Novos compostos orgânicos reticuláveis para aplicações em células fotovoltaicas

Trabalho Final de Mestrado para obtenção do grau de mestre em Engenharia Química e Biológica

Effect of different dopant elements on the properties of ZnO thin films

Vacuum, Vol. 64

Numerical simulation of plasmonic effects in amorphous silicon induced by embedded aluminium nanoparticles

This work reports a theoretical study aimed to identify the plasmonic resonance condition for a system formed by metallic nanoparticles embedded in an a-Si: H matrix. The study is based on a Tauc-Lorentz model for the electrical permittivity of a-Si: H and a Drude model for the metallic nanoparticles. It is calculated the The polarizability of an sphere and ellipsoidal shaped metal nanoparticles with radius of 20 nm. We also performed FDTD simulations of light propagation inside this structure reporting a comparison among the effects caused by a single nanoparticles of Aluminium, Silver and, as a comparison, an ideally perfectly conductor. The simulation results shows that is possible to obtain a plasmonic resonance in the red part of the spectrum (600-700 nm) when 20-30 nm radius Aluminium ellipsoids are embedded into a-Si: H.

Solution-Processable Donor-Acceptor-Donor Oligomers with Cross-Linkable Functionality

Electron-acceptor units, combined with bithiophene substituted with flexible chains end-functionalized with cross-linkable moieties, provide soluble donor-acceptor-donor (DAD) it-conjugated oligomer-type molecules with cross-linking ability and broad absorption in the visible spectrum. A study on the cross-linking conditions of the new oligomers to yield insoluble polymer networks is presented, including conditions for obtaining polymer films over poly(3,4-ethylenedioxythiophene):polystyrene sulfonate-covered substrates. The combination of the DAD molecular design and cross-linking functionality opens prospects for applications in solution-processed small-molecule solar cells with morphologically-stable organic layers.

L'energia solar fotovoltaica

Treball de recerca realitzat per alumnes d'ensenyament secundari i guardonat amb un Premi CIRIT per fomentar l'esperit cientí­fic del Jovent l'any 2009. Després d'una breu introducció sobre l'energia solar, l'estudi analitza quin és el procés de fabricació que se segueix per fer les plaques solars fotovoltaiques policristal·lines i monocristal·lines i quin és el seu funcionament. És a dir, com és possible obtenir energia elèctrica gràcies a la llum del Sol. També es descriuen les instal·lacions autònomes i les connectades a la xarxa, així com els elements que les integren. S'inclou, a més, un punt explicant quins són els factors que condicionen l'obtenció d'energia i els avenços més recents en aquest camp de la tecnologia. Per finalitzar la part teòrica, s'analitza una instal·lació fotovoltaica situada a Cervera i la seva producció. Pel que fa al treball de camp, es va construir un seguidor solar.

A fully automated hot-wall multiplasma-monochamber reactor for thin film deposition

We present a study on the development and the evaluation of a fully automated radio-frequency glow discharge system devoted to the deposition of amorphous thin film semiconductors and insulators. The following aspects were carefully addressed in the design of the reactor: (1) cross contamination by dopants and unstable gases, (2) capability of a fully automated operation, (3) precise control of the discharge parameters, particularly the substrate temperature, and (4) high chemical purity. The new reactor, named ARCAM, is a multiplasma-monochamber system consisting of three separated plasma chambers located inside the same isothermal vacuum vessel. Thus, the system benefits from the advantages of multichamber systems but keeps the simplicity and low cost of monochamber systems. The evaluation of the reactor performances showed that the oven-like structure combined with a differential dynamic pumping provides a high chemical purity in the deposition chamber. Moreover, the studies of the effects associated with the plasma recycling of material from the walls and of the thermal decomposition of diborane showed that the multiplasma-monochamber design is efficient for the production of abrupt interfaces in hydrogenated amorphous silicon (a-Si:H) based devices. Also, special attention was paid to the optimization of plasma conditions for the deposition of low density of states a-Si:H. Hence, we also present the results concerning the effects of the geometry, the substrate temperature, the radio frequency power and the silane pressure on the properties of the a-Si:H films. In particular, we found that a low density of states a-Si:H can be deposited at a wide range of substrate temperatures (100°C

PEN as substrate for new solar cell technologies

The possible use of polyethylene naphthalate as substrate for low-temperature deposited solar cells has been studied in this paper. The transparency of this polymer makes it a candidate to be used in both substrate and superstrate configurations. ZnO:Al has been deposited at room temperature on top of PEN. The resulting structure PEN/ZnO:Al presented good optical and electrical properties. PEN has been successfully textured (nanometer and micrometer random roughness) using hot-embossing lithography. Reflector structures have been built depositing Ag and ZnO:Al on top of the stamped polymer. The deposition of these layers did not affect the final roughness of the whole. The reflector structure has been morphologically and optically analysed to verify its suitability to be used in solar cells.

Celdas solares fotoelectroquímicas basadas en Bi2WO6

In this study, photoelectrochemical solar cells based on bismuth tungstate electrodes were evaluated. Bi2WO6 was synthesized by a hydrothermal method and characterized by scanning electron microscopy, UV-Vis reflectance spectroscopy, and X-ray powder diffraction. For comparison, solar cells based on TiO2 semiconductor electrodes were evaluated. Photoelectrochemical response of Grätzel-type solar cells based on these semiconductors and their corresponding sensitization with two inexpensive phthalocyanines dyes were determined. Bi2WO6-based solar cells presented higher values of photocurrent and efficiency than those obtained with TiO2 electrodes, even without sensitization. These results portray solar cells based on Bi2WO6 as promising devices for solar energy conversion owing to lower cost of production and ease of acquisition.

Research and development of III-V semiconductor surfaces for improved device interfaces

This thesis is devoted to understanding and improving technologically important III-V compound semiconductor (e.g. GaAs, InAs, and InSb) surfaces and interfaces for devices. The surfaces and interfaces of crystalline III-V materials have a crucial role in the operation of field-effect-transistors (FET) and highefficiency solar-cells, for instance. However, the surfaces are also the most defective part of the semiconductor material and it is essential to decrease the amount of harmful surface or interface defects for the next-generation III-V semiconductor device applications. Any improvement in the crystal ordering at the semiconductor surface reduces the amount of defects and increases the material homogeneity. This is becoming more and more important when the semiconductor device structures decrease to atomic-scale dimensions. Toward that target, the effects of different adsorbates (i.e., Sn, In, and O) on the III-V surface structures and properties have been investigated in this work. Furthermore, novel thin-films have been synthesized, which show beneficial properties regarding the passivation of the reactive III-V surfaces. The work comprises ultra-high-vacuum (UHV) environment for the controlled fabrication of atomically ordered III-V(100) surfaces. The surface sensitive experimental methods [low energy electron diffraction (LEED), scanning tunneling microscopy/spectroscopy (STM/STS), and synchrotron radiation photoelectron spectroscopy (SRPES)] and computational density-functionaltheory (DFT) calculations are utilized for elucidating the atomic and electronic properties of the crucial III-V surfaces. The basic research results are also transferred to actual device tests by fabricating metal-oxide-semiconductor capacitors and utilizing the interface sensitive measurement techniques [capacitance voltage (CV) profiling, and photoluminescence (PL) spectroscopy] for the characterization. This part of the thesis includes the instrumentation of home-made UHV-compatible atomic-layer-deposition (ALD) reactor for growing good quality insulator layers. The results of this thesis elucidate the atomic structures of technologically promising Sn- and In-stabilized III-V compound semiconductor surfaces. It is shown that the Sn adsorbate induces an atomic structure with (1×2)/(1×4) surface symmetry which is characterized by Sn-group III dimers. Furthermore, the stability of peculiar ζa structure is demonstrated for the GaAs(100)-In surface. The beneficial effects of these surface structures regarding the crucial III-V oxide interface are demonstrated. Namely, it is found that it is possible to passivate the III-V surface by a careful atomic-scale engineering of the III-V surface prior to the gate-dielectric deposition. The thin (1×2)/(1×4)-Sn layer is found to catalyze the removal of harmful amorphous III-V oxides. Also, novel crystalline III-V-oxide structures are synthesized and it is shown that these structures improve the device characteristics. The finding of crystalline oxide structures is exploited by solving the atomic structure of InSb(100)(1×2) and elucidating the electronic structure of oxidized InSb(100) for the first time.

Synthesis, characterization and chemical sensor application of conducting polymers

Polymeric materials that conduct electricity are highly interesting for fundamental studies and beneficial for modern applications in e.g. solar cells, organic field effect transistors (OFETs) as well as in chemical and bio‐sensing. Therefore, it is important to characterize this class of materials with a wide variety of methods. This work summarizes the use of electrochemistry also in combination with spectroscopic methods in synthesis and characterization of electrically conducting polymers and other π‐conjugated systems. The materials studied in this work are intended for organic electronic devices and chemical sensors. Additionally, an important part of the presented work, concerns rational approaches to the development of water‐based inks containing conducting particles. Electrochemical synthesis and electroactivity of conducting polymers can be greatly enhanced in room temperature ionic liquids (RTILs) in comparison to conventional electrolytes. Therefore, poly(para‐phyenylene) (PPP) was electrochemically synthesized in the two representative RTILs: bmimPF6 and bmiTf2N (imidazolium and pyrrolidinium‐based salts, respectively). It was found that the electrochemical synthesis of PPP was significantly enhanced in bmimPF6. Additionally, the results from doping studies of PPP films indicate improved electroactivity in bmimPF6 during oxidation (p‐doping) and in bmiTf2N in the case of reduction (n‐doping). These findings were supported by in situ infrared spectroscopy studies. Conducting poly(benzimidazobenzophenanthroline) (BBL) is a material which can provide relatively high field‐effect mobility of charge carriers in OFET devices. The main disadvantage of this n‐type semiconductor is its limited processability. Therefore in this work BBL was functionalized with poly(ethylene oxide) PEO, varying the length of side chains enabling water dispersions of the studied polymer. It was found that functionalization did not distract the electrochemical activity of the BBL backbone while the processability was improved significantly in comparison to conventional BBL. Another objective was to study highly processable poly(3,4‐ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT:PSS) water‐based inks for controlled patterning scaled‐down to nearly a nanodomain with the intention to fabricate various chemical sensors. Developed PEDOT:PSS inks greatly improved printing of nanoarrays and with further modification with quaternary ammonium cations enabled fabrication of PEDOT:PSS‐based chemical sensors for lead (II) ions with enhanced adhesion and stability in aqueous environments. This opens new possibilities for development of PEDOT:PSS films that can be used in bio‐related applications. Polycyclic aromatic hydrocarbons (PAHs) are a broad group of π‐conjugated materials consisting of aromatic rings in the range from naphthalene to even hundred rings in one molecule. The research on this type of materials is intriguing, due to their interesting optical properties and resemblance of graphene. The objective was to use electrochemical synthesis to yield relatively large PAHs and fabricate electroactive films that could be used as template material in chemical sensors. Spectroscopic, electrochemical and electrical investigations evidence formation of highly stable films with fast redox response, consisting of molecules with 40 to 60 carbon atoms. Additionally, this approach in synthesis, starting from relatively small PAH molecules was successfully used in chemical sensor for lead (II).

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.

Studies on Chemical Bath Deposited Semiconducting Copper Selenide and Iron Sulfide Thin Films Useful For Photovoltaic Applications

Chemical bath deposition (CBD)is one of the simplest, very convient and probably the cheapest method for thin film preparation. Photovoltaic is the cleanest and the most efficient mode of conversion of energy to electrical power. Silicon is the most popular material in this field. The present study on chemical bath deposited semiconducting copper selenide and iron sulfide thin films useful for photovoltaic applications. Semiconducting thin films prepared by chemical deposition find applications as photo detectors, solar control coatings and solar cells. Copper selenide is a p-type semiconductor that finds application in photovolitics. Several heterojunction systems such as Cu2-xSe/ZnSe (for injection electro luminescence), Cu2Se/AgInSe2 and Cu2Se/Si (for photodiodes), Cu2-xSe/CdS, Cu2-xSe/CdSe, CuxSe/InP and Cu2-xSe/Si for solar cells are reported. A maximum efficiency of 8.3% was achieved for the Cu2-xSe/Si cell, various preparation techniques are used for copper selenide like vacuum evaporation, direct reaction, electrodeposition and CBD. Instability of the as-prepared films was investigation and is accounted as mainly due to deviation from stoichiometry and the formation of iron oxide impurity. A sulphur annealing chamber was designed and fabricated for this work. These samples wee also analysed using optical absorption technique, XPS (X-ray Photoelectron Spectroscopy) and XRD.(X-Ray Diffraction).The pyrite films obtained by CBD technique showed amorphous nature and the electrical studies carried out showed the films to be of high resistive nature. Future work possible in the material of iron pyrite includes sulphur annealing of the non-stochiometric iron pyrite CBD thin films in the absence of atmospheric oxygen

Spray Pyrolysed CuInS2/In2S3 Solar Cell: Material Characterization and Device Fabrication

As emphasis towards sustainable and Renewable energy resources grows world-wide,interest in the capture and use of solar energy is increasing dramatically.Solar cells have been known and used for many years,but depletion of conventional energy resources resulted in the intensification of research on solar cells leading to new design and technique of fabrication.The current emphasis is directed towards high effiency inexpensive solar cells.This thesis includes deposition and characterization of CuInS2 and In2S3 thin films using chemical Spray Pyrolysis(CSP) technique.The optimum condition for these films to be used as absorber and buffer layer respectively in solar cells were thus found out.Solar cell with the stucture,ITO/CuInS2/In2S3/metal electrode was fabricated using these well-characterized films,which yielded an efficiency of 9.5%.

Optimization of Two Stage Process for the Growth of In2S3 , CuInSe2 and CuIn (Sel-xSx)2Thin Films for Solar Cell Application

Two stage processes consisting of precursor preparation by thermal evaporation followed by chalcogenisation in the required atmosphere is found to be a feasible technique for the PV materials such as n-Beta In2S3, p-CulnSe2, p-CulnS2 and p-CuIn(Sel_xSx)2. The growth parameters such as chalcogenisation temperature and duration of chalcogenisation etc have been optimised in the present study.Single phase Beta-In2S3 thin films can be obtained by sulfurising the indium films above 300°C for 45 minutes. Low sulfurisation temperatures required prolonged annealing after the sulfurisation to obtain single phase Beta-1n2S3, which resulted in high material loss. The maximum band gap of 2.58 eV was obtained for the nearly stoichiometric Beta-In2S3 film which was sulfurised at 350°C. This wider band gap, n type Beta-In2S3 can be used as an alternative to toxic CdS as window layer in photovoltaics .The systematic study on the structural optical and electrical properties of CuInSe2 films by varying the process parameters such as the duration of selenization and the selenization temperature led to the conclusion that for the growth of single-phase CuInSe2, the optimum selenization temperature is 350°C and duration is 3 hours. The presence of some binary phases in films for shorter selenization period and lower selenization temperature may be due to the incomplete reaction and indium loss. Optical band gap energy of 1.05 eV obtained for the films under the optimum condition.In order to obtain a closer match to the solar spectrum it is desirable to increase the band gap of the CulnSe2 by a few meV . Further research works were carried out to produce graded band gap CuIn(Se,S)2 absorber films by incorporation of sulfur into CuInSe2. It was observed that when the CulnSe2 prepared by two stage process were post annealed in sulfur atmosphere, the sulfur may be occupying the interstitial positions or forming a CuInS2 phase along with CuInSe2 phase. The sulfur treatment during the selenization process OfCu11 ln9 precursors resulted in Culn (Se,S)2 thin films. A band gap of 1.38 eV was obtained for the CuIn(Se,S)2.The optimised thin films n-beta 1n2S3, p-CulnSe2 and p-Culn(Sel-xSx)2 can be used for fabrication of polycrystalline solar cells.

Spray Pyrolysed Tin Chalcogenide Thin Films: Optimization of optoelectronic properties of SnS for possible photovoltaic application as an absorber layer

In the early 19th century, industrial revolution was fuelled mainly by the development of machine based manufacturing and the increased use of coal. Later on, the focal point shifted to oil, thanks to the mass-production technology, ease of transport/storage and also the (less) environmental issues in comparison with the coal!! By the dawn of 21st century, due to the depletion of oil reserves and pollution resulting from heavy usage of oil the demand for clean energy was on the rising edge. This ever growing demand has propelled research on photovoltaics which has emerged successful and is currently being looked up to as the only solace for meeting our present day energy requirements. The proven PV technology on commercial scale is based on silicon but the recent boom in the demand for photovoltaic modules has in turn created a shortage in supply of silicon. Also the technology is still not accessible to common man. This has onset the research and development work on moderately efficient, eco-friendly and low cost photovoltaic devices (solar cells). Thin film photovoltaic modules have made a breakthrough entry in the PV market on these grounds. Thin films have the potential to revolutionize the present cost structure of solar cells by eliminating the use of the expensive silicon wafers that alone accounts for above 50% of total module manufacturing cost.Well developed thin film photovoltaic technologies are based on amorphous silicon, CdTe and CuInSe2. However the cell fabrication process using amorphous silicon requires handling of very toxic gases (like phosphene, silane and borane) and costly technologies for cell fabrication. In the case of other materials too, there are difficulties like maintaining stoichiometry (especially in large area films), alleged environmental hazards and high cost of indium. Hence there is an urgent need for the development of materials that are easy to prepare, eco-friendly and available in abundance. The work presented in this thesis is an attempt towards the development of a cost-effective, eco-friendly material for thin film solar cells using simple economically viable technique. Sn-based window and absorber layers deposited using Chemical Spray Pyrolysis (CSP) technique have been chosen for the purpose