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Sol-Gel Nano Materials and Process

Prof. Byeong-Soo Bae


Dept. of Materials Sci. & Eng.
bsbae@kaist.ac.kr
I.
II.
III.
IV.
V.
VI.

Introduction
Chemistry of Precursors Solutions
Sol-Gel Process of Silica
Sol-Gel Process of Complex Oxides (Ferroelectrics)
Sol-Gel Process of Hybrid Materials
Sol-Gel Process of Mesoporous Materials

Text:
1.
2.

A. C. Pierre, Introduction to Sol-Gel Processing, Kluwer Academic


Publisher, 1998
C. J. Brinker, G. W. Scherer, Sol-Gel Science, Academic Press, 1990

Prof. ByeongByeong-Soo Bae

MS512 Nano Technology

I. Introduction
Sol-gel Processing
Sol-gel processing is a wet chemical route to synthesis of a colloidal suspension of solid
particles or clusters in a liquid (sol) and subsequently to formation of a dual phase material of
a solid skeleton filled with a solvent (wet gel) through sol-gel transition (gelation). When the
solvent is removed, the wet gel converts to a xerogel through ambient pressure drying or an
aerogel through supercritical drying. Thin (~ 100 nm), uniform and crack-free films can be
readily formed on various materials by dip, spin, or spray-coating; thick films can be obtained
by multiple coatings.

In the sol preparation, the precursors (either organic or inorganic) undergo two chemical
reactions: hydrolysis and condensation or polymerization, typically with acid or base as
catalysts, to form small solid particles or clusters in a liquid (either organic or aqueous
solvent). The solid particles or clusters are so small (1~1,000 nm) that gravitational forces are
negligible and interactions are dominated by van der Waals, coulombic and steric forces. Sols
are stabilized by an electric double layer, or steric repulsion, or their combination.

Prof. ByeongByeong-Soo Bae

MS512 Nano Technology

Colloid: a suspension in which the dispersed

phase is so small ( 1~1000 nm) that gravitational


forces are negligible and interactions are dominated by short-range forces, such as Van der Waals
attraction and surface charges.

Sol: a colloidal suspension of solid particles in a liquid .


Gel: a solid network filled with a second phase of colloidal dimensions, either liquid or gas that also
forms a three dimensional inter-connected network.

Gelation: also called sol-gel transition that begins with the formation of solid fractal aggregates that
grow until they extends throughout the sol.

Xerogel: a gel in which the solvent has been removed by evaporation at an ambient environment.
Aerogel: a gel in which the solvent has been removed by supercritical drying. An aerogel typically
has a porosity >75% and a BET surface area > 1000 m2/g.

Supercritical drying: a process of removing the liquid from the pores of wet gel above the critical
temperature and critical pressure.

Precursor: a starting compound for preparation of a colloid (or sol). It consists of a metal or
metalloid element surrounded by various ligands. It includes inorganic salts and organic compounds.

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Hydrolysis: a chemical reaction in which hydroxyl groups become attached to the metal atom
by replacing the ligands in the precursor.

Condensation (or polymerization): A process that hydroxyl groups merge to form metaloxygen-metal bonds, while releasing a water molecule, resulting in formation of solid particles or
clusters through combining monomers, growth of particles or clusters, and linking of particles or
clusters into chains and networks that extend through the sol.

Steric force: a repulsion which results from polymers adsorbed to the interacting surfaces.
The physical basis of the steric repulsion is a combination of a volume restriction effect arising
from the decrease in possible configurations in the region between the two surfaces and an
osmotic effect due to the relatively high concentration of adsorbed polymers in the region
between the two surfaces as they approach one another.

Electric double layer: forms at the vicinity of a solid particle in a sol. When a solid
submerges into a liquid, the surface will be electrically charged and subsequently an electric
double layer forms due to the combination of coulombic, entropic and other specific forces. When
two particles approach each other, as soon as the double layers overlap, a repulsive electrostatic
force arises to prevent two solid particles to aggregate so that the sol is stabilized.

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MS512 Nano Technology

Sol-gel processing is a simple technology in principle but has required considerable effort to
become of practical use. Sol-gel enables materials to be mixed on an atomic level and thus
crystallization and densification to be accomplished at a much low temperature. However, a true
atomic level homogeneity in a multiple component system is an endeavor; the difficulty arises
from the fact that the chemical reactivity varies greatly from precursor to precursor. Precursor
modification and step-wise partial hydrolysis are the common approaches to homogeneity in
multiple component systems.

The advantages of the sol-gel process in general are high purity, homogeneity, and low
temperature. For a lower temperature process, there is a reduced loss of volatile components and
thus the process is more environmental friendly. In addition, some materials that cannot be made
by conventional means because of thermal and thermodynamical instability, can be made by this
process. The sol-gel process has many applications in synthesis of novel materials. Examples
include aerogels used in space crafts to capture stellar dust, xerogels as matrix in biosensors, and
high power laser materials.

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Alkoxides:M(OR)n

M= Si,Ti,Zr,Al
R= -CH3, -CH2CH3

H ydrolysis
OR

OR
RO

OR

RO

H 2O

OH

ROH

OR

OR

Condensation
OR
RO

OR
OH + RO

OR

OR
OR

RO

OR

OR
O

OR

OR

OR
+ ROH

OR
RO

M
OR

OR
OH + HO

OR
OR

OR

RO

M
OR

OR
O

OR

OR
+ HOH

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Definitions of Sol-Gel Process


Alkoxide Sol-Gel
Dislich - Procedure to prepare the multicomponent oxides that are homogeneous at the
atomic level
should include the colloidal coprecipitates of hydroxides and oxyhydrates
restrict to the gels synthesized from metal alkoxides
Coloidal Sol-Gel
Segal Production of inorganic oxides either from colloidal dispersion or from the
metal alkoxides
non-oxides such as nitrides and sulfides, and organic-inorganic hybrids
Colloidal route used to synthesize ceramics with an intermediate stage including a sol
and/or gel state

Production of inorganic oxides either from colloidal dispersion or from the metal
alkoxides
Chemical processing to synthesize ceramics glasses, and hybrids from wet chemicals

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Inorganic Polymerization
Solution

Sol

Monomer

Dimer
O

O
O

O
O

O
O

O
O

O
O

Oxide
O

O
O

O
O

O
O

O
M

M
O

O
O

Solid

Prof. ByeongByeong-Soo Bae

M
O

O
M

O
M

Colloid

O
O

M
O

O
O

Gelation

O
M

Oligomer

Sintering

Drying

Gel

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Processing of Sol-Gel Materials


Powders

Monoliths

Coatings and Thin Films


Porous Materials and Aerogel

Fibers

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Melting and Sol-Gel Process for Glass Fabrication

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Advantages and Disadvantages of Sol-Gel Process


Advantages

Disadvantages

High purity from raw materials

High cost of raw materials

Good homogeneity from raw materials

Large shrinkage during processing

Low processing temperature

Residual fine pores and hydroxyls

Good shape ability

Health hazards of organic solution

Production of new composition glasses

Easily cracking during the drying stage


Long processing times

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Characteristics of Sol-Gel Process


Low temperature process of fine ceramics and glasses
Bottom-up fabrication from chemicals
Aqueous-based chemistry and process
Immobilization & encapsulation over wide range of sizes,
chemistries and functions
Mild & easily controlled conditions
Molecular level dispersion

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Fabrication of Sol-Gel Optical Fiber Preform

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Sol-Gel Coatings on Display

Antiglare

t
gh
Li

1.0% of incident light


<Interference effect>

Silica layer

AR layers
Conductive
layer

Glass

G
Phosphor

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Preparation of Nano Materials by Sol-Gel Processing

<100C

Solution

<100C

Sol

<150C

Wet
gel

<500C

Dry
gel

<1200C

Heated
gel

Glass,
Ceramics

Porous gels

Pores

Gels dispersed
with organic
molecules

Inorganicorganic
composites

Gels
dispersed with
inorganic or
metal particles

Organic molecules

Prof. ByeongByeong-Soo Bae

Organic polymer

Inorganic network

Glass

Ceramics

Particles
Grains

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II. Chemistry of Precursors Solutions


Precursor Solution
Chemical Precursor
Chemical reactant which contain the cation M present
in the final inorganic sol or gel
Metallic salts - MmXn, eq) AlCl3
Metal alkoxides M(OR)n, eq) Al(OC2H5)3
Organometalic compounds

Solvents
Water
Non-aqueous solution
Protic solvent
Aprotic solvent
Acidic solvent
Basic solvent
Amphoretic solvent
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Hydrolysis of Metal Salts Solution


Ions Solvation
Dissolution is solution
MX
Mz+ + Xz- in the solution
Cation solvation
Solvatation shell [M(H2O)N]Z+

Hydrolysis
Deprotonation of a solvated metal cation
Aquo ligand H2O
hydroxo ligand(OH-)or an oxo ligand(O2-)

Formation of Hydroxo Ligands


Solvated metal: an acid, Water: Lewis base
[M(OH2)N]Z+ + hH2O [M(OH)(OH2)N-1](z-1) + + H3O+
acid + Lewis base conjugates base conjugated acid
[M(OH)h(OH2)N-h] aquo-hydroxo complex

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Formation of Oxo Ligands


Deprotonation of an hydroxo ligand
[M(OH)(OH2)N-1](Z-1)+ + hH2O [MOh(OH2)N-h] (Z-h)+ + hH3O+
acid + Lewis base conjugated base + conjugated acid
[MO(OH2)N-1]z-2 aquo-oxo ligand complex

[M(OH2)N]Z+ + hH2O [M(OH)(OH2)N-1](z-1) + + H3O + hH2O [MOh(OH2)N-h] (Z-h)+ + hH3O+


: [MONH2N]Z+
aquo-ion
0<h<N : [M(OH)X(OH2)N-x](Z-X)+
hydroxo-aquo complex
h=N
: M(OH)N](N-Z)hydroxo complex
N<h<2N : [MOX(OH)N-x](N+X-Z)oxo-hydroxo complex
h=2N
: [MON](2N-Z)oxo-ion

h=0

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Condensation of Metal Salt Solution


Condensation and Polymerization
Hydroxo ligand (M-OH)

ol bridge (M-OH-M)

oxo bridge (M-O-M)

Condensation by Olation
For the low charge cations dissociative SN1 mechanism
-M-OH + -M- M-OH-MH2OM -M- + H2O
For the higher charge cations nucleophilic addition reaction AN
-M-OH + -M-OH M-OH-M-OH
For the transition elements associative SN2 mechanism

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Condensation by Oxolation
For the low charge cations dissociative SN1 mechanism
-M-OH + -M- M-OH-MH2OM -M- + H2O
For the higher higher charge cations nucleophilic addition reaction AN
-M-OH + -M-OH M-OH-M-OH
For the transition elements associative SN2 mechanism

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Alkoxide Precusors
Alkoxides:M(OR)n

M= Si,Ti,Zr,Al
R= -CH3, -CH2CH3

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Hydrolysis of Metal Alkoxides


Hydrolysis
Alkoxy group (OR)

Hydroxo(OH) or Oxo(O) ligands

(1) Nature of alkoxy group


(2) Nature of solvent
(3) Concentration in solvent
(4) Water to alkoxide molar ratio rw = [H2O]/[alkoxide]
(5) temperature

Formation of Hydroxo Ligands


M(OR)z + H2O M(OH)(OR)z-1 + ROH

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Hydrolysis of Silicon Alkoxide


Acidic solution (pH < 2.5)
- Negatively charged particles
- [H3O]+ attack the oxygen in alkoxy group

Basic solution (pH > 2.5)


- Positively charged particles
- OH- attacks the Si in alkoxides

Formation of Oxo Ligands


Lewis base
Water vapor

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Condensation of Metal Alkoxides


Condensation by Olation
SN2 nucleophilic substitution mechanism

Condensation of Oxolation
Transfer of the H to an OR ligand

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Transfer of the H to an OH group

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Condensation of Silicon Alkoxides


Acidic solution (pH < 2.5)
- Two step SN2 type mechanism condensation
- Protonation of silanol group
- Hydrolysis is faster than condensation
- Linear polymer
Basic solution (pH > 2.5)
- Deprotonation of silanol group
- Condensation is faster than hydrolysis
- Dense solid

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Precursor Mixing
Mixing Two Alkoxides
Double alkoxides
- Mixing two alkoxides in same non-aqueous solvent
Simultaneous hydrolysis of simple alkoxides
- Simultaneous refluxing in solvent
Matching the hydrolysis rates of different alkoxides
- Partially hydrolyzed Si(OR)4 and Al(OR)3

Mixing Two Metal Salts


Mixing a Alkoxide with a Metal Salt
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17

III. Sol-Gel Process of Silica

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17Aqueous Silicate
Kinetics of hydrolysis and condensation
is slower

Polymerization at pH 2 - 7
Proportional to [OH-]
3-D gel network by aggregation
Hydrolysis with water

Polymerization above pH 7 - 10
Stable sol
Particle growth rather than aggregation
Thermal decomposition

Polymerization below pH 2
Proportional to [H+]
Metastable

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17Silicon Alkoxide Sol-Gel


hydrolysis
S i- O R + H 2 O
estrification

S i- O H + R O H

alcohol con den sation


S i- O- Si
S i- OR + HO- Si
alcoholysis
water con den sation
S i- O - S i
S i- O H + HO - S i
hydrolysis

+ ROH

+ H 2O

Precursor Solution
Silicon alkoxide + water + alcohol + catalyst
H2O:Si molar ratio (r) 1~ over 50
Concentrations of acids or bases 0.01 ~ 7 M

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Precursor Molecules
Tetraalkoxysilanes
Si(OR)4 :
TEOS(tetraethoxysilane),
TMOS(tetramethoxysilane)

Organoalkoxysilanes
RnSi(OR)3 :
MTMS(Metyltrimethoxysilane),
DMDMS(Dimetyldimethoxysilane)

Molecular Building Blocks


Hexamethoxydisiloane
Octamethoxytriethoxtsilane
Methoxylated cubic octamer - Silsiquioxane

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17Hydrolysis of Silicon Alkoxides


Effects of Catalyst
H2O/Si Ratio (r)

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17 Steric and Inductive Effects


Effects of Solvents
Protic solvent enhance hydrolysis

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17Condensation of Silicon Alkoxides


Effect of Catalyst
Minimum at about pH 1.5
Maximum at intermediate pH
Acid catalyzed condensation (pH<2)
protonated silanol
Base catalyzed condensation (pH>2)
deprotonated silanol

Steric and Inductive Effects


Acidity of silanol higher pH IEP
Basicity of silanol lower pH IEP
In acid-catalyzed,
steric effects > inductive effects

Effects of Solvent
Protic solvent acid-catalyzed condensation
Aprotic solvent base-catalyzed condensation

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17Structural Summary
Low pH Condition
Hydrolysis rate > condensation rate
Cluster-cluster growth network structure

High pH Condition
Unhydrolyzed monomers
Monomer-monomer growth - particles

Intermediate pH Condition
Minimum hydrolysis rate rate limiting

General Condition
Acid catalyzed, low water system drawing fiber
Acid catalyzed, high-water system bulk gels
Base catalyzed, high-water system particles
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16

IV. Sol-Gel Process of Complex Oxides

Solution Process of Electo or Optical Ceramics

Sol-Gel Ferroelectrics

Lead

Titanium

Zirconium

Metallorganic Precursors
Metal alkoxides
Zr n-propoxide [Zr(OC3H7)4]
Ti isopropoxide [Ti(OCH(CH3)2)4]
Ethoxides, Butoxides
Inorganic or organic salts
La nitrate
Pb acetate

Solvents
Primary solvent - stablization
Chemical modifiers
- methoxyethanol, acetic acid glycol
Chelating agents
- -diketone (acetylacetone)
Secondary solvent
Ethylene glycol, propanol, methanol or water
Control in viscosity, pH, surface tension
Prof. ByeongByeong-Soo Bae

Alcohol or Water

Gelation Control
Firing Additives
Viscosity Adjustment

Precursor Solution
Dipping,Spraying
or Spin Coating
Drying and Organic
Removal
280-400C

Multilayer
Coatings

Crystallization
400-700 C
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Preparation of Ferroelectric Solutions


17
Alcohol-Based Solution
Pb acetate trihydrate, Ti isopropoxide, Zr n-propoxide
2-methoxyethanol + 2-methoxyethanol/water
Change to methoxides and partial hydrolysis

Water-Based Solution
Pb acetate trihydrate, Ti isopropoxide, Zr n-propoxide
Acetic acid + water, propanol, glycols
Hydrolysis with water

MOD Solution
Pb acetate, Ti acetylacetonate, Zr acetate
Pb 2-ethyl hexanonate, Ti isopropoxide, Zr tetra-n-butoxide
Water + methanol, hexane
Thermal decomposition

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Fabrication of Ferroelectric Films

La nitrate

Pb acetate

Sr metal

Ba metal

Nb(OC2H5)5

2-Methoxyethanol2 2-Methoxyethanol
2-Methoxyethanol
Distillation

Distillation

2-Methoxyethanol

Ti isopropoxide
In dry N2 gas

Refluxing

Refluxing (12h)

0.4M precusor solution

0.1M SBN sol

Coating
Iteration

Coating
Iteration

Drying

Drying

Heat Treatment
for Crystallization

Heat Treatment
for Crystallization

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Preparation of Stable Solution


Dilution
Pb acetate trihydrate, Ti isopropoxide, Zr n-propoxide
2-methoxyethanol + 2-methoxyethanol/water
Change to methoxides and partial hydrolysis
Chemical Modification and Complexation
Pb acetate trihydrate, Ti isopropoxide, Zr n-propoxide
Acetic acid + water, propanol, glycols
Hydrolysis with water
Surface Modification of Nanoparticles
Stablization of particles

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IV. Sol-Gel Process of Hybrid Materials


size
mm

/
/
/
/
/
/
(FRP,FRC,FRM)

Physical
hybridization

Nanocomposite

1nm
Nanohybrid
1
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Chemical
hybridization
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Class I (Nanocomposite)
Organic dyes embedded in sol-gel matrix
Organic dyes, inorganic ions or molecules + silica, aluminosilicate, zirconia, titania
fluorescence, photochromic, non-linear optical properties

Inorganic particles embedded in a polymer


Inorganic particles + polymer blend

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Organic monomers embedded in sol-gel matrices


Polymerizable organic monomer + sol-gel inorganic matrices

Polymerization

Sol-gel

Polymers filled with in-situ generated inorganic particles


Inorganic particle formation by sol-gel reaction in a polymer matrices

Sol-gel

Polymerization
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Simultaneous formation of interpenetrating organic-inorganic networks


Alkoxides functionalized by liable plymerizable group
Polymerization

Sol-gel

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Obtension of ordered organic-inorganic structures


Insertion of organic molecules polymers into an anisotropic inorganic network
Build anisotropic inorganic particles using organic molecules and self assembled aggregates

Sol-gel

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Class II (Nanohybrids)
Organically modified silicon alkoxides

Sol-gel

Polyfunctional alkoxysilanes

RxSi(OR)4-x

Polymerization

(RO)3Si-R-Si(OR)3
Sol-gel

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Alkoxysilanes functionalized by polymers (RO)3Si-Polymer-Si(OR)3


Sol-gel

Surface modification by organoalkoxysilanes

Polymerization

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Template building blocks


Polymerization

Ordered hybrid materials


Self-assembly of molecular units on surface hydroxyl groups

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Hybrids from Sol-Gel Process of Organoalkoxysilanes


RnSi(OR)4-n
Network modifier ( R' : unreactable)

Network former ( R' :polymerizable)


O

CnH2n+1-Si(OR)3

methyl, ethyl

H2C

phenyl

Si(OR)3

O
amino

H2N-(CH2)3-Si(OR)3

CH-O-(CH2)3-Si(OR)3

epoxy

O-(CH2)3-Si(OR)3

methacrylate
mercaptopropyl

HS-(CH2)3-Si(OR)3

H2C
vinyl

C Si(OR)3

fluoro

CF3-(CF2)n-(CH2)2-Si(OR)3

H
R

=O
= Si,Ti,Zr,...
R inorganic
modifier
R entrapped
molecule

Modification
Functionalization
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organic
polymeric
chain

Crosslinking
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Sol-Gel Hybrid Materials (HYBRIMER)

Organic Modification

Heterometal Network

Polymer Network
Silica Network

Compensation of Characteristics
Hard and Stable
Soft and Flexible
Easy Process
Cheap
Functionalization
Modification
New function
Transparency
Optical materials
Functional coating

ORMOCER,
ORMOCER, CERAMER,
CERAMER, POLYCERAM,
POLYCERAM,
Hybrid
Hybrid Sol-Gel
Sol-Gel Glass,
Glass, Hybrid
Hybrid Polymer,
Polymer, HYBMRIMER
HYBMRIMER
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Characteristics of HYBRIMER
Transparency
Functionality
Compensation of Characteristics
Modulation & Tunability of Characteristics
Easy Process & Fabrication
High Thermal & Chemical Stability
Easy Encapsulation with Better Compatibility

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Transparency of HYBRIMER
Hybrids of molecular level
Coloration by doping of dyes or colloids
Application of optics, display, and coatings

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Compensation of Characteristics

Ref.: Fraunhofer ISC


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Compensation of Characteristics
Compensation of Polymer and Glass Properties

Polymers

Glass

Refractive index

1.40 - 1.65

1.35 1.95

Dielectric Constant

Low

High

dn/dT (10-7)

-140 to -85

-8 to 6

Thermal Expansion

150 to 700

-10 to 160

Youngs Modulus (Mpa)

1 -10

4 -130

Thermal Stability

90 -250

450 -950

Hardness

Low

High

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Compensation of Characteristics
Mechanical Properties

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Silica/PDMS HYBRIMER

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Functionality of HYBRIMER
Hydrophilic and Hydrophobic Coatings

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Optical Application of HYBRIMER


Solid state dye laser materials
Rare-earth emission materials
Nonlinear optical and photorefractive materials
Photochemical hole burning materials
Photochromic materials
Optical sensor matrials
Optical waveguide materials

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Functionality of HYBRIMER
NLO Chromophore HYBRIMER
(OEt)3Si

Unpoled
Unpoled
Sol-Gel
Polymers

Si(OEt)3

Hybrids

NLO

heating around Tg
electric field on
cooling
electric field off

- H2O

HCl / DMF
- CH3OH

Poled
Poled
Sol-Gel
Polymers
Hybrids

(a)

Si

Si

O
Si

O
O Si
O

O
O

(b)

Si

LO
Si

O
Si

Si

Si
O
NL
O
O O
O O
O
Si
Si
Si
O
O
ON Si
Si O O
LO
Si
NL
O Si
O
O

NLO

NLO

Si

NL
O

(c)

SHG

EO

wave length change


Frequancy Doubling

spatial, wave front


Spatial Light Modulators

O
NL

NL O
Si

O
Si

Si

NL O

Si

NLO

Si

NL
OO

Prof. ByeongByeong-Soo Bae

EO
amplitude, wave form
E-O Modulators

,
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Silica vs. Polymer for Waveguide Materials


Silica
Silica

Polymer
Polymer

FHD,CVD
High temp
Difficult,Expensive.

Spin-on
Low temp.
Easy, Cheap
Versatile

Lower
High
High
Low
Not
Not
Stress
Prof. ByeongByeong-Soo Bae

Process
Absorption
Mechanical
Thermal

Low
Low
Low

Thermo-optics
Design
Functionality

Versatile

Polarization
dependence

Anisotropy

High
Versatile

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Advantages of HYBRIMER Waveguide


Silica Waveguide
Manipulation of refractive index in a broad range
Easy fabrication
Easy incorporation of inorganic/organic doponts

HYBRIMER Waveguide
Thick films without cracks
Hydrogen bonding to stabilize
organic dopants
Photoimprinting, Easy process

Sol-Gel Silica Waveguide


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Manipulation of refractive index


in a broad range
Thermally and chemically stable
Hardness for end facet polishing

Polymer Waveguide
MS512 Nano Technology

Micro-Patterning in HYBMRIMER by Photo-polymerization

UV

Photo-initiator

R'=CH3;C2H4OH
= - C3H6OOC -

Prof. ByeongByeong-Soo Bae

Selective etching

developing

Fabrication of waveguides

MS512 Nano Technology

Encapsulation & Immobilization in HYBRIMER


Entrapment of biomolecules and chemical species in porous structure
Better compatibility in organic environments
Applications in biosensor, bioreactors, chemical sensor, catalysis

Prof. ByeongByeong-Soo Bae

MS512 Nano Technology

VI. Sol-Gel Process of Mesoporous Materials


Micelle Structure
Spherical micelle
Cylindrical micelle
Lamellar micelle
Inverse micelle

Prof. ByeongByeong-Soo Bae

MS512 Nano Technology

Ordered Mesoporous Materials


Hexagonal packing of cylindrical micelles
Cubic packing of spherical micelles
Planar packing of micellar micelles

Hexagonal

Cubic

Cubic

Lamellar

Fabrication Procedure
Micellar rods with a surfactant
micelles in a hexagonal array
add inorganic
precursor solution in a polar solvent
array of hollow oxide cylinders organic
heart elimination by washing or by calcination
Micelles with inorganic precursor solution
Prof. ByeongByeong-Soo Bae

MS512 Nano Technology

Surfactants
Alkyl-ammonium halide (cationic surfactant)
[CnH2n+1N(CH3)3]X- , X=Cl or Br Cetyltrimethylammonium bromide (CTAB)
Poly(oxyethylene) non-ionic surfactant [n-alkylpolyethylene glycol ethers]
CH3(CH2)n-1(OCH2CH2)mOH = CnEOm

Brij 56, C16H33(OCH2CH2)10OH

Poly(ethylene oxide)-block-poly(propylene oxide)-block-poly(ethylene oxide)

Prof. ByeongByeong-Soo Bae

MS512 Nano Technology

Prof. ByeongByeong-Soo Bae

MS512 Nano Technology

Pure Silicate Composition


Liquid Crystal Templating Mechanism
Silica source TEOS, Ludox, fumed silica, sodium silicate
Alkyltrimethylammonium halide surfactant - cetyltrimethylammonium bromide (CTAB)
Base - sodium hydroxide or tetramethylammonium hydroxide (TMAOH)
Water

Silicate Rod Assembly

Prof. ByeongByeong-Soo Bae

MS512 Nano Technology

Silicate Layer Puckering

Charge Density Matching

Folding Sheets

Prof. ByeongByeong-Soo Bae

MS512 Nano Technology

Silicatropic Liquid Crystals

Prof. ByeongByeong-Soo Bae

MS512 Nano Technology

General Liquid Crystal Templating Mechanism: Electrostatic Mechanism

Prof. ByeongByeong-Soo Bae

MS512 Nano Technology

Applications
Catalysis

- High Surface Areas and Thermal Stability


Sorption and Separation
Inclusion of Nanostructured Materials
Optical Applications

- Dye Inclusion
- Nanocrystals (Quantum Dots)
- Organometallic Complexes
- Polymer Inclusions
- NLO and Laser Materials
- Photochromic Materials
Chemical Sensors

Insulator Materials
Low k Materials
Hydrogen Storage and Electrode Materials

- Carbon Nanotubes

Prof. ByeongByeong-Soo Bae

MS512 Nano Technology

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