Ryan J. Scott, Neno Fuller, Adithya Sadanandan, Pavel Valencia-Acuna, Wai-Lun Chan, Qunfei Zhou* and Hui Zhao*,
{"title":"石墨烯- ptcdi - tiopc三层异质结构中的长寿命电荷转移激子","authors":"Ryan J. Scott, Neno Fuller, Adithya Sadanandan, Pavel Valencia-Acuna, Wai-Lun Chan, Qunfei Zhou* and Hui Zhao*, ","doi":"10.1021/acs.jpcc.5c0096910.1021/acs.jpcc.5c00969","DOIUrl":null,"url":null,"abstract":"<p >Excitation transfer across the interfaces between graphene, perylenetetracarboxylic diimide (PTCDI), and titanyl phthalocyanine (TiOPc) was studied by using transient absorption and photoluminescence spectroscopy. Both photoluminescence quenching and transient absorption measurements confirm the presence of a type-II interface between PTCDI and TiOPc. While the graphene/PTCDI interface is expected to exhibit type-I behavior, transient absorption measurements indicate that only electrons transfer from PTCDI to graphene, with no evidence of hole transfer. Density functional theory calculations reveal significant ground-state electron transfer from graphene to PTCDI, resulting in band bending that prevents excited holes from transferring from PTCDI to graphene. This feature is exploited in a trilayer heterostructure of graphene/PTCDI/TiOPc, where the spatial separation of photoexcited electrons and holes in graphene and TiOPc, respectively, leads to the formation of long-lived photoexcitations with a lifetime of approximately 500 ps. Furthermore, spatially resolved transient absorption measurements reveal the immobile nature of these excitations, confirming that they are charge-transfer excitons rather than free electrons and holes. These results provide valuable insights into the complex interlayer photoexcitation transfer properties and demonstrate precise control over the layer population and the recombination lifetime of photocarriers in such hybrid heterostructures.</p>","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"129 14","pages":"6882–6889 6882–6889"},"PeriodicalIF":3.2000,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Long-Lived Charge-Transfer Excitons in a Graphene–PTCDI–TiOPc Trilayer Heterostructure\",\"authors\":\"Ryan J. Scott, Neno Fuller, Adithya Sadanandan, Pavel Valencia-Acuna, Wai-Lun Chan, Qunfei Zhou* and Hui Zhao*, \",\"doi\":\"10.1021/acs.jpcc.5c0096910.1021/acs.jpcc.5c00969\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >Excitation transfer across the interfaces between graphene, perylenetetracarboxylic diimide (PTCDI), and titanyl phthalocyanine (TiOPc) was studied by using transient absorption and photoluminescence spectroscopy. Both photoluminescence quenching and transient absorption measurements confirm the presence of a type-II interface between PTCDI and TiOPc. While the graphene/PTCDI interface is expected to exhibit type-I behavior, transient absorption measurements indicate that only electrons transfer from PTCDI to graphene, with no evidence of hole transfer. Density functional theory calculations reveal significant ground-state electron transfer from graphene to PTCDI, resulting in band bending that prevents excited holes from transferring from PTCDI to graphene. This feature is exploited in a trilayer heterostructure of graphene/PTCDI/TiOPc, where the spatial separation of photoexcited electrons and holes in graphene and TiOPc, respectively, leads to the formation of long-lived photoexcitations with a lifetime of approximately 500 ps. Furthermore, spatially resolved transient absorption measurements reveal the immobile nature of these excitations, confirming that they are charge-transfer excitons rather than free electrons and holes. These results provide valuable insights into the complex interlayer photoexcitation transfer properties and demonstrate precise control over the layer population and the recombination lifetime of photocarriers in such hybrid heterostructures.</p>\",\"PeriodicalId\":61,\"journal\":{\"name\":\"The Journal of Physical Chemistry C\",\"volume\":\"129 14\",\"pages\":\"6882–6889 6882–6889\"},\"PeriodicalIF\":3.2000,\"publicationDate\":\"2025-03-27\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"The Journal of Physical Chemistry C\",\"FirstCategoryId\":\"1\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/acs.jpcc.5c00969\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"The Journal of Physical Chemistry C","FirstCategoryId":"1","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acs.jpcc.5c00969","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
Long-Lived Charge-Transfer Excitons in a Graphene–PTCDI–TiOPc Trilayer Heterostructure
Excitation transfer across the interfaces between graphene, perylenetetracarboxylic diimide (PTCDI), and titanyl phthalocyanine (TiOPc) was studied by using transient absorption and photoluminescence spectroscopy. Both photoluminescence quenching and transient absorption measurements confirm the presence of a type-II interface between PTCDI and TiOPc. While the graphene/PTCDI interface is expected to exhibit type-I behavior, transient absorption measurements indicate that only electrons transfer from PTCDI to graphene, with no evidence of hole transfer. Density functional theory calculations reveal significant ground-state electron transfer from graphene to PTCDI, resulting in band bending that prevents excited holes from transferring from PTCDI to graphene. This feature is exploited in a trilayer heterostructure of graphene/PTCDI/TiOPc, where the spatial separation of photoexcited electrons and holes in graphene and TiOPc, respectively, leads to the formation of long-lived photoexcitations with a lifetime of approximately 500 ps. Furthermore, spatially resolved transient absorption measurements reveal the immobile nature of these excitations, confirming that they are charge-transfer excitons rather than free electrons and holes. These results provide valuable insights into the complex interlayer photoexcitation transfer properties and demonstrate precise control over the layer population and the recombination lifetime of photocarriers in such hybrid heterostructures.
期刊介绍:
The Journal of Physical Chemistry A/B/C is devoted to reporting new and original experimental and theoretical basic research of interest to physical chemists, biophysical chemists, and chemical physicists.