Recently, materials such as hole conductors (CuI, CuSCN) and light absorbers (Ru-complexes, CuInS2) have been actively investigated for application in nanocrystalline solar cells. In this thesis combinations of these materials have been studied. In the first part of the thesis, various methods were applied to characterize the electronic structure and photoconversion mechanism of the dye molecule Ru(dcbpyH2)2(NCS)2 when combined with materials for the use in photovoltaic devices. Specifically, the adsorption and electronic structure of the dye molecules adsorbed to semiconductors were investigated by means of photoelectron spectroscopy. The results indicate a chemical bond between the dye molecules and the hole conductors (CuI, CuSCN) via the NCS- groups. In addition, preparation of a TiO2/Ru-dye/CuI solid state model system was studied in situ. These experiments showed a partial breaking of the TiO2-dye bond caused by CuI evaporation. Photovoltage measurements were also performed. These investigations showed a shift in the light absorption threshold of the dye molecules adsorbed onto the hole conductors (CuI and CuSCN), indicating new defect states at the dye/CuSCN interface. Also, charge accumulation and transport in solar cells with CuSCN were compared to liquid electrolyte cells. Measurements showed that the lifetime and transport time of electrons in solar cells with CuSCN are much shorter than in electrolyte cells. In the second part of the thesis, the deposition of CuInS2 onto various metal oxides by spray pyrolysis has been studied with x-ray diffraction and photoelectron spectroscopy. The measurements showed that the morphologies of the substrates play a significant role in the formation of CuInS2 layers. Also, the presence of CdS at TiO2 has a positive influence on the formation of CuInS2.

In dye-sensitized solar cells, the functions of light absorption and charge transport are separated. A photosensitive ruthenium-polypyridine dye in the cell absorbs light, injects an electron to a semiconductor and is then regenerated by a redox couple, typically iodide/triiodide. Quantum chemical calculations of the electronic structure of triiodide have been carried out with the restricted active space SCF method, including spin-orbit coupling, and with density functional theory. It was shown that the difference in charge density between the terminal and central atoms results in a splitting of the core levels. The calculations gave a value of the splitting of 0.8 - 1.0 eV for the 3d and 4d levels. Experimentally, the electronic structure has been investigated with photoelectronspectroscopy. The measured terminal/center splitting is 1.1 eV.The spin-orbit interaction of the 4d levels of triiodide has also been calculated. The splitting was determined to be 1.6 eV. The experimental value is 1.7 eV. An assignment of the peaks in the computed spectrum of triiodide was made and the features of the experimental spectrum have beenidentied.The theoretical valence spectrum of triiodide has been computed and assigned. The results can be used in the analysis of photoelectron spectra of the molecule. Information about the electronic structure of the redox couple can help in the understanding of the electron transfer processes and forfurther development of the solar cells.  Furthermore, the solvation structure of the prototype dye, the tris(bipyridine)ruthenium(II) complex, in water and its interaction with iodide and chloride has been studied by means of molecular dynamics simulations. The trajectory analysis showed that the water molecules in the first solvation shell form a chain in between the bipyridine ligands. It was found that the iodide ions are more likely than chloride to enter between the ligands, which can be important for the electron transfer processin the solar cell.

The dye-sensitized solar cell is a promising solar cell technology. In these systems the key process for light to electricity conversion is molecular in nature and is initiated in dye molecules adsorbed at a semiconducting surface. This thesis focuses on the electronic and molecular surface structure of the dye/TiO2 interface, and the experimental results were obtained from surface sensitive X-ray based electron spectroscopic methods. Two families of dyes, triarylamine based organic dyes and ruthenium based inorganic dyes, were investigated. The effect of dye structural modications on the interfacial properties was studied, such as the surface concentrations, dye molecular surface orientation, molecular interactions, and energy level matching. Also, the impact of additional parameters such as the incorporation of coadsorbents and the solvents used for dye sensitization were studied and complementary photoelectrochemical characterization was used to demonstrate functional properties corresponding to changes in the molecular layers. The experiments provided information on how specic structural modications change the frontier electronic structure. The results also showed that the adsorption of the organic dye leads to submolecular electronic changes, and that the dye surface orientations in general favor effcient energy conversion. Moreover, effects of solvents and coadsorbents, on both energy level matching between the dye and the TiO2 substrate and the surfacemolecular structure were quantied.

Escape of photoelectrons, Compton-scattered photons and Ge X-rays from a HPGe detector was studied as a function of energy in the range 8-52 keV. A variable-energy source producing Cu, Rb, Mo, Ag, Ba, and Tb X-rays was used. All three mechanisms for energy loss were observed in the same experiment for Ba and Tb, while only X-ray and photoelectron escapes were evident in the spectra for Ag, Mo, Rb, and Cu. Spectral features and possible mechanisms for partial energy deposition were investigated. A Monte Carlo program was used to simulate the relevant interactions and to estimate the escape probabilities.

Allyl methacrylate, AMA was polymerized by chemical initiator and by &amp / #947 / -radiation under different conditions. The polymer obtained is mostly gel type with some soluble fractions at lower conversions. Arrhenius activation energy is 82.3 kJ/mol for chemical initiated polymerization. The polymer was characterized by FT-IR, NMR, DSC, TGA, XPS, XRD, DLS, and MS methods. It was found that about 98-99% of allyl side groups retained as pendant even after completion of the polymerization, while 1-2% may give crosslinking and/or cyclization that yields lactones and anhydrides. The spectroscopic and thermal results of the work showed that the reaction is not cyclopolymerization, but may have end group cyclization. Molecular weight of 1.1x106 was measured by DLS. Therefore, insolubility is due to the high molecular weight of polymer, even in the early stage of polymerization rather than crosslinking. The Tg of PAMA was observed as 94&ordm / C before curing, upon curing at 150-200&ordm / C, Tg increased to 211&ordm / C as measured by DSC. The thermal treatment of polymer at about 350&ordm / C gave anhydride by linkage type degradation, following side group cyclization. The XPS analysis showed the presence of radical fragments of AIBN and CCl4 associated with oligomers. The MS and TGA thermograms showed two or three stage degradations depending on solubility. The first stage was mostly linkage type degradation for the fragmentation of pendant allyl groups at 225-350&ordm / C. In the second stage, at 395-515&ordm / C, the degradation is random scission and depolymerization.

DC and RF magnetron co-sputtering techniques are one of the most suitable techniques in fabrication of thin films with different compositions. In this work, Al2O3 and Si/Al2O3 thin films were fabricated by using magnetron co-sputtering technique. For Al2O3 films, the stoichiometric, optical and crystallographic analyses were performed. For Si contained Al2O3 films, the formation conditions of Si nanocrystals were investigated. To do so, these thin films were sputtered on Si (100) substrates. Post annealing was done in order to clarify the evolution of Al2O3 matrix and Si nanocrystals at different temperatures. Crystallographic properties and size of the nanocrystals were investigated by X-ray diffraction (XRD) method. The variation of the atomic concentrations and bond formations were investigated with X-ray photoelectron spectroscopy (XPS). The luminescent behaviors of Si nanocrystals and Al2O3 matrix were investigated with photoluminescence (PL) spectroscopy. Finally, the characteristic emissions from the matrix and the nanocrystals were separately identified.

Diese Dissertation unter dem Titel Experimentelle Bestimmung der elektronischen Eigenschaften anwendungsrelevanter Grenzflächen organischer Halbleiter mittels Photoelektronenspektroskopie wurde am Leibniz Institut für Festkürper- und Werkstoffforschung (IFW) Dresden am Institut für Festkörperforschung (IFF) unter der Betreuung von Prof. Dr. B. Büchner angefertigt. Zur wissenschaftlichen Untersuchung kamen hierbei zwei Typen anwendungsrelevanter Grenzflächen. Zum einem wurde der Einfluss einer Elektrodenpräparation unter Normalbedingungen mittels ex-situ Reinigungsverfahren im Vergleich zu insitu präparierten Kontakten auf das elektronische Verhalten des organischen Halbleiters Sexithiophen an Grenzflächen zu metallischen Substraten studiert. Als Substratmaterialien kamen hierbei die Metalle Silber, Palladium, Gold und Platin zum Einsatz. In einer zweiten Studie wurden die Grenzflächen der organischen Halbleiter Sexithiophen und Kupfer(II)- Phthalocyanin in Kontakt zu dünnen Filmen des Übergangsmetalloxides La0.7Sr0.3MnO3 untersucht. Auch hier wurde eine vergleichende Untersuchung für ex-situ und in-situ gereinigte La0.7Sr0.3MnO3-Kontakte durchgeführt. Die hierzu verwendeten Filme wurden im IFW Dresden am Institut für Metallische Werkstoffe (IMW) hergestellt. Auch im Rahmen dieser Untersuchungen stand der Einfluss von Sauerstoff auf das elektronische und chemische Verhalten an den Grenzflächen im Vordergrund.

<p>The main objective for the work described in this PhD thesiswas to formulate a friction model to characterize thefrictional behavior of paper. More specifically, the modelshould explain a phenomenon that is typical for paper grades,viz.: that the level of paper-to-paper friction is dependent onthe direction and the number of previous slides. The modelshould also explain the lubricating effect oflow-molecular-mass lipophilic compounds (LLC) that occur inpaper on paper-to-paper friction. Furthermore, the model shoulddescribe the types of forces that influence paper-to-paperfiction and explain the mechanism by which the LLC decreasepaper-to-paper friction.</p><p>This thesis consists of a literature review of the basicconcepts of tribology and a summary of the main results andconclusions from four studies on the frictional characteristicsof paper and a study on the friction and adhesion of cellulosesurfaces together with some unpublished material.</p><p>The purpose of the investigation described in the firstpaper was to explain a phenomenon that is typical for papergrades, viz.: the level of paper-to-paper friction is dependenton the direction and the number of previous slides. Thisbehavior is called“friction hysteresis”by theauthors, and it has its origin in the reorientation of thefibers on the surface of a paper and their alignment relativeto the sliding direction.</p><p>The second paper describes a study that was aimed atidentifying lubricants that occur natively in paper. Filterpapers were impregnated with model compounds representing woodextractives, i.e. low-molecular-weight lipophilic compounds,which are present in wood, pulp and paper, and thepaper-to-paper friction was determined. The results of thatstudy show that a wood extractive must fulfill severalstructural criteria in order to lubricate a paper surface: Itmust have a hydrophilic group that can attach to the papersurface and a linear hydrocarbon backbone of sufficientlength.</p><p>Although it is not specifically stated in the second paper,the authors proposed a type of lubrication by which woodextractives decrease paper-to-paper friction that is, ineffect, boundary lubrication. The purpose of the investigationdescribed in the third paper was to clarify whether woodextractives and other low-molecular-mass lipophilic compoundsthat occur in paper can act as boundary lubricants on papersurfaces. The main objective of that study was to investigatethe role of chemical structure of LLC for their orientationrelative to the paper surface, which is an important criterionfor boundary lubrication. Filter papers were impregnated withmagnesium salts of different lipophilic acids, which were usedfor model compounds for the LLC. The deposited layers ofmagnesium salts were characterized by X-ray photoelectronspectroscopy (XPS) and contact angle goniometry and thefriction of the impregnated paper sheets was determined. Theresults show that the degree of lubrication and the resistanceto wear of the layers of a magnesium salt increased withincreasing chain length and increasing degree of linearity ofthe lipophilic acid. Based on the results of that study and ofearlier studies, it is concluded that boundary lubrication isthe type of lubrication by which low-molecular-mass lipophiliccompounds that occur natively in paper decreasepaper-to-paper-friction.</p><p>In boundary lubrication, surfaces are covered withmonolayers of lubricant molecules that comprise an active headgroup that can attach to the surface, e.g. a carboxyl group,and an inert linear backbone, such as a long saturatedhydrocarbon chain. Such compounds form ordered monolayers onsurfaces, so that the backbone points vertically out of planeof the surface. The friction is then determined by theinteractions between the monolayers, which are weaker than theinteractions between the clean surfaces and this gives a lowerfriction.</p><p>The fourth paper describes a study on the origin of thedifferences in friction levels between different linerboardsbased on recycled fiber (old corrugated container, OCC). Thesheets were subjected to two extraction stages and analyzedwith respect to surface roughness and their content oflow-molecular-mass lipophilic compounds (LLC). The resultsshowed that a high amount of LLC in the sheets lead to lowfriction, due to lubrication.</p><p>The fifth paper describes a study that was aimed atdetermining the types of forces that influence the frictionbetween the surfaces of hydrophilic polymers and explaining themechanism by which boundary lubricants decrease the friction.The adhesion and the friction of model systems was measuredwith atomic force microscopy (AFM) using regenerated cellulosefilms and functionalised AFM tips and the effect of fatty acidsand humidity was investigated. The friction significantlyincreased with increasing humidity and that there was a strongcorrelation between the ability of a fatty acid to form ahydrophobic surface and its lubricating performance. Measuredadhesion forces at high humidity were well predicted bytheoretical models that took into account the effect of theLaplace pressure acting in a water meniscus formed aroundcontact regions due to capillary condensation. The resultsindicated that the degree of capillary condensation may beeffectively suppressed by increasing the hydrophobicity of thecontacting surfaces, causing adhesion and friction to decrease.These results suggest that friction between paper surfacesunder ambient conditions is greatly influenced by the degree ofcapillary condensation. Furthermore, lubrication by fatty acidsis achieved by the formation of a vertically oriented,hydrophobic monolayer that can withstand the stresses duringsliding and increase the hydrophobicity of the paper surfaceand thereby suppress capillary condensation.</p><p><b>Keywords:</b>Friction, paper-to-paper friction, frictionhysteresis, fibers, orientation, sliding direction, woodextractives, low-molecular-mass lipophilic compounds, boundarylubrication, adhesion, capillary condensation, Laplacepressure, surface forces, JKR theory, gas chromatography-massspectroscopy, X-ray photoelectron spectroscopy, contact angle,atomic force microscopy</p>

Τις τελευταίες δεκαετίες το επιστημονικό ενδιαφέρον έχει στραφεί στη μελέτη οργανικών ημιαγώγιμων υλικών με σκοπό να κατασκευαστούν ηλεκτρονικές διατάξεις με χαμηλότερο κόστος και μεγαλύτερη απόδοση από τις εμπορικές διατάξεις με ανόργανους ημιαγωγούς, που κυκλοφορούν ήδη στην αγορά. Η οικογένεια των φθαλοκυανινών (Phthalocyanines, Pcs) ανήκει στα οργανικά υλικά που ανταγωνίζονται επάξια τους ανόργανους ημιαγωγούς στις εφαρμογές σε ηλεκτρονικές διατάξεις όπως φωτοεκπομπές δίοδοι (LEDs), τρανζίστορ επίδρασης πεδίου (FETs), φωτοβολταϊκά στοιχεία (PVs), ηλιακά στοιχεία (solar cells), αισθητήρες (sensors), διατάξεις αποθήκευσης πληροφορίας (data storage devices) και μπαταρίες (batteries). Τα υλικά αυτά είναι εύκαμπτα, εύκολα επεξεργάσιμα, με χαμηλό κόστος παρασκευής και αξιόλογη χημική και θερμική σταθερότητα, ενώ οι ηλεκτρικές και οπτικές τους ιδιότητες τα καθιστούν ελκυστικά υλικά για εφαρμογή στη μικροηλεκτρονική. Σε αυτού του είδους τις εφαρμογές παίζουν σημαντικό ρόλο οι φυσικές και χημικές αλληλεπιδράσεις που συμβαίνουν στις διεπιφάνειες μεταξύ των ενεργών οργανικών υμενίων και των υλικών που χρησιμοποιούνται ως ηλεκτρόδια, καθώς επηρεάζουν τη συμπεριφορά των διατάξεων ως προς την αγωγή του ρεύματος και επομένως τη λειτουργία τους. Καθίσταται επομένως σαφές ότι η μελέτη της ηλεκτρονικής δομής των οργανικών υμενίων και των διεπιφανειών που αυτά σχηματίζουν με μέταλλα, ανόργανους, αλλά και οργανικούς ημιαγωγούς είναι απαραίτητη και καθοριστική για την κατανόηση του τρόπου λειτουργίας των ηλεκτρονικών διατάξεων και για την εύρεση τρόπων βελτίωσης της απόδοσής τους. Στην παρούσα εργασία έγινε η πρώτη πειραματική μελέτη με φασματοσκοπίες φωτοηλεκτρονίων από ακτίνες-Χ και υπεριώδη ακτινοβολία (XPS και UPS) της ηλεκτρονικής δομής μεταλλικών φθαλοκυανινών, νικελίου (NiPc) και κοβαλτίου (CoPc), και των διεπιφανειών που σχηματίζονται κατά την απόθεση, με θερμική εξάχνωση, του οργανικού αυτού υλικού πάνω σε διάφορα υποστρώματα, σε συνθήκες υπερυψηλού κενού. Αρχικά μελετήθηκαν υμένια NiPc πάνω σε φασματοσκοπικά καθαρή επιφάνεια φύλλου πολυκρυσταλλικού χρυσού (Au) και αργύρου (Ag). Η επιλογή των μετάλλων αυτών οφείλεται στην ευρεία εφαρμογή που έχουν ως ηλεκτρόδια ή υποστρώματα σε πολλές διατάξεις, όπως FETs και LEDs. Υμένια NiPc αποτέθηκαν επίσης πάνω σε οξείδιο ινδίου-κασσιτέρου (ITO), το οποίο αποτελεί υλικό ανόδου σε OLEDs εξαιτίας της υψηλής ηλεκτρικής αγωγιμότητας και της εξαιρετικής του διαπερατότητας στο ορατό, καθώς και σε κρύσταλλο Si(100) με σκοπό να διερευνηθεί αν η παρουσία NiPc ως επίστρωση στην επιφάνεια του πυριτίου μπορεί να βελτιώσει τη λειτουργία των ανόργανων ηλεκτρονικών διατάξεων όπως τα FETs. Τέλος, μελετήθηκε η αλληλεπίδραση μεταξύ NiPc και οργανικών υλικών όπως το PEDOT:PSS και το PEDOT:PTSA, που είναι μίγματα πολυμερών και τα οποία, σύμφωνα με τη βιβλιογραφία, διευκολύνουν την έγχυση οπών σε μια διάταξη. Η χρήση του PEDOT:PTSA έχει στόχο να αντικαταστήσει σε διάφορες εφαρμογές το PEDOT:PSS του οποίου η σύνθεση είναι αρκετά περίπλοκη. Επίσης, μελετήθηκαν οι διεπιφάνειες μεταξύ υμενίων φθαλοκυανίνης κοβαλτίου (CoPc) και υποστρωμάτων πολυκρυσταλλικού χρυσού και ITO, με σκοπό να διερευνηθεί η επίδραση του κεντρικού μεταλλικού στοιχείου του μορίου της φθαλοκυανίνης, στη συμπεριφορά και τις ιδιότητες των διεπιφανειών με αντίστοιχα υποστρώματα. Από τα πειραματικά αποτελέσματα (XPS και UPS), προσδιορίζονται οι μεταβολές των ενεργειακών ζωνών των οργανικών και ανόργανων ημιαγωγών, η δομή της ζώνης σθένους και η τιμή του έργου εξόδου όλων των υλικών που χρησιμοποιούνται, καθώς και η θέση του υψηλότερου κατειλημμένου μοριακού τροχιακού (Highest Occupied Molecular Orbital, HOMO) των οργανικών ημιαγωγών (NiPc, CoPc). Επίσης προσδιορίζονται η διεπιφανειακή διπολική ροπή (eD) και το φράγμα έγχυσης οπών (Φbh) στις σχηματιζόμενες διεπιφάνειες, μεγέθη τα οποία καθορίζουν και επηρεάζουν τη μεταφορά φορτίου μεταξύ των υλικών σε επαφή κατά τον σχηματισμό της διεπιφάνειας. Η μελέτη των παραπάνω διεπιφανειών έδειξε ότι καταλληλότερο ηλεκτρόδιο για την έγχυση οπών είναι το PEDOT:PSS, καθώς το ύψος του φράγματος έγχυσης οπών στη διεπιφάνεια με υμένιο NiPc προσδιορίστηκε ίσο με 0.5 eV και είναι χαμηλότερο από αυτό που δίνουν οι διεπιφάνειες με τα μέταλλα (~0.9 eV), το ITO (1.0 eV) αλλά και το PEDOT:PTSA (0.8 eV). Από τη μελέτη της διεπιφάνειας NiPc/Si προέκυψε ότι η επιφανειακή δομή του Si(100) πιθανόν να επηρεάζει την διάταξη των μορίων της NiPc, τα οποία στα πρώτα στάδια ενδεχομένως να αναπτύσσονται στρωματικά πάνω στο υπόστρωμα, με αποτέλεσμα τα χαρακτηριστικά του οργανικού υμενίου να σχηματίζονται πλήρως στις αρχικές αποθέσεις μέχρι τα ~2 μονοστρώματα (ML). Σε κανένα από τα υπό μελέτη συστήματα δεν παρατηρήθηκε χημική αντίδραση των οργανικών μορίων με το υπόστρωμα, ενώ διαπιστώθηκε αλληλεπίδραση μέσω μεταφοράς φορτίου με σκοπό την αποκατάσταση θερμοδυναμικής ισορροπίας στη διεπιφάνεια. Επίσης, όλα τα συστήματα αποκλίνουν από τον κανόνα Schottky-Mott. Στη διεπιφάνεια NiPc/PEDOT:PSS παρατηρείται πάγωμα του επιπέδου Fermi εντός του χάσματος της NiPc. Συγκρίνοντας τα αποτελέσματα για τις δύο μεταλλικές φθαλοκυανίνες, προκύπτει ότι η παρουσία υμενίων CoPc διευκολύνει την έγχυση οπών στην επαφή με το ΙΤΟ, δίνοντας χαμηλότερες τιμές Φbh από την αντίστοιχη διεπιφάνεια με υμένια NiPc, ενώ οι διεπιφάνειες των MePcs με τον χρυσό παρουσιάζουν παρόμοια συμπεριφορά. Τέλος, έγιναν ηλεκτρικές μετρήσεις σε διατάξεις τύπου ΟFET με παχύτερα υμένια NiPc και CoPc, τα οποία παρασκευάστηκαν με εξάχνωση πάνω σε υπόστρωμα SiO2/Si αλλά και με τα παράγωγά τους με υποκαταστάτες θειϊκές ομάδες (SO3Na), τα οποία παρασκευάστηκαν από διάλυμα με τη μέθοδο της εναπόθεσης με σταγόνα (drop-casting) ή με περιστροφή (spin-coating). Οι διατάξεις ΟFET που προέκυψαν και ιδιαίτερα αυτές των σουλφονωμένων φθαλοκυανινών νικελίου, παρουσιάζουν ικανοποιητικές ευκινησίες. Τα κύρια ηλεκτρικά χαρακτηριστικά που προκύπτουν είναι ικανοποιητικά για το είδος των εφαρμογών για τις οποίες προορίζονται τα υλικά αυτά. / Recently, there is a great interest in the application of organic semiconductor thin films as active layers in electronic devices, in order to improve their efficiency and reduce the cost of their preparation. The family of Phthalocyanines (Pcs) present some of the most promising materials that can be compared to the conventional inorganic semiconductors for application in electronic devices, such as light emitting diodes (LEDs), field effect transistors (FETs), photovoltaic cells (PVs), solar cells, gas-sensors, data storage devices and batteries. The Pcs possess beneficial properties, such as quite high conductivity, thermal and chemical stability, compatibility with plastic substrates and low cost of deposition processes and are already used in gas sensor technology and in electronic devices. In this kind of devices, the properties of the interface between the active organic layer and the materials used as electrodes (metals, inorganic and organic semiconductors) affect the device performance therefore, it is important that they be determined. The present work, concerns the first experimental study by X-Ray and UV Photoelectron Spectroscopies (XPS, UPS), of the electronic structure of the interfaces formed upon evaporating, under UHV conditions, thin films of metal phthalocyanines (MePcs), such as Nickel (NiPc) and Cobalt (CoPc), on substrates with different chemical and physical properties. The choice of the substrates depends on the materials that are applied as electrodes and substrates in conventional electronic devices. Thin films of NiPc were deposited on the clean surface of metals with different work function values (polycrystalline gold and silver foils), on Indium-Tin Oxide (ITO) coated-glass substrate, a common electrode in OLEDS due to its excellent transparency in the visible, and on a silicon wafer (Si(100) n-type) used in FET structures. Also, the interaction of NiPc with organic substrates, such as PEDOT:PSS and PEDOT:PTSA which are polymer mixtures, is investigated. It has been reported that when PEDOT:PSS is applied at the anode of a device it enhances the injection of positive charge carriers. The PEDOT:PTSA substrate is investigated in order to decide whether it can replace PEDOT:PSS in several applications, as its synthesis is simpler than that of PEDOT:PSS. Also, the interfaces formed between CoPc and polycrystalline Au foil, as well as ITO, were studied by XPS and UPS and compared with the corresponding NiPc layers, in order to determine the role of the central metal atom of the metal phthalocyanine molecule in the properties of the interface. The experimental results (XPS and UPS) provide information about the valence band structure and the work function of the materials, the position of the highest occupied molecular orbital (HOMO) of the organic semiconductor (NiPc, CoPc) and the possible shifts of the energy levels of the materials. Furthermore, factors which affect and specify the charge transfer and the carrier mobility across the interface, such as the interfacial dipole (eD) and the barrier for the injection of holes (Φbh), can be determined. The results showed that the most appropriate material for the injection of holes is PEDOT:PSS, as the Φbh at the interface with NiPc was determined equal to 0.5 eV, significantly lower than that in the case of metals (0.9 eV), ITO (1.0 eV), as well as PEDOT:PTSA (0.8 eV). The study of the NiPc/Si(100) interface showed that the structure of the Si surface might affect the arrangement of the NiPc molecules, which could lay with their molecular plane parallel to the substrate, as evidenced by the fact the characteristics of the NiPc layer are fully developed at the early steps of deposition up to ~2 monolayers. No chemical interaction was observed in any of the studied systems, while in all cases charge transfer occurs in order to achieve thermodynamic equilibration. All the interfaces divert from the Schottky-Mott rule. In the case of the NiPc/PEDOT:PSS interface, a pinning of the Fermi level at the energy gap of NiPc occurs. Comparing the results for the interfaces formed between NiPc and CoPc with polycrystalline Au foil and ITO, it is found that in the case of Au the results are similar, while in the case of ITO substrate the presence of the CoPc layer leads to lower Φbh compared to NiPc layers, which would facilitate the mobility of positive carriers injected from the anode of a device. Finally, electrical measurements were performed on OFET structures using thicker NiPc and CoPc films, prepared by thermal evaporation on SiO2/Si substrates, as well as the same MePcs substituted with SO3Na groups, which were prepared from solution by drop-casting or spin-coating. All studied OFET structures and especially those of the sulfonated MePcs showed quite promising results for such type of applications.

No description available.