Second harmonic generation from synthesized ZnS quantum dots

Madhumita Paul*, Sandeep Chanda Department of Electronics and Communcation Engg, National Institute of Technology Silchar, Assam, India. *email-mita_paul@rediffmail.com

Abstract: We report synthesis of ZnS quantum dots by chemical route at room temperature. In this technique ZnS specimen are produced by simple chemical reactions where polyvinyl alcohol (PVA), acting as matrix, plays the key role in controlling particle growth during synthesis. After that, the samples have been characterized to UV/VIS absorption spectroscopy. Results of these characterizations indicate the formation of quantum dots with particle size less than 100 nm. The specimens are then subjected to photoluminescence study with the help of a spectrophotometer and second harmonic generation is detected. A comparison is also made with the results obtained from bulk and a significant increase in efficiency is obtained in the case of a quantum dot.

Key words: Quantum dot, Blue shift, second harmonic, spectrophotometer.

1. Introduction: Synthesis of semiconductor quantum dots and their different applications in electronics, photonics and non linear optics are frontier research areas at present [1-12]. Many methods like Molecular beam epitaxy (MBE), Radio frequency (RF) Sputtering and Liquid phase epitaxy (LPE) are adopted to synthesize semiconductor quantum dots now a days but manifold advantages
[1,3,4]

chemical route is found to be more attractive. In the present investigation,

chemical method has been adopted for fabrication of quantum dots at room temperature. Polyvinyl alcohol (PVA) which is a polymer and acting as matrix, plays the key role in controlling the size and shape of quantum dots3 during sample fabrication. After synthesis, the samples have been characterized by different techniques to reveal their nano nature

2. Materials and Methods Synthesis of quantum dots by chemical method is a low cost and simple process. To synthesize ZnS quantum dots by chemical route at room temperature, 8 grams of PVA are dissolved into 120 ml double distilled water. This mixture is taken in a three necked flask fitted with thermometer pocket and N2 inlet. The solution is stirred in a magnetic stirrer at a stirring rate of 200 rpm at a constant temperature of 70 0 C for 5 hours. Thus, a transparent water solution of PVA has been prepared. Similarly, ZnCl2 solution is made by dissolving 7 gms of ZnCl2 in 100 ml double distilled water. The solutions are degassed by boiling N2 for 3 to 4 hours. Next, PVA solution and ZnCl2 solution have been mixed and few drops of HNO3 is added to the mixture followed by moderate stirring while aqueous solution of Na2S is put into it slowly by means of a dropper unless the whole solution turns yellow. This solution is kept in dark chamber at room temperature for 14 hours for its stabilization followed by its casting over glass substrate and drying it in oven at 600 C. This casted film contains ZnS quantum dots embedded in PVA matrix. Perkin Elmer Lamda 351.24),.
.

Prepared samples have been characterized UV/VIS absorption spectroscopy (using

3. Second harmonic generation Second harmonic (SH) generation in which one generates an optical beam of frequency 2w from the interaction of a high power laser beam of frequency w with the quantum dot. SH generation is due to the nonlinear dependence of the polarization on the electric field. The intensity of second harmonic generation with that of the non linear susceptibility13

..(a) Where n is the surface concentration of the particles V is the average volume of the particles Iw is the incident intensity X2 s the quadratic susceptibility From this relation we get

The enhancement factor describing the size dependence of the quadratic optical response can be given as follows

(b)

From the relation we can infer that the enhancement factor ie. Intensity decreases as R increases or smaller the quantum dot better is the efficiency of generation. The relation (a) stands valid for semiconductor quantum dots like CdSe, hence it can also be used for ZnS quantum dot in our case as both posses similar characteristics.

4. Result and discussion: Absorption spectroscopy (fig 1) of the samples shows strong blue shift in absorption edge in compare to that of bulk specimen [7-9].

Fig 1: UV/VIS absorption spectra of quantum dots and bulk specimen ZnS

From blue shifted absorption edge, particle size has been assessed by using Hyperbolic band

model

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R=

2 2 h 2 Egb Where, R is quantum dot radius (2R is the diameter and m * (Egn 2 Egb 2 )
Egb is the bulk band gap, Egn is quantum dot band gap (calculated

hence the particle size),

from the strong absorption edge which is 200 nm for ZnS as shown in fig 1) h is plancks constant, m* is effective mass of specimen (3.64 x 10-31 Kg for ZnS) and it comes around

9nm. For accurate size assessment by UV/VIS absorption spectroscopy10, particle should be exactly circular in shape. Photoluminescence study of the samples are done in order to detect the second harmonic generation. As we are concerned with the second harmonic only the spectrophotometer is so tuned so as to be able to detect that frequency. The instrument used in this case is F-2500 FL SPECTROPHOTOMETER and the measurement type used is a wavelength scan. Two tests are carried out with the incident wavelength at 800nm and 750nm. In both the cases the second harmonic is obtained: at 400 and 375 respectively. The tests are carried out for both the quantum dot and the bulk which shows an impressive increase in efficiency in the case of a quantum dot. In the fig for 800nm incident wavelength, the significant improvement in the efficiency can be seen as the 400nm peak for the quantum dot is obtained at around 900v whereas that of the bulk is obtained at around 560v.

Fig: second harmonic at 400nm for ZnS quantum dot

Fig: second harmonic at 400nm for bulk The enhancement factor from equation (b) can thus be calculated to be around 1.6. Similar is the case obtained for the incident wavelength at 750 nm. The second harmonic generated at 375 nm show a peak amplitude of around 280v and 750v respectively for bulk and ZnS quantum dot and the enhancement factor comes out to be 2.7(calculated from equation b). [From the calculation it has been observed that the enhancement factor is 1.6 for 400nm and 2.7 for 375 nm. So we can infer that as the frequency increases the swcond harmonic efficiency increases.]

Fig: second harmonic at 375nm for ZnS quantum dot

Fig: second harmonic at 375nm for bulk 8

5. Conclusion: From the study it thus can be concluded that the synthesized ZnS quantum dots show second harmonic generation which again has a considerable improvement in efficiency over the bulk. From relation (a) the second harmonic intensity also depends on the size(radius) of the quantum dot which has to be optimized for obtaining utmost efficiency in second harmonic generation. This property of the quantum dot can be utilized in the fabrication of an high power tunable laser.

Acknowledgement: Authors thank Prof. A Choudhury (Vice Chancellor, Gauhati University, Guwahati, Assam, India) and Dr. D K Avasthi (Scientist G, IUAC, Delhi, India) for their valuable suggestions and assistances during this work.

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