@phdthesis{Lehmann2007, author = {Lehmann, Carsten}, title = {Elektronische Struktur d{\"u}nner Halbleiterfilme (Chalkopyrite) als Absorbermaterialien f{\"u}r D{\"u}nnschichtsolarzellen}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:co1-opus-4319}, school = {BTU Cottbus - Senftenberg}, year = {2007}, abstract = {Ziel der Arbeit war es, erstmalig die Bandstruktur des in D{\"u}nnschichtsolarzellen verwendeten Absorbermaterials CuInS2 zu bestimmen. Zu diesem Zweck konnte ein neues GSMBE-Verfahren mit TBDS als Schwefel-Precursor etabliert werden, um die Verwendung von elementarem Schwefel in einem UHV-System zu ersetzen. Zus{\"a}tzlich zu den abgeschiedenen Schichten wurde eine Spaltfl{\"a}che pr{\"a}pariert. Die Charakterisierung der Proben erfolgte in situ mittels XPS/UPS und LEED. F{\"u}r weitere ex situ Untersuchungen standen XRD und SEM zur Verf{\"u}gung. Die ARUPS-Untersuchungen zur Bestimmung der Bandstruktur fanden unter Verwendung von Synchrotronstrahlung statt. Die aufgenommenen Bandstrukturen wurden mit Bandstrukturberechnungen Eyerts und Zungers verglichen. Dabei gestattete eine Zusammenarbeit mit Eyert eine exakte Verifizierung jenseits hochsymmetrischer Verl{\"a}ufe. CuInS2(001) und CuInS2(112) wurden auf Si und GaAs abgeschieden und zeigte Wachstumsraten, die im Vergleich mit MBE-Verfahren {\"a}lterer Arbeiten um bis zu 85 \% geringer waren. Dies f{\"u}hrte auf Si zur Ausbildung von CuSi-Phasen, so dass sich Si als Substrat in diesem Verfahren als ungeeignet erwies. Die CuInS2-Abscheidung auf GaAs zeigte eine starke Abh{\"a}ngigkeit von der vorhandenen Oberfl{\"a}chenrekonstruktion. Eine 2x1-Rekonstruktion auf GaAs(100) f{\"u}hrte zu einer terrassierten CuInS2-Schicht. Eine Abscheidung auf der 2x2-rekonstruierten GaAs(111)A-Oberfl{\"a}che hatte eine facettierte CuInS2-Oberfl{\"a}che zur Folge. Auf schwefelpassiviertem, rekonstruktionsfreien GaAs(111)B zeigte sich dagegen facettenfreies CuInS2(112)-Wachstum in vorherrschender Chalkopyrit-Struktur. An den Oberfl{\"a}chen von Cu-reichen CuInS2-Schichten bildeten sich CuS-Kristallite. Diese polykristallinen Ablagerungen f{\"u}hrten bei ARUPS-Untersuchungen zu nicht-dispergierenden Zust{\"a}nden, die die Bandstrukturen der CuInS2-Schichten {\"u}berlagerten. Bei k-senkrecht-Messungen zeigte sich ein Zustand, dessen Dispersion stark von Berechnungen Eyerts abweicht. Sein Ursprung konnte nicht eindeutig abgeleitet werden konnte, da der Beobachtungsraum aufgrund von Endzustandseffekten und Satellitenst{\"o}rungen stark eingeschr{\"a}nkt war. Generell zeigt ein Vergleich der Berechnungen nach Eyert bzw. Zunger mit entsprechenden Messungen, dass beide Modellrechnungen zu Bindungsenergien f{\"u}hren, die gegen{\"u}ber den Messwerten zu niedrig sind. Die energetische Ausdehnung der charakteristischen Bereiche und deren Lage zueinander wird jedoch zutreffend beschrieben. Konsistent mit Beobachtungen in anderen Arbeiten an analogen Systemen erweist sich dabei die theoretische Behandlung der d-Zust{\"a}nde bei der Modellierung als kritisch. Die Bandl{\"u}cke zwischen d-Charakter-dominierten und p-Charakter-dominierten Bereich wird von Eyert {\"u}bersch{\"a}tzt, von Zunger dagegen untersch{\"a}tzt. Dies l{\"a}sst sich auf die verwendeten N{\"a}herungen (LDA (Zunger), GGA (Eyert)) des Austauschkorrelationspotentials zur{\"u}ckf{\"u}hren. Bei einer Anpassung der von Eyert berechneten Bandstrukturen durch einen geeigneten Energieoffset zeigten sich im Vergleich mit k-parallel-Messungen im Allgemeinen gute, nahezu perfekte {\"U}bereinstimmungen von beobachteten Dispersionsverl{\"a}ufen. Es konnten die effektiven Massen der L{\"o}cher f{\"u}r die k-parallel-Messungen bestimmt werden. Die Werte liegen in der Gr{\"o}ßenordnung des Literaturwertes, jedoch im Mittel bei doppelt so hohen Werten. Ein signifikanter, richtungsabh{\"a}ngiger Trend l{\"a}sst sich aufgrund der starken Streuung nicht feststellen. Im Rahmen der vorliegenden Arbeit konnte ausserdem gezeigt werden, dass die Verwendung eines (111)-Substrates zu einer Dom{\"a}nenbildung aufwachsender CuInS2(112)-Schichten f{\"u}hrt. ARUPS-Messungen an derartigen Schichten bestehen daher aus einer {\"U}berlagerung von Bandstrukturen entlang unterschiedlicher Richtungen. F{\"u}r zuk{\"u}nftige Arbeiten bietet es sich daher an, die (111)-substratinduzierte Fehlorientierung von (112)-Schichten durch ein Step-Flow-Wachstum auf Substraten mit Miscut zu unterbinden.}, subject = {Photovoltaik; D{\"u}nnschichtsolarzelle; Bandstruktur; Chalkopyrit; ARUPS; CIS; DFT; Band structure; Chalcopyrite; ARUPS; CIS; DFT}, language = {de} } @phdthesis{Handick2016, author = {Handick, Evelyn}, title = {Surface and interface characterization by X-ray and electron spectroscopies - revealing the peculiarities of Cu(In,Ga)Se₂ chalcopyrite and CH₃NH₃PbI(₃-ᵪ)Clᵪ perovskite-based thin film solar cell structures}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:co1-opus4-42431}, school = {BTU Cottbus - Senftenberg}, year = {2016}, abstract = {This thesis focuses on the investigation and characterization of the surfaces and interfaces of chalcopyrite-based Cu(In,Ga)Se₂ (CIGSe) and organo-metal mixed halide perovskites, specifically CH₃NH₃PbI(₃-ᵪ)Clᵪ thin film solar cell absorbers using various x-ray and electron spectroscopies. In particular, the impact of alkali treatments on the chemical and electronic surface and near-surface structure of CIGSe absorbers is studied. For CH₃NH₃PbI(₃-ᵪ)Clᵪ the compound formation is monitored and the peculiarities of the interface formation of CH₃NH₃PbI(₃-ᵪ)Clᵪ on compact and mesoporous TiO₂ are examined. Laboratory and synchrotron-based photoelectron spectroscopy are used to gain a depth-dependent picture of the chemical and electronic structure in the surface and near-surface region of CIGSe absorbers, focusing on the influence of NaF and NaF/KF post-deposition treatments (PDT) when compared to alkali-free CIGSe absorbers. The alkali-free and NaF-PDT absorbers show similar chemical properties, having a Cu and Ga poor surface region compared to the nominal bulk and the same chemical environment for indium and selenium. For the NaF/KF-PDT samples a K-In-Se compound is present on top of a Cu-In-Ga-Se compound, with a nanopatterned surface that is almost devoid of Cu and Ga. Further, for the NaF-PDT sample a near-surface electronic band gap of 1.61[+0.14/-0.51] eV is derived. In contrast, a large and more gradual change towards the surface is obtained for the NaF/KF-PDT absorber exhibiting a significant band gap widening of the surface, which is in agreement with a Cu- and Ga-devoid surface region and the formation of a K-In-Se surface compound. To in-situ monitor the compound formation of CH₃NH₃PbI(₃-ᵪ)Clᵪ on compact TiO₂ (c-TiO₂) hard x-ray photoelectron spectroscopy is used. During in-situ annealing a drop-casted layer of precursor solution on c-TiO₂ shifts in the perovskite related core levels can be observed upon reach the "transition temperature" of 80-100°C. Further the Cl signal decrease at the onset of annealing and shows a depletion in the surface region for annealing temperatures above 50°C. In addition, the chemical and electronic structure of the interface between perovskite and mesoporous TiO₂ (mp-TiO₂) or c-TiO₂ using different perovskite layer thicknesses are studied.}, subject = {Chalcopyrit; Perovskite; Photoelectron spectroscopy; Thin film solar cell; Chalkopyrite; Perowskite; Photoelektronenspektroskopie; D{\"u}nnschichtsolarzelle; Kupferkies; Perowskit; Photoelektronenspektroskopie; D{\"u}nnschichtsolarzelle}, language = {en} } @phdthesis{FelixDuarte2016, author = {Felix Duarte, Roberto}, title = {Analysis and optimization of interfaces in "wide-gap" chalcopyrite-based thin film solar cell devices}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:co1-opus4-37402}, school = {BTU Cottbus - Senftenberg}, year = {2016}, abstract = {The chemical and electronic structure of chalcopyrite absorbers with different bulk band gap energies, Egbulk, [i.e., low-gap Cu(In,Ga)Se2 (CIGSe, Egbulk ~ 1.2 eV) and wide-gap CuInS2 (CIS, Egbulk ~ 1.5 eV)] and of buffer/absorber heterointerfaces based on these materials are studied with soft and hard x-ray spectroscopy techniques. Mechanisms that benefit (limit) the performance of low(wide)-gap chalcopyrite-based solar cells are identified. This knowledge is used to develop surface tailoring treatments to optimize buffer/absorber heterointerfaces based on wide-gap chalcopyrites and improve the performance of their solar cells. Photoemission spectroscopy (PES) characterization of the two absorbers (i.e., CIGSe and CIS) reveal compositional-depth profiles. The changes detected in CIGSe include: a near surface Ga-depletion, a strongly Cu-poor surface and a strong presence of surface Na that (likely) occupies Cu vacancies. A similar Cu-deficiency is found in CIS. The depth-composition changes result in significant widening of the band gap at the surface, Egsurf, (i.e., CIGSe, Egsurf: 1.70 ± 0.2 eV and CIS, Egsurf: 1.88 ± 0.2 eV) as evident by ultraviolet photoelectron spectroscopy (UPS) and inverse photoemission spectroscopy (IPES) measurements. Differences in the interaction of the CIGSe and CIS surfaces with deposited buffer materials are identified. PES and modified Auger parameter studies reveal strong intermixing at the CdS/CIGSe and ZnS/CIGSe heterointerfaces. S L2,3 x-ray emission spectroscopy (XES) measurements of CIGSe substrates submitted to CdS chemical bath deposition (CBD-CdS) treatments show the formation of In2S3 and defect-rich/nanostructured CdS at the interface, compounds with higher band gap values than the measured Egsurf for CIGSe. S L2,3 XES spectra of CIGSe substrates submitted to CBD-ZnS treatments reveal the formation of (Zn,In)(S,Se)2 chemical analogs at the interface. PES and XES measurement series show that the CdS/CIS heterointerface is more abrupt, with no detected interface chemical species. Direct measurement of the band alignment of these heterointerfaces reveals: an ideal conduction band offset (CBO) configuration for CdS/CIGSe (i.e., CBO: +0.11 ± 0.25 eV), a spike CBO configuration for ZnS/CIGSe (i.e., CBO: +1.06 ± 0.4 eV), and a highly unfavorable cliff CBO configuration for CdS/CIS (i.e., CBO: -0.42 ± 0.25 eV). The performance of solar cell devices based on these heterointerfaces is correlated to their CBO configuration. Two surface tailoring approaches intended to correct the CBO configuration of the CdS/CIS heterointerface are presented. One method is based on rapid thermal processing (RTP) selenization treatments of CIS absorbers, aiming to exchange Se for S in treated samples. The idea behind this approach is to modify the surface of a wide-gap chalcopyrite so that it forms a more favorable heterointerface with CdS, such as heterointerfaces within low-gap chalcopyrite devices. X-ray fluorescence analysis and PES measurements of RTP-treated CIS samples show a greater treatment effect at the surface of the sample compared to the bulk (i.e., surface [Se]/[S+Se] range: 0.23 ± 0.05 to 0.83 ± 0.05, compared to bulk [Se]/[S+Se] range: 0.01 ± 0.03 to 0.24 ± 0.03). Tuning of the Cu:In:(S+Se) surface composition from a Cu-poor 1:3:5 to a 1:1:2 stoichiometry is observed in RTP-treated CIS samples with lower to higher surface Se contents, respectively. UPS measurements show a shift in valence band maximum toward the Fermi level in samples with higher surface Se content (i.e., -0.88 ± 0.1 to -0.51 ± 0.1 eV), as expected for a reduction in Egsurf due to exchange of Se for S. Ultraviolet-visible spectrophotometry reveals a reduction in the optical band gap of samples with greater Se incorporation (i.e., from 1.47 ± 0.05 to 1.08 ± 0.05 eV), allowing for a working window for optimization purposes. The second tailoring method involves surface functionalization of CIS absorbers with dipole-charge-inducing self-assembled monolayers (SAM) of benzoic acid derivatives and thiol molecules. The introduction of dipole charges between a heterointerface can tune the relative alignment of the electronic bands composing its electronic structure; thus, use of a suitable dipole-inducing SAM could correct the CBO misalignment in the CdS/CIS heterointerface. UPS measurements of the secondary electron cut-off region of CIS samples treated with a selected set of SAMs show a work function modulation of CIS (i.e., 4.4 ± 0.2 eV - 5.2 ± 0.2 eV). Small gains in solar cell parameters of solar cells based on SAM-modified heterointerfaces are measured. An overview of the performance of chalcopyrite(kesterite)-based solar cells in relation to the electronic properties of their corresponding buffer/absorber heterointerface suggests that optimization approaches extending beyond the buffer/absorber heterointerface may be needed for further performance gains in wide-gap chalcopyrite-based solar cell devices.}, subject = {Photovoltaics; Thin Film Solar Cells; Chalcopyrite absorbers; Solid-state Physics; Photovoltaik; R{\"o}ntgenspektroskopie; D{\"u}nnschichtsolarzelle; Chalkopyrit-Absorbermaterialien; Festk{\"o}rperphysik; X-ray spectroscopy; Kupferkies; D{\"u}nnschichtsolarzelle; Festk{\"o}rperphysik; Fotovoltaik}, language = {en} } @phdthesis{Hartmann2018, author = {Hartmann, Claudia}, title = {Surface and interface characterization of CH₃NH₃PbI₍₃₋ₓ₎Clₓ and CsSnBr₃ perovskite based thin-film solar cell structures}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:co1-opus4-46358}, school = {BTU Cottbus - Senftenberg}, year = {2018}, abstract = {The chemical and electronic structure of hybrid organometallic (CH₃NH₃PbI₍₃₋ₓ₎Clₓ) and inorganic (CsSnBr₃) perovskite materials on compact TiO₂ (c-TiO₂) is studied using x-ray and electron based spectroscopic techniques. The morphology and local elemental composition of CH₃NH₃PbI₍₃₋ₓ₎Clₓ, used as absorbers in PV devices, defining the film quality and influencing the performance of respective solar cells is studied in detail by using photoemission electron microscopy (PEEM). An incomplete coverage, with holes reaching down to the c-TiO₂ was revealed; three different topological regions with different degrees of coverage and chemical composition were identified. Depending on the degree of coverage a variation in I oxidation and the formation of Pb⁰ in the vicinity of the c-TiO₂ is found. The valence band maxima (VBM) derived from experimental data for the perovskite and c-TiO₂, combined with information from literature on spiro-MeOTAD suggests an energy level alignment resulting in an excellent charge selectivity at the absorber/spiro-MeOTAD and absorber/c-TiO₂ interfaces respectively. Further, the derived energy level alignment indicates a large recombination barrier (~2 eV), preventing shunts due to direct contact between c-TiO₂ and spiro-MeOTAD in the pin-holes. In-situ ambient pressure hard x-ray photoelectron spectroscopy (AP-HAXPES) studies of 60 and 300 nm CH₃NH₃PbI₍₃₋ₓ₎Clₓ have been performed under varies conditions (i.e. vacuum/water and dark/UV light) to gain insight into the degradation mechanism responsible for the short lifetime of the absorber. The 60 nm perovskite forms Pb⁰ in water vapor (non-defined illumination) in presence of x-rays. The 300 nm perovskite sample shows a complex behavior under illumination/dark. In water vapor/dark the perovskite dissolves into its organic (MAI) and inorganic (PbI₂) components. Under illumination PbI₂ further decomposes to Pb⁰ induced by UV light and x-rays. For alternative inorganic CsSnBr₃ perovskites, the impact of SnF₂ on the chemical and electronic structure is studied to identify its role for the improved performance of the solar cell. HAXPES and lab-XPS measurements performed on CsSnBr₃ with and without SnF₂ indicate two Sn, Cs, and Br species in all samples, where the second Sn species is attributed to oxidized Sn (Sn⁴⁺). When adding SnF₂ to the precursor solution, the coverage is improved and less Sn⁴⁺ and Cs and Br secondary species can be observed, revealing an oxidation inhibiting effect of SnF₂. Additionally, SnF₂ impacts the electronic structure, enhancing the density of states close to the VBM.}, subject = {Perovskite; Photoelectron spectroscopy; Thin-film solar cell; Solid-state physics; Photovoltaics; Photovoltaik; Festk{\"o}rperphysik; D{\"u}nnschichtsolarzelle; Photoelektronenspektroskopie; Perowskite; Fotovoltaik; Halbleiter; D{\"u}nnschichtsolarzelle; Perowskit; Photoelektronenspektroskopie}, language = {en} }