD has been engaged in development of the technology for over two decades, and introduced materials for multiple generations of lithography. The first generation Chemical Shrink material, AZ® R200 was commercialized for i-line and KrF applications around 2000. From then on, several commercial platforms were released targeting for ArF, ArF-immersion, and ArF NTD (Negative Tone Development) photoresists. Shrink amount depends on the material platforms and photoresists, it can be controlled from several nm to 100 nm with the process conditions, mainly shrink bake temperature. Well-controlled through-pitch proximity is one of the key advantages of the technique as well. Chemical shrink process is a straightforward and well-established in-track process. Not only smaller pattern sizes are achieved, effective DOF (Depth of Focus) is improved, but also surface smoothing of photoresist is expected. Rinse materials are a unique offering from EMD to alleviate capillary force hence mitigate pattern collapse in very fine photoresist pattern through reducing surface tension with novel surfactants. Based on the knowledge and know-hows learned during the development of rinse materials for ArF and ArF immersion lithography processes in the past decades, new material platforms have been developed to extend the technique to meet the ever more critical requirements in EUV lithography. AZ® Extreme 10 was commercialized as the world first rinse material dedicated for EUV lithography, designed for L/S (Line and Space) pattern of 22nm hp patterning. To further improve the compatibility with the latest EUV photoresists for finer pattern, 18nm hp and beyond, AZ® SPC-708 is newly commercialized in 2018. It is expected that AZ® SPC-708 helps reduce photoresist residues during development process in addition to its function of collapse mitigation. EMD Performance Materials is committed to providing novel solutions to confront the increasing technical challenges in advanced patterning.
EMD高性能材料为光刻提供了广泛的材料组合，化学收缩和EUV冲洗材料是两类水性材料，可以实现先进的图案。化学收缩材料通过化学/物理相互作用在光刻胶图案表面产生额外的层，从而产生更精细的沟槽或孔结构。该技术通过放宽对光刻的要求，帮助IC制造商提高工艺利润并降低拥有成本。EMD从事光刻技术的开发已有二十多年，并推出了多代光刻材料。第一代化学收缩材料AZ®R200在2000年左右被商业化用于i-line和KrF应用。从那时起，几个针对ArF, ArF沉浸和ArF NTD(负色调显影)光刻胶的商业平台发布。收缩量取决于材料平台和光阻剂，它可以控制在几nm到100 nm的工艺条件下，主要是收缩烘烤温度。良好控制的全螺距接近度也是该技术的关键优势之一。化学收缩工艺是一种简单、成熟的工艺。不仅实现了更小的图案尺寸，提高了有效的焦深(DOF, Depth of Focus)，而且光刻胶的表面平滑性也得到了提高。冲洗材料是EMD提供的独特产品，可以减轻毛细力，从而通过使用新型表面活性剂降低表面张力，减轻非常精细的光刻胶图案的图案崩溃。基于过去几十年在ArF和ArF浸没式光刻工艺的冲洗材料开发过程中所学到的知识和技能，新的材料平台已经开发出来，以扩展该技术，以满足EUV光刻中越来越关键的要求。AZ®Extreme 10是世界上第一个用于EUV光刻的冲洗材料，专为22nm hp图案的L/S(线和空间)图案而设计。为了进一步提高与最新EUV光刻胶的兼容性，以实现更精细的图案，18nm hp及更高，AZ®SPC-708于2018年首次商业化。预计AZ®SPC-708有助于减少光刻胶在开发过程中的残留，除了其功能的崩溃缓解。EMD高性能材料致力于提供新颖的解决方案，以应对日益增长的先进模式技术挑战。
{"title":"Aqueous materials for advanced lithography (Conference Presentation)","authors":"Yi Cao, Tatsuro Nagahara, T. Hirayama","doi":"10.1117/12.2516031","DOIUrl":"https://doi.org/10.1117/12.2516031","url":null,"abstract":"EMD Performance Materials provides a broad material portfolio for photolithography, Chemical Shrink and EUV Rinse materials are two categories of aqueous materials enabling advanced patterning. \u0000\u0000Chemical Shrink materials generate an additional layer on the surface of photoresist pattern through chemical/physical interactions, resulting in finer trench or hole structures. The technique helps IC manufacturers improve process margin and reduce cost of ownership by relaxing the requirements for lithography. EMD has been engaged in development of the technology for over two decades, and introduced materials for multiple generations of lithography. The first generation Chemical Shrink material, AZ® R200 was commercialized for i-line and KrF applications around 2000. From then on, several commercial platforms were released targeting for ArF, ArF-immersion, and ArF NTD (Negative Tone Development) photoresists. Shrink amount depends on the material platforms and photoresists, it can be controlled from several nm to 100 nm with the process conditions, mainly shrink bake temperature. Well-controlled through-pitch proximity is one of the key advantages of the technique as well. Chemical shrink process is a straightforward and well-established in-track process. Not only smaller pattern sizes are achieved, effective DOF (Depth of Focus) is improved, but also surface smoothing of photoresist is expected.\u0000\u0000Rinse materials are a unique offering from EMD to alleviate capillary force hence mitigate pattern collapse in very fine photoresist pattern through reducing surface tension with novel surfactants. Based on the knowledge and know-hows learned during the development of rinse materials for ArF and ArF immersion lithography processes in the past decades, new material platforms have been developed to extend the technique to meet the ever more critical requirements in EUV lithography. AZ® Extreme 10 was commercialized as the world first rinse material dedicated for EUV lithography, designed for L/S (Line and Space) pattern of 22nm hp patterning. To further improve the compatibility with the latest EUV photoresists for finer pattern, 18nm hp and beyond, AZ® SPC-708 is newly commercialized in 2018. It is expected that AZ® SPC-708 helps reduce photoresist residues during development process in addition to its function of collapse mitigation.\u0000\u0000EMD Performance Materials is committed to providing novel solutions to confront the increasing technical challenges in advanced patterning.","PeriodicalId":437977,"journal":{"name":"Advances in Patterning Materials and Processes XXXVI","volume":"24 1","pages":"0"},"PeriodicalIF":0.0,"publicationDate":"2019-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"133182113","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
R. Wojtecki, M. Mettry, N. F. Nathel, A. Friz, Anuja De Silva, N. Arellano, H. Shobha
Lithography faces an increasing number of challenges as errors in pattern overlay and placement become increasingly significant as scaling continues. The flexibility of removing a lithography step offers a significant advantage in fabrication as it has the potential to mitigate these errors. Furthermore, this strategy also relaxes design rules in semiconductor fabrication enabling concepts like self-alignment. The use of selective area atomic layer deposition with self-assembled monolayers that incorporate different side group functionalities was evaluated in the deposition of a sacrificial etch mask. Monolayers with weak supramolecular interactions between components (e.g. Van der Waals) were found to exhibit significant defectivity when depositing this material at and below 100nm feature sizes. The incorporation stronger supramolecular interacting groups in the monolayer design, such as hydrogen bonding units or pi-pi interactions, did not produce an added benefit over the weaker interacting components. However, incorporation of reactive moieties in the monolayer component enabled the subsequent reaction of a SAM surface generating a polymer at the surface and providing a more effective barrier, greatly reducing the number and types of defects observed in the selectively deposited ALD film. These reactive monolayers enabled the selective deposition of a film with critical dimensions as low as 15nm. The deposited film was then used as an effective barrier for standard isotropic etch chemistries, allowing the selective removal of a metal without degradation to the surrounding surface. This work enables selective area ALD as a technology by (1) the development of a material that dramatically reduces defectivity and (2) the demonstrated use of the selectively deposited film as an etch mask and its subsequent removal under mild conditions.
{"title":"Defectivity reduction in area selective atomic layer deposition by monolayer design (Conference Presentation)","authors":"R. Wojtecki, M. Mettry, N. F. Nathel, A. Friz, Anuja De Silva, N. Arellano, H. Shobha","doi":"10.1117/12.2515465","DOIUrl":"https://doi.org/10.1117/12.2515465","url":null,"abstract":"Lithography faces an increasing number of challenges as errors in pattern overlay and placement become increasingly significant as scaling continues. The flexibility of removing a lithography step offers a significant advantage in fabrication as it has the potential to mitigate these errors. Furthermore, this strategy also relaxes design rules in semiconductor fabrication enabling concepts like self-alignment. The use of selective area atomic layer deposition with self-assembled monolayers that incorporate different side group functionalities was evaluated in the deposition of a sacrificial etch mask. Monolayers with weak supramolecular interactions between components (e.g. Van der Waals) were found to exhibit significant defectivity when depositing this material at and below 100nm feature sizes. The incorporation stronger supramolecular interacting groups in the monolayer design, such as hydrogen bonding units or pi-pi interactions, did not produce an added benefit over the weaker interacting components. However, incorporation of reactive moieties in the monolayer component enabled the subsequent reaction of a SAM surface generating a polymer at the surface and providing a more effective barrier, greatly reducing the number and types of defects observed in the selectively deposited ALD film. These reactive monolayers enabled the selective deposition of a film with critical dimensions as low as 15nm. The deposited film was then used as an effective barrier for standard isotropic etch chemistries, allowing the selective removal of a metal without degradation to the surrounding surface. This work enables selective area ALD as a technology by (1) the development of a material that dramatically reduces defectivity and (2) the demonstrated use of the selectively deposited film as an etch mask and its subsequent removal under mild conditions.","PeriodicalId":437977,"journal":{"name":"Advances in Patterning Materials and Processes XXXVI","volume":"2 1","pages":"0"},"PeriodicalIF":0.0,"publicationDate":"2019-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"132541671","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Wyatt A. Thornley, H. Truong, M. Sanchez, D. Sanders, G. Wallraff, O. Kostko, D. Ogletree, D. Slaughter
The looming industry transition towards EUV for high-volume manufacture of semiconductors has demonstrated the need for high sensitivity resists capable of delivering the resolution enhancements offered by the 13.5 nm platform. Inorganic and organometallic based resists have demonstrated themselves viable alternatives to traditional chemically amplified (CA) photoresists, as the EUV absorptivity enhancement of metal nuclei can enable efficient reactivity at minimal photon doses. Despite the demand for EUV photoreactive materials, relatively little has been reported on the fundamental reactivity of inorganic and organometallic compounds towards EUV that may enable the rational design of metal-based resists. To facilitate the design of next-generation metal-based resists, we have evaluated the reactivity of well-known metal-based model photosystems that undergo ligand-to-metal charge-transfer (LMCT), metal-to-ligand charge-transfer (MLCT), outer-sphere charge-transfer (OSCT), and ligand field (LF) based photochemistry in the UV and visible towards EUV and 100 KeV e-beam, with product characterization carried out by infrared, Raman, and UV-Vis spectroscopies. We will report the findings of these studies, emphasizing the relationships between quantum yields in the UV-Vis and EUV, role of the EUV absorption cross-section of the central metal, and trends in reaction classes and their relative sensitivity towards EUV.
{"title":"Model reactivity of inorganic and organometallic materials in EUV (Conference Presentation)","authors":"Wyatt A. Thornley, H. Truong, M. Sanchez, D. Sanders, G. Wallraff, O. Kostko, D. Ogletree, D. Slaughter","doi":"10.1117/12.2515134","DOIUrl":"https://doi.org/10.1117/12.2515134","url":null,"abstract":"The looming industry transition towards EUV for high-volume manufacture of semiconductors has demonstrated the need for high sensitivity resists capable of delivering the resolution enhancements offered by the 13.5 nm platform. Inorganic and organometallic based resists have demonstrated themselves viable alternatives to traditional chemically amplified (CA) photoresists, as the EUV absorptivity enhancement of metal nuclei can enable efficient reactivity at minimal photon doses. Despite the demand for EUV photoreactive materials, relatively little has been reported on the fundamental reactivity of inorganic and organometallic compounds towards EUV that may enable the rational design of metal-based resists.\u0000\u0000To facilitate the design of next-generation metal-based resists, we have evaluated the reactivity of well-known metal-based model photosystems that undergo ligand-to-metal charge-transfer (LMCT), metal-to-ligand charge-transfer (MLCT), outer-sphere charge-transfer (OSCT), and ligand field (LF) based photochemistry in the UV and visible towards EUV and 100 KeV e-beam, with product characterization carried out by infrared, Raman, and UV-Vis spectroscopies. We will report the findings of these studies, emphasizing the relationships between quantum yields in the UV-Vis and EUV, role of the EUV absorption cross-section of the central metal, and trends in reaction classes and their relative sensitivity towards EUV.","PeriodicalId":437977,"journal":{"name":"Advances in Patterning Materials and Processes XXXVI","volume":"18 1","pages":"0"},"PeriodicalIF":0.0,"publicationDate":"2019-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"116455753","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Ji Yeon Kim, N. Ito, Xiaoming Yang, Stephen M. Sirard, Austin P. Lane, Gregory Blachut, Y. Asano, Christopher J. Ellison, Nathaniel A. Lynd, C. Willson
Directed self-assembly (DSA) of block copolymers (BCPs) is one approach to the pattern density multiplication required to achieve high-volume manufacturing of the next-generation memory and storage devices. One important application for DSA is in manufacturing of nanoimprint templates for the next-generation bit patterned media. A hybrid chemo-/grapho-epitaxy DSA process has been developed that produced 5 nm line-and-space DSA patterns on a chromium hard mask surface. The guide lines for this process were produced by imprint lithography. The process requires a polar guide stripe, which is the trim-etched imprint resist, and a near neutral substrate, which is the etched chromium. This requires selective grafting of near neutral polymer brushes to the etched chromium and not to the etched imprint guidelines. This selectivity is one critical requirement for the process [1]. Orientation and alignment of line-and-space patterns that traverse through the entire BCP film were successfully employed to pattern the chromium hard mask. We have investigated the reactivity of etched chromium surfaces with various polymer brush chemistries and found that the choice of the end-functional groups, monomer structures, and grafting temperature all play significant roles in selective functionalization. The etched chromium surface was found to be more reactive with various polymer brushes than etched silicon under mild brush grafting conditions. Hence, lower grafting temperatures could be exploited for achieving selectivity of polymer brush to the etched chromium while not reacting with the etched imprint guidelines. Thus, several polymer brushes that form a thin layer of brush on etched chromium were found to modify the surface energy of the etched chromium without significant interaction with the etched imprint resist. Successful pattern transfer of 5 nm line-and-space patterns was achieved. 1. Lane, A. P., et al. ACS Nano (2017), 11 (8), 7656–7665.
{"title":"Design of selective brush chemistry and surface functionalization for directed self-assembly of block copolymers (Conference Presentation)","authors":"Ji Yeon Kim, N. Ito, Xiaoming Yang, Stephen M. Sirard, Austin P. Lane, Gregory Blachut, Y. Asano, Christopher J. Ellison, Nathaniel A. Lynd, C. Willson","doi":"10.1117/12.2514793","DOIUrl":"https://doi.org/10.1117/12.2514793","url":null,"abstract":"Directed self-assembly (DSA) of block copolymers (BCPs) is one approach to the pattern density multiplication required to achieve high-volume manufacturing of the next-generation memory and storage devices. One important application for DSA is in manufacturing of nanoimprint templates for the next-generation bit patterned media. A hybrid chemo-/grapho-epitaxy DSA process has been developed that produced 5 nm line-and-space DSA patterns on a chromium hard mask surface. The guide lines for this process were produced by imprint lithography. The process requires a polar guide stripe, which is the trim-etched imprint resist, and a near neutral substrate, which is the etched chromium. This requires selective grafting of near neutral polymer brushes to the etched chromium and not to the etched imprint guidelines. This selectivity is one critical requirement for the process [1]. Orientation and alignment of line-and-space patterns that traverse through the entire BCP film were successfully employed to pattern the chromium hard mask. We have investigated the reactivity of etched chromium surfaces with various polymer brush chemistries and found that the choice of the end-functional groups, monomer structures, and grafting temperature all play significant roles in selective functionalization. The etched chromium surface was found to be more reactive with various polymer brushes than etched silicon under mild brush grafting conditions. Hence, lower grafting temperatures could be exploited for achieving selectivity of polymer brush to the etched chromium while not reacting with the etched imprint guidelines. Thus, several polymer brushes that form a thin layer of brush on etched chromium were found to modify the surface energy of the etched chromium without significant interaction with the etched imprint resist. Successful pattern transfer of 5 nm line-and-space patterns was achieved. 1. Lane, A. P., et al. ACS Nano (2017), 11 (8), 7656–7665.","PeriodicalId":437977,"journal":{"name":"Advances in Patterning Materials and Processes XXXVI","volume":"33 1","pages":"0"},"PeriodicalIF":0.0,"publicationDate":"2019-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"122019661","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Extreme-ultraviolet (~13.5 nm) lithography is much different than the previous lithographic wavelength such that chemical reactions within the resist are caused by electrons generated from ionization. As the lithographic community moves towards printing more advanced nodes, the secondary electron blur from extreme-ultraviolet photons becomes more critical. Understanding the range of the secondary electrons from the photoionization site would provide insight into patterning capabilities for different photoresists and aid in the development of improved models. Here, we aim to determine the range of electrons by measuring the thickness loss due to top-down electron beam exposure. More importantly, this work focuses on measuring the thickness loss due to incident electrons with energies less than 80 eV for two different resist systems: (1) a chemically amplified photoresist where acid diffusion affects the depth of solubility changing reactions, and (2) a non-chemically amplified photoresist, PMMA, where no acid diffusion occurs. Photoresists are exposed to electrons, baked, and developed; subsequent ellipsometry is used to quantify the depth at which solubility changing reactions occur based on the incident energy and dose. Quencher concentration and post-exposure bake parameters are varied to mitigate acid diffusion to extrapolate the electron range. The results are then compared to the thickness loss of the non-chemically amplified photoresist.
{"title":"Measuring extreme-ultraviolet secondary electron blur (Conference Presentation)","authors":"Steven Grzeskowiak, R. Brainard, G. Denbeaux","doi":"10.1117/12.2515428","DOIUrl":"https://doi.org/10.1117/12.2515428","url":null,"abstract":"Extreme-ultraviolet (~13.5 nm) lithography is much different than the previous lithographic wavelength such that chemical reactions within the resist are caused by electrons generated from ionization. As the lithographic community moves towards printing more advanced nodes, the secondary electron blur from extreme-ultraviolet photons becomes more critical. Understanding the range of the secondary electrons from the photoionization site would provide insight into patterning capabilities for different photoresists and aid in the development of improved models. Here, we aim to determine the range of electrons by measuring the thickness loss due to top-down electron beam exposure. More importantly, this work focuses on measuring the thickness loss due to incident electrons with energies less than 80 eV for two different resist systems: (1) a chemically amplified photoresist where acid diffusion affects the depth of solubility changing reactions, and (2) a non-chemically amplified photoresist, PMMA, where no acid diffusion occurs. Photoresists are exposed to electrons, baked, and developed; subsequent ellipsometry is used to quantify the depth at which solubility changing reactions occur based on the incident energy and dose. Quencher concentration and post-exposure bake parameters are varied to mitigate acid diffusion to extrapolate the electron range. The results are then compared to the thickness loss of the non-chemically amplified photoresist.","PeriodicalId":437977,"journal":{"name":"Advances in Patterning Materials and Processes XXXVI","volume":"59 1","pages":"0"},"PeriodicalIF":0.0,"publicationDate":"2019-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"134522342","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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