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Craig Prater, CTO

Research Challenges for Nanomanufacturing Systems

Februay 11-12th, 2008

Nanoscale Thermal Analysis

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Motivations

• Nanomanufacturing needs characterization for research, product development & process control.

– “You can’t manage what you can’t measure”

Rear Admiral Grace Hopper:– “One accurate measurement is worth one thousand

expert opinions”

• Successful nanomanufacturing needs robust, easy-to-use instruments– Instruments operated by technicians and

manufacturing floor personnel

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Some driving questions…• What the &%*# is that?• Where did component X go?• What phase is my material?• Throughput...

AFM images courtesy of Veeco Instruments

High Impact Engineering Plastic

Syndiotacticpolystyrene

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AFM Introduction

Z driveGain

Setpoint Error

Cantilever motion

LaserXY scan

Atomic Force Microscope

(AFM) Image

Z

XY

Photodetector

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ThermoMechanical Analysis (TMA)• Thermomechanical analysis measures sample displacement as a function of temperature, time and applied force

• Identify thermal transitions (e.g. glass transitions)

•Transitions signatures of material composition

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Microfabricated Thermal Probes*

IR pulse

• R = V/I ~ Tip Temperature (T)• ΔT direct measure of absorbed heat• Also heat locally to measure thermal expansion

* Developed in collaboration with Prof. W. King, UIUC

VI

I

ΔT

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•AFM probe with an integrated heater to measure thermal properties of samples

• Ramp tip temperature and monitor the lever to see observe thermal transitions (Tg, Tm)

Nano Thermal Analysis (NanoTA)

Infrared Microscopy

200 μm200 μm

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Correlation to Bulk Thermal Analysis

Three crystalline samples and three amorphous samples were measured by TMA (left) and DSC (right) and compared against nano-TA measurements.

y = 1.0088x - 3.8173R2 = 0.9811

y = 1.0027x + 0.2778R2 = 0.9701

y = 1.0047x + 2.9657R2 = 0.95810

50

100

150

200

250

300

0.0 100.0 200.0 300.0

TMA onset

Nano

Ta O

nset

0.1°C/s1°C/s10°C/s

Slopes: 1.003 - 1.009Offsets: -4 to +3ºC

y = 0.996x + 7.0995R2 = 0.9888

y = 1.0018x + 1.6592R2 = 0.9978

y = 0.9949x + 4.5541R2 = 0.9943

0

50

100

150

200

250

300

0.0 100.0 200.0 300.0

DSC onset

Nan

oTA

Der

iv O

nset

0.1°C/s1°C/s10°C/s

Slopes: 0.995- 1.002Offsets: +2 to +7ºC

Data courtesy of G. Meyers and A. Pasztor, DOW

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Example Applications• Thermal analysis can enable localized identification of

components in blends, composites, multilayers

• Detection of material changes caused by wear, defects, UV exposure, etc.

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Advantages over bulk thermal analysis

• Conventional AFM images with sub-30nm spatial resolution

• Thermal analysis on heterogeneous samples with sub-100 nm resolution

• Local heating to over 500 C at heating rates up to 600,000˚ C/min– Eliminates thermal drift issues that plague bulk sample heating

approaches– Provides much faster sample throughput

• Map the temperatures across the sample with a resolution of <0.1 ºC

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Sample: Toner particles embedded in epoxy and microtomedShown below is a 15 x 7.5 µm topographic scan of toner particles embedded in epoxy and microtomed. To the left are the corresponding nano-TA scans.

Toner ParticleCenter RegionMiddle layer Outer layerEpoxy

74.3 ºC

70.4 ºC

60.4 ºC

Toner Particles

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Data averaged from 3 lenses

The AFM images reveal different microstructures

and the nano-TMA results show very different behavior through the glass

transition

Lens ALens BLens C

Contact Lens

instrumentsanasysData courtesy of M. Reading, D Craig and L. Harding, UEA

The existence of different solid-state forms such as polymorphs, solvates, hydrates, and amorphous form in pharmaceutical drug substances and excipients have downstream consequences in drug products and biological systems

Nanoscale Drug Analysis

Crystalline only Crystalline and amorphousIndomethacin

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•AFM image with simultaneous nanoscale temperature metrology

Scanning Thermal Microscopy

Magnetic recordinghead

Epoxy composite

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Brightfield Optical Microscope

XY Stage

Laser Detection System

Thermal Probe

Sample

Point & Click Nanothermal Analysis

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An optical image and nano-TA measurement on the four layers in a multilayer film composed of Nylon, PET and two forms of low density polyethylene.

94˚ C

88˚ C

180˚ C 218˚ C++ +

+

Multilayer Film

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• Nano-TA extends the capabilities of the AFM by adding localized thermal analysis for localized identification of components and material forms in nanoscale polymers, pharmaceuticals and devices

• Scanning Thermal Microscopy can map thermal conductivity and temperature distributions

• New instruments allow rapid, automated, easy to use localized thermal analysis in environments ranging from R&D to process quality control

Summary

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Backup

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NanoTA AFM accessory

New DSP based control electronics and software have been designed to more accurately control the nano-TA probes with faster ramping and improved signal to noise. This controller is an accessory that operates on most commercial SPMs.