{"title":"Imaging domain boundaries of rubrene thin crystallites by photoemission electron microscopy","authors":"Moha Naeimi, Katharina Engster, Waqas Pervez, Ingo Barke, Sylvia Speller","doi":"10.1016/j.ultramic.2025.114239","DOIUrl":null,"url":null,"abstract":"<div><div>The progress of designing organic semiconductors is extensively dependent on the quality of prepared organic molecular assemblies, since the charge transport mechanism is strongly efficient in highly ordered crystals compared to amorphous domains. Here we present a comprehensive photoemission electron microscopy (PEEM) and time-of-flight (TOF) spectroscopic study of rubrene (<span><math><mrow><msub><mrow><mi>C</mi></mrow><mrow><mn>48</mn></mrow></msub><msub><mrow><mi>H</mi></mrow><mrow><mn>24</mn></mrow></msub></mrow></math></span>) thin crystals focusing on recently developed orthorhombic crystalline morphologies applied in organic electronic devices. Using femtosecond pulsed lasers with photon energies between 3–6 eV, we explore the interplay between photoemission processes, crystal morphology, and defect states. In a 2-photon photoemission process (2PPE), the PEEM images reveal dominant emission localized at domain boundaries, indicating strong contributions from trap states. In contrast, in 1PPE nm excitation uniform emission across the crystal surface is observed, highlighting a fundamental difference in photoemission mechanisms. Furthermore, in the intermediate photon energy range, we identify a nonlinear, non-integer photon order, where mostly the triclinic morphology contributes to the emission, distinguishing it from the orthorhombic phase. These findings provide a new framework for assessing the quality and internal structure of organic semiconductor thin films via wavelength-dependent photoemission imaging and spectroscopy.</div></div>","PeriodicalId":23439,"journal":{"name":"Ultramicroscopy","volume":"279 ","pages":"Article 114239"},"PeriodicalIF":2.0000,"publicationDate":"2025-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Ultramicroscopy","FirstCategoryId":"5","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0304399125001378","RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"MICROSCOPY","Score":null,"Total":0}
引用次数: 0
Abstract
The progress of designing organic semiconductors is extensively dependent on the quality of prepared organic molecular assemblies, since the charge transport mechanism is strongly efficient in highly ordered crystals compared to amorphous domains. Here we present a comprehensive photoemission electron microscopy (PEEM) and time-of-flight (TOF) spectroscopic study of rubrene () thin crystals focusing on recently developed orthorhombic crystalline morphologies applied in organic electronic devices. Using femtosecond pulsed lasers with photon energies between 3–6 eV, we explore the interplay between photoemission processes, crystal morphology, and defect states. In a 2-photon photoemission process (2PPE), the PEEM images reveal dominant emission localized at domain boundaries, indicating strong contributions from trap states. In contrast, in 1PPE nm excitation uniform emission across the crystal surface is observed, highlighting a fundamental difference in photoemission mechanisms. Furthermore, in the intermediate photon energy range, we identify a nonlinear, non-integer photon order, where mostly the triclinic morphology contributes to the emission, distinguishing it from the orthorhombic phase. These findings provide a new framework for assessing the quality and internal structure of organic semiconductor thin films via wavelength-dependent photoemission imaging and spectroscopy.
期刊介绍:
Ultramicroscopy is an established journal that provides a forum for the publication of original research papers, invited reviews and rapid communications. The scope of Ultramicroscopy is to describe advances in instrumentation, methods and theory related to all modes of microscopical imaging, diffraction and spectroscopy in the life and physical sciences.