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Junction Based Gallium Nitride Power DevicesMa, Yunwei 05 September 2023 (has links)
Power electronics plays an important role in many energy conversion applications in modern society including consumer electronics, data centers, electric vehicles, and power grids, etc. The key components of power electronic circuits are power semiconductor devices including diodes and transistors, which determine the performance of power electronics circuits. Traditional power devices are based on the semiconductor silicon (Si), which have already reached the silicon's material limit. Gallium nitride (GaN) is a wide bandgap semiconductor with high electron mobility and high critical electric field. GaN-based power devices promise superior device performance over the Si-based counterpart.
The primary design target of a unipolar power device is to achieve low on-resistance and high breakdown voltage. Although GaN high electron mobility transistor (HEMT) is commercially available in a voltage class from 15 V to 900 V, the performance of GaN devices is still far below the GaN material limit, due to several reasons: 1) To achieve the normally-off operation in a GaN HEMT, the density of two-dimensional electron gas (2DEG) channel cannot be too high; this limits the on-resistance reduction in the access region. 2) The gate capacitance of GaN HEMT is usually low so that the carrier concentration in the channel underneath the gate is relatively low, limiting the on-resistance reduction in the gated channel region. 3) The electric-field distribution in the drift region is not uniform, resulting in a limited breakdown voltage. We proposed to use the junction-based structure in GaN power devices to address the above problems and fully exploit GaN's material properties.
The first part of this dissertation characterizes nickel oxide (NiO) as a p-type material to construct the junction-based GaN power devices. Although the homogenous p-GaN/n-GaN junction is preferred in many devices, the selective-area, p-GaN regrowth can lead to excessive leakage current; in comparison, the p-NiO/n-GaN junction is stable without leakage. This section describes the optimization of NiO deposition as well as the NiO characterization. Although acceptor in NiO is not generated by impurity doping, the acceptor concentration modulation is realized by tuning the O2 partial pressure during the sputtering process. Practical breakdown electric field is also characterized and confirmed to be higher than GaN. These results provide the design guidelines for NiO-GaN junction-based power devices.
The second part of this dissertation demonstrates the 3D NiO-GaN junction gate to improve the GaN HEMT's on-resistance. The 3D junction gate structure enables a high carrier concentration under the gate region in the device on-state. Meanwhile, the strong depletion effect of the junction-based gate allows for a robust normally-off operation; as a result, the GaN wafer with a higher 2DEG concentration can be used to achieve both normally-off and low on-state resistance in HEMT devices. Simulation is also performed to project the performance space of trigate GaN junction HEMTs using the p-GaN instead of NiO.
The third part of this dissertation presents the application of the p-GaN/n-GaN junction in the drift region of the multi-channel lateral devices to achieve the high breakdown voltage. Here p-GaN is grown in-situ with the multi-channel AlGaN/GaN structure, and there is no leakage problem. The structure is designed to achieve charge balance between the acceptor in p-GaN and the net donor in the multichannel AlGaN/GaN. This design enables a uniform electric field distribution and breakdown voltage over 10 kV.
The fourth part of this dissertation presents the application of the p-NiO/n-GaN junction in vertical superjunction (SJ) devices. We show the design and simulation of this heterojunction structure in a SJ and confirm the uniform electric field and high breakdown voltage under the charge balance. Then the device fabrication is presented in detail, which mainly comprises the deep GaN trench etch, NiO self-aligned lift off, and photoresist trench planarization. The optimized device shows a trade-off between its drift region specific on-resistance versus breakdown that exceeds the 1D GaN's limit.
The last part of this dissertation is exploring the design and fabrication of p-GaN/n-GaN based SJ devices. First, the challenges in p-GaN regrowth especially the introduction of interface impurities are discussed, followed by device simulation and modeling to optimize the SJ performance considering these interface impurities. The activation of regrown p-GaN in deep trenches is more difficult than planar p-GaN, and we present the characterization and physical model for the activation of the deep buried p-GaN. Last, the results of p-GaN filling regrowth and the acceptor concentration calibration in the lightly doped p-GaN are presented and discussed.
In summary, our work combines experimental device fabrication and characterization, TCAD simulation, and device modeling to demonstrate the benefit of multi-dimensional, junction-based GaN power devices as compared to the traditional GaN power devices. The junction-based structure at gate region can provides stable normally-off operation and low on-resistance. When being applied to the drift region, the multidimensional junction structure can push the device specific on-resistance versus breakdown voltage trade-off near or even exceeding the material limit. These results will advance the performance and application spaces of GaN power devices. / Doctor of Philosophy / Power electronics plays an important role in many energy conversion applications in modern society including consumer electronics, data centers, electric vehicles, and power grids, etc. The key components of power electronic circuits are power semiconductor devices including diodes and transistors, which determine the performance of power electronics circuits. Traditional power devices are based on the semiconductor silicon (Si), which have already reached the silicon's material limit. Gallium nitride (GaN) is a wide bandgap semiconductor with high electron mobility and high critical electric field. GaN-based power devices promise superior device performance over the Si-based counterpart.
Currently, GaN power devices performance is still far below its material limit due to several reasons: 1) To achieve normally-off operation, the carriers at gate region need to be fully depleted at zero bias. Due to a relatively limited depletion capability of the planar gate, the normally-off operation poses an upper limit on the channel carrier density, which increases the device on-resistance. 2) The electric field distribution is not uniform when the device is blocking off-state voltage, and the crowded electric field will cause the device premature breakdown.
This work proposed to use multi-dimensional, p-n junction-based device structure to overcome the above challenges. The devices with diverse structures are fabricated, characterized, and compared with the commercially available devices. The multi-dimensional, junction-based gate structure provides strong electrostatic control to realize normally-off operation and allow for higher carrier concentration and lower on-resistance. The devices with multi-dimensional, junction-based drift region enables the uniform electric field distribution at the device off-state, allowing devices to block high voltage without compromising the on-state resistance. Examples of such devices investigated in this dissertation include the tri-gate junction transistors, reduced-surface-field (RESURF) diodes, and superjunction diodes.
In summary, this work demonstrates the multi-dimensional, junction-based device structure to overcome the performance limitations of planar devices and fully exploit GaN's material benefits for power devices. The multi-dimensional, junction-based devices are experimentally fabricated and characterized, manifesting the superior performance over traditional GaN devices. This work will significantly boost the performance and application space of GaN power devices.
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Modelling and design of Low Noise Amplifiers using strained InGaAs/InAlAs/InP pHEMT for the Square Kilometre Array (SKA) applicationAhmad, Norhawati Binti January 2012 (has links)
The largest 21st century radio telescope, the Square Kilometre Array (SKA) is now being planned, and the first phase of construction is estimated to commence in the year 2016. Phased array technology, the key feature of the SKA, requires the use of a tremendous number of receivers, estimated at approximately 37 million. Therefore, in the context of this project, the Low Noise Amplifier (LNA) located at the front end of the receiver chain remains the critical block. The demanding specifications in terms of bandwidth, low power consumption, low cost and low noise characteristics make the LNA topologies and their design methodologies one of the most challenging tasks for the realisation of the SKA. The LNA design is a compromise between the topology selection, wideband matching for a low noise figure, low power consumption and linearity. Considering these critical issues, this thesis describes the procedure for designing a monolithic microwave integrated circuit (MMIC) LNA for operation in the mid frequency band (400 MHz to 1.4 GHz) of the SKA. The main focus of this work is to investigate the potential of MMIC LNA designs based on a novel InGaAs/InAlAs/InP pHEMT developed for 1 µm gate length transistors, fabricated at The University of Manchester. An accurate technique for the extraction of empirical linear and nonlinear models for the fabricated active devices has been developed. In addition to the linear and nonlinear model of the transistors, precise models for passive devices have also been obtained and incorporated in the design of the amplifiers. The models show excellent agreement between measured and modelled DC and RF data. These models have been used in designing single, double and differential stage MMIC LNAs. The LNAs were designed for a 50 Ω input and output impedance. The excellent fits between the measured and modelled S-parameters for single and double stage single-ended LNAs reflects the accurate models that have been developed. The single stage LNA achieved a gain ranging from 9 to 13 dB over the band of operation. The gain was increased between 27 dB and 36 dB for the double stage and differential LNA designs. The measured noise figures obtained were higher by ~0.3 to ~0.8 dB when compared to the simulated figures. This is due to several factors which are discussed in this thesis. The single stage design consumes only a third of the power (47 mW) of that required for the double stage design, when driven from a 3 V supply. All designs were unconditionally stable. The chip sizes of the fabricated MMIC LNAs were 1.5 x 1.5 mm2 and 1.6 x 2.5 mm2 for the single and double stage designs respectively. Significantly, a series of differential input to single-ended output LNAs became of interest for use in the Square Kilometre Array (SKA), as it utilises differential output antennas in some of its configurations. The single-ended output is preferable for interfacing to the subsequent stages in the analogue chain. A noise figure of less than 0.9 dB with a power consumption of 180 mW is expected for these designs.
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Efficient Dislocation Reduction Methods for Integrating Gallium Nitride HEMTs on SiMohan, Nagaboopathy January 2014 (has links) (PDF)
Gallium Nitride (GaN) and its alloys with InN and AlN, the III-nitrides, are of interest for a variety of high power-high frequency electronics and optoelectronics applications. However, unlike Si and GaAs technology that have been developed on native substrates, III-nitride devices have been developed on non-native substrates such as Si, sapphire and SiC. This is because bulk cheap native III-nitride substrates are unavailable. Among the known substrates, III-nitride technology development on Si is desirable because of its large substrate size and low cost. However, the large lattice and thermal expansion mismatch between the III-nitrides films and Si substrate leads to a high level of dislocations, 1010 cm-2, and tensile stress which results in cracking. For successful integration of crack free and low dislocation density GaN on Si various kinds of transition layer schemes are used that help to incorporate a compressive growth stress to neutralize the tensile thermal mismatch stresses and also to reduce dislocation densities to levels required by devices. These transition schemes, ranging from 400 nm to 7 m, involve the use of graded AlGaN layers, high/low temperature interlayers and superlattices.
The aim of the research described in this thesis was a systematic comparison of the different transition layer schemes currently used with the objective of increasing the efficiency of integrating device quality, crack free, low dislocation density, <109 cm-2, GaN with Si. A metal organic chemical vapor deposition equipped with an in-situ stress monitor was used for growth. Transmission electron microscopy was used for quantitative measurement of dislocation density.
The research shows, for the first time, that all transition layer optimization depends critically on the Si surface made available for growth of the first AlN layer. It needs to be optimally cleaned such that it is oxide free and smooth. A quantitative TEM comparison of various currently used transition layer schemes shows that while they have interesting mechanistic differences, they are not very different in their dislocation reduction efficiency. All of them yield a final dislocation density in a probe GaN layer of 1-3×109 cm-2. In contrast, a combination of Si doping and compressive growth stress has a synergistic effect on dislocation reduction. A simple 210 nm transition layer based on this understanding, the lowest reported yet, yields GaN layers that are crack free and have lower <1x109 cm-2 dislocation density, than those obtained by the aforementioned more complicated schemes. High electron mobility transistor characteristics performance on the probe GaN layers obtained on these transition layers supports the structural observations above.
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Développement de nouvelles hétérostructures HEMTs à base de nitrure de gallium pour des applications de puissance en gamme d'ondes millimétriques / Development of new gallium nitride based HEMT heterostructures for microwave power applicationsRennesson, Stéphanie 13 December 2013 (has links)
Les matériaux III-N sont présents dans la vie quotidienne pour des applications optoélectroniques (diodes électroluminescentes, lasers). Les propriétés remarquables du GaN (grand gap, grand champ de claquage, champ de polarisation élevé, vitesse de saturation des électrons importante…) en font un candidat de choix pour des applications en électronique de puissance à basse fréquence, mais aussi à haute fréquence, par exemple en gamme d'ondes millimétriques. L’enjeu de ce travail de thèse consiste à augmenter la fréquence de travail des transistors tout en maintenant une puissance élevée. Pour cela, des hétérostructures HEMTs (High Electron Mobility Transistors) sont développées et les épaisseurs de cap et de barrière doivent être réduites, bien que ceci soit au détriment de la puissance délivrée. Une étude sera donc menée sur l’influence des épaisseurs de cap et de barrière ainsi que le type de barrière (AlGaN, AlN et InAlN) de manière à isoler les hétérostructures offrant le meilleur compromis en termes de fréquence et de puissance. De plus, les moyens mis en œuvre pour augmenter la fréquence de travail entrainent une dégradation du confinement des électrons du canal. De manière à limiter cet effet, une back-barrière est insérée sous le canal. Ceci fera l’objet d’une deuxième étude. Enfin, une étude de la passivation de surface des transistors sera menée. La combinaison des ces trois études permettra d’identifier la structure optimale pour délivrer le plus de puissance à haute fréquence (ici à 40 GHz). / Nitride based materials are present in everyday life for optoelectronic applications (light emitting diodes, lasers). GaN remarkable properties (like large energy band gap, high breakdown electric field, high polarization field, high electronic saturation velocity…) make it a promising candidate for low frequency power electronic applications, but also for high frequency like microwaves range for example. The aim of this work is to increase the transistors working frequency by keeping a high power. To do this, high electron mobility transistor heterostructures are developed, and cap and barrier thicknesses have to be reduced, although it is detrimental for a high power. A first study deals with the influence of cap and barrier thicknesses as well as the type of barrier (AlGaN, AlN and InAlN), in order to isolate heterostructures offering the best compromise in terms of power and frequency. Moreover, the means implemented to increase the working frequency lead to electron channel confinement degradation. In order limit this effect, a back-barrier is added underneath the channel. It will be the subject of the second study. Finally, a transistor surface passivation study will be led. The combination of those three parts will allow identifying the optimum structure to deliver the highest power at high frequency (here at 40 GHz).
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High Power GaN/AlGaN/GaN HEMTs Grown by Plasma-Assisted MBE Operating at 2 to 25 GHzWaechtler, Thomas, Manfra, Michael J, Weimann, Nils G, Mitrofanov, Oleg 27 April 2005 (has links)
Heterostructures of the materials system GaN/AlGaN/GaN were grown by molecular beam epitaxy on 6H-SiC substrates and high electron mobility transistors (HEMTs) were fabricated. For devices with large gate periphery an air bridge technology was developed for the drain contacts of the finger structure. The devices showed DC drain currents of more than 1 A/mm and values of the transconductance between 120 and 140 mS/mm. A power added efficiency of 41 % was measured on devices with a gate length of 1 µm at 2 GHz and 45 V drain bias. Power values of 8 W/mm were obtained. Devices with submicron gates exhibited power values of 6.1 W/mm (7 GHz) and 3.16 W/mm (25 GHz) respectively. The rf dispersion of the drain current is very low, although the devices were not passivated. / Heterostrukturen im Materialsystem GaN/AlGaN/GaN wurden mittels Molekularstrahlepitaxie auf 6H-SiC-Substraten gewachsen und High-Electron-Mobility-Transistoren (HEMTs) daraus hergestellt. Für Bauelemente mit großer Gateperipherie wurde eine Air-Bridge-Technik entwickelt, um die Drainkontakte der Fingerstruktur zu verbinden. Die Bauelemente zeigten Drainströme von mehr als 1 A/mm und Steilheiten zwischen 120 und 140 mS/mm. An Transistoren mit Gatelängen von 1 µm konnten Leistungswirkungsgrade (Power Added Efficiency) von 41 % (bei 2 GHz und 45 V Drain-Source-Spannung) sowie eine Leistung von 8 W/mm erzielt werden. Bauelemente mit Gatelängen im Submikrometerbereich zeigten Leistungswerte von 6,1 W/mm (7 GHz) bzw. 3,16 W/mm (25 GHz). Die Drainstromdispersion ist sehr gering, obwohl die Bauelemente nicht passiviert wurden.
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Packaging of Enhancement-Mode Gallium Nitride High-Electron-Mobility Transistors for High Power Density ApplicationsLu, Shengchang 27 June 2022 (has links)
Gallium nitride (GaN) high-electron-mobility transistors (HEMTs) are favored for their smaller specific on-resistance, lower switching losses, and higher theoretical temperature limits as compared to traditional silicon (Si) power switches. They have the potential to dramatically increase the power density and efficiency of power electronics systems by replacing traditional Si-based switches.
However, GaN HEMTs have a faster switching speed compared to their Si-based counterparts. Minimizing the parasitic loop inductances of the GaN HEMT package is crucial for reducing electromagnetic interference (EMI) noise and voltage spikes. Another concern with GaN HEMTs comes from their lower thermal conductivity and smaller die size. The HEMTs generally have a higher heat flux density, and accordingly, demand better heat dissipation. Thus, innovations are needed for making GaN HEMT packages with low parasitic inductances and higher thermal performances to further their applications in high-frequency, high-power-density converters.
To reduce loop inductance, other researchers have embedded GaN HEMTs in a printed circuit board (PCB) and used plated vias for interconnections and heat dissipation. However, this approach requires more complex manufacturing steps and has lower thermal performance.
This dissertation introduces different embedded packaging techniques for 650V, 150A GaN HEMTs; this method involves interconnecting the bare chips between direct-bonded copper (DBC) and a PCB or between two DBCs, as discussed in Chapter 2. Vertical interconnections by gold pins and silver rods are introduced and implemented in embedded packages to limit the parasitic loop inductance within 1.5 nH and parasitic resistances within 1.5 mΩ.
The thermal performance of the embedded GaN HEMT packages is experimentally verified in Chapter 2; then, the junction-to-case thermal resistance (RthJC) measurement is discussed in Chapter 3. The common temperature-sensitive electrical parameters (TSEPs) of a GaN HEMT for junction temperature measurement lack sufficient sensitivity or stability due to the electron-trapping effect. The non-uniform distribution of the case temperature and a large temperature gradient between the case and heatsink also make it difficult to accurately measure the case temperature. In Chapter 3, gate-to-gate resistance (Rg2g) is selected as the TSEP for junction temperature measurement. The stacked thermal interface material (TIM) technique was used to reduce errors in case temperature measurement. This technique was implemented in a custom GaN HEMT package and in embedded GaN HEMT packages for measuring junction-to-case thermal resistance. The discrepancy between measurement and simulation is less than 20%, and the junction-to-case thermal resistance for embedded packages is within 0.1 °C/W.
Chapter 4 evaluates the reliability of the GaN HEMT embedded packages developed in Chapter 2 by utilizing a power cycling test. Monitoring the junction temperature of the embedded packages online is challenging during the power cycling test. Other approaches have used the on-resistance as the TSEP in order to monitor junction temperature for GaN HEMTs but this is not accurate due to electron trapping. As discussed in Chapter 3, Rg2g is chosen as the TSEP to monitor the junction temperature without worrying about the influence of electron trapping, and this approach cycles the embedded packages at 75 A from 25°C to 125°C. The packages can endure 23,000 power cycles before failure.
This work is the first to develop, fabricate, and characterize embedded packages for 650V, 150A GaN HEMT bare chips. These embedded packages with high-power-rated GaN HEMT bare dice provide an opportunity to reduce the number of paralleled power switches, reduce the system's cooling size, and increase the system's power density. In addition, this work is the first to develop the junction-to-case thermal resistance measurement technique by gate-to-gate electrical resistance and stacked-TIM for GaN HEMT packages. The technique helps enable solid thermal design for power electronics systems. / Doctor of Philosophy / Power switches are everywhere in our daily life. They are the fundamental elements in power converters for converting power to electric vehicles. As global power demand for these applications continues to increase, high levels of both efficiency and power density are crucial for power switches. However, traditional silicon-based switches are already very mature, and their properties are very close to their theoretical limits. For further improvement, researchers have tried to replace traditional Si switches with wide-bandgap switches, which have much higher theoretical limits. Gallium nitride high-electron-mobility transistors (GaN HEMTs) are one of the candidates.
However, packaging these switches (GaN HEMTs) is challenging due to their initial properties. They naturally switch very quickly and have smaller sizes compared to traditional Si-based switches. The fast switching speed brings high dv/dt and di/dt during the switching period. It causes voltage spikes and electromagnetic interference (EMI) issues. And the smaller size contributes to higher heat flux density, thus requiring more efficient heat dissipation. To solve the challenge of packaging GaN HEMTs, this dissertation has developed embedded packaging techniques to achieve quiet switching and good heat dissipation. These packaging techniques enable GaN HEMTs' advantages and increase the power density and efficiency of power electronics systems.
To experimentally verify the thermal performance of the embedded packages developed a junction-to-case thermal resistance measurement technique was introduced. The thermal resistance of a custom GaN HEMT package was measured, as were those of the embedded packages CPES also developed. The simulation results and the experimental results are close to each other.
Finally, to further evaluate whether or not the newly developed embedded packages are reliable, power cycling tests were carried out at I = 75 A. The packages survived over 23,000 cycles before failure.
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Radiation Effects on GaN-based HEMTs for RF and Power Electronic Applications / Strålningseffekter på GaN-baserade HEMTs för RF- och EffektelektroniktillämpningarHolmberg, Wilhelm January 2023 (has links)
GaN-HEMTs (Gallium Nitride-based High Electron Mobility Transistors) have, thanks to the large band gap of GaN, electrical properties that are suitable for applications of high electrical voltages, high currents, and fast switching. The large band gap also gives GaN-HEMTs a high resistance to radiation. In this degree project, the effects of 2 MeV proton irradiation of GaN-HEMTs constructed on both silicon carbide and silicon substrates are investigated. 20 transistors per substrate were irradiated in the particle accelerator 5 MV NEC Pelletron in the Ångström laboratory at Uppsala University. These transistors were exposed to radiation doses in the range of 10^11 to 10^15 protons/cm^2. The analysis shows that both transistors on silicon, as well as silicon carbide, are unaffected by proton irradiation up to a dose of 10^14 protons/cm^2. GaN-on-Si transistors show less influence of radiation than GaN-on-SiC transistors. The capacitances between gate and drain as well as drain and source for both GaN-on-SiC and GaN-on-Si HEMTs show hysteresis as a function of forward and backward gate voltage sweeps for the radiation dose of 10^15 protons/cm^2. / GaN-HEMTs (Galliumnitridbaserade High Electron Mobility Transistors) har tack vare det stora bandgapet i GaN goda elektriska egenskaper som lämpar sig för höga elektriska spänningar, höga strömmar och snabb växling mellan av- och på-tillstånd. Det stora bandgapet ger även GaN-HEMTs ett stort motstånd mot strålning.I detta examensarbete undersöks effekterna av 2 MeV protonbestrålning av GaN-HEMTs. Dessa HEMTs är konstruerade på både kiselkarbid- och kiselsubstrat.20 transistorer per transistorsubstrat bestrålades i partikelacceleratorn 5 MV NEC Pelletron i Ångströmslaboratoriet vid Uppsala Universitet. Dessa transistorer utsattes för strålningsdoser inom intervallet 10^11 till 10^15 protoner/cm^2. Resultaten visar att både tranisistorer på kisel såsom kiselkarbid är opåverkade av strålning upp till en dos av 10^14 protoner/cm^2. GaN-på-Si-transistorer visar en mindre påverkan av protonstrålning än GaN-på-SiC-transistorer. Ytterligare uppstod hysteresis för kapacitanser mellan gate och drain och mellan gate och source som en funktion av fram- och bakriktad gate-spänning efter en strålningsdos av 10^15 protoner/cm^2.
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Full-wave Electromagnetic Modeling of Electronic Device Parasitics for Terahertz ApplicationsKarisan, Yasir 15 May 2015 (has links)
No description available.
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Investigation of electrically-active defects in AlGaN/GaN high electron mobility transistors by spatially-resolved spectroscopic scanned probe techniques.Cardwell, Drew 16 September 2013 (has links)
No description available.
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Synthesis and Characterization of Diketopyrrolopyrrole- based Copolymers for Organic Electronic ApplicationsWang, Qian 04 June 2024 (has links)
Diketopyrrolopyrrole (DPP)-based polymers currently rank among the best performing organic materials for high charge carrier mobility applications due to their high structural planarity and the simple synthetic access. Through chemical modifications on DPP-based polymers, the type of charge carrier transport (p-type, n-type or ambipolar) and the charge carrier mobility can be both modulated. In this thesis, the synthesis of a new n-type dithiazolyldiketopyrrolopyrrole (TzDPPTz)-based copolymer PTzDPPTzF4 with tetrafluorobenzene (F4) as comonomer is reported. PTzDPPTzF4 has a deeper lowest unoccupied molecular orbital (LUMO) energy level compared to the existing dithienyldiketopyrrolopyrrole (ThDPPTh)-based copolymer PThDPPThF4 due to the electron-deficient thiazole flanking units on the bicyclic DPP core. Moreover, the influence of homocoupling (hc) defects and backbone conformation on the properties of PTzDPPTzF4 is systematically investigated. Lastly, in order to further modulate the structural and electrical properties of DPP-based copolymers, polar side chains and comonomers with a different electron-withdrawing ability are introduced to the polymer backbone. In detail, a series of PTzDPPTzF4 polymers with similar molecular weight but varying TzDPPTz hc content from 0.6 – 12.4% is prepared via direct arylation polymerization (DAP) for the investigation of the hc-property relationship. Hc defects are found to red-shift the absorption, decrease the photoluminescence, and lower the LUMO energy level. In contrast, an influence on the film morphology or electron mobility is not observed. In order to study the conformation-property relationship, a structural variation in the DPP monomer is explored, i.e. the replacement of Tz by Th. To this end, a detailed comparative study of the properties between PTzDPPTzF4 and PThDPPThF4, which are prepared via DAP and have both comparable molecular weight and hc content, is presented. It is found that the replacement of Tz flanking units by Th flanking units on the DPP core has significant impact on the backbone conformation due to the occurrence of intramolecular hydrogen bonds, and thus strongly influences the opto-electronic and structural properties of the two polymers. PThDPPThF4 exhibits a stronger aggregation ability, a higher degree of crystallinity, a lower degree of paracrystallinity and an increased long-range order, which finally translates into a 20 times higher field-effect electron mobility. Finally, comonomer and side chain variations of DPP-based polymers are carried out for their potential use in thermoelectric investigations. Through the optimization of the polymerization conditions, a number-average molecular weight of 19.1 kg/mol is achieved for ThDPPTh-based polymers with single-oxygen side chains and F4 as comonomer. In addition, two ThDPPTh-based copolymers with biEDOT as comonomer are synthesized, which contain polar triethylene glycol (TEG) side chains as well as branched aliphatic side chains in different ratios. In summary, the economically efficient and ecologically green DAP method is demonstrated to be an efficient and versatile synthetic tool for copolymerizing TzDPPTz or ThDPPTh monomers bearing either aliphatic or polar side chains with either electron-rich or electron-deficient comonomers.
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