Organic solar cells using carbon based materials have the potential to deliver cheap solar electricity. The aim is to be able to produce solar cells with common printing techniques on flexible substrates, and as organic materials can be made soluble in various solvents, they are well adapted to such techniques. There is a large variation of organic materials produced for solar cells, both small molecules and polymers. Alterations of the molecular structure induce changes of the electrical and optical properties, such as band gap, mobility and light absorption. During the development of organic solar cells, the step of mixing of an electron donor and an electron acceptor caused a leap in power conversion efficiency improvement, due to an enhanced exciton dissociation rate. Top performing organic solar cells now exhibit a power conversion efficiency of over 10%. Currently, a mix of a conjugated polymer, or smaller molecule, and a fullerene derivative are commonly used as electron donor and acceptor. Here, the blend morphology plays an important role. Excitons formed in either of the donor or acceptor phase need to diffuse to the vicinity of the donor-acceptor interface to efficiently dissociate. Exciton diffusion lengths in organic materials are usually in the order of 5-10 nm, so the phases should not be much larger than this, for good exciton quenching. These charges must also be extracted, which implies that a network connected to the electrodes is needed. Consequently, a balance of these demands is important for the production of efficient organic solar cells. Morphology has been found to have a significant impact on the solar cell behaviour and has thus been widely studied. The aim of this work has been to visualize the morphology of active layers of organic solar cells in three dimensions by the use of electron tomography. The technique has been applied to materials consisting of conjugated polymers blended with fullerene derivatives. Though the contrast in these blends is poor, three-dimensional reconstructions have been produced, showing the phase formation in three dimensions at the scale of a few nanometres. Several material systems have been investigated and preparation techniques compared. Even if excitons are readily dissociated and paths for charge extraction exist, the low charge mobilities of many materials put a limit on film thickness. Although more light could be absorbed by increased film thickness, performance is hampered due to increased charge recombination. A large amount of light is thus reflected and not used for energy conversion. Much work has been put into increasing the light absorption without hampering the solar cell performance. Aside from improved material properties, various light trapping techniques have been studied. The aim is here to increase the optical path length in the active layer, and in this way improve the absorption without enhanced extinction coefficient. At much larger dimensions, light trapping in solar cells with folded configuration has been studied by the use of optical modelling. An advantage of these V-cells is that two materials with complementing optical properties may be used together to form a tandem solar cell, which may be connected in either serial or parallel configuration, with maintained light trapping feature. In this work optical absorption in V-cells has been modelled and compared to that of planar ones.

Two of the main technological challenges of the century are the production of clean energy, on the one hand, and the development of new materials for electronic and spintronic applications that could increase the speed and the storage capacity of regular electronic devices, on the other hand. Organic materials, including fullerenes, organic polymers and organic molecules with metal centres are promising candidates for low-cost, flexible and clean technologies that can address these challenges. A thorough description of the electronic properties of such materials is, therefore, crucial. The interaction of electromagnetic radiation with the molecule can provide the needed insight into the electronic and vibrational levels and on possible chemical interactions. In order to explain and interpret experimentally measured spectra, a good theoretical description of the particular spectroscopy is necessary. Within density functional theory (DFT), the current thesis discusses the theoretical tools used to describe the spectroscopic properties of molecules with emphasis on two classes of organic materials for photovoltaics, molecular electronics and spintronics. Specifically, the stability of the fullerene derivative PC60BM is investigated in connection with its use as an electron acceptor in organic solar cells and the valence band electronic structure of several transition metal phthalocyanines is studied for their possible application in electronics and spintronics. The spectroscopies discussed in the current work are: the photoelectron spectroscopy of the valence band, X-ray photoelectron spectroscopy of the core levels, near-edge X-ray absorption fine structure, Infrared and Raman vibrational spectroscopies

The development of organic photovoltaics (OPVs) has attracted a lot of attention due to their potential to create a low cost flexible solar cell platform. In general, an OPV is comprised of a number of layers of thin films that include the electrodes, active layers and barrier films. Thus, with all of the interfaces within OPV devices, the potential for failure exists in numerous locations if adhesion at the interface between layers is inherently low or if a loss of adhesion due to device aging is encountered. To date, few studies have focused on the basic properties of adhesion in organic photovoltaics and its implications on device reliability. In this dissertation, we investigated the adhesion between interfaces for a model multilayer barrier film (SiNx/PMMA) used to encapsulate OPVs. The barrier films were manufactured using plasma enhanced chemical vapor deposition (PECVD) and the interfacial fracture toughness (Gc, J/m2) between the SiNx and PMMA were quantified. The fundamentals of the adhesion at these interfaces and methods to increase the adhesion were investigated. In addition, we investigated the adhesive/cohesive behavior of inverted OPVs with different electrode materials and interface treatments. Inverted OPVs were fabricated incorporating different interface modification techniques to understand their impact on adhesion determined through the interfacial fracture toughness (Gc, J/m2). Overall, the goal of this study is to quantify the adhesion at typical interfaces used in inverted OPVs and barrier films, to understand methods that influence the adhesion, and to determine methods to improve the adhesion for the long term mechanical reliability of OPV devices.

My research on metal oxide electron-harvesting interlayers for organic solar cells was focused as three interrelated projects in this dissertation: i) development of a chemical vapor deposition (CVD) system for titanium dioxide (TiO₂) film; ii) an electrochemical methodology to evaluate ZnO thin film charge (hole) blocking ability; iii) the effects of plasma modifications on sol-gel ZnO and sol-gel ZnO/organic (active layer) interfaces. In i), we showed that nanoscale (12-36 nm) CVD TiO₂ film deposited at 210 °C from our system obtains properties of conformal growth with ITO substrate, superior hole blocking ability, stoichiometric metal to oxide ratio, and close energetic alignment with electron acceptors, e.g., fullerenes. The introduction of CVD TiO₂ film as an electron transport layer (ETL) into organic solar cell significantly improves its J-V characteristics compared to bare ITO electrode. The optimum TiO₂ thickness in the OPV device applications was found to be 24 nm with a high fill factor (0.58) and power conversion efficiency (3.7%) obtained. In ii), simple electrochemical methods, i.e., cyclic voltammetry, impedance spectroscopy have been used to evaluate sol-gel derived ZnO (sg-ZnO) and sputtered ZnO (sp-ZnO) porosity and pinhole density. We showed that sg-ZnO with high surface area porous structure allows the probe molecules and poly-thiophene (P3HT) thin layer to direct contact ITO substrate, whereas sp-ZnO with dense structural property efficiently eliminates the probe molecule diffusion and the penetration of P3HT layer to ITO substrate. This electrochemical property difference also directly reflects on the device shunt resistance (Rp), where we observed larger leakage current for the devices using sg-ZnO than that of devices using sp-ZnO. We envision these simple electrochemical characterizations can be applied into other similar metal oxide interlayers as well as on flexible TCO substrates, in which pinholes and physical imperfections, e.g., cracking may occur after multiple bending processes. In iii), we demonstrated low power (10.5 watts) radio frequency (RF) O₂ and Ar plasma treatments have significant impacts on sg-ZnO near-surface chemical compositions, which in turn influence the onset potential of sg-ZnO electron injection from the underlying ITO substrate and its energetic alignment with electron acceptors, e.g., C₆₀. Using UPS, we found the presence of localized mid-gap states near the Fermi-level (Ef) of sg-ZnO, which induces the most favorable band bending and the largest vacuum level shift due to significant electron transfer from sg-ZnO to C₆₀. As a result, the resultant solar cells show the best device performance. Upon the plasma treatments, the passivation effects eliminate the mid-gap state. Therefore, we observed less degree of band bending at ZnO/C₆₀ interface and poorer device performance for the plasma treated sg-ZnO. The study demonstrates the importance of oxide/organics interface in operations of organic solar cells and provides a modification method to tune surface properties of oxide materials which can apparently be applied in other organic electronic devices, e.g., field effect transistors (FETs), organic light emitting diodes (OLEDs), etc.

Easy manufacturing, light weight and inexpensive materials are the key qualities of organic solar cells that makes them a highly researched area. To make organic solar cells adequate for the market, the efficiency of power conversion has to increase further, and the lifetime of organic solar cells has to improve. Avoiding recombination losses is a piece in the puzzle that can make organic solar cells more efficient. Organic solar cells with two different hole transport layers were therefore examined by I-V measurements. It was found that the organic solar cell with MoO3 as the HTL possesses a higher current density in both the reverse region and forward region. The higher current density in both regions points towards a less successful blocking of electrons travelling to the anode (reverse region) and a better ability to transport holes from the active layer to the anode. Insight to different state of recombination was also found from the slope values in the Voc and Jsc as a function of light intensity plots. It was concluded that both solar cells experience a dominant monomolecular recombination under short circuit condition and evolved into bimolecular recombination under open circuit condition. However, the cell with CuSCN showed a more dominant bimolecular recombination, which was shown from a slope closer to one unity kT/q in the Voc as a function of light intensity plot.

As one of the most promising solar cell technologies, organic solar cells have unique superiorities distinct from inorganic counterparts, such as semitransparency, flexibility and solution-processability, as well as tunable photophysical properties, which originate from the structural verstailities of organic semiconductors. A major breakthrough in OSCs was the exploration of novel non-fullerene electron acceptor (NFAs): In comparison with traditional fullerene derivative acceptors, NFA possesses several advantages, such as low synthesis cost, tunable absorption range and adjustable energetic level, which effectively provides a wide light-harvesting window with low energetic loss. In recent decades, fused-ring electron acceptors (FREAs) have obtained an irreplaceable status in the development of OSCs. However, there are still initial drawbacks to FREA-based devices including: 1: the degree of molecular packing and the corresponding impact on device performance, which has not been studied in depth; 2: the feasibility of approaches for controlling the bulk heterojunction morphology of the film, which also has not been systemic researched; 3: the presence of bulk (geminate and non-geminate) and surface recombination which significantly affects the efficiency and stability of working devices. In this thesis, I took the above three issues as my main doctoral research subjects. In the first part of the thesis, I shine light onto the strength of π-conjugated backbones in FREA molecular structures, which strongly affect the intramolecular interaction. Herein, two FREA with different conjugated framework (IDT core vs IDTT core) are synthesized and employed as electron acceptors in OSCs. A significantly enhanced power conversion efficiency of 11.2% is obtained from IDTTIC-based devices in comparison with that of IDTIC-based devices (5.6%). After considering the electron-donating part in FREA molecules, I also study the effect of the terminal unit, which has a strong relationship with the intramolecular charge transfer effect and intermolecular interactions. Solvent additives are another powerful strategy to further improve the photovoltaic efficiency. 1-chloronaphthalene (CN) was found to be useful in the PTB7-Th:IEICO-4F system, which show a PCE improvement from 9.5% to 12.8%. Furthermore, by utilizing a small molecule donor, BIT-4F-T, as a third component, an optimum PCE of 14.0% is achieved in the devices based on PTB7-Th:IEICO-4F.

Abstract: Even though improvements in the efficiency of organic solar cells encouraged the commercialization of this technology in the past two decades, the stability of organic solar cells is still an active area of research. The effect of photo-oxidative degradation on the performance of organic solar cell devices is significant. One way to lower the rate of photooxidation degradation is by preventing oxygen molecules from reaching the active layer of organic solar cells. This could be achieved by fabricating the devices in an inert environment in the absence of oxygen. Once the devices are fabricated, they would be encapsulated in a transparent material.1, 2 Even though this is a viable solution, there are two main issues. First, it was shown that oxygen molecules could diffuse through the encapsulating material and degrade the devices.3 Second, implementing this solution would increase the fabrication cost of these devices, which would make this solution commercially unfeasible compared to other solar cell technologies.3 Speller and his colleges reported a possible mechanism of the photo-oxidative degradation and showed a relationship between the rate of degradation and LUMO energy levels of electron acceptor molecule4. In this thesis, we report the photo-oxidative degradation rate of O-IDTBR and O-IDTBR-(C3N2)2. The later electron acceptor is analogous to O-IDTBR with deeper LUMO by 0.1 eV. After four hours of constant irradiation from a 1-sun intensity xenon solar simulator, the maximum UV-Vis absorbance of O-IDTBR is reduced by 12% relative to O-IDTBR-(C3N2)2. Lower absolute degradation rates were observed when 1-sun LED solar simulator was used compare to xenon solar simulator.

No description available.

This thesis discusses two different photovoltaic systems, organic solar cells, and photonic power converters. The open-source software package Solcore was used to simulate and analyze optoelectronic properties of both systems. It is widely accepted that the transition from a fossil-fuel driven economy is necessary in the coming future. Organic solar cells are an alternative energy generation method with potential for fast energetic and economic payback periods. Bulk heterojunction organic solar cells are a common design, as they have particularly low manufacturing costs due to a simple device architecture. In this work, two bulk heterojunction blends are experimentally assessed using the acceptor molecule silicon phthalocyanine (bis(tri-n-butyl silyl oxide) silicon phthalocyanine ((3BS)2-SiPc) as a potential low-cost non-fullerene alternative to the typical acceptor [6,6]-phenyl-C61-butyric acid methyl ester (PC₆₁BM). These acceptors are compared within blends with the typical donor compound poly(3-hexylthiophene) (P3HT), and also poly[(2,6-(4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)-benzo [1,2-b:4,5-b’]dithiophene))-alt-(5,5-(1′,3′-di-2- thienyl-5′,7′-bis(2-ethylhexyl)benzo[1′,2′-c:4′,5′-c’]dithiophene-4,8-dione)] (PBDB-T). Device performance was assessed under standard conditions, increased angles of incidence, and reduced light intensities. Devices with the P3HT:(3BS)2-SiPc blend achieved a power conversion efficiency (PCE) of 3.6%, which outperformed P3HT:PC₆₁BM devices with a PCE of 3.0% due to a higher open-circuit voltage (VOC) of 0.76 V as opposed to 0.53 V. The PBDB-T:(3BS)2-SiPc achieved a high VOC of 1.09 V, but had a lower PCE of 3.4% in relation to the PBDB-T:PC₆₁BM device with a PCE of 6.4% and a VOC of 0.78 V. Photonic power converters are devices in optical networks that allow for optical power transmission rather than the conventional method of electrical power transmission. This provides benefits such as electrical isolation and resistance to electromagnetic interference, along with the ability to propagate along the same cable as data. These power converters are used to convert optical power to electrical power, and operate similarly to a solar cell with a narrow bandwidth. Multijunction designs are often used for increased operating voltage and efficiency. In such designs employing a vertical architecture, the bottom-most junction has the largest thickness along with the lowest efficiency due to increased recombination losses. To improve this lower efficiency, light trapping techniques can be employed to decrease the junction thickness while retaining the optical thickness. In this work, a current-matched 5- junction GaAs photonic power converter was simulated with both metallic and distributed Bragg reflectors at the rear of the device. These reflectors allowed for the thinning of the bottommost junction, which resulted in an increase in efficiency and overall power output of the power converter.

The state-of-the-art organic solar cells (OSC) use bulk heterojunction (BHJ) blend architecture in the photo-active layer. The BHJ is formed by finely mixing polymer donor and small molecule acceptor, which was predominantly fullerene derivatives until the last five years. However, the emergence of non-fullerene acceptor (NFA) materials has been the viable alternative to overcome high synthetic costs, limited optical absorption, and poor bandgap tunability of fullerene-based acceptors. These unique properties of NFA has resulted in a rapid improvement of OSC efficiency and opened doors for wide variety of applications including building integrated photovoltaics, green houses and agrivoltaics. Despite these advantages, the shorter device lifetime under light and heat is a major concern for their commercialization. This dissertation is focused on improving poor photo- and thermal stability of high efficiency OSC based on the widely used NFA, ITIC and Y-series derivatives. The light-induced changes in the acceptor molecular structure and the active layer nanostructure results in the photo-induced traps in photo-aged devices. The selective addition of third component to the active layer impedes the changes in the active layer nanostructure and suppress trap formation. Under constant thermal stress, the growth of acceptor crystals results increases the trap-assisted recombination in thermally aged devices. Similar to photo-stability the selective addition of third or more component/s arrests the crystal growth by minimizing the Gibbs free energy. The results suggest that the fabricated hexanary and ternary OSC display a superior thermal stability than the respective binary devices. In addition, the hexanary devices displayed thickness independent thermal stability, which is essential for the active layer thermal stability printed via high throughput techniques.