Nonlinear propagation of fs laser pulses in liquids and evolution of supercontinuum generation

Nonlinear propagation of fs laser pulses in liquids and the dynamic processes of filamentation such as self-focusing, intensity clamping, and evolution of white light production have been analyzed by using oneand two-photon fluorescence. The energy losses of laser pulses caused by multiphoton absorption and conical emission have been measured respectively by z-scan technique. Numerical simulations of fs laser propagation in water have been made to explain the evolution of white light production as well as the small-scale filaments in liquids we have observed by a nonlinear fluorescence technique. © 2005 Optical Society of America OCIS codes: (190.5530) Nonlinear optics, pulse propagation and solitons; (190.7110) Ultrafast nonlinear optics. References and links 1. P. B. Corkum, C. Rolland, and T. Srinivasan-Rao, “Supercontinuum Generation in Gases,” Phys. Rev. Lett. 57, 2268–2271 (1986). 2. A. Brodeur, and S. L. 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Introduction
Filamentation of ultrashort high power laser pulses has been well observed for many years in gases, liquids and solids. And it still attracts considerable attention since many applications can be found such as white light production [1][2][3], pulse compression [4][5][6][7], remote sensing using lidar [8,9], and optical switch [10]. Since the first observation of self-trapping of optical beams at the very dawn of nonlinear optics [11], quite a number of models have been developed to explain the nonlinear processes of laser pulses propagating in optical media [12][13][14][15][16][17][18][19]. It is now well recognized that self-phase modulation (SPM), dispersion, diffraction and plasma behaviour are the main causes of what we have observed such as supercontinuum generation, pulse splitting, X waves in the nonlinear propagation of such laser beam. The filamentation in bulk media is generally accompanied by conical emission (CE) which appears on a screen as a concentric rainbow with colors ranging outward from red to green. CE has been addressed as another form of paraxial X-wave and considered as a key for the interpretation of the out-of-axis energy emission in the splitting process of fs laser pulses in normally dispersive materials [15]. The filaments release a fraction of their energy through CE which interact with background and create additional filaments [20]. The formation of CE has been explained in different ways such as Cerenkov process, four-photon parametric process, plasma process and three-wave mixing picture [21][22][23][24][25][26]. However, a good understanding of the formation and evolution as well as the role of CE in the propagation of fs laser pulses in transparent media is still lacking. Recently we have found that CE is inherently caused by the space-frequency coupling mainly from the interplay among SPM, dispersion and phase mismatching [27]. The strongly conical wave plays a major role of energy redistribution in space and induces energy loss in the on-axis part of the pulse [27,28].
The aim of this paper is to demonstrate nonlinear propagation of fs laser pulses in liquids and the dynamic processes of filamentation such as self-focusing, intensity clamping as well as evolution of white light production by using one-and two-photon fluorescence. The energy losses of laser pulses caused by multiphoton absorption (MPA) and CE have also been measured respectively by z-scan technique. Numerical simulations of fs laser propagation in water have been made to explain the evolution of white light production as well as the smallscale filaments in liquids we have observed by a nonlinear fluorescence technique. Conical emission plays an important role of energy redistribution and can prevent laser beam from self-guiding over a long distance. A nonlinear fluorescence technique as described in Ref. [29,30] has been used to visualize the formation of filaments behind a slit (200 μ m×5.0 mm). By this way we can observe the dynamic processes of filamentation such as self-focusing, intensity clamping, and white light production. The experimental setup is shown in Fig. 1. The Ti: sapphire laser parameters in front of the slit in standard operations are: 1 kHz, 800 nm, 2.0 mJ, pulse duration T=44 fs, and radius r 1/e =4.3 mm respectively. The slit is placed in front of a glass cell (the length of the cell is 20 mm). The dilute test solutions which have the same concentrations of ~10 16 cm -3 are Coumarin 500, fluorescein 27 and DODCI in ethanol, and their absorption wavelengths are 395, 512, and 585 nm respectively. Here we call them blue, green and red dye respectively. The laser energy behind the slit was 44 μ J which corresponds to 1GW, or ~1.0×10 11 W/cm 2 . The picture of multi-filamentation is taken from the side by a CCD camera. We use the slit arrangement because all the filaments are created in one column which can be projected onto the detector plane of the CCD array without any ambiguity.

Visualization of filamentation of fs laser pulses in liquids
In Fig. 2 we show the development of a one-dimension filament array in ethanol behind a slit by using blue, green and red dye respectively. The fluorescence is excited by two-photon absorption of the fundamental laser beam and one-photon absorption of white light due to self-steeping. The pictures are taken by a single shot with the same condition except the dyes. For coumarin 500, the two-photon absorption of the fundamental laser beam is close to the resonance absorption and therefore the two-photon fluorescence signal emitted by Coumarin 500 is bigger compared to Flurescein 27 and DODCI. The picture size shown here is H×L=2.5 mm ×10.7 mm and L corresponds to the propagation distance from the left to the right. The three pictures (d), (e) and (f) which are taken with a higher spatial resolution (2.5   Here for example only one filament (the first one on the top in each case, by chance) is used to investigate the filamentation process in detail. In Fig. 3 we show the evolution of the fluorescence intensity from Coumarin 500 as well as the diameter of the first filament along the propagation. The fluorescence signal is integrated over the whole size of the first filament. For two-photon fluorescence the integrated signal ( ) I r z t is the intensity of the laser beam. If the laser intensity is assumed as a spatio-temporal Gaussian profile, the maximum laser intensity on the axis is proportional to , and the laser intensity is clamped here. However at the second maximum position z = 8.6 mm, the linear profile becomes broader and has a pedestal signal with a radius of ~ 40 μ m (here the radius is meant for the radius of the pedestal signal and calculated from the maximum fluorescence intensity to the minimum fluorescence intensity since the profile is not Gaussian). The radius of the pedestal signal increases rapidly and becomes ~70μm at z=9.0mm. The speed the pedestal signal spreads outward can be defined by a diverging angle arctan( / ) r z θ = Δ Δ . r Δ is the change of the radius of the pedestal signal and z Δ is the propagation distance. For blue dye this diverging angle is calculated from the experimental data to be ~4.4º. The diverging angles for green and red dyes are calculated as ~3º and ~2.3º respectively in the same way by analyzing Fig. 2(e) and (f) respectively. This is one proof that the increase of fluorescence intensity at the second maximum position together with the pedestal signal shown in Fig. 2 is caused by one-photon fluorescence due to the absorption of the spreading blue light of the supercontinuum [29]. The blue light spreads outward at the largest angle which exhibits the sign of CE [21,22].  The evolution of fluorescence intensity emitted by blue, green and red dye respectively from the same filament is shown in Fig. 5(a). An interesting thing shown in Fig. 5(a) is the big difference of the position of the second peaks which correspond to one-photon fluorescence emitted by blue, green and red dyes respectively. It shows an "anomalous" phenomenon that blue light (from the blue dye) comes first, and then green light later and red light comes last. Shot to shot measurements is shown in Fig. 5(b) and they are highly reproducible in our experiments. Our explanation is that this "anomalous" phenomenon is related to CE. Since blue light diverges more rapidly compared to red light, the intensity of blue light decreases more rapidly. Blue light can not last and be amplified over a longer distance as red light can. So it ends earlier.
For comparison with our numerical simulation, in Fig. 6(a) we show a one-dimension filament array in water behind a slit. The test dye is Rhodamine B and its maximum absorption wavelength is 556 nm. (The reason why we use Rhodamine B in water as our test sample is because the known optical parameters of water are better studied than ethanol.) The evolution of fluorescence intensity along the first filament is shown in Fig. 6(b). The second peak shows the evolution of white light whose spectrum covers the absorption band of Rhodamine B. The visualization of filamentation of Ti:sapphire femtosecond laser pulses in liquids shows that only small-scale filaments can be observed in our case. The filaments can only persist for only around 2 mm and have diameters around 12 μ m. In our case white light is produced in a very short distance after the laser intensity is clamped. White light which is produced from the fundamental laser beam diverges and spreads outward rapidly as shown in Fig. 4. This is the well known CE. However we have observed it at its very beginning of production by this fluorescence technique. The filaments dye out coincidently with the production of white light, which implies that white light is not in phase with the fundamental laser beam and its outward spreading by the way of CE will unavoidably take some energy from the fundamental laser beam inside the filament.

Reference
Far field energy (mJ)

Mesh distance (mm)
Water Ethanol CS2 We have measured the energy loss caused by nonlinear effect such as MPA as well as CE respectively by using a z-scan technique. The experimental setup is shown in Fig. 7(a). A metal mesh (5×5 meshes, unit cell 497 µm × 497 µm, wire width 54µm) is placed in the laser beam before the laser passes through a sample cell in which water is filled. The cell is 12 mm long and the inside length is 10 mm. The position of the mesh can be scanned from the surface of the cell to 400mm away along the propagation axis. By changing the mesh distance multifilamentation and white light production can be controlled [30,31] because the laser intensity on the entrance surface of the sample cell will change due to the diffraction of the laser beam in free space by the mesh. Moreover, the steep intensity gradient of the near field diffraction pattern caused by the mesh is very efficient for the creation of filaments and white light without making the fundamental laser beam diverging as a focusing lens usually does. In order to measure the energy loss caused by MPA, an energy meter is placed close to the exit surface of the sample cell to measure the energy of the laser after it propagates through the cell. This arrangement can guarantee most of the laser beam including the white light be collected by the energy meter. Three measurements are made in this case. 1) Energy measurement of the laser beam without the sample cell as the position of the mesh is scanned. 2) Energy measurement with the sample cell included but the laser pulse is adjusted to be 1 ps to avoid nonlinear effect. 3) Energy measurement with the sample cell included but the laser pulse is adjusted to be 44fs to include strong nonlinear effect. The measurement result is shown in Fig. 7(b). The position 0 of the mesh distance on the x-axis corresponds to the surface of the sample cell. The energy measurement of the laser beam with a pulse duration of 1 ps shows the transmission efficiency of the sample cell is about 91%. Therefore the linear absorption of the laser by the sample cell is very small if the reflectivity of the two outer surfaces (around 8%, without including the two inner surfaces) is considered. When the laser pulse is adjusted to be 44 fs, by scanning the position of the mesh, strong white light and CE can be observed. The energy measurement shows the maximum energy loss is less than 3%. It is mainly caused by nonlinear absorption like MPA. Placing the energy meter 2 meters away from the exit surface of the cell along the propagation axis, the same z-scanned measurements of laser energy are shown in Fig. 7(c). After the nonlinear propagation and filamentation in the liquid, the laser beam including white light continues to propagate in free air. And at 2 meters away, most white light except the fundamental laser beam will not be collected by the energy meter due to CE. So by this way we can measure the conversion efficiency of CE due to the strong filamentation of laser pulses in water. The maximum conversion efficiency of CE is about 40% when the mesh distance is set as 50 mm. So the energy loss caused by CE is much higher compared to MPA. When the position of the mesh is scanned from the surface of the sample cell to 400 mm away along the propagation axis, the laser intensity distribution on the entrance surface of the sample cell will change due to the diffraction of the laser beam in free space by the mesh. The change of the laser intensity on the entrance surface of the sample cell will have influence on the filamentation of fs pulses in liquids as well as the conical emission and MPA.
In Fig. 7(d) we show the z-scan measurement of energy loss caused by CE for water, ethanol and CS 2 respectively. The reference is given as the energy measured when the pulse duration is adjusted to be 2 ps. It can be seen that energy loss caused by CE for CS 2 is as high as 86%. The energy loss caused by CE for water and ethanol is 38% and 41% respectively. Small difference of energy loss between water and ethanol is attributed to their small difference of nonlinear refractive index (2.7×10 -16 cm 2 / W and 5.0×10 -16 cm 2 / W respectively) and linear refractive index (1.33 and 1.36 respectively). However, for CS 2 , its nonlinear refractive index is much higher (2.4×10 -15 cm 2 /W [32]) and the linear refractive index is 1.63 (a large linear refractive index means a large group velocity dispersion), a much stronger CE can be observed. That is why the energy loss caused by CE is much higher compared to water and ethanol because CE for CS 2 has a larger diverging angle. CE is quite dependent on different materials. Available theories of nonlinear propagation equation of waves normally include three main parameters which might have contribution to CE. They are n 2 (SPM), group velocity dispersion (GVD) and multi-photon ionization (MPI) rate (plasma). Most of phenomena we have observed can be explained by these parameters. However these three parameters are not independent but related, which makes it difficult to explain which parameter is more important in some cases. Some early experiments show that supercontinnum generation is dependent on bandgap of materials. For some materials such as CS 2 , supercontinuum cannot be generated when the bandgap is smaller than a threshold and thus the clamping intensity is low [2]. Here what we have observed from the measurement of energy loss caused by CE indicates that CE for CS 2 is much stronger compared to water which has a larger bandgap of 7.5 eV.
We have measured beam profiles of CE centred at red (λ=680nm) and green (λ=520nm) light for water and CS 2 respectively. The experimental setup is shown in Fig. 8(a). A metal mesh (5×5 meshes, unit cell 497 µm × 497 µm, wire width 54µm) is placed in the laser beam before the laser passes through a sample cell in which water or CS 2 is filled. The cell is 12 mm long and the inside length is 10 mm. The energy and the pulse duration of the laser pulse after passing through the mesh are 0.3 mJ and 44 fs respectively. The distance between the mesh and the cell is ~ 7 cm. CE which is produced from filamentation of fs laser pulses in water or CS 2 is stopped by a screen plate and imaged onto a CCD camera. The distance between the screen plate and the cell is ~ 15 cm. Red and green band-pass filters are placed respectively in front of the screen plate to select CE centred at red and green light respectively. The bandwidths of the filters are ~70 nm. The measured beam profiles of CE centred at red and green light for CS 2 and water are shown respectively in Fig. 8(b) and (c) respectively. It is shown that the profiles of CE have ring structures and CE for CS 2 is much stronger compared with water.

Numerical simulation
experiment) and the input power is 14.5 P cr . The critical power for a cw beam collapse is P cr =2.74 MW for a nonlinear coefficient n 2 =2.7×10 -16 cm 2 W -1 . The frequency dependent refractive index of water is chosen as expressed in a formula given in Ref. [34]. In our simulation, the linear loss caused by water is not included in the frequency dependent refractive index since the length of the propagation in water is only 1 cm and the linear absorption is very small and neglected. Similarly the influence of absorption of the dyes on the propagation of laser pulses in liquids is neglected since the concentrations of the dyes are very low. The incident laser beam profile for numerical simulation is chosen as a spatiotemporal Gaussian profile without chirp. In Fig. 9 we show the simulated evolution of the onaxis maximum laser intensity, the size of the laser beam and two-photon plus one-photon (556 nm for Rhodamine B) fluorescence as a function of propagation distance in order to compare the simulation results with the experiments. The two-photon plus one-photon fluorescence is calculated by respectively. β is a coefficient which corresponds to the relative intensity of two-photon and one-photon fluorescence. The evolution of two-photon plus one-photon fluorescence intensity shown in Fig. 9 is close to what we have observed in Fig. 6(b). Compared with the evolution of the on-axis laser intensity, the first peak at 10.6 mm in Fig. 9 corresponds to the position where the laser intensity is clamped. The diameter of the laser beam reaches its minimum value of 10 μ m. After that, the on-axis laser intensity decreases gradually, however the intensity of the white light at 556 nm continues to increase until the laser beam propagates to 12.7 mm. The simulated evolution of the maximum on-axis laser intensity together with the evolutions of the intensities of white light centred at different wavelengths (at 636, 520, and 420 nm, and we call them red, green and blue light respectively) is shown in Fig. 10. The intensities of the red, green and blue light are calculated by a Fourier transformation of a segment of spectrum with a band-width of 30 nm and their central wavelengths are 636, 520 and 420 nm respectively. The evolutions of red light, green light and blue light related to the maximum on-axis laser intensity show a qualitative similarity with that shown in Fig. 5(a) although the simulation is made for water instead of ethanol used in Fig. 5. The intensity of red light can increase over a longer distance compared to green and blue light and therefore the onset of the peak intensity of red light occurs later. This can be explained as a consequence of CE because the diverging angle for blue and green light is larger. Blue light can not last and be amplified over a longer distance as red light can. So it ends earlier. White light is produced in a very short distance (~ 1 mm) after the laser intensity is clamped. It takes the form of CE and plays a very important role of energy redistribution in space and induces energy loss in the on-axis part of the laser pulse. CE provides a dissipative mechanism which can arrest catastrophic self-focusing and prevent laser beam from self-guiding over a long distance [27]. In this simulation, the peak electron density is calculated as 1.3×10 18 cm -3 . And the energy loss caused by MPA is ~ 5% which is comparable with the measurement of energy loss caused by MPA for water in Sec. 3. Our numerical simulations indicate that when the laser power for our laser parameters is lower than 8 times the critical power for strong self focusing, MPI as well as MPA plays a neglectable role [27]. In this case, CE which is mainly caused by SPM and the dispersion plays an important role of energy loss in the on-axis part of laser pulse.

Conclusion
In summary, we have demonstrated nonlinear propagation of fs laser pulses in liquids and the dynamic processes of filamentation such as self-focusing, intensity clamping as well as evolution of white light production by using one-and two-photon fluorescence. The energy losses of laser pulses caused by MPA and CE have also been measured respectively by z-scan technique. Numerical simulations of fs laser propagation in water have been made to explain the evolution of white light production as well as the small-scale filaments in liquids we have observed by a nonlinear fluorescence technique.