Organic/Inorganic Hybrid Nanocomposite Infrared Photodetection by Intraband Absorption
The ability to detect infrared radiation is vital for a host of applications that include optical communication, medical diagnosis, thermal imaging, atmospheric monitoring, and space science. The need to actively cool infrared photon detectors increases their operation cost and weight, and the focus of much recent research has been to limit the dark current and create room-temperature infrared photodetectors appropriate for mid-to-long-wave infrared detection. Quantum dot infrared photodetectors (QDIPs) provide electron quantum confinement in three dimensions and have been shown to demonstrate high temperature operation (T>150 K) due to lower dark currents. However, these inorganic devices have not achieved sensitivity comparable to state-of-the-art photon detectors, due in large part to the inability to control the uniformity (size and shape) of QDs during strained-layer epitaxy.
The purpose of this dissertation research was to investigate the feasibility of room-temperature infrared photodetection that could overcome the shortfalls of QDIPs by using chemically synthesized inorganic colloidal quantum dots (CQDs). CQDs are coated with organic molecules known as surface ligands that prevent the agglomeration of dots while in solution. When CQDs are suspended in a semiconducting organic polymer, these materials are known as organic/inorganic hybrid nanocomposites. The novel approach investigated in this work was to use intraband transitions in the conduction band of the polymer-embedded CQD for room-temperature photodetection in the mid-wave, and possibly long-wave, infrared ranges. Hybrid nanocomposite materials promise room-temperature operation due to: (i) large bandgaps of the inorganic CQDs and the semiconducting polymer that reduce thermionic emission; and (ii) low dark current due to the three-dimensional electron confinement in the CQD and low carrier mobility in the semiconducting polymer. The primary material system investigated in this research was CdSe CQDs embedded in the conjugated polymer poly[2-methoxy-5-(2'-ethylhexyloxy)-1,4-(1-cyanovinylene)phenylene] (MEH-CN-PPV).
Photoluminescence (PL) spectroscopy of MEH-CN-PPV thin films was conducted to determine the dependence of polymer morphology on deposition method in order to identify a reliable device fabrication technique. Three different deposition methods were investigated: drop-casting and spin-casting, which are solution-based; and matrix-assisted pulsed laser evaporation (MAPLE), which is a vacuum-based method that gently evaporates polymers (or hybrid nanocomposites) and limits substrate exposure to solvents. It was found that MAPLE deposition provides repeatable control of the thin film morphology and thickness, which is important for nanocomposite device optimization.
Ultra-fast PL spectroscopy of MEH-CN-PPV/CdSe thin films was investigated to determine the charge generation and relaxation dynamics in the hybrid nanocomposite thin films. The mathematical fitting of time-integrated and time-resolved PL provided a rigorous and unique model of the charge dynamics, which enabled calculation of the radiative and non-radiative decay lifetimes in the polymer and CQD. These results imply that long-lived electrons exist in the conduction band of the CQD, which demonstrate that it should be possible to generate a mid- to long-wave infrared photocurrent based on intraband transitions. In fact, room-temperature, intraband, mid-infrared absorption was measured in thin films of MEH-CN-PPV/CdSe hybrid nanocomposites by Fourier transform infrared (FTIR) absorbance spectroscopy. In addition, the hybrid nanocomposite confined energy levels and corresponding oscillator strengths were calculated in order to model the absorption spectrum. The calculated absorption peaks agree well with the measured peaks, demonstrating that the developed computer model provides a useful design tool for determining the impact of important materials system properties, such as CQD size, organic surface ligand material choice, and conduction band offset due to differences in CQD and polymer electron affinities.
Finally, a room-temperature, two terminal, hybrid nanocomposite mid-infrared photoconductor based on intraband transitions was demonstrated by FTIR spectral response measurements, measuring a spectral responsivity peak of 4.32 µA/W at 5.5µm (5 volts), and calibrated blackbody spectral photocurrent measurements, measuring a spectral responsivity peak of 4.79 µA/W at 5.7 µm (22 volts). This device characterization demonstrated that while the novel approach of intraband infrared photodetection in hybrid nanocomposites is feasible, significant challenges exist related to device fabrication and operation. Future work is proposed that could address some of these important issues.
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