Synthesis of new non-fullerene acceptors based on indacenodithiophene core for organic solar cells

Due to the low cost, lightness and flexibility, Polymer Solar Cell (PSC) technology is considered one of the most promising energy technologies. In the past decades, PSCs using fullerenes or fullerene derivatives as the electron acceptors have made great progress with best power conversion efficiency (PCE) reaching 11%. However, fullerene type electron acceptors have several drawbacks such as complicated synthesis, a low light absorption coefficient and poor tuning in energy levels, which prevent the further development of fullerene-based PSCs. Hence the need to have a new class of electron acceptors as an alternative to conventional fullerene compounds. Non-fullerene acceptors (NFAs) have developed rapidly in the last years and the maximum PCEs have exceeded 14% for single-junction cells and 17% for double-junction tandem cells. By combining an electron-donating backbone, generally with several fused rings with electron-withdrawing units, we can simply construct NFA of the acceptor–donor–acceptor type (A–D–A). Versatile molecular structures have been developed using methods such as acceptor motif engineering and donor motif engineering. However, there are only a few electron-donating backbones that have been proved to be successful. Therefore, it is still necessary to develop promising building blocks to further enrich the structural diversity. An indacenodithiophene (IDT) unit with just five fused rings has a sufficiently rigid coplanar structure, which has been regarded as one of the promising electron-rich units to design high-performance A–D–A NFAs. In this work, performed at the King Abdullah University of Science and Technology in Saudi Arabia, a new nine-cyclic building block (TBIDT) with a two benzothiophene unit was synthesized and used for designing new non-fullerene electron acceptors.

Contrasting photoelectrochemical behaviour of two isomeric supramolecular dyes based on meso-tetra(pyridyl)porphyrin incorporating four (mu(3)-oxo)- triruthenium(III) clusters

A saddle shaped tetracluster porphyrin species containing four [Ru(3)O(OAc)(6)(py)(2)](+) clusters coordinated to the N-pyridyl atoms of 5,10,15,20-tetra(3-pyridyl)porphyrin, H(2)(3-TCPyP), has been investigated in comparison with the planar tetra(4-pyridyl) porphyrin analogue H(2)(4-TCPyP). The steric effects from the bulky peripheral complexes play a critical role in the H(2)(3-TCPyP) species, determining a non-planar configuration around the porphyrin centre and precluding any significant pi-electronic coupling, in contrast with the less hindered H(2)(4-TCPyP) species. Both systems exhibit a photoelectrochemical response in the presence of nanocrystalline TiO(2) films, involving the porphyrin excitation around 450 nm. However, only in the H(2)(4-TCPyP) case do the cluster moieties also contribute to the photoinduced electron injection process at 670 nm, reflecting the relevance of the electronic coupling between the porphyrin centre and the peripheral complexes.

A DC-DC Step-Up mu-Power Converter for Energy Harvesting Applications, Using Maximum Power PointTracking, Based on Fractional Open Circuit Voltage

A DC-DC step-up micro power converter for solar energy harvesting applications is presented. The circuit is based on a switched-capacitorvoltage tripler architecture with MOSFET capacitors, which results in an, area approximately eight times smaller than using MiM capacitors for the 0.131mu m CMOS technology. In order to compensate for the loss of efficiency, due to the larger parasitic capacitances, a charge reutilization scheme is employed. The circuit is self-clocked, using a phase controller designed specifically to work with an amorphous silicon solar cell, in order to obtain themaximum available power from the cell. This will be done by tracking its maximum power point (MPPT) using the fractional open circuit voltage method. Electrical simulations of the circuit, together with an equivalent electrical model of an amorphous silicon solar cell, show that the circuit can deliver apower of 1132 mu W to the load, corresponding to a maximum efficiency of 66.81%.

Nanotech thin film photovoltaics

Trabalho Final de Mestrado para obtenção do grau de Mestre em Engenharia de Electrónica e Telecomunicações

Growth and Raman scattering characterization of Cu2ZnSnS4 thin films

In the present work we report the results of the growth, morphological and structural characterization of Cu2ZnSnS4 (CZTS) thin films prepared by sulfurization of DC magnetron sputtered Cu/Zn/Sn precursor layers. The adjustment of the thicknesses and the properties of the precursors were used to control the final composition of the films. Its properties were studied by SEM/EDS, XRD and Raman scattering. The influence of the sulfurization temperature on the morphology, composition and structure of the films has been studied. With the presented method we have been able to prepare CZTS thin films with the kesterite structure.

Growth pressure dependence of Cu2ZnSnSe4 properties

In this work, we show a set of growth conditions, for the two step process, with which the growth of CZTSe is successful and reproducible. The properties of the best CTZSe thin films grown by this method were examined by SEM/EDS, XRD, Raman scattering, AFM/EFM, transmittance and reflectance measurements, photoluminescence (PL) measurements and hot point probe. A broad emission band was observed in the photoluminescence spectrum of the CZTSe thin film. The band gap energy was estimated to be around 1.05 eV at room temperature, using the transmittance and reflectance data, and CZTSe samples show p-type conductivity with the hot point probe. The different characterization techniques show that we could grow single phase CZTSe thin films with our optimized process conditions.

Detection of ZnS phases in CZTS thin-films by EXAFS

Copper zinc tin sulfide (CZTS) is a promising Earthabundant thin-film solar cell material; it has an appropriate band gap of ~1.45 eV and a high absorption coefficient. The most efficient CZTS cells tend to be slightly Zn-rich and Cu-poor. However, growing Zn-rich CZTS films can sometimes result in phase decomposition of CZTS into ZnS and Cu2SnS3, which is generally deleterious to solar cell performance. Cubic ZnS is difficult to detect by XRD, due to a similar diffraction pattern. We hypothesize that synchrotron-based extended X-ray absorption fine structure (EXAFS), which is sensitive to local chemical environment, may be able to determine the quantity of ZnS phase in CZTS films by detecting differences in the second-nearest neighbor shell of the Zn atoms. Films of varying stoichiometries, from Zn-rich to Cu-rich (Zn-poor) were examined using the EXAFS technique. Differences in the spectra as a function of Cu/Zn ratio are detected. Linear combination analysis suggests increasing ZnS signal as the CZTS films become more Zn-rich. We demonstrate that the sensitive technique of EXAFS could be used to quantify the amount of ZnS present and provide a guide to crystal growth of highly phase pure films.

Investigation of defect formation and electronic transport in microcrystalline silicon deposited by hot-wire CVD

We have investigated doped and undoped layers of microcrystalline silicon prepared by hot-wire chemical vapour deposition optically, electrically and by means of transmission electron microscopy. Besides needle-like crystals grown perpendicular to the substrate's surface, all of the layers contained a noncrystalline phase with a volume fraction between 4% and 25%. A high oxygen content of several per cent in the porous phase was detected by electron energy loss spectrometry. Deep-level transient spectroscopy of the crystals suggests that the concentration of electrically active defects is less than 1% of the undoped background concentration of typically 10^17 cm -3. Frequency-dependent measurements of the conductance and capacitance perpendicular to the substrate surface showed that a hopping process takes place within the noncrystalline phase parallel to the conduction in the crystals. The parasitic contribution to the electrical circuit arising from the porous phase is believed to be an important loss mechanism in the output of a pin-structured photovoltaic solar cell deposited by hot-wire CVD.

Fotoiniciação de polimerização vinílica

The initiation step of the light-induced polymerization kinetics of vinyl monomers using dye-sensitized photoinitiators to generate active radicals is discussed. The photoredox processes of basic dyes with amines and sulfinates are described as photochemical systems capable of starting free-radical polymerization of vinyl monomers in homogeneous and microheterogeneous media. Photophysical techniques like laser flash photolysis and time-correlated single photon counting are used to investigate the excited-state kinetics of the dyes.

Performance and scalability of isolated DC-DC converter topologies in low voltage, high current applications

Fuel cells are a promising alternative for clean and efficient energy production. A fuel cell is probably the most demanding of all distributed generation power sources. It resembles a solar cell in many ways, but sets strict limits to current ripple, common mode voltages and load variations. The typically low output voltage from the fuel cell stack needs to be boosted to a higher voltage level for grid interfacing. Due to the high electrical efficiency of the fuel cell, there is a need for high efficiency power converters, and in the case of low voltage, high current and galvanic isolation, the implementation of such converters is not a trivial task. This thesis presents galvanically isolated DC-DC converter topologies that have favorable characteristics for fuel cell usage and reviews the topologies from the viewpoint of electrical efficiency and cost efficiency. The focus is on evaluating the design issues when considering a single converter module having large current stresses. The dominating loss mechanism in low voltage, high current applications is conduction losses. In the case of MOSFETs, the conduction losses can be efficiently reduced by paralleling, but in the case of diodes, the effectiveness of paralleling depends strongly on the semiconductor material, diode parameters and output configuration. The transformer winding losses can be a major source of losses if the windings are not optimized according to the topology and the operating conditions. Transformer prototyping can be expensive and time consuming, and thus it is preferable to utilize various calculation methods during the design process in order to evaluate the performance of the transformer. This thesis reviews calculation methods for solid wire, litz wire and copper foil winding losses, and in order to evaluate the applicability of the methods, the calculations are compared against measurements and FEM simulations. By selecting a proper calculation method for each winding type, the winding losses can be predicted quite accurately before actually constructing the transformer. The transformer leakage inductance, the amount of which can also be calculated with reasonable accuracy, has a significant impact on the semiconductor switching losses. Therefore, the leakage inductance effects should also be taken into account when considering the overall efficiency of the converter. It is demonstrated in this thesis that although there are some distinctive differences in the loss distributions between the converter topologies, the differences in the overall efficiency can remain within a range of a few percentage points. However, the optimization effort required in order to achieve the high efficiencies is quite different in each topology. In the presence of practical constraints such as manufacturing complexity or cost, the question of topology selection can become crucial.

Valosähköisten aurinkopaneeleiden hyötysuhteet

Aurinkopaneeleiden hyötysuhde vaikuttaa niiden tuottaman sähköenergian määrään ja kilpailukykyyn. Aurinkopaneeleiden hyötysuhteeseen vaikuttaa monta tekijää kuten paneelin rakenne ja materiaalit, säteilyn spektri ja tulokulma sekä ympäristön lämpötila. Aurinkopaneeleiden hyötysuhteet määritetään standardiolosuhteissa, jolloin niitä voidaan vertailla toisiinsa. Todellisissa olosuhteissa paneeleiden toiminta-arvot kuitenkin muuttuvat, joten tietyllä alueella energiantuottohyötysuhde voi poiketa suuresti standardiolosuhteissa määritetystä tehontuottohyötysuhteesta. Kaupallisesti saatavilla olevissa aurinkopaneeleissa hyötysuhteet ovat parhaimmillaan noin 20 % luokkaa normaalin hyötysuhteen ollessa 13 - 16 % välillä. Ohutkalvoisilla aurinkopaneeleilla hyötysuhteet jäävät matalammiksi. Parhaat kennohyötysuhteet saavutetaan moniliitoskennoilla, jopa 44 %, mutta tällaisten järjestelmien hinnat ovat korkeita, ellei käytetä keskittäviä peilejä tai linssejä. Viime vuosina kehitys on ollut nopeinta kolmannen sukupolven teknologioilla. Niihin kohdistuu suuria odotuksia ja niiden avulla voidaan ylittää aikaisemmille sukupolville asetetut rajat. Teollisessa tuotannossa näitä ei kuitenkaan toistaiseksi ole paljoa alhaisen hyötysuhteen vuoksi.

Auringon asemaa seuraavan aurinkopaneelijärjestelmän kehittäminen

Tässä diplomityössä käsitellään Aurinkoa seuraavan aurinkopaneelijärjestelmän kehittämistä Suomen olosuhteisiin. Työ on tehty osana Lappeenrannan teknillisen yliopiston Green Campus-projektia, jossa tarkoituksena on tuottaa yliopistolle energiaa uusiutuvilla menetelmillä ja käyttää niitä apuna tutkimuksessa sekä opetuksessa. Tavoitteena työssä on ymmärtää Auringon seuraamisen hyödyt sekä mahdolliset haitat aurinkopaneeli sovellutuksissa. Aikaisemman tutkimustiedon ollessa vähäistä, on työssä pyritty löytämään laskentamalli tuottavuuden laskentaan riippumatta siitä, missä päin maapalloa aurinkopaneelijärjestelmä sijaitsee. Työ alkaa kirjallisuustutkimuksella, jossa käydään läpi aurinkopaneelien toimintaperiaate, aurinkoenergian ja auringonpaistetuntien suuruusluokat Suomessa, sekä Suomen sääoloista johtuvat vaatimukset aurinkopaneelijärjestelmille. Tämän jälkeen on vertailtu kaupallisia järjestelmiä. Lopuksi järjestelmällistä tuotesuunnittelua hyväksikäyttäen suunnitellaan oma versio Aurinkoa seuraavasta aurinkopaneelijärjestelmästä. Oman suunnitelman järkevyyttä simuloidaan pienoismallilla Matlab-Arduino ympäristössä ja pyritään löytämään mahdollisia heikkouksia. Suomessa aurinkoenergiasta 90 % saadaan maalis – syyskuun aikana. Nykyisillä akkujärjestelmillä aurinkoenergia Suomessa ei sovellu kuin täydentäväksi energianlähteeksi. Aurinkoa seuraamalla voidaan saavuttaa 25-30 % tuottavuuden lisäys kesäaikana verrattuna staattiseen järjestelmään. Talvella hyöty tippuu 0-10 % luokkaan. Pienoismallilla simuloidut ohjaustavat osoittivat, että Aurinkoa on mahdollista seurata ilman sensoreita laskemalla Auringon paikka tähtitieteen kaavoista.

Aurinkosähkön mikrotuotanto Suomessa

Tässä kandidaatintyössä käydään läpi aurinkosähkön kehitystä ja kannattavuutta Suomessa. Aurinkosähkön kehityksen osalta keskitytään aurinkopaneelien tekniikan ja aurinkosähkön tuotannon kehittymistä viime vuosina. Pienten aurinkosähköjärjestelmien hinnat ovat laskeneet viime vuosina siten, että sähkön kuluttajien oman paikallisen tuotannon kannattavuus on noussut merkittävästi. Työssä käsitellään aluksi aurinkosähköä yleisellä tasolla, jonka jälkeen pääpaino siirtyy aurinkosähkön mikrotuotantoon Suomessa. Kannattavuutta tutkitaan työssä esisuunniteltavan laitoksen avulla. Esisuunnittelussa tutkitaan kohdekiinteistön pohjakuormaa erityisesti tuotantohuippujen aikana. Tällä varmistetaan, että esisuunniteltavan järjestelmän sähköntuotanto pystytään kuluttamaan itse. Näin saavutetaan suurin hyöty. Aurinkosähköjärjestelmällä tuotetusta sähköstä saadaan tällä hetkellä noin 2,5 kertaa suurempi hyöty, kun sähkö käytetään itse verrattuna siihen, että sähkö myytäisin energiayhtiöille. Aurinkosähköjärjestelmä kytketään kuitenkin valtakunnan verkkoon, jotta mahdollinen satunnaisesti syntyvä ylijäämätuotanto voidaan myydä sähköyhtiölle. Järjestelmän suunnittelun jälkeen käydään läpi järjestelmän hankinta ja asentaminen. Tämän jälkeen tutkitaan järjestelmän kannattavuutta määrittämällä kustannukset ja tuotannosta saatavat säästöt. Järjestelmälle lasketaan takaisinmaksuaika ja pohditaan riskejä. Yhteenvedossa käydään läpi aurinkosähkön mikrotuotannon mahdollisuuksia ja kannattavuutta Suomessa.

Synthesis and characterization of nanoperforated metal oxide thin films

For advanced devices in the application fields of data storage, solar cell and biosensing, one of the major challenges to achieve high efficiency is the fabrication of nanopatterned metal oxide surfaces. Such surfaces often require both precise structure at the nanometer scale and controllable patterned structure at the macro scale. Nowadays, the dominating candidates to fabricate nanopatterned surfaces are the lithographic technique and block-copolymer masks, most of which are unfortunately costly and inefficient. An alternative bottom-up approach, which involves organic/inorganic self-assembly and dip-coating deposition, has been studied intensively in recent years and has proven to be an effective technique for the fabrication of nanoperforated metal oxide thin films. The overall objective of this work was to optimize the synthesis conditions of nanoperforated TiO2 (NP-TiO2) thin films, especially to be compatible with mixed metal oxide systems. Another goal was to develop fabrication and processing of NP-TiO2 thin films towards largescale production and seek new applications for solar cells and biosensing. Besides the traditional dip-coating and drop-casting methods, inkjet printing was used to prepare thin films of metal oxides, with the advantage of depositing the ink onto target areas, further enabling cost-effective fabrication of micro-patterned nanoperforated metal oxide thin films. The films were characterized by water contact angle determination, Atomic Force Microscopy, Scanning Electron Microscopy, X-ray Photoelectron Spectroscopy and Grazing Incidence XRay Diffraction. In this study, well-ordered zinc titanate nanoperforated thin films with different Zn/Ti ratios were produced successfully with zinc precursor content up to 50 mol%, and the dominating phase was Zn2Ti3O8. NP-TiO2 structures were also obtained by a cost-efficient means, namely inkjet printing, at both ambient temperature and 60 °C. To further explore new biosensing applications of nanoperforated oxide thin films, inkjet printing was used for the fabrication of both continuous and patterned polymeric films onto NP-TiO2 and perfluorinated phosphate functionalized NP-TiO2 substrates, respectively. The NP-TiO2 films can be also functionalized with a fluoroalkylsilane, resulting in hydrophobic surfaces on both titania and silica. The surface energy contrast in the nanoperforations can be tuned by irradiating the films with UV light, which provides ideal model systems for wettability studies.

Growth and Characterisation of Radio Frequency Magnetron Sputttered Indium Tin Oxide Thin Films

The increasing interest in the interaction of light with electricity and electronically active materials made the materials and techniques for producing semitransparent electrically conducting films particularly attractive. Transparent conductors have found major applications in a number of electronic and optoelectronic devices including resistors, transparent heating elements, antistatic and electromagnetic shield coatings, transparent electrode for solar cells, antireflection coatings, heat reflecting mirrors in glass windows and many other. Tin doped indium oxide (indium tin oxide or ITO) is one of the most commonly used transparent conducting oxides. At present and likely well into the future this material offers best available performance in terms of conductivity and transmittivity combined with excellent environmental stability, reproducibility and good surface morphology. Although partial transparency, with a reduction in conductivity, can be obtained for very thin metallic films, high transparency and simultaneously high conductivity cannot be attained in intrinsic stoichiometric materials. The only way this can be achieved is by creating electron degeneracy in a wide bandgap (Eg > 3eV or more for visible radiation) material by controllably introducing non-stoichiometry and/or appropriate dopants. These conditions can be conveniently met for ITO as well as a number of other materials like Zinc oxide, Cadmium oxide etc. ITO shows interesting and technologically important combination of properties viz high luminous transmittance, high IR reflectance, good electrical conductivity, excellent substrate adherence and chemical inertness. ITO is a key part of solar cells, window coatings, energy efficient buildings, and flat panel displays. In solar cells, ITO can be the transparent, conducting top layer that lets light into the cell to shine the junction and lets electricity flow out. Improving the ITO layer can help improve the solar cell efficiency. A transparent ii conducting oxide is a material with high transparency in a derived part of the spectrum and high electrical conductivity. Beyond these key properties of transparent conducting oxides (TCOs), ITO has a number of other key characteristics. The structure of ITO can be amorphous, crystalline, or mixed, depending on the deposition temperature and atmosphere. The electro-optical properties are a function of the crystallinity of the material. In general, ITO deposited at room temperature is amorphous, and ITO deposited at higher temperatures is crystalline. Depositing at high temperatures is more expensive than at room temperature, and this method may not be compatible with the underlying devices. The main objective of this thesis work is to optimise the growth conditions of Indium tin oxide thin films at low processing temperatures. The films are prepared by radio frequency magnetron sputtering under various deposition conditions. The films are also deposited on to flexible substrates by employing bias sputtering technique. The films thus grown were characterised using different tools. A powder x-ray diffractometer was used to analyse the crystalline nature of the films. The energy dispersive x-ray analysis (EDX) and scanning electron microscopy (SEM) were used for evaluating the composition and morphology of the films. Optical properties were investigated using the UVVIS- NIR spectrophotometer by recording the transmission/absorption spectra. The electrical properties were studied using vander Pauw four probe technique. The plasma generated during the sputtering of the ITO target was analysed using Langmuir probe and optical emission spectral studies.