Colloidal quantum dots (CQD) are used in the fabrication of efficient, low-cost solar cells synthesized in and deposited from solution. Breakthroughs in CQD materials have led to a record efficiency of 7.0%. Looking forward, any path toward increasing efficiency must address the trade-off between short charge extraction lengths and long absorption lengths in the near-infrared spectral region. Here we exploit the localized surface plasmon resonance of metal nanoparticles to enhance absorption in CQD films. Finite-difference time-domain analysis directs our choice of plasmonic nanoparticles with minimal parasitic absorption and broadband response in the infrared. We find that gold nanoshells (NS) enhance absorption by up to 100% at λ = 820 nm by coupling of the plasmonic near-field to the surrounding CQD film. We engineer this enhancement for PbS CQD solar cells and observe a 13% improvement in short-circuit current and 11% enhancement in power conversion efficiency.

Colloidal quantum dots (CQD) are used in the fabrication of efficient, low-cost solar cells synthesized in and deposited from solution. Breakthroughs in CQD materials have led to a record efficiency of 7.0%. Looking forward, any path toward increasing efficiency must address the trade-off between short charge extraction lengths and long absorption lengths in the near-infrared spectral region. Here we exploit the localized surface plasmon resonance of metal nanoparticles to enhance absorption in CQD films. Finite-difference time-domain analysis directs our choice of plasmonic nanoparticles with minimal parasitic absorption and broadband response in the infrared. We find that gold nanoshells (NS) enhance absorption by up to 100% at λ = 820 nm by coupling of the plasmonic near-field to the surrounding CQD film. We engineer this enhancement for PbS CQD solar cells and observe a 13% improvement in short-circuit current and 11% enhancement in power conversion efficiency.

Multijunction solar cells made from a combination of CQDs of differing sizes and thus bandgaps are a promising means by which to increase the energy harvested from the Sun’s broad spectrum. In this dissertation, we first report the systematic engineering of 1.6 eV PbS CQD solar cells, optimal as the front cell responsible for visible wavelength harvesting in tandem photovoltaics. We rationally optimize each of the device’s collecting electrodes—the heterointerface with electron accepting TiO2 and the deep-work-function hole-collecting MoO3 for ohmic contact—for maximum efficiency. Room-temperature processing enables flexible substrates, and permits tandem solar cells that integrate a small-bandgap back cell atop a low thermal-budget larger-bandgap front cell. We report an electrode strategy that enables a depleted heterojunction CQD PV device to be fabricated entirely at room temperature. We develop a two-layer donor-supply electrode (DSE) in which a highly doped, shallow work function layer supplies a high density of free electrons to an ultrathin TiO2 layer via charge-transfer doping. Using the DSE we build all-room-temperature-processed small-bandgap (1 eV) colloidal quantum dot solar cells suitable for use as the back junction in tandem solar cells. We further report in this work the first efficient CQD tandem solar cells. We use a graded recombination layer (GRL) to provide a progression of work functions from the hole-accepting electrode in the bottom cell to the electron-accepting electrode in the top cell. The recombination layers must allow the hole current from one cell to recombine, with high efficiency and low voltage loss, with the electron current from the next cell. We conclude our dissertation by presenting the generalized conditions for design of efficient graded recombination layer solar devices. We demonstrate a family of new GRL designs experimentally and highlight the benefits of the progression of dopings and work functions in the interlayers.

In recent years, the Surface Plasmon Polariton effect has played an important role for entering the Nano-world. When the metallic materials reach the nanometer level, many special characteristics show up. As the progress of advanced technology development, the equipments which can be operated in nano grade level are more stabilized. Many special surface Plasmonic properties have been discovered through the measurements. This research is to focus on using the Surface Plasmon coupling to excite colloidal quantum dots and observing the emissive behavior of quantum dots. The experiments of changing the distance between the quantum dots and the metal film were performed. The blinking effect disappeared when the quantum dots are very close to the metal film. It showed that some other mechanism is competing with Auger recombination in the quantum dots. The lifetime modification and emission intensity were measured when one quantum dot was placed near a silver cube. The coupling between the surface Plasmon polariton and the quantum dot was discussed.

Multijunction solar cells made from a combination of CQDs of differing sizes and thus bandgaps are a promising means by which to increase the energy harvested from the Sun’s broad spectrum. In this dissertation, we first report the systematic engineering of 1.6 eV PbS CQD solar cells, optimal as the front cell responsible for visible wavelength harvesting in tandem photovoltaics. We rationally optimize each of the device’s collecting electrodes—the heterointerface with electron accepting TiO2 and the deep-work-function hole-collecting MoO3 for ohmic contact—for maximum efficiency. Room-temperature processing enables flexible substrates, and permits tandem solar cells that integrate a small-bandgap back cell atop a low thermal-budget larger-bandgap front cell. We report an electrode strategy that enables a depleted heterojunction CQD PV device to be fabricated entirely at room temperature. We develop a two-layer donor-supply electrode (DSE) in which a highly doped, shallow work function layer supplies a high density of free electrons to an ultrathin TiO2 layer via charge-transfer doping. Using the DSE we build all-room-temperature-processed small-bandgap (1 eV) colloidal quantum dot solar cells suitable for use as the back junction in tandem solar cells. We further report in this work the first efficient CQD tandem solar cells. We use a graded recombination layer (GRL) to provide a progression of work functions from the hole-accepting electrode in the bottom cell to the electron-accepting electrode in the top cell. The recombination layers must allow the hole current from one cell to recombine, with high efficiency and low voltage loss, with the electron current from the next cell. We conclude our dissertation by presenting the generalized conditions for design of efficient graded recombination layer solar devices. We demonstrate a family of new GRL designs experimentally and highlight the benefits of the progression of dopings and work functions in the interlayers.

Here we present direct investigation of the lasing behaviour by performing gain spectroscopy of solution-based CQDs enabled via in-situ tuning of the feedback wavelength of an open-access hemispherical microcavity. The investigation is performed on two different types of CQDs, namely spherical CdSe/CdS core-shell CQDs and nanopletelets (NPs). The lasing threshold and the differential gain/slope efficiency of the fundamental cavity mode are measured as a function of their spectral position over a spectral range of ∼ 32 nm and of ∼ 42 nm for the spherical CQDs and NPs, respectively. The results of the gain spectroscopy are described using theoretical models, providing insights into the mechanism governing the observed lasing behaviour. Furthermore, the open-access cavity architecture provides a very convenient way of producing in-situ tunable lasing, and single-mode lasing of the fundamental cavity mode over a spectral range of ∼ 25 nm and ∼ 37 nm is demonstrated using spherical CQDs and NPs, respectively. In addition, the stability of laser emission is investigated, with the lasing intensity of the fundamental cavity mode remaining constant over a time period of almost 6 mins. It is hoped that the results will provide a detailed understanding of the lasing behaviour of CQDs. This information can be fed back into the design of CQDs in which the lasing threshold can be reduced to the point where useful devices can be constructed, and in the design of resonant optical feedback structures for which the appropriate wavelength must be carefully selected.

In this thesis type II colloidal quantum dots (CQDs) with zinc blende crystal structure were investigated. The optical properties were characterized by steady state absorption and photoluminescence (PL) spectroscopy for all the samples, and the PL quantum yield was measured for selected samples by using both absolute and relative methods. Exciton dynamics and interactions were investigated by time-resolved PL (TRPL).The exciton-exciton interaction energy for CdSe, CdSe/CdTe and CdSe/CdTe/CdS CQDs was investigated using TRPL spectroscopy, an established method. The TRPL results were compared with previous results from ultrafast transient absorption (TA) measurements and theoretical predictions. The discrepancies between the TRPL and TA results and the theoretical calculations suggest that TRPL data has been misinterpreted in the literature. The single exciton recombination dynamics for CdSe, CdSe/CdTe and CdSe/CdTe/CdS CQDs were investigated. The effects of non-radiative recombination were identified from the PL transients by using a theoretically-calculated radiative lifetime as a fitting parameter. The combined rate of the non-radiative processes thus found was consistent with the localisation of holes into shallow traps by an Auger-mediated process. A rate equation analysis also showed how shallow trapping can give rise to the tri-exponential PL dynamics observed experimentally. Chloride passivation of CdTe CQDs resulted in a near-complete suppression of surface traps, producing a significant enhancement of the optical properties. PL quantum yield (PLQY) and PL lifetime in particular benefit from the chloride treatment. The radiative recombination rate that now could be extracted from PL transients for chloride treated samples was used to calculate the non-radiative recombination rate for the untreated samples. In addition, a study of the effects of air exposure on the PL, observed for both treated and untreated samples was undertaken and revealed the importance of the influence of the dielectric environment surrounding the traps states on recombination dynamics.

Controlled patterning of light emitting diodes on semiconductors enables a vast variety of applications such as structured illumination, large-area flexible displays, integrated optoelectronic systems and micro-total analysis systems for real time biomedical screening. We have demonstrated a series of techniques of creating quantum-based (QD) patterned inorganic light emitting devices at room temperature on silicon (Si) substrate. In particular: (I) A combination of QDs self-assembly and microcontact printing techniques were developed to form the light emission monolayer. We expand the self-assembly method with the traditional Langmuir-Schaeffer technique to rapidly deposit monolayers of core: shell quantum dots on flat substrates. A uniform film of QDs self-assembled on water was transferred using hydrophobic polydimethylsiloxane stamps with various nano/micro-scale patterns, and was subsequently stamped. A metal oxide electron transport layer was co-sputtered onto the QDs. The structure was completed by an e-beam evaporating thin metal cathode. Multicolor light emission was observed on application of voltage across the device. (II) We also demonstrate the photolithographic patterning capability of a metal cathode for top emitting QDLEDs on Si substrates. Lithographic patterning technique enables site-controlled patterning and controlled feature size of the electrode with greater accuracy. The stability of inorganic silicon materials and metal oxide based diode structure offers excellent advantages to the device, with no significant damage observed during the patterning and etching steps. Efficient electrical excitation of QDs was demonstrated by both the methods described above. The technique was translated to create localized QD-based light sources for two applications: (1) Three-dimensional scanning probe tip structures for near field imaging. Combined topographic and optical images were acquired using this new class of “self-illuminating” probe in commercial NSOM. The emission wavelength can be tuned through quantum-size effect of QDs. (2) Multispectral excitation sources integrated with microfluidic channels for tumor cell analyses. We were able to detect the variation of sub-cellular features, such as the nucleus-to-cytoplasm ratio, to quantify the absorption at different wavelength upon the near-field illumination of individual tumor cells towards the determination of cancer developmental stage. / text

Colloidal quantum dots (CQDs) are potentially low-cost, solution-processable semiconductors which are endowed, through their nanoscale dimensions, with strong absorption, band gap tunability, high dielectric constants and enhanced stability. CQDs are contenders as a standalone PV technology as well as a potential back layer for augmenting established photovoltaic (PV) technologies, such as Si. However, owing to their small size (ca. few nanometers), CQDs are prone to surface trap states that inhibit charge transport and threaten their otherwise wonderful optoelectronic properties. Surface traps have also, indirectly, impeded scalable and industry-compatible fabrication of these solar cells, as all of the reports, to date, have relied on spin-coating with sophisticated and tedious ligand exchange schemes, some of which need to be performed in low humidity environments. In this thesis, we posit that an in-depth understanding of the process-structure-property-performance relationship in CQDs can usher in fresh insights into the nature and origin of surface traps, lead to novel ways to mitigate them, and finally help achieve scalable fabrication. To this end, we probe the CQD surfaces and their interactions with process solvents, linkers, and ambient environment employing a suite of spectroscopic techniques. These fundamental insights help us develop facile chemical and physical protocols to mitigate surface traps such as solvent engineering, remote molecular doping, and oxygen doping, directly leading to better-performing solar cells. Our efforts finally culminate in the realization of >10% efficient, air-stable CQD solar cells scalably fabricated in an ambient environment of high, uncontrolled R.H. (50-65%). As-prepared solar cells fabricated in high humidity ambient conditions are found to underperform, however, an oxygen-doping recipe is devised to mitigate the moisture-induced surface traps and recover device performances. Importantly, these solar cells are fabricated at coating speeds of >15 m min-1 with roll-to-roll compatible techniques such as blade and bar coating requiring 1/25th the CQD material consumed by the standard spin-coated devices, overcoming the two major challenges of manufacturability and scalability faced by CQD PV.

In this thesis, the strength of the LBIC system is enhanced in different aspects that includes its feasibility as a non-destructive characterization tool, the signal analysis and development of analytical solution to have better understanding on the defects and inhomogeneities in the quantum dot based hetero-structures for device applications, finally understanding its limits due to the size of the laser beam and interpretation of artefacts in the signal appearance due to the presence of co-devices. Chapter#1 provides the introduction and literature survey of the LBIC system. It covers the importance and area of application of the LBIC. Chapter#2 various tools and instrumentation are discussed briefly for the systems that are developed in the lab as well as standard tools utilised for the material characterization. A LBIC instrumentation a novel colloidal quantum dots (CQD) thin film deposition system is discussed. In the last part along with the standard characterization systems a software tool (semiconductor device simulator) is discussed, which is used to visualize and understand the LBIC profile that is obtained experimentally. Chapter#3 provides the information of colloidal synthesis of PbS and HgxCd1-xTe quantum dots. Device fabrication process is explained step by step for the following devices. p-n junction silicon diodes, PbS-CQD/Si hetero-structures, ITO/PbS-CQD/Al crossbar structures and HgCdTe-CQD/Si hetero-structures. Chapter#4 deals with the major constraints imposed on the LBIC due to the need of Ohmic contacts. To overcome this major limitation, in this work, the origin of the signal is studied with the remote contact geometry for silicon p-n junction devices. It was observed that the signals can be collected with the capacitively coupled remote contacts, where LBIC was ultimately demonstrated as contactless measurement tool without any compromise on the measurements and thus obtained physical parameters. The effect of finite laser beam size is also described, which was found to have effect on the actual dimensions measured with the LBIC images. LBIC utility is further enhanced with the Si/CQD based hetero-structure devices, which are the potential candidates in the evolving device technology to be utilized in various modular systems such as PDs and LED applications. Chapter#5 discusses the origin and possible mechanisms for lateral photo-voltage which is closely monitored in the PbS-CQD/Si hetero-junction device systems. Interestingly, it is observed that there are two different line profiles for n and p type Si substrates. Different mechanisms that give rise to this kind of profiles were found to be distinct and are related to the band alignment of the CQD/Si hetero-structure. It lead to the revelation of an interesting phenomenon and believed to be universally observed irrespective of the materials involved in the formation of hetero-junction. Simulations and experimental results are quite consistent and in agreement with each other, which confirm the underlying physical mechanism that connects the LBIC anomalies with the band alignment. Chapter#6 deals with the spatial variations in the transverse photocurrent in the PbS-CQD film which is studied as a function of applied bias. Analytical equation is setup for the photocurrent in the CQD film under applied bias with the help of available transport mechanism and equations from the literature. The spatial non-uniformity that exists in the photocurrent proved to be the result of spatial inhomoginities in the physical parameters. By correlating the spatial data to the analytical equation, it is shown that the inhomoginities can be predicted. This approach is important for the devices, where monolithic detectors are fabricated by depositing CQD film on Read-Out-Integrated-Circuit (ROIC), where the manifestation of non-uniformity can be understood and probably fixed. Chapter#7 HgCdTe CQD based devices are studied for the purpose of photo-detector applications in MWIR (3  5 μm) region. HgxCd1-xTe Colloidal quantum dots are technologically important due to their wide absorption range that covers different regions of the atmospheric window. HgxCd1-xTe are successfully synthesised, which covers the absorption edge up to ~6.25 m in the IR region. Absorption and photo-response studies are carried out on HgxCd1-xTe/Si hetero-junctions under incident IR radiation. It is observed that the band gap of the quantum dots can be tuned easily by controlling the growth time as a parameter, thus moulded HgxCd1-xTe CQD/Si hetero-structures were found to have good photo-response. Chapter#8 the summary and the future direction and scope of the work is discussed. This includes the interesting observations during this thesis work which are not reported here in details.