DCG Recording with Red Light: Discovery of a new Electron Donor system

Jeff Blyth
7 , Bath Street Brighton BN1 3TB (U.K.) T.0273 202069

Abstract
Bright and scatter-free reflection holograms of about 4 cm. diameter
can now be made in DCG using a lOmw HeNe laser and a one minute
exposure. This breakthrough in DCG technology comes from the
discovery of a new electron donor compound (tetramethylguanidine)
used in conjunction with methylene blue. Other dyes will allow much
greater sensitivity to green light than normally exists in DCG. This
can lead to both easier fabrication of HOE'S and full color DCG
holograms. Furthermore, the high alkalinity of the system allows the
unexposed coated material to have an effective lifetime at room
temperature of weeks rather than hours. It has a much lower quantity
of hexavalent chromium than normal unexposed DCG, thus making its
toxicity comparatively much lower.
Introduction
For all practical purposes, pure dichromate and gelatin has no
sensitivity to red light. The fact that the addition of methylene
blue (MB) can give enough sensitivity to make a hologram with red
light, has been known for some years now. (1)(2). To make volume
gratings, it has been found necessary to use exposure levels to
red light which are an order of magnitude higher than those needed
with normal DCG exposed to blue light, (3)(1). To try to improve the
comparatively low sensitivity of MB sensitized DCG so called
"external electron donor compounds were added. (2; (4).
"

Changkakoti et alia ( 4 ) made a detailed study on the addition of

three external electron donors". These were all tertiary amines
with the 3 bonds of the nitrogen atom attached to groups other
than hydrogen. They chose; ethylenediaminetetra-acetic acid (EDTA);
triethanolamine (TEA); N,N-dimethylformamide (DMF). These were added
to MB sensitized DCG. Their results indicated that the advantages of
adding these compounds to MB sensitized dichromated gelatin (MBDCG)
were rather limited. I decided to find more effective compounds among
the huge number of tertiary amines available. There is a substantial
number of papers to be found in the chemistry journals on the
photobleaching of methylene blue by amines. These reactions do not
involve dichromate. Work of Kayser and Young ( 5 ) was a particularly
useful source since they had investigated the reaction time of over
20 amines with photoexcited MB in flash photolysis experiments. These
amines can provide electrons to photoexcited MB via the transitory
formation of a "charge transfer" complex which is thought to be
produced . The MB is thus turned into a colorless form known as
leuco-methylene blue. This is a reactive reducing agent able to
gradually return to the colored form of MB by reacting with oxygen
from the air.

190 / SPIE Vol. 1212 Practical Holography IV (1990)

 Experimental procedure to find the most reactive amines.
To investigate the comparative abilities of various amines to cause
methylene blue to fade under red light illumination, I prepared a
nunber of samples containing equal mass concentrations of MB,
gelatine and amine. To prevent the highly alkaline amines from
hydrolysing the gelatin the pH of the mixtures were kept to about
pH 8 with increments of acetic acid and it was also found necessary
to iise alkali resistant gelatin known as "limed ossein". ( A
photographic grade from Croda Gelatin Ltd, Luton UK.) Each sample
was coated onto a glass sheet and dried in warm air. Samples were
left at an ambient humidity of about 60% in the dark for at
least 30 minutes before exposing. No dichromate salts were involved
in these initial tests. The coatings were then covered by a simple
photographic negative (of some lettering), followed by red filter
material which removed light of a wavelength shorter than 600 nm.
Exposures about 6 inches from a 100 watt bulb were made and the
time taken for the exposed area to bleach as monitored by
transmitted light was compared. The image created by the negative
mask was useful to observe how long the bleached area took to
recover its color at ambient humidity in the dark due to oxygen
absorption.
Results of studies on amines.
The general characteristic of the amine groups that caused the
fastest photobleaching effect on methylene blue was that they
contained a nitrogen atom attached to three alkyl groups. These
groups needed to have an electron donating inductive effect on the
nitrogen atom. Kayser and Young (5) used flash photolysis of
solutions of methylene blue with an amine, whereas I was using
continuous illumination of "dried" gelatin coatings containing the
amine. The comparative ability of amines to photobleach the dye
appeared to be in the same order as those obtained by Kayser and
Young for the limited number of amines I examined. For example, they
found the fastest photobleaching from using 1,4
diazabicyclo[2.2.2.]octane (DABCO). This reacted about 9 times faster
than triethanolamine and about 3 times faster than tri-n-propylamine
on a mole f o r mole basis. Under my conditions I found DABCO reacted 2
times faster than tri-n-propylamine and 6 times faster than
triethanolamine on a gram for gram basis.
I then went on to discover two other amines which each seemed
to react about 30% faster than DABCO. These were :
N,N,N,N- tetramethylethylenediamine (TMED)
1 , 1 , 3 , 3 , tetramethylguanidine ( TMG 1

It is interesting to note here that the disodium salt of EDTA

(ethylenediaminetetra-aceticacid) which was used by Kubota et al.
( 2 ) in their dichromate system, I found to be markedly less
effective at the dye-bleach reaction. (6). However if I used the
free acid EDTA to neutralize the above amines instead of using
acetic acid as described, there was a moderate further increase in
dye-bleaching rate over that obtainable by the amines neutralized by
acetic acid. Hence a significant small contribution to the fading
reaction was coming from the EDTA anion over and above that of the
amine cation. This gave the fastest rate of photo dye-bleaching I
have yet managed to achieve.
SPIE Vol. 1212 Practical HolographylV (1990)/ 191
 The effect of adding dichromate ion to the amine svstems.
Methylene blue forms an insoluble product below pH 8 with
dichromate ions (Graube 1). Accordingly dichromate addition was
carried out on test formulations which had a pH of at least 9. Using
the same experimental conditions as before, it was found that the
addition of as little as 0.02% ammonium dichromate to the gelatin
solution seemed to cause the photobleaching reaction to be arrested
with all amines tested unless the exposure intensity was very high or
the coating was made very dry. This apparent lack of photobleaching
turned out to be deceptive and in reality what was happening was
that the bleached form of MB (leuco MB) was reducing the chromium
compound so quickly that the blue color seemed to remain constant.
Since the exposures were made through a negative mask of some
lettering . It was expected that a relief image of the lettering
might be detectable by treating the exposed sample with cold water
and then partially drying it in an alcohol bath to accentuate the
differential swelling between exposed and unexposed areas. It was
at this stage that a major discovery was made. At an arbitrarily
chosen exposure level , the 3 amines found earlier to react fastest
with MB in the absence of dichromate were now tested with it present
in the formulation. After water swelling and partially drying in
alcohol, no relief image could be detected in the case of either
DABCO or TMED. However in the case of TMG (tetramethylguanidine)
the relief image was so strong that gentle washing under warm water
left only the exposed lettering on the sheet.
More such tests with more amines and higher exposure levels showed
that doubling the first exposure just managed to produce a relief
image when tri-n-propylamine was the amine chosen. DABCO failed to
produce any image until the exposure level was 4 times greater than
the original level which gave a good relief image with TMG. Even at
this level the relief image disintegrated when an attempt was made to
remove unexposed areas with warm water. TMED however, failed to allow
any relief image to be produced. Furthermore if a formulation was
prepared with the amine content shared equally between TMG and TMED,
then this formula also failed to produce any relief image even with
very high exposure levels and hence it could be inferred that TMED
spoiled the good ability of TMG to enable relief images to be made
from photo-crosslinked gelatin.
As expected, it was found that ability to form strong relief images
in red light corresponded with the ability to form high diffraction
holograms with a helium-neon laser at 6 3 3 nm using the single beam
method of Denisyuk. The clarity and brightness of reflection
holograms made using a formulation incorporating TMG was quite
spectacular.
Tentative explanations for the extraordinary results.with TMG.
Why should DABCO and TMED inspite of being two of the most
reactive amines for bleaching photoexcited methylene blue, fail to
produce formulations which would give satisfactory photocrosslinking
of the gelatin in red light in the presence of chromate ions? The
explanation for this is that inspite of its long full name, DABCO
could more simply be called "triethylenediamine". TMED is
tetramethylethylenediamine, and EDTA is ethylenediaminetetra -acetic
acid. (continued)
192 / SPIE Vol. 12 12 Practical Holography IV (1 990)
Hence we have here the same chemical family based on ethylenediamine
and these are exceptionally strong complexing ligands able to form
strong chelate ring structures with chromium due to the double
electron donating action of the two ends of the diamine group.(7)
Thus any chromium 3 + ions produced by the photoreduction of chromate
ions would form stronger complexes with the diamine groups than with
the groups on the gelatin . Thus the gelatin will be ineffectively
crosslinked and hardened. However, EDTA in very limited
concentration, certainly has been shown to aid dye initiated
hologram formation ( 2 ) , ( 4 ) . On the other hand, TMG from structural
considerations (Fig.l), is presumably not a more powerful complexing
agent than gelatin itself and neither also would be TEA or
tri-n-propylamine. It has already been pointed out that TEA has been
found to have comparatively weak ability to produce the
photobleaching reaction. ( 5 ) . Tri-n-propylamine, which is
structurally similar to TEA except for the absence of OH groups on
each of the 3 alkyl groups, works much better than TEA in the
photobleaching reaction. ( 5 ) . This obviously indicates the reduced
inductive effect which the hydroxyl groups cause in the case of
triethanolamine. Furthermore, I found that TEA has the disadvantage
of undergoing a dark reaction (over a 30 minute period) when
dichromate is added even in quite alkaline conditions . ( This is in
agreement with Graube (1) and at variance with statements made by of
Changkakoti et a1.(4).
TMG, apart from not being a complexing agent in the same class as
the ethylenediamines, may have a very important additional property
involved. To find evidence for this, I substituted guanidine
(as carbonate salt) for TMG. This worked surprisingly well at
enabling holograms to be produced at exposure levels between two
and 3 times longer than those used with TMG in the formulation.
This put guanidine in the same class of effectiveness as
tri-n-propylamine but without the malodorous nature of the latter.
The fact that this unsubstituted amine does work that well as an
electron donor is rather unexpected, Primary and secondary amines
are known to be generally rather poor as electron donors (8).
Perhaps it is the "resonating structure" of guanidine which allows
easier electron donation than can occur with other simple amines.
If this is so, then the same resonating structure in TMG must also
be very important.(Fig 1).

F i g . 1. Resonating structures of 1,1,3,3-tetramethylganidine.

SPIE Vol. 12 12 Practical Holography IV (1 990) / 193

 The Lone: Room-temperature Shelf-life of the TMG/DCG SY stem.

Strictly speaking dichromate ions(Crz07 1 in a high pH solution are

converted to chromate ions (CrO4) in an alkaline system, but still in
the same oxidation state as dichromate. Chromate ions are
substantially less reactive than dichromate ions and hence do not
undergo such a rapid dark reaction. In the formulation provided
below, those experienced in the manufacture of DCG holograms may be
surprised by the small concentration of chromate used. However,
unlike the established technology, chromate or dichromate ions are
not used to absorb the light and are only used as crosslinking ions
once they have been reduced by the leuco MB. It has been found that
the photoreduction reaction rate is independent of the concentration
of Cr(V1) ions.(2)
The Yield Point model and "Noise"
It is of course most important that holographic optical elements
should be free of scatter or noise. Using a very simple processing
procedure described at the end of this paper, it is possible to
produce bright holograms free of noise. This noiseless result is
inclined to occur after the coating is over 2 days old. Although this
aging behaviour does not appear to differ from that of ordinary DCGj
an obvious difference follows over the next month when a coating is
not refrigerated. Ordinary unexposed month-old DCG reminds one of the
rubber in a toy balloon in terms of its elasticity and lack of water-
solubility, whereas the TMG/DCG coating is only marginally different
in its ability to form bright holograms from what it was when it was
a week old. Perhaps the dark reaction in TMG/DCG causes the chromium
entity to bind to gelatin in single linkages while still leaving the
option for further bonding to form crosslinkages after the
photobleaching reaction has taken place.
The following simple mechanical model can explain some of the
noise phenomenon, but is a particularly useful concept to optimize
the processing. We are all familiar with what happens when we
increase a load on an extension spring. There comes a'point called
the "yield point" where the load has reached a critical value and
once removed from the spring , the spring does not rec3ver its
original unextended length and remains permanently distorted. Had
the spring originally been stiffer it could have supported that
particular load without permanent distortion. Increasing the
temperature will normally reduce the load the spring can support
without reaching its "yield point". Gelatin coatings in water show
similar behaviour. If a hologram is recorded in freshly coated
gelatin, then even water below 20 C. can force the unexposed regions
to stretch beyond the "yield point" of the material.
Using the onion skin model of Curran and Shankoff ( 6 ) , one might say
that in the finished hologram the layers have buckled when they
should be smooth. The "dark reaction" however, can increase the
spring stiffness overall so that cold water no longer takes the
gelatin beyond its yield point.
The art of producing the brightest reflection or tranmission DCG
holograms without noise, is to process the hologram in water at a
temperature which will swell the material by an amount just less
than that which would stretch it beyond its yield point.

194 / SPIE Vol. 12 12 Practical Holography IV (1990)

 The Importance of PH control
It seems that reducing the pH of gelatin solutions of these amines
with weak acids such as acetic or carbonic, still allows the amines
to act as electron donors when the pH is still above 7. This is
fortunate since an appreciable quantity of the free base would
irreversibly damage the gelatin by hydrolysis. Neutralization of
the amines by strong acids on the other hand would turn the amine
molecules into positive ions and render them ineffective as
electron donors. In the formulation given below, control of the pH
values is essential to obtain bright holograms. A balance has to be
struck between damaging the gelatin at high pH values of 10 or more
and precipitating the dye out of solution in the presence of
dichromate (6) at pH values below 9. It was found that
complications were being produced by the presence of free ammonia
released if ammonium dichromate was used in these alkaline
formulations. The ammonia evaporated from coatings as they dried
and left them too acid and devoid of active dye. Accordingly the
slightly alkaline salt potassium chromate is used instead. The
proportion of hexavalent chromium is very low compared to the usual
DCG formulations and it should be noted that increasing the level
substantially is of no benefit and is generally detrimental.
Full color holofframrecording.
Work is progressing well to obtain this goal. Sensitivity to the
514nm line of an argon ion laser by the choice of suitable dyes in
addition to methylene blue has been found to be many times greater
than is the case with normal DCG recording. One such dye being
riboflavin. Panchromatic recording in DCG will be the subject of a
later paper.
Patent applications for the use of guanidine compounds in hologram
recording systems have been filed in the author’s name.

FORMULATION AND PROCESSING DETAILS

The following instructions will produce approximately lOOcc of
material. Note: The toxicity of the formulation below is much LESS
than that of normal DCG formulations because of the very low
hexavalent chromium content.
Preparation of stock solution of 25% v/v TMG
l11,3,3-tetramethylguanidine:50 cc.
Deionized water: add until total volume reaches 200 CC.

Preparation of stock solution of TMG acetate.

25% stock solution of 1,1,3,3-tetramethylguanidine: 80 cc.
Glacial acetic acid 8 cc. (approx).
This quantity should be added very slowly while stirring and
adjusted if necessary to give pH of roughly 7 . (Note: although pure
TMG is a caustic volatile liquid which should be handled with care,
the neutralized material is innocuous with a low odour level.)
SPIE Vol. 12 I2 Practical Holography IV ( I 990) / I95
 Preparation of stock solution of 5% w/v Dotassium chromate
Potassium chromate (K2 Cr04 ) : 5.0 gram
made up to 100 cc. with deionized water. (Potassium dichromate could be
substituted here but NOT ammonium dichromate.)

Preparation of stock 0.4% methylene blue solution

Methylene blue : 1.0 g .
Deionized water: 250 cc.
Any undissolved impurity can be filtered out.
Preparation of coatinn solution.
Deionized water (cold) 80 cc.
Gelatin 12 g.
The gelatin grade needs to have a low "Iso-electric point" of about 4 to
5. Photographic grade "limed ossein" from Croda Gelatin Ltd, Luton, UK.
(Te1.0582 31151). gives excellent results.
Place container in a water-bath and heat up contents to between 45 and
50 C. while mechanically stirring slowly. This may require 20 minutes or
more. Check that no undissolved gelatin particles remain.
Maintaining the tempsrature between 40 and 44C, continue as follows:
Stock 5% potassium chromate solution : 1.0 cc.
Stock solution TMG acetate : 16 cc. **
**(Note that as this quantity is increased the light sensitivity is
increased. The "trade-off" is however that in Denisyuk holograms made
with HeNe laser light at an ambient relative humidity of 6 0 % , the replay
color shifts can shift towards the blue and the surface becomes rather
tacky because TMG is hygroscopic.

pH ad.iustment step.

From this point on, before adding the methylene blue, it is VERY
IMPORTANT to maintain the pH between 9.0 and 9.4. The adjustment 1,s
carried out by very carefully adding stock 25% TMG solution dropwise
while the solution is well stirred. If the pH rises above 9.5 it should
be brought back at once by a drop of acetic acid. It is not possible to
give a precise value of the quantities of either of these reagents at
this point because it will depend on the batch of gelatin being used.

Finally, under green or dim yellow safe-light which can

conveniently be much brighter than for silver halide work.
6 cc.* stock methylene blue solution.
* This quantity is for a coating thickness of about 5 microns. Coatings
which are substantially thicker may need less dye to prevent too much
light absorption in single beam mode.

196 / SPIE Vol. 12 12 Practical Holography I V (1 990)

 Storage
The mixture has an effective live time at 20C of well over a month,
although it is best to store it in a cool place. It should not be frozen.

Very simple trial COatinP method. "Veil Coating"

Under green safelighting (brighter than would have to be used for

silver halide holographic recording).
1) Warm the solution to between 40 and 45 C. in a beaker with a spout.
Do not overheat.
2) Hold a clean and warm glass plate upright at an angle of about 80
degrees with its base resting in a flat and clean tray which is as
small as the glass edge will allow. (In the case of a 4" x 5" plate it
is easier to put the 4 inch side along the vertical
and to leave about 1 cm. uncoated along each 4" side.)
3 ) Position the spout of beaker at a point about 1 cm. from the top
of the glass and 1 cm from the edge closest to you .
4) Start to pour out the solution and at the same time move your arm
slowly parallel with the top of the glass plate.
The liquid should fall like an evenly spread veil on that side of
the glass.
5) keep the plate upright and allow the bottom edge to drain for a
minute. (The balance between gravitational and surface tension
forces can give a surprisingly even coating.)
6) After the coating has gelled, the thick layer at the bottom edge
of plate can be either wiped off or removed by dipping the bottom
edge in warm water. Pour the tray contents back into the beaker.
The coating is now best left to dry for at least 24 hours in a
darkened room. It may be possible to coat over twenty
5 x 4" plates with 100 cc. of material.

Ex~osing
Do not expose a coating before it is 24 hours old. (Coatings a week old
may be at their best.)
To make a bright Denisyuk hologram on a 5 x 4 plate may need about 3 or
4 minutes exposure to a 25 mw. HeNe. of object. Firstly, a
trial-and-error test on exposure levels is essential. The first trial
should preferably contain a range of exposure levels on one plate. Note
that doubling the beam diameter may increase the exposure time needed by
a factor of 4.

SPIE Vol. 1212 Practical Holography IV f1990) / 197

 Processing.
It is helpful to keep in mind the "yield point" model already described
in the text. The art of making the most noise-free and yet bright DCG
holograms, is to take the gelatin as close as possible to its yield
point without exceeding it. Stretching gelatin beyond its yield point
creates noise in the finished hologram although it can also give
extremely bright replay in white light because it becomes much more
broadband. Using the onion layer analogy of Curran and Shankoff ( 2 1 , the
holographic fringe layers might resemble dried out onion with
crinkled-up layers if the yield point is exceeded.
SimPle Processing Method
(It is strongly recommended that this simple method is tried before
other methods you may know of.)
No meaningful tests should be carried out until the coating is at
least 2 4 hours old.
The first trial hologram is best processed so that the yield point of
the gelatin is just exceeded, and some noise or scatter is generated
deliberately in the finished hologram. This is necessary to be sure
that any lack of hologram after processing, is not due to insufficient
swelling in the first water bath and therefore must be due to
insufficient exposure or relative movement between object and
holographic plate. Once one has establised the necessary exposure level
then one can produce holograms devoid of any noise by processing at a
level which takes the gelatin just below its yield point.
After exposure, the sample may benefit from being left for a few minutes
before processing.
1) The sample is first swollen in water at a temperature of 26 deg.C
for about 1 minute with gentle agitation.
2.) Shake off excess water droplets and plunge plate into cold
iso-propyl alcohol. Agitate vigorously for at least 1 minute. (The
water content of this bath can be allowed to be anything from zero
to 10%.)
3.) Put plate into another iso-propyl alcohol bath but this
time insure that its water content is less than 1%. .Agitate for
2 minutes at least. (Insufficiently dry alcohol in this bath will
result in drying marks marks which replay in the blue.)
4 . ) Blow alcohol off the plate with a strong blast of tepid air. Do not
allow very hot air onto the plate at this stage.
Prolonged inhalation of the alcohol vapour is harmful and hence the
drying process should be carried out with air extraction. The alcohol
baths should also be covered. Remember also that the alcohol rapidly
absorbs moisture from the air.
No image may be visible until all the alcohol has escaped from
within the fringes; a process helped by leaving the sample in a warm,
dry place.

198 / SPIE Vol. 1212 Practical Holography IV (1990)

 If the finished result is completely clear and shows neither scatter
nor hologram, then the chances are that the fringe voids or cracks
have not formed properly in the alcohol bath by the "Shankoff effect"
and the hologram simply needs reprocessing using water at a higher
temperature in the first bath. If the hologram is noisy or "milky"
then that means that the gelatin has had its yield point exceeded and
nothing can be done about this noise except to shoot another plate
and process it in water at say 18 deg.C so that the yield point is
not exceeded. Plates which are a month old and have been left at room
temperature, may need a water temperature of about 35 deg. C.
Getting the water temperature just right, can produce the most
noiseless and bright single-beam holograms.
Note that since TMG is hygroscopic it is important that the finished
hologram no longer contains any of this material or it will attract
moisture into the hologram. Hence the importance of not reusing the
same water bath and keeping the final alcohol bath fresh.(TMG is
soluble in alcohol). One should seal holograms if they are going to
be carried around. Otherwise a cold hologram brought into a warm
room can create surface moisture and cause the notorious
disappearing trick of DCG holograms. (They can be reprocessed in
water and alcohol if that happens.) Note that sprays should not be
generally used as sealants sincesthey can penetrate into the
fringes. Viscous UV curing resin and a glass backing sheet seems to
work well.
The author has made patent applications on the use of guanidine
derivatives as electron donors in dye-sensitised recording in DCG.
Acknowledgement. I am very grateful for the help of George Clare who
has made many independent tests of formulations.
REFERENCES
I . A. Sraube, 'Holograms Recorded in Red l i g h t in Dye Sensitiied Dichromated g e l a t i n 4 Opt. Coemun, 8, 251 11973)

2. T.k'ubota ! T.Ose, tl,Sasaki, and K. Honda! "Haloyran Formation Hith Red Liyht i n liethylene Blue sensitized
Uichrosated Gelatin." Appl.Dptics 15, 556 (197bi

2. R.Changkakoti, S.V. Pappu "Towards optifium d i f f r a c t i o n efficiency for methylene blue s e n s i t i i e d dichromated
g e i a i i h Iiolograc5' Optics k Laser Technology Vol. 21 No,4 (14693,

4. R. Changkakuti., S.S.C.Babu, and S,V,Pappu, "Role of External Electron Donor i n #ethylene Blue Sensitized
Dichrocated Gelatin Holograms' Appl. Optics 27, 324 11988)

5. R.Kayser and R.Young "The Photoreduction of Hethylene Blue by Amines" Photochem.Photobio1. 24, 395 11776)

6. G,Oster and N.#otherspoon, 'Photoreduction o i Methylene Blue by Ethylenediaminetetraacetic a c i d n J.An.Cher.5~~. 79,

4636 (1957)

7. F.Cotton and 6. Nilkinson, "Advanced Inorganic Chemistryn 4 t h edition John Wiley f Sons, p.71 (1980).

e. H.Obata, E.Eoyasaka and H. Ectizuai, 'Photochemical Reactions between Hethylene Blue and Tri, Di and Hono
Methylamines' Bull, Chera Sac, Japan 30, 135 (17573

10, R.Curran and T. Shankoff, 'The Hechanise o f Hologram Formation in Dichroaated Gelatin' Lppl.Opt. 7, 1651 11970)

SPlE Vol. 12 12 Practical Holography IV (7 990)/ 199