J. K. Bal

Role of metal ions in growth and stability of Langmuir-Blodgett films on homogeneous and heterogeneous surfaces

AbstractStructure and stability of cadmium arachidate (CdA) Langmuir-Blodgett (LB) films on homogeneous (i.e., OH-, H-passivated Si(001) substrates) and heterogeneous (i.e., Br-passivated Si(001) substrates) surfaces were studied using X-ray reflectivity and atomic force microscopy techniques and compared with those of nickel arachidate (NiA) LB films. While on OH-passivated Si, an asymmetric monolayer (AML) structure starts to grow, on H-passivated Si, a symmetric monolayer (SML) of CdA forms, although for both the films, pinhole-type defects are present as usual. However, on heterogeneous Br-passivated Si substrates, a combination of AML, SML, shifted SML and SML on top of AML (i.e., AML/SML), all types of structures are found to grow in such a way that, due to the variation of heights in the out-of-plane direction, ring-shaped in-plane nanopatterns of CdA molecules are generated. Probably due to stronger head-head interactions and higher metal ion-carboxylic ligand bond strength for CdA molecules compared to NiA, easy flipping of SML on top of another preformed SML, i.e. a SML/SML structure formation was not possible and as a result a wave-like modulation is observed for the CdA film on such heterogeneous substrate. The presence of hydrophilic/hydrophobic interfacial stress on the heterogeneous substrate thus modifies the deposited molecular structure so that the top surface morphology for a CdA film is similar to monolayer buckling while that for NiA film is similar to monolayer collapse.n

Reorganization of Au nanoparticle Langmuir-Blodgett films on wet chemically passivated Si(001) surfaces

Growth of dodecanethiol-encapsulated Au nanoparticles on differently terminated (OH-, H-, or Br-terminated) Si(001) substrates by Langmuir-Blodgett method at a constant monolayer surface pressure and their out-of-plane structural modification with time have been investigated. As the substrates have different gradations in the hydrophilic/hydrophobic nature, three different out-of-plane structures have been formed. On H-terminated Si (hydrophobic surface), a fluctuating monolayer of Au nanoparticles has been formed, whereas on Br- (coexistence of hydrophilic and hydrophobic surfaces) and OH-terminated Si (hydrophilic surfaces), trilayer of Au nanoparicles have been formed, but the top layer coverage is more for the OH-terminated Si. The growth of Au nanoparticles on H-terminated Si is similar to the Frank-van der Marwe mode, whereas on Br- and OH-terminated Si, the growth is similar to the Stranski-Krastanov mode. These three different structures modify with time and finally become a thicker monolayer of h...

Evolution of Interdiffused Gaussian-Shape Nanolayer in Au-Si(111) System at Ambient Condition

Evolution of interdiffused Gaussian-shape nanolayer of Au-Si, formed due to diffusion of Au into Si(111) substrate at ambient conditions, depends strongly on the Si surface pretreatment/passivation conditions. Negligible diffusion in the Au-OSi(111) sample, confirms the strong barrier action of the oxide-layer against diffusion, while large diffusion in the Au-HSi(111) sample compared to that in the Au-BrSi(111) sample suggests that the H-passivated Si(111) surface is more stable. This nature of the Au-Si(111) system is qualitatively similar to that of the Au-Si(001) system but it differs quantitatively. The size, electronegativity and bond-energy of the passivating elements and the number of dangling bonds on the Si surface influence the instability of the Si surface. This instability, parameterized by growth-time of oxide layer alone, can be utilized to tune the amount of diffusion into the sub-surface Si region. The distribution of growth-time and fractional passivated area, which are related to the improper Si surface passivation, are against such control and needs perfection.

Surface correlation behaviors of metal-organic Langmuir-Blodgett films on differently passivated Si(001) surfaces

Langmuir-Blodgett films of standard amphiphilic molecules like nickel arachidate and cadmium arachidate are grown on wet chemically passivated hydrophilic (OH-Si), hydrophobic (H-Si), and hydrophilic plus hydrophobic (Br-Si) Si(001) surfaces. Top surface morphologies and height-difference correlation functions g(r) with in-plane separation (r) are obtained from the atomic force microscopy studies. Our studies show that deposited bilayer and trilayer films have self-affine correlation behavior irrespective of different passivations and different types of amphiphilic molecules, however, liquid like correlation coexists only for a small part of r, which is located near the cutoff length (1/κ) or little below the correlation length ξ obtained from the liquid like and self-affine fitting, respectively. Thus, length scale dependent surface correlation behavior is observed for both types of Langmuir-Blodgett films. Metal ion specific interactions (ionic, covalent, etc.,) in the headgroup and the nature of the te...