Upload
virpara
View
213
Download
0
Tags:
Embed Size (px)
DESCRIPTION
Glass course material
Citation preview
Prof. Prof. ByeongByeong--Soo BaeSoo Bae MS512 MS512 Nano Nano TechnologyTechnology
Sol-Gel Nano Materials and ProcessProf. Byeong-Soo Bae
Dept. of Materials Sci. & [email protected]
I. IntroductionII. Chemistry of Precursors SolutionsIII. Sol-Gel Process of SilicaIV. Sol-Gel Process of Complex Oxides (Ferroelectrics)V. Sol-Gel Process of Hybrid MaterialsVI. Sol-Gel Process of Mesoporous Materials
Text:1. A. C. Pierre, Introduction to Sol-Gel Processing, Kluwer Academic
Publisher, 19982. C. J. Brinker, G. W. Scherer, Sol-Gel Science, Academic Press, 1990
Prof. Prof. ByeongByeong--Soo BaeSoo Bae MS512 MS512 Nano Nano TechnologyTechnology
I. IntroductionSol-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. Prof. ByeongByeong--Soo BaeSoo Bae MS512 MS512 Nano Nano TechnologyTechnology
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 Waalsattraction 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.
Prof. Prof. ByeongByeong--Soo BaeSoo Bae MS512 MS512 Nano Nano TechnologyTechnology
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 metal-oxygen-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.
Prof. Prof. ByeongByeong--Soo BaeSoo Bae MS512 MS512 Nano Nano TechnologyTechnology
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.
Prof. Prof. ByeongByeong--Soo BaeSoo Bae MS512 MS512 Nano Nano TechnologyTechnology
Condensation
RO OH
OR
OR
M RO OR
OR
OR
M RO O
OR
OR
M+ OR
OR
OR
M
RO OH
OR
OR
M HO OR
OR
OR
M RO O
OR
OR
M+ OR
OR
OR
M
+ ROH
+ HOH
Hydrolysis
RO OR
OR
OR
M RO OH
OR
OR
M+ H 2O + ROH
Alkoxides:M(OR)n M= Si,Ti,Zr,Al R= -CH3, -CH2CH3
Prof. Prof. ByeongByeong--Soo BaeSoo Bae MS512 MS512 Nano Nano TechnologyTechnology
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 oxyhydratesrestrict 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 hybridsColloidal 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
Prof. Prof. ByeongByeong--Soo BaeSoo Bae MS512 MS512 Nano Nano TechnologyTechnology
Inorganic Polymerization
Monomer
O
M
O
OO
Solution
Dimer
O
M
O
OO M
O
O
O
Oligomer
O
M
O
OO M
O
O
O M
O
O
O M
O
O
O
Sol
Gel
O
M
O
OO M
O
O
O M
O
O
O
O
M
O
OO M
O
O
O M
O
O
O
O
M
O
OO M
O
O
O M
O
O
O M
O
O
O
O
M
O
OO M
O
O
O
O
M
O
OO M
O
O
O M
O
O
O M
O
O
O M O
O
M
O
O
O
M
O
OO M
O
O
O M
O
O
O M
O
O
O
O
M
O
OO M
O
O
O
O
M
O
OO M
O
O
O M
O
O
O M
O
O
O M O
O
M
O
O
Solid
ColloidOxideGelation
DryingSintering
Prof. Prof. ByeongByeong--Soo BaeSoo Bae MS512 MS512 Nano Nano TechnologyTechnology
Processing of Sol-Gel Materials
Powders
Monoliths
Fibers
Coatings and Thin Films
Porous Materials and Aerogel
Prof. Prof. ByeongByeong--Soo BaeSoo Bae MS512 MS512 Nano Nano TechnologyTechnology
Melting and Sol-Gel Process for Glass Fabrication
Prof. Prof. ByeongByeong--Soo BaeSoo Bae MS512 MS512 Nano Nano TechnologyTechnology
Advantages and Disadvantages of Sol-Gel Process
Advantages
♦High purity from raw materials
♦Good homogeneity from raw materials
♦Low processing temperature
♦Good shape ability
♦Production of new composition glasses
Disadvantages
♦High cost of raw materials
♦Large shrinkage during processing
♦Residual fine pores and hydroxyls
♦Health hazards of organic solution
♦Easily cracking during the drying stage
♦Long processing times
Prof. Prof. ByeongByeong--Soo BaeSoo Bae MS512 MS512 Nano Nano TechnologyTechnology
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
Prof. Prof. ByeongByeong--Soo BaeSoo Bae MS512 MS512 Nano Nano TechnologyTechnology
Fabrication of Sol-Gel Optical Fiber Preform
정화정화소결소결
혼합혼합 및및 캐스팅캐스팅 탈착탈착 건조건조
Prof. Prof. ByeongByeong--Soo BaeSoo Bae MS512 MS512 Nano Nano TechnologyTechnology
Sol-Gel Coatings on Display
GlassGlass
ConductiveConductivelayerlayer
Silica layerSilica layer
LightLight
1.0% 1.0% of incident lightof incident light<Interference effect><Interference effect>
AntiglareAntiglare
RR GG BB
PhosphorPhosphor
AR layersAR layers
Prof. Prof. ByeongByeong--Soo BaeSoo Bae MS512 MS512 Nano Nano TechnologyTechnology
Preparation of Nano Materials by Sol-Gel Processing
Solution Glass, Ceramics
Heated gelSol Dry
gelWet gel졸-겔 생성물
Porous gels
Pores
Gels dispersed with organic
molecules
Inorganic-organic
composites
CeramicsGlassGels dispersed with inorganic or
metal particles
Organic moleculesOrganic polymer Inorganic network
ParticlesGrains
<100°C <150°C <500°C <1200°C<100°C
미세구조
나노구조재 나노하이브리드 나노복합체나노복합체
Prof. Prof. ByeongByeong--Soo BaeSoo Bae MS512 MS512 Nano Nano TechnologyTechnology
II. Chemistry of Precursors SolutionsPrecursor Solution
Chemical Precursor♦Chemical reactant which contain the cation M present
in the final inorganic sol or gel
♦Metallic salts - MmXn, eq) AlCl3Metal alkoxides – M(OR)n, eq) Al(OC2H5)3Organometalic compounds
Solvents♦Water♦Non-aqueous solution
♦Protic solventAprotic solvent
♦Acidic solventBasic solventAmphoretic solvent
Prof. Prof. ByeongByeong--Soo BaeSoo Bae MS512 MS512 Nano Nano TechnologyTechnology
Hydrolysis of Metal Salts Solution
Ions Solvation♦Dissolution is solution
MX Mz+ + Xz- in the solution
♦Cation solvationSolvatation 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
Prof. Prof. ByeongByeong--Soo BaeSoo Bae MS512 MS512 Nano Nano TechnologyTechnology
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+
h=0 : [MONH2N]Z+
aquo-ion0<h<N : [M(OH)X(OH2)N-x](Z-X)+
hydroxo-aquo complexh=N : M(OH)N](N-Z)-
hydroxo complexN<h<2N : [MOX(OH)N-x](N+X-Z)-
oxo-hydroxo complexh=2N : [MON](2N-Z)-
oxo-ion
Prof. Prof. ByeongByeong--Soo BaeSoo Bae MS512 MS512 Nano Nano TechnologyTechnology
Condensation of Metal Salt SolutionCondensation 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
H2OM ⇔ -M- + H2O -M-OH + -M- ⇔ M-OH-M-
♦For the higher charge cations – nucleophilic addition reaction AN-M-OH + -M-OH ⇔ M-OH-M-OH
♦For the transition elements – associative SN2 mechanism
Prof. Prof. ByeongByeong--Soo BaeSoo Bae MS512 MS512 Nano Nano TechnologyTechnology
Condensation by Oxolation♦For the low charge cations – dissociative SN1 mechanism
H2OM ⇔ -M- + H2O -M-OH + -M- ⇔ M-OH-M-
♦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
Prof. Prof. ByeongByeong--Soo BaeSoo Bae MS512 MS512 Nano Nano TechnologyTechnology
Alkoxide PrecusorsAlkoxides:M(OR)n M= Si,Ti,Zr,Al
R= -CH3, -CH2CH3
Prof. Prof. ByeongByeong--Soo BaeSoo Bae MS512 MS512 Nano Nano TechnologyTechnology
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
Prof. Prof. ByeongByeong--Soo BaeSoo Bae MS512 MS512 Nano Nano TechnologyTechnology
Hydrolysis of Silicon Alkoxide♦Acidic solution (pH < 2.5)
- Negatively charged particles- [H3O]+ attack the oxygen in alkoxy group
Formation of Oxo Ligands♦ Lewis base♦ Water vapor
♦Basic solution (pH > 2.5)- Positively charged particles- OH- attacks the Si in alkoxides
Prof. Prof. ByeongByeong--Soo BaeSoo Bae MS512 MS512 Nano Nano TechnologyTechnology
Condensation of Metal Alkoxides
Condensation by Olation♦ SN2 nucleophilic substitution mechanism -
Condensation of Oxolation♦ Transfer of the H to an OR ligand ♦ Transfer of the H to an OH group
Prof. Prof. ByeongByeong--Soo BaeSoo Bae MS512 MS512 Nano Nano TechnologyTechnology
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
Prof. Prof. ByeongByeong--Soo BaeSoo Bae MS512 MS512 Nano Nano TechnologyTechnology
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
Prof. Prof. ByeongByeong--Soo BaeSoo Bae MS512 MS512 Nano Nano TechnologyTechnology
III. Sol-Gel Process of Silica17
Prof. Prof. ByeongByeong--Soo BaeSoo Bae MS512 MS512 Nano Nano TechnologyTechnology
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
Prof. Prof. ByeongByeong--Soo BaeSoo Bae MS512 MS512 Nano Nano TechnologyTechnology
17Silicon Alkoxide Sol-Gel
hydrolysis
estrification
Si- OR + H2O Si- OH + ROH
alcohol condensation
alcoholysis
Si- OR + HO- Si Si- O- Si + ROH
water condensation
hydrolysisSi- OH+ HO- Si Si- O- Si + H2O
Precursor Solution♦Silicon alkoxide + water + alcohol + catalyst
♦H2O:Si molar ratio (r) – 1~ over 50
Concentrations of acids or bases – 0.01 ~ 7 M
Prof. Prof. ByeongByeong--Soo BaeSoo Bae MS512 MS512 Nano Nano TechnologyTechnology
Tetraalkoxysilanes♦ Si(OR)4 : ♦ TEOS(tetraethoxysilane),
TMOS(tetramethoxysilane)
Organoalkoxysilanes♦ R‘nSi(OR)3 : ♦ MTMS(Metyltrimethoxysilane),
DMDMS(Dimetyldimethoxysilane)
Precursor Molecules
Molecular Building Blocks♦ Hexamethoxydisiloane
OctamethoxytriethoxtsilaneMethoxylated cubic octamer - Silsiquioxane
Prof. Prof. ByeongByeong--Soo BaeSoo Bae MS512 MS512 Nano Nano TechnologyTechnology
17Hydrolysis of Silicon Alkoxides
Effects of Catalyst
H2O/Si Ratio (r)
Prof. Prof. ByeongByeong--Soo BaeSoo Bae MS512 MS512 Nano Nano TechnologyTechnology
17 Steric and Inductive Effects
Effects of Solvents♦ Protic solvent enhance hydrolysis
Prof. Prof. ByeongByeong--Soo BaeSoo Bae MS512 MS512 Nano Nano TechnologyTechnology
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
Prof. Prof. ByeongByeong--Soo BaeSoo Bae MS512 MS512 Nano Nano TechnologyTechnology
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
Prof. Prof. ByeongByeong--Soo BaeSoo Bae MS512 MS512 Nano Nano TechnologyTechnology
16
Sol-Gel FerroelectricsMetallorganic Precursors♦Metal alkoxides
Zr n-propoxide [Zr(OC3H7)4]Ti isopropoxide [Ti(OCH(CH3)2)4]Ethoxides, Butoxides
♦Inorganic or organic saltsLa nitratePb acetate
Solvents♦Primary solvent - stablization
Chemical modifiers- methoxyethanol, acetic acid glycol
Chelating agents- β-diketone (acetylacetone)
♦Secondary solventEthylene glycol, propanol, methanol or waterControl in viscosity, pH, surface tension
Lead Titanium Zirconium
Gelation Control Firing Additives
Viscosity Adjustment
Precursor Solution
Dipping,Sprayingor Spin Coating
Crystallization400-700 ºC
Drying and Organic Removal280-400ºC
Multilayer Coatings
Alcohol or Water
IV. Sol-Gel Process of Complex OxidesSolution Process of Electo or Optical Ceramics
Prof. Prof. ByeongByeong--Soo BaeSoo Bae MS512 MS512 Nano Nano TechnologyTechnology
17Preparation of Ferroelectric Solutions
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
Prof. Prof. ByeongByeong--Soo BaeSoo Bae MS512 MS512 Nano Nano TechnologyTechnology
Fabrication of Ferroelectric Films
Sr metal Ba metal
2-Methoxyethanol
Nb(OC2H5)5
2-Methoxyethanol
La nitrate Pb acetate
22-Methoxyethanol
0.4M precusor solution
Drying
2-Methoxyethanol
Distillation Distillation Ti isopropoxide
Coating
Heat Treatmentfor Crystallization
Iteration
In dry N2 gas
Coating
Drying
Heat Treatmentfor Crystallization
Iteration
Refluxing Refluxing (12h)
0.1M SBN sol
Prof. Prof. ByeongByeong--Soo BaeSoo Bae MS512 MS512 Nano Nano TechnologyTechnology
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
Prof. Prof. ByeongByeong--Soo BaeSoo Bae MS512 MS512 Nano Nano TechnologyTechnology
IV. Sol-Gel Process of Hybrid Materials size
mm
µm
1nm
1Å
분산상의 크기
복합재료
폴리머/폴리머
유리입자/폴리머
유리섬유/폴리머
세라믹/폴리머
금속/폴리머
세라믹/금속
(FRP,FRC,FRM)
Nanocomposite
Nanohybrid
물리적 혼합
물성은 복합
법칙에 따름
복합법칙에 따르지
않는 새로운 물성이
발견됨
수소결합
화학결합
신물질
신물성
Physical hybridization
Chemical hybridization
Prof. Prof. ByeongByeong--Soo BaeSoo Bae MS512 MS512 Nano Nano TechnologyTechnology
Class I (Class I (NanocompositeNanocomposite))Organic dyes embedded in sol-gel matrixOrganic dyes, inorganic ions or molecules + silica, aluminosilicate, zirconia, titania
fluorescence, photochromic, non-linear optical properties
Inorganic particles embedded in a polymerInorganic particles + polymer blend
Prof. Prof. ByeongByeong--Soo BaeSoo Bae MS512 MS512 Nano Nano TechnologyTechnology
Organic monomers embedded in sol-gel matricesPolymerizable organic monomer + sol-gel inorganic matrices
Polymerization
Sol-gel
Polymers filled with in-situ generated inorganic particlesInorganic particle formation by sol-gel reaction in a polymer matrices
Sol-gel
Polymerization
Prof. Prof. ByeongByeong--Soo BaeSoo Bae MS512 MS512 Nano Nano TechnologyTechnology
Simultaneous formation of interpenetrating organic-inorganic networksAlkoxides functionalized by liable plymerizable group
Sol-gel
Polymerization
Prof. Prof. ByeongByeong--Soo BaeSoo Bae MS512 MS512 Nano Nano TechnologyTechnology
Obtension of ordered organic-inorganic structuresInsertion of organic molecules polymers into an anisotropic inorganic network
Build anisotropic inorganic particles using organic molecules and self assembled aggregates
Sol-gel
Prof. Prof. ByeongByeong--Soo BaeSoo Bae MS512 MS512 Nano Nano TechnologyTechnology
Class II (Class II (NanohybridsNanohybrids))
Organically modified silicon alkoxides R’xSi(OR)4-x
PolymerizationSol-gel
Polyfunctional alkoxysilanes (RO)3Si-R’-Si(OR)3
Sol-gel
Prof. Prof. ByeongByeong--Soo BaeSoo Bae MS512 MS512 Nano Nano TechnologyTechnology
Alkoxysilanes functionalized by polymers (RO)3Si-Polymer-Si(OR)3
Sol-gel
Surface modification by organoalkoxysilanes
Polymerization
Prof. Prof. ByeongByeong--Soo BaeSoo Bae MS512 MS512 Nano Nano TechnologyTechnology
Template building blocks
Polymerization
Ordered hybrid materialsSelf-assembly of molecular units on surface hydroxyl groups
Prof. Prof. ByeongByeong--Soo BaeSoo Bae MS512 MS512 Nano Nano TechnologyTechnology
Hybrids from SolHybrids from Sol--Gel Process ofGel Process of OrganoalkoxysilanesOrganoalkoxysilanes
Network modifier ( R' : unreactable)
CnH2n+1-Si(OR)3 methyl, ethyl
Si(OR)3 phenyl
H2N-(CH2)3-Si(OR)3 amino
CF3-(CF2)n-(CH2)2-Si(OR)3 fluoro
Network former ( R' :polymerizable)
H2CO
CH-O-(CH2)3-Si(OR)3 epoxy
O
O-(CH2)3-Si(OR)3 methacrylate
HS-(CH2)3-Si(OR)3
CH2C
HSi(OR)3
mercaptopropyl
vinyl
R
R
R
= O= Si,Ti,Zr,...inorganicmodifierentrappedmolecule
Rorganicpolymericchain
ModificationFunctionalization Crosslinking
RR’’nnSiSi(OR)(OR)44--nn
Prof. Prof. ByeongByeong--Soo BaeSoo Bae MS512 MS512 Nano Nano TechnologyTechnology
Compensation of CharacteristicsHard and StableSoft and FlexibleEasy ProcessCheap
FunctionalizationModificationNew function
TransparencyOptical materialsFunctional coating
Silica Network
Polymer Network
Heterometal NetworkOrganic Modification
ORMOCER, CERAMER, POLYCERAM,Hybrid Sol-Gel Glass, Hybrid Polymer, HYBMRIMER
ORMOCER, CERAMER, POLYCERAM,Hybrid Sol-Gel Glass, Hybrid Polymer, HYBMRIMER
SolSol--Gel Hybrid Materials (HYBRIMER)Gel Hybrid Materials (HYBRIMER)
Prof. Prof. ByeongByeong--Soo BaeSoo Bae MS512 MS512 Nano Nano TechnologyTechnology
Characteristics of HYBRIMERCharacteristics of HYBRIMERTransparency
Functionality
Compensation of Characteristics
Modulation & Tunability of Characteristics
Easy Process & Fabrication
High Thermal & Chemical Stability
Easy Encapsulation with Better Compatibility
Prof. Prof. ByeongByeong--Soo BaeSoo Bae MS512 MS512 Nano Nano TechnologyTechnology
Transparency of HYBRIMERTransparency of HYBRIMERHybrids of molecular level
Coloration by doping of dyes or colloids
Application of optics, display, and coatings
Prof. Prof. ByeongByeong--Soo BaeSoo Bae MS512 MS512 Nano Nano TechnologyTechnology
Compensation of CharacteristicsCompensation of Characteristics
Ref.: Fraunhofer ISC
Prof. Prof. ByeongByeong--Soo BaeSoo Bae MS512 MS512 Nano Nano TechnologyTechnology
Compensation of CharacteristicsCompensation of Characteristics
Compensation of Polymer and Glass Properties
HighLowHardness
450 -95090 -250Thermal Stability
4 -1301 -10Young’s Modulus (Mpa)
-10 to 160150 to 700Thermal Expansion
-8 to 6-140 to -85dn/dT (10-7℃)
HighLowDielectric Constant
1.35 – 1.951.40 - 1.65Refractive index
GlassPolymers
Prof. Prof. ByeongByeong--Soo BaeSoo Bae MS512 MS512 Nano Nano TechnologyTechnology
Compensation of CharacteristicsCompensation of CharacteristicsMechanical Properties Silica/PDMS HYBRIMER
Prof. Prof. ByeongByeong--Soo BaeSoo Bae MS512 MS512 Nano Nano TechnologyTechnology
Functionality of HYBRIMERFunctionality of HYBRIMERHydrophilic and Hydrophobic Coatings
Prof. Prof. ByeongByeong--Soo BaeSoo Bae MS512 MS512 Nano Nano TechnologyTechnology
Optical Application of HYBRIMEROptical Application of HYBRIMERSolid 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
Prof. Prof. ByeongByeong--Soo BaeSoo Bae MS512 MS512 Nano Nano TechnologyTechnology
Functionality of HYBRIMERFunctionality of HYBRIMERNLO Chromophore HYBRIMER
UnpoledPolymers
PoledPolymers
heating around Tgelectric field oncoolingelectric field off
SHG
EO
EOwave length changeFrequancy Doubling
amplitude, wave formE-O Modulators
spatial, wave frontSpatial Light Modulators
(a)
(b)
(c)
••
••
UnpoledSol-GelHybrids
PoledSol-GelHybrids
이광섭 교수, 한남대
HC
l / DM
F-C
H3 O
H
-H2 O
Si(OEt)3(OEt)3Si
NL
O
Si
SiO
O SiO
OO
SiSi
O
O
O
SiOSi
OSi
OO
SiOSi
O OSi
O
Si
O O
Si
Si O
OSi O
O Si
OSi
OSi
O
O O
O
Si
Si
SiO
O O
O O
O
Si
Si
SiO
O SiO
OO
SiSi
O
O
O
SiOSi
OSi
OO
SiOSi
O OSi
O
Si
O O
Si
Si O
OSi O
O Si
OSi
OSi
O
O O
O
Si
Si
SiO
O O
O O
O
Si
NLO
NLO
NLO
NLO
NLO
NLO
NLO
NLO
NL
O
NL
O
NLO
NLO
Prof. Prof. ByeongByeong--Soo BaeSoo Bae MS512 MS512 Nano Nano TechnologyTechnology
Silica vs. Polymer for Waveguide MaterialsSilica vs. Polymer for Waveguide Materials
SilicaSilica PolymerPolymerSpin-on
Low temp.Easy, Cheap
Versatile
FHD,CVDHigh temp
Difficult,Expensive.Process
AbsorptionLower Low
Mechanical LowHigh
Thermal LowHigh
Thermo-optics HighLowNot VersatileDesign
FunctionalityNot Versatile
PolarizationdependenceStress Anisotropy
Prof. Prof. ByeongByeong--Soo BaeSoo Bae MS512 MS512 Nano Nano TechnologyTechnology
Advantages of HYBRIMER WaveguideAdvantages of HYBRIMER Waveguide
Silica Waveguide
Sol-Gel Silica Waveguide
• Manipulation of refractive index in a broad range• Easy fabrication• Easy incorporation of inorganic/organic doponts
• Manipulation of refractive indexin a broad range
• Thermally and chemically stable• Hardness for end facet polishing
• Thick films without cracks• Hydrogen bonding to stabilize
organic dopants• Photoimprinting, Easy process
HYBRIMER Waveguide
Polymer Waveguide
Prof. Prof. ByeongByeong--Soo BaeSoo Bae MS512 MS512 Nano Nano TechnologyTechnology
Micro-Patterning in HYBMRIMER by Photo-polymerization
hν
R'=CH3;C2H4OH = - C3H6OOC -
Photo-initiator
Selective etchingUV
developing
Fabrication of waveguides
Prof. Prof. ByeongByeong--Soo BaeSoo Bae MS512 MS512 Nano Nano TechnologyTechnology
Encapsulation & Immobilization in HYBRIMEREncapsulation & Immobilization in HYBRIMEREntrapment of biomolecules and chemical species in porous structureBetter compatibility in organic environmentsApplications in biosensor, bioreactors, chemical sensor, catalysis
Prof. Prof. ByeongByeong--Soo BaeSoo Bae MS512 MS512 Nano Nano TechnologyTechnology
VI. Sol-Gel Process of Mesoporous MaterialsMicelle Structure
♦Spherical micelle
♦Cylindrical micelle
♦Lamellar micelle
♦ Inverse micelle
Prof. Prof. ByeongByeong--Soo BaeSoo Bae MS512 MS512 Nano Nano TechnologyTechnology
Ordered Mesoporous Materials♦Hexagonal packing of cylindrical micelles♦ Cubic packing of spherical micelles♦Planar packing of micellar micelles
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
Hexagonal Cubic LamellarCubic
Prof. Prof. ByeongByeong--Soo BaeSoo Bae MS512 MS512 Nano Nano TechnologyTechnology
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. Prof. ByeongByeong--Soo BaeSoo Bae MS512 MS512 Nano Nano TechnologyTechnology
Pure Silicate CompositionLiquid Crystal Templating Mechanism
Silica source – TEOS, Ludox, fumed silica, sodium silicateAlkyltrimethylammonium halide surfactant - cetyltrimethylammonium bromide (CTAB)Base - sodium hydroxide or tetramethylammonium hydroxide (TMAOH)Water
Silicate Rod Assembly
Prof. Prof. ByeongByeong--Soo BaeSoo Bae MS512 MS512 Nano Nano TechnologyTechnology
Silicate Layer Puckering Charge Density Matching
Folding Sheets
Prof. Prof. ByeongByeong--Soo BaeSoo Bae MS512 MS512 Nano Nano TechnologyTechnology
Silicatropic Liquid Crystals
Prof. Prof. ByeongByeong--Soo BaeSoo Bae MS512 MS512 Nano Nano TechnologyTechnology
General Liquid Crystal Templating Mechanism: Electrostatic Mechanism
Prof. Prof. ByeongByeong--Soo BaeSoo Bae MS512 MS512 Nano Nano TechnologyTechnology
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