表面與界面物理化学特論
Physical chemistry of
surface and interface
God made solids, but surfaces were the work of the devil.
------Wolfgang Pauli.
Surfaces are the playground of Solid State Physics
--------E. W. Plummer
Masaki Ujihara ( 氏原 真樹 )
Graduate Institute of
Applied Science and Technology
Review
To prepare proper surfaces.
Mechanical polishing
Nanoparticles: Mechanochemical effects should be considered.
Burning (calcination), evaporation
Impurities in solvents can remain on the surface.
We should use the purest solvent and consider “adsorption” of the potential impurities.
Chemical and physical
A thermal decomposition may result a new material on the surface.
Chemical treatments
Dry process
UV irradiation, plasma treatment, ion etching
can cause direct decomposition, oxidation and the other reactions, and spattering.
Wet process
Oxidation and the other reactions (acid or base)
,which can result anisotropic etching for patterning.
Adsorption film
Electrostatic interactions and covalent bindings
toothpaste (polishing powder)
toothbrush
Mechanical polishing
Chemical treatments
Adsorption film
hydroxyapatite With XF(NaF, SnF2, Na2PO3F)
Ca5(PO4)3(OH)
Ca10(PO4)6F2
+
N
With cetylpyridinium chloride
Adsorption film
Crystal lattice (unit cell of the crystal)
c
A unit cell of the crystal
(FCC: face-centered cubic lattice)
b (0 2 0) plane
a
(h k l) = (1/a 1/b 1/c) This plane is a section of the FCC lattice,
Miller indices
which is divided at the half point of “b” and
Parallel to a and c .
(h k l) = (1/∞ 2 1/ ∞)= (0 2 0)
Diamond-type lattice, Diamond structure
diamond-type lattice
e
lan
) p
1 1
(1
diamond-type lattice Tetrahedral structure (1 1 1) plane
e
lan
p
1 1 )
(0 0 1) plane
-
OH (0 0 1) plane is more reactive
(1 than (1 1 1) plane.
OH
-
For Si surface,
After HF treatment, water on the surface should be removed soon.
Facilitate oxidation
anisotropic elution
(111)
(010)
[Link] (110)
To clean ITO substrates,
ITO(Indium Tin Oxide): metal oxide
Ionic material. Acids and bases can not be used.
Neutral Nonionic surfactant → water → acetone → IPA → UV irradiation
About SiO2 surface,
H+ H2O
OH OH OH OH + OH OH H+
O
OH OH OH H+
hydrophobic
OH- H2O
SiO2 OH OH OH OH O- OH
OH-
Surface can be ionized!
hydrophilic
Ionic materials can adsorb the other ionic molecules,
which have the opposite charge.
Counter ion
Negatively charged Surfactant
OH O- OH OH O- OH
hydrophobic hydrophobic
Alkyl chain
- opposite charge
O O- O- O- O- O- O- M+ M+ M+ M+ M+ M+
hydrophilic hydrophilic
Clean surface is hydrophilic!
Contact angles
hydrophilic are different.
OH O- O- OH O- OH O-
hydrophobic The glass became hydrophobic!
-
O O- O- O- O- O- O-
We can estimate the surface property from the shape of water drop.
If the surface is clean enough, the contact angle should be its specific one.
Adsorption
1918: Langmuir
Adsorption isotherm (t=constant)
Number of adsorbed site: N --- Molecules can bind only on them.
M: empty site Binding ratio = 1:1
M+S MS S : molecule
MS: molecules on the binding site
K: equilibrium constant
K= [MS] ≈ Nθ θ: ratio of occupied sites
[M][S] N(1-θ)P P: concentration, pressure (gas)
aLP
θ= aL = constant (instead of K)
1+ aLP
na aLP na = adsorbed amount N
=
bL 1+aLP bL = saturated adsorbed amount
Langmuir adsorption
Langmuir adsorption (Adsorption isotherm)
1
0.9
0.8
0.7
na aLP
θ = b = 1+a P
coverage
0.6
aL=1
0.5 aL=5 L L
aL=10
0.4
0.3
aL=20
na = adsorbed amount
0.2
bL = saturated adsorbed amount
0.1
0
0 1 2 3 4 5 6 7 8 9 10
concentration, pressure (gas)
Langmuir adsorption (Adsorption isotherm)
M: empty site
M+S MS S : molecule
MS: molecules on the binding site
N
1 saturation
0.9 na aLP
0.8 θ = b = 1+a P
0.7 L L
0.6 na = adsorbed amount
50 % 0.5 P50 bL = saturated adsorbed amount
0.4 aL=1
coverage
0.3 aL=5
When θ = 50 %, aLP = 1
aL=10
θ 0.2
0.1
aL=20
0 equilibrium constant aL = 1/P50
0 0.2 0.4 0.6 0.8 1 1.2 1.4
concentration, pressure (gas)
P
Surface properties can be the half.
Or, use analytical methods to know this point.
Applications of Langmuir adsorption model
𝑛𝑎 𝑎𝐿 𝑃 aLP << 1,
𝜃= = aLP >> 1,
𝑛𝑏 1+ 𝑎 𝐿 𝑃
Reactions on surface
- weak adsorption:
reaction rate: first-order reaction
(proportional to P)
- moderate adsorption:
reaction rate:
- strong adsorption:
reaction rate: zero-order reaction
(independent of P)
- moderate adsorption:
reaction rate:
𝑎𝐿 𝑃
𝜃=
1+ 𝑎 𝐿 𝑃
1
𝜃
Slope:
1
= 1 at P =
𝑃
- moderate adsorption:
reaction rate:
𝑛𝑎 𝑎𝐿 𝑃
𝜃= = 𝑛𝑎 (1+ 𝑎𝐿 𝑃 )=𝑏 𝐿 𝑎 𝐿 𝑃
𝑏 𝐿 1+ 𝑎 𝐿 𝑃
𝑃 1 1
𝑃 = 𝑃+
𝑛𝑎 𝑏𝐿 𝑎𝐿 𝑏 𝐿
𝑛𝑎
Slope:
at P = 0 𝑃
At equilibrium,
ΔG = -RT ln K ∆ 𝐺=− 𝑅𝑇 𝑙𝑛𝑎 𝐿
(adsorption/desorption as reactions)
Physical adsorption: ~25 kJ/mol
Typically,∆ 𝐺
Chemical adsorption: ~100 kJ/mol
For gas adsorption
Arrhenius equation
k: rate constant of adsorption/desorption process
− 𝐸𝑎 / 𝑅𝑇
𝑘= 𝐴𝑒 A: frequency factor
Ea: activation energy
R: gas constant (8.314 J mol-1 K-1)
For first-order reaction in desorption process,
half life (τ, t1/2) as residence time Order of
Physical adsorption: ~10-8 sec
τ= Typically, τ Chemical adsorption: ~103 sec
Surface tension
Surface tension
In the bulk phase, molecular interactions are balanced.
A surface is unstable. Then, it has a tendency to be minimum.
Otherwise, it would adsorb the other materials to cap it.
Capping
with more stable moieties
-H -F
-CH3 -Si(CH3)3
When a molecule comes to surface, surface area increases by Amol.
New surface area (Amol) Number of molecules surrounding
Amol at surface: Zs
in bulk: Zb
interaction (ω)
ω/2 ω/2
energy: is required.
Surface tension (γ)
energy/area:
(energy/area: mJ/m2)
Surfactants
Surfactants assemble to the air/water
interface.
Water : 72.8 mN/m @20 ˚C
Surface tension
Typically 20~40 mN/m.
Depending on surfactants.
Concentration of surfactant
Measuring Surface tension
Wilhelmy method (measurement)
P = force (balanced)
mg = mass x gravity acceleration
P
sh ρg = section area x height x density(l) x gravity acceleration
shrink L γ cos θ = boundary length x surface tension x cos θ
γ
shrink P = mg – shρg + L γ cos θ
θ
P
gravity force
buoyant force
Total force of surface tension
P = mg – shρg + L γ cos θ
Pt plate
glass, filter paper
θ≈0 mg - shρg = constant (in one measurement)
∆P = L ∆γ L = 1 ∆P = ∆γ (mN/m)
Wilhelmy method
KSV Instruments Ltd.
[Link]
P = mg – shρg + L γ cos θ
Pt plate
glass, filter paper
θ≈0 mg - shρg = constant (in one measurement)
∆P = L ∆γ L = 1 ∆P = ∆γ (mN/m)
D
γ = ∆ρgD2/H H: correction coefficient
For bubble
Contact angles
At a liquid/solid interface,
Contact angle
If the (γAS - γSL) becomes small,
Liquid/air : γAL the cos Ѳ also becomes small
Surface tension of
Ѳ to balance the 3 forces.
(the Ѳ becomes bigger)
Liquid/solid Air/solid
γSL γAS
Less surface free energy results
γAS = γSL + γALcos Ѳ Higher contact angle.
(Young’s equation) (more hydrophobic)
3 surface tensions balance at the edge of the drop.
Contact angle: Ѳ
top Watch the drop
from its side.
h
2r
Ѳ = 2 Ѳ1
h Ѳ1 θ ＝ 2arctan(h/r)
r Ѳ1
From a photo, we can calculate the contact angle
Hydrophobic Hydrophilic
Superhydrophobic
Water
Ѳ > 150 Ѳ > 90 Ѳ < 90
Lotus effect
Hydro
ph
obic
Simple model
Lotus effect
Hydro
ph
obic
Gravity Surface tensions
Balanced
Smaller contacting area is enough
to hold the drop. Gravity < Surface tensions
Report: Verify “Ѳ = 2 Ѳ1”
θ
Ѳ1
2Ѳ1
Ѳ1
Larger surface area
weak
“Fractal surface” has advantages.
If the surface is “hydrophilic”?
Water tends to expand its surface are.
Super hydrophilic surface.
Capillary phenomenon
Washed by water
oil
Gibbs-Thomson(GT) effect
Tips can be smaller, and pits will be shallowed.
Surface would be flatten. Lower melting point.
When a molecule attached on the tip,
High pressure
∆G = vm∆P (vm: molecular volume )
∆P = σK (σ: surface energy, K: curvature)
∆G = vmσK > 0 disadvantageous
∆G = vmσK < 0 preferable
Low pressure
Additionally, Unstable
Less motion
Flat surface
Easily move: More heat adsorption than the flat part.
More emission of radiation
as if they are at high temperature.
High voltage potential Charged particles
Equipotential plane
Tips are the gateway of energy.
Smaller drops shrink and disappear;
Larger drops grow fat on them.
Ostwald ripening
Important to stabilize an emulsion.
The smaller, the less stable. P P’
γ
Laplace equation γ
∆P = 2γ/R
Smaller drops have larger pressures.
R R’
Then, materials in smaller drops will be released
and absorbed into bigger drops.
Ostwald ripening
Gibbs-Thomson(GT) effect
Tips can be smaller, and pits will be shallowed. Lower melting point.
Surface would be flatten.
Emulsion polymerization
micelle radical
Monomer Polymer
Molecules of monomer
Mini-emulsion polymerization
Optimize the surfactant to minimize Ostwald ripening.
Polymerization directly takes place
radical in the small droplets.
Ostwald ripening
100 nm Monomer Polymer should be inhibited.
Suitable for the less soluble
monomers.
