Colloidal Quantum Dots and J-Aggregating Cyanine Dyes for Infrared Photodetection

The emergence of nanostructured semiconducting materials enables new approaches toward the realization of photodetectors that operate in the technologically important near- and short-wave infrared (NIR and SWIR) spectral ranges. In particular, organic semiconductors and colloidal quantum dots (QDs) possess numerous advantages over conventional crystalline semiconductors including highly tunable optical and electronic characteristics, the prospect for low-temperature processing, and compatibility with inexpensive and exible substrates. Photodetectors based on such materials may lead to low-cost IR focal plane arrays for night-vision imaging as well as a multitude of novel applications in biological and chemical sensing. This thesis describes the development and detailed characterization of several photodetectors that incorporate colloidal QD and organic semiconductor thin films as active layers. The electronic properties of PbS QDs are thoroughly investigated in a field effect transistor (FET) geometry and several QD-based photoconductive structures exhibiting SWIR photosensitivity are demonstrated. We describe a novel QD-sensitized lateral heterojunction photoconductor in which the functions of optical absorption and charge transport are dissociated into different physical layers that can be independently optimized. This structure is advantageous because it obviates the need for aggressive chemical treatments to the QD film that may compromise the quality of QD surface passivation. Photovoltaic device architectures are addressed, noting their advantages of being operable without an external applied bias and at fast response speeds. We present detailed experimental and theoretical characterization of a photovoltaic structure that is sensitized at NIR wavelengths by a J-aggregating cyanine dye. The high absorption coefficient of the J-aggregate film, combined with the use of a reflective anode and optical spacer layer, enables an external quantum efficiency (EQE) of $16.1\pm0.1\%(\lambda = 756 nm)$ to be achieved at zero-bias in a device that incorporates an $8.1\pm0.3 nm$-thick dye film. The merits and drawbacks of the various device architectures and nanostructured material systems are discussed and the outlook for nanostructured photodetectors that exhibit infrared sensitivity is presented.Engineering and Applied Science

Practical Roadmap and Limits to Nanostructured Photovoltaics

The significant research interest in the engineering of photovoltaic (PV) structures at the nanoscale is directed toward enabling reductions in PV module fabrication and installation costs as well as improving cell power conversion efficiency (PCE). With the emergence of a multitude of nanostructured photovoltaic (nano-PV) device architectures, the question has arisen of where both the practical and the fundamental limits of performance reside in these new systems. Here, the former is addressed a posteriori. The specific challenges associated with improving the electrical power conversion efficiency of various nano-PV technologies are discussed and several approaches to reduce their thermal losses beyond the single bandgap limit are reviewed. Critical considerations related to the module lifetime and cost that are unique to nano-PV architectures are also addressed. The analysis suggests that a practical single-junction laboratory power conversion efficiency limit of 17% and a two-cell tandem power conversion efficiency limit of 24% are possible for nano-PVs, which, when combined with operating lifetimes of 10 to 15 years, could position them as a transformational technology for solar energy markets.Eni-MIT Alliance Solar Frontiers Program (Eni S.p.A. (Firm))National Science Foundation (U.S.). Graduate Research Fellowship ProgramLink FoundationHertz Foundation (Fellowship

Contact printing of colloidal nanocrystal thin films for hybrid organic/quantum dot optoelectronic devices

Novel thin film optoelectronic devices containing both inorganic colloidal semiconductor quantum dots (QDs) and organic semiconductor thin films have been widely investigated in recent years for a variety of applications. Here, we review one of the most versatile and successful methods developed to integrate these two dissimilar material classes into a functional multilayered device: contact printing of colloidal QD films. Experimental details regarding the contact printing process are outlined, and the key advantages of this QD deposition method over other commonly encountered techniques are discussed. The use of tapping mode atomic force microscopy (AFM) to effectively characterize QD film morphology both on an elastomeric stamp (before contact printing) and as-transferred to the organic semiconductor receiving film (after contact printing) is also described. Finally, we offer suggestions for future efforts directed toward the goal of rapid, continuous QD deposition over larger substrates for the advancement of hybrid optoelectronic thin film devices

Large Second Harmonic Kerr rotation in GaFeO3 thin films on YSZ buffered Silicon

Epitaxial thin films of gallium iron oxide (GaFeO3) are grown on (001) silicon by pulsed laser deposition (PLD) using yttrium-stabilized zirconia (YSZ) buffer layer. The crystalline template buffer layer is in-situ PLD grown through the step of high temperature stripping of the intrinsic silicon surface oxide. The X-ray diffraction pattern shows c-axis orientation of YSZ and b-axis orientation of GaFeO3 on Si (100) substrate. The ferromagnetic transition temperature (TC ~ 215 K) is in good agreement with the bulk data. The films show a large nonlinear second harmonic Kerr rotation of ~15 degrees in the ferromagnetic state.Comment: 16 pages, 4 figures, To be published in J. Magn. Magn. Ma

Enamine-based hole transporting materials for vacuum-deposited perovskite solar cells

In a short period of time, the rapid development of perovskite solar cells attracted a lot of attention in the science community with the record for power conversion efficiency being broken every year. Despite the fast progress in power conversion efficiency there are still many issues that need to be solved before starting large scale commercial applications, such as, among others, the difficult and costly synthesis and usage of toxic solvents for the deposition of hole transport materials (HTMs). We herein report new enamine-based charge transport materials obtained via a simple one step synthesis procedure, from commercially available precursors and without the use of expensive organometallic catalysts. The developed materials demonstrated rapid loss of mass during thermogravimetry analysis suggesting that they could be processed not only using solution processing but also via vacuum deposition. Furthermore, all HTMs demonstrated high charge carrier mobility with H2 possessing the highest mobility of 2.5 × 10−2 cm2 V−1 s−1 under strong electric fields. The investigated materials were employed in vacuum-deposited p-i-n perovskite solar cells and champion devices with enamine H2 demonstrate a PCE of 18.4%

Revealing Trap States in Lead Sulphide Colloidal Quantum Dots by Photoinduced Absorption Spectroscopy

Due to their large surface to volume ratio, colloidal quantum dots (CQDs) are often considered to exhibit a significant amount of surface defects. Such defects are one possible source for the formation of in-gap states (IGS), which can enhance the recombination of excited carriers, i.e., work as electrical traps. These traps are investigated for lead sulphide CQDs of different size, covered with different ligands using a mid-infrared photoinduced absorption (PIA) technique. The obtained PIA spectra reveal two distinct absorption bands, whose position depends on the particle size, i.e., the electronic confinement in the CQDs. Smaller particles exhibit deeper traps. The chemical nature of the capping ligand does not affect the resulting position other than due to its change in confinement, but better passivating species lead to smaller signals. Furthermore, ligand specific narrow lines observed are superimposed on the broad electronic background of the PIA spectra, which is attributed to Fano resonances caused by the interplay of the narrow molecular vibrations and the continuum of trap states. Mid-infrared photoinduced absorption represents a valuable tool to unravel distributions of IGS in CQDs and allows for an assessment of the quality of ligand exchanged films. These findings have implications for understanding the performances of CQD-based (opto-) electronic devices, such as solar cells, transistors, or quantum dot light emitting diodes, which are limited by frequent carrier trapping events