Qumica III. Tema 1 M2.

Principios de Nanoqumica

Langmuir-Blodgett technique
Developed by Irving Langmuir y Katharine Blodgett entre 1917 y 1935 in the laboratories of the General Electric Co. Preparation of multilayers of organic molecules onto a solid substrate from a monolayer previously formen onto a water surface

M2 Fundamentos de Nanoqumica Prcticas Pelculas de Langmuir-Blodgett

Dra. Mara Luz Rodrguez Mndez Universidad de Valladolid

Qumica III. Leccion 9. Nanociecia y Nanotecnologia

Tcnica Langmuir-Blodgett Permite obtener pelculas con alta homogeneidad

Monocapas ordenadas Control del grosor Superficies bien definidas
c) c)Transferencia Transfer

Molculas para LB: anfiflicas

a)a) Spreading and evaporation the solvent Distribucin y evaporacin delof disolvente

b)b) Compression Compresin

Control a niveles nanomtricos

Tcnicas de caracterizacin
Caracterizacin de monocapas flotantes
Isoterma presin superficial-rea por molcula Microscopa de ngulo de Brewster

Estudio monocapa flotante de Langmuir

Isotermas: Presin superficial-Area por molcula
P (mN/m)
Solid Phase

Caracterizacin estructural de las Pelculas delgadas

UV-Vis FTIR, RAIRS Raman SEM, TEM, AFM, STM Difraccin
Liquid Phas e

Gas" Phase
Area A /per molecule
2

Informacin sobre:

Zona de slido bidimensional: Informacin sobre la Presin a la que existe una monocapa. Presin de transferencia P de colapso: Informacin sobre la estabilidad Area por molcula: Informacin sobre orden molecular de la monocapa flotante

Isotermas genricas
Informacin sobre:
Zona de slido bidimensional: Informacin sobre la Presin a la que existe una monocapa. Presin de transferencia P de colapso: Informacin sobre la estabilidad Area por molcula: Informacin sobre orden molecular de la monocapa flotante

Isotermas
Ejemplos de isotermas para un cido graso (izda) y un fosfolpido (derecha) Variacin con la temperatura

Temperature
P (mN/m)

Colapso Slido bidimensional Compresibilidad cte.

c = 1 / A ( A / ) T , P , ni

Lquido bidimensional Gas bidimensional

Area A2/per molecule

Transferencia a sustratos slidos

Tcnica de dipping
Sucesivas inmersiones y emersiones del sustrato

Transferencia a sustratos slidos

Tres tipos de transferencia segn las caractersticas del sustrato y las interacciones moleculares

Hidroflico: Tipo Z

Hidrofbico: Tipo X

Hidroflico: Tipo Y

Tcnica Langmuir-Blodgett

Coeficiente de transferencia
AS

AL AS

AL

Transferencia a sustratos slidos

Mtodo de Langmuir-Schaeffer o mtodo de lifting

Monocapas de ms de un compuesto

Monocapas alternas

Monocapas mixtas

Isotermas de monocapas mixtas

Segn la miscibilidad de los componentes individuales entre s , las isotermas pueden presentar distintas formas
Un colapso intermedio al de los constituyentes: componentes solubles Dos colapsos: componentes segregados

Mixed Organic/Inorganic Thin Films

An inorganic network is introduced into traditionally organic assemblies The objective is to create materials where the two networks complement each other to produce interesting combinations of properties. i.e. metal ions are cross-linked by phosponate (PO3) groups

Instrumentacin: Balanza de Langmuir-Blodgett

Medida de la presin superficial. Wilhelmy plate

transductor de desplazamiento

Dipping system Set pressure Comparator Displacement Transducer Substrate Wilhelmy plate
resorte placa de Wilhelmy

Resultante de varias fuerzas: Gravedad Presin superficial Empuje

Barrier Barrier Motor

Refrigeration System

Tipos de balanzas de LB
Variety of shapes and sizes Can adapt a variety of accesories (microscope, T and pH probes, inert ambient, etc)

Clasificacin segn el tipo de compresin

Compresin asimtrica Compresin simtrica

Permetro constante

Balanzas dobles (alternate trough)

Poseen dos cubetas que permiten depositar alternativamente monocapas de dos materiales diferentes

Sustancias para LB
Sustancias anfiflicas: cadenas largas alifticas con un grupo polar en el extremo
cidos grasos de cadena larga son las sustancias patrn

Sustancias para LB
Sustancias no anfiflicas que se ordenan debido a diversos tipos d einteracciones
Ej: interacciones pi-pi entre anillos aromticos
Compuestos aromticos policclicos

Otras molculas capaces de formar LB

Also non polar materials can be spread which form often less stable or very rigid Langmuir films (not necessarily monolayers) depending on the intermolecular interactions
Apolar polymers (soft film) Fullerenes (rigid film) Rigid rod polymers Colloidal particles (polymer latex, Ag nanoparticles

Perylenes

Porphyrins

Phthalocyanines

Caracterizacin de las pelculas

1. Caracterizacin Langmuir
Pelculas flotantes

Estudio monocapa flotante de Langmuir

Isotermas: Presin superficial-Area por molcula

de

las

pelculas

de

2. Caracterizacin de las pelculas transferidas

Langmuir-Blodgett o Langmuir-Schaeffer

P (mN/m)

Zona de slido bidimensional: Informacin sobre la Presin a la que existe una monocapa. Presin de transferencia P de colapso: Informacin sobre la estabilidad Area por molcula: Informacin sobre orden molecular de la monocapa flotante 40
30

20

10

Area seccional ftalocianina no sustituida.

20

40

60

80

100

120

Area A2/por molecula

Isotermas Presin superficial-Area por molcula

Para LnPc2 y LnPc2R rea lmite 802-1202 << 1802 (valor terico rea del anillo de Pc) Molculas se organizan en configuracin edge-on

Surface potential
Measurement of the variations of the surface potential vs. Area per molecule while compressing the monolayer The surface potential values are related to the effective dipole moment of the monolayer. A model of the microscopic polar ordering of the molecules can be established

Left hand figure shows a surface pressure - area isotherm of stearic acid complemented with the surface potential.

Brewster Angle Microscopy (BAM)

Principle: When an electromagnetic wave incides on the interface between two dielectrics (i.e. air/water), refraction and reflection occur. at the Brewster Angle of incidence, ligth can only be reflected with E perpendicular to the plane of incidence: reflected ligth is completely polarised

Brewster angle microscopy

tan B =nwater/nair

Brewster angle depends on the refractive indexes of the substrates involved - for example for air/water, air/glass and air/diamond interfaces the critical (Brewster) angles are 53, 57, and 67.5, respectively. The presence of a film alters the Brewster angle
Reflected ligth is only partially polarised Depends on:
Thickness of the film Anisotropy Rugosity, etc

BAM images

BAM of an uniform floating filmof Cu arachidate

Pelculas mixtas mejoran homogeneidad

Presencia de araqudico (1:10) mejora la homogeneidad de la monocapa flotante de LuPc2

BAM image of a film with microfractures and defects. Interference rings indicate significant differences of thickness of the layer
= 20 mN/m.

= 2 mN/m.

BAM image of a film with aggregate particles

= 50 mN/m colapso.

BAM de LuPc2: araqudico (1:10) registradas durante la compresin

Characterisation of LB films
X-Ray Difracction Ellipsometry Spectroscopy
UV-Vis FTIR Raman

Difraccin de Rayos X

Ley de Bragg Law n=2dhklsen

Microscopy
SEM, TEM SPM

X-Ray diffraction example

43 monolayers of manganese octadecanoate d spacing between monolayers
Ej: fatty acids d=5 nm Low angle =1

Imgenes SEM y TEM

SEM of a Quasi-LB formed by nanotubes TEM Image of a monolayer of a tetratertbutyl CuPc

Monolayer structure
Ej: fatty acid, Y type structure

Imgenes de AFM
Molecular-resolution AFM images (14 nm by 14 nm) of five-layer CdAraquidate2 films on silicon. (A) Film deposited at pH 7 and B) deposited at pH 8.8

AFM: evaluation of thickness

X-ray diffraction is good at providing a two dimensional analysis of Langmuir Blodgett films but these may be far from complete as the AFM image shows. The cross section indicates discrete monolayer steps.

UV-Vis : analysis of thickness

Lambert-Beer Law: A=.c.l Absorbance increases with the number of monolayers Indicates quality of the transfer

UV-Vis: Molecular aggregation

Shifts due to solid state interactions: Exciton theory
Monomer E H aggrega tes
J aggregates

Waveleng th

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Infrarrojo

Ejemplo de una cadena hidrocarbonada

Espectro de Transmision
2919 nm 2850 nm

H C

No vibrations perpendicular: No peaks in RAIRs

Caracterizacin FTIR-RAIRS
Pelicula LB de PrPc2t

Surface selection rule

S Substrate Substrate E E S Substrate ( Au) (Au) Au)

Transmission

ReflectionAbsorption

Spectrochimica Acta, 49A, 965-973 (1993); Chem. Mat. 7, 1443-1448 (1995);

Langmuir , 19, 3747-3751 (2003)

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