Thesis. 1975. Ph.D.--Massachusetts Institute of Technology. Dept. of Electrical Engineering and Computer Science. / Vita. / Includes bibliographical references. / Ph.D.

abstract: Satisfying the ever-increasing demand for electricity while maintaining sustainability and eco-friendliness has become a key challenge for humanity. Around 70% of energy is rejected as heat from different sectors. Thermoelectric energy harvesting has immense potential to convert this heat into electricity in an environmentally friendly manner. However, low efficiency and high manufacturing costs inhibit the widespread application of thermoelectric devices. In this work, an inexpensive solution processing technique and a nanostructuring approach are utilized to create thermoelectric materials. Specifically, the solution-state and solid-state structure of a lead selenide (PbSe) precursor is characterized by different spectroscopic techniques. This precursor has shown promise for preparing thermoelectric lead selenide telluride (PbSexTe1-x) thin films. The precursor was prepared by reacting lead and diphenyl diselenide in different solvents. The characterization reveals the formation of a solvated lead(II) phenylselenolate complex which deepens the understanding of the formation of these precursors. Further, using slightly different chemistry, a low-temperature tin(II) selenide (SnSe) precursor was synthesized and identified as tin(IV) methylselenolate. The low transformation temperature makes it compatible with colloidal PbSe nanocrystals. The colloidal PbSe nanocrystals were chemically treated with a SnSe precursor and subjected to mild annealing to form conductive nanocomposites. Finally, the room temperature thermoelectric characterization of solution-processed PbSexTe1-x thin films is presented. This is followed by a setup development for temperature-dependent measurements and preliminary temperature-dependent measurements on PbSexTe1-x thin films. / Dissertation/Thesis / Doctoral Dissertation Materials Science and Engineering 2020

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The maximum sensitivity of a thermal IR sensor can be available either by means of the sensor material, having its own absorbing properties, or by the deposition of an additional absorber structure on the detector surface. In this thesis, the theory of two absorption structures is discussed. The first is called the interferometric absorber structure. The second structure under investigation uses a lead selenide layer for the IR absorption. In the interferometric structure, a new epoxy material SU8-2002 was used as a dielectric medium. This material has a very low thermal conductivity of 0.3 W/mK, which makes it suitable for thermal detectors. The interferometric structure is based on three layers, a 40–60 Å thick Ti layer, a SU8–2002 layer with a thickness of 2000 Å thick and a 2000Å Al layer. Using standard cleanroom processing an interferometric structure was fabricated. Transfer matrix theory was used in order to simulate the interferometric structure and the lead selenide was fabricated by means of an argon-plasma sputtering process. Both fabricated samples were characterized through Fourier transfer infrared (FTIR) spectroscopy together with a specular reflectance accessory. The thicknesses of the added layers were measured using Atomic force microscopy (AFM) for both the interferometric and lead selenide structure.  It was determined  that by changing the reflective index value of the SU8-2002 from the reported value of 1.575 to about 2.40 that this provided a better agreement with the experimental results. The absorption results for the interferometric structure were determined to be approximately 82–98% for the wavelength region of 2-20µm at 30 degree. The PbSe absorption spectra showed 30%–50% absorption for the wavelength region 2.5 – 6.67μm.

This work describes an experimental investigation of methods of synthesis, determination of structural and physical properties, and analysis and correlation of the properties to the structures of semiconductor quantum dots and quantum dot-polymer hybrid structures. These structures are investigated for applications in flexible solar cell devices. The main synthesis process used in the work was a Laser-Assisted Spray (LAS) process that was developed in our laboratory to deposit surfactant-free PbSe quantum dot (QD) films directly on a substrate. The QD films formed by this technique are in close contact with each other forming a percolation path for charge transport. Analytical instruments that include Atomic Force Microscopy (AFM) and Transmission Electron Microscopy (TEM) were used for structural characterization while optical absorption spectroscopy and photoluminescence were used for determining the quantum confinement of charge carriers in PbSe QDs. In addition, charge transport across lithographically patterned paths was used to determine the transport characteristics and generation of photocurrent in the fabricated structures. Absorption spectroscopy confirmed the quantum confinement of PbSe QDs deposited by LAS deposition. Room temperature current-voltage measurements across a 2 micrometer tunnel junction formed by the QDs produced a power-law dependence of the form I ∝ V2.19 that describes a percolation path of dimensionality slightly above two-dimensional. Absence of surfactants in LAS deposited films improved the conductivity by more than three orders of magnitude. Temperature dependent conductance studies showed thermally activated transport at high temperatures and temperature independent tunneling followed by previously unobserved metallic conduction at low temperatures. The LAS system was successfully modified by incorporating two spray nozzles to transport aerosols of two different precursors, one containing the QDs and the other containing the polymer. This new co-deposition system was successfully used to deposit QDs/Polymer hybrid structures. The TEM and XRD studies of LAS co-deposited films were shown to be uniformly distributed and crystalline. The photo-current experiments of QD/polymer hybrid composites showed clear evidence of enhanced carrier generation and transport as a result of intimate contact between quantum dots (QDs).

The assembly of nanostructures into “multi”-dimensional materials is one of the main topics occurring in nanoscience today. It is now possible to produce high quality nanostructures reproducibly but for their further application larger structures that are easier to handle are required. Nevertheless during their assembly their nanometer size and accompanying properties must be maintained. This challenge was addressed in this work. Lead chalcogenides have been chosen as an example system because they are expected to offer great opportunities as thermoelectric materials. Three different ways to achieve assemblies of lead chalcogenide nanostructures were used and the resulting structures characterized with respect to their potential application as thermoelectric material. The first means by which a “multi”-dimensional assembly of lead chalcogenide quantum dots can be produced is the formation of porous structures such as aerogels and xerogels. A procedure, where the addition of an initiator such as oxidizers or incident radiation is unnecessary, is introduced and the formation process studied by absorption spectroscopy. The time-consuming aggregation step could be significantly reduced by employing a slightly elevated temperature during gelation that does not lead to any observable differences within the resulting gel structures. After either supercritical or subcritical drying, highly porous monolithic gel structures can be achieved. During the gel formation the size and the shape of the particles changed and they were directly linked together. Nevertheless the resulting porous structures remain crystalline and size dependent effects of the optical properties could be shown. Gels produced from a mixture of PbS and PbSe QDs show a homogenous distribution of both materials but it is not clear to what extent they form an alloy. Although the particles are directly linked together the resulting porous structures possess a very high resistivity and so it was not possible to characterize the semiconductor aerogels with regard to their thermoelectric properties. To achieve an enhanced conductivity porous structures containing PbS and Au nanoparticles have been produced. As has been seen for the pure semiconductor gels the size of the PbS quantum dots has increased and elongated particles were formed. In contrast to the PbS QDs the Au nanoparticles did not change their size and shape and are unevenly distributed within the PbS network. Through the use of the gold nanoparticles the conductivity could be increased and although the conductivity is still quite small, it was possible to determine Seebeck coefficients near room temperature for a mixed semiconductor-metal gel. The second means by which QD solids could be formed was by the compaction of the QD building blocks into a material that is still nanostructured. Therefore the synthesis of PbS was optimized to achieve sufficient amounts of PbS quantum dots. The ligands used in the synthesis of the QDs unfortunately act as an insulating layer resulting in QD solids with resistivities as high as 2 Gigaohm. For this reason different surface modification strategies were introduced to minimize the interparticle distance and to increase the coupling between the QDs so as to increase the conductivity of the resulting quantum dot solids. One very promising method was the exchange of the initial ligands by shorter ones that can be destroyed at lower temperatures. By such heat treatments the resistivity could be decreased by up to six orders of magnitude. For the pressing of the quantum dots two different compaction methods (SPS and hydraulic pressing) were compared. While the grain growth within the SPS pressed samples is significantly higher the same densification can be achieved by a cold hydraulic pressing as well as by SPS. The densification could be further increased through the use of preheated PbS QDs due to the destruction of the ligands. Samples which had been surface modified with MPA and subsequently thermally treated show the best results with respect to their thermopower and resistivities. Nevertheless the conductivity of the QD solids is still too high for them to be used as efficient thermoelectric materials. The final assembly method does not involve QDs but instead with one dimensional nanowires. Therefore a synthesis was developed that enables the formation of PbS nanowires of different diameters and one that is easy up-scalable. By the use of a less reactive sulfur precursor and an additional surfactant the formation of nuclei is significantly retarded and within an annealing time of two hours nanowires can be formed presumably by an oriented attachment mechanism. Single crystalline nanowires with a diameter of 65-105 nm could be achieved with the longest axes of the nanowires being parallel to [100]. The resulting nanowires were used as building blocks for film formation on glass substrates by an easily implemented method that requires no special equipment. To characterize the films with a view to their possible application as a thermoelectric material, surface modifications of the films were performed to improve the charge transfer in the films and the Seebeck coefficients of the resulting films measured. Therefore the previous approach of using MPA was applied and a subsequent thermal treatment demonstrated very promising results. In addition an crosslinking ligand was used for surface treatment that leads to similar results as was observed for the thermally treated MPA approach. Both approaches lead to an order of magnitude decrease in the resistivity and due to the fewer grain boundaries present in the films composed of nanowires as compared to the QD assemblies the conductivity is significantly higher. The Seebeck coefficient measurements show that the thermal treatment only slightly affects the Seebeck coefficients. Therefore a significantly higher power factor could be achieved for the nanowire films than for the QD solids.

The assembly of nanostructures into “multi”-dimensional materials is one of the main topics occurring in nanoscience today. It is now possible to produce high quality nanostructures reproducibly but for their further application larger structures that are easier to handle are required. Nevertheless during their assembly their nanometer size and accompanying properties must be maintained. This challenge was addressed in this work. Lead chalcogenides have been chosen as an example system because they are expected to offer great opportunities as thermoelectric materials. Three different ways to achieve assemblies of lead chalcogenide nanostructures were used and the resulting structures characterized with respect to their potential application as thermoelectric material. The first means by which a “multi”-dimensional assembly of lead chalcogenide quantum dots can be produced is the formation of porous structures such as aerogels and xerogels. A procedure, where the addition of an initiator such as oxidizers or incident radiation is unnecessary, is introduced and the formation process studied by absorption spectroscopy. The time-consuming aggregation step could be significantly reduced by employing a slightly elevated temperature during gelation that does not lead to any observable differences within the resulting gel structures. After either supercritical or subcritical drying, highly porous monolithic gel structures can be achieved. During the gel formation the size and the shape of the particles changed and they were directly linked together. Nevertheless the resulting porous structures remain crystalline and size dependent effects of the optical properties could be shown. Gels produced from a mixture of PbS and PbSe QDs show a homogenous distribution of both materials but it is not clear to what extent they form an alloy. Although the particles are directly linked together the resulting porous structures possess a very high resistivity and so it was not possible to characterize the semiconductor aerogels with regard to their thermoelectric properties. To achieve an enhanced conductivity porous structures containing PbS and Au nanoparticles have been produced. As has been seen for the pure semiconductor gels the size of the PbS quantum dots has increased and elongated particles were formed. In contrast to the PbS QDs the Au nanoparticles did not change their size and shape and are unevenly distributed within the PbS network. Through the use of the gold nanoparticles the conductivity could be increased and although the conductivity is still quite small, it was possible to determine Seebeck coefficients near room temperature for a mixed semiconductor-metal gel. The second means by which QD solids could be formed was by the compaction of the QD building blocks into a material that is still nanostructured. Therefore the synthesis of PbS was optimized to achieve sufficient amounts of PbS quantum dots. The ligands used in the synthesis of the QDs unfortunately act as an insulating layer resulting in QD solids with resistivities as high as 2 Gigaohm. For this reason different surface modification strategies were introduced to minimize the interparticle distance and to increase the coupling between the QDs so as to increase the conductivity of the resulting quantum dot solids. One very promising method was the exchange of the initial ligands by shorter ones that can be destroyed at lower temperatures. By such heat treatments the resistivity could be decreased by up to six orders of magnitude. For the pressing of the quantum dots two different compaction methods (SPS and hydraulic pressing) were compared. While the grain growth within the SPS pressed samples is significantly higher the same densification can be achieved by a cold hydraulic pressing as well as by SPS. The densification could be further increased through the use of preheated PbS QDs due to the destruction of the ligands. Samples which had been surface modified with MPA and subsequently thermally treated show the best results with respect to their thermopower and resistivities. Nevertheless the conductivity of the QD solids is still too high for them to be used as efficient thermoelectric materials. The final assembly method does not involve QDs but instead with one dimensional nanowires. Therefore a synthesis was developed that enables the formation of PbS nanowires of different diameters and one that is easy up-scalable. By the use of a less reactive sulfur precursor and an additional surfactant the formation of nuclei is significantly retarded and within an annealing time of two hours nanowires can be formed presumably by an oriented attachment mechanism. Single crystalline nanowires with a diameter of 65-105 nm could be achieved with the longest axes of the nanowires being parallel to [100]. The resulting nanowires were used as building blocks for film formation on glass substrates by an easily implemented method that requires no special equipment. To characterize the films with a view to their possible application as a thermoelectric material, surface modifications of the films were performed to improve the charge transfer in the films and the Seebeck coefficients of the resulting films measured. Therefore the previous approach of using MPA was applied and a subsequent thermal treatment demonstrated very promising results. In addition an crosslinking ligand was used for surface treatment that leads to similar results as was observed for the thermally treated MPA approach. Both approaches lead to an order of magnitude decrease in the resistivity and due to the fewer grain boundaries present in the films composed of nanowires as compared to the QD assemblies the conductivity is significantly higher. The Seebeck coefficient measurements show that the thermal treatment only slightly affects the Seebeck coefficients. Therefore a significantly higher power factor could be achieved for the nanowire films than for the QD solids.