Structure-property and film formation mechanism in PEDOT:PSS based and perovskites systems

Energy harvesting is not only a dream of human beings, but also a real demand from modern society. This thesis aims to reveal the structure-property relationship of two materials promising for energy applications: PEDOT:PSS based organic films for thermoelectric (TE) generator and tin based perovskites for solar cell. Together with knowledge on the film formation and reformation process probed by in situ grazing incidence wide angle X-ray scattering (GIWAXS), the importance of the quality of the PEDOT crystal packing rather than the overall degree of crystallinity as a key factor to reach improved electrical conductivity is highlighted. The nature of the treatment agents is found to play a critical role for engineering the TE properties due to their different interactions with the polymeric films (with PSS or with both PEDOT and PSS, strong interaction or weak interaction). A new method for preparing PEDOT:PSS-nanoparticles hybrid system is also presented. The deposited nanoparticles interact with PSS on the topmost region of the film and lead to a significantly improved properties. Beside of these, the structure and formation mechanism during spin coating of environmental friendly tin based Ruddlesden-Popper perovskites are also unveiled. The function of 2D component is found to be an inhibitor for bulk crystallization during the film formation and thus leads to better orientation. In summary, the results contained in this thesis highlight the importance of structural studies at the nanoscale and often in situ during processing to explain the alteration of the electrical and photovoltaic properties of the materials

Role of the Processing Solvent on the Electrical Conductivity of PEDOT:PSS

Poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) is one of the most studied conductive polymers, holding great potential in many applications such as thermoelectric generators, solar cells, and memristors. Great efforts have been invested in trying to improve its mechanical and electrical properties and to elucidate the structure-property relationship. In this work, a systematic and quantitative study of the effect of solvent polarity and solution processing on the film structure and conductivity is presented. By using grazing-incidence wide-angle X-ray scattering (GIWAXS) together with atomic force microscopy (AFM), the importance of the quality of the PEDOT crystal packing is highlighted as a key factor to reach improved electrical conductivity, rather than the overall degree of crystallinity. Moreover, the (re)structuring mechanisms occurring during the film formation and film exposure processes are also studied by in situ GIWAXS. Different intermediate precursor stages and different pathways to reach improved crystallinity are reported depending on the used solvent. The structural results are interpreted looking at the solvent nature and the PSS/solvent affinity. With this contribution, a guidance is hoped to be given not only on how to improve the PEDOT:PSS electrical conductivity, but also on how to tune the film structural or electrical property for different applications

Boosting the Thermoelectric Properties of PEDOT:PSS via Low-Impact Deposition of Tin Oxide Nanoparticles

Poly(3,4-ethylenedioxy thiophene):poly(styrenesulfonate) (PEDOT:PSS) exhibits valuable characteristics concerning stability, green-processing, flexibility, high electrical conductivity, and ease of property modulation, qualifying it as one of the most promising p-type organic conductors for thermoelectric (TE) applications. While blending with inorganic counterparts is considered a good strategy to further improve polymeric TE properties, only a few attempts succeed so far due to inhomogeneous embedding and the non-ideal organic-inorganic contact. Here a new strategy to include nanoparticles (NPs) without any ligand termination inside PEDOT:PSS thin films is proposed. Spark discharge-generated tin oxide NPs (SnOx-NPs) are "gently" and homogenously deposited through low-energy diffusion mode. Strong interaction between naked SnOx-NPs and PSS chains occurs in the topmost layer, causing a structural reorganization towards an improved PEDOT chains crystalline packing at the bottom, providing a positive contribution to the electrical conductivity. Meanwhile, dedoping and energy filtering effect introduced by the SnOx-NPs cause dramatic Seebeck coefficient enhancement. The optimized power factor of 116 mu Wm(-1) K-2 achieved is more than six times higher than the value found for the film without NPs. This easy and efficient strategy promises well for future mass production of flexible TE devices and the mechanism revealed may inspire future research on TEs and flexible electronics

Cost-Efficient Millimeter Wave Base Station Deployment in Manhattan-Type Geometry

This work is licensed under a Creative Commons Attribution 4.0 International License.Urban millimeter wave (mmWave) communications are limited by link outage due to frequent blockages by obstacles. One approach to this problem is to increase the density of base stations (BSs) to achieve macro diversity gains. Dense BS deployment, however, incurs the increased BS installation cost as well as power consumption. In this work, we propose a framework for connectivity-constrained minimum cost mmWave BS deployment in Manhattan-type geometry (MTG). A closed-form expression of network connectivity is characterized as a function of various factors such as obstacle sizes, BS transmit power, and the densities of obstacles and BSs. Optimization that attains the minimum cost is made possible by incorporating a tight lower bound of the analyzed connectivity expression. A low-complexity algorithm is devised to effectively find an optimal tradeoff between the BS density and transmit power that results in the minimum BS deployment cost while guaranteeing network connectivity. Numerical simulations corroborate our analysis and quantify the best tradeoff of the BS density and transmit power. The proposed BS deployment strategies are evaluated in different network cost configurations, providing useful insights in mmWave network planning and dimensioning

Engineering the Thermoelectrical Properties of PEDOT:PSS by Alkali Metal Ion Effect

Engineering the electrical properties of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) holds great potential for various applications such as sensors, thermoelectric (TE) generators, and hole transport layers in solar cells. Various strategies have been applied to achieve optimal electrical properties, including base solution post-treatments. However, the working mechanism and the exact details of the structural transformations induced by base post-treatments are still unclear. In this work, we present a comparative study on the post-treatment effects of using three common and green alkali base solutions: namely LiOH, NaOH, and KOH. The structural modifications induced in the film by the base post-treatments are studied by techniques including atomic force microscopy, grazing-incidence wide-angle X-ray scattering, ultraviolet–visible–near-infrared spectroscopy, and attenuated total reflectance Fourier-transform infrared spectroscopy. Base-induced structural modifications are responsible for an improvement in the TE power factor of the films, which depends on the basic solution used. The results are explained on the basis of the different affinity between the alkali cations and the PSS chains, which determines PEDOT dedoping. The results presented here shed light on the structural reorganization occurring in PEDOT:PSS when exposed to high-pH solutions and may serve as inspiration to create future pH-/ion-responsive devices for various applications

Scalable, Template Driven Formation of Highly Crystalline Lead-Tin Halide Perovskite Films

Low bandgap lead-tin halide perovskites are predicted to be candidates to maximize the performance of single junction and tandem solar cells based on metal halide perovskites. In spite of the tremendous progress in lab-scale device efficiency, devices fabricated with scalable techniques fail to reach the same efficiencies, which hinder their potential industrialization. Herein, a method is proposed that involves a template of a 2D perovskite deposited with a scalable technique (blade coating), which is then converted in situ to form a highly crystalline 3D lead-tin perovskite. These templated grown films are alloyed with stoichiometric ratio and are highly oriented with the (l00) planes aligning parallel to the substrate. The low surface/volume ratio of the obtained single-crystal-like films contributes to their enhanced stability in different environments. Finally, the converted films are demonstrated as active layer for solar cells, opening up the opportunity to develop this scalable technique for the growth of highly crystalline hybrid halide perovskites for photovoltaic devices

Development of an Aptamer-Conjugated Polyrotaxane-Based Biodegradable Magnetic Resonance Contrast Agent for Tumor-Targeted Imaging

Gadolinium-based magnetic resonance imaging (MRI) contrast agents with biodegradability, biosafety, and high efficiency are highly desirable for tumor diagnosis. Herein, a biodegradable, AS1411-conjugated, α-cyclodextrin polyrotaxane-based MRI contrast agent (AS1411-G2­(DTPA-Gd)-SS-PR) was developed for targeted imaging of cancer. The polyrotaxane-based contrast agent was achieved by the complexation of α-cyclodextrin (α-CD) and a linear poly­(ethylene glycol) (PEG) chain containing disulfide linkages at two terminals. The disulfides enable the dethreading of the polyrotaxane into excretable small units due to cleavage of the disulfide linkages by reducing agents such as intracellular glutathione (GSH). Furthermore, the second-generation lysine dendron conjugated with gadolinium chelates and AS1411, a G-quadruplex oligonucleotide that has high binding affinity to nucleolin generally presenting a high level on the surface of tumor cells, coupled to the α-CD via click chemistry. The longitudinal relaxivity of AS1411-G2­(DTPA-Gd)-SS-PR (11.7 mM–1 s–1) was two times higher than the clinically used Gd-DTPA (4.16 mM–1 s–1) at 0.5 T. The in vitro degradability was confirmed by incubating with 10 mM 1,4-dithiothreitol (DTT). Additionally, the cytotoxicity, histological assessment, and gadolinium retention studies showed that the prepared polyrotaxane-based contrast agent had a superior biocompatibility and was predominantly cleared renally without long-term accumulation toxicity. Importantly, AS1411-G2­(DTPA-Gd)-SS-PR displayed the enhanced performance in MRI of breast cancer cells in vitro as well as a subcutaneous breast tumor in vivo due to the targeting ability of the AS1411 aptamer. The enhanced performance was due to efficient multivalent interactions with tumor cells, producing faster accumulation and longer contrast imaging time at the tumor site. This work clearly confirms that the specially designed and fabricated α-CD-based polyrotaxane is a promising contrast agent with an excellent contrast imaging performance and biosafety for tumor MR imaging

Field-Effect Transistors Based on Formamidinium Tin Triiodide Perovskite

To date, there are no reports of 3D tin perovskite being used as a semiconducting channel in field-effect transistors (FETs). This is probably due to the large amount of trap states and high p-doping typical of this material. Here, the first top-gate bottom-contact FET using formamidinium tin triiodide perovskite films is reported as a semiconducting channel. These FET devices show a hole mobility of up to 0.21 cm(2) V-1 s(-1), an I-ON/OFF ratio of 10(4), and a relatively small threshold voltage (V-TH) of 2.8 V. Besides the device geometry, the key factor explaining this performance is the reduced doping level of the active layer. In fact, by adding a small amount of the 2D material in the 3D tin perovskite, the crystallinity of FASnI(3) is enhanced, and the trap density and hole carrier density are reduced by one order of magnitude. Importantly, these transistors show enhanced parameters after 20 months of storage in a N-2 atmosphere

Influence of the stoichiometry of tin-based 2D/3D perovskite active layers on solar cell performance

2D/3D mixed tin perovskites have the advantages of high crystallinity and preferential orientation compared to pure 3D tin perovskite. However, solar cells based on 2D/3D mixed tin perovskites are still limited by low power conversion efficiency (PCE) when compared to their lead-based counterparts. It is essential to gain deeper insight into the factors that limit the performance of these solar cells in order to further improve them. In this work, we demonstrate that the starting stoichiometry of 2D/3D (PEA(0.08)FA(x)SnI(3)) tin perovskite films influences their crystallization and photophysical properties as well as the solar cell performance. The reference 2D/3D film (x = 0.92, where x refers to the stoichiometry of the precursors) is highly crystalline with the 3D phase preferentially oriented and a small amount of 2D phase located at the bottom of the film. The reference solar cell delivers a PCE of about 8.0%. 2D/3D films with even higher FA concentration (x > 1.0) mainly consist of poorly crystalline and randomly oriented 3D phases, with much higher trap density compared to the reference film. The corresponding solar cells therefore suffer from severe trap-assisted charge recombination, and deliver a poor PCE o

Impact of the Hole Transport Layer on the Charge Extraction of Ruddlesden-Popper Perovskite Solar Cells

Recent works demonstrate that polyelectrolytes as a hole transport layer (HTL) offers superior performance in Ruddlesden-Popper perovskite solar cells (RPPSCs) compared to poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS). The factors contributing to such improvement need to be systematically investigated. To achieve this, we have systematically investigated how the two HTLs affect the morphology, crystallinity, and orientation of the Ruddlesden-Popper perovskite (RPP) films as well as the charge extraction of the RPPSCs. PEDOT:PSS as a HTL leads to RPP films of low crystallinity and with a number of large pinholes. These factors lead to poor charge carrier extraction and significant charge recombination in the RPPSCs. Conversely, a PCP-Na HTL gives rise to highly crystalline and pinhole-free RPPSC films. Moreover, a PCP-Na HTL provides a better energy alignment at the perovskite/HTL interface because of its higher work function compared to PEDOT:PSS. Consequently, devices using PCP-Na as HTLs are more efficient in extracting charge carriers