Application of Atomic Force
Microscopy for Polymers
Yanchun Han
Biology and Biomaterials
? Applications of Atomic Force Microscopy for Contact Lens Manufacturing
? Applications for the Biological Sciences
? Direct Measurement of single Immunocomplex Formation by Atomic Force Microscopy
? High Resolution Imaging of Biological Samples by Scanning Probe Microscopy
Materials Science
? Electrical Testing Application Modules for NanoScope Scanning Probe Microscopes
? Electric Force Microscopy,Surface Potential Imaging and Surface Electric Modification with the
(AFM)
? Studies of Metallic Surfaces and Microstructures With Atomic Force Microscopy
? Using Atomic Force Microscopy for Engineering Low Scatter Thin Film Optics
? Electrochemical Applications of Scanning Probe Microscopy
? Nanoindentation,Scratching and Wear Testing Using Scanning Probe Microscopy
Applications of AFM
Polymers
high-resolution profiling of surface morphology,nanostructure,and molecular order
studies of local materials properties
compositional mapping of heterogeneous samples
probing of sub-surface sample structure
Semiconductors
? Atomic Force Profilometry for Characterzation of Chemical Mechanical Planarization
? Scanning Capacitance Microscopy for Carrier Profiling in Semiconductors
? Atomic Force Microscopy Measurements in Support of Chemical Mechanical Polishing (CMP)
? IC Failure Analysis and Defect Inspection with SPM
Data Storage
? Magnetic Force Microscopy,High-Resolution Imaging for Data Storage
? Applications of Atomic Force Microscopy in Optical Disc Technology
Applications of AFM
Phase Separation Structure
?ABS resin
?PC/AES alloy
?PC/ABS alloy
?ABS/PVC alloy
etc
Lamella Structure
?LD-,MD-,HD- Polyethylene
?Linear LD Polyethylene
?UH Molecular Weight PE
?Polypropylene
etc
Next Generation
?Conducting Polymer
?Organic EL
?Biodegradable Polymer
etc
Thermoplastic Elastomer
?Styrene Butadiene-
?Polyester-
?Polyvinyl Chloride-
etc
SPM Application in Polymer Material
? high-resolution profiling of surface morphology,
nanostructure,and molecular order
? studies of local materials properties
? compositional mapping of heterogeneous samples
? probing of sub-surface sample structure
Applications of AFM for Polymers
Structure Function
Heating/Cooling ＳＰＭ
● Observation in the heating process with the air
● Surface and Interface Information
● Observation in the inert gas
● Difficult sample for TEM（Rubber/Rubber blend）
Structure and Function of Polymer
ー Morphology observation with SPM ー
Visco-elasticity
Friction Force
Adhesive Force
Glass trans.
Phase
Hardness
Polymer characterization in
nano scale level
VE-AFM/DFM
FFM/LM-FFMPM
Adhesion
Material Characterization using SPM
Studies of Polymer Surfaces
with AFM
研究内容：高分子形态、纳米结构、链堆砌和构象等
手段：
Contact Mode AFM
LFM
TappingMode
【Purpose】
◆ Distribution of the characteristics change in the polymer surface can
be observed,
【Principle】
◆ Detecting the phase change in DFM measurement
【Advantage】
◆ Simultaneous imaging with DFM
◆ Same advantage as DFM for the soft or charged surface.
(which is difficult to apply LM-FFM or VE-AFM)
resin
silicon
rubber
Topography（７μｍ） PM image（７μｍ）
Material Characterization
DFM／PM（Phase mode）measurement
Observed image of the
heat shrinkage rubber
（resin/silicon rubber） →
100 nm 100 nm
Topography PM image
PP （matrix）EPR
● Lamella structure can be observed clearly with PM mode.
● Domain of Ethylene Propylene Rubber (EPR) is distributed in the Polypropylene (PP) matrix.
（ SPA-300HV,Environment Control Type Unit）
Data No.１ Lamella structure of Polypropylene
Phase（PM：Phase Mode）measurement
－ Structure and Function of Polymer －
Data No.２ Micro Phase Separation Structure of SBS (Phase Mode)
200 nm
R.T.
200 nm
90℃
200 nm
R.T,after cooling
● Polystyrene phase (hard segment) and Polybutadiene phase (soft segment) is clearly separated
● The initial data indicates non-equilibrium condition,because it disappears once it is heated.
Phase（PM：Phase Mode）measurement
－ Structure and Function of Polymer －
（SPA-300HV,Environment Control Type Unit）
OUTPUT
Deflection
Signal of
Cantilever
INPUT
Vibration
Signal to PZT
(1～ 10kHz)
OUTPUT
Deflection
Signal of
Sample
(Large) (Small)
PZT
Cantilever
（ Large）（ Small）
Material Characterization
VE-AFM/DFM（Micro Viscoelasticity Meas.）
【Purpose】
◆ Distribution of the viscoelasticity
change in the polymer surface can be
observed.
【Principle】
◆ Detecting the amplitude and phase
change of the cantilever distortion
when the cyclic force is applied.
【Advantage】
◆ Simultaneous imaging with
topography
◆ Material difference or distribution
can be detected even no change in
topography
【Application】
◆ Plastics,Rubber,Biological
Materials
Data No.３ Polypropylene Block Copolymer
E’
,G’
/ P
a
Temp,/ ℃
ta
nδ
-150 -100 -50 0 50 100 150
10-2
10-1
100
101
103
102
1010
108
106
104
102
-100℃
-70℃
50℃
120℃
-10℃
E’ PP block copolymer
G’ EPR
tanδ PP block copolymer
tanδ EPR
Tg EPR
ＥＰＲ domain ＰＰ matrix
ＰＥ rich
Structure of PP Block Copolymer
PP,Polypropylene
PE,Polyethylene
EPR,Ethylene Propylene Rubber
*In-situ observation is available with
the temperature controlled SPM
*VE-data of SPA300HV is overlapped
with the data of Dynamic Mechanical
Spectrometer DMS6100.
VE-AFM/DFM（MicroViscoelasticity Measurement Mode）
Observation of Glass Transition in Polymer
（ SPA-300HV,Environment Control Type Unit）
【Purpose】
◆ Mapping friction force
distributed sample surface.
【Principle】
◆ Imaging lateral amplitude of a
cantilever,while a sample is
laterally vibrated,
【Advantage】
◆ Simultaneous observation
of topography and friction force.
◆ Valid for imaging material
character distinction of a
compound which does not be
judged from the topography
image.
【Application】
◆ Lubricant?organic compound?
polymer?plastic?
rubber
Lateral ModulationEdge Effect
Twisting distortion Twisting Amplitude
Topography（ 5μ ｍ） ＦＦＭ ＬＭ－ＦＦＭSample, Oil/Polystyrene Sheet
Material Characterization
LM-FFM（Lateral Modulation FFM）
Friction Force Microscope Lateral Modulation FFM
Twisting Distortion Twisting Amplitude
Small VE Large VE Small VE Large VE
Studies of Polymer Surfaces
with AFM
nanostructure of a microporous isotactic polypropylene membrane
height image,surface topography amplitude (error) image,
lamellar and fibrillar features
Studies of Polymer Surfaces
with AFM
Teflon resin,deposited on a substrate by rubbing
at temperatures of about 200° C
Tapping Mode AFM
time
cantilever
vibration
amplitude
setpoint 1
Dt1
free air
amplitude
setpoint 2
Dt2
Dx
Dx
? At setpoint 1,the AFM is operating close to the free vibration amplitude
very little energy is dissipated to the sample surface
? At setpoint 2,the AFM is operating further away from Ao,The amplitude
builds up more rapidly,but more energy is transferred to the surface,
Light vs Hard Tapping
The level of tip-sample interaction depends on Asp and Ao
Very light tapping:
small Ao (2nm),Asp/Ao ~ 1.0 (ie 0.95)
Light tapping:
Ao = 50-100 nm,Asp = 0.9 to 0.8 Ao
Hard tapping:
Ao = 50-100 nm,Asp = 0.5 to 0.4 Ao
Asp/AoAsp/Ao
Near Surface Structure
poly(styrene)-b-poly(butadiene)-b-poly(styrene) triblock copolymer film
All scans are 2μm x 1μm
Light
Tapping
Hard
Tapping
Height Image Phase Image
Butadiene-rich
topmost layer
Stiffer PS blocks
Cycloline PDMS
Light
Tapping
Hard
Tapping
2.5 micron scans,
Near Surface Structure
Compositional Mapping
FMM
TappingMode
Phase Imaging
Compositional Mapping
LLDPE
The "strips", lamellae
All scans are 15μm x 7.5μm,
All scans are 5μm
Impact-Modified Plastics
rubbery particles of about 1nm in size are the brightest features,
The phase contrast is strongly different for the two major polymer
components,one (darker contrast) is seen as a matrix and the
other is presented as brighter domains within it,
Compositional Mapping
Compositional Mapping
All scans are 3μm x 1.5μm,
Two-Component Latex Blend
The smaller number of bright spheres can be assigned to the high
Tg polymer and the surrounding dark areas to the low Tg polymer
Local Mechanical Properties
local mechanical (stiffness,friction) and adhesive properties
Methods:
FMM
Phase Imaging
Nanoindentation Scratching and Wear Testing
force curves
measure the long range attractive or repulsive forces between
the probe tip and the sample surface,elucidating local chemical
and mechanical properties like adhesion and elasticity,
and even thickness of adsorbed molecular layers or bond rupture
lengths mechanical characteristics of single macromolecules
TriboScope Nanomechanical Test Instruments with SPA-400/SPA-300HV
APPLICTION
ＤＬＣfilm,HD／Head,compound material,
ＩＣ,Polymer,nano-mechanical test of
insulation film,etc.
＜仕 様＞
荷重及び感度,
最大１０ｍＮ，分解能１００ｎＮ
変位及び感度,
最大５ μｍ分解能０．２ｎｍ
PURPOSE
１．ＮａｎｏＩｎｄｅｎｔａｔｉｏｎ
With AFM,surface images of thin films before and after indentation is available.
Hardness and elasticity is also available.
２．Micro scratch
Continuous data,depth of scratch and load,is available.
Useful for analyzing stickiness of ultra-thin film.
３．Ｗｅａｒ Ｔｅｓｔｉｎｇ ａｎｄ Ｍｉｃｒｏｍａｃｈｉｎｉｎｇ
Evaluating wear rate by scanning in any range under various load is realized.
0 50 100 150 200
0
200
400
600
Fo
rce,
?
N
D i spl ace m en t,nm
← Force/Displacement curve
（A graphic chart indicating ideal
repeatability of weighting）
Indent data（AFM image）
Scratch（AFM image）
10 nm DLC on a Head Slider
Material Characterization using SPM
Nanoindentation （mechanical test system）
Indentation by AFM
Lithography
Gray Scale Inverted Image
Microwear on PEEK by AFM
Scan rate,1Hz; Samples/line,128; Tip deflection voltage,5 V
Red blood corpuscle
DFM mode (8um x 8um)
DNA
DFM mode (500nm x 500nm)
Living Chromosome
DFM mode (16um x 16um)
Imaging of biological samples
作业
请简述 AFM 的工作原理及其在高分子研究中
的应用
Microscopy for Polymers
Yanchun Han
Biology and Biomaterials
? Applications of Atomic Force Microscopy for Contact Lens Manufacturing
? Applications for the Biological Sciences
? Direct Measurement of single Immunocomplex Formation by Atomic Force Microscopy
? High Resolution Imaging of Biological Samples by Scanning Probe Microscopy
Materials Science
? Electrical Testing Application Modules for NanoScope Scanning Probe Microscopes
? Electric Force Microscopy,Surface Potential Imaging and Surface Electric Modification with the
(AFM)
? Studies of Metallic Surfaces and Microstructures With Atomic Force Microscopy
? Using Atomic Force Microscopy for Engineering Low Scatter Thin Film Optics
? Electrochemical Applications of Scanning Probe Microscopy
? Nanoindentation,Scratching and Wear Testing Using Scanning Probe Microscopy
Applications of AFM
Polymers
high-resolution profiling of surface morphology,nanostructure,and molecular order
studies of local materials properties
compositional mapping of heterogeneous samples
probing of sub-surface sample structure
Semiconductors
? Atomic Force Profilometry for Characterzation of Chemical Mechanical Planarization
? Scanning Capacitance Microscopy for Carrier Profiling in Semiconductors
? Atomic Force Microscopy Measurements in Support of Chemical Mechanical Polishing (CMP)
? IC Failure Analysis and Defect Inspection with SPM
Data Storage
? Magnetic Force Microscopy,High-Resolution Imaging for Data Storage
? Applications of Atomic Force Microscopy in Optical Disc Technology
Applications of AFM
Phase Separation Structure
?ABS resin
?PC/AES alloy
?PC/ABS alloy
?ABS/PVC alloy
etc
Lamella Structure
?LD-,MD-,HD- Polyethylene
?Linear LD Polyethylene
?UH Molecular Weight PE
?Polypropylene
etc
Next Generation
?Conducting Polymer
?Organic EL
?Biodegradable Polymer
etc
Thermoplastic Elastomer
?Styrene Butadiene-
?Polyester-
?Polyvinyl Chloride-
etc
SPM Application in Polymer Material
? high-resolution profiling of surface morphology,
nanostructure,and molecular order
? studies of local materials properties
? compositional mapping of heterogeneous samples
? probing of sub-surface sample structure
Applications of AFM for Polymers
Structure Function
Heating/Cooling ＳＰＭ
● Observation in the heating process with the air
● Surface and Interface Information
● Observation in the inert gas
● Difficult sample for TEM（Rubber/Rubber blend）
Structure and Function of Polymer
ー Morphology observation with SPM ー
Visco-elasticity
Friction Force
Adhesive Force
Glass trans.
Phase
Hardness
Polymer characterization in
nano scale level
VE-AFM/DFM
FFM/LM-FFMPM
Adhesion
Material Characterization using SPM
Studies of Polymer Surfaces
with AFM
研究内容：高分子形态、纳米结构、链堆砌和构象等
手段：
Contact Mode AFM
LFM
TappingMode
【Purpose】
◆ Distribution of the characteristics change in the polymer surface can
be observed,
【Principle】
◆ Detecting the phase change in DFM measurement
【Advantage】
◆ Simultaneous imaging with DFM
◆ Same advantage as DFM for the soft or charged surface.
(which is difficult to apply LM-FFM or VE-AFM)
resin
silicon
rubber
Topography（７μｍ） PM image（７μｍ）
Material Characterization
DFM／PM（Phase mode）measurement
Observed image of the
heat shrinkage rubber
（resin/silicon rubber） →
100 nm 100 nm
Topography PM image
PP （matrix）EPR
● Lamella structure can be observed clearly with PM mode.
● Domain of Ethylene Propylene Rubber (EPR) is distributed in the Polypropylene (PP) matrix.
（ SPA-300HV,Environment Control Type Unit）
Data No.１ Lamella structure of Polypropylene
Phase（PM：Phase Mode）measurement
－ Structure and Function of Polymer －
Data No.２ Micro Phase Separation Structure of SBS (Phase Mode)
200 nm
R.T.
200 nm
90℃
200 nm
R.T,after cooling
● Polystyrene phase (hard segment) and Polybutadiene phase (soft segment) is clearly separated
● The initial data indicates non-equilibrium condition,because it disappears once it is heated.
Phase（PM：Phase Mode）measurement
－ Structure and Function of Polymer －
（SPA-300HV,Environment Control Type Unit）
OUTPUT
Deflection
Signal of
Cantilever
INPUT
Vibration
Signal to PZT
(1～ 10kHz)
OUTPUT
Deflection
Signal of
Sample
(Large) (Small)
PZT
Cantilever
（ Large）（ Small）
Material Characterization
VE-AFM/DFM（Micro Viscoelasticity Meas.）
【Purpose】
◆ Distribution of the viscoelasticity
change in the polymer surface can be
observed.
【Principle】
◆ Detecting the amplitude and phase
change of the cantilever distortion
when the cyclic force is applied.
【Advantage】
◆ Simultaneous imaging with
topography
◆ Material difference or distribution
can be detected even no change in
topography
【Application】
◆ Plastics,Rubber,Biological
Materials
Data No.３ Polypropylene Block Copolymer
E’
,G’
/ P
a
Temp,/ ℃
ta
nδ
-150 -100 -50 0 50 100 150
10-2
10-1
100
101
103
102
1010
108
106
104
102
-100℃
-70℃
50℃
120℃
-10℃
E’ PP block copolymer
G’ EPR
tanδ PP block copolymer
tanδ EPR
Tg EPR
ＥＰＲ domain ＰＰ matrix
ＰＥ rich
Structure of PP Block Copolymer
PP,Polypropylene
PE,Polyethylene
EPR,Ethylene Propylene Rubber
*In-situ observation is available with
the temperature controlled SPM
*VE-data of SPA300HV is overlapped
with the data of Dynamic Mechanical
Spectrometer DMS6100.
VE-AFM/DFM（MicroViscoelasticity Measurement Mode）
Observation of Glass Transition in Polymer
（ SPA-300HV,Environment Control Type Unit）
【Purpose】
◆ Mapping friction force
distributed sample surface.
【Principle】
◆ Imaging lateral amplitude of a
cantilever,while a sample is
laterally vibrated,
【Advantage】
◆ Simultaneous observation
of topography and friction force.
◆ Valid for imaging material
character distinction of a
compound which does not be
judged from the topography
image.
【Application】
◆ Lubricant?organic compound?
polymer?plastic?
rubber
Lateral ModulationEdge Effect
Twisting distortion Twisting Amplitude
Topography（ 5μ ｍ） ＦＦＭ ＬＭ－ＦＦＭSample, Oil/Polystyrene Sheet
Material Characterization
LM-FFM（Lateral Modulation FFM）
Friction Force Microscope Lateral Modulation FFM
Twisting Distortion Twisting Amplitude
Small VE Large VE Small VE Large VE
Studies of Polymer Surfaces
with AFM
nanostructure of a microporous isotactic polypropylene membrane
height image,surface topography amplitude (error) image,
lamellar and fibrillar features
Studies of Polymer Surfaces
with AFM
Teflon resin,deposited on a substrate by rubbing
at temperatures of about 200° C
Tapping Mode AFM
time
cantilever
vibration
amplitude
setpoint 1
Dt1
free air
amplitude
setpoint 2
Dt2
Dx
Dx
? At setpoint 1,the AFM is operating close to the free vibration amplitude
very little energy is dissipated to the sample surface
? At setpoint 2,the AFM is operating further away from Ao,The amplitude
builds up more rapidly,but more energy is transferred to the surface,
Light vs Hard Tapping
The level of tip-sample interaction depends on Asp and Ao
Very light tapping:
small Ao (2nm),Asp/Ao ~ 1.0 (ie 0.95)
Light tapping:
Ao = 50-100 nm,Asp = 0.9 to 0.8 Ao
Hard tapping:
Ao = 50-100 nm,Asp = 0.5 to 0.4 Ao
Asp/AoAsp/Ao
Near Surface Structure
poly(styrene)-b-poly(butadiene)-b-poly(styrene) triblock copolymer film
All scans are 2μm x 1μm
Light
Tapping
Hard
Tapping
Height Image Phase Image
Butadiene-rich
topmost layer
Stiffer PS blocks
Cycloline PDMS
Light
Tapping
Hard
Tapping
2.5 micron scans,
Near Surface Structure
Compositional Mapping
FMM
TappingMode
Phase Imaging
Compositional Mapping
LLDPE
The "strips", lamellae
All scans are 15μm x 7.5μm,
All scans are 5μm
Impact-Modified Plastics
rubbery particles of about 1nm in size are the brightest features,
The phase contrast is strongly different for the two major polymer
components,one (darker contrast) is seen as a matrix and the
other is presented as brighter domains within it,
Compositional Mapping
Compositional Mapping
All scans are 3μm x 1.5μm,
Two-Component Latex Blend
The smaller number of bright spheres can be assigned to the high
Tg polymer and the surrounding dark areas to the low Tg polymer
Local Mechanical Properties
local mechanical (stiffness,friction) and adhesive properties
Methods:
FMM
Phase Imaging
Nanoindentation Scratching and Wear Testing
force curves
measure the long range attractive or repulsive forces between
the probe tip and the sample surface,elucidating local chemical
and mechanical properties like adhesion and elasticity,
and even thickness of adsorbed molecular layers or bond rupture
lengths mechanical characteristics of single macromolecules
TriboScope Nanomechanical Test Instruments with SPA-400/SPA-300HV
APPLICTION
ＤＬＣfilm,HD／Head,compound material,
ＩＣ,Polymer,nano-mechanical test of
insulation film,etc.
＜仕 様＞
荷重及び感度,
最大１０ｍＮ，分解能１００ｎＮ
変位及び感度,
最大５ μｍ分解能０．２ｎｍ
PURPOSE
１．ＮａｎｏＩｎｄｅｎｔａｔｉｏｎ
With AFM,surface images of thin films before and after indentation is available.
Hardness and elasticity is also available.
２．Micro scratch
Continuous data,depth of scratch and load,is available.
Useful for analyzing stickiness of ultra-thin film.
３．Ｗｅａｒ Ｔｅｓｔｉｎｇ ａｎｄ Ｍｉｃｒｏｍａｃｈｉｎｉｎｇ
Evaluating wear rate by scanning in any range under various load is realized.
0 50 100 150 200
0
200
400
600
Fo
rce,
?
N
D i spl ace m en t,nm
← Force/Displacement curve
（A graphic chart indicating ideal
repeatability of weighting）
Indent data（AFM image）
Scratch（AFM image）
10 nm DLC on a Head Slider
Material Characterization using SPM
Nanoindentation （mechanical test system）
Indentation by AFM
Lithography
Gray Scale Inverted Image
Microwear on PEEK by AFM
Scan rate,1Hz; Samples/line,128; Tip deflection voltage,5 V
Red blood corpuscle
DFM mode (8um x 8um)
DNA
DFM mode (500nm x 500nm)
Living Chromosome
DFM mode (16um x 16um)
Imaging of biological samples
作业
请简述 AFM 的工作原理及其在高分子研究中
的应用
