How to avoid cracks in thin

films during annealing?

There are two sources for film cracks when films are deposited from solution: first, from loss of water
and/or organics that may be in the film, and second from thermal expansion mismatch, so that the
annealed film expands/contracts at a different rate than the substrate. The first effect is minimized by
applying multiple thin films, annealing after each one. The second cannot be avoided entirely but
mostly can be handled if the film is not made too thick. A rule of thumb is that a film cannot be more
than 0.5 microns without having cracking problems unless it is well-matched to the substrate in
terms of CTE.
A mismatch in thermal expansion coefficients of the finally reacted thin film product, and the
substrate used can cause cracks. Moreover the film thickness also can create a problem.
a) Try thinner films - if the problems exists, then
1) Try to compare the thermal expansion coefficients of the film material and substrate.
2) Try to select an appropriate substrate with similar thermal properties.
3) There is problem with glass substrates for temperatures greater than 550 deg. C.
3A) Most soda lime glass substrates have a softening point beyond 550 deg C.
4) See if you can decrease your annealing temperatures, or adopt
5) A two step annealing procedure to get the final reacted product, rather than a slow annealing
process all through to the highest temperature.
5A) React your thin film material at a lower temperature say 350 deg C, for some time, and then
increase the temperature to 550 deg C slowly.
6) Select a proper Corning glass substrate with a close match in thermal expansion coefficients - if
possible.
7) Alternately select the appropriate substrate materials, grow your own tin oxide coatings on it, and
then grow the films to sort out if thermal expansion mismatch is really creating the problem.

ou might try to:

1. reduce the stress of the film on the substrate, as Paul Herrmann already pointed out. In order to
do that, you should change your deposition conditions studying how they affect film stress;
2. deposit your film on a lift-off mask in order to decrease the area of the film on the substrate. For
that you should choose a proper material for the lift-off mask that stands the temperature and can be
easily removed after the annealing.

Carlos! Please describe your paradigm better.

1. What material system? Film & substrate. "titania on conductive glass"
2. Film thicknesses?
3. Polycrystalline? Nano size?
4. Interface strains, lattice mismatch? Thermal conductivity mismatch.
5. Thermal gradients? Heating & cooling rates? "550C for 30 minutes, incrementing the temperature
by 1C per minute"
6. What else? Surface treatments, ambient atmosphere during annealing, etc.
Our suggestions would be more focused & useful then.
cracks in thin films are mostly due to the uneven expansion of substrates. also the temperature
gradient. I too observed the sane in spray deposited SnO2 thin films in FTO coated sodalime glass. I
didn't observe any in quartz substrate.
A simple but illustrative method to SEE the thermal mismatch between film and substrate ist to apply
the film on a very thin (say 0.1mm) substrate. The convex or concave bending shows you if you
have compressive stress (good if moderate) or not (bad!), with elastic constants of the substrate and
its thickness the internal film stresses can be DETERMINED. Carefully prestressed thin substrates
(preferably of circular geometry) can be used to compensate for destructive cracking in thin films.
Especially when the choice of substrate material to match TE is not possible -> some times the only
trick.

Here are some proposals an addition to those mentioned by the colleagues:

A simple and trivial solution may be to make slits in the film to restrict its expatiation length to a value
that can not be cracked by the thermal stresses.If this is not allowed, you have to restrict the
annealing temperature to avoid cracking.That is you can reduce the annealing temperature and
increase the annealing time.
I think that this will work :
You may use local annealing heat source such as LASER. In this cases the length of the hot zone
will be small and the strain will be much less.
"reduce the annealing temperature and increase the annealing time" will always work to reduce
residual stresses in both the film and the substrate simultaneously, as Abdelhalim has suggested.

In addition: the cracks can appear if the film is not uniform,i. e. you have difference in thickness in a
neighbor region, or you have some particles incorporated in the film. More uniform films, thinner
films and film with good elasticity don't crack.
You should cool the samples also slowly as you heate them.
What is the content of your solution for deposition, and what is the thickness of the film?
It is possible that 30 min is not enough time.
The deposition technique can also cause influence of the entity of the film, i.e. cracks.
You can have a look on:
V. Blaskov, I. Ninova (Kuznetsova), L. Znaidi, I. Stambolova, J.P. Michel, S. Vassilev, M.

Beauverger, D. Klissurski, A. Kanaev

"SEM characterization of spin-coated nanocrystalline TiO2 thin film influenced by the presence of
acetyl acetone during the sol-gel preparation in: E. Balabanova, I. Dragieva (Eds.), Nanoscience
and Nanotechnology, Vol. 4, Heron Press, Sofia (2004) 191-193.
I.N. Kuznetsova, V. Blaskov, I. Stambolova, L. Znaidi, A. Kanaev
"TiO2 pure phase brookite with preferred orientation, synthesized as a spin-coated film", Mater. Lett.
59 (2005) 3820-3823,
I. Stambolova, V. Blaskov, I.N. Kuznetsova, N. Kostova, S. Vassilev
Effect of the thermal treatment on the morphology and optical properties of nanosized TiO2 films,
J. Optoelectr. Adv. Mater. 13 (2011) 381-386
L. Znaidi, T. Touam, D. Vrel, I. N. Kuznetsova, A. Fischer, A. Boudrioua
Waveguide properties of nanostructured TiO2 thin films synthesized by sol-gel process AIP
Conference Proceedings, 1400, pp. 268-273, (2011)

I completely agree with Dr. K. Sreenivas this:

"A mismatch in thermal expansion coefficients of the finally reacted thin film product, and the
substrate used can cause cracks. Moreover the film thickness also can create a problem.".
Furthermore, as I know the contact beetwen two medium (the film material and the substrate) is also
a crutial source which produces the thermal stresses hence the cracks of the thin film. So, I suggest:
- Improving the surface roughness of the substrate by carefully physical and chemical treatment,
such as by Flame treatment, followed by UV pre-treatment oven, Reactive-ion etching,...
- Reducing the surface tension: Surface tension is also influenced by organic contaminations due to
the production process (oil, grease or other sliding agents). Dust and other components of ambient
air, even in the electrolytic conductors may deposit onto the surfaces during the electrolytic
deposition. This can be minimised by an appropriate storage or transport.
That's all of my suggestion.
You have to consider so many factors.. Annealing ambient, thermal expansion of substrate and
annealing process. Try to increase the increment temperature... And reduce the annealing
temperature if you want the same substrate.
Hi Carlos, I would suggest at first to have a look at thermal expansion properties of both materials
and if you would see a big difference then I would recommend of using some thin buffer layer that
would reduce the gap between thermal expansion properties of those two materials. Cheers, Andrew
Hi Carlos, thin films are very sensitive to temperature gradient of substrate, method of introduction
and withdrawal temperature. So anneal the electroplated titania on the conductive glass under Argon
for that duration and remove at a room temperature thereafter.

Cracking or delamination?

hi Carlos, what I'm suspecting in your sample thermal stress is generating. so you have to take care
about its different thermal expansion by choosing proper annealing atmosphere. And try to hold little
more time at holding temperature for temperature homogenization.

Why dont you try rapid annealing by microwaves??

Dear Researcher,
I have no detail idea about sol gel method. But I had faced such problem during the initial stage of
my research work. I would like to suggests that two things,
1) Coefficient of thermal expansion
2) Rate of heating and cooling should be gradual.

Try spin-coating. You will get thinner films that won't crack that easily.

I suggest you use a quartz glass substrate to avoid thermal strain.

I would propose to test effect of surface roughness of the substrate in order to get better adhesion of
the deposited film. Of cource, its thiskness should be not too high.
Dear, to prepare the film using a sol-gel method, you need to take in account the thermal expansion
coefficient between the film and substrate( should be small). reduce the film thickness. Also,
reducing the thickness of the film might be effect on the other properties. I mean if you work on the
characterization needs thick film
I agree with Asha. I faced similar cracking issues when depositing mesoporous silica films through
dip coating of a sol precursor solution and more recently with CZTS films. You may try to dilute your
solution and/or optimize film deposition conditions to reduce film thickness.
The issue of tension in films and subsequent cracking prevails if you deposit films at high
temperatures, or perform any post-deposition annealing, due to CTE mismatch.

Common causes of cracking may be

1. Surface roughness of substrates
2. Mismatch in the coefficients of thermal expansion of the film and substrate.
3. Increasing thickness of the film
4. Brittleness of the film produced
5. Temperature at which the film is deposited.
Trying some other method like spin coating may be helpful. From the picture it is not clear whether it
is completely separated or having a wedged shape.

Cracking of the thin film is influence by a number of factors.

As maintained ... the thermal coefficient mismatch ...
Lattice constant mismatch .....
strain development of your film while heating.....
surface finish before your film development .. is also very important
As the surface are very active and try to make bond while come in to the atmosphere...
Before coating, plasma etching makes surface very clean .. and active .... which can make easily
bond between the surface atom and the film .... If the film thickness is less then no doubt the crack
effect will be less

I prepared thin films by other technique and I ve found that substrate with nearly the same thermal
expansion coeffecient with the films reduces the cracks and peeling of the films. so, in my point of
view select a substrate of the same thermal epansion coefficient with your material in general you
may obtain better success
all details of cracs characterizations are found in the paper of study of the substrate types in PbSnTe
thin films
Good luck
Try to clarify the thermal expansion coefficient matching between the substrates and films that you
deposite and control the deposition rate of the film. I once faced the cracking issue in a-Si/a-SiNx
system where the thickness matching may diminish the total tension in the system.
Thin films tend to crack when they are unstable and expands suddenly. Usually a short term heat
treatment at low temperature around 200 degrees to stabilize the film may help.

As many have already stated, the coefficient of thermal expansion (TEC) will play a large role in thin
film cracking. You can determine the strain resulting from a thin film on a substrate if you know the
TEC of the film and substrate materials and the processing and final temperatures (T1 and T2).
Thermal strain = integral from T1-T2 of (TEC of film - TEC of substrate)dT
Cracking in thin films takes place because of high tensile strain within film. this tensile strain arises
mainly because of
1. differences in the thermal expansion coefficient of film material and that of substrate.
2. lattice mismatch of the same
As the thickness of film increases, magnitude of strain is also increases and after a critical thickness
the film tries to relax by cracking (in case of tension). If you keep reducing the thickness of your film,
after certain thickness you will see there is no crack in your film.

I had a similar problem in the past. It is better to start with a low thickness. You can do mulitple
layers ( coat-anneal-cool-coat-anneal...).
If you are annealing your samples make sure that you increase the temperature gradually (510C/min).
After coating each layer blow dry them (helps to reduce the amount of solvent in the film-worked for
me!).
After annealing do not take out your sample from the oven until at least it comes back to 60-70
degrees ( prevents thermal shock).
Dip coating gives higher thickness compared to spin coating. If your sample is small enough you
would try spinning the sol otherwise try a higher dipping rate to have a low thickness (or use a low
viscosity sol)
If you need help you can contact me.

The presence of cracks will also depend on the thickness of the thin films, if you reduce the
thickness the amount of cracks will be lower. So, try to find a good viscosity of the resin and use less
volume to obtain films not so thick and then you will avoid cracks on them. Beyond that, the use of
tributylphosphate as plasticizer may be assisting in the formation of cracks.

Creating thin film is a delicate processes. As we know, inhomogeneous forces at micro, or

nanoscale level can be said as huge. Therefore, any small forces that is formed during handling of
samples, can be a major contribution to thin film cracking. So, my advice is, different scale need
different approach. Thin film more than 100 micron will less affected by small scale forces, but the
thinner is of the materials, the more it approach to atomic level condition, we should considered how
forces will react to the thin film.

There are a lot of parameters which effect the crack formation on the film surface. I will list a few of
them first come to my mind.
. cleaning of the substrate: May be you can not see by eyes but if you have some dust particles on
your substrate surface, they can cause the formation of crack after coating. You have to be sure that
your substrate surface is clean enough before coating.
. heat treatment: If you use a high heating rate during anealing of the fims, it can also result in thin
films with cracks. You can change your heating rate.
. viscosity of your sol: if you have a sol with high viscosity, it means that you will end up with thick
film. When you increase the film thickness, you have more chance to have cracks on your film. So, if
you use spin coating, you can increase the spin speed to get thinner films.

I would suggest you to do drying at around 60-80 C followed by annealing at higher temperatures for
every layer coating (if you are using a spin coater) or after every dip (if you are doing dip coating)
with low heating and cooling rates. The organic particles trapped in subsequent layers often lead to
film cracking during annealing.
Crack formation in your film is obviously due to stress in the film. You have to look for the reasons
behind it. You can try different substrates to confirm that. A careful and selective evaluation of the
peak shift or broadening in XRD peaks can quantify that.

this is what i have done so far...

first: preparation of polypyrrole
second : preparation of sol-gel ( teos:ethanol:HCl) ratio (1:1:4)
third :Ppy and sol gel added together with small amount of plasticizer (tributylphosphate) and {binder
(PEG) under vigorous stirring
lasly: fabricated onto glass slide and let in dry at room temperature.
my film thickness is 0.2 to 0.3 cm
my objective is to make it thin as my thin film as it need to trap in VOCs...where my thin film will act
as VOCs sensor
I think in your case two factors could give such cracks
1) high thermal treatment, which is one step of thin film finishing by sol gel. This temperature should
depend on the properties of the film material
2) high film thickness, some films shows high internal stress could cause such thing especially in
high thickness. If high thickness is important u can grow your film in steps i.e. If your goal to obtain
1um film u can first introduce 100nm as a buffer layer then added thicker layers.
Most probably these cracks are water places due to high annealing process. Can u try to reduce the
water content in the material like working with more dense gel!!! I am very interesting to know about
that just if u can contact me at co3o42000@yahoo.com

Dear Dr. Bavani Kasinathan

Please try next
1- The balance of of the coater during coating process ( it should be no vibrations)
2- This is may be due to high thickness so try different thicnesses
3- If you deal with annealing try first DTA or DSC to determine the suitable annealing temperature
Note: you don't mentioned if this cracks for the as prepared or annealed films and what is the
thickness value.
Best wishes

Cracking could happened when the bond or forces between materials are not homogenous.
Therefore, you need to looks on how to create homogenous forces for your thin film fabrication.
Thermal differences, thickness differences and materials used are some parameters to be
controlled.

As a lot of scientist already mentioned, all could be good way to solve your problem as candidate.
I would like to suggest several ways to solve the problem, which is based on my research
experience.
1) Lattice mismatch between film and substrate
In general, cracking film with no matter what it was synthesized by is caused by mismatching the
lattice between film and substrate you used.
2) Difference of Thermal Expansion
As it was already mentioned by another person, it is very important to affect to make crack which
starts from the surface or inside of sample. Please check it as well.
3) Thermal Shock
When you annealed or baked the sample, the increasing rate of temperature would be affected to
making the crack.
It is also related to difference of thermal expansion as above. Please be careful to make the
increasing rate of temperature slow when you anneal or bake the films.