Optimizing amplitude and time in the dual-beam mode-mismatched thermal lens spectrometry

Rubens Silva1,2 , Marcos A. C. de Arajo1 , Sanclayton S. G. u Moreira2 , Petrus Alcantara Jr.2 , and Paulo C. de Oliveira1

Departamento de F sica, Centro de Cincias Exatas e da Natureza, e Universidade Federal da Para ba, Joo Pessoa 58051-970, Para a ba, Brazil and 2 Faculdade de F sica, Instituto de Cincias Exatas e Naturais, e Universidade Federal do Par, Belm, 66093-020, Brazil a e Based on a model introduced by Shen et al. for cw laser induced mode-mismatched dual-beam thermal lens spectrometry (TLS) we explored the parameters related with the geometry of the laser beams and the experimental apparatus that inuence the amplitude and time evolution of the transient thermal lens (TL) signal. By keeping the sample cell at the minimum waist of the excitation beam, our results show that high amplitude TL signals, very close to the optimized value, combined with short transient times, may be obtained by reducing the curvature radius of the probe beam and the distance between the sample cell and the detector. The sample used in the experiments was oleic acid, which is present in vegetable oils and is very transparent in the visible spectral range. I. INTRODUCTION

Since the rst reports on the thermal lens eect in 1964 and 1965 [13] a great number of applications exploring this eect were developed, including the measurement of very low absorption coecients of transparent liquids, such as water, ethanol, etc. [36], and today the technique is known as Thermal Lens Spectrometry (TLS). Another very important application is in determination of thermal diusivities [7, 8]. Other studies such as the measurement of quantum eciency and dimerization equilibria of laser dyes were also reported [9, 10]. In TLS experiments a Gaussian TEM00 excitation beam is partially absorbed by the sample, creating a refractive index gradient in the radial direction. When a probe beam travels along the heated path, phase dierences appear between points of the wavefront with dierent radial distances. These phase dierences distorts the wavefront, causing a lenslike eect. The rst systematic study of the inuence of beam geometric positions in dual-beam thermal lens experiment was done by Berthoud et al. [16]. They showed that TL signal is maximum when the excitation beam is focused in the sample cell, and when the distance between the focus of the probe beam and the cell is changed the signal amplitude pass through a maximum at a distance approximately 31/2 Zc , where Zc is the Rayleigh parameter of the probe beam. Recently, Marcano et al. optimized the amplitude of TL signals, approaching the theoretical limit value, by expanding and collimating the probe beam [5]. Although a great advancement was achieved, the TL transient time increased almost two orders of magnitude. All the above mentioned works investigated only the optimization of the amplitude of the TL signals,

without paying attention that the transient time also depends on the geometrical parameters. It is the purpose of this Letter to investigate the geometrical congurations of the laser beams and experimental arrangement that gives high amplitude TL signals with short transient times. The sample used in the experiments was oleic acid, which is present in most of the vegetable oils and is very transparent in the visible spectral range.

II.

THEORY

Electronic

address: pco@fisica.ufpb.br

This work is based on a model introduced by Shen et al. for cw laser induced mode-mismatched dual-beam thermal lens spectrometry (TLS) [11, 12] that takes into account the Fresnel diraction theory to the imaging of the probe beam at the detector plane. A model with a different approach was reported by Bialkowski and Chartier [13], where they calculated cumulative electric-eld phase shifts produced by a series of Gaussian refractive-index perturbations produced by the photothermal eect. Due to the simplicity of the equations we preferred to use Shens model. In our analysis, instead of working with the beam parameters e , 1p , 0p , and the confocal parameters, we prefer to work with the parameters m and V described by Eq. 2 and 4, and after nding the m and V that maximize the TL signal we analyze how they can be adjusted experimentally. The scheme of the laser beams is shown in Fig. 1a and 1b. Fig. 1a shows the traditional scheme, with the sample positioned at the minimum waist of the excitation beam, and a probe beam which minimum waist is at a distance Z1 from the sample cell. Fig. 1b shows a modied version of the traditional scheme, recently introduced by Marcano et al. [5]. The modication introduced in Ref.[5] is that the probe beam is collimated (Z1 = ) and the beam radius at the sample cell (1p ) is increased. According to the model introduced by Shen

2
a)
L
Detector Plane

w1p w0p
Excitation Beam

2we
Probe Beam Sample cell

Z1

Z2

b)

Detector Plane

w1p
Excitation Beam

2we
Probe Beam Sample cell

Z2

Symbol Description I(t) Intensity of the center of the probe laser at the detector e excitation beam waist 1p probe beam waist at the sample cell position R1p curvature radius of the probe beam at the cell position Pe excitation laser power p probe beam wavelength k thermal conductivity absorption coecient at the excitation beam wavelength L sample thickness dn/dT temperature coecient of the refractive index at the probe beam wavelength tc characteristic thermal lens time constant D thermal diusivity Z1 distance from the probe beam waist to the sample cell Z2 distance from the sample cell to the detector TABLE I: Description of the symbols used in Eqs. 1-4 and in Fig. 1.

FIG. 1: Schema of the geometric position of the beams in a mode-mismatched TL experiment.(a) Traditional scheme, introduced by J. Shen et al., and (b) scheme introduced by A. Marcano et al..

D=

2 e 4tc

(5)

et al., the intensity of the TL signal at the center of the probe beam, in the plane of the detector, is given by I(t) = I(0)
2

A.

The amplitude of the TL signal

1 where,

tan1

(V 2 +(1+2m)2 ) tc +V 2 +1+2m 2t (1)

2mV

With the intensity of the light at the detector given by Eq. (1), the steady-state TL fractional signal amplitude may be dened as [11] S= I(0) I() I(0) (6)

m=

2 1p , 2 e

(2)

After substitution of Eq. (1) into the above equation we get tan1 2 2mV 1 + 2m + V 2
2

= and, V =

Pe L p k

dn dT

(3)

S =1 1

(7)

2 1p p

1 1 + R1p Z2

(4)

All parameters appearing in Eqs. 1-4 are described in Table 1. A few other parameters will be described as they appear in the text. The Eq. (1) will be used to t the experimental data of the transient TL signals, giving the values of the both, and tc parameters. The latter will be used to nd the thermal diusivity, given by

From this equation we may see that for a xed excitation power (xed ), the maximum amplitude of the TL signal will be obtained when the argument of the arc tangent function is maximum. I(t) is a function of the two geometrical parameters m and V , and both depend on 1p , but for the sake of simplicity we will analyze them as independent parameters. By analyzing the dependence of S on V we veried that the amplitude of the TL signal has a maximum when V = 1 + 2m. (8)

3 is not the only parameter that inuences the time evolution of the TL signal. It is well known that the bigger the parameter m is, the longer the signal takes to reach the steady-state regime, and consequently, the longer will be the measurement time. In order to optimize the TL signal one must increase the amplitude without aecting too much the measurement time. To make a quantitative analysis of the time expended in a TL experiment we dened a quantity that we call half-amplitude time (t1/2 ), obtained by
50

1.5

m = 10000

m = 300 m = 100

1.0

S/

0.5

m = 10

m = 5

m = 1 0.0 0 10 20 30 40

I(t1/2 ) =

I(0) + I() 2

(10)

FIG. 2: Amplitude of the TL signal divided by , for = 0.1, for various values of the parameter m (1, 5, 10, 100, 300, 10000) as a function of V.

Expanding Eq. (1), and dismissing terms proportional to 2 , we get V 2 + (1 + 2m)2 2 + 4m2 V 2 1 t1/2 = t c 2 4m2 V 2 2 + 4m2 V 2 (11) where, = V 2 + 1 + 2m (12)

On the other hand, an analysis of the dependence of S on m, keeping V at the maximum value, reveals that S grows as m goes to innity, approaching a limit, given by 4
2

Smax = 1 1

(9)
m = 10000 10000 m = 1000 1000

Experimentally m may reach very large values by increasing the relation between the probe and excitation beams waists at the sample position. Marcano et al. [5, 18] optimized the TL signal, approaching the theoretical limit value, by expanding and collimating the probe beam. In their experiments the diameter of the probe beam at the sample position was about 6 mm, which corresponds to a value of m of the order of 10000, but from their data V is estimated to be only about 30, while the optimized value of V is around 120. This will not affect too much the amplitude of the TL signal, but as we will see in the next section it will greatly aect the time necessary to reach the steady-state regime. In Fig. 2 we show the amplitude of the TL signals for various values of the parameter m as a function of V . It is noticed that larger values of m gives rise to larger amplitudes of TL signals, but we also noticed that this behavior saturates for m around a few hundreds. For example, the maximum TL signal for m = 300 is very close to the TL signal for m = 10000, diering by only 3% from each other, at V = 30.

1/2

/t

100

m = 100

m = 10 10

m = 1 1

0.1 0.1 1 10 100 1000 10000

FIG. 3: Half-amplitude time for the TL signal for various values of the parameter m (1, 10, 100, 1000, 10000) as a function of V.

Fig. 3 shows the half-amplitude time (t1/2 ) as a function of V , for various values of m. After a graphical analysis we noticed that when m >> V >> 1, Eq. (11) may be approximated by t1/2 m tc . V (13)

B.

The time dependence of the TL signal

Another very important parameter in an experiment is how fast a physical phenomenon is, and how long a measurement will take. In TLS, tc , given by Eq. (6), is the characteristic time constant, and is inversely proportional to the thermal diusivity of the sample material. But this

This result shows that, by keeping m xed, we may decrease the half-amplitude time of the transient TL signals by increasing the parameter V . In practice this may be performed by reducing the curvature radius of the probe beam (R1p ), and also by reducing the distance (Z2 ) from the detector to the sample cell. The above results may be explained as follows: An increment in the mode-mismatching parameter m means

4
M Ar Laser M He:Ne Laser L1 L2
+

P M

BS

P scope M PD

M PH

FIG. 4: Experimental setup for thermal lens spectroscopy. M - mirror, P - polarizer prism, BS - nonpolarizer beam-splitter prism, S - sample, PH - pinhole, PD - photodetector, L1 (f1 = 20 cm), and L2 (f2 = 10 cm) lenses.

that the probe beam will probe a larger area of the sample and the heat will take a longer time to propagate to the border and reach the steady-state rgime. Consequently the TL transient time will be longer. On the other hand the amplitude of the TL signal will be higher due to the increment in the phase dierences. The parameter V is related to the initial phase dierences between the waves passing at the center and the waves passing at the probe beam waist. The larger is the initial phase dierence the faster will be the transient regime.

The beam radii e , 1p , and 0p , and the Rayleigh parameters of the excitation and probe beams, Zce and Zcp , respectively, were measured by the knife-edge technique [14, 15]. For the rst set of measurements R1p was calcu2 2 lated from R1p = Z1 + Zcp /Z1 , and for the second set it was calculated by a linear regression of the data of the beam radius taken at several positions around the sample position. For both sets of measurements the distance Z2 , from the detector to the sample cell was varied, and we have studied the thermal lens signal as a function of the parameter V , that is related with Z2 through Eq. (4). The TL signal was detected by a silicon photodiode, in front of which there was a 200 m of diameter pinhole. The data acquisition was made by a Tektronix DPO 3012 digital oscilloscope, synchronized with the switching-on of the excitation laser, and an average of 128 measurements was made.
IV. RESULTS AND DISCUSSION

III.

THE EXPERIMENTS

In order to demonstrate the above results we performed a set of experiments. The experimental setup is shown in Fig. 4. The excitation laser was an Ar+ laser operating at a wavelength of 514 nm, and focused by the lens L1 , which has focal length f1 = 20 cm. The probe laser was a He:Ne laser emitting at 632.8 nm, and aligned counterpropagating with the excitation laser. With this arrangement we guarantee that the laser beams are completely superposed throughout the sample extension. Two polarizers with orthogonal orientations were used at the output of each laser in order to eliminate light from one laser to enter the cavity of the other. The experiment was divided into two sets of measurements. The rst set of measurements was done with the scheme of Fig. 1a, where the probe beam was focused by a 10 cm focal length lens (L2 ) and the sample cell was positioned at the minimum waist of the excitation laser, that was about 20 cm from this lens. With this conguration the probe laser beam diameter at the sample position was about 1.2 mm, which is almost the same diameter of the original He:Ne laser beam, and R1p was 10.7 cm for this conguration. The second set of measurements was done with the scheme of Fig. 1b, where the lens L2 was replaced by a pair of collimating lenses, that were adjusted to maintain the same diameter of the rst set of measurements. R1p was 1605 cm for this conguration.

Fig. 5 shows transient TL signals obtained with the detector placed at dierent distances from the sample cell. In this experiment we have used the scheme of Fig. 1b, where the probe beam is collimated. The upper curve was taken at a distance of 208 cm, which corresponds to V = 1.0, while the lower curve was taken at a distance of only 15 cm, which corresponds to V = 12.6. We may notice that an increasing of the amplitude and shortening of the transient time occurs simultaneously as we reduce the distance of the detector from the sample cell. Since the probe beam diameter is of the order of 1 mm, and the shortest distance of the sample to the detector of about 15 cm, we believe that the far eld approximation is still valid for our experiments.

1.00

m = 290

0.95

I(t)/I(0)

0.90

V 1.0 1.4 1.9 6.6

0.85

9.4 12.6

t (s)

FIG. 5: Normalized transient TL signals for m = 290, and various values of the parameter V .

The increasing of the amplitude of the TL signal, as well as the shortening of the transient time with V are shown in Figs. 6 and 7, respectively. Due to geometrical limitations the data points for V between 1 and 15 were obtained using the scheme of Fig. 1b, while the data

5 set with the same value for both schemes. The experiments conrmed the theoretical predictions in both cases, amplitude and transient times. Besides this, the data of Fig. 7 helped us to determine the characteristic time of the TL, which was tc = 3.08 ms. With e = 36 m the thermal diusivity of the oleic acid was determined as 10.5104 cm2 /s, a value very close to 10.3104 cm2 /s, obtained by Dadarlat et al. using a photopyroelectric method [19]. Since we have dismissed the terms proportional to 2 in the derivation of Eq. (11), a special care must be taken when comparing this equation with the experimental results. From numerical simulations of Eq. (1) we observed that a correction factor (1/3) in the value of t1/2 must be applied. In our experiments an average = 0.132 was obtained, which gives a correction factor equal to 0.956 to t1/2 . This correction was essential for the correct estimation of tc , which was used to calculate the thermal diusivity.

1.6

1.4

1.2 m = 290 = 0.132 1.0

S/
0.8 0.6 0.4 0 5 10 15 20 25 30 35

FIG. 6: Amplitude of the thermal lens signal as a function of the parameter V . Data points for V up to about 15 were obtained in the collimated probe beam conguration, and above 15 were obtained in the focused probe beam conguration. The solid line is the result given by Eq. (7) with m = 290 and = 0.132.

V.
1

CONCLUSION

0.1 m = 290 t
c

= 3.08 ms

0.01 1 10

FIG. 7: Half-amplitude time of the thermal lens signal as a function of the parameter V . Data points for V up to about 15 were obtained in the collimated probe beam conguration, and above 15 were obtained in the focused probe beam conguration. The dashed line is the result given by Eq. (11), and the solid line is the approximated result given by Eq. (13), both with m = 290 and tc = 3.08 ms.

By an analysis of the Shens theoretical model for dualbeam mode-mismatched thermal lens spectrometry we derived a simple relation for the half-amplitude time of the TL signal with the geometrical parameters of the laser beams and the characteristic thermal lens time. We demonstrated, theoretically and experimentally, that high amplitude TL signals, very close to the optimized value, combined with short measurement times, may be obtained by reducing the curvature radius of the probe beam and the distance between the sample cell and the detector. The half-amplitude time of the TL signals showed to be more precis and easier to measure than the characteristic TL time tc , and may be used to estimate the thermal diusivity of the samples. We have succesfully demonstrated this applicability by estimating the thermal diusivity of oleic acid, which agreed with the literature value.

1/2

(s)

Acknowledgments

points for V > 15 were taken using the scheme of Fig. 1a. The probe beam radius at the sample cell 1p was

The authors thank nancial support from FAPESPA, FINEP, CNPq and CAPES, Brazilian agencies.

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