Kink Blocking

Sambita Choudhury
Muhammad Osman Khalid

1
 Cr ys tal g r o w th mo d if ie rs: S te p p in ning

2 Chakrabarti et al. Cryst. Growth Des. 2021

 K in k b lo c king

• Impurities block the solute particles from entering the

crustal surface at kinks
• Modifiers may attach to the kinks, and block access of
solute molecules en route to incorporate into the crystal

3 Ma et al. Nature 2020

 E ff e c t o f k in k b lo c kers

Step Velocity

Step Velocity
Modifier Concentration Solute Concentration

• Kink blockers do not force complete growth cessation,

even at high modifier concentrations
• The correlation between the step velocity and the solute
concentration remains linear

4 Chakrabarti et al. Cryst. Growth Des. 2021

 E ff ect o f k in k b lo c kers o n f r e e e n e rgy

Parameters :
➢ Decrease in the surface free energy of the step edge ∆γ
➢ Density of kinks occupied by adsorbed kink blockers 𝑛𝑠,B
➢ Step height 𝑎
➢ Kink blocker concentration 𝑐B
➢ Fraction of kinks occupied by inhibitor molecules 𝜃B
➢ Chemical potential of the inhibitors in the solution µ

Where, 𝜇𝐵0 is the standard value of 𝜇𝐵, kB is the Boltzmann constant and T is
temperature.
The sum of occupied and free kinks:
𝑛𝑠,𝐵 + 𝑛𝑘,𝐵 = 𝑛𝑘,0 and
where 0 < 𝜉 < 1

5
 E ff ect o f k in k b lo c kers o n f r e e e n e rgy

Gibbs-Thomson relation
Ω𝛾
𝑅𝑐 =
Δ𝜇

6 Ma et al. Nature 2020

 E ff ect o f k in k b lo c kers o n s te p v e lo c ity

Parameters :
➢ Step velocity v
➢ Step velocity in absence of kink blocker v0
➢ Kink density in absence of inhibitor 𝑛k,0
➢ Density of kinks unoccupied by kink blocker
present in the bulk solution 𝑛k,B
v is proportional to the kink density 𝑛k,B

𝑣 ∝ 𝑛𝑘,𝐵 = 𝑛𝑘,0(1 − 𝜉 𝜃B) and 𝑣 = 𝑣0(1 − 𝜉 𝜃B), where 0 < 𝜉 < 1.

(1)
As 𝜃𝐵 → 1 , 𝑣𝑠at = 𝑣0(1 − 𝜉) and 𝑣0𝜉 = 𝑣0 − 𝑣𝑠at
(2)

Combining equations (1) and (2),

𝑣 = 𝑣0 − (𝑣0 − 𝑣𝑠at)𝜃B (3)
7
 E ff ect o f k in k b lo c kers o n s te p v e lo c ity

Modelling 𝜃B with Langmuir adsorption isotherm:

Assumptions
• Finite number of equivalent adsorption sites
• No interactions between adsorbed molecules
• Desorption rate independent of inhibitor concentration
• Equilibrium between inhibitors between surface and the bulk

where, KLB is the Langmuir adsorption

constant

CB/CTotal

As 𝑐𝐵 increases, v decreases monotonically from 𝑣0 at 𝑐𝐵 = 0 to its saturation value 𝑣𝑠at.

8 Ma et al. Nature 2020
 E ff ect o f k in k b lo c kers o n s te p v e lo c ity

• Rate of solute association depends on the supersaturation, whereas the probability of detachment
is dictated by the bonds a molecule forms with its neighbors
• Assumption for blocker molecules: Two of the lateral bonds are stronger and that the remaining
two are weaker than for the solute molecules.
• Preferential binding of kink blockers to the kinks at steps reducing v
9 Ma et al. Nature 2020
 THANK YOU
Leave this out