LASER ABLATION AND AEROSOL PARTICLES

P. Parisa, M. Laan and H. Valtna.

The University of Tartu, Institute of Experimental Physics and Technology.

Abstract: In the paper the electrical parameters of plasma created by laser ablation are related with the regularities of corresponding particle spectrum. An explanation of a faint dependence of laser-created particle spectrum on humidity is given.

1. INTRODUCTION
We found [1] that under certain experimental conditions the spectrum of the laser-created aerosol particles is very similar to that created by pulsed streamer corona. At the same time the regularities of particle growth with humidity for these two cases differ considerably. Corona-created particles are hygroscopic, their concentration and the mean size grow rapidly with the growth of humidity [2]. In contrast, the laser-created particle spectrum is only weakly influenced by humidity. As it was assumed in [2] and proved later [3], the different influence of the water vapor is connected with active species produced by streamer corona. Another reason for the discrepancy could be that the water vapor diminishes the concentration of precursors needed for nucleation. In the plasma plume created by the radiation-surface interaction the concentration of charged particles is high. This gives a basis to consider that the ion-induced process [4] is the most likely mechanism of the nucleation. Consequently, the correspondence between charge carriers and particle spectrum should highlight the latter assumption. The main purpose of the study is the comparison of trends caused by the humidity on the current pulses and on the particle spectrum, both induced by the laser ablation.

2. EXPERIMENTAL 2.1. Set-up

PD

FIGURE 1. Sketch of experimental device

Peeter.Paris@ut.ee.

The main parts of the experimental device are presented in Figure 1. Experiments are carried out in the flow of the filtered ambient air. Because of a high-efficiency filter the total background particle concentration is less than 103 cm-3. The rate of the airflow is 1 l/s and it is possible to change the relative humidity RH in the limits 5 90 %. The temperature of the air is kept at 20 0C. In some experiments gas from the external ozoniser is added to the main air stream; in these cases the air mixture entering the cell contains 45 ppm of O3 and 1 ppm of NOx. Laser ablation is studied in a discharge cell. The distance between the cell electrodes is 6 mm. The radiation of a pulsed XeF laser ( = 248 nm, energy per pulse 300 mJ, pulse duration 40 ns, repetition rate of pulses used is 0.5 5 s-1) is focused on a target. In present experiments brass is used as the target material. In most of the experiments the area of the target irradiated is 3 mm2. Using an attenuator the fluence of the laser beam at the target is changed in the limits 0.1 3 Jcm-2. The target electrode is grounded over the resistor of 50 and the voltage drop is measured by digital oscilloscope TDS-220. The opposite electrode of the cell with a hole in its center is stressed. Photodiode PD records the radiation of the plasma plume at difference distances from the target surface with 0.05-mm spatial resolution. Aluminum pipeline of 80-cm length connects the discharge cell to the electrical aerosol spectrometer (EAS). The design and technical data of EAS are presented in [5]. The version of EAS, used in experiments, records particles starting from 3.2 nm in diameter. The measurement range is split into fractions uniformly in logarithmic scale. The noise-level of AES is 100 cm-3 per fraction. Recordingtime of a spectrum is 10 s. In this study the averaging-time of spectra is set at 3 min.

2.2. Characteristics of laser ablation

4.00E-04 1 Light 2.4 J cm-2 3.00E-04

Current, A

Laser Current 0.5

0.6 J cm-2 2.00E-04

1.00E-04

0.00E+00 0.0E+00 2.0E-07 4.0E-07 6.0E-07 0.00E+00 1.00E-07 2.00E-07 3.00E-07

Time, s

Time, s

Figure 2. A - normalized temporal changes of laser pulse, current and light emitted by plasma plume at the distance 0.3 mm from target; B - current pulses for two different fluencies.

Figure 2A presents the time sequence of events observed in laser ablation. Independently of laser fluence and at DC bias voltages |U | > 5V, the waveform of the current pulse at its initial part almost follows that of the laser pulse. The half-width of the corresponding light pulse emitted by the plasma plume has a much longer duration. At the target surface the light emission starts simultaneously with the laser pulse and the larger is the distance from the target surface the later the light emission is recorded. The peak of current pulses is followed by a long tail lasting 250 ns (Figure 2B). For all voltages used in experiment, the dependence of the peak value of the current as a function of the laser fluence (Figure 3A) demonstrates a slightly sublinear behavior. The fitting curves to the dependencies cross the X-axis at the fluence 0.1 Jcm-2; the value may be treated as the onset of the laser ablation. At a certain fluence the amplitude of the current pulses is almost proportional to the bias voltage applied. From the viewpoint of the study the most striking dependencies are in Figure 3B: the

peak value of the current decreases exponentially with the relative humidity. The decay constants for all three dependencies are very close to each other. Addition of ozone does not have any remarkable influence on current pulses.

8.0E-04 U = 20V 6.0E-04 Current, A Current, A U = 10V 4.0E-04 U = 5V 2.0E-04

5.0E-04 2.4 J cm-2 4.0E-04 3.0E-04 2.0E-04 1.0E-04 0.0E+00 0 1 2 3 0 20 40 60 80 100 Laser fluence, J cm-2 RH % 0.6 J cm-2 0.3 J cm-2

0.0E+00

FIGURE 3. A - peak value of the current as a function of the fluence; B - peak value of the current as a function of relative humidity.

2.3. Aerosol spectra

The concentration of aerosol particles is proportional to the repetition rate of laser pulses. The particle spectrum has a strong dependence on the laser fluence and the addition of O3/NOx, but no reliable influence of the voltage applied to the discharge cell is observed. Near the ablation onset (0.1 Jcm-2), the particles are recorded only at the first fractions of the spectrometer and their concentration is low (Figure 4A). A considerable part of the particles is out of the detection limit of EAS. At the fluence 0.6 Jcm-2 the concentration is two orders of magnitude higher, the maximum of the spectrum shifts to higher values of diameters and now the main part of particles is detectable.

400 Number concentration, cm-3

6.0E+04

6.0E+04

F = 0.6 J cm-2 200 F = 0.1 J cm -2

4.0E+04

Number conc entration, cm

F = 0.15 J cm-2 4.0E+04

-3

With ozone Without ozone

2.0E+04

2.0E+04

0 3.2 5.6 10 17.8 31.6 56 100 178 Diameter, nm

0.0E+00

0.0E+00 3.2 5.6 10 17.8 31.6 56 100 178

Diameter, nm

FIGURE 4. A - particle spectra for two fluence values, RH = 80 %; B - effect of O3/NOx addition; RH = 5 %

As it is found earlier [3], the addition of O3/NOx mixture leads to a considerable growth of particle concentration. The procedure gives a possibility to achieve more reliable/reproducible recordings near the ablation onset and especially at low values of the humidity. Figure 4B demonstrates the effect of ozone addition at a low value of the humidity: the spectral distribution remains unchanged but in every fraction of AES the concentration increases remarkably. Near the ablation threshold the growth of humidity causes a gradual increase in concentrations at the first fractions leaving the spectral

distribution unchanged (Figure 5). At higher values of the fluence the spectrum becomes more complicated and it is not presented here.

4.0E+04
-3

F = 0.1 J cm -2 RH = 80% RH = 40%

4.0E+03

Number concentration, cm

3.0E+04

3.0E+03

2.0E+04

RH = 10%

2.0E+03

1.0E+04

1.0E+03

0.0E+00 3.2 5.6 10 17.8 31.6 56 100 Diam eter, nm

0.0E+00

FIGURE 5. Particle spectra near the ablation onset for different relative humidities; air + O3/NOx mixture.

3. DISCUSSION
Starting from the ablation onset fluence 0.1 Jcm-2 plasma plume forms near the target surface. Because of a short laser wavelength the absorption of the radiation in plasma plume is small and the plasma current is almost a linear function of the laser fluence (Figure 3A). The current pulse recorded (Figure 2) reflects mainly the drift of electrons. As the electric field between the cell electrodes is low, during the recording times used, electrons drift a much shorter distance than the electrode separation. Consequently the duration of the current must be determined by some high-rate loss mechanism of electrons between electrodes. The time constant of the attachment to oxygen has duration of few tens of nanosecond. However, the strong dependence of the current peak on the humidity (Figure 3B) can not be explained only by this phenomenon. Another known fast loss-mechanism is the ion-ion recombination. The exponential decay of the current with humidity growth may be explained, assuming the recombination of O2- with some water-vapor product like hydronium ion H3O+ [6]. Above we assumed that the ion-induced nucleation is the dominant process leading to the aerosol particle formation. The decay of the charge carriers with the humidity means that the water vapor diminishes considerably the concentration of the main precursors of nuclei. As it was proved earlier [2], mainly sticking of water molecules to the nuclei causes the condensation growth of the particles. It means that at certain humidity a change of the laser fluence should lead only to the growth of the particle concentration. Actually we observe (Figure 4A) that the increase of the fluence causes besides the concentration growth also a considerable increase of the mean size of the particles. Apparently it is the result of the coagulation growth mechanism. The addition of O3/NOx mixture to the air remains the spectral distribution of particles unchanged (Figure 4B) but gives rise to their concentrations in the fractions. The likely reason of the effect is that the admixture enlarges the sticking ability of the water vapor to nuclei [3]. Distributions in Figure 5 demonstrate that the change of the humidity in large limits has a negligible effect on the shape of spectrum, the only remarkable effect is the growth of the particle concentrations in fractions. At the same time the mean size of the particles in the air + O3/NOx mixture should

effectively grow with humidity [2, 3]. The only explanation of the contradiction between our earlier and present studies is that the recombination-caused decrease of the concentration of charge carriers as precursors of the nuclei balances the increase of detectable particle concentration due to condensation.

4. CONCLUSIONS
The most important findings of the paper are: In the plasma plume the ion-ion recombination is the dominant loss mechanism of the charged particles. One of the components participating in the recombination is an ion formed at the basis of the water molecule. At higher fluencies of the laser radiation the coagulation plays an important role in the growth of particles. The water vapor acts in the particle evolution in two alternative directions: (i) the growth of the humidity diminishes the concentration of the nuclei; (ii) the growth of the humidity increases the mean size of particles. The independence of the particle mean size and the width of the detectable spectrum on the humidity are results of this competition.

ACKNOWLEDGMENTS
We are grateful to A. Mirme and E. Tamm from the Institute of the Environmental Physics of the University of Tartu who kindly presented us EAS and took part in lively discussions.

REFERENCES
[1] P. Paris, M. Laan, A. Mirme, The influence of corona discharge on aerosol spectra, Proc. HAKONE VII, Greifswald, 1, 44-8 (2000) [2] P. Paris, A. Mirme, M. Laan, Study of corona discharge aerosol with an electrical aerosol spectrometer, J. Aerosol. Sci. 29 (1998), Suppl. 1, S845-S846 [3] P. Paris, M. Laan, A. Mirme, E. Tamm, Influence of active species on laser-created aerosol spectrum, to be published [4] F. Yu and P. Turco, The formation and evolution of aerosols, J. Geophys. Research, 103, (1998), pp. 25,915-25,934 [5] M. Laan, A. Mirme, Aerosols and corona discharges, In: Electrical Discharges for Environmental Purposes, ed. E. M. van Veldhuizen Nova Science Books and Jrnls. (1999), Ch. 8,193 220 [6] V. A. Bityurin, B. V. Potapkin, M. A. Deminski, Chemical activity of discharges, In: Electrical Discharges for Environmental Purposes, ed. E. M. van Veldhuizen Nova Science Books and Jrnls. (1999), Ch.4, pp. 49118