Page 1
Two-photon absorption standards in the 550-1600 nm
excitation range: establishing a correction curve for accurate
cross section calibration
Nikolay S. Makarov, Mikhail Drobizhev, Aleksander RebaneDepartment of Physics, Montana State University, Bozeman, MT
Page 3
Motivation
yx
W
hFA PA
2
22
yxC
11
2
1
22
22
12/3
2/3
2 10ln
101)(
)()2(ln2
ODyxg
F
F
h
h
W
W OD
Absolute 2PA cross section:
Relative 2PA spectrum:
Correction curve:
)()(
)()( ,2
,2
,2,2
referencePAreference
samplesamplePA A
F
FA
If the 2PA reference standards were available:
referenceregsamplesampleregreference
regreferencereferenceregsamplesample CF
CF,2
,2
,2,2 )()(
)()(
If there are no standards (establishing standards):
Absolute 2PA cross section:
Relative 2PA spectrum:
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Pulse duration
1100 1200 1300 1400 1500 16000
20
40
60
80
100
0
20
40
60
80
100
0
20
40
60
80
100
120
140
550 600 650 700 750 800
0
20
40
60
80
100
120
140
Pu
lse
du
ratio
n, f
s
Signal wavelength, nm
Fundamental signal
SH signal
SH signal wavelength, nm
600 800 1000 1200 1400 16000
20
40
60
80
100
120
140
600 800 1000 1200 1400 1600
0
20
40
60
80
100
120
140
Pu
lse
du
ratio
n, f
s
Wavelength, nm
SH signal
SH idler Signal
Measured with SHG autocorrelator Clark MXR AC-150~ 70 – 140 fs pulse duration range~ 5% fixed wavelength measurement error~ 3% step-to-step relative measurement error
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600 800 1000 1200 1400 16000.00
0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.08
0.09
0.10600 800 1000 1200 1400 1600
0.00
0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.08
0.09
0.10
Be
am
dia
me
tr, c
m
Wavelength, nm
horizontal diameter vertical diameter
model: (OPA is 2 meters before the lens, d0=0.065 cm)
Beam profile
SH signal
SH idler
Signal
Measured with CCD camera Xillix MicroImager PMI1400~ 0.03 – 0.10 cm diameter range~ 4% fixed wavelength measurement error
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2PA standard: Rhodamine 6G
300 350 400 450 500 5500
20
40
60
80
100
120
140
160
180
200600 700 800 900 1000 1100
0
20
40
60
80
100
120
140
160
180
200
Hermann, 1972Oulianov, 2001 Kauert, 2006 Sengupta, 2000 Tian, 2002 Kapoor, 2003 Clay, 2007 Kaatz, 1999 Bradley, 1972 Li, 1982 Catalano, 1982 Penzkofer, 1987 Sperber, 1986 This work Albota, 1998 Sailaja, 2007
2, G
M
Transition wavelength, nm
Laser wavelength, nm
Page 9
2PA standard: Rhodamine B
300 350 400 450 500 550 600 6500
20
40
60
80
100
120
140
160
180
200
220
240
260
280
300600 700 800 900 1000 1100 1200 1300
0
20
40
60
80
100
120
140
160
180
200
220
240
260
280
300
Xu, 1996 Xu, 1996 Xu, 1996 Hermann, 1972 Clay, 2007Li, 1982 Bradley, 1972 Catalano, 1981 Oulianov, 2001 Xu, 1996 Kauert, 2006 Kaatz, 1999 Sperber, 1986 Karotki, 2006 This work Sailaja, 2007
2, G
M
Transition wavelength, nm
Laser wavelength, nm
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2PA standards:Full set
280 300 320 340 360 380 4000.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0560 600 640 680 720 760 800
0.000
1.250x103
2.500x103
3.750x103
5.000x103
6.250x103
7.500x103
8.750x103
1.000x104
1.125x104
1.250x104
9-Chloroanthracene, CH2Cl
2
2, G
M
Transition wavelength, nm
Laser wavelength, nm
, M
-1cm
-1
280 300 320 340 360 380 4000
1
2
3
4
5
6
7
8
9
10560 600 640 680 720 760 800
0.00
2.50x103
5.00x103
7.50x103
1.00x104
1.25x104
1.50x104
1.75x104
2.00x104
9,10-Dichloroanthracene, CH2Cl
2
2, G
M
Transition wavelength, nm
Laser wavelength, nm
, M
-1cm
-1
280 320 360 400 440 4800
40
80
120
160
200
240
280
320
360
400560 640 720 800 880 960
0.0
4.0x104
8.0x104
1.2x105
1.6x105
2.0x105
2.4x105
2.8x105
3.2x105
3.6x105
4.0x105
Bis-diphenylaminostilbene, CH2Cl
2
2, G
M
Transition wavelength, nm
Laser wavelength, nm
, M
-1cm
-1
280 320 360 400 440 4800
1
2
3
4
5
6560 640 720 800 880 960
0
1x104
2x104
3x104
4x104
5x104
6x104
Perylene, CH2Cl
2
2, G
M
Transition wavelength, nm
Laser wavelength, nm
, M
-1cm
-1
300 350 400 450 500 5500
5
10
15
20
25
30
35
40
45
50600 700 800 900 1000 1100
0.00
2.50x103
5.00x103
7.50x103
1.00x104
1.25x104
1.50x104
1.75x104
2.00x104
2.25x104
2.50x104
Coumarin 540A, CCl4
2, G
M
Transition wavelength, nm
Laser wavelength, nm
, M
-1cm
-1
300 350 400 450 500 5500
5
10
15
20
25
30
35
40600 700 800 900 1000 1100
0.0
2.0x103
4.0x103
6.0x103
8.0x103
1.0x104
1.2x104
1.4x104
1.6x104
1.8x104
2.0x104
Coumarin 485, MeOH
2, G
M
Transition wavelength, nm
Laser wavelength, nm
, M
-1cm
-1
300 350 400 450 500 5500
12
24
36
48
60
72
84
96
108
120600 700 800 900 1000 1100
0.00
1.20x104
2.40x104
3.60x104
4.80x104
6.00x104
7.20x104
8.40x104
9.60x104
1.08x105
1.20x105
Fluorescein, Water, pH11
2, G
M
Transition wavelength, nm
Laser wavelength, nm
, M
-1cm
-1
300 350 400 450 500 5500.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0600 700 800 900 1000 1100
0.0
5.0x103
1.0x104
1.5x104
2.0x104
2.5x104
3.0x104
3.5x104
4.0x104
Lucifer yellow, MeOH
2, G
M
Transition wavelength, nm
Laser wavelength, nm
, M
-1cm
-1
400 450 500 550 600 650 700 750
0
10
20
30
40
50
60
70
80
90
100800 900 1000 1100 1200 1300 1400 1500
0.00
2.50x104
5.00x104
7.50x104
1.00x105
1.25x105
1.50x105
1.75x105
2.00x105
Zinc-tetra-tert-butyl-phthalocyanine, CCl4+Pyridine
2, G
M
Transition wavelength, nm
Laser wavelength, nm
, M
-1cm
-1
350 400 450 500 550 600 650 700 750 8000
1
2
3
4
5
6
7
8
9
10700 800 900 1000 1100 1200 1300 1400 1500 1600
0.0
5.0x104
1.0x105
1.5x105
2.0x105
2.5x105
3.0x105
3.5x105
4.0x105
4.5x105
5.0x105
Tetraphenyl-porphine, CCl4
2, G
M
Transition wavelength, nm
Laser wavelength, nm
, M
-1cm
-1
400 450 500 550 600 650 700 7500
50
100
150
200
250
300
350800 900 1000 1100 1200 1300 1400 1500
0.00
2.50x104
5.00x104
7.50x104
1.00x105
1.25x105
1.50x105
1.75x105
Zinc-tetrakis-(phenylthio)-phthalocyanine, CCl4+Pyridine
2, G
M
Transition wavelength, nm
Laser wavelength, nm
, M
-1cm
-1
450 500 550 600 650 700 750 8000
100
200
300
400
500
600
700
800
900
1000900 1000 1100 1200 1300 1400 1500 1600
0
1x105
2x105
3x105
4x105
5x105
6x105
7x105
8x105
9x105
1x106
Silicon-naphthalocyanine dioctyloxide, CCl4
2, G
M
Transition wavelength, nm
Laser wavelength, nm
, M
-1cm
-1
450 500 550 600 650 700 750 8000
100
200
300
400
500
600
700
800900 1000 1100 1200 1300 1400 1500 1600
0
1x104
2x104
3x104
4x104
5x104
6x104
7x104
8x104
Styryl 9M, Chloroform
2, G
M
Transition wavelength, nm
Laser wavelength, nm
, M
-1cm
-1
400 450 500 550 600 650 700 750 800 850
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
400 450 500 550 600 650 700 750 800 850
Nor
mal
ized
flu
ores
cenc
e in
ten
sity
Wavelength, nm
9-Chloroanthracene, CH2Cl2
9,10-Dichloroanthracene, CH2Cl2
Bis-diphenylaminostilbene, CH2Cl2
Perylene, CH2Cl2
Coumarin 540A, CCl4
Coumarin 485, MeOH
Fluorescein, H2O pH11
Lucifer yellow, MeOH
Rhodamine 590, MeOH
Rhodamine 610, MeOH
Tetraphenyl-porphine, CCl4
Zn-tetra-tert-butyl Pc, CCl4+Pyr
Zn-tetrakis-(phenylthio)-Pc, CCl4+Pyr
Si-Nc dioctyloxide, CCl4
Styryl 9M, Chloroform
400 450 500 550 600 650 700 750 800 850
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
400 450 500 550 600 650 700 750 800 850
Nor
mal
ized
flu
ores
cenc
e in
ten
sity
Wavelength, nm
400 450 500 550 600 650 700 750 800 850
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
400 450 500 550 600 650 700 750 800 850
Nor
mal
ized
flu
ores
cenc
e in
ten
sity
Wavelength, nm
9-Chloroanthracene, CH2Cl2
9,10-Dichloroanthracene, CH2Cl2
Bis-diphenylaminostilbene, CH2Cl2
Perylene, CH2Cl2
Coumarin 540A, CCl4
Coumarin 485, MeOH
Fluorescein, H2O pH11
Lucifer yellow, MeOH
Rhodamine 590, MeOH
Rhodamine 610, MeOH
Tetraphenyl-porphine, CCl4
Zn-tetra-tert-butyl Pc, CCl4+Pyr
Zn-tetrakis-(phenylthio)-Pc, CCl4+Pyr
Si-Nc dioctyloxide, CCl4
Styryl 9M, Chloroform
Page 11
Conclusions
• 2PA of 15 commercially available dyes in 550–1600 nm• 10% estimated accuracy of 2PA cross sections• Values are in good agreement with literature data
(fluorescence technique)• Data can be used as reference for determining absolute 2PA
cross sections and spectra
This work is supported by AFOSR Grant No. FA9550-05-1-0357
Acknowledgement