| 1. |
- Andersson, T., et al.
(författare)
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Electronic structure transformation in small bare Au clusters as seen by x-ray photoelectron spectroscopy
- 2017
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Ingår i: Journal of Physics B. - : IOP Publishing. - 0953-4075 .- 1361-6455. ; 50:1
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Tidskriftsartikel (refereegranskat)abstract
- Free bare gold clusters in the size range from few tens to few hundred atoms (<= 1 nm dimensions) have been produced in a beam, and the size-dependent development of their full valence band including the 5d and 6s parts has been mapped 'on the fly' by synchrotron-based photoelectron spectroscopy. The Au 4f core level has been also probed, and the cluster-specific Au 4f ionization energies have been used to estimate the cluster size. The recorded in the present work valence spectra of the small clusters are compared with the spectra of the large clusters (N similar to 10(3)) created by us using a magnetron-based gas aggregation source. The comparison shows a substantially narrower 5d valence band and the decrease in its splitting for gold clusters in the size range of few hundred atoms and below. Our DFT calculations involving the pseudopotential method show that the 5d band width of the ground state increases with the cluster size and by the size N = 20 becomes comparable with the experimental width of the valence photoelectron spectrum. Similar to the earlier observations on supported clusters we interpret our experimental and theoretical results as due to the undercoordination of a large fraction of atoms in the clusters with N similar to 10(2) and below. The consequences of such electronic structure of small gold clusters are discussed in connection with their specific physical and chemical properties related to nanoplasmonics and nanocatalysis.
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| 2. |
- Hautala, Lauri, et al.
(författare)
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Experimental observation of structural phase transition in CsBr clusters
- 2017
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Ingår i: Physical Review B. - 1098-0121. ; 95:4
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Tidskriftsartikel (refereegranskat)abstract
- Formation and growth of CsBr clusters embedded in unsupported Ar clusters was studied using synchrotron radiation photoelectron spectroscopy. The development of the core-level electronic structure for cluster sizes between a few and a few hundred atoms contained information about the local coordination of the constituent particles. The experimental results indicate that a gradual structural phase transition from NaCl structure to CsCl structure for CsBr clusters takes place at around 160 atoms per cluster.
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| 3. |
- Tchaplyguine, M., et al.
(författare)
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Metal-passivated PbS nanoparticles : Fabrication and characterization
- 2017
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Ingår i: Physical Chemistry Chemical Physics. - : Royal Society of Chemistry (RSC). - 1463-9076 .- 1463-9084. ; 19:10, s. 7252-7261
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Tidskriftsartikel (refereegranskat)abstract
- Organic-shell-free PbS nanoparticles have been produced in the size range relevant for quantum-dot solar cells (QDSCs) by a vapor aggregation method involving magnetron reactive sputtering. This method creates a beam of free 5-10 nm particles in a vacuum. The dimensions of the particles were estimated after their deposition on a substrate by imaging them using ex situ SEM and HRTEM electron microscopy. The particle structure and chemical composition could be deduced "on the fly", prior to deposition, using X-ray photoelectron spectroscopy (XPS) with tunable synchrotron radiation. Our XPS results suggest that under certain conditions it is possible to fabricate particles with a semiconductor core and 1 to 2 monolayer shells of metallic lead. For this case the absolute energy of the highest occupied molecular orbital (HOMO) in PbS has been determined to be (5.0 ± 0.5) eV below the vacuum level. For such particles deposited on a substrate HRTEM has confirmed the XPS-based conclusions on the crystalline PbS structure of the semiconductor core. Absorption spectroscopy on the deposited film has given a value of ∼1 eV for the lowest exciton. Together with the valence XPS results this has allowed us to reconstruct the energy level scheme of the particles. The results obtained are discussed in the context of the properties of PbS QDSCs.
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| 4. |
- Tchaplyguine, M., et al.
(författare)
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Tin-oxide nanoparticles deposited from a beam : what happens to the composition?
- 2019
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Ingår i: Physical chemistry chemical physics : PCCP. - : Royal Society of Chemistry (RSC). - 1463-9084 .- 1463-9076. ; 21:11, s. 6287-6295
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Tidskriftsartikel (refereegranskat)abstract
- The debate around the oxidation states occurring in laboratory-prepared tin-oxide samples has been for a long time an obstacle for an unambiguous assignment of characterization studies performed on such samples. In particular the changes in the Sn core-level energies caused by oxidation - i.e. the chemical shifts - as measured by photoelectron spectroscopy (PES) have been under discussion. The assignment problem is especially pronounced for nanoscale structures, which are important for photovoltaics, electronics, catalysis, and gas sensing. The reasons for the difficulties lie both in the natural properties of tin oxides, which can have substantial deficiencies of oxygen and tin in the lattice, and in the shortcomings of the fabrication and PES-characterization procedures themselves. Our recent PES study on tin-oxide nanoparticles fabricated by vapour-aggregation gave a chemical shift two times larger than earlier reported for Sn(iv) oxide for the Sn 4d level. The implemented fabrication technique forms an in-vacuum beam of particles whose composition can be both controlled and characterized by PES. In the present work SnO and SnO2 nanoparticles fabricated this way were deposited from the beam and probed by PES directly, as well as after exposure to air. The deposited nanoparticle films were also imaged by TEM (Transmission Electron Microscopy). The effects of the deposition process and exposure to air on the chemical composition were studied. The PES study of deposited SnO2 nanoparticles in the Sn 4d and Sn 3d core-level regions revealed the same core level shift as for unsupported nanoparticles, indicating that the chemical composition is preserved in the deposition process. The TEM study demonstrated a crystalline structure of separate SnO2 particles with lattice constants close to the macroscopic Sn(iv)-oxide. The PES study on the particles exposed to air showed changes in the composition. For the film of initially SnO particles a higher intermediate oxide was created. For the SnO2 nanoparticle film a lower, but strong, intermediate oxide was observed, likely at the surface.
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| 5. |
- Babenkov, Sergey V., et al.
(författare)
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Hybrid organic-inorganic systems formed by self-assembled gold nanoparticles in CuPcF4 molecular crystal
- 2016
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Ingår i: Organic Electronics. - : Elsevier BV. - 1566-1199. ; 32, s. 228-236
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Tidskriftsartikel (refereegranskat)abstract
- In this work we have fabricated and studied hybrid organic-inorganic nanocomposite system formed by gold nanoparticles self-assembled in organic semiconductor thin film - copper tetrafluorophthalocyanine (CuPcF4). By means of Photoelectron Spectroscopy and Transmission Electron Microscopy (TEM) the evolution of the morphology and electronic structure of the system as a function of nominal gold content have been investigated. The gold atoms, deposited onto the CuPcF4 surface, diffuse into the organic matrix and self-assemble to nanoparticles in a well-defined manner with a narrow size distribution, which depends on the amount of deposited gold. Using High-Resolution TEM, we were able to observe the atomic planes of single gold nanoparticles and their coalescence processes. Photoelectron spectroscopy has not revealed any detectable chemical reaction between gold and organic. However, the strong upward band bending, induced by gold nanoparticles in the organic film, takes place.
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