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SUPPLEMENTARY INFORMATIONDOI: 10.1038/NPHOTON.2011.355

NATURE PHOTONICS | www.nature.com/naturephotonics 1

Towards high-speed imaging of infrared photons with bio-inspired nanoarchitectures

Andrew D. Pris,1 Yogen Utturkar,1 Cheryl Surman,1 William G. Morris,1 Alexey Vert,1 Sergiy Zalyubovskiy,1 Tao Deng,1 Helen T. Ghiradella,2 and Radislav A. Potyrailo1*

1 General Electric Global Research Center, Niskayuna, NY 2 Department of Biological Sciences, University at Albany-SUNY, Albany, NY

*Corresponding author - email: [email protected]

Supplementary Information Functionalization of nanostructures of Morpho butterfly scales Single-walled carbon nanotubes (SWNTs) were functionalized with octadecylamine to be soluble in toluene. These functionalized SWNTs were obtained from Sigma and were dispersed in toluene (Sigma, reagent grade) at a 0.3 mg/ml concentration via bath sonication. Dried Morpho sulkowskyi butterflies were obtained from Butterfly Utopia (Brooklyn, NY). Small ~1 x 1 cm pieces were cut from the wings and were functionalized by applying 12 μl of the SWNT solution onto the photonic dorsal side of the wing and allowing it to air dry. Thermal excitation with MWIR illumination setup The IR photons were created by a blackbody element (Newport, model 6363) mounted within a Newport IR illuminator (Model 7340) and powered by a 140-W Newport constant current supply (Model 68938). The fan house within the illuminator was operated at all times that the globar was above room temperature. A 1-inch filter holder mounted to the exit of the illuminator sequentially held a CaF2 lens (50 mm focal length, 0.2 - 8 μm spectral transmission range) and a 3-μm long pass interference filter (Newport SP1000-3902). This combination produced a spectral profile of illumination from 3 to 8 μm, corresponding to the MWIR spectral range. A variable speed optical chopper (Stanford Research Systems, Inc., Model SR541) was positioned immediately following the filter holder. The mounted Morpho wing sample was placed ~1 cm from the illuminator exit assembly. The wing was mounted such that the non-iridescent ventral side of both wing and scales was facing the MWIR assembly. The focused MWIR radiation produced an approximate 1 x 1cm spot, as determined by removing the 3-μm long pass filter and observing the small amount of emitted visible light. To validate the temperature output of the filtered MWIR source, a pre-calibrated, high response speed 0.001” diameter, 12-inch long type-T thermocouple (Omega, Model COCO-001) was placed within the focused filtered MWIR spot. The thermocouple response was amplified 5000X and passed through a 100-Hz low pass electronic filter using a low noise preamplifier (Stanford Research Systems, SR570). The amplified signal was monitored and recorded by a digitizing oscilloscope (Tektronix, TDS5054). Measurements of optical response The visible spectral characteristics of the Morpho reflectors were determined using an optical setup that included a white light source and a fast data acquisition spectrograph. A 20-W halogen light source (Mikropack, HL-2000-FHSA) was coupled to a bifurcated optical fiber reflection probe, with the common arm of the probe positioned via an XYZ micromanipulator stage to illuminate a ~ 1 mm diameter spot of the photonic dorsal side of the mounted Morpho wing. The other end of the bifurcated fiber was coupled with an inline filter holder containing a set of two short pass filters (750-nm 03SWP416 and 800-nm 03SWP618, both Melles Griot). Two filters were used for more efficient blocking of radiation at unwanted wavelengths. The filtered reflected light was coupled to a HR2000+ spectrometer (Ocean Optics) operated with a data acquisition and control program custom written in LabVIEW. Evaluation of spectra from the Morpho wing sample upon translation and rotation effects was performed by positioning the sample on an XYZ stage (Newport, 462-XYZ) and on a goniometer stage (Melles Griot, 07GON501).

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2 NATURE PHOTONICS | www.nature.com/naturephotonics

SUPPLEMENTARY INFORMATION DOI: 10.1038/NPHOTON.2011.355

Numerical simulations of spectral response Numerical simulations of light reflectance were performed for several Morpho photonic structures, with geometries and dimensions of their profiles obtained from SEM and TEM data. The physical optics models simulated reflectance of light from a nanostructure with seven parallel ridges and detection of light reflectance in the far field. The physical optics simulation approach utilized ray-tracing software (ASAP, Breault Research Organization, Tucson, Arizona) with modeling reflection of Gaussian beams from photonic structures. Square areas of ~ 5 x 5 m containing several parallel ridges were utilized in the model. The incident light wave front was decomposed into highly diverging beams to accurately include possible diffraction effects and to precisely account for the geometry of the modeled structure. These beams carry information about the direction and the phase of the reflected light to precisely recreate the shape of the reflected wave front and to follow its propagation. Thermal effects in chitin-based Morpho wing structure decorated with SWNTs Chitin has several IR-active absorption bands corresponding to the presence of single and/or double bonds at 3 μm (C-H, N-H, and O-H bonds), 6 μm (C=O bond), and 9 μm (C-O bond).1,2 The IR-active vibrational modes of SWNTs are at 3, 6, and 8 μm corresponding to the C-Hx bonds, G band, and D band, respectively.3-5 The MWIR radiation, absorbed by these molecular vibrations, decays to thermal energy6,7 and locally heats up the Morpho wing structure. The photoexcitation-induced excitons of the SWNTs produced by the infrared radiation also relax to local heat through the picosecond coupling of the excitons into phonons.8,9 Bio-inspired technological implications of nano-engineered materials and structures

Recent examples of bio-inspired technological implications of nano-engineered materials and structures are illustrated in Table S1.10-17 Thermal mass calculation Thermal mass of individual pixels of such advanced bolometer types as cantilevers, Fabry-Perot resonators19, and microbolometers20 was calculated and compared to the calculated thermal mass of our new detector based on Morpho butterfly scales. Thermal mass per pixel Cth (in J/K) was calculated as21,22

Cth = ρCpV, (S1) where ρ is the density, Cp is the specific heat capacity of material, and V is the pixel volume. The calculated thermal mass of individual pixels of the advanced bolometer types and of the new detector based on Morpho butterfly scales is compared in Table S2.18-20,23,24 These calculations were performed assuming operation of devices well above cryogenic temperatures. It is well known that the thermal mass decreases as the operating temperature approaches absolute zero,25 making possible achieving thermal mass of 10-18 – 10-15 J/K at cryogenic temperatures.26,27 Modeling of thermal effects When a quantity of heat Q is supplied to a sample of mass m and specific heat capacity Cp, the resulting increase in temperature T of the sample is given by:28

T = Q / m Cp. (S2)

When an IR source is employed to supply heat Q to the sample, this supplied heat can be expressed as:29

Q = Qflux A D / f, (S3)

where Qflux is the amount of IR radiation over surface area A, D is the duty cycle of the IR source modulation, and f is the modulation frequency. When IR absorption efficiency of the sample is , and taking into account Eq. S3, the increase in temperature T of the sample can be expressed as:

T = Qflux A D /(f m Cp). (S4)




Eq. S4 demonstrates that the temperature rise T of the sample upon exposure to IR radiation with flux Qflux depends on such intrinsic properties of the sample as its specific heat capacity Cp, IR absorption efficiency , mass m, and its surface area A, and on the IR system parameters such as the duty cycle of the IR source modulation D and the modulation frequency f. The increase in temperature T of a sample leads to the thermal expansion of the sample L described as30 L = Lo T, where is the coefficient of linear thermal expansion and Lo is the initial length of the sample. The increase in temperature T of the sample with refractive index n leads to the decrease of the sample refractive index described with the material thermo-optic coefficient dn/dT.31 Thus, upon temperature change T of a sample such as a Morpho wing, due to its exposure to MWIR radiation, its reflectivity spectrum will be affected by and dn/dT. Table S1. Recent examples of bio-inspired technological implications of nano-engineered materials and structures.

Potential technological applications

Bio-inspiration Reference

Security labels, coatings Wing scale structure of Papilio blumei butterfly 10 Ultraviolet reflectors Wing scale structure of Euploea mulciber butterfly 11 Circularly polarized beam splitters, super prisms

3D network with cubic symmetry of wing scale structure of Callophrys rubi butterfly

12

Paper, cosmetics, fabrics Elytra of Cyphochilus beetle, wing scale structures of Morpho butterflies

13

Devices with ultra-large angular dispersion

Elytra of Heterorrhina sexmaculata beetle 14

Biosensors, optical functional devices

Wing scale structure of Chrysiridia rhipheus moth 15

Sensors based on surface-enhanced Raman scattering

3D networks of wing scale structures of butterflies 16

Gas sensors Wing scale structure of Morpho didius butterfly 17

Table S2. Thermal mass of individual pixels of several advanced bolometer types and of the new detector based on Morpho butterfly scales.

Detector type Pixel material

Material density (kg/m3)

Specific heat capacity (J/kg-K)

Pixel volume (thickness x area, μm x μm x μm)

Thermal mass

per pixel (J/K)

Cantilever18 SiNx 2400 690 1 x 120 x 120 3.1 x 10-8 Au 19300 129 0.2 x 120 x 120

Fabry-Perot Resonator19 SiNx 2400 690 1.5 x 30 x 30 2.2 x 10-9 Microbolometer20

SiNx 2400 690 0.4 x 25 x 25 4.3 x 10-10 VOx 5800 487 0.15 x 25 x 25 Ti 4500 520 0.01 x 25 x 25

Fluke Ti50FT Uncooled Bolometer23

SiNx 2400 690 0.4 x 20 x 20 4.3 x 10-10 Vox 5800 487 0.15 x 20 x 20

FLIR Photon 640 Uncooled Bolometer24

SiNx 2400 690 0.4 x 25 x 25 6.8 x 10-10 Vox 5800 487 0.15 x 25 x 25

Morpho butterfly scales (this work)

Chitosan 200 1100 1.7 x 0.77 x 0.77 2.2 x 10-13




a

b

c

3 m

1 m

500 nm

R

CR

R

CR

L MR

L

MR

1700

70

153

236

318

318

318

318

318

112

194

277

318

318

318

318

29

770

62

150

64d

Figure S1. Details of hierarchical photonic structure of a Morpho butterfly scale. a–c, Different tilts and magnifications of SEM images. d, Schematic and dimensions (in nanometers) of Morpho photonic structures employed in optical modeling as estimated from TEM and SEM images. Abbreviations in (a – c): R – ridge; CR – crossrib; L – lamella; MR - microrib.

Wav

elen

gth

(nm

)

Scanned Distance (mm)

Ref

lect

ance

(arb

. uni

ts)

Figure S2. Spatially-resolved (100- m step size) characterization of reflectivity of scales of an intact Morpho butterfly demonstrating the stability of the reflectivity peak. Inset, direction and scan position of a Morpho butterfly (wingspan = 87 mm).




10

5

Time (min)

Ref

lect

ance

(%)

30

35

4045

50 5560

Temp (oC)Run01Run02

80

85

90

95

100

30 35 40 45 50 55 60 65

Ref

lect

ance

(%)

Temperature (oC)

80

85

90

95

100

105

350 450 550 650 750

30354045505560

Ref

lect

ance

(%)

Wavelength (nm)

a b

Figure S3. Thermal response of a Morpho butterfly wing sample achieved using a heating stage. a, Spectral features. b, Thermal response curve with the error bars of one standard deviation from two measurements. Inset, response reproducibility.

Z

X

Y MWIR

1 m

Figure S4. Schematic of a setup for studies of spectral responses arising from non-thermal effects on the Morpho scales. Positioning of a Morpho butterfly wing sample on XYZ and goniometer stages and of moving the sample in X, Y, and Z directions and rotating the structure for + 1o and – 1o angles for comparison of observed spectra with thermally induced spectra. The MWIR arrow shows direction of the incoming infrared radiation.




80

85

90

95

100

350 400 450 500 550 600 650 700 750

Refle

ctanc

e (%

)

Wavelength (nm)

96

97

98

99

100

101

102

103

104

350 400 450 500 550 600 650 700 750

Refle

ctanc

e (%

)

Wavelength (nm)

c

90

92

94

96

98

100

102

104

350 400 450 500 550 600

Refle

ctanc

e (%

)

Wavelength (nm)

ba

0 m

X = - 200 m

0 m

X = + 200 m

0 m

Y = - 200 m

0 m

Y = + 200 m 0 m

Z = - 200 m

0 m

Z = + 200 m

80

85

90

95

100

105

0 50 100 150 200

Ref

lect

ance

(%)

Time (s)

92

94

96

98

100

102

104

0 50 100 150 200R

efle

ctan

ce (%

)

Time (s)

96

97

98

99

100

101

102

103

104

0 50 100 150

Ref

lect

ance

(%)

Time (s)

88

92

96

100

104

0 20 40 60 80 100

Ref

lect

ance

(%)

Time (s)

88

92

96

100

104

350 400 450 500 550 600 650 700 750Wavelength (nm)Wavelength (nm)

Ref

lect

ance

(%)

0o

1o

-1o

0o

d

Figure S5. Results of studies of spectral responses arising from non-thermal effects on the Morpho scales. Spectral changes in reflection upon (a – c) XYZ translation and (d) rotation of the Morpho butterfly wing sample. Translation in X (a), Y (b) and Z (c) directions. The structure was moved in increments of 50 m in all directions. d, Summary of spectral changes in reflection upon rotation of the Morpho butterfly wing sample on a goniometer stage in increments of 0.5o.




15 Hz 20 Hz 25 Hz

35 Hz30 Hz 40 Hz

3 Hz 5 Hz 10 Hz

Frequency (Hz)

Sig

nal P

ower

Figure S6. Response speed of Morpho reflectors. Results of Fourier transform analysis of 3 – 40 Hz dynamic response of the Morpho wing reflectors, plotted as signal power vs. modulation frequency.

Noise level100

1000

10000

100000

1000000

0 5 10 15 20 25 30 35 40

Sig

nal P

ower

Frequency (Hz)

SWNT loading(μg/cm2)

0.91.8

0

Figure S7. The effect of the loading levels of SWNTs on the dynamic response of Morpho reflectors.




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