Jason W. L. Lee

Multimass velocity-map imaging with the Pixel Imaging Mass Spectrometry (PImMS) sensor: an ultra-fast event-triggered camera for particle imaging.

We present the first multimass velocity-map imaging data acquired using a new ultrafast camera designed for time-resolved particle imaging. The PImMS (Pixel Imaging Mass Spectrometry) sensor allows particle events to be imaged with time resolution as high as 25 ns over data acquisition times of more than 100 μs. In photofragment imaging studies, this allows velocity-map images to be acquired for multiple fragment masses on each time-of-flight cycle. We describe the sensor architecture and present bench-testing data and multimass velocity-map images for photofragments formed in the UV photolysis of two test molecules: Br(2) and N,N-dimethylformamide.

PImMS, a fast event-triggered monolithic pixel detector with storage of multiple timestamps

PImMS, or Pixel Imaging Mass Spectrometry, is a novel high-speed monolithic CMOS imaging sensor tailored to mass spectrometry requirements, also suitable for other dark-field applications. In its application to time-of-flight mass spectrometry, the sensor permits ion arrival time distributions to be combined with 2D imaging, providing additional information about the initial position or velocity of ions under study. PImMS1, the first generation sensor in this family, comprises an array of 72 by 72 pixels on a 70 μm by 70 μm pitch. Pixels independently record digital timestamps when events occur over an adjustable threshold. Each pixel contains 4 memories to record timestamps at a resolution of 25 ns. The sensor was designed and manufactured in the INMAPS 0.18 μm process. This allows the inclusion of significant amounts of circuitry (over 600 transistors) within each pixel while maintaining good detection efficiency. We present an overview of the pixel and sensor architecture, explain its functioning and present test results, ranging from characterisation of the analogue front end of the pixel, to verification of its digital functions, to some first images captured on mass spectrometers. We conclude with an overview of the upcoming second generation of PImMS sensors.

The application of the fast, multi-hit, pixel imaging mass spectrometry sensor to spatial imaging mass spectrometry

Imaging mass spectrometry is a powerful technique that allows chemical information to be correlated to a spatial coordinate on a sample. By using stigmatic ion microscopy, in conjunction with fast cameras, multiple ion masses can be imaged within a single experimental cycle. This means that fewer laser shots and acquisition cycles are required to obtain a full data set, and samples suffer less degradation as overall collection time is reduced. We present the first spatial imaging mass spectrometry results obtained with a new time-stamping detector, named the pixel imaging mass spectrometry (PImMS) sensor. The sensor is capable of storing multiple time stamps in each pixel for each time-of-flight cycle, which gives it multi-mass imaging capabilities within each pixel. A standard velocity-map ion imaging apparatus was modified to allow for microscope mode spatial imaging of a large sample area (approximately 5 × 5 mm(2)). A variety of samples were imaged using PImMS and a conventional camera to determine the specifications and possible applications of the spectrometer and the PImMS camera.

Top Notch Design for Fiber-Loop Cavity Ring-Down Spectroscopy

Fiber-loop cavity ring-down spectroscopy (CRDS) is a highly sensitive spectroscopic absorption technique which has shown considerable promise for the analysis of small-volume liquid samples. We have developed a new light coupling method for fiber-loop CRDS, which overcomes two disadvantages of the technique: low efficiency light coupling into the cavity and high loss per pass. The coupler is based on a 45° reflective notch polished between 10 and 30 μm into the core of a large-core-diameter (365 μm) optical fiber, and allows for nearly 100% light coupling into the cavity, with a low loss per pass (<4%). The coupler has the additional advantage that the input and output light is spatially separated on opposite sides of the fiber. The detection sensitivity of a fiber-loop CRD spectrometer employing the new coupling method is established from ring-down measurements on aqueous rhodamine 6G (Rh6G) at 532 nm. The results are compared with data obtained using the same light source and detector, but a conventional bend-coupled small-core-diameter (50 μm) optical fiber loop. With our new coupler, a detection limit of 0.11 cm(-1) is found, which corresponds to detection of 0.93 μM Rh6G in a volume of only 19 nL. This is an improvement of over an order of magnitude on our bend-coupled small-core optical fiber results, in which a detection limit of 5.3 cm(-1) was found, corresponding to a detection of 43 μM Rh6G in a volume of 20 pL.

Three-dimensional imaging of carbonyl sulfide and ethyl iodide photodissociation using the pixel imaging mass spectrometry camera

The Pixel Imaging Mass Spectrometry (PImMS) camera is used in proof-of-principle three-dimensional imaging experiments on the photodissociation of carbonyl sulfide and ethyl iodide at wavelengths around 230 nm and 245 nm, respectively. Coupling the PImMS camera with DC-sliced velocity-map imaging allows the complete three-dimensional Newton sphere of photofragment ions to be recorded on each laser pump-probe cycle with a timing precision of 12.5 ns, yielding velocity resolutions along the time-of-flight axis of around 6%-9% in the applications presented.

Exploring surface photoreaction dynamics using pixel imaging mass spectrometry (PImMS)

A new technique for studying surface photochemistry has been developed using an ion imaging time-of-flight mass spectrometer in conjunction with a fast camera capable of multimass imaging. This technique, called pixel imaging mass spectrometry (PImMS), has been applied to the study of butanone photooxidation on TiO2(110). In agreement with previous studies of this system, it was observed that the main photooxidation pathway for butanone involves ejection of an ethyl radical into vacuum which, as confirmed by our imaging experiment, undergoes fragmentation after ionization in the mass spectrometer. This proof-of-principle experiment illustrates the usefulness and applicability of PImMS technology to problems of interest within the surface science community.

High-sensitivity online detection for microfluidics via cavity ringdown spectroscopy

We report the coupling of cavity ringdown spectroscopy (CRDS) with a microfluidic chip fabricated using a rapid prototyping method, in order to demonstrate high-sensitivity, non-contact online detection in microfluidics. Conventional UV-vis absorption techniques are largely ineffective for microfluidic detection due to the small sample volumes and short path lengths. The multipass absorption achieved in cavity ringdown spectroscopy increases the effective absorption pathlength by several orders of magnitude, and hence enhances the detection sensitivity. A cavity ringdown spectrometer, operating at a single wavelength of 532 nm for the purposes of the proof-of-concept measurements presented here, has been developed for online detection on a polymer/glass microchip fabricated by frontal photopolymerisation. High sensitivity absorption measurements on liquid samples with volumes of tens to hundreds of nanolitres and absorption pathlengths ranging from tens to hundreds of microns are demonstrated. A series of proof-of-concept experiments show that the technique has the ability to monitor both static and time-varying analyte concentrations. Firstly, the detection limit of the system is estimated from a three-standard-deviation error analysis of absorption measurements made on dilute aqueous solutions of potassium permanganate (natural absorption coefficient (4805 ± 10) M−1 cm−1 at 532 nm). The detection limit was found to be ∼210 nM for a 466 μm pathlength, corresponding to an absorption of 1.0 × 10−3 cm−1. Online pH measurements on a 20 nL sample are performed by monitoring the absorption of phenolphthalein indicator present at millimolar concentrations. Finally, CRDS has been applied, for the first time, to monitoring chemical reaction kinetics on a microfluidic chip, tracking the oscillation period of the well-known Belousov–Zhabotinsky reaction.

Alignment, Orientation, and Coulomb Explosion of Difluoroiodobenzene Studied with the Pixel Imaging Mass Spectrometry (PImMS) Camera

Laser-induced adiabatic alignment and mixed-field orientation of 2,6-difluoroiodobenzene (C6H3F2I) molecules are probed by Coulomb explosion imaging following either near-infrared strong-field ionization or extreme-ultraviolet multi-photon inner-shell ionization using free-electron laser pulses. The resulting photoelectrons and fragment ions are captured by a double-sided velocity map imaging spectrometer and projected onto two position-sensitive detectors. The ion side of the spectrometer is equipped with a pixel imaging mass spectrometry camera, a time-stamping pixelated detector that can record the hit positions and arrival times of up to four ions per pixel per acquisition cycle. Thus, the time-of-flight trace and ion momentum distributions for all fragments can be recorded simultaneously. We show that we can obtain a high degree of one-and three-dimensional alignment and mixed-field orientation and compare the Coulomb explosion process induced at both wavelengths.

Coulomb-explosion imaging of concurrent CH2BrI photodissociation dynamics.

The dynamics following laser-induced molecular photodissociation of gas-phase CH2BrI at 271.6 nm were investigated by time-resolved Coulomb-explosion imaging using intense near-IR femtosecond laser pulses. The observed delay-dependent photofragment momenta reveal that CH2BrI undergoes C-I cleavage, depositing 65.6% of the available energy into internal product states, and that absorption of a second UV photon breaks the C-Br bond of CH2Br. Simulations confirm that this mechanism is consistent with previous data recorded at 248 nm, demonstrating the sensitivity of Coulomb-explosion imaging as a real-time probe of chemical dynamics.

Ultraviolet photochemistry of 2-bromothiophene explored using universal ionization detection and multi-mass velocity-map imaging with a PImMS2 sensor

The ultraviolet photochemistry of 2-bromothiophene (C4H3SBr) has been studied across the wavelength range 265-245 nm using a velocity-map imaging (VMI) apparatus recently modified for multi-mass imaging and vacuum ultraviolet (VUV, 118.2 nm) universal ionization. At all wavelengths, molecular products arising from the loss of atomic bromine were found to exhibit recoil velocities and anisotropies consistent with those reported elsewhere for the Br fragment [J. Chem. Phys. 142, 224303 (2015)]. Comparison between the momentum distributions of the Br and C4H3S fragments suggests that bromine is formed primarily in its ground (2P3/2) spin-orbit state. These distributions match well at high momentum, but relatively fewer slow moving molecular fragments were detected. This is explained by the observation of a second substantial ionic product, C3H3+. Analysis of ion images recorded simultaneously for several ion masses and the results of high-level ab initio calculations suggest that this fragment ion arises from dissociative ionization (by the VUV probe laser) of the most internally excited C4H3S fragments. This study provides an excellent benchmark for the recently modified VMI instrumentation and offers a powerful demonstration of the emerging field of multi-mass VMI using event-triggered, high frame-rate sensors, and universal ionization.