{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/105702"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/105702","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"A tale of two studies: Syntheses of silicon nitride chemical vapor deposition precursors and divalent lanthanide N,N-dimethylaminodiboranate complexes","abstract":"Silicon nitride thin films have key industrial applications in the manufacturing of semiconductors, but these applications impose strict requirements on the film growth process. Specifically, the SiN films must be deposited at temperatures below 400 °C to avoid device degradation, and they must be deposited conformally to meet the demand of smaller feature sizes. In chapter 1, the synthesis and deposition of a new precursor for silicon nitride thin films, 1,1-diazido-1-silacyclopent-3-ene (1) is described. Precursor 1, a known compound, was synthesized by treating 1,1-dichloro-1-silacyclopent-3-ene with two equivalents of NaN3 in acetonitrile, and was purified by distillation under reduced pressures. Deposition experiments were performed in a hot-wall chemical vapor deposition (CVD) reactor show that 1 deposits films at temperatures as low as 400 °C and with excellent conformality in trenches with aspect ratios up to 3.5:1. Elemental characterization of these films, performed by Auger spectroscopy, show that these films contain Si (~10 %) and N (~10 %) in a 1:1 ratio but have high C (~40 %) and O (~40 %) contents, which is likely attributed to the presence of residual moisture and oxygen in the reaction chamber and the slow removal of volatile organic byproducts. In chapter 2, we describe the syntheses and molecular structures of new SmII and TmII N,N-dimethylaminodiboranate (DMADB) complexes. Treatment of solutions of SmI2(thf)2 in thf with Na(H3BNMe2BH3) results in the formation of Sm(H3BNMe2BH3)2(thf)3 which can be readily converted to the dimethyoxyethane (dme) adduct, Sm(H3BNMe2BH3)2(dme)2 by treatment with dme. We also show that Sm(H3BNMe2BH3)2(thf)3 can be prepared by the reduction of the SmIII compound, Sm(H3BNMe2BH3)3(thf), with KC8,and that addition of 18-crown-6 to this reaction mixture results in the formation of Sm(H3BNMe2BH3)2(18-crown-6). The new TmII complexes were synthesized analogously to 1; treatment of TmI2 solutions in thf with Na(H3BNMe2BH3) resulted in the formation of 1:1 mixtures of Tm(H3BNMe2BH3)2(thf)3 and Tm(H3BNMe2BH3)2(thf)2. IR and 1H NMR data are reported for all these compounds along with their crystal structures.","abstract_html":"Silicon nitride thin films have key industrial applications in the manufacturing of semiconductors, but these applications impose strict requirements on the film growth process. Specifically, the SiN films must be deposited at temperatures below 400 °C to avoid device degradation, and they must be deposited conformally to meet the demand of smaller feature sizes. In chapter 1, the synthesis and deposition of a new precursor for silicon nitride thin films, 1,1-diazido-1-silacyclopent-3-ene (1) is described. Precursor 1, a known compound, was synthesized by treating 1,1-dichloro-1-silacyclopent-3-ene with two equivalents of NaN3 in acetonitrile, and was purified by distillation under reduced pressures. Deposition experiments were performed in a hot-wall chemical vapor deposition (CVD) reactor show that 1 deposits films at temperatures as low as 400 °C and with excellent conformality in trenches with aspect ratios up to 3.5:1. Elemental characterization of these films, performed by Auger spectroscopy, show that these films contain Si (~10 %) and N (~10 %) in a 1:1 ratio but have high C (~40 %) and O (~40 %) contents, which is likely attributed to the presence of residual moisture and oxygen in the reaction chamber and the slow removal of volatile organic byproducts. In chapter 2, we describe the syntheses and molecular structures of new SmII and TmII N,N-dimethylaminodiboranate (DMADB) complexes. Treatment of solutions of SmI2(thf)2 in thf with Na(H3BNMe2BH3) results in the formation of Sm(H3BNMe2BH3)2(thf)3 which can be readily converted to the dimethyoxyethane (dme) adduct, Sm(H3BNMe2BH3)2(dme)2 by treatment with dme. We also show that Sm(H3BNMe2BH3)2(thf)3 can be prepared by the reduction of the SmIII compound, Sm(H3BNMe2BH3)3(thf), with KC8,and that addition of 18-crown-6 to this reaction mixture results in the formation of Sm(H3BNMe2BH3)2(18-crown-6). The new TmII complexes were synthesized analogously to 1; treatment of TmI2 solutions in thf with Na(H3BNMe2BH3) resulted in the formation of 1:1 mixtures of Tm(H3BNMe2BH3)2(thf)3 and Tm(H3BNMe2BH3)2(thf)2. IR and 1H NMR data are reported for all these compounds along with their crystal structures.","abstract_has_math":false,"creators":["Anderson, Nels T."],"institution":"University of Illinois at Urbana-Champaign","degree_name":"M.S.","degree_level":"Thesis","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":["Girolami, Gregory S"],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2019,"date_issued":"2019-11-26T20:35:12Z","date_published":"2019-11-26T20:35:12Z","updated_at":"2026-07-22T22:24:44Z","subjects":["Chemical Vapor Deposition","f-block elements","lanthanides","silicon nitride","divalent samarium","divalent thulium"],"languages":["en"],"rights":["Copyright 2019 Nels T. Anderson"],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"http://hdl.handle.net/2142/105702","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Girolami, Gregory S"]},{"key":"dc:creator","label":"Author","values":["Anderson, Nels T."]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2019-11-26T20:35:12Z","2019-07-16","2019-08"]},{"key":"dc:type","label":"Dc Type","values":["text"]},{"key":"thesis:degree_discipline","label":"Discipline","values":["Chemistry"]},{"key":"thesis:degree_level","label":"Degree Level","values":["Thesis"]},{"key":"thesis:degree_name","label":"Degree Name","values":["M.S."]},{"key":"thesis:institution_name","label":"Thesis Institution Name","values":["University of Illinois at Urbana-Champaign"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["Chemical Vapor Deposition","f-block elements","lanthanides","silicon nitride","divalent samarium","divalent thulium"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["en"]},{"key":"dc:rights","label":"Dc Rights","values":["Copyright 2019 Nels T. Anderson"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["http://hdl.handle.net/2142/105702"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Silicon nitride thin films have key industrial applications in the manufacturing of semiconductors, but these applications impose strict requirements on the film growth process. Specifically, the SiN films must be deposited at temperatures below 400 °C to avoid device degradation, and they must be deposited conformally to meet the demand of smaller feature sizes. In chapter 1, the synthesis and deposition of a new precursor for silicon nitride thin films, 1,1-diazido-1-silacyclopent-3-ene (1) is described. Precursor 1, a known compound, was synthesized by treating 1,1-dichloro-1-silacyclopent-3-ene with two equivalents of NaN3 in acetonitrile, and was purified by distillation under reduced pressures. Deposition experiments were performed in a hot-wall chemical vapor deposition (CVD) reactor show that 1 deposits films at temperatures as low as 400 °C and with excellent conformality in trenches with aspect ratios up to 3.5:1. Elemental characterization of these films, performed by Auger spectroscopy, show that these films contain Si (~10 %) and N (~10 %) in a 1:1 ratio but have high C (~40 %) and O (~40 %) contents, which is likely attributed to the presence of residual moisture and oxygen in the reaction chamber and the slow removal of volatile organic byproducts. In chapter 2, we describe the syntheses and molecular structures of new SmII and TmII N,N-dimethylaminodiboranate (DMADB) complexes. Treatment of solutions of SmI2(thf)2 in thf with Na(H3BNMe2BH3) results in the formation of Sm(H3BNMe2BH3)2(thf)3 which can be readily converted to the dimethyoxyethane (dme) adduct, Sm(H3BNMe2BH3)2(dme)2 by treatment with dme. We also show that Sm(H3BNMe2BH3)2(thf)3 can be prepared by the reduction of the SmIII compound, Sm(H3BNMe2BH3)3(thf), with KC8,and that addition of 18-crown-6 to this reaction mixture results in the formation of Sm(H3BNMe2BH3)2(18-crown-6). The new TmII complexes were synthesized analogously to 1; treatment of TmI2 solutions in thf with Na(H3BNMe2BH3) resulted in the formation of 1:1 mixtures of Tm(H3BNMe2BH3)2(thf)3 and Tm(H3BNMe2BH3)2(thf)2. IR and 1H NMR data are reported for all these compounds along with their crystal structures.","Submission original under an indefinite embargo labeled 'Open Access'. The submission was exported from vireo on 2019-11-26 without embargo terms","The student, Nels Anderson, accepted the attached license on 2019-07-16 at 08:53.","The student, Nels Anderson, submitted this Thesis for approval on 2019-07-16 at 09:02.","This Thesis was approved for publication on 2019-07-16 at 09:51.","DSpace SAF Submission Ingestion Package generated from Vireo submission #14338 on 2019-11-26 at 12:53:46","Made available in DSpace on 2019-11-26T20:35:12Z (GMT). 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Specifically, the SiN films must be deposited at temperatures below 400 °C to avoid device degradation, and they must be deposited conformally to meet the demand of smaller feature sizes. In chapter 1, the synthesis and deposition of a new precursor for silicon nitride thin films, 1,1-diazido-1-silacyclopent-3-ene (1) is described. Precursor 1, a known compound, was synthesized by treating 1,1-dichloro-1-silacyclopent-3-ene with two equivalents of NaN3 in acetonitrile, and was purified by distillation under reduced pressures. Deposition experiments were performed in a hot-wall chemical vapor deposition (CVD) reactor show that 1 deposits films at temperatures as low as 400 °C and with excellent conformality in trenches with aspect ratios up to 3.5:1. Elemental characterization of these films, performed by Auger spectroscopy, show that these films contain Si (~10 %) and N (~10 %) in a 1:1 ratio but have high C (~40 %) and O (~40 %) contents, which is likely attributed to the presence of residual moisture and oxygen in the reaction chamber and the slow removal of volatile organic byproducts. In chapter 2, we describe the syntheses and molecular structures of new SmII and TmII N,N-dimethylaminodiboranate (DMADB) complexes. Treatment of solutions of SmI2(thf)2 in thf with Na(H3BNMe2BH3) results in the formation of Sm(H3BNMe2BH3)2(thf)3 which can be readily converted to the dimethyoxyethane (dme) adduct, Sm(H3BNMe2BH3)2(dme)2 by treatment with dme. We also show that Sm(H3BNMe2BH3)2(thf)3 can be prepared by the reduction of the SmIII compound, Sm(H3BNMe2BH3)3(thf), with KC8,and that addition of 18-crown-6 to this reaction mixture results in the formation of Sm(H3BNMe2BH3)2(18-crown-6). The new TmII complexes were synthesized analogously to 1; treatment of TmI2 solutions in thf with Na(H3BNMe2BH3) resulted in the formation of 1:1 mixtures of Tm(H3BNMe2BH3)2(thf)3 and Tm(H3BNMe2BH3)2(thf)2. IR and 1H NMR data are reported for all these compounds along with their crystal structures.","Submission original under an indefinite embargo labeled 'Open Access'. The submission was exported from vireo on 2019-11-26 without embargo terms","The student, Nels Anderson, accepted the attached license on 2019-07-16 at 08:53.","The student, Nels Anderson, submitted this Thesis for approval on 2019-07-16 at 09:02.","This Thesis was approved for publication on 2019-07-16 at 09:51.","DSpace SAF Submission Ingestion Package generated from Vireo submission #14338 on 2019-11-26 at 12:53:46","Made available in DSpace on 2019-11-26T20:35:12Z (GMT). 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