Scott M. Geyer

A broadband Fourier transform microwave spectrometer based on chirped pulse excitation

Designs for a broadband chirped pulse Fourier transform microwave (CP-FTMW) spectrometer are presented. The spectrometer is capable of measuring the 7-18 GHz region of a rotational spectrum in a single data acquisition. One design uses a 4.2 Gsampless arbitrary waveform generator (AWG) to produce a 1 mus duration chirped pulse with a linear frequency sweep of 1.375 GHz. This pulse is sent through a microwave circuit to multiply the bandwidth of the pulse by a factor of 8 and upconvert it to the 7.5-18.5 GHz range. The chirped pulse is amplified by a traveling wave tube amplifier and broadcast inside the spectrometer by using a double ridge standard gain horn antenna. The broadband molecular free induction decay (FID) is received by a second horn antenna, downconverted, and digitized by a 40 Gsampless (12 GHz hardware bandwidth) digital oscilloscope. The second design uses a simplified pulse generation and FID detection scheme, employing current state-of-the-art high-speed digital electronics. In this spectrometer, a chirped pulse with 12 GHz of bandwidth is directly generated by using a 20 Gsampless AWG and upconverted in a single step with an ultrabroadband mixer. The amplified molecular emission is directly detected by using a 50 Gsampless digital oscilloscope with 18 GHz bandwidth. In both designs, fast Fourier transform of the FID produces the frequency domain rotational spectrum in the 7-18 GHz range. The performance of the CP-FTMW spectrometer is compared to a Balle-Flygare-type cavity-FTMW spectrometer. The CP-FTMW spectrometer produces an equal sensitivity spectrum with a factor of 40 reduction in measurement time and a reduction in sample consumption by a factor of 20. The CP-FTMW spectrometer also displays good intensity accuracy for both sample number density and rotational transition moment. Strategies to reduce the CP-FTMW measurement time by another factor of 90 while simultaneously reducing the sample consumption by a factor of 30 are demonstrated.

In Vacuo Photoemission Studies of Platinum Atomic Layer Deposition Using Synchrotron Radiation.

The mechanism of platinum atomic layer deposition using (methylcyclopentadienyl)trimethylplatinum and oxygen is investigated with in vacuo photoemission spectroscopy at the Stanford Synchrotron Radiation Lightsource. With this surface-sensitive technique, the surface species following the Pt precursor half cycle and the oxygen counter-reactant half cycle can be directly measured. We observed significant amounts of carbonaceous species following the Pt precursor pulse, consistent with dehydrogenation of the precursor ligands. Significantly more carbon is observed when deposition is carried out in the thermal decomposition temperature region. The carbonaceous layer is removed during the oxygen counter reactant pulse, and the photoemission spectrum shows that a layer of adsorbed oxygen remains on the surface as previously predicted.

Structural evolution of platinum thin films grown by atomic layer deposition

The structural properties of Pt films grown by atomic layer deposition (ALD) are investigated with synchrotron based x-ray scattering and x-ray diffraction techniques. Using grazing incidence small angle scattering, we measure the lateral growth rate of the Pt islands to be 1.0 A/cycle. High resolution x-ray diffraction reveals that the in-plane strain of the Pt lattice undergoes a transition from compressive strain to tensile strain when the individual islands coalescence into a continuous film. This transition to tensile strain is attributed to the lateral expansion that occurs when neighboring islands merge to reduce their surface energy. Using 2D grazing incidence x-ray diffraction, we show that the lattice orientation becomes more (111) oriented during deposition, with a sharp transition occurring during coalescence. Pt ALD performed at a lower deposition temperature (250 °C) is shown to result in significantly more randomly oriented grains.

The low temperature atomic layer deposition of ruthenium and the effect of oxygen exposure

We have studied the atomic layer deposition (ALD) of ruthenium using bis(2,4-dimethylpentadienyl) ruthenium and oxygen. We show that the process is achievable at a low operating temperature of 185 °C. Variation in the exposure time and pressure of the oxygen counterreactant has significant effects on the nucleation, growth rate and composition of the deposited ruthenium films. High oxygen pressure helps to promote the nucleation of ruthenium on a silicon dioxide substrate. Although saturation conditions are achieved with the Ru precursor, saturation of the ruthenium growth rate with oxygen exposure is observed only for a small range of oxygen exposure. Increasing the oxygen exposure further results in the incorporation of oxygen in the deposited film to form ruthenium oxide, a process which is enhanced at higher deposition temperature. We propose that the slow diffusion of oxygen to the subsurface region is a rate-limiting step in this process. We demonstrate that the composition of the deposited films from metallic ruthenium to ruthenium oxide, as well as the average grain size, may be regulated by tuning the pressure and exposure time of the oxygen counterreactant. Hence, this low temperature ALD process provides a flexible route to the deposition of Ru-based films.

Portable atomic layer deposition reactor for in situ synchrotron photoemission studies

We report the design of a portable atomic layer deposition (ALD) reactor that can be integrated into synchrotron facilities for in situ synchrotron photoemission studies. The design allows for universal installation of the system onto different beam line end stations. The ALD reactor operates as a fully functional, low vacuum deposition system under the conditions of a typical ALD reactor while allowing the samples to be analyzed in an ultrahigh vacuum (UHV) chamber through a quick transfer without vacuum break. This system not only minimizes the exposure of the UHV chamber to the ALD reactants, but it also eliminates the necessity of a beam alignment step after installation. The system has been successfully installed at the synchrotron and tested in the mechanistic studies of platinum ALD following individual half reaction cycles.

An atomic layer deposition chamber for in situ x-ray diffraction and scattering analysis

The crystal structure of thin films grown by atomic layer deposition (ALD) will determine important performance properties such as conductivity, breakdown voltage, and catalytic activity. We report the design of an atomic layer deposition chamber for in situ x-ray analysis that can be used to monitor changes to the crystal structural during ALD. The application of the chamber is demonstrated for Pt ALD on amorphous SiO2 and SrTiO3 (001) using synchrotron-based high resolution x-ray diffraction, grazing incidence x-ray diffraction, and grazing incidence small angle scattering.