Utilizing Constant Energy Difference between sp-Peak and C 1s Core Level in Photoelectron Spectra for Unambiguous Identification and Quantification of Diamond Phase in Nanodiamonds
The modification of nanodiamond (ND) surfaces has significant applications in sensing devices, drug delivery, bioimaging, and tissue engineering. Precise control of the diamond phase composition and bond configurations during ND processing and surface finalization is crucial. In this study, we condu...
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MDPI AG
2024-03-01
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| Series: | Nanomaterials |
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| Online Access: | https://www.mdpi.com/2079-4991/14/7/590 |
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| author | Oleksandr Romanyuk Štěpán Stehlík Josef Zemek Kateřina Aubrechtová Dragounová Alexander Kromka |
| author_facet | Oleksandr Romanyuk Štěpán Stehlík Josef Zemek Kateřina Aubrechtová Dragounová Alexander Kromka |
| author_sort | Oleksandr Romanyuk |
| collection | DOAJ |
| description | The modification of nanodiamond (ND) surfaces has significant applications in sensing devices, drug delivery, bioimaging, and tissue engineering. Precise control of the diamond phase composition and bond configurations during ND processing and surface finalization is crucial. In this study, we conducted a comparative analysis of the graphitization process in various types of hydrogenated NDs, considering differences in ND size and quality. We prepared three types of hydrogenated NDs: high-pressure high-temperature NDs (HPHT ND-H; 0–30 nm), conventional detonation nanodiamonds (DND-H; ~5 nm), and size- and nitrogen-reduced hydrogenated nanodiamonds (snr-DND-H; 2–3 nm). The samples underwent annealing in an ultra-high vacuum and sputtering by Ar cluster ion beam (ArCIB). Samples were investigated by in situ X-ray photoelectron spectroscopy (XPS), in situ ultraviolet photoelectron spectroscopy (UPS), and Raman spectroscopy (RS). Our investigation revealed that the graphitization temperature of NDs ranges from 600 °C to 700 °C and depends on the size and crystallinity of the NDs. Smaller DND particles with a high density of defects exhibit a lower graphitization temperature. We revealed a constant energy difference of 271.3 eV between the sp-peak in the valence band spectra (at around 13.7 eV) and the sp<sup>3</sup> component in the C 1s core level spectra (at 285.0 eV). The identification of this energy difference helps in calibrating charge shifts and serves the unambiguous identification of the sp<sup>3</sup> bond contribution in the C 1s spectra obtained from ND samples. Results were validated through reference measurements on hydrogenated single crystal C(111)-H and highly-ordered pyrolytic graphite (HOPG). |
| first_indexed | 2024-04-24T10:38:21Z |
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| issn | 2079-4991 |
| language | English |
| last_indexed | 2024-04-24T10:38:21Z |
| publishDate | 2024-03-01 |
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| record_format | Article |
| series | Nanomaterials |
| spelling | doaj.art-bd1bd39e8ba349dcbe0943156e9857f52024-04-12T13:23:52ZengMDPI AGNanomaterials2079-49912024-03-0114759010.3390/nano14070590Utilizing Constant Energy Difference between sp-Peak and C 1s Core Level in Photoelectron Spectra for Unambiguous Identification and Quantification of Diamond Phase in NanodiamondsOleksandr Romanyuk0Štěpán Stehlík1Josef Zemek2Kateřina Aubrechtová Dragounová3Alexander Kromka4Institute of Physics of the Czech Academy of Sciences, Cukrovarnická 10, 162 00 Prague, Czech RepublicInstitute of Physics of the Czech Academy of Sciences, Cukrovarnická 10, 162 00 Prague, Czech RepublicInstitute of Physics of the Czech Academy of Sciences, Cukrovarnická 10, 162 00 Prague, Czech RepublicInstitute of Physics of the Czech Academy of Sciences, Cukrovarnická 10, 162 00 Prague, Czech RepublicInstitute of Physics of the Czech Academy of Sciences, Cukrovarnická 10, 162 00 Prague, Czech RepublicThe modification of nanodiamond (ND) surfaces has significant applications in sensing devices, drug delivery, bioimaging, and tissue engineering. Precise control of the diamond phase composition and bond configurations during ND processing and surface finalization is crucial. In this study, we conducted a comparative analysis of the graphitization process in various types of hydrogenated NDs, considering differences in ND size and quality. We prepared three types of hydrogenated NDs: high-pressure high-temperature NDs (HPHT ND-H; 0–30 nm), conventional detonation nanodiamonds (DND-H; ~5 nm), and size- and nitrogen-reduced hydrogenated nanodiamonds (snr-DND-H; 2–3 nm). The samples underwent annealing in an ultra-high vacuum and sputtering by Ar cluster ion beam (ArCIB). Samples were investigated by in situ X-ray photoelectron spectroscopy (XPS), in situ ultraviolet photoelectron spectroscopy (UPS), and Raman spectroscopy (RS). Our investigation revealed that the graphitization temperature of NDs ranges from 600 °C to 700 °C and depends on the size and crystallinity of the NDs. Smaller DND particles with a high density of defects exhibit a lower graphitization temperature. We revealed a constant energy difference of 271.3 eV between the sp-peak in the valence band spectra (at around 13.7 eV) and the sp<sup>3</sup> component in the C 1s core level spectra (at 285.0 eV). The identification of this energy difference helps in calibrating charge shifts and serves the unambiguous identification of the sp<sup>3</sup> bond contribution in the C 1s spectra obtained from ND samples. Results were validated through reference measurements on hydrogenated single crystal C(111)-H and highly-ordered pyrolytic graphite (HOPG).https://www.mdpi.com/2079-4991/14/7/590nanodiamondshydrogenationXPSUPSRaman spectroscopysurface graphitization |
| spellingShingle | Oleksandr Romanyuk Štěpán Stehlík Josef Zemek Kateřina Aubrechtová Dragounová Alexander Kromka Utilizing Constant Energy Difference between sp-Peak and C 1s Core Level in Photoelectron Spectra for Unambiguous Identification and Quantification of Diamond Phase in Nanodiamonds Nanomaterials nanodiamonds hydrogenation XPS UPS Raman spectroscopy surface graphitization |
| title | Utilizing Constant Energy Difference between sp-Peak and C 1s Core Level in Photoelectron Spectra for Unambiguous Identification and Quantification of Diamond Phase in Nanodiamonds |
| title_full | Utilizing Constant Energy Difference between sp-Peak and C 1s Core Level in Photoelectron Spectra for Unambiguous Identification and Quantification of Diamond Phase in Nanodiamonds |
| title_fullStr | Utilizing Constant Energy Difference between sp-Peak and C 1s Core Level in Photoelectron Spectra for Unambiguous Identification and Quantification of Diamond Phase in Nanodiamonds |
| title_full_unstemmed | Utilizing Constant Energy Difference between sp-Peak and C 1s Core Level in Photoelectron Spectra for Unambiguous Identification and Quantification of Diamond Phase in Nanodiamonds |
| title_short | Utilizing Constant Energy Difference between sp-Peak and C 1s Core Level in Photoelectron Spectra for Unambiguous Identification and Quantification of Diamond Phase in Nanodiamonds |
| title_sort | utilizing constant energy difference between sp peak and c 1s core level in photoelectron spectra for unambiguous identification and quantification of diamond phase in nanodiamonds |
| topic | nanodiamonds hydrogenation XPS UPS Raman spectroscopy surface graphitization |
| url | https://www.mdpi.com/2079-4991/14/7/590 |
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