Bader AlQattan1,2, Joelle Doocey1, Murad Ali2, Israr Ahmed2, Ahmed E Salih2, Fahad Alam2, Magdalena Bajgrowicz-Cieslak3, Ali K Yetisen4, Mohamed Elsherif2, Haider Butt2. 1. Nanotechnology Laboratory, School of Engineering, University of Birmingham, Birmingham B15 2TT, United Kingdom. 2. Department of Mechanical Engineering, Khalifa University of Science and Technology, P.O. Box 127788, Abu Dhabi, United Arab Emirates. 3. Manufacturing Group, University of Warwick, Coventry CV4 7AL, United Kingdom. 4. Department of Chemical Engineering, Imperial College London, London SW7 2AZ, United Kingdom.
Abstract
Direct texturing of nanostructures on consumable substrates and products is a challenge because of incompatible ingredients and materials' properties. Here, we developed a direct laser-based method to print nanostructured holograms on dried films of consumable corn syrup solutions. A holographic laser (λ = 1050 nm) interference system was used to construct the nanostructures of the holograms on food for rainbow effects. The relationship between wavelength and periodicity contributed to the changing diffraction angle through the change of the refractive index (1.642). Increasing the sugar concentration (25-175 mg) in the syrup increased the diffraction efficiency of these holograms. The added amount of sugar in the composition increased the refractive index (7%) and decreased the light absorption (12.9%), which influenced the change of diffraction angle by 4.4°. The surface holograms displayed wideband visual diffraction of light extending from violet to red wavelengths. These holograms on edible materials can be imprinted onto commercial food products for adding aesthetic value and controlling perception.
Direct texturing of nanostructures on consumable substrates and products is a challenge because of incompatible ingredients and materials' properties. Here, we developed a direct laser-based method to print nanostructured holograms on dried films of consumable corn syrup solutions. A holographic laser (λ = 1050 nm) interference system was used to construct the nanostructures of the holograms on food for rainbow effects. The relationship between wavelength and periodicity contributed to the changing diffraction angle through the change of the refractive index (1.642). Increasing the sugar concentration (25-175 mg) in the syrup increased the diffraction efficiency of these holograms. The added amount of sugar in the composition increased the refractive index (7%) and decreased the light absorption (12.9%), which influenced the change of diffraction angle by 4.4°. The surface holograms displayed wideband visual diffraction of light extending from violet to red wavelengths. These holograms on edible materials can be imprinted onto commercial food products for adding aesthetic value and controlling perception.
The use of
holograms in food
could potentially improve sensory appeal and, through biosensing,
could increase health and safety.[1,2] Holograms can
even be used to store information as edible microtags.[3] They are also attractive to the eye as they produce rainbow
patterns with light. Using edible holograms on foods, not only as
decoration but also to sense harmful bacteria, could improve food
quality/lifetime monitoring.[4,5] Food holograms which
signify a qualitative information about the sugar contents could be
of value in controlling the sugar consumption, that is challenging
to be measured at the moment.[6] The potential
uses of nanotechnology in the food industry have been steadily increasing.[7] There was a suggestion of using a CO2 laser in the food industry to peel fruits and vegetables.[8] There are also many applications for using nanoparticles
in the food industry, including the following: food packaging and
security; improving food functionality by preventing deterioration,
and food safety for the consumer.[9] Additionally,
there have even been discussions about the possibility of using nanotechnology
to create portable devices for analyzing foods and detecting harmful
properties.[10] Moreover, security holograms
have been reported to be used on household food items.[11] However, using nanoparticles can lead to generation
of reactive oxygen species (ROS) (a nanoparticle associated toxicity)
or oxidative stress, meaning a screening method is vital as a preventative
measure against these nanoparticle-induced toxicities.[12] It can be a laborious process to get approval
for using nanotechnology in food because of standards and regulations
from agencies, such as the U.S. Food and Drug Administration (FDA).[13] Also, research suggests consumers can be reluctant
to accept nanotechnology in the food market because of growing concerns
associated with using nanostructures and nanoparticles in food industries.[9,14] However, as applications for nanotechnology are developed and it
becomes more widely used, regulations will adapt to allow nanotechnology
in the industry, thus giving consumers the confidence that if the
food is on the market it has passed the relevant safety tests.[13] In the future, FDA clearance could allow manufacturers
to use ultraviolet (UV) or electron beam sources to “cured
inks, coatings, and adhesives”, for producing nanoparticle
holograms.[15]Historically dichromated
gelatin (DCG) has a long history of being
used in making holograms.[16] Hardened dichromated
gelatin is considered as one of the known materials today for the
fabrication of holographic optical elements.[17] These hardened DCG holograms are formed by exposing the gelatin
to actinic radiation then removing residual chemical compounds in
a development stage.[17] Similarly, a simplified
production method was developed to create holograms in hardened DCG.
In this case, gelatin is hardened by soaking in ammonium dichromate
to produce holograms recorded at a wavelength of 488 nm and with 90%
diffraction efficiency.[18] More recently,
different forms of gelatin have been contemplated for application
in diffraction optics.[19]Computer-generated
holograms were produced on sugar (sucrose) crystals
by UV microlithography techniques (λ = 240 nm), with a diffraction
efficiency of around 45%.[20] Sugar concentration
could be measured in aqueous solutions through the spacing of an optical
fiber.[10] Corn syrup has also been used
to create holograms by using thin layers with potassium dichromate
solution. It was photosensitized with He–Ne laser (λ
= 530 nm) to create holograms with 4% diffraction efficiency.[21] However, there are some indications that potassium
dichromate may be toxic to human or animal health, rendering the holograms
inedible.[22] Therefore, a lithographic rubbing
technique was used to create phase or amplitude relief holograms in
corn syrup, with a diffraction efficiency of 8.4% when using an amplitude
mask or 36% when using a relief mask, all without the use of any photosensitive
salts or dyes.[23] Moreover, many different
nanomanufacturing techniques can be used to create holographic interference
patterns. E-beam lithography was used to create computer-generated
holograms.[24] Additionally, phase controlled
holographic lithography was conducted with a He–Ne laser (λ
= 532 nm) to create holograms on liquid crystals.[25] Laser interference lithography can also create many different
periodic structures depending on how many interference beams are used.[26,27] Carbon nanotube scattering can also produce holograms.[28] However, these methods can be complicated and
require multiple stages, including pre and post baking and using solutions
such as acetone to dissolve the resist layer.[29]In this work, a holographic direct laser interference pattering
(DLIP) method was developed to pattern holograms on edible materials.
Holographic DLIP is direct, simple, low cost and rapid technique requiring
only one processing step in comparison to conventional methods.[30] This repeatable method is also preferable as
it does not require masks or templates and can create periodic patterns
covering a large area in a range of sizes.[31] Additionally, it has been used on the surfaces of many different
materials from metals to ceramics.[32] The
holographic DLIP method was developed to pattern one-dimensional (1D)
nanostructures on edible substrates. Multiple periodic structures
were produced to study the effect of the periodicity. Angle-resolved
spectral measurements were performed to characterize their optical
properties. The nanostructures were studied to determine their light
diffraction properties in response to monochromatic and broadband
white light. The influence of increasing sugar concentration in the
edible solutions was analyzed to determine the optimal fabrication
parameters.
Results and Discussion
Fabrication of Nanostructures using Edible
Materials
Dried films of corn syrup were used as substrate
for imprinting holograms
by using the DLIP method, which is the chosen method as it is a simple
and swift process as compared with other methods of nanomanufacturing.[33] Corn syrup was made from a blend of sugars gained
from corn-starch (15–20% glucose). Some “light”
varieties contain vanilla flavoring, and other “dark”
varieties do not. The dark coloring and flavors are similar to molasses.[34] A “light” corn syrup was used
in this work and the effects of adding extra vanilla extract to the
corn syrup solution were explored. The samples were left in room temperature
for 3 h until they fully dried. The thickness of each sample was of
the order of 100 μm. Different solutions were prepared and the
samples with optimum properties were selected, with a composition
of 1.5 mL of vanilla extract, 2 mL of corn syrup, and 0.5 mL of water
(Supporting Information, Table S1). This
composition was selected for its superior mechanical strength and
hardness at room temperature as compared with other solutions.A thin layer of synthetic black dye was deposited (900 nm thickness)
onto the corn syrup thin films of each sample (Supporting Information, Table S2).[35] The composition of edible materials and the thickness of the black
dye was optimized to achieve absorbance properties for laser ablation
(Supporting Information, Table S1 and Figure
S1). This dye was chosen because it was competent in maximizing the
laser pulse absorption, which enabled the ablation process to generate
low-cost nanostructures on the surface of the corn syrup film. Figure a shows a schematic
of the hologram recording setup in Denisyuk ablation mode. The laser
beams (λ = 1064 nm, the laser energy from 210 mJ, 3.5 ns) initially
directed by a mirror traveled to the black dye on the corn syrup thin
film (recording medium) and reflected off a plane mirror, placed below,
to ablate the localized regions on the medium.
Figure 1
“Denisyuk”
reflection interference laser ablation
setup. (a) Laser setup schematic for producing holograms on edible
thin films using a nanosecond laser with wavelength λ = 1064
nm. (b) Holographic grating produced on dried corn syrup solution.
(c) Laser interference causing contrasting areas of high and low intensity
laser energy causing the production of holographic grating on thin
film surfaces. Scale bar: 5 μm.
“Denisyuk”
reflection interference laser ablation
setup. (a) Laser setup schematic for producing holograms on edible
thin films using a nanosecond laser with wavelength λ = 1064
nm. (b) Holographic grating produced on dried corn syrup solution.
(c) Laser interference causing contrasting areas of high and low intensity
laser energy causing the production of holographic grating on thin
film surfaces. Scale bar: 5 μm.The laser interference pattern that causes the periodic structure
(Figure b) is due
to the beam reflected off the plane mirror and the incident beam coinciding
with it to form bright and dark fringes (nanopatterning structure).[8,36] This laser interference forms a standing wave, creating periodic
constructive interference (Figure c) fringes which ablate the thin film into a periodic
nanostructure with dimensions related to the wavelength of the laser
and the sample tilt angle.[33,35] The periodicity of
the two interfered laser waves can be described bywhere y1, y2, A, v, t, and λ indicate incident laser beam propagation,
reflected laser beam propagation, amplitude, velocity, time, and wavelength.
This periodicity corresponds to the constructive interference peaks
occurring at approximately λ/2.[37,38] The tilt angle
as the sample is tilted from the horizontal also has an effect on
the periodicity of the structure produced. To analyze the relationship
between the periodicity and diffraction angle, the nanostructures
were observed under a microscope (eq ). This relationship is given bywhere Λ,
λ, and θ represent
periodicity of the nanogratings, wavelength, and tilt angle.[38] This relationship was utilized in the experiments
to create holographic structures of varying sizes by varying the tilt
angle. The periodicity of each sample was measured using the optical
microscope, and therefore, the relationship between the two parameters
could be defined. Optical transmission analysis (normal incidence)
was conducted on the nanostructured holograms produced on the corn
syrup films.The holographic nanopatterns were produced on top
of the corn syrup
films, and uniform morphology was observed under the optical microscope
(Figure a1–a6).
These images were used to calculate the periodicity of the nanogratings. Table shows the periodicity
ranging from 2850–1050 nm as the tilt angle is changed from
10–35°, and Figure b shows a graph of this data compared with the theoretical
periodicity (eq ). The
average difference between the graphs are about 3%, validating that
periodicity of diffraction gratings is a function of tilt angle.[38]Figure c shows the change in optical transmission in between the
glass slide (with no corn syrup), plain corn syrup thin film, and
with ink coating. Interestingly, the optical transmission of the corn
syrup thin film and glass slide are very similar because of the transparency
of the corn syrup solution. In the previous studies, researchers created
ink holograms onto glass slides,[39] and
this similarity in between the optical transmission between the glass
slides and the corn syrup films gave an indication of a positive response
with our holographic DLIP system.[33] Otherwise,
the nanopattering of the hologram would not be successful on the corn
syrup films.[35] When comparing (Figures c,d), the optical
transmission of the black dye quoted corn syrup film was <5%, whereas
after laser ablation (Figure d), for all tilt angles, the transmission of the material
increased by up to 20%. This was less than plain corn syrup, which
has an optical transmission of about 30%. This proves that after ablation,
a significant portion of the black dye gets removed from the corn
syrup films.
Figure 2
Periodic gratings produced on the corn syrup thin films observed
under the optical microscope. (a1–a6) Samples produced at tilt
angles: 10°, 15°, 20°, 25°, 30°, 35°.
(b) Tilt angle variation with periodicity, corresponding to (a1–a6).
(c) Optical transmission spectra comparing plain corn syrup thin film,
black ink coated thin film, and plain glass slide. (d) Optical transmission
for varying tilt angles; legend represents the tilt angle. Scale bar
= 5 μm.
Table 1
Results for Varying Tilt Angles and
the Comparison between Calculated and Experimentally Obtained Periodicities
of the Nanostructuresa
sample
tilt angle, θ (deg)
actual periodicity (nm)
calculated
periodicity (nm)
1
10
2850
3063
2
15
1970
2055
3
20
1480
1555
4
25
1200
1258
5
30
1080
1064
6
35
1050
927
X®
22.5
1605
1654
σ̅
9.4
699.5
788.7
average, σ: standard deviation.
Figure 4
Diffraction produced from nanostructures
holograms (1050 nm) when
illuminated with monochromatic light of varying wavelength. (a–c)
Diffraction patterns produced when nanostructures were illuminated
with monochromatic light of wavelength 450 nm (blue), 532 nm (red),
635 nm (green), respectively. (d) Diffraction angle vs normalized
light intensity graph comparing different wavelengths; graph color
corresponds to laser wavelength, respectively. (e,f) Graph of refractive
index and absorption of light respectively against diffraction angle,
comparing calculated and actual periodicity used in calculations for
all three wavelengths; colors of points correspond to laser wavelength.
Scale bar = 5 cm.
average, σ: standard deviation.Periodic gratings produced on the corn syrup thin films observed
under the optical microscope. (a1–a6) Samples produced at tilt
angles: 10°, 15°, 20°, 25°, 30°, 35°.
(b) Tilt angle variation with periodicity, corresponding to (a1–a6).
(c) Optical transmission spectra comparing plain corn syrup thin film,
black ink coated thin film, and plain glass slide. (d) Optical transmission
for varying tilt angles; legend represents the tilt angle. Scale bar
= 5 μm.Because of the mechanical strength
of the corn syrup holograms,
their optical transmission analysis could be conducted (Figure d). The transmission, and thus
absorption, of the material affects the properties of the resulting
periodic grating as per to the relationship: absorption % = 1 –
transmission %.[39] Absorption gives an indication
of the laser light interaction with the material. Increasing the absorption
would contribute toward improving the ablation efficiency with the
Nd:YAG laser beam, enhancing the interaction of laser light with the
material. The highlighted region between 540 nm and 620 nm shows that
by increasing the tilt angle from 10–35°, the transmission
decreases from approximately 20% to 5%. The reduced light transmission
with changing tilt angle could be due to the increase in absorption
due to more unablated ink material on the thin film. At larger title
angles, smaller sized nanogratings are produced, which have higher
diffraction angles. The large diffraction angles also result in lower
optical transmission recorded in normal incidence.[39,40]Diffraction analysis was performed to measure the effectiveness
of the optical holograms produced. The relationship between the light
passing through the gaps, in this case the holographic grating structure,
and the positioning of the diffracted light was analyzed. The angle
at which the light is diffracted increases when the grating’s
period size decreases. Therefore, a relationship between the diffraction
of light for each sample and the periodicity can be established to
determine the optimum tilt angle. By validating the experimental results
with theory, the concept was proved to be effective. The optical diffracting
produced by the holographic nanostructure in response to monochromatic
red light (Figure a–f) shows normalized intensity of light against diffraction
angle for the changing sample periodicities. Figure g combines the graphs for comparison; the
diffraction angles have a large range from 8.29° for sample “a”
(tilt angle = 10°) to 42.7° for sample “f”
(tilt angle = 35°), showing there is a proportionality relationship
between tilt angle and diffraction angle (eq ).[38] The intensity
of diffraction also reduces with increasing diffraction angle. This
is reflected in the transmission analysis (Figure d); a decrease in the optical transmission
corresponds to the reduction of the structure size. Figures h plots refractive index against
diffraction angle when using red laser light and when changing the
wavelength. In both cases, calculated and experimental results had
the same trend, and diffraction angle is inversely proportional to
refractive index. Using diffraction analysis, the refractive index
and absorption of light can be calculated, by rearranging eqs –5:where m, n0, Λ, Ø, Q, and h are diffraction
order, refractive index, periodicity, diffraction angle, absorption
of light, and grating thickness.[39,42] As eqs and 4 show, the wavelength of light and periodicity of the grating are
affected by both the refractive index and absorption parameters. Therefore,
diffraction experiments were conducted to see the effects of changing
wavelength and periodicity. These equations can be used to determine
if efficiency as absorption of light is related to ablation efficiency
of the laser beam: holograms with a low absorption have the least
efficiency (Table ).[35]
Figure 3
Diffraction produced from nanostructure
holograms on edible substrates
when illuminated with monochromatic red laser light of wavelength
635 nm. (a–f) Tilt angle: 10°, 15°, 20°, 25°,
30°, 35° respectively. (g) Combined graph of diffraction
angle vs intensity showing tilt angles from 10–35°. First-,
second-, and third-order diffraction peaks are highlighted. (h) Graph
of refractive index against diffraction angle, comparing calculated
and actual periodicity used in calculations. (i) Graph of absorption
of light against diffraction angle, comparing calculated and actual
periodicity used in calculations. Scale bar = 5 cm.
Table 2
Intensity, Diffraction Angle, Calculated
Refractive Index, and Absorption of Light at First-Order Diffraction
Peaks for Samples 1–6
sample
max normalized
intensity at first-order diffraction
diffraction
angle at first-order diffraction (deg)
refractive
index, n0 (experimental periodicity)
absorption
of light, Q (experimental periodicity)
refractive
index, n0 (calculated periodicity)
absorption
of light, Q (calculated periodicity)
1
56.5
8.29
1.746
2.61
1.883
2.61
2
48.5
13.9
1.714
7.37
1.843
7.37
3
53.8
16.6
1.739
10.6
1.881
10.6
4
45.4
25.1
1.699
24.6
1.817
24.6
5
46.2
31.3
1.680
39.2
1.806
39.2
6
32.9
42.7
1.642
77.6
1.769
77.6
Diffraction produced from nanostructure
holograms on edible substrates
when illuminated with monochromatic red laser light of wavelength
635 nm. (a–f) Tilt angle: 10°, 15°, 20°, 25°,
30°, 35° respectively. (g) Combined graph of diffraction
angle vs intensity showing tilt angles from 10–35°. First-,
second-, and third-order diffraction peaks are highlighted. (h) Graph
of refractive index against diffraction angle, comparing calculated
and actual periodicity used in calculations. (i) Graph of absorption
of light against diffraction angle, comparing calculated and actual
periodicity used in calculations. Scale bar = 5 cm.Figure shows the diffraction analysis results when changing
wavelength of monochromatic light on the structure spacing of 1050
nm. The images taken are shown in Figure a–c. They were then analyzed, and Figure d shows a comparison
of the graphs that were produced for normalized light intensity against
diffraction angle (graph color corresponds to different laser wavelengths).
The numerical results of the experiment are shown in Table , with calculations of refractive
index and absorption of light.
Table 3
Intensity,
Diffraction Angle, Calculated
Refractive Index, and Absorption of Light at First-Order Diffraction
Peaks for Changing Wavelengths
wavelength (nm)
max
intensity
first
first angle (deg)
n0 (exp. periodicity)
Q (exp. periodicity)
n0 (cal. periodicity)
Q (cal. periodicity)
450
65.2
22.5
1.678
19.7
1.710
19.7
532
41.8
29.2
1.665
33.8
1.694
33.8
635
37.6
43.0
1.642
78.9
1.666
78.9
Diffraction produced from nanostructures
holograms (1050 nm) when
illuminated with monochromatic light of varying wavelength. (a–c)
Diffraction patterns produced when nanostructures were illuminated
with monochromatic light of wavelength 450 nm (blue), 532 nm (red),
635 nm (green), respectively. (d) Diffraction angle vs normalized
light intensity graph comparing different wavelengths; graph color
corresponds to laser wavelength, respectively. (e,f) Graph of refractive
index and absorption of light respectively against diffraction angle,
comparing calculated and actual periodicity used in calculations for
all three wavelengths; colors of points correspond to laser wavelength.
Scale bar = 5 cm.Figure shows diffraction
with white light for different grating spacings. In response to white
light, a diffraction pattern with a rainbow effect is produced. The
length of these rainbow spectra is compared with the tilt angle (Supporting Information Table S2). There is a
clear relationship observed when the tilt angle increases (decreasing
periodicity); the spectra widths and diffraction angles increase.
Therefore, clearer diffraction can be seen with smaller periodicities.
Figure 5
Rainbow
diffraction pattern produced when passing white light from
the holograms. Samples produced at tilt angles: 10°, 15°,
20°, 25°, 30°, 35° for panels a–f, respectively.
(g) Graph comparing tilt angle with length of the rainbow diffraction
pattern produced. Scale bar = 1 cm.
Rainbow
diffraction pattern produced when passing white light from
the holograms. Samples produced at tilt angles: 10°, 15°,
20°, 25°, 30°, 35° for panels a–f, respectively.
(g) Graph comparing tilt angle with length of the rainbow diffraction
pattern produced. Scale bar = 1 cm.
Effect of Sugar Contents on Diffraction Properties
Corn
syrup and vanilla extract are both largely made up of sugars,
33.3% and 40%, respectively (total sugar: 1.26 g). The refractive
index of these solutions was directly proportional to the solution’s
sugar concentrations.[1,2,43] To
further improve the properties of the holograms, the effect of adding
extra sugar (25–175 mg) to the solutions was investigated and
validated using diffraction analysis. As the applications of edible
holograms will be in the food industry, the possibility of improving
taste with added sugar will also be considered. Figure compares the holograms produced on corn
syrup films with varied amounts of added sugar, along with refractive
index and absorption of light graphs against diffraction angle for
the different solutions used. Table shows the refractive index and absorption of light
for each of the holograms calculated (eqs –5). Increasing
sugar concentration contributed to a decrease in the angle of diffraction,
as shown in the diffraction analysis results in Figure . Figure a1–a7 shows the graph of diffraction angle against
normalized intensity of light, with Figure b,c showing a clearer image of the relationship
between the increases in sugar for the parameters. Figure d1–d7 shows the images
taken during the experimentation used to create the graphs. The graphs
indicate that with increasing the amount of sugar in each sample solution
from 1.285 to 1.435 g the diffraction angle decreases from 42°
to 38.6° and the normalized light intensity peak from 48.25 to
41.96. The increasing sugar in corn syrup (decreasing diffraction
angle) due to the increase in refractive indexes by 7%, 1.773 to 1.793,
and absorption of light decreases by 12.9% (Figure e,f).[2,41]
Figure 6
Diffraction analysis
conducted using red monochromatic light of
wavelength 635 nm to see the effects of increasing sugar concentration.
(a) Diffraction angle against light intensity for varying amounts
of sugar added in samples 1a–7a, insets (b) and (c) are included
to represent the data more clearly. (Inset b1) Peak light intensity
compared to diffraction angle in negative region. (Inset b2) Same
as (b1) but in positive region. (Inset c1) Clearer view of negative
region of diffraction against intensity curves, with added trend line.
(Inset c2) Same as (c1) but in positive region. (d1–d7) Diffraction
spots captured from samples with increasing sugar contents: 25–175
mg for d1–d7, respectively. (e) Refractive index against diffraction
angle. (f) Absorption of light against diffraction angle.
Table 4
Amount of Icing Sugar Added to Create
Solutions 1a–7a and the Calculated Amounts of Total Sugar Contained
in Each Solution of Corn Syrup, Vanilla Extract, Water, and Sugar
sample
total sugar (g)
total sugar,
solution (mqL–1)
diffraction
angle (deg)
refractive
index, n0
absorption
of light, Q
1a
1.285
1428
42.0
1.773
74.7
2a
1.31
1456
41.3
1.777
71.9
3a
1.335
1483
40.9
1.779
70.3
4a
1.36
1511
40.5
1.781
68.8
5a
1.385
1539
40.1
1.783
67.3
6a
1.41
1567
39.5
1.287
65.0
7a
1.435
1594
38.6
1.793
61.8
Diffraction analysis
conducted using red monochromatic light of
wavelength 635 nm to see the effects of increasing sugar concentration.
(a) Diffraction angle against light intensity for varying amounts
of sugar added in samples 1a–7a, insets (b) and (c) are included
to represent the data more clearly. (Inset b1) Peak light intensity
compared to diffraction angle in negative region. (Inset b2) Same
as (b1) but in positive region. (Inset c1) Clearer view of negative
region of diffraction against intensity curves, with added trend line.
(Inset c2) Same as (c1) but in positive region. (d1–d7) Diffraction
spots captured from samples with increasing sugar contents: 25–175
mg for d1–d7, respectively. (e) Refractive index against diffraction
angle. (f) Absorption of light against diffraction angle.Although this indicates decreasing ablation efficiency,
which is
apparent from the decrease in light intensity in Figure a–c, the decrease of
both absorption and intensity of diffracted light are both minor and
could be due to impurities in the sugar solution.[1,10] Although
the ablation efficiency is not favorable with increased sugar concentration,
all of the holograms produced measurable results which were within
a 15% range of each other. The results suggest that corn syrups with
different sugar contents, display dissimilar diffraction profiles
and intensities. Hence, this could be used as a measure or tag to
represent the sugar contents in consumable products. The holograms
will not sense the sugar contents in food product but rather act as
an indicator (e.g., barcodes) to represents the product’s sugar
content category. Figure a–h shows the range of colors visible on one hologram
when tilted at different viewing angles. This color composition is
visually represented in Figure i which shows the intensity of red, green, and blue present
in each color. Holographic images showing potential applications for
this method of producing holograms on consumable thin films are shown
in Figure j,k. The
holograms are also long-lasting as the ink used will not decay and
corn syrup has a long life and can be kept at ambient temperatures.
Figure 7
Rainbow
colors produced when tilting the hologram produced on corn
syrup films. (a) Lilac. (b) Dark blue. (c) Light blue. (d) Dark green.
(e) Light green. (f) Yellow. (g) Orange. (h) Red. (i) The intensity
of red, green, and blue in each sample a–h. (j1–3) “Nano”
holographic image displaying rainbow colors. (k1–k3) “Edible”
holographic image displaying rainbow colors. Scale bar = 2 mm.
Rainbow
colors produced when tilting the hologram produced on corn
syrup films. (a) Lilac. (b) Dark blue. (c) Light blue. (d) Dark green.
(e) Light green. (f) Yellow. (g) Orange. (h) Red. (i) The intensity
of red, green, and blue in each sample a–h. (j1–3) “Nano”
holographic image displaying rainbow colors. (k1–k3) “Edible”
holographic image displaying rainbow colors. Scale bar = 2 mm.
Conclusions
We developed a quick
and low-cost fabrication method for producing
holograms on corn syrup films. The pattern created by the holographic
method depends on the number of interfering beams and their incident
angles, polarization, and intensity. Using diffraction analysis, in
both red laser light and white light, the optimum tilt angle was found
to be 35° as it produced the smallest periodic gratings (1050
nm) with the highest efficiency. The diffraction efficiency is affected
by the size of the structure (grating spacing) and the sugar contents
in the solution. The corn syrups with varying sugar contents displayed
different diffraction profiles and intensities. Hence, the holograms
can be used as optical tags to represent the sugar contents in certain
foods. Hologram surfaces diffracted a wide range of visible wavelengths
depending on the tilt angle of the hologram with respect to the incident
light. This is an economical and direct method for imprinting nanostructures
onto edible films. However, the work is limited because of its current
usage of the commercial synthetic black dye (Staedtler Lumocolor).
The dye was used to improve the laser absorption and ablation of the
edible corn syrup surface. The black dye thin film was 900 nm in thickness
and a significant portion of it was removed after the ablation process.
The 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl-2H-tetrazolium
bromide (MTT) assay testing of the black dye thin film showed that
it was nontoxic and had a viability of 98% (Supporting Information Figure S2). In the future, food-grade dyes can
be used to optimize pulsed laser’s parameters accordingly for
producing edible holograms. The holograms were visually analyzed and
observed to maintain their optical performance for several months.
However, a thorough future study is needed to quantify the shelf life
of these holograms in different storage conditions. The effects of
temperature and moisture on the corn syrup could be also investigated
as such parameters are related to the food’s shelf life and
expiration.
Materials and Methods
Preparation of the Recording
Media of Edible Corn Syrup
In the first step, 2 mL of corn
syrup, 0.5 mL of water, and varying
amounts of vanilla extract from 0–1.5 mL are mixed at intervals
of 0.5 mL to create 4 solutions. The measurements were considered
in grams and millimoles per liter of sugar in each of the solutions.
Droplets of each solution were placed onto clean glass slides with
a border created from sticky tape with a thickness of 100 μm
and distributed evenly across the slide. This creates thin films of
solution of approximately 100 μm thickness. However, some variation
in thickness can be expected because of the high surface tension of
the solutions. The solutions are left at room temperature on the glass
slides until they are dry (solid). A Synthetic black dye (Staedtler
Lumocolor) was deposited onto the dry corn syrup layer. The diluted
ink solutions (1:8, v/v in ethanol) were spin coated on 1 mm thick
glass slides at 200 rpm for 35 s. The dyes used were permanent and
had a long-term durability based on the manufacturer and from previous
experiments.[39]
Fabrication of Diffraction
Gratings on the Edible Corn Syrup
Layer
Holographic direct laser interference patterning was
used in a Denisyuk reflection mode. A nanosecond pulsed laser (λ
= 1064 nm, the laser energy from 210 mJ, 3.5 ns) was used to ablate
the black dye deposited on the corn syrup surface. The interference
between the incident and reflected laser beams ablated the localized
regions on the dye medium. The exposure angle of all dye films was
10–35° from the surface of the plain mirror.
Spectroscopic
Measurements of the Ink Gratings
The
diffraction of light from 1D and 2D gratings was analyzed by normally
illuminating the periodic samples with blue (λ = 450 nm), green
(λ = 532 nm), and red (λ = 635 nm) laser beams and recording
the transmitted light on a flat screen placed perpendicularly 15 cm
away from the sample. The testing was performed on a black patterned
nanostructure. The images captured diffracted monochromatic light
for analysis.
Angle-Resolved Measurements of the Gratings
A halogen
light source (HL-2000, Ocean Optics) with a goniometer setup was used
to achieve angle-resolved measurements of diffraction efficiency on
the ink nanogratings. Analysis of the diffracted wavelengths was carried
out by placing the sample 17 cm away from the optical probe. A motorized
rotating stage was used for the broadband spectroscopic analysis of
the rainbow diffraction, which was produced by the nanostructure gratings.
The image captured of diffracted light for analysis.
Authors: J Schwenke; E Lorek; R Rakowski; X He; A Kvennefors; A Mikkelsen; P Rudawski; C M Heyl; I Maximov; S-G Pettersson; A Persson; A L'Huillier Journal: J Microsc Date: 2012-06-07 Impact factor: 1.758