Optimization of purification procedures in organic semiconductor synthesis for improving the performances of organic field-effect transistors

The aim of the research activity focused on the investigation of the correlation between the degree of purity in terms of chemical dopants in organic small molecule semiconductors and their electrical and optoelectronic performances once introduced as active material in devices. The first step of the work was addressed to the study of the electrical performances variation of two commercial organic semiconductors after being processed by means of thermal sublimation process. In particular, the p-type 2,2′′′-Dihexyl-2,2′:5′,2′′:5′′,2′′′-quaterthiophene (DH4T) semiconductor and the n-type 2,2′′′- Perfluoro-Dihexyl-2,2′:5′,2′′:5′′,2′′′-quaterthiophene (DFH4T) semiconductor underwent several sublimation cycles, with consequent improvement of the electrical performances in terms of charge mobility and threshold voltage, highlighting the benefits brought by this treatment to the electric properties of the discussed semiconductors in OFET devices by the removal of residual impurities. The second step consisted in the provision of a metal-free synthesis of DH4T, which was successfully prepared without organometallic reagents or catalysts in collaboration with Dr. Manuela Melucci from ISOF-CNR Institute in Bologna. Indeed the experimental work demonstrated that those compounds are responsible for the electrical degradation by intentionally doping the semiconductor obtained by metal-free method by Tetrakis(triphenylphosphine)palladium(0) (Pd(PPh3)4) and Tributyltin chloride (Bu3SnCl), as well as with an organic impurity, like 5-hexyl-2,2':5',2''-terthiophene (HexT3) at, in different concentrations (1, 5 and 10% w/w). After completing the entire evaluation process loop, from fabricating OFET devices by vacuum sublimation with implemented intentionally-doped batches to the final electrical characterization in inherent-atmosphere conditions, commercial DH4T, metal-free DH4T and the intentionally-doped DH4T were systematically compared. Indeed, the fabrication of OFET based on doped DH4T clearly pointed out that the vacuum sublimation is still an inherent and efficient purification method for crude semiconductors, but also a reliable way to fabricate high performing devices.

Novel organic semiconductors and their applications in electronics

The main goals of this thesis were the design, synthesis, and characterization of novel organic semiconductors, together with their applications in electronics, such as OFETs, OPVs, and OLEDs. The results can be summarized as follows:rn1. In chapter II, two novel angular n-type molecules were presented. Their different alkyl chains play a pivotal role in the molecular orientation relative to surface. One molecule with longer branched chains is tilted with respect to the substrate, thereby resulting in poor device performance, while the other adopt an edge-on orientation with an OFET electron mobility of 0.01 cm2 V-1 s-1.rn2. In chapter III, fused bis-benzothiadiazoles with different molecular geometries, namely linear benzoquinone-fused bis(benzothiadiazole) and V-shaped sulfone-fused bis(benzothiadiazole), were shown. This work not only contributes to the diversity of electron acceptors based on bis-benzothiadiazole moieties, but also highlights the important role of molecular shape for the solid-state packing of organic conjugated materials. In chapter IV, we demonstrated the synthesis of layered acceptors via dimerization of thiadiazole end-capped acenes. Interestingly, they feature huge differences in their photophysical properties. One compound showed a new strong emission in the near-infrared region introduced by the aggregation effect. The planosymmetric compound featured intramolecular excimer (IEE) fluorescence in solution. rn3. In chapter V and VI, we have demonstrated the synthesis of novel spiro-bifluorene based asymmetric and symmetric cruciform electron acceptors with dicyanovinylene substitutions. The solar cells based on PTB7:asymmetric acceptor yields the highest PCE of 0.80%. Such results demonstrate for the first time that dicyanovinylene substituted acceptor could be an alternative to fullerene-based acceptors. rn4. In chapter VII, two novel blue-emitting compounds were shown, which consist of dihydroindenofluorenyl units and ladder-type poly-p-phenylene groups, respectively. The two novel cruciform rigid compounds present not only excellent thermal and electrochemical stability but also high PLQYs. Through analysis of their triplet energy levels, both molecules can be served as hosts for other normal fluorescent or phosphorescent materials.rn

Effect of Impurities upon Current Efficiency in the Electrolysis of Zinc Sulphate Solution

There are many elements which are detrimental to the current efficiency in the electrolysis of zinc sulphate solution. Fortunately the majority of these elements are easily removed in the purification process and cause no further trouble. The elements that are likely to cause trouble in ordinary plant operations are antimony, arsenic, cobalt, nickel, manganese and germanium. The following tests were made to determine the mutual effect on the current efficiency when several of the impurities were present in the electrolyte.

Comparing the Luttinger–Kohn–Pikus–Bir and the Empiric K·P Hamiltonians in quantum dot intermediate band solar cells manufactured in zincblende semiconductors

The calculation of the energy spectrum and absorption coefficients of quantum dot nanostructured intermediate band solar cells using the Empiric K·P Hamiltonian method and its agreement with experimental data are summarized. The well established Luttinger Kohn Hamiltonian modified by Pikus and Bir for strained material, such as quantum dot arrays, is presented using a simplified strain field that allows for square band offsets. The energy spectrum and absorption coefficients are calculated with this new Hamiltonian. With the approximations made the energy spectrum results to be exactly the same but the absorption coefficient fits experiments less accurately. The computer time using the latter Hamiltonian is much longer than the former one.

Subband energy in two-band δ-doped semiconductors

We study electron dynamics in a two-band δ-doped semiconductor within the envelope-function approximation. Using a simple parametrization of the confining potential arising from the ionized donors in the δ -doping layer, we are able to find exact solutions of the Dirac-type equation describing the coupling of host bands. As an application we then consider Si δ -doped GaAs. In particular we find that the ground subband energy scales as a power law of the Si concentration per unit area in a wide range of doping levels. In addition, the coupling of host bands leads to a depression of the subband energy due to nonparabolicity effects.

Polarized interacting exciton gas in quantum wells and bulk semiconductors

We develop a theory to calculate exciton binding energies of both two- and three-dimensional spin polarized exciton gases within a mean field approach. Our method allows the analysis of recent experiments showing the importance of the polarization and intensity of the excitation light on the exciton luminescence of GaAs quantum wells. We study the breaking of the spin degeneracy observed at high exciton density (5×1010 cm2). Energy level splitting between spin +1 and spin -1 is shown to be due to many-body interexcitonic exchange while the spin relaxation time is controlled by intraexciton exchange. © 1996 The American Physical Society.

Coherently photoinduced ferromagnetism in diluted magnetic semiconductors

Ferromagnetism is predicted in undoped diluted magnetic semiconductors illuminated by intense sub-band-gap laser radiation . The mechanism for photoinduced ferromagnetism is coherence between conduction and valence bands induced by the light which leads to an optical exchange interaction. The ferromagnetic critical temperature TC depends both on the properties of the material and on the frequency and intensity of the laser and could be above 1K.

Optical spin transfer in ferromagnetic semiconductors

Circularly polarized laser pulses that excite electron-hole pairs across the band gap of (III,Mn)V ferromagnetic semiconductors can be used to manipulate and to study collective magnetization dynamics. The initial spin orientation of a photocarrier in a (III,V) semiconductors is determined by the polarization state of the laser. We show that the photocarrier spin can be irreversibly transferred to the collective magnetization, whose dynamics can consequently be flexibly controlled by suitably chosen laser pulses. As illustrations we demonstrate the feasibility of all optical ferromagnetic resonance and optical magnetization reorientation.

Optical spin transfer in ferromagnetic semiconductors [poster]

Poster presented in the International Conference of Magnetism, Rome, July 2003.

Commercial organic analysis. A treatise on the properties, proximate analytical examination, and modes of assaying the various organic chemicals and products employed in the arts, manufactures, medicine, etc., with concise methods for the detection and determination of their impurities, adulterations, and products of decomposition.

v.I. Introduction. Alcohols, neutral alcoholic derivatives, sugars, starch and its isomers, vegetable acids, etc. 2d ed., rev. & enl.--v.II. Fixed oils, fats, waxes, glycerol, nitroglycerin and nitroglycerin explosives. Hydrocarbons, petroleum and coal-tar products, asphalt, phenols and creosotes. 2d ed., rev. & enl.--v. III, pt.I. Acid derivatives of phenols, aromatic acids, resins, and essential oils. Tannins, dyes, and colouring matters, writing inks. 2d ed., rev. & enl.--v. III, pt.II. Amines and ammonium bases, hydrarzines, bases from tar, vegetable alkaloids. 2d ed., rev. and enl. [1892] --v.III, pt.III. Vegetable alkaloids (concluded), non-basic vegetable bitter principles, animal bases, animal acids, cyanogen and its derivatives. 2d ed., rev. & enl. [1896]--v.IV. Proteids and albuminous principles, proteoïds or albuminoïds. 2d ed., rev. & enl. 1898.

Allen's commercial organic analysis; a treatise on the properties, modes of assaying, and proximate analytical examination of the various organic chemicals and products employed in the arts, manufactures, medicine, etc., with concise methods for the detection and estimation of their impurities, adulterations, and products of decomposition ...

Vols. 3-9 edited by W.A. Davis and Samuel S. Sadtler.

Investigation of the effects of low energy high dose ion bombardment in metals and compound semiconductors

The effect of low energy nitrogen molecular ion beam bombardment on metals and compound semiconductors has been studied, with the aim to investigate at the effects of ion and target properties. For this purpose, nitrogen ion implantation in aluminium, iron, copper, gold, GaAs and AIGaAs is studied using XPS and Angle Resolve XPS. A series of experimental studies on N+2 bombardment induced compositional changes, especially the amount of nitrogen retained in the target, were accomplished. Both monoenergetic implantation and non-monoenergetic ion implantation were investigated, using the VG Scientific ESCALAB 200D system and a d. c. plasma cell, respectively. When the samples, with the exception of gold, are exposed to air, native oxide layers are formed on the surfaces. In the case of monoenergetic implantation, the surfaces were cleaned using Ar+ beam bombardment prior to implantation. The materials were then bombarded with N2+ beam and eight sets of successful experiments were performed on each sample, using a rastered N2+ ion beam of energy of 2, 3, 4 and 5 keV with current densities of 1 μA/cm2 and 5 μA/cm22 for each energy. The bombarded samples were examined by ARXPS. After each complete implantation, XPS depth profiles were created using Ar+ beam at energy 2 ke V and current density 2 μA/cm2 . As the current density was chosen as one of the parameters, accurate determination of current density was very important. In the case of glow discharge, two sets of successful experiments were performed in each case, by exposing the samples to nitrogen plasma for the two conditions: at low pressure and high voltage and high pressure and low voltage. These samples were then examined by ARXPS. On the theoretical side, the major problem was prediction of the number of ions of an element that can be implanted in a given matrix. Although the programme is essentially on experimental study, but an attempt is being made to understand the current theoretical models, such as SATVAL, SUSPRE and TRIM. The experimental results were compared with theoretical predictions, in order to gain a better understanding of the mechanisms responsible. From the experimental results, considering possible experimental uncertainties, there is no evidence of significant variation in nitrogen saturation concentration with ion energy or ion current density in the range of 2-5 ke V, however, the retention characteristics of implantant seem to strongly depend on the chemical reactivity between ion species and target material. The experimental data suggests the presence of at least one thermal process. The discrepancy between the theoretical and experimental results could be the inability of the codes to account for molecular ion impact and thermal processes.

Why is it possible to detect doped regions of semiconductors in low voltage SEM:a review and update

There is an urgent need for fast, non-destructive and quantitative two-dimensional dopant profiling of modern and future ultra large-scale semiconductor devices. The low voltage scanning electron microscope (LVSEM) has emerged to satisfy this need, in part, whereby it is possible to detect different secondary electron yield values (brightness in the SEM signal) from the p-type to the n-type doped regions as well as different brightness levels from the same dopant type. The mechanism that gives rise to such a secondary electron (SE) contrast effect is not fully understood, however. A review of the different models that have been proposed to explain this SE contrast is given. We report on new experiments that support the proposal that this contrast is due to the establishment of metal-to-semiconductor surface contacts. Further experiments showing the effect of instrument parameters including the electron dose, the scan speeds and the electron beam energy on the SE contrast are also reported. Preliminary results on the dependence of the SE contrast on the existence of a surface structure featuring metal-oxide semiconductor (MOS) are also reported. Copyright © 2005 John Wiley & Sons, Ltd.

Excitonic behaviour in polymeric semiconductors : the effect of morphology and composition in heterostructures

La compréhension des interrelations entre la microstructure et les processus électroniques dans les polymères semi-conducteurs est d’une importance primordiale pour leur utilisation dans des hétérostructures volumiques. Dans cette thèse de doctorat, deux systémes diffèrents sont étudiés ; chacun de ces systèmes représente une approche diffèrente pour optimiser les matériaux en termes de leur microstructure et de leur capacité à se mettre en ordre au niveau moléculaire. Dans le premier système, j’ai effectué une analyse complète des principes de fonctionnement d’une cellule photovoltaïque hybride à base des nanocristaux d’oxyde de zinc (ZnO) et du poly (3-hexylthiophène) (P3HT) par absorption photoinduite en régime quasi-stationnaire (PIA) et la spectroscopie PIA en pompage modulé dépendant de la fréquence. L’interface entre le donneur (le polymère P3HT) et l’accepteur (les nanoparticules de ZnO), où la génération de charges se produit, joue un rôle important dans la performance des cellules photovoltaïques hybrides. Pour améliorer le mécanisme de génération de charges du P3H: ZnO, il est indispensable de modifier l’interface entre ses constituants. Nous avons démontré que la modification d’interface moléculaire avec cis-bis (4, 40 - dicarboxy-2, 20bipyridine) ruthénium (II) (N3-dye) et a-Sexithiophen-2 yl-phosphonique (6TP) a améliorée le photocourant et la performance dans les cellules P3HT: ZnO. Le 6TP et le N3 s’attachent à l’interface du ZnO, en augmentant ainsi l’aire effective de la surface donneur :accepteur, ce qui contribue à une séparation de charge accrue. De plus, le 6TP et le N3 réduisent la densité de pièges dans le ZnO, ce qui réduit le taux de recombinaison des paires de charges. Dans la deuxième partie, jai introduit une matrice hôte polymérique de polystyréne à masse molaire ulra-élevée, qui se comporte comme un solide pour piéger et protéger une solution de poly [2-méthoxy, 5- (2´-éthyl-hexoxy) -1,4-phénylènevinylène- PPV] (MEHPPV) pour utilisation dans des dispositifs optoèlectroniques quantiques. Des travaux antérieurs ont montré que MEH-PPV en solution subit une transition de conformation, d’une conformation enroulé à haute température (phase bleue) à une conformation de chaîne étendue à basse température (phase rouge). La conformation de la chaîne étendue de la solution MEH-PPV favorise les caractéristiques nécessaires à l’amélioration des dispositifs optoélectroniques quantiques, mais la solution ne peut pas être incorporées dans le dispositif. J’ai démontré que la caractéristique de la phase rouge du MEH-PPV en solution se maintient dans une matrice hôte polymérique de polystyrène transformé de masse molaire très élevée, qui se comporte comme un solide (gel de MEH-PPV/UHMW PS), par le biais de la spectroscopie de photoluminescence (PL) dépendant de la température (de 290K à 80 K). La phase rouge du gel MEH-PPV/UHMW PS se manifeste par des largeurs de raie étroites et une intensité augmentée de la transition 0-0 de la progression vibronique dans le spectre de PL ainsi qu’un petit décalage de Stokes entre la PL et le spectre d’absorption à basse température. Ces approches démontrent que la manipulation de la microstructure et des propriétés électroniques des polymères semi-conducteurs ont un impact direct sur la performance de dispositifs pour leurs développements technologiques continus.