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Chalcogenide custom glass development Nathan Carlie DSS Conference, 04/25/12, [email protected]

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Page 1: Chalcogenide custom glass developmentspie.org/Documents/Industry relations/IR standards... · 2012. 5. 23. · SCHOTT is committed to providing the highest quality materials available,

Chalcogenide custom glass development

Nathan Carlie

DSS Conference, 04/25/12, [email protected]

Page 2: Chalcogenide custom glass developmentspie.org/Documents/Industry relations/IR standards... · 2012. 5. 23. · SCHOTT is committed to providing the highest quality materials available,

Business Unit/Department

Qualification of US-produced IG-series glasses

SCHOTT recently transferred the Vitron IG-series glasses to the US for production in

Duryea, PA.

• All properties for IG2-IG6 have been verified as being in-specification compared to Vitron.

• Physical and Thermal property measurements are straight-forward, refractive index is more

challenging.

• Refractive index guaranteed to

0.0005 RIU

• To date, all index measurements have been carried out by 3rd-party vendor M3MSI

• Current reproducibility of measurements seems to be

0.0002 RIU.

• dn/dT relative measurements carried out from -50 to 75

C in 5

C increments.

• SCHOTT is conducting per-piece inspection down to 0.1mm resolution in-house.

• IR interferometer under development for homogeneity/birefringeance measurements.

• Prism system for per-melt verification of index/dispersion online, and being upgraded to 0.0002 RIU

2

Page 3: Chalcogenide custom glass developmentspie.org/Documents/Industry relations/IR standards... · 2012. 5. 23. · SCHOTT is committed to providing the highest quality materials available,

Business Unit/Department

Reference mirrors (removable)

Pin hole

Beam splitter

(removable)

I

G Striae

Inclusions

Sub-surface

damage

3

IR Quality Inspection

Page 4: Chalcogenide custom glass developmentspie.org/Documents/Industry relations/IR standards... · 2012. 5. 23. · SCHOTT is committed to providing the highest quality materials available,

Business Unit/Department

Slide 4

Refractive index measurments

• Index resolution

0.0002 RIU

• Absolute accuracy

0.0005 RIU

• Wavelength range: 405nm – 12.2 μm

4x Diode laser

405, 650, 785,1550 nm

Mirror

Beam Splitter (Uncoated Ge)

Polarizer (Glan-Taylor)

Beam Splitter (Pellicle)

Detector (Si/InGaAs)

Detector (HgCdTe)

IR Tunable laser

6-12 μm

4

Page 5: Chalcogenide custom glass developmentspie.org/Documents/Industry relations/IR standards... · 2012. 5. 23. · SCHOTT is committed to providing the highest quality materials available,

Business Unit/Department

Origin of the Sellmeier dispersion relation

5

0 2 4 6 8 10 12

2.76

2.78

2.80

2.82

2.84

2.86

2.88

2.90

2.92

2.94

Re

fra

ctiv

e I

nd

ex

Wavelength [ m]

Kramers-Heisenberg Q.M. Oscillator

-Formulated according to Drude model

Converted from frequency to wavelength

and constants collected

Refractive index of IG6 at 20

C

0.0002

Band-gap

50

Phonon frequency

• Incident light at a harmonic frequency is absorbed – results in an asymptote (pole) in refractive index

• Crystals are well-defined but complex, dispersion may be calculated from first principles

• Glasses have only short-range structure and not known a-priori – must be determined empirically.

• Minimum of 2 oscillators are needed:

• Activation of vibrations (phonon modes) by infrared radiation

• Promotion of electrons from conduction to valence band in UV-Vis (NIR).

Page 6: Chalcogenide custom glass developmentspie.org/Documents/Industry relations/IR standards... · 2012. 5. 23. · SCHOTT is committed to providing the highest quality materials available,

Business Unit/Department

Residuals from refractive index data fitting.

6

0 2 4 6 8 10 12-0.0012

-0.0010

-0.0008

-0.0006

-0.0004

-0.0002

0.0000

0.0002

0.0004

0.0006

Re

gu

lar

Re

sid

ua

l [R

IU]

Wavelength [ m]

0 2 4 6 8 10 12

-0.00004

-0.00003

-0.00002

-0.00001

0.00000

0.00001

0.00002

0.00003

0.00004

C2 = 0.3362

C2 = 0.5866

C2 = 0.8157

Re

gu

lar

resid

ua

l [R

IU]

Wavelength [ m]

Fitting residuals: 2-poles Fitting residuals: 3 poles

• Residuals too large 0.001

• Systematic trend shows poor reproduction of

dispersion shape.

Too few terms!

• Residuals below measurement uncertainty and

randomly distributed.

• C2 can be any value with equally low residuals

Equation over parameterized. Too many terms!

6-term equation usable but not optimal. How can we reconcile this?

Page 7: Chalcogenide custom glass developmentspie.org/Documents/Industry relations/IR standards... · 2012. 5. 23. · SCHOTT is committed to providing the highest quality materials available,

Business Unit/Department

Refractive index has an extra component

7

• Fitting residuals are as a low as for the 6-term version

• A unique value is now found for all terms.

• Each term has physical meaning, rather than being a simple fitting parameter

Philosophically satisfying result.

0 2 4 6 8 10 12

-0.00004

-0.00002

0.00000

0.00002

0.00004

0.00006

Re

gu

lar

Re

sid

ua

l [R

IU]

Wavelength [ m]

Index is derived from the real part of

the dielectric constant.

Dielectric constant exists even at ν = 0 (DC).

A fifth term must be added for

DC component (ε0)

We can use this form to look at systematic variations.

Page 8: Chalcogenide custom glass developmentspie.org/Documents/Industry relations/IR standards... · 2012. 5. 23. · SCHOTT is committed to providing the highest quality materials available,

Business Unit/Department

Evolution of Thermo-optic coefficient with wavelength.

8

0 2 4 6 8 10 12

30

40

50

60

70

80

Th

erm

o-o

ptic c

oe

ffic

ien

t [p

pm

/K]

Wavelength [ m]

dn/dT seems to follow expected trend.

Page 9: Chalcogenide custom glass developmentspie.org/Documents/Industry relations/IR standards... · 2012. 5. 23. · SCHOTT is committed to providing the highest quality materials available,

Business Unit/Department 9

0 2 4 6 8 10 12

2.76

2.78

2.80

2.82

2.84

2.86

2.88

2.90

2.92

2.94

-50oC

-25oC

0oC

25oC

50oC

75oC

Re

fra

ctive

In

de

x

Wavelength ( m)

-60 -40 -20 0 20 40 60 803.94

3.96

3.98

4.00

4.02

4.04

4.06

4.08

A

B1

B2

Temperature

3.68

3.70

3.72

3.74

3.76

3.78

3.80

3.82

3.84

1.723

1.724

1.725

1.726

1.727

1.728

1.729

1.730

1.731

0 2 4 6 8 10 12

-0.00008

-0.00006

-0.00004

-0.00002

0.00000

0.00002

0.00004

0.00006

-50 oC

-25 oC

0 oC

25 oC

50 oC

75 oC

Re

gu

lar

Re

sid

ua

l [R

IU]

Wavelength [ m]

Variation of Sellmeier coefficients with temperature.

Effects of temperature on Sellmeier coefficients

are as predicted from dn/dT curve.

• A term has negative dependence, mostly due to

thermal expansion.

• Influence of B1 is larger and overcomes effect of

CTE on index.

Can also expect changes in dispersion.

• Impact of B2 is negligible.

Page 10: Chalcogenide custom glass developmentspie.org/Documents/Industry relations/IR standards... · 2012. 5. 23. · SCHOTT is committed to providing the highest quality materials available,

Business Unit/Department

Change in dispersion with temperature (d2n/dλdT)

10

-60 -40 -20 0 20 40 60 80

-0.015

-0.010

-0.005

0.000

0.005

0.010

0.015

0.020

0.025

VSWIR

VMWIR

VLWIR

% C

ha

ng

e in

Ab

be

nu

mb

er

Temperature (oC)

-60 -40 -20 0 20 40 60 80

13.1

13.2

13.3

13.4

13.5

13.6

Ch

an

ge

in

Ab

be

nu

mb

er V

SWIR

VMWIR

VLWIR

Temperature (oC)

166

167

168

169

170

171

172

159.5

159.6

159.7

159.8

159.9

160.0

160.1

160.2

160.3

As expected from previous examples, dispersion varies with temperature.

• Difficult to compare in absolute terms due to different scales for various IR bands.

• When presented in % change (ie. Impact on chromaticity) trends become more clear.

10x Larger change in dispersion in SWIR/MWIR bands with little change in LWIR.

• Critical knowledge for designing athermal multi-spectral systems.

Page 11: Chalcogenide custom glass developmentspie.org/Documents/Industry relations/IR standards... · 2012. 5. 23. · SCHOTT is committed to providing the highest quality materials available,

Business Unit/Department

A note on some new data

11

-10 0 10 20 30 40 50 60 70 80

2.7760

2.7765

2.7770

2.7775

2.7780

2.7785

2.7790

2.7795

IG6 @ 10.6 m

Re

fra

ctive

In

de

x

Temperature (oC)

• dn/dT is clearly nonlinear, average value will depend on the temperature range used.

• Wavelength-dependence of the nonlinearity has not yet been determined.

• Importance of this effect is not yet known, but is expected to be most significant at extreme temperatures.

-10 0 10 20 30 40 50 60 70 80-0.0003

-0.0002

-0.0001

0.0000

0.0001

0.0002

0.0003

Lin

ea

r F

ittin

g r

esid

ua

lTemperature (

oC)

Page 12: Chalcogenide custom glass developmentspie.org/Documents/Industry relations/IR standards... · 2012. 5. 23. · SCHOTT is committed to providing the highest quality materials available,

Business Unit/Department

Conclusions

US-produced chalcogenide glasses are now fully qualified.

Higher accuracy refractive index and thermo-optic measurements are critical for next-

generation multispectral and wide FOV imaging systems.

Systematic definition of the Sellmeier equation format from first principles allows the

systematic analysis of various influences on the glass (temperature, composition, etc.)

SCHOTT is committed to providing the highest quality materials available, and aims to be the

industry leader in metrology and quality control.

SCHOTT currently has conventional finishing, SPDT and coating capabilities online in the US.

New IR glass compositions are now under development.

Contact for all your IR materials and optics needs.

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