On Ultrafast Time-Domain TeraHertz Spectroscopy in the Condensed Phase: Linear Spectroscopic Measurements of Hydrogen-Bond Dynamics of Astrochemical Ice Analogs and Nonlinear TeraHertz Kerr Effect Measurements of Vibrational Quantum Beats

Much of the chemistry that affects life on planet Earth occurs in the condensed phase. The TeraHertz (THz) or far-infrared (far-IR) region of the electromagnetic spectrum (from 0.1 THz to 10 THz, 3 cm^-1 to 300 cm^-1, or 3000 μm to 30 μm) has been shown to provide unique possibilities in the study of condensed-phase processes. The goal of this work is to expand the possibilities available in the THz region and undertake new investigations of fundamental interest to chemistry. Since we are fundamentally interested in condensed-phase processes, this thesis focuses on two areas where THz spectroscopy can provide new understanding: astrochemistry and solvation science. To advance these fields, we had to develop new instrumentation that would enable the experiments necessary to answer new questions in either astrochemistry or solvation science. We first developed a new experimental setup capable of studying astrochemical ice analogs in both the TeraHertz (THz), or far-Infrared (far-IR), region (0.3 - 7.5 THz; 10 - 250 cm^-1) and the mid-IR (400 - 4000 cm^-1). The importance of astrochemical ices lies in their key role in the formation of complex organic molecules, such as amino acids and sugars in space. Thus, the instruments are capable of performing variety of spectroscopic studies that can provide especially relevant laboratory data to support astronomical observations from telescopes such as the Herschel Space Telescope, the Stratospheric Observatory for Infrared Astronomy (SOFIA), and the Atacama Large Millimeter Array (ALMA). The experimental apparatus uses a THz time-domain spectrometer, with a 1750/875 nm plasma source and a GaP detector crystal, to cover the bandwidth mentioned above with ~10 GHz (~0.3 cm^-1) resolution.

Using the above instrumentation, experimental spectra of astrochemical ice analogs of water and carbon dioxide in pure, mixed, and layered ices were collected at different temperatures under high vacuum conditions with the goal of investigating the structure of the ice. We tentatively observe a new feature in both amorphous solid water and crystalline water at 33 cm^-1 (1 THz). In addition, our studies of mixed and layered ices show how it is possible to identify the location of carbon dioxide as it segregates within the ice by observing its effect on the THz spectrum of water ice. The THz spectra of mixed and layered ices are further analyzed by fitting their spectra features to those of pure amorphous solid water and crystalline water ice to quantify the effects of temperature changes on structure. From the results of this work, it appears that THz spectroscopy is potentially well suited to study thermal transformations within the ice.

To advance the study of liquids with THz spectroscopy, we developed a new ultrafast nonlinear THz spectroscopic technique: heterodyne-detected, ultrafast THz Kerr effect (TKE) spectroscopy. We implemented a heterodyne-detection scheme into a TKE spectrometer that uses a stilbazoiumbased THz emitter, 4-N,N-dimethylamino-4-N-methyl-stilbazolium 2,4,6-trimethylbenzenesulfonate (DSTMS), and high numerical aperture optics which generates THz electric field in excess of 300 kV/cm, in the sample. This allows us to report the first measurement of quantum beats at terahertz (THz) frequencies that result from vibrational coherences initiated by the nonlinear, dipolar interaction of a broadband, high-energy, (sub)picosecond THz pulse with the sample. Our instrument improves on both the frequency coverage, and sensitivity previously reported; it also ensures a backgroundless measurement of the THz Kerr effect in pure liquids. For liquid diiodomethane, we observe a quantum beat at 3.66 THz (122 cm^-1), in exact agreement with the fundamental transition frequency of the υ4 vibration of the molecule. This result provides new insight into dipolar vs. Raman selection rules at terahertz frequencies.

To conclude we discuss future directions for the nonlinear THz spectroscopy in the Blake lab. We report the first results from an experiment using a plasma-based THz source for nonlinear spectroscopy that has the potential to enable nonlinear THz spectra with a sub-100 fs temporal resolution, and how the optics involved in the plasma mechanism can enable THz pulse shaping. Finally, we discuss how a single-shot THz detection scheme could improve the acquisition of THz data and how such a scheme could be implemented in the Blake lab. The instruments developed herein will hopefully remain a part of the groups core competencies and serve as building blocks for the next generation of THz instrumentation that pushes the frontiers of both chemistry and the scientific enterprise as a whole.

35 GHz passive mode-locking of InGaAs/GaAs quantum dot lasers at 1.3 μm with Fourier-limited pulses

We report 35 GHz passive mode-locking and 20 GHz hybrid mode-locking of quantum dot (QD) lasers at 1.3 μm. Our investigations show ultrafast absorber recovery times and for the first time transform-limited mode-locked pulses. © 2003 Optical Society of America.

Low power all-optical switch in a passive InGaAsP multiple quantum well waveguide

We demonstrate the use of resonant bandfilling nonlinearity in an InGaAsP/InGaAsP Multiple Quantum Well (MQW) waveguide due to photogenerated carriers to obtain switching at pulse powers, which can readily be obtained from an erbium amplified diode laser source. In order to produce gating a polarisation rotation gate was used, which relies on an asymmetry in the nonlinear refraction on the principle axes of the waveguide.

Single-photon detection using a quantum dot field effect transistor

A novel device for detection of single photons based on a GaAs/AlGaAs modulation doped field effect transistor (MODFET) which does not rely on avalanche processes is proposed. The optimal channel electron densities and quantum dot parameters for detection of single photons are discussed.

Multiplexed classical and quantum transmission for high bitrate quantum key distribution systems

We report the operation of a gigahertz clocked quantum key distribution system, with two classical data communication channels using coarse wavelength division multiplexing over a record fibre distance of 80km. © 2012 OSA.

Multiplexed classical and quantum transmission for high bitrate quantum key distribution systems

We report the operation of a gigahertz clocked quantum key distribution system, with two classical data communication channels using coarse wavelength division multiplexing over a record fibre distance of 80km. © OSA 2012.

Picosecond pulse generation in narrow stripe mode-locked quantum dot master oscillator power amplifier

This paper reports a monolithically integrated mode-locked narrow stripe QD MOPA operating at 1300nm generating a stable 20GHz pulse train with an average power of 46.4mW and a pulse duration of 8.3ps. © Optical Society of America.

Superradiant emission from a tapered quantum-dot semiconductor diode emitter

Superradiant emission pulses from a quantum-dot tapered device are generated on demand at repetition rates of up to 5 MHz. The pulses have durations as short as 320 fs at a wavelength of 1270 nm. © 2010 Optical Society of America.

Sub-kHz RF electrical linewidth from a 10GHz passively mode-locked quantum-dot laser diode

A packaged 10GHz monolithic two-section quantum-dot mode-locked laser is presented, with record narrow 500Hz RF electrical linewidth for passive mode-locking. Single sideband noise spectra show 147fs integrated timing jitter over the 4MHz-80MHz frequency range. © 2009 Optical Society of America.

270GHz, 580fs Optical Pulse Generation from a single-section quantum-dash fabry-pérot laser using frequency multiplication

Pulse generation from a mode-locked single-section 1.55μm quantum-dash FP laser is demonstrated under continuous-wave operation. A 270GHz, 580fs pulse train is achieved by applying frequency multiplication using fiber dispersion. ©2009 Optical Society of America.

Dynamic simulation of mode-locked quantum-dot lasers

A dynamic model of passive mode-locking in quantum-dot laser diodes is presented. It is found that in contrast with quantum-well lasers, rapid gain recovery is key for mode-locking of quantum-dot lasers. © 2008 Optical Society of America.

1.3 μm quantum-dot electro-absorption modulator

The electro-absorption properties and Stark-shift of 1.3μm InGaAs quantum dot waveguide modulators are characterized under reverse bias. 2.5Gb/s data modulation is demonstrated for the first time with clear eye diagrams and error-free back-to-back performance. © 2007 Optical Society of America.

Monolithic mode-locked quantum dot lasers

Quantum-dot active material systems are proving to be an excellent choice for mode-locked laser applications. High-power, high repetition-rate picosecond and sub-picosecond pulse generation is now readily achievable with promising results for ultra-low jitter performance. © 2006 Optical Society of America.

Single mode performance of a single mode injected locked quantum dot laser

An injection locked QD laser is demonstrated to provide single longitudinal mode operation with a 40dB SMSR and an improvement in RIN peak from 1.3-2.3GHz. Alpha factor is measured to be 0.8. © 2005 Optical Society of America.