Spin-coating technique

Spin-coating is a very convenient technique widely applied to thin film deposition. It

can be considered as a special case of solution crystal growth, which allows the formation
of highly oriented layered perovskites on a substrate, while the solvent is evaporating off.
Spin-coating enables deposition of hybrid perovskites on various substrates, including
glass, quartz, plastic, sapphire, and silicon. The relevant parameters for this technique
include the choice of the substrate, the solvent, the concentration of the hybrid in the
solvent, the substrate temperature, and the spin speed. In some cases, pretreating the
substrate surface with an appropriate adhesion promoter improves the wetting properties
of the solution on the desired substrate. In addition, postdeposition low-temperature annealing
(T < 250oC) of the hybrid films is sometimes employed to improve crystallinity
and phase purity. Mitzi et al. (2001b) Comparing with the traditional deposition technique
for inorganic semiconductors, spin-coating method doesn’t require cumbersome
equipments while it gives high-quality films in quite short time (several minutes) in
room environment. Therefore, in our study, we will adopt this method for all film sample
depositions
a) Deposition and optimization
Spin-coating
We have explained the synthesis and preparation of perovskites molecules in Paragraph
2.2.1. From the perovskites solution, 2D crystals can be obtained by evaporation
of solvent. Our thin films samples are realized by spin-coating, by which the perovskites
form 2D crystals by self-organization process. The spin-coating method is a technique
used to apply uniform thin films to flat substrates. As it is shown in Figure 2.19, an
amount of solution is dropped on the substrate which is fixed on the spin-coator, and
then it is rotated at high speed in order to spread the fluid by centrifugal force.

The process of spin-coating is difficult to be modeled in theory. To estimate the

thickness h of a film, an empirical formula can be used: Meyerhofer (1978); Norrman
et al. (2005); Krebs (2009

where ! and t are the spin speed and spin duration, respectively. C is an experimentally
determined constant, which depends on the evaporation rate, viscosity and density of
the solution. x is also an experimentally determined parameter, which is related to the
evaporation rate of the solution. x _ 1
2 for most solvents. x _ 2
3 when the evaporation
rate is independent of !, and x _ 1 for slow evaporation solvent.
The solvent containing R-NH2HX and MX2 is first spin-coated on the substrate.
2D layered perovskites crystals are then obtained upon solvent evaporation. In the
absorption spectra of 2D layered perovskites crystals, a sharp peak appears at room
temperature, which is characteristic of the formation of 2D layered perovskites crystal
structure (see Figure 2.6).
Actually, in order to realize a layer with the desired thickness, we modify the concentration
of perovskites solution keeping the other spin-coating parameters (spin speed,
acceleration and spin duration) fixed. Generally, homogeneous 2D layered perovskites
films with a thickness from 10 nm to 100 nm can be obtained by carefully selecting
the parameters: less concentrated solutions give thinner layers. For example we prepare
some PEPI thin films from their 10%, 3% and 1% in DMF solution. The parameters of
spin-coating are 2500 rpm, 2500 rpms for 30 s (the annealing conditions are 95_C for 1
min, see next paragraph). Their thicknesses measured by AFM are respectively: 36.5
nm, 25.3 nm and 6.21 nm. With the help of a profilemeter or an AFM to estimate the
layer thickness, we can draw a calibration curve (thickness as a function of concentration)
and adjust the concentration of solution in order to produce the desired thickness.
The spin-coated 2D layered perovskites films are very reproducible, and therefore they
are appropriate to be deposited on devices, for instance perovskites based microcavities.
Lanty et al. (2008a)