Submitted by PPG Engenharia e Tecnologia de Materiais (engenharia.pg.materiais@pucrs.br) on 2018-04-24T14:42:28Z No. of bitstreams: 1 Dissertacao Taila Final.pdf: 2384346 bytes, checksum: 8e3d52f21033cdc04d8f1c3449453ceb (MD5) / Approved for entry into archive by Sheila Dias (sheila.dias@pucrs.br) on 2018-05-08T19:50:29Z (GMT) No. of bitstreams: 1 Dissertacao Taila Final.pdf: 2384346 bytes, checksum: 8e3d52f21033cdc04d8f1c3449453ceb (MD5) / Made available in DSpace on 2018-05-08T20:07:12Z (GMT). No. of bitstreams: 1 Dissertacao Taila Final.pdf: 2384346 bytes, checksum: 8e3d52f21033cdc04d8f1c3449453ceb (MD5) Previous issue date: 2018-02-28 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior - CAPES / The solar cells manufactured in n-type silicon, doped with phosphorus, do not present light induced degradation and they have the potential of achieving high efficiency due to the larger minority charge carrier lifetime. Besides, they are less susceptible to contamination by metal impurities. The aim of this work was to analyze different dopants to obtain the p+ region in n+np+ solar cells manufactured in Czochralski silicon wafers, solar grade, n-type, 120 ?m thick. The acceptor impurities used were B, Al, Ga, GaB and AlGa, deposited by spin-on and diffused at high temperature. The temperature, time and gases used in the process of diffusion were ranged. The sheet resistances (R?) of the diffused regions and the impurity concentration profiles were measured. We concluded that the B and GaB can be diffused at 970? C for 20 min to obtain p+ emitters with values of R? suitable to the production of solar cells with screenprinted metal grid. The Ga and AlGa require high temperatures (greater than 1100? C) and long times to produce doping profiles compatible with the production of solar cells. The Al did not produce low sheet resistance regions, even at temperatures of 1100? C. The use of argon gas instead of the nitrogen did not lead to the decreasing of the sheet resistance. The GaB is the only one doping material analyzed that can be a viable replacement for the B in the production of p+ emitter in n-type solar cells.The GaB was the only one doping material analyzed that allowed the manufacture of solar cells with the maximum efficiency of 13.5%, with the diffusion performed at 1020? C for 20 min. The FF was the main parameter that reduced the efficiency of solar cells doped with GaB when compared to the boron doped cells due to a lower shunt resistance. The n+np+ solar cell, 120 ?m thick, that achieved the highest efficiency was doped with boron and reached 14.9%, a value higher than the previously obtained in studies in the NT-Solar with thin silicon wafers. / As c?lulas solares fabricadas em l?minas de sil?cio tipo n, dopadas com f?sforo, n?o apresentam degrada??o por ilumina??o e t?m potencial de obten??o de maior efici?ncia devido ao maior valor do tempo de vida dos portadores de carga minorit?rios. Adicionalmente, s?o menos suscept?veis ? contamina??o por impurezas met?licas. O objetivo deste trabalho foi realizar uma an?lise de diferentes dopantes para obten??o da regi?o p+ em c?lulas solares n+np+fabricadas em l?minas de sil?cio Czochralski, grau solar, tipo n, com espessura de 120 ?m. Os elementos aceitadores utilizados foram o B, Al, Ga, GaB e AlGa, depositados por spin-on e difundidos em alta temperatura. Foram variadas as temperaturas, os tempos e os gases utilizados no processo de difus?o. Foi medida a resist?ncia de folha (R?) das regi?es difundidas e o perfil de concentra??o de impurezas em fun??o da profundidade. Foram desenvolvidas c?lulas solares com B, Ga, GaB e Al. Verificou-se que o B e GaB podem ser difundidos em temperatura de 970 ?C e por 20 min para obten??o de emissores com valores de R? compat?veis com a produ??o de c?lulas solares metalizadas por serigrafia. O Ga e AlGa necessitam de altas temperaturas (maiores que 1100 ?C) e tempos elevados para produzir perfis de dopantes compat?veis. O Al n?o produziu regi?es p+ de baixa R?, mesmo com a difus?o a 1100 ?C. O uso de Ar para substituir o N2 n?o acarretou em diminui??o da resist?ncia de folha. O GaB foi o ?nico dopante analisado que permitiu a fabrica??o de c?lulas solares com efici?ncia m?xima de 13,5 %, com difus?o a 1020 ?C por 20 min. O fator de forma foi o principal par?metro que reduziu a efici?ncia dos dispositivos com GaB quando comparado ao valor obtido com B devido a menor resist?ncia em paralelo. A c?lula solar n+np+ de 120 ?m de maior efici?ncia produzida neste trabalho foi dopada com boro e atingiu a efici?ncia de 14,9 %, sendo maior que as anteriormente obtidas em trabalhos realizados no NT-Solar com l?minas finas.

Made available in DSpace on 2017-07-20T12:40:19Z (GMT). No. of bitstreams: 1 Karine Klider.pdf: 4696661 bytes, checksum: 1625309038e6d64e39214301b4f96f7b (MD5) Previous issue date: 2016-07-27 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / In this study, we evaluated the optical and electrochemical properties of organic compounds of different types in order to analyze their potential for application active layer in photovoltaic devices. The work was divided into three parts. The first discloses the preparation and characterization of a derivative of 1,8-naphthalimide chromophore prepared from the reaction with a benzonitrile unit (also synthesized and characterized in this work). The BID-NB compound showed optical and electrochemical properties equivalent of the chromophore with optical and electrochemical band gap of 3.41 eV and 2.19 eV. Photovoltaic devices using bilayer architecture, constructed with the compound as the active layer, reached 0.9% of power conversion efficiency (PCE) and a current density at short circuit of 5.68 mA cm-2 by using the C70 fullerene as electron acceptor layer, and 1,8-diiodoocthane as additive in the solution for active layer deposition. The second part the work described the preparation of conjugated molecules (with electron donor acceptor characteristics) from the indigo dye modification by addiction of thiophene units. It was found that increasing number of thiophene units resulted in better opto-electrochemical properties. The molecule that showed the best behavior, DHT-IND, presented optical and electrochemical band gap of 1.64 and 1.45 eV respectively. Despite the low band gap value, the bulk heterojunction (BHJ) solar cell constructed with a 1: 3 mixture of DHT-IND and PC71BM as active layer, showed PCE of 0.7% and current density at short circuit of -4.59 mA cm-2. The fill factor (FF) was 26%. In the third part of this work we evaluated the photocurrent generation by the copolymer PPV/DCN-PPV formed by DCN-PPV chains attached to PPV chain. The evaluation performed as film deposited on a glass substrate containing ITO coated, which has exposed to a LED ilumination. After irradiation the copolymer generated current of A cm-2 (unstable), and -2 A cm-2 (stable). / Neste trabalho foram avaliadas as propriedades ópticas e eletroquímicas de deferentes compostos orgânicos, e analisar suas potencialidades para aplicação como camada ativa em dispositivos fotovoltaicos. Dividiu-se o trabalho em três partes. A primeira revelou a preparação e caracterização de um derivado do cromóforo 1,8-naftalimida, preparado a partir da reação com uma unidade de benzonitrila previamente preparada e caracterizada. O composto 4-(2-(1,3-dioxo-1H-benzo[de]isoquinolin-2(3H)-il)etoxi)-2,5-dimetilbenzonitrila, ou BID-NB, apresentou propriedades ópticas e eletroquímicas equivalentes às do cromóforo, com band gap óptico de 3,41 eV e eletroquímico de 2,19 eV. Dispositivos fotovoltaicos de bicamada foram construídos com o composto BID-NB como camada ativa, sendo que a eficiência máxima de conversão foi de 0,9% com uma densidade de corrente de curto circuito de -5,68 mA cm-2. O dispositivo que auferiu tais resultados foi construído com o fulereno elétron-aceptor C70, e com o auxilio do aditivo 1,8-diiodooctano na deposição da camada ativa. A segunda parte do trabalho consistiu da preparação de moléculas conjugadas do tipo doador/aceptor de elétrons, a partir da modificação do corante índigo com unidades de tiofenos. Constatou-se que o aumento da quantidade de unidades de tiofenos nas moléculas favoreceu suas propriedades opto-eletroquímicas. O composto 7,14-bis(3``,4`-diexil-[2,2`:5`,2``-tertiofen]-5-il)diindolo[3,2,1-de:3`,2`,1`-il][1,5]naftiridina-6,13-diona, ou DHT-IND, foi o que apresentou os menores valores de band gap óptico e eletroquímico, nos valores de 1,64 e 1,45 eV respectivamente. O dispositivo fotovoltaico de heterojunção, construído a partir da mistura 1:3 de DHT-IND e PC71BM como camada ativa, apresentou eficiência de conversão de 0,7% e densidade de corrente de -4,59 mA cm-2. Na terceira parte deste trabalho avaliou-se geração de fotocorrente em um copolímero formado por blocos de PPV ligados a blocos de DCN-PPV (PPV/DCN-PPV). A avaliação foi efetuada na forma de filme sobre um substrato de vidro contendo ITO, o qual foi exposto a iluminação de LED. O copolímero gerou corrente de até -4 A cm-2 (instável), e de -2 A cm-2 (estável) após iluminação.

Nesta tese visamos o entendimento aprofundado dos processos e mecanismos que influenciam a performance de células solares sensibilizadas por corante (DSCs), particularmente a influência das interfaces TiO2/corante, TiO2/eletrólito e rutilo/anatase, assim contribuindo para obter dispositivos eficientes. Nesse sentido, foi investigada a influência das propriedades eletrônicas do novo corante [Ru(dcbpyH2)2(tmtH2)]Cl associadas às transições de transferência de carga MLCT e LMCT sobre a eficiência de fotoinjeção e fotoconversão de energia solar nas DSCs. Por meio da aplicação das espécies isoladas (Bu4N)3[Ru(dcbpy)2(tmtH2)], (Bu4N)4[Ru(dcbpy)2(tmtH)] e (Bu4N)5[Ru(dcbpy)2(tmt)] em DSCs, foram demonstradas as contribuições de duas bandas MLCTs e uma LMCT para a fotoconversão de energia, que foram reveladas por deconvolução dos espectros de fotoação. Além disso, aquelas espécies apresentaram valores de eficiência global corrigidos pela quantidade de corante adsorvido no TiO2 maiores do que o corante N719, indicando que os novos corantes de rutênio têm potencial de aplicação como fotossensibilizadores de células solares. Também foi investigado o mecanismo do efeito sinérgico observado em misturas de rutilo e de anatase por meio do estudo das contribuições dos processos de recombinação e de difusão de elétrons nos filmes mesoporosos mistos de TiO2 sobre a performance das DSCs, em função da distribuição daqueles nanocristais em diferentes proporções, confirmadas por microscopia Raman confocal. A impedância das interfaces/junções presentes nas DSCs foi caracterizada por espectroscopia de impedância eletroquímica (EIS) para determinação de parâmetros fundamentais como capacitância química, resistência de difusão, resistências de recombinação, coeficiente de difusão, tempo de vida e comprimento de difusão dos elétrons dos filmes mistos de TiO2. As características I x V das células solares, ou seja, os parâmetros de eficiência global (η), densidade de corrente de curto-circuito (Jsc), voltagem de circuito-aberto (Voc) e fator de preenchimento (FF) foram relacionados com os parâmetros de impedância e o grau de homogeneidade das misturas de nanopartículas de rutilo e de anatase. Em particular, foi demonstrado o papel fundamental das propriedades de difusão de elétrons nos filmes mistos de TiO2 para o aumento da performance das DSCs. Os estudos de simulação dos espectros de impedância de filmes mistos não homogêneos de TiO2 comercial Aldrich mostraram que o coeficiente de difusão de elétrons desses materiais apresenta um máximo na região de 15% de rutilo e 85% anatase, coincidindo com o máximo de eficiência das DSCs de mesma composição. De fato, diferenças sutis nas contribuições da capacitância química e resistência de difusão foram responsáveis pelo aumento do coeficiente de difusão das DSCs baseadas em filmes mistos não homogêneos de TiO2. Por outro lado, quando foi aumentada a área de contato entre as nanopartículas de anatase e de rutilo, foi observado um aumento da capacitância química e tempo de vida dos elétrons nos filmes mistos homogêneos de TiO2. Estes foram atribuídos ao aumento da eficiência de transferência de elétrons entre os nanocristais de rutilo e de anatase, que diminuiram a recombinação de elétrons e promoveram a estabilização de cargas na banda de condução do TiO2. / The understanding of the detailed mechanism and processes that influence the performance of dye-sensitized solar cells (DSCs), particularly the influence of TiO2/dye, TiO2/electrolyte and rutile/anatase interfaces, thus contributing to increase the efficiency of that devices, is the main goal of this thesis. Accordingly, we investigated the influence of the electronic properties of the new dye [Ru(dcbpyH2)2(tmtH2)]Cl associated the MLCT and LMCT charge transfer transitions on the efficiency of photoinjection and solar energy photoconversion in DSCs. The species (Bu4N)3[Ru(dcbpy)2(tmtH2)], (Bu4N)4[Ru(dcbpy)2(tmtH)] and (Bu4N)5[Ru(dcbpy)2(tmt)] were isolated and used in DSCs, revealing the contributions of two MLCTs and a LMCT band for energy conversion by deconvolution of the photoaction spectra. Interestingly, these new ruthenium dyes presented overall efficiency normalized by the amount of dye adsorbed on TiO2 larger than for the N719 dye, indicating a potential for application as photosensitizers. The mechanism of the synergistic effect observed in blends of rutile and anatase was investigated studying the contributions of the recombination and electron diffusion processes in mesoporous mixed TiO2 films on the performance of DSCs, as a function of the distribution of those nanocrystals in different proportions, as confirmed by Raman microscopy (Confocal). The impedance of interfaces/junctions present in the DSCs was carefully characterized by electrochemical impedance spectroscopy (EIS) to determine key parameters such as chemical capacitance, diffusion resistance, recombination resistance, diffusion coefficient, lifetime and the electron diffusion length in mixed TiO2 films. The I x V characteristics, i.e. the overall efficiency parameter (η), density of short circuit current (Jsc), open-circuit voltage (Voc) and fill factor (FF) of solar cells were correlated with the impedance parameters and the degree of homogeneity of mixtures of rutile and anatase nanoparticles. In fact, the essential role of electron diffusion properties in the mixed TiO2 films on the performance of DSCs was demonstrated. Impedance studies of low homogeneity mixed films prepared with commercial TiO2 (Aldrich) by fitting the experimental spectra with a suitable equivalent circuit revealed that the electron diffusion coefficient of these materials exhibits a maximum at 15% rutile and 85% anatase, as expected based on the synergic effect in DSCs. In fact, subtle differences in the contributions of chemical capacitance and diffusion resistance were responsible for the increase of the electron diffusion coefficient in low homogeneity mixed TiO2 films. On the other hand, an increase in the anatase and rutile nanoparticles contact area reflected positively in the chemical capacitance and electron lifetime, as expected for an enhanced electron transfer efficiency between the rutile and anatase nanocrystals, thus decreasing the electron recombination and increasing the stability of the photoinjected charge on the TiO2 conduction band.

In the thesis we have shown that it is possible with current technology, to buildneighborhoods that are largely self-sufficient. We have obtained some information aboutongoing work in the field of energy efficient buildings and active house which we have usedto develop a model. The feasibility study for Ranagård we have e.g been forced tofollow laws on groundwater covered, resulting in the construction of basements for singlefamilyhome is not possible. The model that we have built up overtime has been the central part of the work. The model illustrates very well what an activehouse neighborhood means and potential of such an area. Important to note here is the resultwe finally arrived at only can be applied for Ranagård in Halmstad municipality as theconditions vary so much at the local/municipal level.

Les travaux de recherche menés dans cette thèse s’inscrivent dans le cadre de la réalisation de la technologie cellule solaire intégrée (i-Cell), qui est une technologie innovante de fabrication de cellules solaires à hauts rendements de conversion et à bas coût de production. L’i-Cell consiste en la réalisation de plusieurs cellules élémentaires ou sous-cellules, en feuilles minces de silicium cristallin purifié, qui sont connectées en série sur un substrat de Si fritté bas coût. La technologie i-Cell permet en effet la réduction du coût de la plaquette grâce à la faible épaisseur des feuilles de silicium et grâce à l’utilisation de substrats issus du frittage de poudres de silicium. Dans une telle structure la fonction photovoltaïque est assurée par la feuille mince de surface alors que le transport du courant et la fonction mécanique sont gérés par le substrat fritté ce quipermet de réduire les coûts de fabrication de la cellule. En effet, à l’instar des couches minces, on peut décomposer la couche active en cellules de faibles surfaces et ainsi produire sur une surface standard (156 x 156 mm²), une cellule dans laquelle circule un faible courant qui permet de réduire fortement la consommation des métaux précieux au sein de la cellule (Argent) et entre les cellules du module (Cuivre). En outre, la configuration des cellules à i-Cell permet de s’affranchir des busbars en Ag traditionnellement utilisés dans les technologies silicium. Ceci présente l’avantage d’éviter le masquage de la lumière et donc d'augmenter la puissance de la cellule. Ce travail de thèse s’articule sur deux axes de recherche principaux. Le premier est orienté sur l’étude de la cinétique d’oxydation thermique de substrats de silicium frittés poreux. Le deuxième axe concerne la réalisation du substrat fritté intégré et la réalisation des premiers prototypes d’i-Cells sur ces derniers. Ce travail a permis de démontrer la faisabilité de l’i-Cell et de réaliser des prototypes d’i-Cell sur le substrat fritté intégré. Des rendements de conversion PV supérieurs à 18% ont été ainsi obtenus. / The research work conducted in this thesis are within the framework of the realization of the integrated solar cell technology (i-Cell), which is an innovative solar cell technology with a high conversion efficiency and a low cost production. The i-Cell consists of the realization of several elementary cells or sub-cells, in purified crystalline silicon thin foils, which are connected in series on a low cost sintered silicon substrate. In fact, the i-Cell technology allows the reduction of the cost of the wafer thanks to the low thickness of the silicon foils and through the use of substrates obtained from the sintering silicon powders. In such a structure, the photovoltaic function is provided by the thin purified Si foil on the surface. Whereas both the current transport and the mechanical function are provided by the sintered silicon substrate – thin allows to reduce the cell manufacturing costs. In fact, just like thin films, we can decompose the active layer in small cell surfaces and thus produce, on a standard surface (156 x 156 mm²), a low current cell that greatly reduces the consumption of precious metals within the cell (Silver) and between the cells within the module (Copper). Furthermore, the configuration of cells in the i-Cell technology permits to eliminate the use of Silver busbars traditionally used in the Si solar cell technologies. This offers the advantage of avoiding the masking light and thus increases the power of the i-Cell. This thesis work focuses on two main axes of research: The first axis relates to the study of the kinetics of thermal oxidation of porous sintered silicon substrates. The second axis of research focuses on the realization of the “integrated sintered substrates”, which consists of the realization of local conductive zones on the insulating porous sintered substrate, and the fabrication of the first i-Cells prototypes on them. This work demonstrated the feasibility of i-Cell and produced prototypes of i-Cell on the integrated sintered substrate. High photovoltaic conversion efficiencies, greater than 18%, were obtained.

[pt] As células solares de junções múltiplas detém os atuais recordes mundiais de eficiência de conversão fotovoltaica. Uma dificuldade técnica que existe nestes dispositivos é que a corrente destes dispositivos é limitada pela menor dentre as geradas por cada uma das junções. No caso da célula solar de junção tripla de InGaP/InGaAs/Ge, a célula padrão para aplicações espaciais, a limitação é na célula intermediária. Existe uma proposta de uso de poços quânticos na junção para aumentar a corrente produzida pela célula intermediária, sendo assim, as outras junções pn que compõem a célula tripla precisam ser redesenhadas para que haja um casamento de corrente. O presente trabalho tem como objetivo apresentar um design otimizado para a célula solar de InGaP que é a junção pn do topo. O intuito é encontrar uma estrutura otimizada para o casamento de corrente através de simulações e fabricar a célula solar. As amostras foram crescidas em um reator de deposição epitaxial de metalorgânicos em fase de vapor e os dados utilizados no crescimento das camadas, a saber: espessura e dopagem, foram obtidos a partir das simulações realizadas. Para verificação da qualidade ótica, estrutural e elétrica das camadas crescidas, foram feitos experimentos de fotoluminescência, difração de raio-x e efeito Hall. São apresentadas curvas de resistividade obtidas pelo método da linha de transmissão, curva de corrente-tensão e eletroluminescência que dão um diagnóstico da qualidade do dispositivo produzido. / [en] Multi-junction solar cells hold the current world records of photovoltaic conversion efficiency. A technical difficulty that exists in these devices is that the current of these devices is limited by the smaller of those generated by each of the joints. In the case of the triple junction solar cell of InGaP / InGaAs / Ge, the standard cell for spatial applications, the limitation is on the intermediate cell. There is a proposal to use quantum wells at the junction to increase the current produced by the intermediate cell, so the other pn junctions that make up the triple cell need to be redesigned to have a current match. The present work aims to present an optimized design for the InGaP solar cell which is the top pn junction. The intention is to find an optimized structure for the current matching through simulations and fabricate the solar cell. The samples were grown in a vapor phase epitaxial deposition reactor and the data used in the growth of the layers, namely thickness and doping, were obtained from the simulations. To verify the optical, structural and electrical quality of the grown layers, photoluminescence, x-ray diffraction and Hall effect experiments were performed. Resistivity curves obtained by the transmission line method, current-voltage curve and electroluminescence are presented, which give a diagnosis of the quality of the device produced.

This dissertation describes our study on different physical properties of passivated and chemically modified hybrid metal halide perovskite materials and development of highly efficient charge transport layers for perovskite solar cells. We first developed an efficient electron transport layer via modification of titanium dioxide nanostructure followed by a unique chemical treatment in order to have clean interface with fast electron injection form the absorber layer in the perovskite solar cells. We then explored monovalent cation doping of lead halide perovskites using sodium, copper and silver with similar ionic radii to lead to enhance structural and optoelectronic properties leading to higher photovoltaic performance of the resulting perovskite solar cells. We also performed thorough experimental characterizations together with modeling to further understand the chemical distribution and local structure of perovskite films upon monovalent cation doping. Then, we demonstrate a novel passivation approach in alloyed perovskite films to inhibit the ion segregation and parasitic non-radiative losses, which are key barriers against the continuous bandgap tunability and potential for high-performance of metal halide perovskites in device applications, by decorating the surfaces and grain boundaries with potassium halides. This leads to luminescence quantum yields approaching unity while maintaining high charge mobilities along with the inhibition of transient photo-induced ion migration processes even in mixed halide perovskites that otherwise show bandgap instabilities. We demonstrate a wide range of bandgaps stabilized against photo-induced ion migration, leading to solar cell power conversion efficiencies of 21.6% for a 1.56 eV absorber and 18.3% for a 1.78 eV absorber ideally suited for tandem solar cells. We then systematically compare the optoelectronic properties and moisture stability of the two developed passivation routes for alloyed perovskites with rubidium and potassium where the latter passivation route showed higher stability and loading capacity leading to achieve substantially higher photoluminescence quantum yield. Finally, we explored the possibility of singlet exciton fission between low bandgap perovskites and tetracene as the triplet sensitizer finding no significant energy transfer between the two. We then used tetracene as an efficient dopant-free hole transport layer providing clean interfaces with perovskite layer leading to high photoluminescence yield (e.g. ~18%). To enhance the poor ohmic contact between tetracene and the metal electrode, we added capping layer of a second hole transport layer which is extrinsically doped leading to 21.5% power conversion efficiency for the subsequent solar cells and stabilised power output over 550 hours continuous illumination.

In this dissertation, we investigate two emerging strategies for enhancing the performance of organic photovoltaics. The first takes advantage of a process called singlet exciton fission, and the second embodies an exodus from the fullerene electron acceptors prominent in organic solar cells. Indeed, this versatile class of tunable small molecules are aptly termed nonfullerene acceptors. However, both strategies would benefit from a greater understanding of underlying principles. Singlet exciton fission is a photon-multiplying process in which a singlet exciton from a high-energy absorbed photon splits into two triplet excitons. The process could significantly reduce energy lost to heat in photovoltaic devices, but its mechanisms are still misunderstood. One model involves direct coupling between the singlet and triplet states, and another model involves an intermediate charge transfer state. Transient absorption spectroscopy allowed us to examine singlet fission in films of pentacene, fluorinated pentacene, and coevaporated blends of various mixing ratios. We directly observe an intermolecular charge transfer state during singlet fission in solid films of coevaporated pentacene and peruoropentacene, which supports the model of charge transfer state-mediated singlet fission. Furthermore, we successfully induced singlet fission in one blend by directly exciting the charge transfer state below the bandgap. We use various types of steady state and time-resolved spectroscopy to characterize two types of nonfullerene electron acceptors. The first type is a group of tetraazabenzodiuoranthene diimide (BFI) dimers and a BFI monomer. The BFI dimers were designed to have twisted, nonplanar 3-dimensional structures and have helped achieve power conversion efficiencies of over 8% in organic solar cells. The other type of nonfullerene acceptor is a calamitic small molecule, and we consider the BAF-4CN electron acceptor, which has also been used in a solar cell whose efficiency exceeded 8%. Spectroscopic studies give insight into the performances of these nonfullerene devices in relation to fullerene-derivative counterparts. We find that the nonfullerene blends suffer from more geminate charge recombination. However, despite this drawback, in some cases, slower rates of nongeminate recombination may lead to successful power conversion efficiencies in nonfullerene solar cells.

Nous étudions la possibilité de réaliser des cellules à base de diséléniure de cuivre, indium et gallium (CIGSe) à absorbeur ultra-mince, en réduisant l’épaisseur de la couche de CIGSe de 2500 nm jusqu’à 100 nm, tout en conservant un haut rendement de conversion.Grâce à l’utilisation d’outils de simulation numérique, nous étudions l’influence de la réduction d’épaisseur de l’absorbeur sur les paramètres photovoltaïques de la cellule. Une importante dégradation du rendement est observée, principalement attribuée à une réduction de la fraction de lumière absorbée par le CIGSe ainsi qu’à une collecte des porteurs de charge réduite dans les dispositifs ultraminces. Des solutions permettant de surmonter ces problèmes sont proposées et leur influence potentielle est numériquement simulée ; nous démontrons qu’une ingénierie de face avant (couche tampon alternative, couche anti-réfléchissante…) et de face arrière (contact arrière réfléchissant, diffusion de la lumière) sur une cellule CIGSe à absorbeur ultramince permet de potentiellement améliorer le rendement de la cellule solaire au niveau de celui d’une cellule à absorbeur référence (2.5 μm).Grâce à l’utilisation de techniques de gravure chimique sur des échantillons standards de CIGSe épais, nous réalisons des cellules solaires avec différentes épaisseurs d’absorbeurs, et nous étudions l’influence de l’épaisseur du CIGSe sur les paramètres photovoltaïques des cellules. Le comportement similaire aux simulations numériques.Une ingénierie du contact avant sur des cellules CIGSe à différentes épaisseurs est réalisée pour spécifiquement améliorer l’absorption dans la couche de CIGSe. Nous étudions l’influence d’une couche tampon alternative de ZnS, de la texturation de la fenêtre avant de ZnO:Al, et d’une couche anti-reflet sur la cellule solaire. D’importantes améliorations sont observées quelque soit l’épaisseur de la couche de CIGSe, ce qui permet d’obtenir des rendements de conversions supérieurs à ceux obtenus dans la configuration standard des dispositifs.Une ingénierie du contact arrière à basse température est également réalisée avec l’utilisation d’un procédé novateur combinant la gravure chimique du CIGSe avec un « lift-off » mécanique de la couche de CIGSe afin de la séparer du substrat de Molybdène. De nouveaux matériaux fortement réflecteur de lumière et précédemment incompatible avec le procédé de croissance du CIGSe sont utilisés comme contact arrière pour des cellules CIGSe ultra-minces. Une étude comparative en fonction de l’épaisseur de CIGSe entre des cellules avec contact arrière réfléchissant en Or (Au) et cellules solaires avec contact arrière standard Mo est effectuée. Le contact Au permet d’augmenter significativement le rendement de conversion des cellules solaires à absorbeur sub-microniques comparé au contact standard Mo avec un rendement de conversion supérieur à 10% obtenu sur une cellule CIGSe de 400 nm (comparé à 7.9% avec Mo).Afin de réduire encore plus l’épaisseur de la couche de CIGSe, jusque 100-200 nm, les modèles numériques montrent qu’il est nécessaire d’utiliser un réflecteur lambertien sur la face arrière de la cellule afin de maximiser l’absorption de la lumière. Un dispositif preuve de concept expérimental est réalisé avec une épaisseur de CIGSe de 200 nm et un réflecteur arrière lambertien, et ce dispositif est caractérisé par spectroscopie de transmission/réflexion. La réponse spectrale est déterminée en combinant des valeurs issues de simulation numérique et la mesure expérimental de l’absorption du dispositif. Nous calculons un courant de court circuit de 26 mA.cm-2 pour ce dispositif avec réflecteur lambertien, bien supérieur à ce qui est calculé pour la même structure sans réflecteur (15 mA.cm-2), et comparable au courant mesuré sur une cellule de référence de 2500 nm (28 mA.cm-2). L’utilisation de réflecteur lambertien pour des cellules CIGSe ultraminces est donc particulièrement adaptée pour maintenir de hauts rendements. / In this thesis, we investigate on the possibility to realize ultrathin absorber Copper Indium Gallium Di-Selenide (CIGSe) solar cells, by reducing the CIGSe thickness from 2500 nm down to 100 nm, while conserving a high conversion efficiency.Using numerical modeling, we first study the evolution of the photovoltaic parameters when reducing the absorber thickness. A strong decrease of the efficiency of the solar cell is observed, mainly related to a reduced light absorption and carrier collection for thin and ultrathin CIGSe solar cells. Solutions to overcome these problems are proposed and the potential improvements are modeled; we show that front side (buffer layer, antireflection coating) and back side (reflective back contact, light scattering) engineering of an ultrathin device can potentially increase the conversion efficiency up to the level of a standard thick CIGSe solar cell.By using chemical bromine etching on a standard thick CIGSe layer, we realize solar cells with different absorber thicknesses and experimentally study the influence of the absorber thickness on the photovoltaic parameters of the devices. Experiments show a similar trends to that observed in numerical modeling.Front contact engineering on thin CIGSe solar cell is realized to increase the specific absorption in CIGSe, including alternative ZnS buffer, front ZnO:Al window texturation and anti-reflection coating. Substantial improvements are observed whatever the CIGSe thickness, with efficiencies higher that the default configuration.A back contact engineering at low temperature is realized by using an innovative approach combining chemical etching of the CIGSe and mechanical lift-off of the CIGSe from the original Molybdenum (Mo) substrate. New highly reflective materials previously incompatible with the standard solar cell process are used as back contact for thin and ultrathin CIGSe solar cells, and a comparative study between standard Mo back contact and alternative reflective Au back contact solar cells is performed. The Au back reflector significantly enhance the efficiency of solar cell with sub-micrometer absorbers compared to the standard Mo back reflector; an efficiency higher than 10 % on a 400 nm CIGSe is obtained with Au back contact (7.9% with standard Mo back contact). For further reduction of the absorber thickness down to 100-200 nm, numerical modeling show that a lambertian back reflector is needed to fully absorb the incident light in the CIGSe. An experimental proof of concept device with a CIGSe thickness of 200 nm and a lambertian back reflector is realized and characterized by reflection/transmission spectroscopy, and the experimental spectral response is determined by combining simulation and experimentally measured absorption. A short circuit current of 26 mA.cm-2 is determined with the lambertian back reflector, which is much higher than what is obtained for the same device with no reflector (15 mA.cm-2), and comparable to the short circuit current measured on a reference 2500 nm thick CIGSe solar cell (28 mA.cm-2). Lambertian back reflectors are therefore found to be the most effective way to enhance the efficiency of an ultrathin CIGSe solar cell up to the level of a reference thick CIGSe solar cell.

Le contexte actuel de forte croissance des besoins en énergie dans le monde nécessite une diversification de sa production, notamment vers des sources renouvelables tout en limitant autant qu’il est possible l’émission de gaz à effet de serre. Parmi les énergies renouvelables une des plus prometteuses et abondantes est l’énergie solaire et il apparaît évident que l’énergie solaire, thermique ou photovoltaïque, représente un enjeu crucial pour diminuer la consommation d’énergie fossile. Actuellement 90 % des générateurs solaires sont élaborés en silicium cristallin, ce qui pose un problème d’approvisionnement en matière première, les producteurs de silicium n’ayant pas su anticiper la forte expansion de la filière solaire. Des concepts innovants présentent une forte potentialité en termes de coût de production et d’application, notamment les filières organiques et hybrides (organique/oxyde métallique). En Europe, la France est très active dans ce domaine de recherche, en particulier en ce qui concerne l’utilisation de nouveaux matériaux nanostructurés organiques ou de structures hybrides. C'est pourquoi Disasolar, une start-up française spécialisée dans le photovoltaïque souple, souhaite développer cette activité en élaborant des modules solaires souples par impression jet d'encre. Les objectifs de cette thèse sont d'étudier des nouveaux matériaux d'interface imprimables et d'évaluer l'effet de la dimension des nanoparticules sur la topologie et les performances des dispositifs. Et dans un deuxième temps l'étude portera sur l'impression des matériaux d'interface et la stabilité des cellules solaires organiques. / The current context of strong growth in energy demands in the world requires diversification of its production, in particular towards renewable sources while limiting as far as possible the emission of greenhouse gases. Among the most promising and abundant renewable energies is solar energy and it is evident that solar, thermal or photovoltaic energy represents a crucial issue to reduce the consumption of fossil energy. Currently 90% of the solar generators are made of crystalline silicon, which poses a problem of supply of raw material, as silicon producers did not know how to anticipate the strong expansion of the solar sector. Innovative concepts present a high potential in terms of cost of production and application, in particular organic and hybrid (organic / metal oxide) dies. In Europe, France is very active in this area of research, particularly with regard to the use of new organic nanostructured materials or hybrid structures. This is why Disasolar, a French start-up specializing in flexible photovoltaics, wants to develop this activity by developing flexible solar modules by inkjet printing. The objectives of this thesis are to study new printable interface materials and to evaluate the effect of nanoparticle size on the topology and performance of devices. And secondly, the study will focus on the printing of interface materials and the stability of organic solar cells.