LANGMUIR-SCHAEFER FILMS OF A FERROELECTRIC COPOLYMER FOR INFRARED IMAGING APPLICATIONS

A thesis submitted to Kent State University in partial fulllment of the requirements for the degree of Master of Science

by Revathy Durairaj May, 2012

Thesis written by Revathy Durairaj B.Sc., Bharathidasan University, 2001 M. Sc., Bharathidasan University, 2003

Approved by Dr. Elizabeth K. Mann, Dr. Jim Gleeson, Dr. John R.D. Stalvey, Advisor Chair, Department of Physics Dean, College of Arts and Sciences

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Table of Contents

List of Figures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . List of Tables . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

vi xvi

Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xvii Abstract . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.1 Ferroelectrics and their properties 1.1.1 1.1.2 1.1.3 1.2 . . . . . . . . . . . . . . . . . . . . . . . xix 1 6 9 9 11 13 13 15 16

Ferroelectric polymers . . . . . . . . . . . . . . . . . . . . . . . . . . Structure of PVDF in 3d . . . . . . . . . . . . . . . . . . . . . . . . Structure of PVDF-TrFE . . . . . . . . . . . . . . . . . . . . . . . .

Langmuir Films . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.2.1 The Pressure - Area Isotherm . . . . . . . . . . . . . . . . . . . . .

1.3 1.4

Langmuir-Blodgett lms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Pyroelectricity of PVDF-TrFE . . . . . . . . . . . . . . . . . . . . . . . . .

2 The Brewster Angle Microscopy and other experimental methods for Langmuir lms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.1 2.2 2.3 2.4 Interaction of Light with Air-Water interface . . . . . . . . . . . . . . . . . Interaction of Light with Air-Thin lm-Water interfaces . . . . . . . . . . . The Brewster Angle Microscope . . . . . . . . . . . . . . . . . . . . . . . . . Surface Tension and Free energy . . . . . . . . . . . . . . . . . . . . . . . . 2.4.1 Liquid-liquid interface . . . . . . . . . . . . . . . . . . . . . . . . . . iii 20 20 23 27 29 29

2.4.2 2.4.3

Solid-liquid interface . . . . . . . . . . . . . . . . . . . . . . . . . . . Surface pressure Measurement - Wilhelmy Plate Method . . . . . . .

31 32 35 35 36 37 39 42 42 43 45 50 51 53 57 59 62 63 70 70 71 72 76

3 Experimental methods of Langmuir and Langmuir-Schaefer lms . . . . 3.1 3.2 3.3 3.4 Langmuir trough and other components . . . . . . . . . . . . . . . . . . . . Cleaning procedure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Experiment: How to make a Langmuir lm . . . . . . . . . . . . . . . . . . Langmuir-Schaefer Method . . . . . . . . . . . . . . . . . . . . . . . . . . .

4 Langmuir and Langmuir-Schaefer lms of PVDF-TrFE . . . . . . . . . . 4.1 4.2 4.3 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Polymer monolayer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Surface pressure - Area isotherm . . . . . . . . . . . . . . . . . . . . . . . . 4.3.1 4.3.2 4.3.3 4.4 4.5 4.6 4.7 Comparison with Isotherms in the Literature . . . . . . . . . . . . . Eect of sample concentration . . . . . . . . . . . . . . . . . . . . . Eect of subphase temperature . . . . . . . . . . . . . . . . . . . . .

BAM images of PVDF-TrFE . . . . . . . . . . . . . . . . . . . . . . . . . . Atomic Force Microscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Suggestions for Future Work

5 Numerical simulation of linear plasmonic photodetector . . . . . . . . . . 5.1 5.2 5.3 5.4 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Surface plasmons . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Results of numerical simulation . . . . . . . . . . . . . . . . . . . . . . . . . Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

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6 Conclusions and Recommendations . . . . . . . . . . . . . . . . . . . . . . . 6.1 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

79 79 87 93 93 93 94 94 96

A Reectivity for Langmuir Monolayers . . . . . . . . . . . . . . . . . . . . . B Calculations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . B.1 Molecular weight of PVDF-TrFE . . . . . . . . . . . . . . . . . . . . . . . . B.2 Concentration of the sample in weight percentage . . . . . . . . . . . . . . . B.3 Calculation of Molecular area per structural unit . . . . . . . . . . . . . . . B.4 Calculation of thickness of LB lms . . . . . . . . . . . . . . . . . . . . . . . C MATLAB program for calculating Rs and Rp . . . . . . . . . . . . . . . . . D MATLAB program for plotting dispersion curves of anti-symmetric MDM waveguide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

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List of Figures 1.1 Types of polarization. (Left)Linear polarization: The two orthogonal electric eld components have the same magnitude and same phase, (Middle) Circular polarization: The electric eld components are the same magnitude, but 900 out of phase and (Right) Elliptical polarization: The eld components dier in both magnitude and phase.4 . . . . . . . . . . . . . . . . . . . . . . 1.2 (a) Visible picture of two trucks in the shade (b) Long-wave IR intensity image (c) Long-wave IR polarimetric image. The two trucks in the shade is very clear in the Polarimetric image because of the strong contrast.3 . . . . 1.3 SEM images of the wire grid polarizers that allow (a) vertical (b) horizontal and (c) 450 linearly polarized light. The polarization images of a static scene is shown at the bottom panel. Images (e), (f) and (g) are S0 , S1 and S2 respectively.8 The S0 image is equivalent to typical IR image. Compared with S0 image, things are more apparent in the S1 image. The image contrast is enhanced in this case. But this depends on the orientation of the surfaces with respect to the polarizer as shown in the S2 image, the two halves of the buildings roof is clearly visible. . . . . . . . . . . . . . . . . . . . . . . . . . 1.4 (a)Classication of crystals based on their crystallographic symmetry15 (b)The relation between piezoelectric, pyroelectric and ferroelectric materials.16 . . 1.5 Typical Dielectric hysteresis loop of a Ferroelectric crystal. Here Pr is the remanent polarization, Ps is the spontaneous polarization and Ec is the coercive electric led required for zero polarization.17 . . . . . . . . . . . . . . 8 7 4 3 2

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1.6

Structure of PVDF; (a) Structure of the all-trans conformation, called phase, showing the planer carbon backbone with attached uorine and hydrogen atoms; The arrow shows the direction of dipole moment when viewed along the chain axis. Drawn using Chem3D software. . . . . . . . . . . . . . 10

1.7

Ball and stick model of all-trans conformation PVDF-TrFE (70:30). 30% of the VDF units have been replaced randomly by TrFE units. The arrow shows the net dipole moment uorine to hydrogen.27 . . . . . . . . . . . . . 13

1.8

(A)Typical isotherm of a Langmuir monolayer. When compressing the dilute gas, the area per molecule decreases and the monolayer undergoes several phase transitions from Gas (G) to liquid-disordered (LD) to liquid-ordered (LO) and nally to solid phase (S) in which the molecules are closely packed. The isotherm is taken from the book Interfacial Science: An Introduction 29 and modied. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14

1.9

Techniques for depositing a monolayer on a solid substrate (a) LangmuirBlodgett method - Vertical deposition on a hydrophilic substrate (b) LangmuirSchaefer method - Horizontal deposition (Modied from KSV website: http : //www.ksvnima.com/langmuir and langmuir blodgett troughs) . 15

1.10 (a) Temperature cycle and the corresponding pyroelctric current. A negative current ows through the circuit when the temperature increases and when the temperature decreases, the pyroelectric current is positive. (b) Plot of pyroelectric current vs temperature shows the maximum pyroelectric current near the Curie temperature. (c) Hysteresis of the eective piezoelectric coefcient and the pyroelectric current as the applied dc electric eld was cycled at room temperature.36 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18

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2.1

Reection and transmission at the interface between two media. (a) In spolarization, the electric eld is perpendicular to the plane of incidence and (b)in p-polarization, the electric eld is parallel to the plane of incidence5 . 21 23 24

2.2 2.3 2.4

The total reectivity Rp goes to zero at Brewster Angle . . . . . . . . . . . Reection and transmission of light when there are two or more interfaces . s-polarization reectivity curves for a im of the copolymer PVDF-TrFE at the air-water interface for dierent values of thickness. The refractive indices are: n1 = 1.000, n2 = 1.420 and n1 = 1.333 for air, PVDF-TrFE and water respectively. There is no signicant variation of reectivity with changes in the lm thickness. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

26

2.5

p-polarization reectivity curves for a im of the copolymer PVDF-TrFE at the air-water interface for dierent values of thickness. The refractive indices are n1 = 1.000, n2 = 1.420 and n1 = 1.333 for air, PVDF-TrFE and water respectively. The reectivity goes to zero at the Brewster angle when there is no lm on the water surface, which corresponds to 0nm curve (Black). The blue bordered box is zoomed out and shown in the bottom panel to show the dierence in reectivity between a 0.45nm (Red) lm of PVDF-TrFE and a clean water surface (Black). . . . . . . . . . . . . . . . . . . . . . . . . . . . 27 29

2.6 2.7

A photograph of the Brewster angle microscopy set up in our lab. . . . . . . (a) isotherms of low concentration sample at dierent temperatures. Isotherms shift towards left as the temperature increases. (b)Gibbs free energy calculated from the isotherms is plotted against temperature for dierent surface pressures. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

30 31 33

2.8 2.9

A liquid drop on solid surface . . . . . . . . . . . . . . . . . . . . . . . . . . Forces acting on Wilhelmy plate . . . . . . . . . . . . . . . . . . . . . . . .

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3.1

A photograph of the Langmuir trough used in this work with its components, two barriers and beam dump. . . . . . . . . . . . . . . . . . . . . . . . . . . 36

3.2

Arrangement of the Langmuir trough with beam dump inside the dipping hole and the barriers are kept symmetrically on the trough which will be controlled by the motor. The photograph at the bottom shows the Langmuir trough, Wilhelmy plate for surface pressure measurement. The laser light falls on the monolayer lm at the air-water interface at the Brewster angle and the reected beam is directed to the CCD. . . . . . . . . . . . . . . . . 38

3.3

Three steps involved in Inverse Langmuir-Schaefer technique. The solid substrate is held by tweezers44 . . . . . . . . . . . . . . . . . . . . . . . . . . . 40 42

4.1 4.2

STM image of a single monolayer lm on graphite.45 . . . . . . . . . . . . . Schematic diagram of polymer molecules on water surface during compression. (a) Initially polymer molecules may take a random coil shape. (b) and (c) Note the surface concentration, as in the number of molecules per unit area, is unchanged. Coil untangles and the polymer molecules lls the water surface and hence the surface coverage increases. (d) When the area is decreased by the barriers, polymer chains are closely packed. (e) and (f) On compression, polymer chains overlap on each other and move away from water surface. (b) and (c) are after the presentation [49] . . . . . . . . . . .

45

4.3

Surface pressure - Area isotherm of PVDF-TrFE at 25 C. Here 0 is limiting surface area for close packing of molecules. This can be found by extrapolating to = 0. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46

4.4

log - log plot (black) from the surface pressure-area isotherm. The slope of the linear t (green) gives the value of scaling exponent as 4.97. Choosing another region for the linear t, the value of was found to be 6.55. . . . . 48

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4.5

The elasticity of the Langmuir lm calculated from the isotherm. The elasticity increases with decreasing mean molecular area. At max 0.0045nm2 , elasticity reach a maximum which may mean that the monolayer begins to collapse out of the surface. . . . . . . . . . . . . . . . . . . . . . . 49

4.6

Comparison of isotherms of the present work with the previously published isotherms. The main dierence is that the coarea in the present case is almost 10 times lesser than the coarea found from the isotherm published for the rst time in 1995. In fact, all studies since the initial isotherm shown in red nd much smaller coareas; a typical example is shown in the middle curve. A. Cavalli et al. suggests that the smaller coarea is due to the dissolution of the copolymer into the water. Published isotherms were scanned and the values are extracted by the free software P lotDigitizer. . . . . . . . . . . . 50

4.7

(a)Comparison of isotherms of dierent sample concentrations. (b)The coarea vs sample concentration is shown; 01 and 02 are coareas found from two dierent tangent lines drawn on the isotherms and extrapolated for = 0. These values for each isotherm gives the uncertainty in the calculation of coarea. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52

4.8

Elasticity of dierent concentration samples calculated from isotherms shown in Figure[4.6]. The shift in elasticity may be because of dierence in polymer congurations on water surface and its surface concentration of the polymer. Beginning of lm collapse and rearrangement of polymer molecules may be the reason for the uctuations of elasticity at the higher surface pressures. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54

4.9

(a) isotherms of low concentration sample at dierent temperatures. Isotherms shift towards left as the temperature increases for which the reason may be the balance between adhesive and cohesive properties of the copolymer. (b) Gibbs free energy calculated from the isotherms using equation [4.3] is plotted against temperature for dierent surface pressures. . . . . . . . . 55

4.10 : A schematic diagram of behaviour of polymer molecules on the water surface for increasing temperature. As the temperature increases, monomers will be more soluble in water, so that more segments leave the surface (upper two gures) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.11 (a)BAM image of the water subphase without any lm on it. The reectivity of p-polarized light is nearly zero at the Brewsters angle. This creates the background for BAM imaging. (b)Typical BAM image of PVDFTrFE(70:30) at room temperature taken at very low surface pressure (less than 1mN/m). The brighter regions characterizes the thicker lm while the darker region is for lm with lesser thickness. The bottom right corner of this image is simply water and it is dark. . . . . . . . . . . . . . . . . . . . 58 56

4.12 BAM images of PVDF-TrFE of 0.158mg/ml at low and high surface pressures are shown in left and right columns respectively. (a) and (b) At low temperature, small bright spots are clear, especially at high pressure. The small circular patterns observed in both high and low surface pressures are similar particles which are out of focus because of the incident angle: only a line perpendicular to the plane of incidence, parallel to the horizontal azis on the gures, is in focus. (c) and (d) Near room temperature, there are more spots (out of focus here) at both pressures. (e) and (f) At high temperature, Again many bright, probably 3-d particles are observed. . . . . . . . . . . . 59

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4.13 BAM images of PVDF-TrFE of 1.38 mg/ml at low and high surface pressures are shown in left and right columns respectively. (a) and (b) Low temperature BAM images show that even at very low surface pressures, the polymer molecules completely covered the water surface with only occasional dark areas. Further compression results in overlapping of polymer chains and that can be seen in brighter region of (b). At room temperature, (c) show that the polymer lm is very thick and nonhomogeneous. In gure (d) we can see that the lm is about to collapse. At high temperature, the lms seem much more uniform with few bright particles. Moreover, we can see some domains with ne boundaries. From the Table [4.2], we can note that the value of 0 is less for the all the three temperatures. As recommended before in Section [4.3.3], we can try BAM imaging for deposition of polymer solution at low temperature and compression of the lm at high temperature . . . . . . . . 4.14 AFM images of 0.2% high concentration sample are shown. Top left 2D AFM image represents the LS lm of PVDF-TrFE prepared at 250 C at low surface pressure, 5mN/m. The scan size is 2m 2m. Top right 2D AFM image is for the same concentration sample, but prepared at low temperature 120 C at 5mN/m. The scan size is 1m 1m. Their 3D images are shown in the bottom panel. The blue box indicates a void, that will be enlarged in Figure [4.15]. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.15 Enlarged image of void (blue box) drawn in Figure [4.9]. The height proles of lines 1 and 2 show that the lm is not homogeneous. . . . . . . . . . . . 4.16 Comparison of height proles of the two lms prepared at room temperature and low temperature. For comparison the height proles are drawn only for the length of blue lines drawn on the images. . . . . . . . . . . . . . . . . . 67 66 66 65

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4.17 Comparison of roughness of two lms is shown here. Lower the area under the curve, the better the smoothness. Therefore, the lm prepared at room temperature shows more smoothness compared to the one prepared at low temperature. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.18 AFM picture of the same low concentration sample prepared at room temperature, low surface pressure. The area of blue box is enlarged to show that the void exists in low concentration samples also. The height prole is also shown below corresponding to the blue line. . . . . . . . . . . . . . . . . . . 4.19 (a)Comparison of roughness of low (green curve) and high concentration (red curve) samples. This shows that the LS lm of high concentration sample has more roughness. (b)Roughness of low concentration lm is compared with that of simple Silicon substrate without any lm on it. The roughness of both the lm and Silicon substrate looks similar. The green curve implies that there may be a very thin layer of polymer molecule is formed on Si substrate. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.20 2D and 3D AFM images of the LS lm of low concentration sample prepared at room temperature at 5mN/m is shown on the left side. We observed some triangular patterns. The reason is now known and this needs further investigation. The right side AFM image is for simple Silicon substrate without any lm on it. From these images it is clear that the Silicon substrate itself is not smooth. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69 68 68 67

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5.1

(a) Schematic illustration of electromagnetic wave and surface charges at the interface between the metal and the dielectric material,(b) the locally electric eld component is enhanced near the surface and decay exponentially with distance in a direction normal to the interface and (c) Dispersion curve of a SP wave; kSP and k are the wavevectors of SP and light wavevectors, respectively. This shows that the momentum of the SP wave is larger than that of the light photon in free space for the same frequency ().67 . . . . . 72

5.2

Side view of the linear plasmonic photodetector with periodicity d = 1300, slit width a = 400nm and height h = 100nm. The dielectric medium is a copolymer PVDF-TrFE polarization of which changes when it absorbs infrared radiation. The thickness of the polymer layer is 20nm. . . . . . . . . . . 73

5.3

(a) Real and (b) imaginary values of dielectric permittivity of the copolymer PVDF-TrFE shows that the polymer is anisotropic as these values are dierent in parallel and perpendicular directions of the polymer surface.40 . 74 75 76 77

5.4 5.5 5.6 5.7

Snap shot of the total electric eld at = 20THz. . . . . . . . . . . . . . . Snap shot of the total electric eld at resonant = 43.64THz. . . . . . . . Snap shot of the total electric eld at = 60THz. . . . . . . . . . . . . . . (a) Dispersion curves of anti-symmetric mode in metal-dielectric-metal waveguide in the infra-red region and (b) The propagation length of SP wave along x-direction. A MATLAB program for solving the dispersion equations is given in Appendix D. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

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5.8

The ratio of the z components of electric elds obtained from simulations with x- and y- polarized incident light demonstrating the detection of xpolarized light. The peak corresponds to the resonant frequency between SP and incident light. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78 88

A.1 Reectivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xiv

A.2 Reectivity for the tilt angle t = 450 and dierent polarizer angles = 00 , 300 , 600 and 900 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . A.3 Reectivity for the tilt angle t = 900 and dierent polarizer angles = 00 , 300 , 600 and 900 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91 91

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List of Tables 4.1 4.2 Concentration of dierent samples studied . . . . . . . . . . . . . . . . . . . Langmuir lm parameters derived from the isotherms of three samples are shown. Two dierent determinations of the coarea, 01 and 01 , values provide the uncertainty in the coarea calculation. The dierent values of scaling factor show that the slope of the slope of the isotherm in each case is dierent. Moreover, the water surface is a good solvent environment in some experiments as values are closer to 3 which is the good solvent condition. The coarea corresponds to maximum elasticity max decreases with increasing temperature showing the isotherm shift towards left for higher temperatures. 57 52

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Acknowledgements First of all, I owe my deepest gratitude to my advisor, Dr. Elizabeth Mann. She accepted me as her student immediately without any hesitation. She always explained the concepts in very simple words with more patience which helped me to gain knowledge eciently and quickly. I learned a lot from her, especially during the preparation of the thesis and defense presentation. In spite of her busy schedule, she reviewed my thesis and gave valuable suggestions. I cant say thank you enough for her understanding, guidance and encouragement. I am also extremely indebted to my coadvisor, Dr. Qi-Huo Wei for giving me an opportunity to work on such a new innovative project. I feel motivated and inspired every time I attend his group meeting. My special thanks goes to Dr. David Allendar for his careful review and important comments on my thesis. I must thank my seniors, Fanindra Bhatta and Pritam Mandal for sharing their knowledge and ideas with me. Particularly, I thank Pritam for his cooperation on scheduling BAM usage. I extend my sincere thanks to Feng Wang for his support at the last minute to complete the simulation part. Thanks must also go to my classmates Prashanth, Piotr, Pengtao and Xinyi for cheering me up all the time. In particular, I appreciate Piotrs help to understand pyroelectricity and its relation with symmetry group. Many thanks are due to Xinyi for listening to me patiently at the time of practice sessions. This list would be incomplete, if I do not mention our graduate secretary Loretta for her constant and valuable support through out my time in KSU. Thank you, Loretta for all your help! xvii

Next, I want to thank my parents for all their support, love, blessings and encouragement. I am grateful to my parents for taking good care of my daughter for the past two years. I thank my sisters, Mano and Nirmal, for being with me all the way. Finally, I would like to thank my husband, Siva, for his patience throughout.

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Abstract Poly vinlydene ouride (PVDF) and its random copolymers with triuoroethylene [P(VDFTrFE)] and tetrauoroethylene [P(VDF-TFE)] have many technological applications due to their strong ferroelectric, piezoelectric and pyroelectric properties. All of these are related to the spontaneous polarization property of this ferroelectric copolymer. We are particularly interested in the pyroelectric property that is the change in polarization states due to the change in temperature. The pyroelectricity depends strongly on the degree of structural order of the polymer lm. We use the Langmuir-Blodgett technique to make such ordered lms by transferring the polymer monolayer at the water surface onto a solid substrate. The goal of this work is to determine the transfer condition to maximize the lm organization and thus its pyroelectric response. In the rst part of this work, we study the formation and characterization of PVDF-TrFE(70:30) copolymer by variations in the Langmuir-Blodgett technique. These lms are rst made by depositing the P(VDF-TrFE) copolymer in a solution at the airwater surface. The self-assembly of the copolymer lm is controlled by changing the area of the lm by means of two barriers. We apply Brewster Angle Microscopy (BAM) imaging technique to monitor the Langmuir lm formation. In the next step, we transfer this lm onto a solid substrate (for example, Silicon). Finally, the lm characterization is done using Atomic Force Microscopy (AFM). The Langmuir-Blodgett lms of PVDF-TrFE can be used as a dielectric sensitive to Infra-red radiation in metal-dielectric-metal (MDM) waveguides. A simple metallic grating nano structure, called a linear plasmonic photodector, is designed. Numerical simulations of this structure are done for two linear polarization states to show how the photodetector recognizes dierent linear polarization states of the incoming light. For this purpose, CST xix

Microwave studio software which is used to solve Maxwells equation numerically.

xx

Chapter 1 Introduction Recently, the Infrared Polarimetric Imaging technique has been exploited for remote sensing and military applications1, 2 . Typical IR imaging sensors give us information about the intensity of infrared light reected or emitted by objects in a scene. But IR polarimetric imaging sensors measure the polarization states of light coming from all points in a scene.3 The polarization state of light is characterized by the phase and amplitude relationships between any two perpendicular components of the electric eld vectors. For reected light these components are conveniently chosen with respect to the incident plane, which is the plane dened by the direction of incidence and the normal to the surface. Since light is a transverse electromagnetic wave, the electric elds oscillate perpendicular to the direction of propagation as shown in Figure [1.1]. If the two electric components have same amplitude but with 900 phase dierence, then it is called circular polarized light. If both amplitude and phase are dierent between the two electric eld components then it is called elliptically polarized light.4 The polarization state of reected light strongly depends on the type of reecting surface, i.e., the refractive index of the medium and its surface structure as well as the polarization of the light that illuminates the surface. For example, man-made objects have very smooth surfaces which reect more light than natural objects such as grass, trees and sand. Reection from the objects changes the phase and amplitude of the electric eld components and thus the polarization. In fact, if light with its electric eld vibrating in the plane of incidence falls on an optically smooth surface at the incident angle called the Brewster angle,

the reection is zero. Thus light reecting o a smooth surface at this angle becomes perfectly linearly polarized perpendicular to the incident plane. The reected light is partially polarized in a wide range of angles around the Brewster angle.5 Therefore, polarimetry imaging oers good contrast sucient to identify dierent materials in a scene or objects with dierent surface structures or at dierent orientations. Figure[1.2] shows the color (visible region) image of two trucks in the shade, along with long-wave IR intensity and polarization images. It can be easily seen from the gure that the polarimetry image has more contrast than the IR intensity image (Figure 1.2 (b)) which helps us to see the two trucks in the shade.

Figure 1.1: Types of polarization. (Left)Linear polarization: The two orthogonal electric eld components have the same magnitude and same phase, (Middle) Circular polarization: The electric eld components are the same magnitude, but 900 out of phase and (Right) Elliptical polarization: The eld components dier in both magnitude and phase.4

Ideally, polarimetry completely characterizes the polarization of the light. However, one rarely measures the electric eld, but rather the intensity (in a vacuum, the squared magnitude of the eld), so that the phase information is lost. One means of completely characterizing the polarization of light through intensity measurements is by the four Stokes

parameters:6

2 2 S0 Ex + Ey I0 + I90 2 2 S1 Ex Ey I0 I90 = S= S2 2Ex Ey cos I45 I135 S3 2Ex Ey sin IL IR

(1.1)

Here, S0 is the total intensity of the light, S1 is the dierence between horizontal and vertical polarizations, S2 is the dierence between linear +450 and 450 polarization, and S3 is the dierence between right and left circular polarization; is the phase dierence between the two electric eld components. The measurements of the rst three parameters are simple using a simple linear polarizer. But measurement of S3 involves practical difculties as the circular polarization is typically measured by using both a linear polarizer at 450 and a waveplate.7 In 1999, Nordin et al.8 and in 2008 Zhi Wu et al.,9 fabricated

Figure 1.2: (a) Visible picture of two trucks in the shade (b) Long-wave IR intensity image (c) Long-wave IR polarimetric image. The two trucks in the shade is very clear in the Polarimetric image because of the strong contrast.3

a wiregrid micropolarizer array that permits the measurement of the rst three Stokes vector components in each pixel of an imaging polarimeter . The SEM images of the micropolarizer and the polarization images from these publications are shown in Figure [1.3]. However, these are only sensitive to linear polarization states and thus do not contain complete polarization information. The fourth Stokes parameter which characterizes an objects circular polarization should also be detected for improved imaging sensitivity. Monolithic photodetectors which can distinguish the status of both circularly and linearly polarized light, though highly desired, do not currently exist. For measuring all the four Stokes parameters, Professor Qi-Huo Wei from the Liquid Crystal Institute proposed a design he calls Plasmonic Metal-Dielectric-Metal (MDM) Photodetectors that can distinguish intensity and the status of both linearly and circularly polarized light.

Figure 1.3: SEM images of the wire grid polarizers that allow (a) vertical (b) horizontal and (c) 450 linearly polarized light. The polarization images of a static scene is shown at the bottom panel. Images (e), (f) and (g) are S0 , S1 and S2 respectively.8 The S0 image is equivalent to typical IR image. Compared with S0 image, things are more apparent in the S1 image. The image contrast is enhanced in this case. But this depends on the orientation of the surfaces with respect to the polarizer as shown in the S2 image, the two halves of the buildings roof is clearly visible.

This photodetector uses nanostructures to dierentiate between the dierent polarization states, with an underlying infrared-sensitive lm. P(VDF-TrFE 70:30), a copolymer of 70% vinylidene uoride (VDF), and 30% triuoroethylene (TrFE) is a natural choice for

this layer because of its strong pyroelectric properties, which makes it sensitive to IR light. The structure and the properties of this copolymer are discussed in Section [1.1.2]. Pyroelectricity originates in the change of the net polarization of a sample under an electric eld with an increase in temperature. It depends strongly on the degeree of order in the polymer.10 The Langmuir-Blodgett (LB) technique allows one to produce thin highly ordered organic lms by rst organizing a monomolecular layer at the water surface, as a so-called Langmuir layer, and then repeated transfer of this layer onto a solid substrate.11 Therefore, the polymer layer for the proposed super pixel is made by using the LB technique. The rst step of LB deposition method is the formation of a well-dened monolayer at the air-water interface. To form a good Langmuir monolayer, the layer molecules should be amphiphilic, i.e., possess both hydrophilic and hydrophobic groups, and be insoluble in water. The experimental details are given in section [3.3] titled How to make a Langmuir lm. The LB technique is one of the most promising techniques for preparing this organic thin lm as it enables (i) the precise control of the monolayer thickness, (ii) homogeneous deposition of the monolayer over large areas, (iii) multilayer structures with varying layer composition and (iv) deposition on almost any kind of solid substrate.12 PVDF and its copolymers are not good amphiphiles and hence, it can be dicult for them to form well-organized monolayers.13 In that case, a complete monolayer characterization is required in order to optimize conditions for making LB lms of PVDF-TrFE. This optimization is the focus of this thesis. In this chapter, we present an overview of the ferroelectric properties of ferroelectric polymers and copolymers. Also, the phase transition behaviour and the electrical properties of these polymers are discussed briey. Then, we introduce about Langmuir lms along with the Langmuir-Blodgett and Langmuir-Schaefer techniques used for transferring thin lms onto a solid surface.

1.1

Ferroelectrics and their properties In 1921, Valasek observed dielectric hysteresis in sodium potasium tartrate tetrahydrate,

usually called Rochelle salt, which was analogous to the magnetic hysteresis in the case of iron.14 Ferroelectricity owes its name because of this analogy with ferromagnetism. Basically, ferroelectric is dened as a material with a spontaneous electric polarization that can be reversed by an applied electric eld. The general properties of ferroelectric materials include crystal symmetry, spontaneous polarization, ferroelectric domains, dielectric hysteresis loop and a phase transition at the Curie point. We summarize these properties in the following sections. It is well-known that crystals are classied into 32 classes based on their symmetry with respect to a point. Among these 32 classes, eleven are centrosymmetric and the remaining 21 are non-centrosymmetric. Crystals which have a center of symmetry are non-polar and behave like normal dielectric materials. Twenty out of the 21 non-centrosymmetric crystals show the piezoelectric eect. These crystals develop electrical polarity when subject to stress. They show the converse eect as well, i.e., an external electric eld changes the length of the dipole moments resulting in structural deformation. Ten out of these 20 piezoelectric crystals have a unique polar axis whereby the whole crystal is polarized. The spontaneous polarization in these polar crystals depends on temperature. Thus if the temperature of the crystal is changed, a change in polarization occurs. This is called the pyroelectric eect. Therefore, the ten polar classes are also called pyroelectric crystals. Hence, it is clear that all pyroelectrics are piezoelectrics but the reverse is not true. For example, quartz crystal is a piezoelectric material but not pyroelectric. In addition, all ferroelectrics are piezoelectric and pyroelectric, but not vice versa. Although they have spontaneous polarization like ferroelectrics, the polarization can not be reversed in all pyroelectric and piezoelectric materials by applying electric eld. The relationship between the piezoelectric, pyroelectric and ferroelectric materials is shown graphically in Figure [1.4].

Figure 1.4: (a)Classication of crystals based on their crystallographic symmetry15 (b)The relation between piezoelectric, pyroelectric and ferroelectric materials.16

Usually, the ferroelectric materials acquire domains in which the dipoles are all aligned in one particular direction. There are many domains in a single ferroelectric crystal separated by domain walls. The direction of the polarization vector is dierent in dierent domains. These domains are visible under polarized light. Polarization reversal, the main characteristic of any ferroelectric crystal can be seen in the hysteresis loop. This loop can be obtained by plotting the change in polarization P with respect to the applied eld E. Let us say that the polarization vectors in the domains are randomly oriented before the application of an electric eld. In other words, the vector sum of dipole moments of the individual domains vanishes and hence the net polarization is zero in the crystal initially. When the electric eld is increased in the positive direction, the domains start aligning parallel to the eld which increases the polarization. This is given by the curve OA in the hysteresis loop (Figure 1.5). If the electric eld is increased further, the domain walls disappears at B and the crystal has only one domain. This means that all the dipole moments are now parallel

to the E. Now, if we decrease the electric eld through CBD, the polarization decreases but does not go to zero when E is completely removed. Instead it takes the value D which is called the remanent polarization Pr . In the case of a completely polarized crystal, Ps is the spontaneous polarization obtained by extrapolating the curve BC onto the polarization axis.The negative electric eld required to make this polarization zero is called the coercive eld Ec which is represented by F in the Figure. A further increase in electric eld in the negative direction results in polarization reversal at the point G in Figure [1.5]. Most ferroelectrics have a transition temperature called the Curie temperature Tc above which they act like a non-polar, normal dielectric (or paraelectric) material. As said before, the spontaneous polarization Ps is temperature dependent. It decreases as temperature increases and disappears at Tc .. The ferroelectric phase transition is a structural phase transition.

Figure 1.5: Typical Dielectric hysteresis loop of a Ferroelectric crystal. Here Pr is the remanent polarization, Ps is the spontaneous polarization and Ec is the coercive electric led required for zero polarization.17

In summary, ferroelectric materials have the following properties:18, 19

They lack centrosymmetry and hence belong to one of the 10 polar class crystals. They exhibit spontaneous polarization which makes one side of the crystal positive and the opposite side negative. The spontaneous polarization decreases with increase in temperature and vanishes at the Curie Temperature. They possess a dielectric hysteresis loop which shows that the polarization is reversible by the application of external electric eld. The hysteresis will disappear at the Curie Temperature. They have domain structure, which can be visible in polarized light. 1.1.1 Ferroelectric polymers In the 1970s, ferroelectric properties were found in liquid crystals and in polymers.20 The most familiar ferroelectric polymer, poly(vinlydine uoride) (PVDF), was rst known for its large dielectric constant. But it was experimentally proved that PVDF is a ferroelectric polymer by Furukawa, Date and Fukada in 1980 and Furukawa and Johnson in 1981. 1.1.2 Structure of PVDF in 3d The structure of one monomer unit of PVDF is -(CH2 -CF2 )- with a dipole moment pointing from negative uorine to positive hydrogen atoms. These dipoles are strongly attached to the main-chain carbons; thus the orientation depends on the conformation and packing of molecules. The two most common conformations are (i) all-trans TTTT conformation and (ii) alternate trans-gauche TGTG conformations. When compact the chains pack into dierent crystalline structure, one of the most common structure for the all trans conformation is called the phase. The lattice constants are a = 0.858nm, b = 0.491nm, and c = 0.256nm. The dipoles in all-trans conformation lie in a zig-zag plane; they

10

are perpendicular to the chain axis. Since the size of the uorine atom (0.270nm) is slightly greater than the distance between the two carbon atoms along the c-axis, overlapping of two the uorine atoms occurs. To avoid this overlapping, the CF2 groups are deected to right and left of the zig-zag plane in the all-trans phase.20 In the other major crystal structure ( phase) the chain has alternate trans/gauche bonds and no net dipole moment. The molecular conformation of phase is shown in Figure [1.6]. From the previous section, we know that a crystal structure should be polar for it to be ferroelectric. But it is mainly the instability of this polar structure which leads to polarization reversal and the phase transition from ferroelectric to paraelectric. Only the phase is non-polar: it is paraelectric. The other phases are polar structures. However, the phase has spontaneous polarization double than that of other phases, because the dipoles are oriented in one direction. Using an external electric eld this polarization was shown to be switchable and hence, the phase is ferroelectric.

Figure 1.6: Structure of PVDF; (a) Structure of the all-trans conformation, called phase, showing the planer carbon backbone with attached uorine and hydrogen atoms; The arrow shows the direction of dipole moment when viewed along the chain axis. Drawn using Chem3D software.

The Curie temperature of PVDF is higher than its melting point. Therefore, the ferroelectric properties are mainly studied in its copoymer called Poly(vinylidene uoridetriuoroethylene),PVDF-TrFE. In 1980, PVDF-TrFE copolymer was synthesized by Yagi et al. with dierent compositions of PVDF and TrFE. In this PVDF-TrFE copolymer, VDF and TrFE units are randomly distributed and so that it is called a random copolymer. The

11

hydrogen atoms of PVDF are replaced by bigger uorine atoms; again, uorine-uorine overlapping happens, in the phase. Because of this the PVDF-TrFE copolymer takes the phase. The structure and properties of this copolymer is discussed in the following section. In general, ferroelectric materials undergo two types of transitions (called the displacive transition and the order-disorder transition) based on whether the transition is due to the displacement of ions or the ordering of permanent dipoles. The phase transition in the PVDF-TrFE copolymer is a rst order, order-disorder transition with a structural transformation from all-trans chains to a mixtures of trans-gauche bonds. 1.1.3 Structure of PVDF-TrFE The chemical formula of PVDF-TrFE is ((CF2 CH2 )x (CF2 CHF)1x )n . The VDF and TrFE units are randomly distributed along the molecular chain to form a random copolymer (Figure [1.7]). The copolymers of PVDF like PVDF-TrFE and PVDF-TeFE have great advantages over VDF homopolymer for the following reasons: Introduction of a small amount of TrFE or TeFE into PVDF induces direct crystallization of phase from the melt. Therefore, ferroelectric lms can be directly produced from the melt. But PVDF takes many polymorphic structures which needs to be treated electrically or thermally to yield the phase. PVDF-TrFe shows higher crystallinity ( 90%) whereas the crystallinity of PVDF is only 50%.21 The dielectric hysteresis loops of PVDF-TrFE copolymer are sharper than those for various crystalline phases of the PVDF homopolymer. This means, that only a small amount of eld is required for polarization reversal. The reason for this dierence

12

is that in the copolymer, the addition of triuoroethylene expands the crystal structure and hence reduces the steric hindrance to chain rotations. Therefore, dipole reorientation occurs at lower elds. PVDF does not have a Curie point below its melting temperature, which is estimated as 195 197 C,22 which is less than its hypothetical Curie point. This means that the melting of the ferroelectric phase of PVDF and the ferroelectric to paraelectric transition happens in the same temperature range. In the case of copolymers with TrFE or TeFE with 50 80% VDF, the temperature of the phase transition is lower than in PVDF..23 This is due to the fact that the unit cell of copolymer is larger than that of PVDF polymer because uorine atoms are bigger than hydrogen atoms. Because of this PVDF-TrFe copolymer is less stable than the pure PVDF. This instability is responsible for the ferroelectric to paraelectric transition on heating at lower Curie temperature. A. V. Bune et al.24 found that the surface ferroelectric transition at 200 C is distinct from the bulk ferroelectric to paraelectric phase transition at about 800 C.24, 25 At the same time, the spontaneous polarization of PVDF will be reduced when it forms PVDF-TrFE copolymer. Because some hydrogen atoms are replaced by uorine atoms that reduces the dipole moment. The pyroelectricity of the copolymer depends on many factors like temperature, crystallinity, thickness, impurities and composition. Therefore, structurally-ordered polar thin lms are required to achieve maximum pyroelectricity. The Langmuir-Blodgett technique can be used to prepare such lms with high degree of order perpendicular to the plane.26 In plane-order can be introduced by compress the lm on water before transfer. All these considerations refer to bulk structure. A Langmuir lm is, ideally, a single quasi-2d layer. The appropriate symmetry groups are the 2d ones. However, the asymmetry of the surface introduced a preferred dipole direction if, for

13

example, the uorine groups are preferentially directed towards the water. In the following sections, we explain about the LB technique in more detail.

Figure 1.7: Ball and stick model of all-trans conformation PVDF-TrFE (70:30). 30% of the VDF units have been replaced randomly by TrFE units. The arrow shows the net dipole moment uorine to hydrogen.27

1.2

Langmuir Films A Langmuir lm is dened as a molecularly thin layer trapped at the gas-uid inter-

face.28 Generally, it is air-water interface and the molecules that make a Langmuir lm are amphiphilic. A amphiphile molecule consists of two parts, a hydrophilic (water-loving) head-group and a hydrophobic (water-fearing) hydrocarbon chain. Therefore, at the airwater interface the head groups are immersed in the water surface and the tail groups point away from water. 1.2.1 The Pressure - Area Isotherm

In a typical experiment , the sample of interest is dissolved in a volatile solvent and drops of this solution are spread on water. The solvent evaporates and leaves a monolayer of molecules on the water surface. More details of how to make monolayers are given in Chapter 3. The amount of sample to be spread should be calculated to make a monomolecular layer. At this stage, the monolayer is in a gas phase as the molecules are far apart and there is no interaction between them. Hence, the surface pressure is low. While the monolayer is compressed by a movable barrier, the surface pressure and the area per molecule is recorded.

14

Figure 1.8: (A)Typical isotherm of a Langmuir monolayer. When compressing the dilute gas, the area per molecule decreases and the monolayer undergoes several phase transitions from Gas (G) to liquid-disordered (LD) to liquid-ordered (LO) and nally to solid phase (S) in which the molecules are closely packed. The isotherm is taken from the book Interfacial Science: An Introduction 29 and modied.

The surface pressure = 0 is dened as the dierence between the surface tension of pure water (0 ) and that of surface with the monolayer (). We already know the number of molecules spread on the surface and the total area of the monolayer. Therefore, we can calculate the area per molecule and plot as a function of area per molecule. The whole experiment is done at constant temperature and hence, the A plot is called as isotherm. The A isotherm is very important because it has information about the stability of the monolayer at the air-water interface, and about phase transitions. A typical surface pressure - area isotherm is shown in Figure [1.8]. If the monolayer is further compressed, it changes from gaseous phase to liquid phase. There are two liquid phases called liquid disordered and liquid ordered phases. In the liquid disordered phase the chains are disordered whereas in liquid ordered phases the chains are fully extended and uniformly oriented. Now a small reduction in area leads to phase transition from liquid condensed to solid phase. This phase is characterized by steep linear isotherm at low area per molecule. In the solid phase all the molecules are closely packed. Further compression of the monolayer leads to monolayer collapse because the molecules are forced out of the

15

surface and form multilayers. 1.3 Langmuir-Blodgett lms The transfer of Langmuir lms from the air-water interface to a solid substrate is known as Langmuir-Blodgett-style deposition.30, 31 The deposition process depends on the hydrophilicity or hydrophobicity of the solid substrate. For example, if the solid substrate is hydrophilic, then the monolayer is transferred by an upward movement through the water and the Langmuir layer, and if it is hydrophobic the transfer is done by downward movement through the layer. Usually, the substrate is placed in the subphase before the monolayer is spread. The transfer of monolayer onto a solid substrate can be done in two methods called the Langmuir-Blodgett (LB) and Langmuir-Schaefer (LS) methods. In the LB method,

Figure 1.9: Techniques for depositing a monolayer on a solid substrate (a) Langmuir-Blodgett method - Vertical deposition on a hydrophilic substrate (b) Langmuir-Schaefer method - Horizontal deposition (Modied from KSV website: http : //www.ksvnima.com/langmuir and langmuir blodgett troughs)

the solid substrate moves vertically while transferring the monolayer from the air-water interface. There are many reports related to the arrangement of molecules on the solid substrate after deposition.31 In some instances, such as highly viscous monolayers, the classic vertical deposition does not yield favorable results and alternate methods are required.

16

Langmuir and Schaefer found that for highly viscous monolayers a horizontal depostion process was suitable.32 In the LS method, the solid substrate is placed horizontally on the monolayer lm and then lifted up. This method is mainly useful for the deposition of very rigid lms, for example, monolayers of protein and polymers.31, 32 The oating monolayer will be less disturbed in LS technique than in the LB method.11 In the present work, we use the Langmuir-Schaefer method, as explained in Chapter 3, for monolayer transfer. 1.4 Pyroelectricity of PVDF-TrFE In the present work, we are most interested in the pyroelectricity of the copolymer PVDF-TrFE, with the goal of using Langmuir-Blodgett lms of this polymer for infra-red photodetectors. Therefore, in this section we discuss the pyroelectric eect of the copolymer. As said before, a material is pyroelectric if each unit cell has an electric dipole. These dipoles are produced because the center of the positive and that of negative charges do not coincide. If these electric dipoles orient in such a way that they do not cancel each other, then the material has spontaneous polarization. When there is a change in temperature of the material, there will be a change in the atomic positions or interatomic bonding which aects the spontaneous polarization. This change in spontaneous polarization due to a change in temperature is called the pyroelectric eect. The spontaneous polarization can be written in the form, s = 1 P dV V

(1.2)

where is the dipole moment per unit volume. From this equation, it is clear that for Ps to be non-zero, the dipole moment should be non-zero. In order to satisfy this criteria, the crystal should have a non-centrosymmetric unit cell and should show no axis of rotational symmetry. As discussed in Section[1.1], only 10 out of 32 crystal classes obey the symmetry requirements of pyroelectricity. The derivative of spontaneous polarization with respect to temperature at constant

17

stress and electric eld gives the pyroelectric coecient: ( p= Ps T ) (1.3)

E

The following physical properties of pyroelectric materials are required for a good IR detector:33 1. Large Pyroelectric Coecient (p): Since the detector response is directly proportional to the pyroelectric coecient, large p values are required. 2. High Curie Temperature (Tc ): The pyroelectric detector is used below Tc , because they have large p value below that temperature. Tc of the detector is preferred to be much over room temperature because p is not constant around room temperature. 3. Small Dielectric constant (): Small dielectric constant corresponds to small electric capacity of the detector. Therefore, the voltage across the detector, i.e., the pyroelectric response will be better for small dielectric value. 4. Small Heat capacity (Cs ): Small heat capacity is required for maximum pyroelectric response so that a small amount of IR absorption is sucient to change the temperature of the detector. The heat capacity can be reduced by using a thinner lm since it is an extensive property of the system. These properties are satised by PVDF-TrFE copolymer and hence it is a very good material for IR detection. The pyroelectric coecient of the PVDF-TrFE copolymer is signicantly larger than that of the PVDF homopolymer. For example, the pyroelectric coecient for PVDF ( phase) is 1.8 109 C/cm2 K but for the copolymer with ratio 65:35, it is 2.9 109 C/cm2 K. The benet of using pyroelectric polymers are: Very thin lms can be easily fabricated, their cost is low and they are exible to conform to a curved surface.

18

In 1995, crystalline lms of ferroelectric P(VDFTrFE) copolymers were formed by the LangmuirBlodgett method.34, 35 These lms possess ferroelectric properties close to those of bulky lms, including switching and a rst-order ferroelectric phase transition. In the best studied copolymers, the VDF:TrFE ratio is about 70:30. The pyroelectric properties of Langmuir-Blodgett lms of PVDF-TrFE(70:30) were studied by A. V. Bune et al. in 1999.36 Figure [1.10(a)] shows the typical temperature prole and the corresponding pyroelectric current. The pyroelectric current vanishes at temperature greater than Tc which shows the ferroelectric behaviour of the copolymer LB lm (Figure [1.10(b)]). The hysteresis behaviour of the pyroelectric and piezoelectric responses show a low polarizing voltage. In this way, LB ferroelectric lms are more advantageous than the traditional lms.

Figure 1.10: (a) Temperature cycle and the corresponding pyroelctric current. A negative current ows through the circuit when the temperature increases and when the temperature decreases, the pyroelectric current is positive. (b) Plot of pyroelectric current vs temperature shows the maximum pyroelectric current near the Curie temperature. (c) Hysteresis of the eective piezoelectric coecient and the pyroelectric current as the applied dc electric eld was cycled at room temperature.36

19

In this thesis I will focus on optimizing the order within a single LS lm of the P(VDFTrFE) copolymer, inspired by the earlier work. We will characterize the originating Langmuir lms at the air/water interface through Brewster angle microscopy (discussed in chapter 2) and surface pressure isotherms (discussed in chapter 3) as a function of deposition conditions and temperature. The results will be discussed in chapter 4. Next, we will optimize the dimensions of the metal-dielectric-metal photodetector using a commercial software called Computer Simulation Technology (CST) for identifying the linear polarization state of the incoming light. The details of the simulation and the results are discussed in chapter 5. In the end, concluding remarks and recommendations for future work are given in Chapter 6.

Chapter 2 The Brewster Angle Microscopy and other experimental methods for Langmuir lms Brewster angle microscopy uses the special condition of the light reecting o a surface at the Brewster angle to image lms as thin as 0.5 nm thick. This chapter starts with the overall concept of light propagation through dierent interfaces between two or three homogeneous media. Then it discusses about the basic theory behind Brewster Angle Microscope (BAM), along with the conditions necessary for good sensitivity of our lms. Also, we give details of the Wilhelmy plate method which is used to measure the surface pressure of Langmuir lms. 2.1 Interaction of Light with Air-Water interface In general, when light travels from one medium to another medium, reection and refraction occur at the interface between the two media.5, 37 Consider a light wave with electric eld Ei incident on the surface at angle i . It will be partially reected from the surface and partially transmitted through the medium as shown in Figure [2.1]. Now, there are two main equations that relate the angle of incidence i to the angle of reection r and the angle of refraction t . The rst one is called the law of reection which can be written as i = r The second law, called law of refraction or Snells law, can be given as n1 sini = n2 sint (2.2) (2.1)

20

21

where n1 and n2 are refractive indices of the two isotropic media. From this law, it is clear that when n1 is less than n2 , i.e., when light travels from low refractive index medium to high refractive index medium, i > t and therefore the transmitted light is closer to the normal and vice-versa. Conventionally, the direction of the electric eld vector is taken as the direction of polarization. The plane in which the electric eld vector lies is called plane of polarization. In Figure [2.1], the electric elds of reected and transmitted light waves are represented as Er and Et and their direction of propagation is given by propagation vectors, r and k t respectively. It can be noted that the propagation vectors of incident, reected and k transmitted light waves are all in the same plane called the plane of incidence. Depending on the direction of the electric eld vector of the incident light, there are two types of polarization (1) p- polarization if the electric eld is in the plane of incidence and (2) spolarization if the electric eld is perpendicular to the plane of incidence.

Figure 2.1: Reection and transmission at the interface between two media. (a) In s-polarization, the electric eld is perpendicular to the plane of incidence and (b)in p-polarization, the electric eld is parallel to the plane of incidence5

According to the Fresnel equations, the amplitude of the reection coecient (which is the ratio of the tangential component of the reected wave electric eld and that of incident

22

wave electric eld) for p-polarization can be written as,5 rp = n2 cosi n1 cost . n1 cost + n2 cosi (2.3)

Similarly for s-polarization, the reection coecient will be, rs = n1 cosi n2 cost n1 cosi + n2 cost (2.4)

Then, the total reectivity can be calculated as Rp = |rp |2 and Rs = |rs |2 (2.5)

for p- and s- polarized incident light wave respectively. The total reectivity Rp and Rs for light incident on an air-water interface has been plotted using equation (2.5) with n1 = 1 for air and n2 = 1.333 for water. It can be seen from the Figure [2.2] that the total reectivity Rp is equal to zero when the incident angle i = 53.1230 . This angle of incidence is called Brewsters angle. This means that when unpolarized light falls on an interface at the Brewster angle, then the light wave with electric eld perpendicular to the plane of incidence (rs ) will only be reected and hence the light becomes polarized. The Brewster angle can also be derived from equation (2.3) as follows: rp = n2 cosi n1 cost =0 n1 cost + n2 cosi (2.6)

If i + t = 900 , then the above equation will become, 1 and B = i = tan

1

n1 tani = 0 n2 ( )

(2.7)

n2 n1

(2.8)

Therefore, the Brewster angle can be determined if we know the refractive indices of the two media which makes the interface. In the next section, we will derive the total reectivity for light travelling through two interfaces.

23

Figure 2.2: The total reectivity Rp goes to zero at Brewster Angle

2.2 Interaction of Light with Air-Thin lm-Water interfaces I will want to form polymer lms only a monomer thick. In principle, we should consider reectivity at the molecular scale. However, for reasonably smooth lms, it has been found that the resulting reectivity is very close to that of a uniform thin lm.38 Therefore we will approximate our lms as uniform thin lms for the purposes of estimating the reectivity and contrast we can expect with the Brewster angle microscope. The reectivity from a uniform thin lm has been treated in several standard references; here we follow the treatment of reference.5, 39 Consider a thin lm of thickness d on a substrate. This system actually forms two interfaces:(i)the boundary between the air and the thin lm and (ii) the boundary between the thin lm and the substrate. Let us say that the refractive indices of air, thin lm and the substrate are n1 , n2 and n3 in that order. Now, if an incident light hits the thin lm at angle 1 , as explained in the previous section, it will be partially reected and partially transmitted at the air-thin lm interface. The transmitted light reaches the substrate and at the line between thin lm and the substrate, it will be again reected

24

back to the surface of the thin lm and transmitted if the substrate is not opaque. In this way, multiple reections occur at the surface of the thin lm as shown in the Figure [2.3]. Clearly, we can see that the second reected wave travels more distance A-B-C than the

Figure 2.3: Reection and transmission of light when there are two or more interfaces

rst reected wave. The dierence in optical path length between the rst and the second reected rays can be written as, ( ( ) ) = n2 AB + BC n1 AD Then, from the traingle ABC we can write, AB = BC = and AC = 2dtan2 (2.11) d cos2 (2.10) (2.9)

where 2 is the angle of refraction. Now, the distance travelled by rst ray AD can be calculated from the traingle ADC as, AD = ACsin1 (2.12)

25

Next substituting equation (2.10) and (2.12) in equation (2.9) and along with Snells Law (2.2), the optical path length dierence can be derived in terms of known quantities as given below: = 2n2 d 2n2 dsin2 tan2 = 2n2 dcos2 cos2 (2.13)

Consequently, the dierence in phase angles, called the phase dierence , between the rst and second reected waves will become = k Here, k is the magnitude of the propagation vector which is equal to
2 .

(2.14) is the wavelength

of the incident light wave. On the whole, if the light falls on a multi-layered system, the total reection can be written as, rsum = r12 + t12 r13 t12 ei + t12 r23 r21 r23 t21 e2i + . . . (2.15)

where r and t are the reection and transmission coecients. The representation r12 means that the light travels across the interface between medium 1 and medium 2 and r21 represents that the light travels across the same interface but this time from the medium 2 to medium 1. In the same way, the transmission coecients are also represented . On simplifying the above equation we will get the amplitude of total reection as rsum = r12 + t12 r23 t21 ei 1 r21 r23 ei (2.16)

However, we know that r12 = r21 from Fresnel equations which means that the light travels in the same direction either way from the low dense medium to high or from high dense medium to low. Therefore, using the other properties of Fresnel equations, like, r + t = 1
2 and t12 t21 = 1 r12 , the above equation will become

rsum =

r12 + r23 ei 1 + r12 r23 ei

(2.17)

26

Consequently, the total reectivity can be written as R = |rsum |2 = | r2 + r2 + 2r12 r23 cos r12 + r23 ei 2 | = 12 2 23 2 1 + r12 r23 ei 1 + r12 r23 + 2r12 r23 cos (2.18)

Let us consider a thin lm of the copolymer PVDF-TrFE at the air-water interface. The refractive indices are: n1 = 1.000, n2 = 1.420 and n1 = 1.333 for air, PVDF-TrFE and water respectively.40 Using Equation[2.18], the total reectivity R can then be plotted for s-polarization and p-polarization for dierent values of thickness d. They are shown in Figures [2.4] and [2.5]. we assumed that the air-water interface is an ideal Fresnel interface. But practically, the reectance of the water surface is not zero because of surface roughness. As can be seen from Figure [2.4], Rs increases with increasing angle of incidence. Also, it is

Figure 2.4: s-polarization reectivity curves for a im of the copolymer PVDF-TrFE at the airwater interface for dierent values of thickness. The refractive indices are: n1 = 1.000, n2 = 1.420 and n1 = 1.333 for air, PVDF-TrFE and water respectively. There is no signicant variation of reectivity with changes in the lm thickness.

hard to dierentiate between dierent thickness values. The p-polarization reectivity, Rp (Figure[2.5]) is sensitive to the lm thickness near the Brewster angle (B 53.120 ). The reectivity is large away from the Brewster angle. Therefore, the imaging of a monolayer should be done close to Brewster angle with p-polarization since at this angle there exists a

27

good contrast between the lms of dierent thickness. For example, the dierence between the p-reectivities of water surface(0nm) and 0.45nm lm is large near the Brewster angle. Therefore, collimation of the incident beam is very important. From the zoomed out bottom panel of Figure [2.5], we say that the collimation of laser beam should be within 0.0150 . Moreover, Figure[2.5] shows the values of p-reectivity is very small ( 108 ). Therefore, intense incident light and a high sensitive camera is required for imaging the small reection from the thin lm.

Figure 2.5: p-polarization reectivity curves for a im of the copolymer PVDF-TrFE at the airwater interface for dierent values of thickness. The refractive indices are n1 = 1.000, n2 = 1.420 and n1 = 1.333 for air, PVDF-TrFE and water respectively. The reectivity goes to zero at the Brewster angle when there is no lm on the water surface, which corresponds to 0nm curve (Black). The blue bordered box is zoomed out and shown in the bottom panel to show the dierence in reectivity between a 0.45nm (Red) lm of PVDF-TrFE and a clean water surface (Black).

2.3

The Brewster Angle Microscope The Brewster Angle Microscope (BAM) is based on the following principle: When p-

polarized light falls on a perfectly at abrupt Fresnel interface, the intensity of the reected light goes to zero at a certain angle of incidence called the Brewster angle. Physically, it means that the induced dipole moments in the medium oscillate in a direction parallel to

28

the propagation vector of the reected light wave and hence, there is no dipole radiation along this direction. The air/water interface is typically the best possible approximation to a Fresnel interface and sets the dark background of the image. In practice, water surface is not a perfect Fresnel interface, because it has a natural roughness of about 0.3nm due to thermal uctuations. So, the reectivity is slightly greater than zero at the Brewster angle. This gives a small brightness in the background image. Now, when we have a monolayer with a refractive index dierent from that of water, it acts like a third optical medium. Reection occurs at the two interfaces and the total reectivity can be calculated as explained in the beginning of this chapter. Therefore, the change in the refractive index of the system and the corresponding change in the reectivity leads to high contrast images that help us to visualize the monolayer on the water surface. BAM consists of, on one side, a laser light source ( = 488nm), a collimator, a polarizer for illuminating the sample with a p-polarized light and on the other side, a converging lens with a CCD camera on the imaging plane for the detection of reected light. In order to study the anisotropy of the monolayer lm, an analyzer should be added at the detection side. The optical components associated with each side are attached to goniometers equipped with adjustable mounts which can be used to set the incident and detection angles close to the Brewster angle. Additionally, the set-up can be moved in all the three directions easily using a translational x-y-z stage. The monolayer formation is imaged by a CCD camera at the rate of 30 frames per second. Then the images are extracted from the video le using Ulead VideoStudio 6.0 software. To facilitate high quality of imaging, the whole system is placed on a isolation vibration table to minimize any mechanical vibrations. This is important not only for the BAM imaging; the surface pressure measurement (discussed at the end of this chapter), is also sensitive to mechanical vibrations.

29

Figure 2.6: A photograph of the Brewster angle microscopy set up in our lab.

2.4

Surface Tension and Free energy Consider a lm formed in a system with a movable barrier of length L. Now, the lm

experiences some inward force on all the boundaries as shown in the Figure [7(a) (a)]. Let us say that the barrier is moved by a small distance dx by an external force F . Then, if we dene the surface tension as the force acting perpendicular to the boundary of the frame per unit length, then the work done to expand the lm will be41 dW = F dx = Ldx (2.19)

Here, Ldx is the change in area of the lm dA. Hence, the work done on the system will now become, dW = dA (2.20)

This equation implies that the surface tension has dimensions of force per unit length, N m1 . 2.4.1 Liquid-liquid interface Suppose two homogeneous surfaces, pure water surface denoted by and a thin lm on water surface denoted by , are divided by a movable barrier as seen in the Figure [7(a)(b)].

30

(a)

(b)

Figure 2.7: (a) isotherms of low concentration sample at dierent temperatures. Isotherms shift towards left as the temperature increases. (b)Gibbs free energy calculated from the isotherms is plotted against temperature for dierent surface pressures.

For this system, the total change in the Gibbs free energy can be written as,42, 28 dG = dG + dG + dGs (2.21)

where dGs is the change corresponding to interface region. If the barrier is moved by an area dA at constant pressure, then the above equation can be rewritten as dG = S dT S dT + 0 dA0 + dA Since dA0 = dA, we can write, dG = (S + S ) dT + (0 ) dA = (S + S ) dT + dA (2.23) (2.22)

As we see in the above equation, the surface pressure is dened as the dierence between two surface tensions, = 0 Therefore, for constant temperature, equation can be written as ( = G A ) (2.25)
T

(2.24)

In this way, surface tension can also be considered as change in free energy per unit area.

31

Figure 2.8: A liquid drop on solid surface

2.4.2 Solid-liquid interface In practice, the surface tension of a gas/liquid interface is determined by exploiting the solid/liquid/gas interface. In our experiment this is done via the Wilhelmy plate, discussed in this section. Like the liquid-liquid interface, the solid-liquid interface will also have its surface free energy. If a liquid drop is placed on a solid surface, it would change its shape to attain minimum surface free energy. As we can see from the Figure [2.8], there are three interfaces in this system (a) solid-vapour interface, (b) solid-liquid interface and (c) liquid-vapour interface. We can also observe that the liquid-vapour interface makes an angle with the solid surface. This angle is called the contact angle, the characteristic of a particular solid-liquid-vapour system. If we consider the small changes in areas as dALV , dASL and dASV of the vapour-liquid interface corresponding to the solid-liquid and solid-vapour regions respectively, then the change in Gibbs free energy can be written as, dG = LV dALV + SL dASL + SV dASV (2.26)

32

Also, we can write dASL = dASV and therefore, dG = LV dALV + (SL SV ) dASL (2.27)

At equilibrium, the relation between the surface tensions can be written by minimizing the above equation as43 SV = SL + LV cos (2.28)

Here, we assume that dALV = dASL . This equation, called Youngs equation, shows that the contact angle of a particular system depends on the surface tensions between dierent phases present in the system. At this point, we can think of three cases as explained below: When > 900 , the surface tension at solid-liquid interface is equal to the sum of the surface tensions of the separate liquid-vapour and solid-vapour systems. Hence, we can write LS LV + SV and the liquid drop takes spherical shape at equilibrium. The degree of wetting is very less. If = 900 , then SL = SV which means that the liquid molecules behave as if they are in bulk phase. In this case, the shape of the liquid drop will be a hemisphere. And if < 900 and if LV < SV then the solid-liquid interaction will be large to minimize the free energy which leads to high degree of wetting. For = 0, the liquid drop perfectly wets the solid surface. 2.4.3 Surface pressure Measurement - Wilhelmy Plate Method In this method, the surface pressure is measured by measuring the change in the force acting on a thin platinum plate because of the change in surface tension. Typically the plate it is suspended in such a way that one third of it is below the liquid surface. The various forces involved in this system are: (i) the downward gravitational force due to the weight of the plate, FG , (ii) the buoyancy force acting upward due to capillary rise FB and

33

Figure 2.9: Forces acting on Wilhelmy plate

(iii) the surface tensions at dierent interfaces denoted as SL , SV and LV (Figure [2.9]). Therefore, the total force will be F = FG FB + 2 (t + w) (SL + LV cos SV ) (2.29)

where t is the thickness and w is the width of the Wilhelmy plate. The contact angle must be zero for complete wetting which is critical in this experiment because if cos < 1, then the measured surface tension is less and the corresponding surface pressure will be larger than the actual value. Now, if we represent the density of the plate and the density of the liquid as p and l respectively, then the total force in equation for complete wetting can be rewritten as F = p glwt + 2 (t + w) LV l gtwh Therefore, the change in surface tension which is called as surface pressure will be = = F 2 (t + w) (2.31) (2.30)

In other words, the gravity and the buoyancy terms are independent of surface area changes and they are ruled out. So the surface pressure depends only on changes in surface tensions

34

normal to the perimeter of the plate. The plate used in our lab has dimentions:(t + w) = 19.62mm. For t << w, the surface pressure is calculated as, = F 2w (2.32)

The change in force is measured by the electro-balance to which the platinum plate is attached. In this chapter we have discussed about the theory of BAM and surface pressure measurements. Next, we will present the experimental methods of making Langmuir and LangmuirSchaefer lms of the pyroelectric copolymer PVDF-TrFE.

Chapter 3 Experimental methods of Langmuir and Langmuir-Schaefer lms This chapter discusses experimental methods used for the present work. A step wise procedure for making Langmuir lms is given at this time. In particular, it will focus on various means of transferring the Langmuir lms of pyroelectric polymer on to a solid substrate using the Langmuir-Schaefer method. 3.1 Langmuir trough and other components A Langmuir trough is a shallow rectangular trough made up of Teon. It is used to make monolayers of amphiphilic molecules. Because Teon is a hydrophobic material, it is easy to clean the trough after every experiment. The dimensions of the trough, made by KSV inc., measure 364 75mm. This trough is mounted on an aluminum base which is used to control the temperature of the subphase (water) by means of circulating water. Two symmetrically movable barriers are used to control the surface area. They are made of Delrin which is a hydrophilic material. The hydrophobic Teon trough and hydrophilic Delrin barriers system provides good contact with water so as to prevent the leakage of the materials on the surface across the barriers. This can be experimentally veried by keeping the surface area constant and observing the change in surface pressure. If a surface pressure does not decrease in time, it is sure that material is not leaking across the barrier. The rate of compression and expansion can be controlled by the user through KSV Software provided with the trough by KSV. There is a dipping well of 70mm depth at the center of the trough as shown in the Figure. This hole is generally used for transferring the lm on to a solid substrate which is explained in Section [3.4].

35

36

Light that falls on the air-water interface is reected not only from the surface but also from the bottom of the trough. In order to avoid this back scattering, a beam dump was designed by previous graduate students Zou Lu and Ji Wang.38, 44 This beam dump has two components: a cylinder and a cone attached to a disk as shown in Figure [3.1]. Both of theese are made of Delrin and hence, cleaning is relatively easy. As explained in Section [2.4.3], the surface pressure is measured by a Whilhelmy plate. The whole Langmuir trough system is attached to the Brewster angle microscope set up for imaging the monolayer as seen in Figure [3.2].

Figure 3.1: A photograph of the Langmuir trough used in this work with its components, two barriers and beam dump.

3.2

Cleaning procedure In our lab, we use pure water from the PurelabPlus/UV system (with resistivity 18.2M /cm),

for cleaning the trough, barriers, Whilhelmy plate and beam dump. Not only for cleaning, this pure water is also used as the subphase when we make Langmuir lms. To conrm that there is minimal water contamination, we do a shake test before lling the Langmuir trough. To do this, we rst half-ll the round bottom ask with pure water and then swirl thoroughly. We can observe many bubbles coming to the surface of water and break. If they do not break immediately, then we can say that the water is contaminated by some

37

surface-active material. We follow a certain procedure for cleaning all the materials mentioned above. 1. Prepare soap solution by mixing 30ml of ExtranT M with 1000ml of water. 2. Clean the trough, barriers and beam dump with the prepared soap solution. 3. Rinse thoroughly with cold water rst and then with hot water. 4. Then use deionized water and nally ultra-pure water from Purelab plus for further cleaning. 5. The Wilhelmy plate is usually cleaned with chloroform and then with pure water. One should take so much care while cleaning this plate as it is delicate such that a small torque developed by the heavy ow of water along the sides of the plate will cause damage to the plate. 3.3 Experiment: How to make a Langmuir lm The copolymer used in my experiment called poly(vinylidene Fluoride-Triuoroethylene) was purchased from Kunshan Hisense Electronics Co., Ltd., China, in powder form and it was used without any further purication. From the literature45 I found that the PVDF and its copolymers do not dissolve in volatile and water-immiscible solvents, such as chloroform and hexane, which are frequently used in making Langmuir lms. They are soluble in polar solvents, such as acetone and dimethyl sulfoxide (DMSO). At the same time, we know that DMSO is highly toxic and for safety reasons we preferred not use it. Also, it is known that DMSO tends to leave traces in the Langmuir layer.46 Therefore, we decided to use acetone (purchased from Sigma-Aldrich) for sample preparation. The concentration of the sample ranged between 0.063 mg/ml and 1.58 mg/ml; the lower value is equivalent to a 0.01 weight percent. The weight percentage calculation is given in Appendix B. The process of making Langmuir lm has following important steps:

38

Figure 3.2: Arrangement of the Langmuir trough with beam dump inside the dipping hole and the barriers are kept symmetrically on the trough which will be controlled by the motor. The photograph at the bottom shows the Langmuir trough, Wilhelmy plate for surface pressure measurement. The laser light falls on the monolayer lm at the air-water interface at the Brewster angle and the reected beam is directed to the CCD.

The rst step is to prepare the polymer solution of the desired concentration (e.g. 0.6mg/ml) by carefully weighing a certain amount of the copolymer and mixing it with the solvent Acetone. We prepared samples of dierent concentrations which will be discussed in the next section. For all the measurements discussed here, I used the solution for 3 weeks. Longer storage leads to dierent isotherms. Before each experiment, the trough and barriers should be cleaned by using the method in the previous section. Assemble the Langmuir trough system as shown in Figure [3.2(a)] and place it in the Brewster angle microscope set-up. Fill the trough with ultra pure water in such a way that the surface of the water is two or three millimeters above the trough.

39

Attach the Wilhelmy plate to the KSV electrobalance. Usually, one third of the plate will be immersed in the plate. Using the vacuum-system aspirator tip, empty the trough from the surface at least two times. For the third time, we let the barriers move inwards and run the tip of the pipette everywhere on the surface of the water to remove any contamination. A contamination check can also be done by observing the change in the surface pressure with changing area. A signicant change in the surface pressure indicates a surfactant on the water surface. Fill a syringe with the prepared copolymer solution. We use a gas-tight Hamilton syringe for depositing the sample on water surface. Gently push on the syringe to produce a droplet at the end of the needle and then touch the surface. We should not let the drop fall from the needle onto the subphase, as some of the sample might be lost in the subphase by diusion. Wait for approximately 15 min for the solvent to evaporate, after which the surface pressure measurement can start. The surface pressure is measured by the forces acting on the Wilhelmy plate. 3.4 Langmuir-Schaefer Method As mentioned in Chapter 1, we use the Langmuir-Schaefer method of deposition for transferring the Langmuir lm on to a solid substrate. Because our copolymer forms very sti lms on air-water interface; the lm may not bend if we choose vertical deposition (LB) technique. In our experiment, we use silicon (Si) as the solid substrate. The Si was cut into small pieces of dimension 1 1mm which is a convenient size for taking atomic force microscopy (AFM) images. Like other components used in this experiment, the cleaning of Si is also important. I used the same cleaning procedure explained in Section [3.2] for

40

cleaning this Si plate. After that, it was cleaned with isopropyl alcohol (IPA) and then with Acetone and nally blown dry with clean nitrogen gas.

Figure 3.3: Three steps involved in Inverse Langmuir-Schaefer technique. The solid substrate is held by tweezers44

In the Langmuir-Schaefer method, I tried three types of deposition. METHOD 1: First, the Si substrate was kept under the water before the sample is spread on water. Once the Langmuir layer is formed, the Silicon substrate was taken out of the water. I found some disadvantages of this method. The monolayer was disturbed by the tweezers when I tried to take out the Si substrate. Also, there may be a water layer on the Si substrate along with the monolayer. Hence, this method is not suitable for making good quality lms. METHOD 2: In this case, I touch the monolayer lm by one side of the substrate from top of the water surface and took it out. Here, the problem was that water was dripping o the substrate when I tried to turn the substrate back for drying. METHOD 3: This technique called as Inverse Langmuir-Schaefer method was used by the previous graduate student Ji Wang. She found this method as the better one

41

among other methods she tried. In the rst step, we held the solid substrate using tweezers and it was dipped into the monolayer at a small angle. Then it was taken out carefully by rotating the tweezers, lifting the solid substrate upward out of the monolayer. Then, it is kept for drying as shown as step 3 in Figure [3.3]. In this method, the tweezers do not disturb the monolayer as in the Method 1 explained above.

Chapter 4 Langmuir and Langmuir-Schaefer lms of PVDF-TrFE 4.1 Introduction Langmuir-Blodgett lms of PVDF and its copolymers have been studied for many years, at least since 1995. Especially, S. Ducharme and his group from the University of NebraskaLincoln have been studying various structural, electrical and optical properties of LB lms of PVDF-TrFE(70/30) random copolymer in collaboration with researchers from the Russian Academy of Sciences. They made high quality lms as shown by scanning tunnelling microscopy (STM) picture [4.1] of a transferred lm from a single Langmuir layer onto on graphite. However, they found that the average thickness of single lm was three times the molecular diameter. Another group, in Japan, did extensive studies of dierent copolymer ratios. They conclude that the range 50-80% PVDF gave the best crystallinity. However, they also found that the Langmuir lms appeared thicker than a single monolayer.

Figure 4.1: STM image of a single monolayer lm on graphite.45

With the aim of preparing high quality Langmuir-Schaefer (LS) lms of PVDF-TrFE 42

43

copolymer, I searched for suitable experimental conditions. I have tried to reproduce earlier work, and improve the order in the layers. The results are discussed in this chapter. I made Langmuir lms following the same process explained in Chapter 3. I used Acetone rather than DMSO for the solvent, both for increased laboratory safety and because DMSO is known to stay in the surface layer. I also varied the temperature and the concentration in the spreading solution. As a rst step, it is essential to study the properties of the polymer molecules on water surface to make highly ordered structure of LS lms. The lms are characterized by their surface tension and elasticity isotherms as a function of apparent molecular area. The transferred lms will be characterized by atomic force microscopy (AFM). 4.2 Polymer monolayer Unlike low molecular weight substances, strong amphiphilic character is not strictly required for polymers; macromolecules without pronounced amphiphility, and even watersoluble polymers, can form a distinct surface layer on liquids.47 The reason for this is essentially that even a small decrease in free energy for each monomer adsorbed to the surface can, over many monomers, lead to a substantial free energy advantage for the adsorbtion. Not all polymers produce true Langmuir monolayers, where the entire polymer chain lies at at the airwater interface; segments many monomers thick may extend partially into the water.48 If the monomers are suciently surface-active, then they are all tethered to the surface, and the conguration is eectively two-dimensional. It is this constraint at the asymmetric interface, forcing the organization of monomers there, that makes Langmuir and Langmuir-Blodgett lms a powerful technique for increasing the organization of the lms. A exible polymer in a dilute three-dimensional solvent, like the original acetone for PVDF-TrFE, will be in a random-coil conguration: in a poor solvent the conguration

44

will be compact, for a good solvent the conguration will be extended; for the intermediate solvent the statistics of the polymer path exactly follow a random walk. Therefore, the polymer, deposited on the surface in the spreading solvent, will be in a 3-dimensional random coil conguration, as indicated in gure [4.2a]. The conguration the polymer takes at the surface as the spreading solvent evaporates depends on the balance of interactions between the polymer monomers and between the monomers and the water solution, specically the water surface. If the monomers are suciently amphiphilic, then in equilibrium they will all be tethered to the surface. The exible polymer will be in either a compact 2-d coil or a more stretched out conguration, depending on whether the water surface acts as a poor or good solvent for the 2-d polymer, in direct analogy to polymer behavior in a 3-d solvent. For short molecules, the equilibrium can be reached quite quickly, but for a polymer, the process can be much slower, particularly if the anity for the water surface is less strong. Thus, the polymer conguration may evolve with time from a more 3-d conguration as shown in gure [4.2a] to a more 2-d conguration as shown in [4.2b]. During this process, the polymers will ll more of the surface. Also, depending on the surface coverage and the type of eective solvent, the individual molecules may remain well-isolated in an approximately 2-d gas or they may phase-separate into a gas and a 2-d condensed liquid or solid phase. Moving the barriers (Figure [4.2c]) inward slowly compresses the polymer monolayer, until the gas phase is squeezed out and all of the individual polymer chains must interact with each other, and the pressure begins to increase rapidly. This is the critical molecular area per polymer unit (0 ). This more compressed layer is shown in Figure [4.2c] and [4.2d]. The later suggests that compression may force the polymer to organize in a crystalline or near-crystalline form. Higher pressure creates bending of the polymer chain away from the water surface due to fewer adsorption sites on water surface (Figure 4.2e). Finally, if compressed more the number of loops increases and the polymer lm collapses and thus the surface pressure

45

Figure 4.2: Schematic diagram of polymer molecules on water surface during compression. (a) Initially polymer molecules may take a random coil shape. (b) and (c) Note the surface concentration, as in the number of molecules per unit area, is unchanged. Coil untangles and the polymer molecules lls the water surface and hence the surface coverage increases. (d) When the area is decreased by the barriers, polymer chains are closely packed. (e) and (f) On compression, polymer chains overlap on each other and move away from water surface. (b) and (c) are after the presentation [49]

goes down (Figure 4.2f). Note that the coil structure, the untangling of coils and the overlapping of polymer chains depend on physical properties of the particular polymer, including its interactions with the water and the air/water interface. 4.3 Surface pressure - Area isotherm As mentioned in Chapter 1, the copolymer used in this present work, PVDF-TrFE is not a good amphiphile. However, it can be dispersed on top of the water subphase to form a suciently stable Langmuir layer.45 The typical surface pressure, - area isotherm of PVDF-TrFE is given in Figure [4.3]. In general, the isotherm shows a smooth increase from low to high pressures without obvious kinks or plateaus indicating phase transitions. This is common for the condensed lms of most polymeric materials on a water surface.42 At very large areas, the polymer molecules are so far apart that there are negligible interactions between them. As the

46

Figure 4.3: Surface pressure - Area isotherm of PVDF-TrFE at 25 C. Here 0 is limiting surface area for close packing of molecules. This can be found by extrapolating to = 0.

barriers compress the monolayer, the surface pressure increases very slowly as the density is low at these regions. On further compression, the surface pressure will display a sharp increase because the molecules are closely packed. The highest pressure is reached when the barriers are at the closest attainable distance ( 40mm). The limiting area per structural unit, 0 , corresponding to close packing can be found by extrapolating the isotherm from the linear region to zero pressure. The value of 0 obtained from the isotherm is 0.0073 nm2 which is small compared to the expected value of 0.057 nm2 from the molecular model given in.34 Here, the area per structural unit27 is assumed as 0.259 0.22nm2 according the molecular model shown in Figure [1.7]. The calculation of mean molecular area is given in Appendix B. I also calculated the surface concentration = 1/ corresponding to the limiting area assuming that the entire mass of the spread polymer remains on the surface without any diusion into the water subphase. It is equal to 137 mol/nm2 (almost 8 times larger than the expected value).

47

The critical area per molecule 0 is thus much less than the expected value from molecular models of close packed, completely untangled polymer chains. This may be due to the dissolution of polymer molecules into the water subphase, with perhaps deposition on one of the other trough surfaces. Another possible reason may be that in our experiment, the polymer chains may be looped perpendicular to the water surface well before the critical molecular area. The factors that determine the polymer conguration at the surface, and thus the coarea may be: (1) The concentration of the polymer sample solution, (2) the temperature of the subphase (3) atoms present in the polymer backbone, and (4) the dimensions of the polymer chain (Radius of gyration, correlation length, etc.). Points (1) and (2),the eect of concentration and temperature on the copolymer monolayer, are explored in the following sections. In practice, the deposition process itself may have a large eect on the initial conguration. Ideally the spreading solvent simply spreads on the surface carrying the polymer with it. However, solvents of this polymer are also miscible with water, so particular care must taken while spreading the sample to avoid penetration of solvent into the water subphase. Thus, the size and speed of a drop of sample solution as it approaches the surface may be important factors. However, some of the polymer may have penetrated into the solution, and either remain there or deposit on other surfaces. Thus, when I give the mean molecular area , we must always keep in mind that this an apparent value, assuming that all of the polymer stays at the air/water interface. Thus, the absolute values of the surface concentration may be o by a constant factor. However, the shape of the isotherm should be characteristic of the polymer. This shape can be analyzed in two major ways: by looking for power law relationships between pi and sigma and by calculating the elasticity of the monolayer. Often at moderate pressures, a power law relationship exists between and for a polymer monolayer at the air-water interface.50, 51, 52 The scaling behaviour of polymer

48

monolayers is given below: (4.1)

where is the scaling exponent. The value of can be found from a log() log() plot of the semi-dilute region (small molecular area region) as shown in Figure [4.4]. The curve is clearly not linear in the high , low region, where the uncertainties in the measurement dominate. Further, at high pressure the monolayer is expected to collapse, and the slope decrease. In the intermediate pressure region, the curve appears approximately linear. Taking two dierent regions, we found values of = 5.0 and 6.5. The theoretical prediction of for a exible polymer in two dimensions is 3 for good solvent. For poor and theta solvents is greater than 3.50, 53, 54 In general, the value of this exponent indicates how good the solvent environment is for the two dimensional polymer lm. The exponents we nd for the copolymer PVDF-TrFE are typical of a poor solvent.

Figure 4.4: log - log plot (black) from the surface pressure-area isotherm. The slope of the linear t (green) gives the value of scaling exponent as 4.97. Choosing another region for the linear t, the value of was found to be 6.55.

Another parameter for characterization of polymer monolayer is elasticity which can

49

also be found from the isotherm by using the following equation, ( = ) (4.2)
T

I used Origin software to perform the dierentiation in the above equation, averaging over 60 points. The result is shown in Figure [4.4]. From the gure, we observed that the elasticity of the monolayer increases as the area decreases. This implies that the monolayer is less compressible in the condensed state. The elasticity reaches the maximum value at max = 0.0045nm2 . The decrease in the elasticity curve near high surface pressures probably indicates some type of collapse out of surface. At high surface pressures ( 16mN/m), the values of elasticity become small. These correspond to non-equilibrium polymer conguration and domain collapse of the monolayer.

Figure 4.5: The elasticity of the Langmuir lm calculated from the isotherm. The elasticity increases with decreasing mean molecular area. At max 0.0045nm2 , elasticity reach a maximum which may mean that the monolayer begins to collapse out of the surface.

50

Figure 4.6: Comparison of isotherms of the present work with the previously published isotherms. The main dierence is that the coarea in the present case is almost 10 times lesser than the coarea found from the isotherm published for the rst time in 1995. In fact, all studies since the initial isotherm shown in red nd much smaller coareas; a typical example is shown in the middle curve. A. Cavalli et al. suggests that the smaller coarea is due to the dissolution of the copolymer into the water. Published isotherms were scanned and the values are extracted by the free software P lotDigitizer.

4.3.1 Comparison with Isotherms in the Literature Figure [4.6] compares the isotherm of the copolymer PVDF-TrFE with the published isotherms in Ref.[55]. These include the rst isotherm found in the literature as well as typical isotherms in more recent publications. In both case, the authors prepared the Langmuir lm of this polymer by dissolving it in a 0.01% solution of dimethyl sulfoxide (DMSO). In the present work, we made a 0.01% sample solution with acetone. The isotherms are similar except for the dierent coarea. The coarea calculated from our isotherm, 0 = 0.0073nm2 , is almost 10 times less than 0 = 0.0073nm2 from the rst isotherm published in the literature. There are many factors that aects the isotherm as discussed in the previous section. However, the one possibility is that much of the polymer is not deposited on the water surface; it may be dissolved in water or remain in an emulsion with the solvent there or

51

deposit eventually on solid surfaces within the trough. Indeed, the literature isotherms since the 1995 paper (including those by the same group) show isotherms much closer to the one we nd. For example, A. Cavalli et al. studied the Langmuir monolayer of the copolymer PVDF-TrFE by dissolving it into DMSO in the concentration range from 0.008% to 0.5%.13 and also reported the small apparent molecular area (0 0.015nm2 ) compared to the expected value. In 2005, Stephen Ducharme45 and his group found that the copolymer PVDF-TrFE tends to produce (3 times) thicker lms on water surface than a monolayer; it is not a good amphiphile. They mentioned that the polar solvents, DMSO and acetone are water miscible due to which most of the polymer molecules may go under water surface along with the solvent. They suggested that only about 10% of the copolymer stays on the surface. The comparison of our isotherm with the isotherms published before suggests that the copolymer PVDF-TrFE solutions prepared using acetone also produce similar results. As mentioned in Chapter 3, DMSO is toxic and hence, it is safer to use acetone. Further, DMSO is known to remain in the monolayer, so other solvents are preferable both for the monolayer and for the experimenter. 4.3.2 Eect of sample concentration How well the sample is deposited on the surface may depend on many factors. The most important one, besides the nature of the spreading solvent, is the concentration of the sample in the spreading solution. In order to study how the concentration of the spreading solution aects the coarea, I prepared three dierent samples of dierent concentrations given in Table [4.1]. The surface pressure measurements were done at room temperature ( 250 C) for all the samples. The comparison of isotherms are shown in Figure [7(a)]. The coarea shifts lower as the concentration of the solution decreases. To understand this better, the coarea for these three concentrations are plotted against spreading solution concentration.

52

The coareas are signicantly greater when the sample concentration is approximately equal to 0.01%, indicating a greater fraction of the monomers at the surface. The reason may be that the smaller initial surface concentration allows the polymer chain to untangle from random coil without overlapping with other chains. Concentration Mole Fraction % mg/ml Sample#1 0.010 0.063 Sample#2 0.077 0.606 Sample#3 0.174 1.380

Table 4.1: Concentration of dierent samples studied

(a)

(b)

Figure 4.7: (a)Comparison of isotherms of dierent sample concentrations. (b)The coarea vs sample concentration is shown; 01 and 02 are coareas found from two dierent tangent lines drawn on the isotherms and extrapolated for = 0. These values for each isotherm gives the uncertainty in the calculation of coarea.

The corresponding elasticities are also calculated for three samples using the same method explained in Section [4.3]. They are shown in Figure [4.8]. Two main things can be observed from this gure: (i) Overall the elasticity of the lm shifts towards higher apparent molecular area and (ii) the maximum elasticity is less in the case of low sample concentration compared to high concentrations. The third small observation may be that

53

at higher surface pressure, the elasticity uctuates more in the case of high and lowest concentration, whereas for the medium concentration the elasticity is very smooth; Such instability may be due to the stability of the layer, but in may also be due to the mechanical stability of the tensiometer making the surface pressure measurements. Since we see no clear trend with solution or monolayer concentration in the instability, the latter (instrumental) instability is more likely. Observation (i) may simply be due to the possibility that the true surface concentration is less with higher solution concentrations. However, observation (ii) suggests that there may be a real dependence of the conguration of the polymer at the surface on the initial spreading solution concentration. We can say that the Langmuir lm of higher concentrations are less compressible. Thus, the high elasticity value at higher solution concentrations may be due to the compression of polymer chains which are trapped in a more 3-d conguration. But at the lowest concentration, the polymer chains may be well separated and further compression will lead to rearrangement of molecules on surface in a more 2-d conguration. 4.3.3 Eect of subphase temperature The subphase temperature is very important when we study Langmuir monolayer systems as it aects the interaction (cohesive force) between the molecules that form the lm and between the lm molecules and the subphase molecules (adhesive force). We studied the Langmuir monolayer of the copolymer PVDF-TrFE at three temperatures, 120 C,250 C,400 . The isotherms are plotted together and shown in Figure [9(a)]. The concentration of the sample used for this study is 0.158mg/ml and the amount of deposition is 250l. As can be seen, the isotherms shift towards lower molecular area as the temperature of the water subphase increases. Polymer molecules may be more soluble in water as the temperature increases. In other words, the solubility of this copolymer may increase with temperature which leaves very few molecules on the surface of the water. This is shown schematically in

54

Figure 4.8: Elasticity of dierent concentration samples calculated from isotherms shown in Figure[4.6]. The shift in elasticity may be because of dierence in polymer congurations on water surface and its surface concentration of the polymer. Beginning of lm collapse and rearrangement of polymer molecules may be the reason for the uctuations of elasticity at the higher surface pressures.

Figure [4.10]. So at high temperatures, the coarea is very less. The temperature experiments were done in the following way: First ll the trough with Ultra pure water. Then by using a temperature bath, the water subphase temperature was set to the desired temperature, the polymer solution was dispersed at constant surface area (the barriers are xed at the end of the trough). I then waited for ten minutes for equilibration of polymer molecules on the water surface. Finally, the barriers were set to move inwards for compression. After compression, the trough and other components were cleaned completely. Then the next experiment was set up for another desired temperature.

In the future, it might be interesting to try this experiment in a dierent way to separate the eect of subphase temperature on the initial spreading and on the isotherms. For that, the subphase temperature should be set to the required lower temperature and then

55

(a)

(b)

Figure 4.9: (a) isotherms of low concentration sample at dierent temperatures. Isotherms shift towards left as the temperature increases for which the reason may be the balance between adhesive and cohesive properties of the copolymer. (b) Gibbs free energy calculated from the isotherms using equation [4.3] is plotted against temperature for dierent surface pressures.

deposit the polymer solution. Then the temperature can be increased to a particular high temperature. Remember polymer is on the water subphase while temperature is rising. After attaining high temperature, we can start the compression and measure surface pressure. I recommend this experiment. The Gibbs free energy is an important parameter to study the dependence of the surface pressure with temperature. The change in Gibbs free energy at constant temperature can be expressed as, G = NA
0

(4.3)

where NA = 6.023 1023 mol1 is Avagadros number. This can be calculated from the measured isotherms. rst I plotted vs and then the area under the curve was found by integration option in Origin software. Finally, the integration value was multiplied with NA to express G in N m/mol or J/mol. The change in Gibbs free energy was calculated for dierent surface pressures for each

56

Figure 4.10: : A schematic diagram of behaviour of polymer molecules on the water surface for increasing temperature. As the temperature increases, monomers will be more soluble in water, so that more segments leave the surface (upper two gures)

isotherm and represented in Figure [9(b)]. It can be observed that the change in Gibbs free energy decreases with increasing temperature except at the lowest surface pressure 1mN/m. At the lowest surface pressure, the value of the Gibbs free energy is higher at 250 C than at 120 C and 400 C. There is no discontinuity observed at higher surface pressures. This indicates that there is no phase transition occurs in the temperature range from 120 C to 400 C with surface pressure greater than 5mN/m. These curves also give information on another important thermodynamic quantity which is entropy. This is dened as S= ( ) (4.4)

G T

Therefore, the negative of the slope of the Gibbs free energy curves will give the value of the entropy. Entropy is a measure of disorder. The higher the entropy the higher the disorder. In Figure [9(b)], the change in Gibbs free energy with temperature gives a negative slope, which in turn makes entropy a positive value. It can also be noted that the slope increases for higher surface pressures. Therefore the entropy increases and the order decreases at higher pressure. At lowest surface pressure, Gibbs free energy seems peaked at intermediate temperatures 250 C and hence, entropy is negative for lower temperature

57

below 250 C and positive at higher ones. The reason may be that at low surface pressure the system undergoes a transition from an ordered to disordered state due to rearrangement of molecules on surface. For making Langmuir-Schaefer lms of PVDF-TrFE, it is important to nd the right surface pressure that corresponds to close packing of copolymer molecules on the water surface. Therefore, lower surface pressure, nearly 5mN/m, which seems to have higher order is suggested for making LS lm of the copolymer PVDF-TrFE. Table [4.2] gives the summary of dierent parameters studied in the present work. Sample Concentration (mg/ml) 0.158 Temperature (0 C) 12 25 40 12 25 40 12 25 40 01 (nm2 ) 0.01042 0.00644 0.01110 0.00833 0.00497 0.00218 0.00470 0.00296 0.00266 02 (nm2 ) 0.01559 0.00861 0.01532 0.01067 0.00653 0.00340 0.00586 0.00430 0.00387 3.66 6.06 2.56 6.24 5.49 3.44 3.68 3.21 3.06 max (mN/m) 67.85 32.21 6.77 84.74 65.22 25.73 60.90 68.44 24.61 max (nm2 ) 0.00698 0.00444 0.00354 0.00587 0.00326 0.00125 0.00317 0.00212 0.00145

0.606

1.38

Table 4.2: Langmuir lm parameters derived from the isotherms of three samples are shown. Two dierent determinations of the coarea, 01 and 01 , values provide the uncertainty in the coarea calculation. The dierent values of scaling factor show that the slope of the slope of the isotherm in each case is dierent. Moreover, the water surface is a good solvent environment in some experiments as values are closer to 3 which is the good solvent condition. The coarea corresponds to maximum elasticity max decreases with increasing temperature showing the isotherm shift towards left for higher temperatures.

4.4

BAM images of PVDF-TrFE Brewster angle microscopy is used to visualize the morphology of the Langmuir lm

formed on the air-water interface. The principle of working of BAM is discussed in Chapter 2. In short, when p-polarized light falls on the water surface, the reectivity is nearly zero at the Brewsters angle. The low reectivity is captured by our CCD and shown in Figure [11(a)]. The introduction of polymer lm on top of water surface increases the reected light. For example, the image of the polymer lm when the barriers are far apart, corresponding

58

(a)

(b)

Figure 4.11: (a)BAM image of the water subphase without any lm on it. The reectivity of p-polarized light is nearly zero at the Brewsters angle. This creates the background for BAM imaging. (b)Typical BAM image of PVDF-TrFE(70:30) at room temperature taken at very low surface pressure (less than 1mN/m). The brighter regions characterizes the thicker lm while the darker region is for lm with lesser thickness. The bottom right corner of this image is simply water and it is dark.

to zero surface pressure, is shown in Figure [11(b)]. The image size is 720 pixels x 480 pixels. The brighter regions corresponds to high molecular density (high thickness) whereas darker regions represents low density (small thickness). In general, we observe concentric circular patterns in the BAM image of PVDF-TrFE. These indicate diraction. Such diraction is seen from 3-d particles, but also when the surface is out of focus. Further experiments are needed to determine the cause of these diraction circles. A series of BAM images of the Langmuir lm of PVDF-TrFE for high and low concentrations are presented in this section. The barriers were stopped at desired surface pressures and a short video of the lm was taken at the rate of 30 frames per second. Then the video was converted into images of size 720 x 480 pixels using software called U lead. Finally, a scaling factor of 7.45m/pixel is used to express the size of the image in terms of millimeters. In all the images shown in this section, the scale bar is 1mm. Generally, the lms are visibly inhomogenoeous, and the strong diraction circles suggest 3-d material. The lms at higher temperatures appear more uniform. It may be initially form the lms at higher temperature, and perhaps cool these lms to attempt to increase

59

the order in the formed lms.

(a) 5mN/m, T 120 C

(b) 15mN/m, T 120 C

(c) 5mN/m, T 250 C

(d) 15mN/m, T 250 C

(e) 5mN/m, T 400 C

(f) 15mN/m, T 400 C

Figure 4.12: BAM images of PVDF-TrFE of 0.158mg/ml at low and high surface pressures are shown in left and right columns respectively. (a) and (b) At low temperature, small bright spots are clear, especially at high pressure. The small circular patterns observed in both high and low surface pressures are similar particles which are out of focus because of the incident angle: only a line perpendicular to the plane of incidence, parallel to the horizontal azis on the gures, is in focus. (c) and (d) Near room temperature, there are more spots (out of focus here) at both pressures. (e) and (f) At high temperature, Again many bright, probably 3-d particles are observed.

4.5 Atomic Force Microscopy BAM characterizes the macroscopic uniformity of the initial lm on the water surface. The pyroelectric behavior of interest will depend on the molecular organization of the lm after transfer to a solid. In the present work, we used Atomic Force Microscopy (AFM) for

60

LB lm characterization at the intermediate mesoscopic. AFM is an instrument used for studying surface properties of materials at the atomic level. The basic principle the AFM is to measure the forces between a sharp tip mounted on a exible cantilever and a sample surface. Forces between the tip and the sample typically range from 1011 to 106 N.56 AFM produces images by scanning the sample with respect to the tip and measuring the deection of the cantilever as a function of lateral position. In the earlier stage of the present work, high concentration sample (0.2%) was used for preparing Langmuir-Schaefer lms. Films were prepared at dierent conditions as given below: 1. Two LS lms prepared at low temperature ( 110 C) using Method 1 and Method 3 explained in Section [3.4]. 2. Two LS lms prepared at high temperature ( 400 C) using Mehtod 1 and Method 3. 3. Two LS lms prepared at high ( 15mN/m) and low surface pressures ( 5mN/m) at room temperature. 4. Two LS lms prepared at high and low surface pressures in room temperature with additional cleaning of silicon substrates done at LCI. The AFM images of these lms were taken using Veeco Dimension Icon AFM instrument at Michigan State University. Due to time constraints, we could not take images of all the samples. Here, the images of items (1) and (4) are presented in Figure [4.14]. Both the lms are prepared at 5mN/m, the left side image represents the lm prepared at room temperature and the image on right side represents the lm prepared at low temperature. The corresponding three dimensional images are given in the bottom panel. It can be observed there are small voids (black spots) on both the images, but on the left one more black spots are seen. One of the voids is zoomed-out from the left image and shown in

61

Figure [4.15] along with height proles. A comparison of height proles along the blue line are given in Figure [4.16]. They merely show dierent height proles ranging from 0 nm to 12 nm. In order to extract more information from these images by using the AFM software, I plotted the roughness proles and the comparison is shown in Figure [4.17]. This shows that the lm prepared at room temperature is more smooth than the lm prepared at low temperature. However, to make a general conclusion on roughness of samples made at dierent temperatures AFM images of at least two more samples have to be compared. The thickness of the lm can be calculated approximately by assuming the density of the polymer as 1g/cc. The thickness calculation is given in Appendix [B.4]. If we use the value of 0 corresponding to the spreading solution concentration 1.38mg/ml given in Table [4.2], we found the thickness is 30nm. This shows that the lm on silicon substrate is several times more than the thickness (= 0.6nm) of one single monolayer.45, 57 In the later stage of the present work, LS lms of low concentration (0.01%) samples were prepared. The AFM images of these samples were taken using NanoScope III Atomic Force Microscope at the Liquid Crystal Institute of Kent State University by Ms. Liou Qiu. The AFM image of low concentration sample transferred on to Si substrate at room temperature, is shown in top left panel of Figure [4.20]. We observed triangular shaped patterns which are oriented towards right. I suggested that in future one should track both compression direction and the substrate dipping direction while making LS lms, since the orientation of these patterns may depend on either of these. The roughness of this low concentration sample (0.01%, Green curve) is compared with that of high concentration sample (0.2%, Red curve) in Figure [7(a)]. The two peaks in the green curve are due to steps made by triangular patterns as can be clearly seen in the equivalent three dimensional image. Although the maximum height of low concentration sample is smaller (4.21nm) than that (6.06nm) of high concentration, the thickness of low concentration lm is still larger than the expected lm thickness of 0.5nm. Then, AFM image of silicon substrate (without

62

any lm) was taken which is shown in right side panel of Figure [4.20]. It is clear from the two and three dimensional image that Silicon substrate itself has roughness with maximum height of 4nm. Other AFM images of the same sample is given in Figure [4.18]. The blue boxed area is enlarged and shown next to it. The height prole is drawn along the diagonal line. This image also shows void as seen before in the image of high concentration LS lm. Now, what can be the source of these voids? Are those triangular patterns due to the roughness of Silicon plate used for making LS lms? To answer these type of questions, it is suggested to make LS lms of the low concentration solution on dierent substrates, for example, mica and glass. 4.6 Conclusion The properties of the PVDF-TrFE Langmuir and Langmuir-Schaefer lms depended strongly on the deposition conditions. In particular, they depended on both the concentration of the copolymer in the spreading solution and on the temperature at which lm was formed. We found that the apparent coarea, corresponding to the close packing of polymer molecules on the water surface, is smaller for the lowest spreading solution concentration of 0.0632 mg/ml (0.01% mol fraction). However, this coarea is almost ve times smaller than the expected value of 0.57nm2 , which would correspond to a layer 25 times thicker than a nominal monolayer. This descrepency could be due to the formation of true multilayers, but it could also be due to the dissolution of the polymer molecules into the water so that the true coarea is much larger, or to polymer chain overlapping or folding. Furthermore, the scaling exponent found from the isotherm is greater than 3. This shows that the water surface does not serve as a good solvent for this copolymer. This may also be a reason for multilayer conguration of polymer molecules on water surface a smaller. More recent results published in literature, which also demonstrate that PVDF-TrFE polymer does not form a monolayer on the air-water interface.

63

Subsequently, we studied the inuence of subphase temperature on Langmuir lms of the copolymer. The Gibbs free energy was calculated from the isotherms and plotted against temperature. Based on this plot, we conclude that the surface pressure equal or lower than 5mN m1 is appropriate for making Langmuir-Schaefer lms since the entropy increases for higher surface pressures. Nevertheless, these experiments can be repeated for other intermediate temperatures so as to ensure any discontinuity in the Gibbs free energy in the temperature range 120 C - 400 C. Brewster angle microscopy images of low concentration sample taken at dierent temperatures show a homogeneous lm only at the highest temperatures, 400 C. However, the order within these lms may also be less. It would be interesting to compress the lms at higher temperature and then decrease the temperature, to see if the greater spreading of the lms at higher temperatures is maintained in a more ordered lm. Langmuir-Schaefer lms of PVDF-TrFE were prepared on silicon substrates at dierent temperatures for lms made with high concentration spreading solutions. AFM images of high concentrated sample show a uniformly bumpy lm surface at room temperature. AFM images of low concentrated sample needs further investigation as they show some strange triangular patterns. I will discuss some ideas for improving this lm quality in the next section. 4.7 Suggestions for Future Work Various properties of Langmuir-Blodgett lms of PVDF-TrFE(70:30) copolymer were studied and reported in many publications. As we know, the making a good Langmuir lm is the rst step in the process of making good quality Langmuir-Blodgett lms or Langmuir-Schaefer lms. Hence, it is necessary to study the basic physical properties of the Langmuir lm of this copolymer. For example, the thermodynamic properties, like Gibbs free energy, entropy and order parameter can be investigated further. As of my knowledge,

64

these properties are not studied before. Furthermore, the visoelastic properties, like, static and dynamic elasticities can be studied using surface light scattering (SLS) experiment which is also not studied for this polymer before. Apart from that, there are many other experiments suggested based on the present work: Temperature experiment: In all the temperature experiments studied in the present work, I rst heated the water subphase to the desired temperature and then I dispersed the polymer solution. These experiments can be done in a dierent way to study the eect of subphase temperature on the monolayer. That is rst deposit polymer solution on water surface and start heating the subphase. This will change the monolayer temperature slowly and we can study the change in the isotherm compared to the isotherms plotted in the present work. Langmuir-Schaefer lms can be prepared on mica substrate and compare the roughness of the lms that were prepared on Silicon substrate. All these experiments may be considered as a complete study of PVDF-TrFE using BAM instrument.

65

(a) 5mN/m, T 120 C

(b) 15mN/m, T 120 C

(c) 5mN/m, T 250 C

(d) 15mN/m, T 250 C

(e) 5mN/m, T 400 C

(f) 15mN/m, T 400 C

Figure 4.13: BAM images of PVDF-TrFE of 1.38 mg/ml at low and high surface pressures are shown in left and right columns respectively. (a) and (b) Low temperature BAM images show that even at very low surface pressures, the polymer molecules completely covered the water surface with only occasional dark areas. Further compression results in overlapping of polymer chains and that can be seen in brighter region of (b). At room temperature, (c) show that the polymer lm is very thick and nonhomogeneous. In gure (d) we can see that the lm is about to collapse. At high temperature, the lms seem much more uniform with few bright particles. Moreover, we can see some domains with ne boundaries. From the Table [4.2], we can note that the value of 0 is less for the all the three temperatures. As recommended before in Section [4.3.3], we can try BAM imaging for deposition of polymer solution at low temperature and compression of the lm at high temperature

66

Figure 4.14: AFM images of 0.2% high concentration sample are shown. Top left 2D AFM image represents the LS lm of PVDF-TrFE prepared at 250 C at low surface pressure, 5mN/m. The scan size is 2m 2m. Top right 2D AFM image is for the same concentration sample, but prepared at low temperature 120 C at 5mN/m. The scan size is 1m 1m. Their 3D images are shown in the bottom panel. The blue box indicates a void, that will be enlarged in Figure [4.15].

Figure 4.15: Enlarged image of void (blue box) drawn in Figure [4.9]. The height proles of lines 1 and 2 show that the lm is not homogeneous.

67

Figure 4.16: Comparison of height proles of the two lms prepared at room temperature and low temperature. For comparison the height proles are drawn only for the length of blue lines drawn on the images.

Figure 4.17: Comparison of roughness of two lms is shown here. Lower the area under the curve, the better the smoothness. Therefore, the lm prepared at room temperature shows more smoothness compared to the one prepared at low temperature.

68

Figure 4.18: AFM picture of the same low concentration sample prepared at room temperature, low surface pressure. The area of blue box is enlarged to show that the void exists in low concentration samples also. The height prole is also shown below corresponding to the blue line.

(a)

(b)

Figure 4.19: (a)Comparison of roughness of low (green curve) and high concentration (red curve) samples. This shows that the LS lm of high concentration sample has more roughness. (b)Roughness of low concentration lm is compared with that of simple Silicon substrate without any lm on it. The roughness of both the lm and Silicon substrate looks similar. The green curve implies that there may be a very thin layer of polymer molecule is formed on Si substrate.

69

Figure 4.20: 2D and 3D AFM images of the LS lm of low concentration sample prepared at room temperature at 5mN/m is shown on the left side. We observed some triangular patterns. The reason is now known and this needs further investigation. The right side AFM image is for simple Silicon substrate without any lm on it. From these images it is clear that the Silicon substrate itself is not smooth.

Chapter 5 Numerical simulation of linear plasmonic photodetector 5.1 Introduction In the literature, it has been pointed out that a metal grating with period smaller than the wavelength of the incident light acts like a linear polarizer as it transmits only one polarization which is perpendicular to the grating slit.58, 59, 44 Recently, in 2008, Zhi Wu et al. reported a metal wiregrid micropolarizer array, that has dierent transmission axes within a group of pixel, for IR imaging polarimetry.60 They also mentioned that a focal plane array detector integrated with metal wire grid polarizer array can be used to extract the full Stokes parameters in polarimetric imaging applications. However, integrating focal plane array and the plasmonic polarizer array may have practical diculties. For example, the distance between the focal plane array and the polarizer array is critical for imaging since the loss increases with propagation distance.61 The new design not only identies the polarization state of the incoming IR light, it can also be used to measure the intensity of the incoming light since the dielectric medium is a pyroelectric copolymer PVDF-TrFE. A simple plasmonic structure is taken for numerical study to explain how the structure recognizes two dierent linear polarized states. Basically, the geometrical dimensions of the linear plasmonic photodetector (hereafter called as linear polarizer) can be optimized by the numerical simulation. For this purpose, the commercial software package CST Microwave Studio (MWS)62 is used. This software applies nitedierence time domain (FDTD) method for solving Maxwells equations for which Yees algorithm is used.63 It rst divides the physical system into small space grids and solve two curl Maxwells equations at each point in the grid along with suitable boundary conditions. 70

71

This algorithm basically uses two numerical techniques: (1) central dierence technique for space derivatives and (2) Leapfrog technique for time derivatives. Electric eld components are rst solved at constant volume space and then magnetic eld components are nd at next instant of time for the same volume of space.64 Here, the goal is to distinguish electric eld vibrations along the x and y directions of the incident p-polarized light in infra-red range. This chapter summarizes the results of numerical simulation of the linear polarizer. To begin with, I give a short introduction to surface plasmons (SP) and go on with results of the numerical simulation. 5.2 Surface plasmons Surface plasmons are collective charge oscillations that occur at the metal-dielectric interface. They are basically a combined oscillation of the electromagnetic eld and the surface charges of the metal.65 The properties of surface plasmons, as depicted in Figure[5.1], are: (i)SPs are p-polarized called transverse magnetic (TM), i.e., the magnetic eld is parallel to the interface (Figure[5.1 (a)]). (ii) Only p-polarized light can be coupled to SP mode, because only then does the electric eld in this case has a component normal to the surface and hence generate surface charges on the metal surface. (iii) The electric eld component perpendicular to the surface decays exponentially into both the medium (Figure[5.1(b)]). (iv) The dispersion relation for the surface plasmons can be written as:66 ksp = k0 m d m + d (5.1)

where m and d are permittivity of metal and dielectric respectively. Usually, the Drude model is used to calculate the permittivity m of metals. It is given by, () =
2 p ( i)

(5.2)

Here, is the high-frequency bulk permittivity, p is the bulk plasmon frequency and is the electron collision frequency.

72

Figure 5.1: (a) Schematic illustration of electromagnetic wave and surface charges at the interface between the metal and the dielectric material,(b) the locally electric eld component is enhanced near the surface and decay exponentially with distance in a direction normal to the interface and (c) Dispersion curve of a SP wave; kSP and k are the wavevectors of SP and light wavevectors, respectively. This shows that the momentum of the SP wave is larger than that of the light photon in free space for the same frequency ().67

The dispersion curve for SP is shown in Figure[5.1]. It shows that at the same frequency, , the SP wavevector ksp is greater than the wavevector of light k0 . This frequency is called the surface plasmon resonant frequency sp .68 SPs have optical frequencies ( 1015 Hz) but the wavelength is in the x-ray region (1nm). It is this property of SP which is utilized to overcome the diraction limit that light cannot be transmitted through a sub-wavelength aperture if its wavelength is greater than two times the diameter of the aperture.69 Moreover, in order to satisfy momentum conservation between the incident light and the surface plasmon, a grating structure with periodicity is introduced on the metal surface. When light falls on the metal surface ,the wavevector of the surface plasmon will become ksp = 2/ at resonance. This should be matched with ksp given in Equation [5.1] to nd the resonant wavelength of excitation. 5.3 Results of numerical simulation The schematic side view of the structure used for numerical simulation is shown in Figure [5.2]. Here, a and h are the width and height of the slit; d is the period of the grating.

73

These are the key parameters for making this structure to excite surface plasmons and hence enhanced transmission of light into the polymer layer which is sandwiched between top and bottom gold layers.

Figure 5.2: Side view of the linear plasmonic photodetector with periodicity d = 1300, slit width a = 400nm and height h = 100nm. The dielectric medium is a copolymer PVDF-TrFE polarization of which changes when it absorbs infra-red radiation. The thickness of the polymer layer is 20nm.

For the simulation, we take a = 400nm, h = 100nm and d = 1300nm. The plane wave falling on this structure is in z direction. The dielectric parameters of gold can be calculated from the Drude model given in Equation [5.2] with = 3.5, p = 1.3 1016 rad/s, and = 6 1013 Hz. The refractive indices parallel (nx ) and perpendicular to the surface (ny ) and the corresponding attenuation constants kx and ky of the copolymer were obtained from Dr. Mengjun Bai from University of Nebraska-Lincoln who studied Infrared spectroscopic ellipsometry study of vinylidene uoride (70%)-triuoroethylene (30%) copolymer LangmuirBlodgett lms.40 The real and imaginary parts of the principal components of the dielectric tensor for the copolymer are calculated by using the relation, () = + i = (n + ik)2 They are shown in Figure [5.3]. (5.3)

74

(a)

(b)

Figure 5.3: (a) Real and (b) imaginary values of dielectric permittivity of the copolymer PVDFTrFE shows that the polymer is anisotropic as these values are dierent in parallel and perpendicular directions of the polymer surface.40

When light falls on the structure, surface charges are excited at each metal-dielectric interface and develops local electric eld along z-direction. If the two interfaces are brought together, by adjusting the slit width, then coupling between the two electric elds occurs by constructive and destructive interference. This gives rise to symmetric and anti-symmetric modes.70, 71, 72 Two simulations are done for incident plane waves polarized (1) along the x-direction perpendicular to the grating slit and (2) along the y-direction parallel to the grating slits. The frequency of the incident radiation is set from 20THz to 80THz. For the x-polarized incident radiation, we observed that the resonance occurs at 48.7 THz. In other words, the surface plasmon is excited and propagates along the interface between the metal and polymer on either side of the slit. The snap shots of the electric eld inside the gap at resonant frequency (43.64THz) and at frequencies away from resonance (20THz and 60THz) are shown in Figure [5.4 - 5.6]. From these electric eld distributions, we rst

observed that the incident x-polarized light excites surface plasmons and the y-polarized

75

Figure 5.4: Snap shot of the total electric eld at = 20THz.

light does not since it does not induce surface charges. Therefore, this plasmonic structure can be used to detect linear polarization. Secondly, we can see that the magnitude of the z-component of the electric eld decreases as it propagates along the x-direction which is generally due to the absorption property of metals. At last, the simulation results show that anti-symmetric mode exists for this nanostructure with Ez oscillating in opposite directions at the interface and they have minimum at the center of the slit. This is because the xcomponent of incident light induce positive charges on one side of slit and negative charges on the other side. The dispersion relation for anti-symmetric mode can be written as:73 [( ) ( )2 ] [ ] km xx yy kd xx yy kd 2 m + km 2 m (5.4) tanh(2kd d) = [ [( ] ) ( ) ]2
km xx yy kd 2 m

xx yy kd

km m

where

2 km = 2 m 2 c ( )2 2 kd = yy xx c yy xx = xx yy zz xz yy zx

76

Figure 5.5: Snap shot of the total electric eld at resonant = 43.64THz.

and = xx zz zxxz The dispersion curves plotted using the above set of equations, for dierent slit widths ranging from d = 20nm to d = 100nm, are shown in Figure[5.5(a)]. Here we take xx = yy for a uniaxial material. The imaginary values of kx give propagation length as shown in Figure[5.5(b)]. The propagation length decreases with increasing frequency of incident light. The simulation was repeated for the structure with the same dimensions as before, but the incident light polarization was changed to y-direction. The ratio between Ez of xpolarization and y-polarization is plotted in Figure[5.6]. This clearly shows that the Ez for x-polarization is nearly 108 times greater than that of y-polarization. 5.4 Conclusions The numerical simulation of new plasmonic design shows a clear dierence between x- and y- polarized light. However, these design is not get optimized. One can run the simulations for varying slit width and hence the periodicity of the grating. The dielectric thickness can also be varied for another set of simulations and study how it aects the

77

Figure 5.6: Snap shot of the total electric eld at = 60THz.

propagation length of the surface plasmons at metal-dielectric interface.

78

(a)

(b)

Figure 5.7: (a) Dispersion curves of anti-symmetric mode in metal-dielectric-metal waveguide in the infra-red region and (b) The propagation length of SP wave along x-direction. A MATLAB program for solving the dispersion equations is given in Appendix D.

Figure 5.8: The ratio of the z components of electric elds obtained from simulations with x- and y- polarized incident light demonstrating the detection of x-polarized light. The peak corresponds to the resonant frequency between SP and incident light.

Chapter 6 Conclusions and Recommendations 6.1 Conclusions From this work, we learned that a monolayer of PVDF-TrFE is dicult to form on the water surface. However, I have made progress towards making good quality LangmuirSchaefer lms of the copolymer PVDF-TrFE by carefully choosing the subphase temperature and the concentration of the polymer in the spreading solution. The lm thickness and the order of polymer molecules in the thin lm determines the quality of the lm. Suggestions for further imporving the lm properties are given in chapter 4. The nal test of lm-quality would be to measure the pyroelectricity of the LS lms. This could be done by LangmuirSchaefer deposition on a glass substrate covered by aluminium or ITO.36 The top electrode for electrical measurements can be prepared by evaporating aluminium on top of the polymer lm. There are two types of pyroelectric measurements: The light absorption method called Chynoweth method74 and the heating/cooling method.75 In the Chynoweth method the sample was heated by a laser light, its polarization changes and the corresponding pyroelectric current is measured by an electrometer. In the heating/cooling method, the sample is mounted on a cyrostat for heating or cooling the sample. Next, I have shown by simulation that a simple nanostructure grating as part of a metaldielectric-metal waveguide can determine the linear polarization states of the incident light. The structure period is optimized for focussing the light onto the polymer layer through surface plasmon excitation. We found that the electric eld enhancement is about 7 times that of the incident light. Also, the electric eld of one linear polarization state is 108 times greater than that of other linear polarization. The structure can further be optimized 79

80

to yield a resonance curve with a narrow width. The structure of the device can be modied to select circular polarized light and then be optimized by simulation.76 The next important step would be to calculate the device sensitivity which is the minimum change in temperature required to produce a detectable pyroelectric current. This depends on many dierent physical properties of the copolymer, including the pyroelectric coecient, the dielectric constant and the specic heat capacity.

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[40] Bai, M., Poulsen, M., Sorokin, A. V., Ducharme, S., Herzinger, C. M., and Fridkin, V. M. Journal of Applied Physics 94(1), 195200 (2003). [41] Francis W. Sears, G. L. S. Thermodynamics, kinetic theory and statistical thermodynamics. Addison-Wesley Pub. Co., (1975). [42] Gaines, G. L. Insoluble monolayers at liquid-gas interfaces. Interscience Publishers, NY, (1966). [43] David B. Thiessen, K. F. M. Surface Tension Measurement. CRC Press LLC, (2000). [44] Wang, J. Langmuir and Langmuir/Schaefer Films for Bent Core Molecules. phdthesis. [45] Ducharme, S. IEEE Transactions on Device and Materials Reliability 5(4), 720735 (2005). [46] Kooijman, E. E. personal communication . [47] Arslanov, V. V. Russian Chemical Reviews 63(1), 1 (1994). [48] Gaines, G. L. Langmuir 7(5), 834839 (1991). [49] http://wiki.ornl.gov/sites/cnmsimaging/website/pdfs/Ducharme20FE20Polymers.pdf. [50] Kim, C., Esker, A. R., Runge, F. E., and Yu, H. Macromolecules 39(14), 48894893 (2006). [51] Doi, M. and Edward, S. F. The Theory of Polymer Dynamics. Oxford University Press, (1986). [52] M. Rubinstein, R. H. C. Polymer Physics. Oxford University Press, (2003). [53] de Gennes, P. G. Scaling concepts in Polymer Physics. Cornell University Press, (1979). [54] A. R. Esker, C. K. and Yu, H. Advances in Polymer Science 209, 59110 (209).

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[55] Blinov, L., Bune, A., Dawben, P., Ducharme, S., Fridkin, V., Palto, S., Verkhovskaya, K., Vizdrik, G., and Yudin, S. Phase Transitions 77(1-2), 161173 (2004). [56] Khulbe, K. C., Feng, C., and Matsuura, T. Synthetic Polymeric Membranes: Characterization by Atomic Force Microscopy. Springer, (2008). [57] Ou-Yang, W., Weis, M., Chen, X., Manaka, T., and Iwamoto, M. Journal of Chemical Physics 131(10) (2009). Cited By (since 1996): 2. [58] Bird, G. R. and Maxeld Parrish, J. J. Opt. Soc. Am. 50(9), 886 Sep (1960). [59] Yamada, I., Kintaka, K., Nishii, J., Akioka, S., Yamagishi, Y., and Saito, M. Opt. Lett. 33(3), 258260 Feb (2008). [60] Wu, Z., Powers, P. E., Sarangan, A. M., and Zhan, Q. Opt. Lett. 33(15), 16531655 Aug (2008). [61] http://www.sandia.gov/mstc/documents/fact-sheets/Science [62] http://www.cst.com/content/products/mws/overview.aspx. [63] Yee, K. S. IEEE Trans. Antennas and Propagation , 302307 (1966). [64] http://en.wikipedia.org/wiki/Finite-dierencetime-domainmethodcitenoteyee660. [65] J. R. Sambles, G. W. B. and Yang, F. Contemporary Physics 32(3), 173183 (1991). [66] Raether, H. Surface Plasmons. Springer-Verlag, Berlin, (1988). [67] William L. Barnes, A. D. and Ebbesen, T. W. Nature 424, 824830 (2003). [68] Liu, Z.-W., Wei, Q.-H., and Zhang, X. Nano Letters 5(5), 957961 (2005). [69] Bethe, H. A. Phys. Rev. 66, 163182 (1944).

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[70] Wang, F., Xiao, M., Sun, K., and Wei, Q.-H. Opt. Express 18(1), 6371 Jan (2010). [71] Dionne, J. A., Sweatlock, L. A., Atwater, H. A., and Polman, A. Phys. Rev. B 73, 035407 Jan (2006). [72] Wuenschell, J. and Kim, H. K. Opt. Express 14(21), 1000010013 Oct (2006). [73] Jacob, J., Babu, A., Mathew, G., and Mathew, V. Superlattices and Microstructures 44(3), 282 290 (2008). [74] Chynoweth, A. G. Journal of Applied Physics 27(1), 7884 (1956). [75] Roberts, G. G. Ferroelectrics 91(1), 2138 (1989). [76] Wei, Q.-H. personal communication . [77] Henon. phdthesis. [78] Tabe, Y. and Yokoyama, H. Langmuir 11(3), 699704 (1995). [79] Wang, J., Zou, L., Jkli, A., Weissog, W., and Mann, E. K. Langmuir 22(7), 31983206 (2006).

Appendix A Reectivity for Langmuir Monolayers Consider a Lagmuir monolayer on water substrate as shown in Figure. The coordinate system is chosen in such a way that the air-thin lm interface is in xy plane and the properties of the medium in the three layer system changes along z direction. Suppose a plane wave described by the following equations r E = E0 ei(k.t) r H = H0 ei(k.t) (A.1a) (A.1b)

falls on an interface between air and thin lm. Here, the plane of incidence is taken as x-z plane and hence ky = 0. The Maxwells equations are: D H = t B E = t where D = 0 (z)E and B = 0 H (A.5) (A.4) (A.2)

(A.3)

The solution of these equations can be found using a standard method called, 4 x 4 matrix method which has been discussed in the text by Azzam and Bashara39 and in other publications.77, 78, 79 The derivation of reectivity is given here with the help of references mentioned above. 87

88

Figure A.1: Reectivity

If we choose the coordinate system such that the x-y plane is the plane of incidence and the origin is taken at the air-monolayer interface, then two Maxwells equations[A.1a and A.1b] can be rewritten as one dierential equation as = i T z c where 0 Ex 0 Ey = 0 Hx 0 Hy 0 11 12 13 0 21 11 23 T = 0 0 0 34 23 13 43 0 (A.6)

(A.7)

and

(A.8)

89

11 = 12 13 21 23

sin t cos t cos 33 2 =1 33 sin t cos t sin = 33 sin2 t cos2 = + 33 2 sin t sin cos = 33

34 = 1 43 = + sin2 t sin2 2 33

33 = + cos2 t = sin B For a monolayer lm of thickness h << , the solution of the Maxwells equation can be approximately written as, ( ) 2h (h) = I + i T (0) P ()(0) where = (A.9)

2h . Also, we can see from the gure that above the monolayer,we have only

contributions from the incident and the reected light and therefore, (z) = i (z) + r (z). At the same time, below it is just the transmitted light represented by t . Hence, the above equation will become ( ) t (h) = P () i (0) + r (0) In terms of Electric elds, we can write as ) ( i r 0 Ex + Ex ) ( i r t 0 Ey 0 Ey + Ey = P () cos i 0 (E i E r ) n cos t 0 E t y y y ) ( i n 1 r t cos t 0 Ex cos i 0 Ex Ex t 0 E x (A.10)

(A.11)

90

Here, the following relations between the electric and the magnetic elds were used: kz 0 Hx = 0 Ey k and kz 0 Hy = 0 Ex k Finally, the reectivity of the Langmuir monolayer was derived as: i r E rpp rps E = i r E E rsp rss
i For the p-polarized incident light, E = 0 and hence, we can write

(A.12)

i rpp E = r i E rsp E
r E

(A.13)

Here, rpp = and rsp = (ikh23 ikh13 ) cosB Suppose the polarization of the reected light from the monolayer is changed by using an analyzer, then the intensity of the reected light can be written in terms of the analyzer angle as,
r r I = |E|2 = |E cos + E sin |2

ikh21 cos2 B ikh12 2 cos B

(A.14)

With these equations, the reectivity equation will now take the following form

R=

[ ( ) ] 1 sin2 t cos2 sin2 B 1 cos2 B (kh)2 {cos 2 + cos2 B + 1 4 cos B + cos2 t + cos2 t 2 sin t sin + sin (cos t sin B + sin t cos cos B )}2 (A.15) + cos2 t

91

Figure A.2: Reectivity for the tilt angle t = 450 and dierent polarizer angles = 00 , 300 , 600 and 900

Figure A.3: Reectivity for the tilt angle t = 900 and dierent polarizer angles = 00 , 300 , 600 and 900

92

The reectivity R vs. the domain orientation for dierent tilt angle t and the analyzer angle , for a monolayer of thickness, h = 50nm for example, is shown in Figure [A.2 and A.3]. The dielectric constants for the P(VDF-TrFE) copolymer = 2.06 and = 1.99, corresponding to the wavelength of light = 500nm, were adopted from the University of Nebraska-Lincoln. So, this model can be used to study any anisotropy present in the monolayer lm. In other words, we can nd the tilt angle and the refractive index anisotropy by measuring the domain reectivity.

Appendix B Calculations There are some calculations required before and after the experiments. They are given in this Appendix. B.1 Molecular weight of PVDF-TrFE The molecular weight of one structural unit of the copolymer PVDF-TrFE(70:30) is calculated by substituting the atomic weights of Hydrogen (H), Fluorine (F) and Carbon (C) atoms in the chemical formula of VDF and TrFE polymers. Atomic weight of H = 1.00794 Atomic weight of F = 18.9984 Atomic weight of C = 12.01 The chemical formula of VDF is CF2 CH2 . Therefore, = 12.01 + 18.99842 + 12.01 + 1.007942 = 64.03268 Similarly, the chemical formula of TrFE is CF2 CHF and hence = 12.01 + 18.99842 + 12.01 + 1.00794 + 18.9984 = 82.02314 For the copolymer PVDF-TrFE (70:30), the molecular weight will be, Mw = 64.03268 0.7 + 82.02314 0.3 = 69.42 B.2 Concentration of the sample in weight percentage The concentration of the sample in weight percentage can be calculated using the following formula: W% = MP V DF T rF E MP V DF T rF E + MAcetone (B.2) g mol (B.1)

93

94

We know that the density of Acetone is = Therefore, MAcetone = 0.791 Since, 1cm3 = 1mL, we can write MAcetone = 19.755g (B.5) g 25mL cm3 (B.4) MAcetone g = 0.791 3 25mL cm (B.3)

The mass of the P(VDF-TrFE) can me measured using a normal weighing balance and substituting it in the equation [B.2], we get the concentration of the sample in weight percentage. B.3 Calculation of Molecular area per structural unit To plot the isotherm, we rst have to calculate the area per structural unit (monomer) of the copolymer.
g Molecular weight per monomer Mw = 69.4 mol

Area of the Langmuir trough at the time of sample deposition A = 30 7.5cm2 Volume of the sample deposited V = 900l Concentration of the sample C = 0.0632 mg ml Now, the area per structural unit can be written as = Mw 0.041nm2 NA CV (B.6)

The above equation can also be used to calculate the spreading volume V for a desired area per molecule. B.4 Calculation of thickness of LB lms Suppose we deposit M grams of polymer material of bulk density on a water surface to prepare a Langmuir lm of thickness t. If A is the area of between the two barriers and

95

V is the volume of the lm, then the average thickness of the lm can be given by t= As we know, M = V = At = t = M A (B.8) V A (B.7)

From the calculation of Mean Molecular Area [B.3], we can write M 1 Mw = A NA Therefore, t= Mw NA
0.01nm2 mol

(B.9)

(B.10)

Substituting the numerical values, we get for =

g 69.4 mol ) ( ) t= ( 10nm 2 0.01 nm 1g 6.023 1023 mol cc

(B.11)

Appendix C MATLAB program for calculating Rs and Rp

clear all close all clc n1 =1; n2 = 1 . 4 2 ; n3 = 1 . 3 3 3 ; a =1; for inc =52:0.05:54 b=1; for t =2:2:8; s t 2 =(n1 . / n2 ) . s i n d ( i n c ) ; s t 3 =(n2 . / n3 ) . s t 2 ; c t 2=s q r t (1 s t 2 2 ) ; c t 3=s q r t (1 s t 3 2 ) ; r 1 2 =(n2 . c o s d ( i n c )n1 . c t 2 ) . / ( n2 . co s d ( i n c )+n1 . c t 2 ) ; r 2 3 =(n3 . ct2n2 . c t 3 ) . / ( n3 . c t 2+n2 . c t 3 ) ; l =500; b e t a = 4 . 1 8 0 . n2 . ( t . / l ) . c t 2 ; Rp( a , b )=(( r 1 2 2 ) + ( 2 . r 1 2 . r 2 3 . co s d ( b e t a . / 2 ) ) + r 2 3 2 ) . / (1+(2. r12 . r23 . cosd ( beta . / 2 ) ) + ( ( r23 2 ) . ( r12 2 ) ) ) ; b=b+1; 96

97

end a=a +1; end c =1; for inc =52:0.05:54 d=1; for t =2:2:8; s t 2 =(n1 . / n2 ) . s i n d ( i n c ) ; s t 3 =(n2 . / n3 ) . s t 2 ; c t 2=s q r t (1 s t 2 2 ) ; c t 3=s q r t (1 s t 3 2 ) ; r 1 2 =(n1 . c o s d ( i n c )n2 . c t 2 ) . / ( n1 . co s d ( i n c )+n2 . c t 2 ) ; r 2 3 =(n2 . ct2n3 . c t 3 ) . / ( n2 . c t 2+n3 . c t 3 ) ; l =500; b e t a = 4 . 1 8 0 . n2 . ( t . / l ) . c t 2 ; Rs ( c , d )=(( r 1 2 2 ) + ( 2 . r 1 2 . r 2 3 . co s d ( b e t a . / 2 ) ) + r 2 3 2 ) . / (1+(2. r12 . r23 . cosd ( beta . / 2 ) ) + ( ( r23 2 ) . ( r12 2 ) ) ) ; d=d+1; end c=c +1; end

Appendix D MATLAB program for plotting dispersion curves of anti-symmetric MDM waveguide

clear all close all c=3e17 ; d=80; x=z e r o s ( 1 0 5 5 , 1 ) ; y=z e r o s ( 1 0 5 5 , 1 ) ; omega=x l s r e a d ( D: \ U s e r s \ Revathy \ Documents \MATLAB \ e p s . x l s x , Sheet1 , a2 : a2100 ) ; % omega=omega . ( 1 e12 ) ; epsxdp=x l s r e a d ( D: \ U s e r s \ Revathy \ Documents \MATLAB \ e p s . x l s x , Sheet1 , b2 : b2100 ) ; epsxdpp=x l s r e a d ( D: \ U s e r s \ Revathy \ Documents \MATLAB \ e p s . x l s x , Sheet1 , e2 : e2100 ) ; epsxd=epsxdp+i . epsxdpp ; epszdp=x l s r e a d ( D: \ U s e r s \ Revathy \ Documents \MATLAB \ e p s . x l s x , Sheet1 , c2 : c2100 ) ; epszdpp=x l s r e a d ( D: \ U s e r s \ Revathy \ Documents \MATLAB \ e p s . x l s x , Sheet1 , f 2 : f2100 ) ; e p s z d=epszdp+i . epszdpp ; %c a l c u l a t i o n o f k0 98

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k0=omega . / c ; %k0=k0 ; %c a l c u l a t i o n o f e p s m e t a l % e p s i n f =3.5; % omegap =1.3 e16 ; % omegac=6e13 ; e p s i n f =3.5; omegap =1.3 e4 ; omegac=6e1 ; epsm=e p s i n f ((omegap 2 ) . / ( omega . ( omegai . omegac ) ) ) ; o p t i o n s = o p t i m s e t ( Algorithm , LevenbergMarquardt , L a r g e S c a l e , on , TolX , 1 e 6); %s o l v i n g e q u a t i o n f o r c a l c u l a t i n g k wg f o r n =1:2099 f=@( x ) tanh ( 2 s q r t ( ( ( ( x 2 ) . ep s z d ( n ) ) . / ( epsxd ( n ) ) ) (( e p sz d ( n ) . omega . 2 ) . / ( c 2 ) ) ) . d ) . . . + ( 2 . ( ( ( ( s q r t ( ( ( ( x 2 ) . ep s z d ( n ) ) . / ( epsxd ( n ) ) ) (( e p s z d ( n ) . omega . 2 ) . / ( c 2 ) ) ) . / e p s z d ( n ) ) . 2 ) + ( s q r t ( ( x 2 (( omega . 2 ) . epsm ( n ) ) . / ( c 2 ) ) ) . / epsm ( n ) ) . 2 ) . . . . ( ( ( s q r t ( ( x 2 (( omega . 2 ) . epsm ( n ) ) . / ( c 2 ) ) ) ) . ( s q r t ( ( ( ( x 2 ) . ep s z d ( n ) ) . / ( epsxd ( n ) ) ) ( ( e p s z d ( n ) . omega . 2 ) . / ( c 2 ) ) ) ) ) . / ( epsm ( n ) . ep s z d ( n ) ) ) ) . . . . / ( ( ( ( ( s q r t ( ( x2 (( omega . 2 ) . epsm ( n ) )

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. / ( c 2 ) ) ) ) . ( s q r t ( ( ( ( x 2 ) . ep s z d ( n ) ) . / ( epsxd ( n ) ) ) ( ( e p s z d ( n ) . omega . 2 ) . / ( c 2 ) ) ) ) ) . / ( epsm ( n ) . ep s z d ( n ) ) ) . 2 ) . . . +((( s q r t ( ( ( ( x 2 ) . e p s z d ( n ) ) . / ( epsxd ( n ) ) ) (( e p sz d ( n ) . omega . 2 ) . / ( c 2 ) ) ) . / e p s z d ( n ) ) . 2 ) + ( s q r t ( ( x 2 (( omega . 2 ) . epsm ( n ) ) . / ( c 2 ) ) ) . / epsm ( n ) ) . 2 ) . 2 ) ) ; x ( n)= f s o l v e ( f , 1 e 4, o p t i o n s ) ; % y ( n)= f e v a l ( f , x ( n ) ) ; end %c a l c u l a t i n g km and kd %x=x ; % km=( s q r t ( epsm . ( k0 .2) x . 2 ) ) ; % kd=( s q r t ( epsd . ( k0 .2) x . 2 ) ) ; %P l o t t i n g d i s p e r s i o n c u r v e and p r o p a g a t i o n l e n g t h x r e a l=r e a l ( x ) ; y1=r e a l ( x ) . / r e a l ( k0 ) ; p l o t ( r e a l ( y1 ) , omega ) ; % y2=imag ( x ) . / k0 ; l p=abs ( 1 . / ( 2 . imag ( x ) ) ) ; p l o t ( lp , omega ) ;