Design of oxide based nanomaterials by ALD

302 Pages·2017·8.44 MB·English

by  Adib Abou Chaaya

Design of oxide based nanomaterials by ALD: from
sensors to membrane application
Adib Abou Chaaya
To cite this version:
Adib Abou Chaaya. Design of oxide based nanomaterials by ALD: from sensors to membrane appli-
cation. Material chemistry. Université Montpellier II - Sciences et Techniques du Languedoc, 2014.
English. ￿NNT: 2014MON20117￿. ￿tel-01563358￿
HAL Id: tel-01563358
https://theses.hal.science/tel-01563358
Submitted on 17 Jul 2017
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Délivré parUNIVERSITE MONTPELLIER 2

Préparée au sein de l’école doctoraleENSCM
Et de l’unité de recherche IEM

Spécialité :Chimie et Physicochimie des matériaux

Présentée par Adib Abou Chaaya

TITRE DE LA THESE

Conception de nanomatériaux à base d’oxyde par ALD: de

la détection aux membranes

Design of oxide based nanomaterials by ALD: from

sensors to membrane application

Soutenue le 09/09/2014 devant le jury composé de

Prof Philippe Miele, IEM Directeur de thèse
Dr MikhaelBechelany,IEM Co-encadrant
Dr IVO Utke, EMPA (Thun, suisse) Rapporteur
Prof Julien Bachmann, FAU(Erlangen, Allemagne) Rapporteur
Dr Lionel Santinacci, CINAM (Marseille, France) Examinateur
Acknowledgment

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Summary
General introduction…………………………………………………..3

Chapter1.Bibliography………………………………………………...7

Chapter2.Synthesis of ALD Zinc oxide thin film and zinc
oxide/Aluminium oxide nanolaminates: studies of their structural
and optical properties..……………………………………………….48

Chapter 3: Atomic layer deposition on nanostructured materials for
sensor applications……...…………………………………………...110

Chapter4.Mechanical properties of Al2O3/ZnO nanolaminates
………………………….……………………………………………..158

Chapter5. ALD modified PET and PC membranes for different
applications…………………………………………………………..193

General Conclusion………………………………………………….244

Annex-a-……………………………………………………………...249
Annex-b-……………………………………………………………..278
Annex-c-……………………………………………………………..285
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General introduction

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‘’Nano’’ is one of the most used world in the research community today. Nanomaterials
by definition are materials having at least one dimension lower than 100 nm. One of the first
scientific reports on nanostructured materials is the colloidal gold particles synthesized by
Michael Faraday in 1857. By the early 1940’s, precipitated and fumed silica nanoparticles were
being manufactured and sold in USA and Germany as substitutes for ultrafine carbon black for
rubber reinforcements.
Nanostructure science and technology is a broad and interdisciplinary area of research
and development that has been growing explosively worldwide in the past few years. It is already
having a significant commercial impact, which will assuredly increase in the near future.
Nanostructure materials are of interest due to their unique optical, magnetic, electrical, and other
emerging properties. These properties allow great impacts in electronics, medicine, energy
harvesting, sensors and other fields. Engineered nanomaterials are resources designed at the
molecular (nanometer) level to take advantage of their small size and novel properties which are
generally not seen in their conventional, bulk counterparts.
The two main reasons why materials at the nanoscale can have different properties are: (i)
increased relative surface area and (ii) new quantum effects. Nanomaterials have a much greater
surface area to volume ratio than their conventional forms, which can lead to greater chemical
reactivity and affect their strength. Also at the nanoscale, quantum effects can become much
more important in determining the materials properties and characteristics, leading to novel
optical, electrical and magnetic behaviors. According to Siegel, nanostructured materials can be
classified as:
· Zero dimensional (spheres and clusters)
· One dimensional (nanofibers, wires, rods, etc.)
· Two dimensional (films, plates, and networks)
· Three dimensional nanostructures (nanophase materials consisting of equiaxed
nanometer sized grains).

Among nanomaterials, nanostructured semiconductors are known to show various non-
linear optical properties. Semiconductor Q-particles also show quantum confinement effects
which may lead to special properties that can be promising in solar cells, UV sensing and others
applications. Nanostructured metal-oxide thin films for instance are receiving a growing
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attention for the realization of gas sensors (NO , CO, CO , CH and aromatic hydrocarbons) with
x 2 4
enhanced sensitivity and selectivity.
Nanomaterials designing can be basically described by two approaches:
· The top down approach refers to slicing or successive cutting of a bulk material to get
nanosized particle.
· The bottom up approach refers to the approach to build a material up from the bottom:
atom-by-atom, molecular-by molecular or cluster-by-cluster.
Using these 2 approaches, many different methods have been used to design
nanostructures such as wet chemical synthesis of nanomaterials, mechanical grinding, heating
and gas phase synthesis of nanomaterials (CVD, PVD, ALD, laser ablation and others). The gas-
phase synthesis methods are of increasing interest because they allow controlling process
parameters in order to be able to design the size, the shape and the chemical composition of the
obtained nanostructures. Among the gas phase synthesis methods, the Atomic layer deposition
(ALD) shows several advantages in the synthesis of nanostructured materials such as:
· A wide range of deposition materials: oxide, nitride, carbide and others
· A conformal coating ability on high aspect ratio templates
· A thickness control on the angstrom range
· A high chemical purity of the deposited films
· A high chemical composition control of the deposited layer
In this context, the aim of this PhD work is the synthesis of different nanostructured
materials based on ALD oxide thin film (Al O , ZnO and Al O /ZnO nanolaminates) deposited
2 3 2 3
on different types of substrates such as silicon substrate, glass, nanofibers, multipores and
monopores membranes, PET and gold coated nickel dogbones. ALD deposition was performed
on those substrates with changing the film thickness (number of cycles), the deposition
temperature, and the film composition (doping, multilayers etc.). After the ALD deposition
chemical, structural, optical, electrical and mechanical characterization were performed on the
ALD deposited layer in order to study the influence of the deposition parameters on the thin film
properties.

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The deposited and characterized ALD films were investigated on different fields:
· Optical properties for solar cell applications (Chapter 2)
· UV detection (Chapter 3)
· Protective coating and gas barrier (chapter 4)
· Ionic transport, water desalination, Mass spectrometry, DNA sequencing and Gas
purification (chapter 5)
The atomic layer deposition technique combined with nanostructured templates show
several advantages on several application fields that will be reported on this thesis. The structural
and properties evolution of the ALD thin film with the deposition parameter evolution leaded to
a doped ZnO layer and Al O /ZnO multilayer with tunable optical, electrical and mechanical
2 3
properties that can be interesting for different applications such as solar cell and UV detection.
The conformal coating on high aspect ratio template with the angstrom range thickness control
offered by the atomic layer deposition technique meted our target on nanopores diameter tuning
for different applications on the nanometeric range such as gas purification. Moreover the
compatibility of the deposited materials with some biological function leaded to a combination
between nanostructure materials and biological function that shows promising results for
different applications such as ionic transport, water desalination, mass spectrometry and DNA
sequencing.
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Chapter1. Bibliography

Chapter 1. Bibliography

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