Brian G. Alberding

Reduced photoconductivity observed by time-resolved terahertz spectroscopy in metal nanofilms with and without adhesion layers

Non-contact, optical time-resolved terahertz spectroscopy (TRTS) has been used to study the transient photoconductivity of nanometer-scale metallic films deposited on fused quartz substrates. Samples of 8 nm thick gold or titanium show an instrument-limited (ca. 0.5 ps) decrease in conductivity following photoexcitation due to electron-phonon coupling and subsequent increased lattice temperatures which increases charge carrier scattering. In contrast, for samples of 8 nm gold with a 4 nm adhesion layer of titanium or chromium, a ca. 70 ps rise time for the lattice temperature increase is observed. These results establish the increased transient terahertz transmission sign change of metallic compared to semiconductor materials. The results also suggest nanoscale gold films that utilize an adhesion material do not consist of distinct layers.

Static and Time-Resolved Terahertz Measurements of Photoconductivity in Solution-Deposited Ruthenium Dioxide Nanofilms

Thin-film ruthenium dioxide (RuO2) is a promising alternative material as a conductive electrode in electronic applications because its rutile crystalline form is metallic and highly conductive. Herein, a solution-deposition multi-layer technique is employed to fabricate ca. 70 ± 20 nm thick films (nanoskins) and terahertz spectroscopy is used to determine their photoconductive properties. Upon calcining at temperatures ranging from 373 K to 773 K, nanoskins undergo a transformation from insulating (localized charge transport) behavior to metallic behavior. Terahertz time-domain spectroscopy (THz-TDS) indicates that nanoskins attain maximum static conductivity when calcined at 673 K (σ = 1030 ± 330 S·cm-1). Picosecond time-resolved Terahertz spectroscopy (TRTS) using 400 nm and 800 nm excitation reveals a transition to metallic behavior when calcined at 523 K. For calcine temperatures less than 523 K, the conductivity increases following photoexcitation (ΔE < 0) while higher calcine temperatures yield films composed of crystalline, rutile RuO2 and the conductivity decreases (ΔE > 0) following photoexcitation.

Direct comparison of time-resolved terahertz spectroscopy and Hall Van der Pauw methods for measurement of carrier conductivity and mobility in bulk semiconductors

Charge carrier conductivity and mobility for various semiconductor wafers and crystals were measured by ultrafast above bandgap, optically excited Time-Resolved Terahertz Spectroscopy (TRTS) and Hall Van der Pauw contact methods to directly compare these approaches and validate the use of the non-contact optical approach for future materials and in-situ device analyses. Undoped and doped silicon (Si) wafers with resistances varying over six orders of magnitude were selected as model systems since contact Hall measurements are reliably made on this material. Conductivity and mobility obtained at room temperature by terahertz transmission and TRTS methods yields the sum of electron and hole mobility which agree very well with either directly measured or literature values for corresponding atomic and photo-doping densities. Careful evaluation of the optically-generated TRTS frequency-dependent conductivity also shows it is dominated by induced free-carrier absorption rather than small probe pulse phase shifts, which is commonly ascribed to changes in the complex conductivity from sample morphology and evaluation of carrier mobility by applying Drude scattering models. Thus, in this work, the real-valued, frequency-averaged conductivity was used to extract sample mobility without application of models. Examinations of germanium (Ge), gallium arsenide (GaAs), gallium phosphide (GaP) and zinc telluride (ZnTe) samples were also made to demonstrate the general applicability of the TRTS method, even for materials that do not reliably make good contacts (e.g., GaAs, GaP, ZnTe). For these cases, values for the sum of the electron and hole mobility also compare very favorably to measured or available published data.

Time-resolved terahertz spectroscopy of electrically conductive metal-organic frameworks doped with redox active species

Metal-Organic Frameworks (MOFs) are three-dimensional coordination polymers that are well known for large pore surface area and their ability to adsorb molecules from both the gaseous and solution phases. In general, MOFs are electrically insulating, but promising opportunities for tuning the electronic structure exist because MOFs possess synthetic versatility; the metal and organic ligand subunits can be exchanged or dopant molecules can be introduced into the pore space. Two such MOFs with demonstrated electrical conductivity are Cu3(1,3,5-benzenetricarboxylate)2, a.k.a HKUST-1, and Cu[Ni(pyrazine-2,3-dithiolate)2]. Herein, these two MOFs have been infiltrated with the redox active species 7,7,8,8-tetracyanoquinodimethane (TCNQ) and iodine under solution phase conditions and shown to produce redox products within the MOF pore space. Vibrational bands assignable to TCNQ anion and triiodide anion have been observed in the Mid-IR and Terahertz ranges using FTIR Spectroscopy. The MOF samples have been further investigated by Time-Resolved Terehertz Spectroscopy (TRTS). Using this technique, the charge mobility, separation, and recombination dynamics have been followed on the picosecond time scale following photoexcitation with visible radiation. The preliminary results show that the MOF samples have small inherent photoconductivity with charge separation lifetimes on the order of a few picoseconds. In the case of HKUST-1, the MOF can also be supported by a TiO2 film and initial results show that charge injection into the TiO2 layer occurs with a comparable efficiency to the dye sensitizer N3, [cis-Bis(isothiocyanato)-bis(2,2’-bipyridyl-4,4’-dicarboxylato ruthenium(II)], and therefore this MOF has potential as a new light absorbing and charge conducting material in photovoltaic devices.

Femtosecond laser eyewear protection: Measurements and precautions for amplified high power applications

Ultrafast lasers have become increasingly important as research tools in laboratories and commercial enterprises suggesting laser safety, personal protection and awareness become ever more important. Laser safety eyewear are typically rated by their optical densities (OD) over various spectral ranges, but these measurements are usually made using low power, large beam size, and continuous beam conditions. These measurement scenarios are vastly different than the high power, small beam size, and pulsed laser beam conditions where ultrafast lasers have extremely high peak powers and broad spectra due to the short pulse durations. Many solid-state lasers are also tunable over a broad wavelength range, further complicating the selection of adequate laser safety eyewear. Eighteen laser eyewear filter samples were tested under real-world conditions using a Ti:Sapphire regenerative amplifier with output pulses centered at 800 nm running from 2 Hz to 1 KHz repetition rate. The typical maximum peak laser irrandiance employed was ca. 3 TW/cm2 (800 nm wavelength, 450 uJ/pulse with 80 fs FWHM pulse duration) or less when damage occurred, depending on the sample. While many samples maintained their integrity under these test conditions, many plastic samples showed signs of failure which reduced their OD, in some cases transmitting 4 to 5 orders of magnitude higher than expected. In general, glass filters performed significantly better than plastic filters, exhibiting less physical damage to the substrate and less absorber degradation.

Ultrafast laser eyewear protection: Measurements and precautions

Ultrafast laser systems are becoming more widespread throughout the research and industrial communities yet eye protection for these high power, bright pulsed sources still require scrupulous characterization and testing before use. Femtosecond lasers, with pulses naturally possessing broad-bandwidth and high average power with variable repetition rate, can exhibit spectral side-bands and subtly changing center wavelengths, which may unknowingly affect eyewear safety protection. Pulse spectral characterization and power diagnostics are presented for a 80 MHz, Ti+3:Sapphire, ≈ 800 nm, ≈40 femtosecond oscillator system. Power and spectral transmission for 22 test samples are measured to determine whether they fall within manufacturer specifications.