Characterization

Within the framework of this thesis the Electrospray Ionization source and the accom- panied quadrupole mass filter have been assembled and tested fully functional. Two types of measurements have been performed. The intention of the first experiment is the implementation and characterization of the Electrospray Ionization source. The second measurement shows the combined ESI-quadrupole mass filter system working properly. In order to measure the total ion current, a Faraday Cup is placed directly after the guiding

60_{150QC, Extrel}

module/board # type function

USB-3112/2 analog out mass command

USB-3112/2 analog out ∆Res

USB-3112/2 analog out ∆M

USB-3112/2 analog out Pole Bias

USB-3112/2 analog out ∗DC volt. L1-1 USB-3112/2 analog out ∗DC volt. L1-2 USB-3112/2 analog out ∗DC volt. lensIn USB-3112/2 analog out ∗DC volt. lensOut

USB-3112/2 digital out Res ON/OFF

USB-3112/2 digital out DC poles reverse USB-3112/3 analog out ∗DC pre/postfiler USB-1208LS/1 analog in Pole Bias Readb.

Table 2.2: Summary of analog I/O and digital out voltages pro- duced by the boards #2 (USB- 3112) and #3 (USB-3112) for the control of the mass selective quadrupole. The respective func- tion is given in the last column. Voltages labeled with _∗ are post- amplified by operational ampli- fiers and directly fed to the cor- responding electrodes.

Figure 2.24: Screen-shot of the two graphical user interfaces for the control of the ESI- source and the quadrupole mass filter. All relevant parameters can be set, controlled and read out. Previous used parameters can be saved and reloaded.

ion current as a function of

constant HV on N2 capillary capillary cylinder octopol

parameters needle pressure voltage temperature lens voltage voltage

HV needle [kV] - 7.9 7.9 7.9 7.9 7.9 N2 pressure [psi] 55 - 55 55 55 55 cap. voltage [V] 30 20 - 17.1 17 30 cap. temp. [◦C] 90 90 90 - 90 90 lens voltage [V] 130 130 90 150 - 130 octup. volt. [V] -20 -20 -20 -20 -20 -

Table 2.3: Summary of the parameters chosen in the experiments presented in figure 2.25. A slightly different set of constant parameters is used for each of the six measurements of the total ion current out of the ESI-source as a function of the corresponding, varying parameter.

octupole of the ESI-source. To measure the ion current, that lies typically in the pA regime, a suitable ampere-meter62 is used. In order to collect the major part of the pos- itively charged single molecules, fragments and clusters leaving the octupole, a potential of -30 V is applied to the cup. With this setup, it is possible to measure the total ion cur- rent of the ESI-source as a function of the six tuning parameters. Figure 2.25 shows the results of these measurements. The syringe pump flow rate of the L-arginin-hydrochlorid solution is kept constant at 10µl/min throughout the measurements. A slightly different set of constant parameters is used in each measurement and table 2.3 gives a summary of the actually used values. The highest total ion current achieved so far amounts to approximately 30 pA, equivalent to 2_·108_{ions/sec. Using the results of these calibration} measurements, a good performance of the ESI source is achieved by applying a voltage of 8 kV on the spraying needle, 55 psi nitrogen sheath gas pressure, a 30 V voltage on the capillary heated to 90◦C, a 130 V voltage on the cylindrical lens and -20 V on the octupole.

The second experiment is performed to show the quadrupole mass filter after the ESI- source functional. In this case, the setup with the MCP as detector, as described above, is used. With the help of the graphical user interface of figure 2.24, all of the necessary tuning parameters of the quadrupole are accessible. Pole Bias applies a DC offset potential to the quadrupole electrodes (poles). The potential difference between the ion source and the Pole Bias offset voltage sets and controls the effective ion energy in the quadrupole. The typical energy range of ions that a quadrupole can resolve is 2 eV to 12 eV. Relatively slow ions spend more time in the filter volume and experience more cycles of the radio- frequency. This increases the filtering effect and allows higher resolution. However, if the velocity of the ions is too small, it is more difficult to focus them into the quadrupole and the overall transmission drops. The best trade-off, according to the manufacturer, are ion energies in the range of 5 eV to 10 eV. The parameters ∆M and Resolution (Res) define the resolution curve of the quadrupole. Res is controlled by a voltage ranging from -5 V to +5 V. A lower value decreases the resolution. The resolution needed, changes

Figure 2.25: Measurements of the total ion current of the ESI-source as a function of the voltages on the spraying needle, the heated capillary, the cylindrical lens and the octupole, as well as the nitrogen sheath gas pressure and the temperature of the heated capillary. For each measurement a slightly different set of constant parameters according to table 2.3 is used. Except for the measurement of the total ion current as a function of temperature, all measurements have been performed twice and are plotted in blue and red respectively.

Figure 2.26: Inverted mass scan of the L-arginin Hydrochlorid test solution between 250 and 315 atomic mass units, assuming only singly charged ions. The voltages used on the quadrupole setup are briefly summarized in table 2.4.

1900 2000 260 280 300 ion sig nal MCP [a.u .] mass [amu]

with the mass, assuming singly charged ions. In order to increase the resolution for lower masses and decrease resolution for higher masses, the ∆M parameter changes the slope of the resolution curve. The other parameters tunable with the help of the GUI, like the voltages on the electrodes of lens L1, the voltages of the focusing lenses and the common DC voltage of the pre-and post filter, have been discussed above. Figure 2.26 shows a mass scan of the test solution between 250 and 315 atomic mass units, assuming singly charged ions. The parameters of the quadrupole used in this experiment are summarized in table 2.4. Several well separated signal fringes are resolved. The measurement is not intended to represent an accurate mass scan with a calibrated mass axis, but merely serves as an indication, that the mass filter option of the combined ESI/Quadrupole setup is working properly. Nevertheless, three mass differences of 18 u are clearly visible, which indicate a separation of H2O out of clusters with water. In order to obtain a valuable mass spectrum the concentration of the solution can be lowered to avoid clusters that are eventually multiply charged.

With the presented experiments, the ESI-source is characterized and the mass selecting quadrupole is proven functional. The next step will be to connect the setup to the ex- perimental apparatus described in 2.1.1. The ESI setup will replace the cryogenic gas inlet stage. Designs including detailed, mechanical computer drawings for the connec- tion of the two setups are already available. An additional conical ion-guide could link the commercial quadrupole mass spectrometer with the quadrupole ion guide and finally with the three Paul-traps. Together with directly laser cooled and trapped 138_Ba+_ions, the protonated molecules out of the ESI-source cover a wide charge-to-mass range up to biologically relevant molecular ions. For a detailed analysis of this point, refer to [31] and chapter 6. The envisioned experiments (refer to the introduction to this thesis) using X-FEL laser pulses with 1013 _{coherent X-ray photons in each single pulse need a target} that can be deterministically prepared with the repetition rate of the laser source. As an example, the current repetition rate of the Linac Coherent Light Source X-FEL amounts

parameter value [unit]

Mass 300.00 [amu]

Lowest Mass 250.00 [amu] Highest Mass 350.00 [amu]

Scan Speed 0.20 [amu/s]

Res -1.20 [a.u.] ∆M 1.20 [a.u.] PoleBias -21.00 [V] L1-1DC -15.00 [V] L1-2DC -40.00 [V] LensInDC -30.00 [V] LensOutDC -40.00 [V] PrefilterDC -28.00 [V]

Table 2.4: The experimental pa- rameters applied to the quadrupole setup, with the help of the GUI shown in figure 2.24. For explana- tion of the used abbreviations see the main text.

to 120 Hz. Taking the newly developed, efficient photoionization scheme for barium atoms (see chapter 4) into account, the source for the cooling agents is estimated to be effec- tive enough. As stated in this section, the ESI-source operated with the test solution, even not optimized for a high production rate, yields a rate of 2·108 ions/sec before the filtering stage. The rate at which ions with the right charge-to-mass ratio emerge from the quadrupole, depends on the used solution and the coupling efficiency of ions from the octupole to the quadrupole. As shown in [85], 10% coupling efficiency is a conservative estimation and a rate of 2_·104ions/sec is a typical value. Therefore, the rate at which suitable molecular ions can be delivered, lies still in the several hundred kHz regime and is thus estimated to be more than sufficient.

Chapter 3

Time-resolved spectroscopy on

single molecular

24

MgH

+

-ions

3.1

Ion trapping and transfer

In this section, the successful implementation of loading, trapping and cooling of atomic 24_Mg+_{and molecular} 24_MgH+_{-ions is described. After the loading routine and direct} laser-cooling of magnesium ions, the used preparation methods for molecular 24_MgH+_- ions and their integration and sympathetic cooling in the crystalline structure of the cold trapped atomic ions is discussed. The second part of this section concentrates on the deterministic transfer of the molecular ion into an isolated region after its creation. For a single ion the efficiency of this transfer process is close to unity and fast (ms). For the transfer of many individual molecular and atomic ions, three schemes suited for different applications are described. The deterministic delivery of a selectable number of externally cold molecular ions, allowing for repetition rates up to kHz is persecuted and an accuracy for spatial positioning of a micrometer is demonstrated.