Мешалкин А.Ю. - application of polymer materials in thin-film...
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Application of polymer materials in thin-film optical devices
Alexei Meshalkin
Institute of Applied Physics of Academy of Sciences of Moldova
Chisinau, Moldova
e-mail: [email protected]
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Advantages of polymer materials
� Excellent optical properties (high optical transmission 92-95%, variable refractive index 1,4÷1,7)
� Smaller density = smaller weight� Easy processing technology� Semiconducting properties, photosensitivity� Much cheaper price!!!� Polymers are gradually replacing inorganic
optical materials.
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The main aims:
1 – obtaining of thin polymer films with desired thickness
2 – accurate measurement of film thickness after deposition
3 – accurate measurement of refractive index of thin films
Thickness measurement of polymer films requires the
application of high precision methods
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Polymer materials
Polyepoxypropylcarbazole(PEPC)
Polyepitiopropylcarbazole(PETPC)
Chemical structure of selected polymers.Polymer materials were selected since they are known to
have excellent film forming properties and be photosensitive.
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Different deposition techniques of polymer layers:self-assemblyextrusion and co-extrusionmoldingspin-coating!sputteringchemical deposition.
Spin-coating is one of the technological and accessible method of obtaining polymeric thin films.
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Spin coating technique
A schematic model describing the film formation during the spin-coating process. After the initial spin-off stage (i), where solvent is evaporated (ii), the
thin film is formed (iii).
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Spin-coater SGS Spincoat G3P-8
Programmable spin-coater have the capacity to store and execute up to 30 programs, with up to 20 steps each. Spin profiles adjustable in 1.0 rpm rotationincrements, 0.1 second timing increments, and 1.0 second increments for dwelltime, with precise repeatability from cycle to cycle. Speed: 0-10000 RPM
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Thickness measurement of thin filmsMost common used and available methods:
Atomic-Force microscopy EllipsometrySpectral transmittance/reflectance methodInterferometry!
Determination of film thickness by optical interferometry is widely used. Method is rapid and relies on the interference of two beams of light, where the optical path difference of these beams is related to film thickness.
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Microinterferometr MII-4
Optical scheme of MII-4 interference microscope. 1 – reference beam, 2 – object beam, O – objectives, D – diaphragms, M – mirrors, P -beam-splitting plate, C – compensating plate, S – sample.
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Interference shift fringe
Interference fringes seen through an interference microscope. The step between the two fringe patterns
correspond to a geometrical phase shift which depends on the film thickness
2λ∗=
D
dh
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Modernized microinterferometer MII-4 equipped with photocamera for interferograms recording and saving. The proposed method is non-contact and can
be applied for thickness measurement in the range of 50 nm – 5 µm.
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Comparison of thickness measurement by AFM research and interferometric OPTIC METER
0 10000 2000055,057,560,062,565,067,570,072,575,077,580,082,585,087,590,092,595,097,5
100,0
Hei
ght,
nmdistance, nm
d=15 nm±6nm d=14 nm±4nmThis experiment demonstrated sufficient convergence of the results of theinterferometric method and AFM method of film thickness measurement. It
shows applicable of interferometric method for thin submicrometre and nanometer thickness measurements.
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Used coating cycle
0 5 10 15 20 25 30 35
Ramp 25 sR
ate
Dwell
Deposition
3 s
Ramp 15 s
Spinning20 s
Rate/time schedule of spin-coating cycle
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PEPC polymer films
0,0 2,5 5,0 7,5 10,0 12,50,0
0,1
0,2
0,3
0,4
0,5
0,6
0,7
0,8
0,9
1,0
Thi
knes
s, µ
m
Concentration, %
Thickness as a function of PEPC solution
0.94 ±0.0112.5%
0.83 ±0.0110%
0.46 ±0.017.5%
0.30 ±0.015%
0.17 ±0.012.5%
Thickness, µm
Concentration
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PETPC polymer films
Thickness as a function of PETPC solution
2 4 6 8 10 12 14 160,50,60,70,80,91,01,11,21,31,41,51,61,71,81,92,02,12,22,32,4
d, µ
m
C(%)
2.27 ±0.0115%
1.74 ±0.0110%
0.97 ±0.015%
0.76 ±0.013%
Thickness, µm
Concentration
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Thickness variation depended on spin-speed(500-10000 rot/min, 20 sec).
Variation of spin-speed
0 1000 2000 3000 4000 5000 6000 7000 8000 9000 100000.4
0.6
0.8
1.0
1.2
1.4
1.6
1.8
2.0
2.2
2.4
Thi
knes
s, µ
m
Speen Speed, rot/m in
3% 5% 10% 15%
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Optical constants determination from transmission spectra
From the transmission spectra both the thickness and the refractive index of obtained films were determined by method of fitting curves proposed by Swanepoel
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30 28 26 24 22 20 18 16 14 12-10
0
10
20
30
40
50
60
70
80
90
100
W avelength, nmT
rans
mitt
ance
, %
W avenum ber, *1000 cm -1
substrate 1 2 3 4 5
400 500 600 700 800 900
30 28 26 24 22 20 18 16 14 12
W aveleng th , nm
Tra
nsm
ittan
ce, %
W avenum ber, *1000 cm -1
1 2 3 4 5
400 500 600 700 800 900
300 400 500 600 700 800 900
1.61
1.62
1.63
1.64
1.65
1.66
1.67
1.68
2
Ref
ract
ive
inde
x
Wavelength, nm
PEPC+10% CHI3
PEPC
1
Transmission spectra of polymer layers
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Comparison of thickness measurement by interferometric and
spectral methods.
2.5 5.0 7.5 10.0 12.5100
200
300
400
500
600
700
800
900
1000
d measured from Tspectrum d measured by microscope
Thi
knes
s, n
m
Concentration, %
The difference of obtained results of two methods averaged not more than 5%.
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Conclusions� It was shown, that the thickness of thin polymer films could be
analyzed with high resolution by the interferometric method.� The broad range of thicknesses (from 100 nm to 3 µm) can be
covered by using polymer solution with varied polymer concentration.
� The film thickness dependence on the concentration of solution is linear, but the spin speed doesn’t lead to essential thickness variation. Therefore this linear dependence can be used to predict the film thickness of spin-coated polymers if the solvent is known.
� The described method of thickness measurement by MII-4 interference microscope provided of developed soft allows controlling the films thickness with accuracy ±10nm.
� Proposed spectral transmission method can be applied for simultaneous determination of thickness and optical constants for thin polymer films of a wide variety of materials.
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The main elements of classical optics.The basis of classical optics is based on lenses, prisms,
mirrors
Classical optics
Diffraction optics
prism beamsplitter lens
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Light source (laser)
Output beaming
?IA
&E
«DOE»
wave-front
object
Applications of diffraction optical elements
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40%
40%
Relief of diffraction grating prepared by holographic recording and etching.
Phase diffraction grating
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up to 100%
Relief of diffraction grating prepared by holographic recording and etching.
Diffraction grating with one diffraction order. Phase plate acts as prism.
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Combination of diffraction grating and lens
Diffraction lens focusing in point line
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Laser beam
Diffraction element
Focused line
Diffraction element focuses light in thin line.
y
x
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Laser beam
perpendicular lines
y
x
Diffraction element
Diffraction element focuses light in perpendicular lines.
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Center: l ≈≈≈≈ 8мкм
Edge: l ≈≈≈≈ 0.6мкм
210-mm diffraction mirror
Diffraction mirror
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HOLOGRAPHIC PROPERTIES OF POLYMER FILMS
Optical scheme of holographic set-up. 1 –Ar laser, 2 – mirror, 3 – investigated
photosensitive film, 4 – collimator, 5 –Не-Nelaser, 6 – photodetector, 7 – measuring card,
8 – PC, 9 – beam splitter.
Scheme of etching set-up:1 –He-Ne laser, 2 – etching curve,
3 – sample, 4 – etching agent, 5 –photodetector,
6 – PC with measuring card.
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Methods of fabricating of photo- and electronoresists as main components of
DOEAs it was indicated main element of diffraction optical elements is
photo- and electronoresists.The technological scheme is indicated below( Laser beam (λ=488 nm Ar+ laser; λ=632 nm He-Ne Laser).
Thin film
2. Holographicor e-beam recording
Etching solution
Substrate Substrate Substrate
1. Obtaining of thin polymer film
3. Selective etching to form
relief phase plate
resist
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The transmittance spectra of PEPC and T-PEPC:PEPC shows:
� the films are transparent T=90% in visible region λλλλ=450-900nm
� irradiation by UV and Ar+ laser (λ=488 nm) resulted in appearing
of strong absorption band at 650 nm
PEPC ETPC
UV irradiation
All synthesized polymers were sensitized with iodoform CHI3. It was determined that to achieve the maximum photosensitivity the optimal
concentration of CHI3 in the polymer was about 10 mass%.
30,0 27,5 25,0 22,5 20,0 17,5 15,0 12,50
10
20
30
40
50
60
70
80
90
0
10
20
30
40
50
60
70
80
90400 500 600 700 800 900
PEPC
PEPC*
Tra
nsm
itta
nce
, %
Wavenumber, x1000 cm-1
652 nm
1
2
3
4
650 Wavelength, nm
350
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DIFFRACTION OPTICAL STRUCTURES ON THE BASIS OF
POLYMERSThe last results were achieved due to special
elaborated methods of exposition by laser and electron beam and by selection of special condition of etching
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Sample of a protecting hologram with the image of a flying stork bearing a grape, recorded in polymer layer; #1, #2 and #3 – 1,0 µm pe rioв gratings, #4 and #5 –
2,0 period gratings.
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Thank you for your attention!!!
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