Optical properties and structural coloration

of chocolate
Cite as: Appl. Phys. Lett. 117, 183701 (2020); https://doi.org/10.1063/5.0028535
Submitted: 06 September 2020 . Accepted: 19 October 2020 . Published Online: 02 November 2020

H. Galinski, E. Jeoffroy, A. Zingg, L. Grob, P. A. Rühs, R. Spolenak, and A. R. Studart

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© 2020 Author(s).
 Applied Physics Letters ARTICLE scitation.org/journal/apl

Optical properties and structural coloration

of chocolate
Cite as: Appl. Phys. Lett. 117, 183701 (2020); doi: 10.1063/5.0028535
Submitted: 6 September 2020 . Accepted: 19 October 2020 .
Published Online: 2 November 2020

H. Galinski,1,a) E. Jeoffroy,2,b) A. Zingg,1 L. Grob,3 € hs,2,c) R. Spolenak,1

P. A. Ru and A. R. Studart2,a)

AFFILIATIONS
1
Laboratory for Nanometallurgy, Department of Materials, ETH Zu€ rich, Vladimir-Prelog-Weg 1-5/10, 8093 Zu€ rich, Switzerland
2
€ rich, Vladimir-Prelog-Weg 1-5/10, 8093 Zu
Complex Materials, Department of Materials, ETH Zu € rich, Switzerland
3
€ rich, Schmelzbergstrasse 9, 8092 Zu
Laboratory of Food Process Engineering, ETH Zu € rich, Switzerland

a)
Authors to whom correspondence should be addressed: henning.galinski@mat.ethz.ch and andre.studart@mat.ethz.ch
b)
€ rich, Switzerland.
Present address: FenX AG, Vladimir-Prelog-Weg 3, 8093 Zu
c)
Present address: Planted Foods AG, Schmelzbergstrasse 7, 8092 Zu € rich, Switzerland.

ABSTRACT
Chocolate consists of cocoa butter, cocoa particles, sugar, and additives, which together determine its taste and optical properties. The optical
properties of chocolate play a vital role in consumer perception, representing type and quality in the blink of an eye. Here, we present a
comprehensive analysis of the optical properties of white, milk, and dark chocolate, while demonstrating how to craft orange to blue
chocolate via a thin food-grade coating. Using Mie theory, we show that chocolate can be treated as a turbid solid, where cocoa butter acts as
a glass-like dielectric while all other ingredients contribute to its scattering and absorption. We expect the proposed coating to be easily
adapted to other food surfaces to bring color to a broader range of edible products.
Published under license by AIP Publishing. https://doi.org/10.1063/5.0028535

Chocolate, sold for the first time in 1678 by a chocolatier named
Giovanni Battista Ari in Turin,1 is a food product that is craved and
indulged world-wide. Chocolate is a complex composite consisting of
cocoa butter and cocoa particles, and its taste is often enhanced with
additional components such as milk, sugars, and/or sweeteners.
A series of processing steps is typically used to produce chocolate.
These steps include the fermentation of cocoa beans on the forest
floor, drying, roasting, grinding, and conching in the factory.2 During
grinding and conching, chocolate is freed from unpleasant flavors and
the size of 80% of all cocoa particles is reduced below 2 lm.2 Finally,
chocolate is tempered under defined temperature zones and shear
fields and molded into the desired shape. Either traditional tempering3
or seeding4 controls the formation of, in general, a polymorphic fat
crystal network, ensuring that only the preferred crystal polymorph bV
is formed. This formation is influenced by the ingredients, tempering
techniques, and cooling conditions, resulting in alteration of the
matrix density.5 When chocolate is not adequately tempered, it will
form a superficial fat bloom over time, leading to an unpleasantly
looking grayish haze on the surface.6
The optical appearance and coloration of chocolate are crucial
for consumers, as they allow us to identify the type of chocolate and to
match taste expectations. White chocolate can be easily colored by the
addition of colorful particles (e.g., green tea powder) as the foundation
is mainly white. Other colors such as pink have been demonstrated by
using specially cultured cocoa beans and slightly acidic treated beans.7
However, controlling the coloration of milk and dark chocolates is not
straightforward due to the prevalence of cocoa particles. Several
attempts have been made to correlate the brown coloration of milk
and dark chocolate with the formation of chromophores during alkali-
zation8 of chocolate (so-called dutching), but a sound picture of the
light interaction with chocolate is still lacking.
To engineer the color of chocolate, it is important to get insights
into the physics of light-matter interactions in such a complex solid.
For this purpose, it is convenient to assume that an electromagnetic
wave impinging on a piece of chocolate is subjected to ordinary
specular reflection and optical scattering at particles immersed in the
fat matrix [Figs. 1(a) and 1(b)]. To evaluate the suitability of this
approach, we first employed spectroscopic ellipsometry to measure the
refractive index of different types of tempered chocolates. Figure 1(c)
reports the refractive indices of cocoa butter, white, milk, and dark
chocolate. The obtained refractive index for cocoa butter is in excellent
agreement with the value of 1.46 reported in the literature.10 Quite
interestingly, the refractive index of cocoa butter is comparable to that
of silica glass (SiO2)9 [see Fig. 1(c)], a transparent dielectric with very

Appl. Phys. Lett. 117, 183701 (2020); doi: 10.1063/5.0028535 117, 183701-1
Published under license by AIP Publishing
 Applied Physics Letters ARTICLE scitation.org/journal/apl

FIG. 1. Optical properties of chocolate. (a) Schematic illustration of light interacting with chocolate. The inset highlights the different mechanism of light interaction contributing
to the optical appearance of chocolate, i.e., specular reflection from the tempered chocolate surface and Mie-scattering from the chocolate matrix. (c) Experimentally deter-
mined refractive index n of cocoa butter, white, milk, and dark chocolate compared to the refractive index of SiO2.9 (d)–(g) Comparison of experimentally determined scattering
(la) and absorption (la) coefficient for different chocolates with computationally retrieved coefficients based on Eqs. (1) and (2). (h)–(k) Complex refractive indices of the scat-
tering particles inside the cocoa fat matrix retrieved solving Eqs. (1) and (2) for different chocolates.

low optical losses. The transition from pure cocoa butter to white and diluted,14 the scattering and extinction coefficient of an ensemble of
milk/dark chocolate manifests in a reduction of the refractive index, particles can be expressed as
while the overall dispersion remains unchanged. ð1 2 X !
In order to determine the scattering properties of the different k 1 2 2
ls ¼ ð2n þ 1Þðjan j þ jbn j Þ  NðrÞdr; (1)
chocolates, we measured the total and diffused transmission and 0 2p n¼1
reflectance of different chocolates in an integrating sphere [see also ð1 2 X !
supplementary material Figs. S3(b) and S3(d)]. Applying the inverse k 1
lt ¼ ð2n þ 1ÞRefan þ bn g  NðrÞdr; (2)
adding-doubling (IAD) method11,12 to these measurements, the scat- 0 2p n¼1
tering and absorption coefficients (ls ; la ) of each type of chocolate
have been determined. Additional information is presented in the where an and bn are the complex Lorenz–Mie coefficients, which
supplementary material. depend on the ratio m ¼ nparticle =nmatrix .15 k is the wavelength in the
To interpret these results, we developed a parallel genetic algo- host medium, while the absorption coefficient is given, due to energy
rithm, which models the light-matter interaction using Mie theory.13 conservation, by la ¼ lt  ls . N(r) is the particle number density dis-
With reference to our ellipsometric data, we can intuitively represent tribution, which is derived from the particle size distribution function.
chocolate as a turbid solid, composed of scattering particles with com- The inversion of these two Fredholm integrals of the first kind is
plex refractive index nparticle immersed in a glassy matrix with achieved numerically. An initial solution is obtained by resorting to a
nmatrix 2 R. Assuming that the scattering particles are spherical and genetic algorithm, while the refinement of the solution is obtained by

Appl. Phys. Lett. 117, 183701 (2020); doi: 10.1063/5.0028535 117, 183701-2
Published under license by AIP Publishing
 Applied Physics Letters
least median squares (LMS) curve fitting. Kramers–Kronig consistency
of the retrieved refractive index is enforced by using a Drude–Lorentz
model. Detailed information is presented in the supplementary
material.
Figures 1(d)–1(g) compare the experimentally obtained scatter-
ing and absorption coefficient of different chocolate slabs with the
numerical solutions. While the scattering and absorption coefficients
were found to monotonically decrease with the wavelength for most
of the investigated specimens, a noticeable peak in the scattering
coefficient was observed for milk and dark chocolate in the visible
spectrum.
Cocoa butter [Fig. 1(d)] behaves as a weakly scattering medium
in the visible spectrum, and the measured scattering coefficient is
proportional to 1=k4 . This relation is valid for scattering of light with
particles smaller than the wavelength and is often referred to as
Rayleigh scattering.14 Here, we expect that grain-boundaries and
impurities in the crystalline fat matrix act as primary scattering
centers. The obtained particle size, i.e., crystallite size, is found numeri-
cally to be in the range of 400 nm (see the supplementary material). By
adding milk powder and sugar to the cocoa butter [see also supple-
mentary material Fig. S3(a)], the absorption coefficient throughout the
visible spectrum is increased [Fig. 1(e)]. Due to Beer’s law,16 the
enhanced absorption coefficient induces an increased opacity of the
material, which combined with the small but finite optical scattering at
particles with a higher refractive index [Fig. 1(i)] results in a white
appearance. Still, Rayleigh scattering is predominant, whereby light is
equally scattered in forward and backward directions [see the supple-
mentary material, Fig. S3(b)]. The measured scattering coefficient is
comparable with scattering properties of raw milk.17
The addition of micrometer-sized cocoa powder [see also supple-
mentary material Fig. S3(c)], conversely, changes the scattering coeffi-
cient such that light in the blue and green regions of the visible
spectrum is predominately scattered [Fig. 1(f)]. In this case, light is not
scattered equally in all directions but forward scattering is prevalent
[see the supplementary material, Fig. S3(d)]. Both features are charac-
teristic for Mie scattering and have a significant consequence for the
appearance of chocolate. Because of enhanced Mie scattering in the
blue and green, incoming light at this wavelength is effectively extinct
by Mie resonances,18 causing a change in coloration from a white to a
reddish-brown color.
In dark chocolate, the scattering coefficient is enhanced through-
out the visible range [Fig. 1(g)], resulting in a dark black appearance of
the chocolate. The retrieved particle size distribution (see the supple-
mentary material) is centered at 1:21 lm, which is in good agreement
with the predominant particle size of 1.4 lm found in cocoa solids.2
This suggests that the genetic algorithm correctly identified the refrac-
tive indices and particle sizes of the different chocolate systems.
Notably, the stark contrast in coloration due to the addition of cocoa
particles is not reflected in the measured and modeled absorption coef-
ficient la. We also observe a very low refractive index contrast between
scattering centers in pure cocoa butter and dark chocolate [see
Figs. 1(h) and 1(k)], which inhibits large variations in the absorption
coefficient.19 Our results suggest that the optical properties of milk
and dark chocolate depend strongly on the prevalent polydisperse par-
ticle size and associated Mie resonances arising from scattering. The
found phenomenon is very similar to structural coloration achieved
by multipolar Mie resonances of polydisperse TiO2 particles.18,20
Appl. Phys. Lett. 117, 183701 (2020); doi: 10.1063/5.0028535
Published under license by AIP Publishing
ARTICLE scitation.org/journal/apl
The occurrence of scattering opens interesting possibilities to engineer
the coloration of dark chocolate by, e.g., shifting the cocoa particle
size distribution to the Rayleigh regime. It is to note that in addition
to the scattering effects demonstrated here, adsorption from
red-chromophores8 cannot be ruled out and has to be considered
to contribute to the coloration of chocolate.
Another approach to change the coloration of chocolate is struc-
tural coloration in the form of a thin optical coating. In this work, we
adapt the concept of nanometric optical absorbers introduced by Kats
et al.,21,22 to food grade materials. In contrast to quarter wave anti-
reflection coatings, the optical losses in these ultra-thin absorbers cause
a non-trivial phase shift / at the interfaces (/ ¼ 6 mod 2p) and enable
light interference in ultra-thin layers whose thickness h falls below the
k 21,23,24
“classical” limit of h ¼ 4n . This simple concept led to a consider-
able research interest, including research on color sensors,25 phase-
change materials,26–28 Janus-faced,29 and other optical coatings.30–32
The reflectance R ¼ j~r j2 of such an optical absorber, composed of an
ultra-thin lossy dielectric and an optically thick Drude metal, is given
by the Fresnel equations at normal incidence, namely,
~
~r 1;2 þ ~r 2;3 e2ib
~r ¼ ; (3)
1 þ ~r 1;2~r 2;3 e2ib~
~ ¼ ð2p=kÞ~
whereby b n 2 d; n
~ 2 is the complex refractive index of the
dielectric, d is the layer thickness, and ~r 1;2 ; ~r 2;3 are the interface
specific reflection coefficients.33
Here, we select an optical coating composed of the food additives
dielectric TiO2 (E171) and Au (E175), a food-grade metallic mirror.
The two materials have been deposited on dark chocolate and paper in
the customized low-vacuum sputter coater shown in Fig. 2, typically
used for (SEM) sample preparation. To prevent the chocolate from
melting, we developed a Cu-holder that is cooled in dry ice before
deposition. This allows us to deposit Au and TiO2 films of various
thicknesses on the chocolate surface. While Au is deposited under an
argon (Ar) atmosphere, ultra-thin TiO2 films have been grown using
reactive sputtering of titanium in an ArþO2 mixed gas. The refractive
FIG. 2. Schematic of the scanning electron microscopy (SEM) sputter coater used
to deposit thin films on chocolate. The sputtering target is situated above the sam-
ple. Non-reactive sputtering is used to deposited gold (Au), while reactive sputtering
under an Ar þO2 atmosphere is used in the case of titania (TiO2). The chocolate
pieces are placed in a pre-cooled Cu-holder that is used as heat sink. The contact
between the chocolate and the heat sink is assisted by an Al-foil.
117, 183701-3
 Applied Physics Letters
FIG. 3. (a) Optical micrographs of food grade optical coatings created by sputtering Au and TiO2 on top of dark chocolate. The strong interference in these coatings results in
structural coloration of the chocolate ranging from gold to blue. (b) Optical micrographs of the same optical coatings on paper. (c) Predicted color evolution of the optical coat-
ings according to Eq. (3). The coating consists of 50 nm gold and a nanometric TiO2 film of different thicknesses. (d)–(f) Measured and calculated reflectance using Eq. (3) as
a function of wavelength, within the range of 300–800 nm, respectively.
indices of Au and TiO2 were measured by ellipsometry and are
reported in the supplementary material.
Figure 3(a) depicts optical micrographs of the colored chocolate.
Although only several nanometers thick, the TiO2 coating on a 50 nm
Au film severely alters the coupling of light to the structure, manifest-
ing in structural coloration. By increasing the coating thickness, we
observe the formation of vivid structural colors spanning from gold,
orange, to dark blue. The colors prove to be robust and reproducible
when applied to very rough substrates, as demonstrated by coatings
deposited on paper [Fig. 3(b)]. The experimentally observed colors are
in good agreement with calculated colors based on Eq. (3).
In order to quantify the electromagnetic response of the colored
chocolates and paper samples, we employed near-normal incidence
reflectometry. The obtained reflectance spectra for three optical coat-
ings are compared in Figs. 3(d)–3(f) with the theoretical predictions
[Eq. (3)]. The minimum reflectance of 0.9% is observed for dark choc-
olate coated with 50 nm Au and 20 nm thick TiO2 at a wavelength of
413 nm, confirming near perfect absorption of light on a piece of choc-
olate. While the experimental reflectance spectra approximate the
functional shape of the calculated reflectance, given by Eq. (3), the
intensity of the experimental spectra is significantly diminished. This
effect most likely results from increased diffuse scattering due to sur-
face roughness.
In summary, we present a comprehensive analysis of light-
interaction with chocolates. We show that both specular reflection on
the tempered, i.e., flat surface and optical scattering by constituent
particles contribute critically to the optical properties and appearance
Appl. Phys. Lett. 117, 183701 (2020); doi: 10.1063/5.0028535
Published under license by AIP Publishing
ARTICLE scitation.org/journal/apl
of chocolates. Using Mie theory, we developed a genetic algorithm to
retrieve the particle size distribution and refractive index of scattering
particles within chocolates. In an approach to color chocolate, we
deposit food-grade optical coatings based on Au and TiO2 to generate
structural coloration on dark chocolates. The coating concept can be
easily adapted to other types of chocolates, also opening up possibili-
ties for engineering the appearance of other edible products with food-
grade optical coatings.
See the supplementary material for the details about the sample
fabrication, optical characterization, and retrieval of the scattering
properties by Mie theory.
AUTHORS’ CONTRIBUTIONS
H.G. and E.J. contributed equally to this work.
DATA AVAILABILITY
The data that support the findings of this study are available
from the corresponding author upon reasonable request.
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