Improving the holographic sensitivity of

dichromated gelatin in the blue–green part of the

spectrum by sensitization with xanthene dyes

Dejan Pantelić and Branka Murić

The holographic properties of dichromated gelatin 共DCG兲 sensitized with various xanthene dyes were
studied, and results are reported. The sensitivity of dyed DCG in the green part of the spectrum
compared with that of pure DCG 共215 mJ兾cm2兲 was significantly improved by addition of Rhodamine 6G
共140 mJ兾cm2兲 or Erythrosin B 共90 mJ兾cm2兲. Diffraction gratings were recorded with a He–Ne laser at
543.5 nm. The maximum diffraction efficiency was found to be 32% at normal incidence of the readout
beam; it was 80% at the Bragg angle. © 2001 Optical Society of America
OCIS codes: 090.2900, 050.1950.

1. Introduction holographic silver halide emulsions.8 Therefore re-

Gelatin sensitized with ammonium dichromate
关dichromated gelatin 共DCG兲兴 is one of the best holo-
graphic recording materials because of its well-
known properties: high diffraction efficiency, large
capacity for refractive-index modulation, high reso-
lution 共as much as 5000 lines兾mm兲, high signal-to-
noise ratio, and good environmental stability 共with a
cover plate or a thin protective coating兲.1,2 A major
shortcoming of DCG is that its spectral sensitivity is
limited to the UV兾blue– green part of the spectrum.1,3
The majority of reported papers concentrate on in-
creasing the spectral sensitivity of DCG to the red
part of spectrum by addition of appropriate dyes 共for
example, Methylene Blue4兲 to the DCG solution 共a
sensitivity of 150 – 400 mJ兾cm2 at 632.8 nm was re-
ported兲.5 Only a few papers have been concerned
with the increase of sensitivity in the green part of
the spectrum.6,7
Although the sensitivity in the blue– green part of
the spectrum is much higher than that in the red
part, it is still low compared with that of materials
such as silver halogenide. That is, DCG is approxi-
mately 102–105 times slower photographically than
D. Pantelić 共e-mail: pantelic@phy.bg.ac.yu兲 and B. Murić 共e-mail:
muric@phy.bg.ac.yu兲 are with the Institute of Physics, Pregrevica,
118, 11080 Zemun, Belgrade, Yugoslavia.
Received 26 October 2000; revised manuscript received 26 Feb-
ruary 2001.
0003-6935兾01兾172871-05$15.00兾0
© 2001 Optical Society of America
cording a hologram requires a powerful and expen-
sive laser such as Ar-ion or He–Cd and large exposure
times.
It was our intention to improve the sensitivity of
DCG in the green part of the spectrum by adding a
dye such that a cheaper and simpler green He–Ne
laser could be used. In this paper we present results
of using various xanthene dyes 共Rhodamine 6G and
Erythrosin B兲 and describe their influence on the
holographic properties of DCG.
2. Experiment
Chemically, gelatin is a polymer, which is composed
of a number of ␣-amino acids and has a complex
molecular structure. The molecular weight of gela-
tin ranges from 768 to 96,000, with an average value
of approximately 27,000.9 DCG possesses good holo-
graphic characteristics. The mechanism of holo-
gram formation in DCG has been described in the
literature.1,10,11
In our experiments, a 2–20% by weight aqueous
gelatin suspension was prepared by the procedure
outlined in Table 1. Various concentrations 共from 5
to 50% by weight of dry gelatin兲 of ammonium dichro-
mate were tested. The DCG film was prepared by
the gravity settling method12; nonphotographic qual-
ity gelatin 共manufacturer trademark Gelatin-ALBA-
Ph. Jug IV兲 was used. A DCG solution of constant
volume was poured onto a precisely leveled and well-
cleaned microscope glass substrate. Thus we were
able to make DCG films with thicknesses that varied
from 15 to 60 ␮m 共thickness of dried films兲.

10 June 2001 兾 Vol. 40, No. 17 兾 APPLIED OPTICS 2871

 Table 1. Procedure for Preparing Dyed DCG Film
Step Description
1. Swell gelatin in deionized water for 60 min.
2. Heat the suspension in a thermostated water
bath at 50 °C, stirring for 10 min.
3. Add an adequate amount 共see text兲 of ammonium
dichromate, by weight of dry gelatin, and heat
in a thermostated water bath at 50 °C, stirring
for 10 min.
4. Add an appropriate amount of xanthene dye 共see
Fig. 3 below for the optimum value兲 to the
DCG solution.
5. Pipette out a known volume of dyed DCG solu-
tion onto a leveled glass microscope plate.
6. Dry the plate overnight.
The DCG plates were dried in the dark, for 24 h, in
relatively stable environmental conditions 共the tem-
perature fluctuated in the 25–27 °C range, and the
relative humidity was 50 – 60%兲. The best results
were obtained with a film made from a 5% aqueous
solution of gelatin, with 10% ammonium dichromate
共by weight of dry gelatin兲 and a thickness of 30 ␮m.
One of the dyes used for DCG sensitization was
Rhodamine 6G, which belongs to the group of xan-
thene dyes 共absorption range, 500 –700 nm兲.13,14
The addition of the dye can be accomplished in any of
a number of ways.15 In our case, various quantities
of a 0.1% aqueous solution of Rhodamine 6G were
introduced into a DCG solution. We found that the
best results were obtained with a dye concentration of
7.5 mg兾l of DCG solution.
Using the same experimental conditions 共thickness
of the DCG film, dichromate and dye concentrations
unchanged兲, we investigated the influence of
Erythrosin B 共another xanthene dye兲 on the holo-
graphic properties of DCG.
The absorption spectra of pure DCG and dyed DCG
films 共Fig. 1兲 were measured with a UV–visible spec-
trophotometer. The three spectra have approxi-
mately the same shape. As expected, at 543.5 nm
the absorption values of dyed DCG films increased
significantly compared with those of pure DCG film.
Transmission diffraction gratings, as the simplest
Fig. 1. Absorption spectra of pure DCG film and dyed DCG films.
2872 APPLIED OPTICS 兾 Vol. 40, No. 17 兾 10 June 2001
Table 2. Procedure for Developing a Dyed DCG Platea
Step Description
1. Wash in water for 5 min.
2. Dehydrate in a 50:50% isopropyl alcohol and water
solution, stirring for 3 min.
3. Dehydrate in a 70:30% isopropyl alcohol and water
solution, stirring for 3 min.
4. Dehydrate in 100% isopropyl alcohol for 1.5 min.
5. Dry plate with flowing hot air for 5 min and then
in a chamber containing a desiccant.
a
Deionized water was used. All steps were at a temperature of
25 °C.
type of hologram, were recorded by interference of
two expanded divergent laser beams that had equal
intensities and optical path lengths. A green He–Ne
laser operating at ␭ ⫽ 543.5 nm 共with an output
power of 1 mW兲 was used as a light source. The total
energy density of the recording light beams was 0.3
mJ兾cm2. The angle between beams was approxi-
mately 35° and, consequently, the spatial frequency
of the transmission gratings was ⬃1000 lines兾mm.
The hologram area was 0.8 cm2. A readout beam at
632.8 nm was used to measure the diffraction effi-
ciency.
During development, an exposed plate was washed
immediately in deionized water and dehydrated in
several baths of isopropyl alcohol with increasing
concentrations 共see Table 2兲.
Also, we measured the diffraction efficiency in real
time as a function of exposure. A schematic dia-
gram of the real-time holographic setup is shown in
Fig. 2. As can be seen, the measurements were not
performed at the Bragg angle. Instead, reconstruc-
tion was done at normal incidence of a 632.8-nm
beam. We found that this configuration is easier to
position accurately and gives better reproducible re-
sults 共a slight deviation from the Bragg angle signif-
icantly influenced our measurements兲.
Fig. 2. Real-time holographic experimental setup: B.S., beam
splitter; MS, mirrors; Ls, lenses.
Fig. 3. Relation of diffraction efficiency to concentration of Rho-
damine 6G for a 30-␮m-thick film with a constant exposure density
of 140 mJ兾cm2. Fig. 4. Relation of diffraction efficiency to exposure for a 30-␮m-
thick film with a constant concentration of Rhodamine 6G of 7.5
mg兾L.
3. Results and Discussion
Diffraction efficiency, as one of the most important holo-
The increase in holographic sensitivity depends
graphic parameters for judging the performance of DCG
only on properties of the chemical composition and
holograms, has been measured. Diffraction efficiency is
processing of DCG films. Although previous mea-
defined as the ratio between the intensities of the first-
surements were made at normal incidence, it is im-
order diffracted light and the incident light.16
portant to determine the maximum diffraction
Our measurements were made at normal incidence
efficiency at the Bragg angle. We did that for the
of the laser beam, both in real time and after devel-
most favorable circumstances for chemical process-
opment. Again, we found this configuration favor-
ing, as previously established 共at normal incidence兲.
able with respect to ease of positioning and
We found a maximum of 80% diffraction efficiency.
reproducibility. Besides, the purpose of our mea-
We found it hard to determine exactly whether our
surements was to determine holographic sensitivity gratings are of a thin, a thick, or an intermediate
of DCG 共DCG ⫹ sensitizer兲, which depends on chem- type.17,18 Because such a determination is not
ical composition and processing and not on the angle within the scope of our research, we give here only a
of the readout beam. For the sake of completeness, brief and incomplete analysis.
we include here our measurement of the maximum Strictly speaking, one can determine the type of
diffraction efficiency that can be obtained with our grating by calculating the so-called Q⬘ and ␥ factors
technique at the Bragg angle 共at wavelengths of both defined in Refs. 19 and 20. Along with other param-
543.5 and 632.8 nm兲. eters 共DCG emulsion thickness, wavelength, grating
The dependence of diffraction efficiency on the con- period, angle of incidence of the readout beam兲, Q⬘
centration of Rhodamine 6G is shown in Fig. 3. As depends on the refractive index of gelatin, which we
the concentration of Rhodamine 6G increases, the did not measure. Therefore we were able only to
diffraction efficiency increases; it reaches a maximum estimate that the parameter value is 77 by assuming
when the dye concentration is 7.5 mg兾l. After the that the refractive index of gelatin is 1.55.21 Like-
maximum concentration is attained, the diffraction wise, the ␥ factor depends on film thickness, wave-
efficiency decreases because Rhodamine 6G precipi- length, angle of incidence, and amplitude of the
tates at higher concentrations in the presence of the
dichromate ion.
The dependence of diffraction efficiency on expo-
sure for pure DCG and for DCG with Rhodamine 6G
is shown in Fig. 4. It is obvious that holographic
sensitivity increases in the presence of Rhodamine
6G. The maximum diffraction efficiency was found
to be 32% for both DCG and DCG with Rhodamine
6G, but the energy densities required for maximum
efficiency were 215 and 140 mJ兾cm2, respectively.
An increase in sensitivity was also observed after
we added Erythrosin B to the DCG solution 共Fig. 5兲.
We can see that the maximum value of the diffraction
efficiency for DCG sensitized with Erythrosin B was
32%, too. Moreover, in the presence of Erythrosin B,
maximum efficiency was obtained at an energy den- Fig. 5. Relation of diffraction efficiency to exposure for a 30-␮m-
sity of 90 mJ兾cm2, which is less than for both DCG thick film with a constant concentration of Erythrosin B of 7.5
sensitized with Rhodamine 6G and pure DCG. mg兾l.

10 June 2001 兾 Vol. 40, No. 17 兾 APPLIED OPTICS 2873

 Fig. 7. Sensitivity 共filled squares, reported values24 –26; open
square, circle, and triangle, our results兲 of DCG as a function of
wavelength.

100% because of scattering, absorption, and Fresnel

losses.
We measured diffraction efficiency at 543.5 nm and
found only slight differences from that at 632.8 nm
共apart from a change of Bragg angle兲.
It is well known that pure DCG is sensitive to
UV兾blue– green light and that this sensitivity is
greater at shorter wavelengths 共the sensitivity ratio
at 488 and 514.5 nm is approximately 5:1兲.16,24 To our
knowledge, sensitivity measurements at 543.5 nm
Fig. 6. Energy distribution among various diffraction orders at were not performed, so we measured this value and
normal incidence and at the Bragg angle. Distribution was mea- found it to be 215 mJ兾cm2.
sured on the same DCG film, optimally exposed and processed. We wanted to correlate our results with the pre-
viously published measurements of DCG sensi-
tivity.24 –26 Therefore in Fig. 7 we illustrate the
refractive-index modulation. The last parameter
sensitivity of DCG 共defined as the energy density
was not measured; instead we took the value ⌬n ⫽
required for the maximum diffraction efficiency兲 as
0.00135 from Ref. 21 and found that ␥ ⫽ 0.2.
a function of wavelength. It is obvious that sensi-
Because of the unpredictable properties of gelatin
tization of DCG results in significant improvement
and of processing peculiarities, ⌬n can have various
of sensitivity at 543.5 nm.
values.22,23 That is, the refractive index of DCG and
We also found that the sensitivity of DCG at 543.5
its variation depend on many parameters, such as
nm 共He–Ne laser兲 in the presence of xanthene dyes—
humidity, temperature, concentration of ammonim
Rhodamine 6G and Erythrosin B—is approximately
dichromate, polarization, birefringence of gelatin,
the same as the sensitivity of pure DCG at 514.5 nm
nonuniformity, and exposure level. Therefore the
共Ar-ion laser兲.
values that we obtained should be taken with a de-
In Fig. 8, we show the real-time diffraction effi-
gree of caution.
At any rate, if the Q⬘ and ␥ values are correct,
according to Ref. 19 our gratings will be on the border
between the Bragg and the Raman–Nath regimes.
To support this conclusion we illustrate the distribu-
tion of energy among various diffraction orders at
normal incidence and at the Bragg angle 共Fig. 6兲. As
can be seen, there is a significant amount of energy
distributed outside 0th and ⫺1st orders at the Bragg
angle. This means that the grating is not purely
Bragg. Also, the grating is not Raman–Nath be-
cause the 0th order should have a higher intensity
than other orders 共for ␥ ⫽ 0.2, as in our case兲. Ad-
ditionally, the diffraction efficiency should not de-
pend significantly on the angle of incidence in an
angular range of ⫾20° 共whereas in our case the dif-
fraction efficiency was 32% at normal incidence,
reaching a maximum of 80% at an angle of ⬃10°兲.
The total diffracted energy 共all orders兲 does not add to Fig. 8. Real-time diffraction efficiency as a function of exposure.

2874 APPLIED OPTICS 兾 Vol. 40, No. 17 兾 10 June 2001

ciency as a function of exposure for pure DCG and for
dyed DCG. The real-time effects confirm the im-
provement in sensitivity of dyed DCG films. Also,
we can see that presence of Rhodamine 6G or
Erythrosin B in DCG, besides increasing the sensi-
tivity of DCG, enhances the real-time diffraction ef-
ficiency. Maxima of 0.004% for pure DCG, 0.008%
for DCG with Erythrosin B, and 0.012% for DCG with
Rhodamine 6G were obtained.
4. Conclusions
The aim of our research was to improve the holo-
graphic sensitivity of DCG in the green part of the
spectrum by sensitization with various xanthene
dyes. Although we used a rather simple method for
preparation and development of pure DCG, our re-
sults are in good agreement with those of previous
research. The sensitivity of DCG was significantly
improved by addition of Rhodamine 6G and
Erythrosin B. The improvement in the sensitivity of
dyed DCG was confirmed by real-time measure-
ments.
The photochemical reaction processes of DCG sen-
sitized with xanthene dyes are complex and not yet
clear. Therefore additional research should be done
in order to elucidate the chemical mechanisms in
more detail.
References
1. B. J. Chang and C. D. Leonard, “Dichromated gelatin for the
fabrication of holographic optical elements,” Appl. Opt. 18,
2407–2417 共1979兲.
2. C. G. Stojanoff, O. Brasseur, S. Tropartz, and H. Schuette,
“Conceptual design and practical implementation of dichro-
mated gelatin films as an optimal holographic recording ma-
terial for large-format holograms,” in Photopolymers and
Applications in Holography: Optical Data Storage, Optical
Sensors, and Interconnects, R. A. Lessard, ed., Proc. SPIE
2042, 301–311 共1993兲.
3. T. Mizuno, T. Goto, M. Goto, K. Matsui, and T. Kubota, “Meth-
ylene Blue sensitized dichromated gelatin holograms: influ-
ence of the moisture on their exposure and diffraction
efficiency,” Appl. Opt. 29, 4757– 4760 共1990兲.
4. M. Sun, J. Wang, J. Zhao, and M. Li, “Methylene-Blue-
sensitized gelatin holograms,” Appl. Opt. 35, 5776 –5779
共1996兲.
5. T. Kubota and T. Ose, “Methods of increasing the sensitivity of
Methylene Blue sensitized dichromated gelatin,” Appl. Opt.
18, 2538 –2539 共1979兲.
6. R. A. Myers, T. L. Helg, T. H. Barnes, A. D. Woolhouse, and
T. G. Haskell, “Characterization of dye-doped media for real-
time holography,” Opt. Commun. 137, 223–228 共1997兲.
7. G. Manivannan, R. Changkakoti, R. A. Lessard, G. Maihot,
and M. Bolte, “Dichromated poly共vinyl alchohol兲–xanthene dye
systems: holographic characterization and electron spin res-
onance spectroscopic study,” in Photopolymers and Applica-
tions in Holography, Optical Data Storage, Optical Sensors,
and Interconnects, R. A. Lessard, ed., Proc. SPIE 2042, 87–97
共1993兲.
8. K. S. Pennington and J. S. Harper, “New phototechnology for
recording phase holograms and similar information in hard-
ened gelatin,” Appl. Phys. Lett. 18, 80 – 84 共1971兲.
9. L. Stroebel, J. Compton, I. Current, and R. Zaria, Photographic
Materials and Processes 共Focal, Boston, Mass., 1985兲.
10. S. Sjöllender, “Dichromated gelatin and light sensitivity,” J.
Imaging Sci. 30, 151–154 共1986兲.
11. C. Lafond, C. Pizzocaro, R. A. Lessard, and M. Bolte, “Primary
photochemical process in films of dichromated gelatin: a
quantitative approach,” Opt. Eng. 39, 610 – 615 共2000兲.
12. T. Keinonen, P. Riihola, K. Huttu, and S. Parkkonen, “Dye
films for optical demonstrations in the undergraduate labora-
tory,” Opt. Mater. 11, 79 – 86 共1998兲.
13. M. Maeda, Laser Dyes 共Academic, London, 1984兲, p. 22.
14. K. P. B. Moosad, T. M. A. Rasheed, and V. P. N. Nampoori,
“Optical phase conjugation in dyes embedded in polymer
films,” Opt. Eng. 29, 47–51 共1990兲.
15. A. Graube and C. Park, “Dye sensitized dichromated gelatin
holographic materials,” U.S. patent 3,963,490 共15 June 1976兲.
16. R. J. Collier, C. B. Burchhart, and L. H. Lin, Optical Hologra-
phy 共Academic, New York, 1971兲, p. 295.
17. R. R. A. Syms, Practical Volume Holography 共Clarendon, Ox-
ford, 1990兲, p. 49.
18. R. Magnusson and T. K. Gaylord, “Diffraction regimes of trans-
mission gratings,” J. Opt. Soc. Am. 68, 809 – 814 共1978兲.
19. M. G. Moharam, T. K. Gaylord, and R. Magnusson, “Criteria
for Raman–Nath regime diffraction by phase gratings,” Opt.
Commun. 32, 19 –23 共1980兲.
20. M. G. Moharam, T. K. Gaylord, and R. Magnusson, “Criteria
for Bragg regime diffraction by phase gratings,” Opt. Commun.
32, 14 –18 共1980兲.
21. T. A. Shankoff, “Phase holograms in dichromated gelatin,”
Appl. Opt. 7, 2101–2105 共1968兲.
22. G. Campbell, T. J. Kim, and R. K. Kostok, “Comparison of
methods for determining the bias index of a dichromated gel-
atin hologram,” Appl. Opt. 34, 2548 –2555 共1995兲.
23. V. M. Rzhevski and N. G. Rupchev, “Influence of photochem-
istry processes on the refractive index and thickness on layers
of dichromated gelatin,” Opt. Spectrosc. USSR 68, 1378 –1380
共1980兲, in Russian.
24. L. H. Lin, “Hologram formation in hardened dichromated gel-
atin films,” Appl. Opt. 8, 963–966 共1969兲.
25. K. Kurokawa, S. Koike, S. Samba, T. Mizuno, and T. Kubota,
“Simplified method for preparing Methylene-Blue-sensitized
dichromated gelatin,” Appl. Opt. 37, 3038 –3043 共1998兲.
26. V. A. Baracevski, New Recording Materials for Holography
共Nauka, Leningrad, 1983兲, in Russian, p. 22.
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