polymer nanocomposites/ ceramics systems · variation of refractive index (633 nm) and Δn with zr...

$: POLYMER NANOCOMPOSITES/ CERAMICS SYSTEMS · Variation of refractive index (633 nm) and Δn with Zr content. (Un: Unexposed, Ex: UV-exposed) EFFECT OF Z R AND UV LIGHT 0 10 20 30 40$
NNT602 Nano Yapılarının Karakterizasyonu

POLYMER NANOCOMPOSITES/

CERAMICS SYSTEMS

Dr. Mehmet Çopuroğlu

Beytepe, Aralık 2011

MEHMET ÇOPUROĞLU

BSc: Chemistry, Hacettepe University

MSc: Chemistry, Hacettepe University; Supervisor: Asst. Prof. Murat Şen

• Ageing characteristics of ethylene-vinyl acetate copolymer and ethylene-

vinyl acetate/carbon black mixture

PhD: Microelectronic Engineering, Tyndall National Institute at National

University of Ireland, Cork (aka UCC); Supervisors: Prof. Gabriel Crean, Dr.

Shane O’Brien

• Development of polymer/nanocomposite thin films

Post-doc: Tyndall National Institute at UCC

• Development of lead-magnesium-niobium titanate-based material systems

for ultra-high-value capacitor applications

PHD-SUMMARY

Developed two material systems

• Inorganic-organic hybrids for potential short-range

photonic interconnect/optical waveguiding

applications

• Ceramics for transparent conducting oxide (TCO)

applications

Sol-gel synthesis

Thin-film deposition and processing

Characterisation

THE SOL-GEL METHOD

Production of materials

• ceramics

• inorganic/organic hybrid materials (e.g.

organically modified silicates (ORMOSILs or

CERAMERs))

THE SOL-GEL METHOD-ADVANTAGES

Low cost

Relatively low-temperature synthesis

Precise control over microstructure and material

properties

Ease of doping

No need for sophisticated instrumentation

THE SOL-GEL METHOD

Involves

• preparation of a colloidal dispersion system (sol)

• gelation of the sol

• removal of the solvent

The sol may

• be produced from inorganic or organic precursors

(e.g. alkoxides, acetates, nitrates)

• consist of dense oxide particles of polymeric

clusters

THE SOL-GEL METHOD

Si OR + H2O Si OH + ROH

hydrolysis

esterification

Si OR + Si O Si + ROH

alcohol condensation

alcoholysis

SiHO

Si OH + Si O Si + H2O

water condensation

hydrolysis

SiHO

Metal Alkoxides:

THE SOL-GEL METHOD

Many parameters:

• H2O:Si ratio

• Other precursor/s and/or metal/s

• type and concentration of the catalyst

• alcohol

• temperature

ORMOSILs

Structural elements of ORMOSILs.

POLYMER NANOCOMPOSITES/ORMOSILs

Structure of nanocomposite. (O. Soppera, C. Croutxé-Barghorn, D. J.

Lougnot, New J. Chem. 25 (2001) 1006.)


Model of ZrO2–methacrylic acid–methacryloxysilane system. (A. D.

Pomogailo, Colloid Journal 67 (2005) 726.)


Various requirements

simultaneously met

• thermal/mechanical stability

• transparency

• biocompatibility, etc.

Combine desired properties of the individual

constituents.

Invaluable for various interdisciplinary

applications

• optoelectronics-waveguides

• coating industry-protective coating

• biotechnology-dental restorative materials

PHD-OUTLINE

Zinc oxide-

dopedZinc oxide-

undopedORMOSIL with

aryl groups

ORMOSIL with

transition metal

Materials

Inorganic/organic

hybridCeramic

STUDY

Investigated parameters:

• refractive index modifier, Zr

• UV light

• sol ageing

Characterised properties:

• structural

• morphological

• optical

• spectroscopical

• thermal

• reliability

SYNTHESIS

Skeletal formulae of the chemicals used, and outline of the synthesis. GDPTMS: (3-

glycidyloxypropyl)trimethoxysilane; DMDMOS: dimethyldimethoxysilane; Zr(OPrn)4: zirconium(IV) n-

propoxide; MAA: methacrylic acid; IPA: isopropanol.

IPA

Zr(OPrn)4 + MAA

Stirring @ room-temperaturefor 30 min

Stirring @ room-temperaturefor 1h

Photo-initiator


H2O + HCl

Sol ageing @room-temperature

GDPTMS + DMDMOS

Zr(OPrn)4

ZrO

O O

O

IPA

HO

O

HO

MAA

Si

O

O

OOO

GDPTMSDMDMOS

Si

O

O

FILM PREPARATION AND PROCESSING

Outline of the film preparation and processing, and waveguide fabrication.

Heating @ 75 °C for 30 min


UV irradiation

Sol-gel mixture

Filtration

Spin-coating @ 800 rpmfor 30 s

Cross-sectional scanning electron microscopy (SEM) image (a) of the films; optical microscopy (OM)

image of the waveguide structures (b); and near-field (NF) image (c) of the guided light output from the

waveguide.

IMAGING

200 µm

(b)

100 µm

(c)

(a)

10 µm

Air

Substrate

Film

Representative UV/vis (a) and IR spectra (b) of the films.

SPECTROSCOPY

200 300 400 500 600 700 8000

20

40

60

80

Ref

lect

ance

(%

)

Wavelength (nm)

(a)

4000 3500 3000 2500 2000 1500 1000 5000.0

0.2

0.4

0.6

0.8

1.0

Ab

sorb

an

ce

Wavenumber (cm-1)

(b)

Epoxy

ring

Si-O

Si-CH3

O-H

C-H

A prism coupling curve.

REFRACTOMETRY

Modes

Variation of refractive index (633 nm) and Δn with Zr content. (Un: Unexposed, Ex: UV-exposed)

EFFECT OF ZR AND UV LIGHT

0 10 20 30 40 501.485

1.500

1.515

1.530

Un

Ex

Refr

acti

ve I

nd

ex

at

63

3 n

m

Zr Content (mol %)

0.0 0.5 1.0 1.5 2.0

1.490

1.495

1.500

1.505

1.510

Un

Ex

Ref

ract

ive

Ind

ex a

t 6

33

nm

Zr Content (mol %)

Zr Content (mol %)

0.00 0.35 0.70 1.2 1.7 3.4 6.6 11 17 28 45

Δn @

633 nm0.017 0.010 0.009 0.008 0.005 0.004 0.003 0.000 0.001 0.000 0.001

M. Çopuroğlu, S. O’Brien, and G. M. Crean, Journal of Sol-Gel Science and Technology 40 (2006) 75.

Variation of thickness with Zr content.


0 10 20 30 40 503

4

5

6

7

8

9

10

Un

Ex

Th

ick

ness

(m

)

Zr Content (mol %)

0.0 0.5 1.0 1.5 2.03

4

5

6

7

8

9

10

Un

Ex

Th

ick

ness

(m

)

Zr Content (mol %)

Dynamic thermograms of the unexposed (a) and the UV-exposed (b) materials in air, and their 1st

derivative curves ((c) and (d), respectively).

100 200 300 400 500 600

40

50

60

70

80

90

100 0.00 mol % Zr

0.70 mol % Zr

1.7 mol % Zr

6.6 mol % Zr

11 mol % Zr

17 mol % Zr

45 mol % Zr

Mass

(%

)

Temperature (oC)

(a)

100 200 300 400 500 600

40

50

60

70

80

90

100 0.00 mol % Zr

0.70 mol % Zr

1.7 mol % Zr

6.6 mol % Zr

11 mol % Zr

17 mol % Zr

45 mol % Zr

Mass

(%

)

Temperature (oC)

(b)

100 200 300 400 500 600

Deri

vati

ve M

ass

(%

/oC

)

(No

t to

Scale

)

45

17

11

6.6

0.70

1.7

0.00

Temperature (oC)

(c)

100 200 300 400 500 600

Deri

vati

ve M

ass

(%

/oC

)

(No

t to

Scale

)

0.00

0.70

1.7

6.6

11

17

45

Temperature (oC)

(d)


M. Çopuroğlu, S. O’Brien, G. M. Crean, Thermochimica Acta 452 (2007) 7.

Variation of refractive index (at 633 nm) (a) and thickness (b) with sol ageing, for the system with 11 mol

% Zr content.

EFFECT OF AGEING

0 50 100 150 200 2501.494

1.497

1.500

1.503

1.506

1.509

1.512

Un

Ex

Refr

acti

ve I

nd

ex

at

63

3 n

m

Sol Ageing (h)

(a)

0 50 100 150 200 250

6

8

10

12

14

16

Un

Ex

Th

ick

nes

s (

m)

Sol Ageing (h)

(b)



EFFECT OF AGEING

100 200 300 400 500 600

40

50

60

70

80

90

100

0 h

24 h

48 h

96 h

144 h

240 h

Mass

(%

)

Temperature (oC)

(a)

100 200 300 400 500 600

40

50

60

70

80

90

100

0 h

24 h

48 h

96 h

144 h

240 h

Mass

(%

)

Temperature (oC)

(b)

100 200 300 400 500 600

Deri

vati

ve

Mass

(%

/oC

)

(No

t to

Sca

le)

0

24

48

96

144

240

Temperature (oC)

(c)

100 200 300 400 500 600

Deri

vati

ve M

ass

(%

/oC

)

(No

t to

Scale

)

0

24

48

96

144

240

Temperature (oC)

(d)

OPTICAL LOSS MEASUREMENT

Optical waveguides

Insertion loss

0

log10P

PossInsertionL

200 µm 100 µm

Near-field imageOptical microscopy

image

OPTICAL LOSS MEASUREMENT

Optical waveguides

Insertion loss

0

log10P

PossInsertionL

OM images of the waveguide structures ((a)-(c)), and NF images of the guided light output from the

waveguides ((d)-(f)) with no Zr, subjected to a temperature cycling treatment between: none (a) and (d); 4

and 38 C (b) and (e); -40 and 65 C (c) and (f) (100 cycles in both cases).

RELIABILITY ANALYSIS

Temperature Range (ºC) Optical Propagation Loss (dB cm-1)

None 0.8

4-38 2.4

-40-65 5.2

200 µm

(a)

200 µm

(b)

200 µm

(c)

100 µm

(d)

100 µm

(e) (f)

100 µm

OUTLINE

Zinc oxide-

dopedZinc oxide-

undopedORMOSIL with

aryl groups

ORMOSIL with

transition metal

Materials

Inorganic/organic

hybridCeramic

STUDY


• refractive index modifier, DPDMS

• UV light

• sol ageing


• structural

• morphological

• optical

• spectroscopical

• thermal

• reliability

SYNTHESIS

Skeletal formulae of the chemicals used, and outline of the synthesis. DPDMS: diphenyldimethoxysilane.

IPA

Stirring @ room-temperaturefor 30 min


Photo-initiator


H2O + HCl

Sol ageing @room-temperature

GDPTMS + DMDMOS

DPDMS

DPDMS

Si

O

O

Si

O

O

OOO

GDPTMS

IPA

HO

DMDMOS

Si

O

O


Outline of the film preparation and processing.

Sol-gel mixture

Filtration



UV irradiation

Heating @ 95 °C for 2 h

Representative cross-sectional SEM image (a) and IR spectrum (b) of the UV-exposed films.

IMAGING AND SPECTROSCOPY

4000 3500 3000 2500 2000 1500 1000 5000.0

0.2

0.4

0.6

0.8

1.0

Ab

sorb

ance

Wavenumber (cm -1)

(b)

Epoxy

ring

Si-O

Si-CH3

Overtones

O-H

C-H

10 µm

(a)

Air

Substrate

Film

Variation of refractive index (at 633 nm) and thickness with DPDMS content.

EFFECT OF DPDMS AND UV LIGHT

0 2 4 6 8 10 121.485

1.490

1.495

1.500

1.505

Ex

Refr

acti

ve I

nd

ex

at

63

3 n

m

DPDMS Content (mol %)

DPDMS Content (mol %)

0.00 1.7 6.6 11

Thickness (μm) 9.2 6.9 8.7 6.5

S. O’Brien, M. Çopuroğlu, G. M. Crean, Thin Solid Films 515 (2007) 5439.



EFFECT OF DPDMS AND UV LIGHT

100 200 300 400 500 600

40

50

60

70

80

90

100

0.00 mol % DPDMS

1.7 mol % DPDMS

3.4 mol % DPDMS

6.6 mol % DPDMS

11 mol % DPDMS

Mas

s (%

)

Temperature (oC)

(a)

100 200 300 400 500 600

40

50

60

70

80

90

100

0.00 mol % DPDMS

1.7 mol % DPDMS

3.4 mol % DPDMS

6.6 mol % DPDMS

11 mol % DPDMS

Mass

(%

)

Temperature (oC)

(b)

100 200 300 400 500 600

Der

ivat

ive

Mas

s (%

/oC

)

(No

t to

Sca

le)

0

1.7

3.4

6.6

11

Temperature (oC)

(c)

100 200 300 400 500 600

Der

ivat

ive

Mas

s (%

/oC

)

(No

t to

Sca

le)

6.6

3.4

1.7

0

11

Temperature (oC)

(d)

M. Çopuroğlu, S. O’Brien, G. M. Crean, Polymer Degradation and Stability 91 (2006) 3185.



EFFECT OF AGEING

100 200 300 400 500 600

40

50

60

70

80

90

100

0 h

24 h

48 h

96 h

144 h

240 h

Mass

(%

)

Temperature (oC)

(a)

100 200 300 400 500 600

40

50

60

70

80

90

100

0 h

24 h

48 h

96 h

144 h

240 h

Mass

(%

)

Temperature (oC)

(b)

100 200 300 400 500 600

Deri

vati

ve M

ass

(%

/oC

)

(No

t to

Scale

)

0

24

48

96

144

240

Temperature (oC)

(c)

100 200 300 400 500 600

Der

ivat

ive

Mas

s (%

/oC

)

(No

t to

Sca

le)

0

24

48

96

144

240

Temperature (oC)

(d)

CONCLUSIONS-ORMOSILS

Two novel ORMOSIL systems synthesised by the

sol-gel method, and their thin-films deposited by the

spin-coating technique

Comparative effects of refractive index modifiers,

UV light and sol ageing on microstructure and

functional properties, and their tunability detailed for

the first time

Planar optical waveguide structures with reasonable

optical propagation loss and reliability obtained for

the Zr-doped system, at its low concentrations

S. O’Brien, M. Çopuroğlu, G. M. Crean, Applied Surface Science 253 (2007) 7969.

OUTLINE

Zinc oxide-

dopedZinc oxide-

undopedORMOSIL with

aryl groups

ORMOSIL with

transition metal

Materials

Inorganic/organic

hybridCeramic

STUDY


• single-/multi-step coating

• Al-doping


• structural

• morphological

• optical

• spectroscopical

• thermal

• reproducibility

• reliability

SYNTHESIS

IPA + MEA

IPA

Zn(C2H3O2)2·2H2O

Sol ageing @ room-temperature for 1 day

Dissolving @ 60 °Cfor 1 h while stirring

Sol of [Zn] + [Al] =[MEA] = 0.7 M

0.2 M ethanolicAl(NO3)3·9H2O

Zn2+

2-

2O-

O

2H2O

Zinc acetate dihydrate

Aluminium nitrate nonahydrate

Al3+9H2ON+

O-

O-O

3-

3

HONH2

MEA

HO

Ethanol

Skeletal formulae of the chemicals used, and outline of the synthesis. MEA: 2-aminoethanol.

M. Çopuroğlu, L. H. K. Koh, S. O’Brien, G. M. Crean, Journal of Sol-Gel Science and Technology 52 (2009) 432.

S. O'Brien, M. Nolan, M. Çopuroglu, J. A. Hamilton, I. Povey, L. Pereira, R. Martins, E. Fortunato, M. Pemble, Thin Solid

Films 518 (2010) 4515.


Outline of the film preparation and processing.

Sol-gel mixture


Multi-layer


Annealing @ 550 °C for 1 h

Forming gas process (FGP)@ 500-550 °C for 1 h

S. O’Brien, L. H. K. Koh, M. Çopuroğlu, and G. M. Crean, Mat. Res. Soc. Symp. Proc. 1035E (2008) L05-09.

IMAGING

Top-view ((a) and (b)), and cross-sectional SEM images ((c) and (d)) of the single- ((a) and (c)), and

multi-layer ((b) and (d)) films.

500 nm

(a)

500 nm

(b)

(c)

500 nm

(d)

500 nm

113 nm325 nm

SPECTROSCOPY

UV/vis spectra (a), and their 1st derivatives (b) of the single- and multi-layer films. The table shows the

data obtained from these spectra.

Property

Film Type% Transmittance

at 550 nm

First Derivative

Maximum (nm)

Band Gap

Energy (eV)

Single-layer 99 376 3.30

Multi-layer 96 380 3.27

300 400 500 600 700 8000

20

40

60

80

100

Single-layer

Multi-layerTra

nsm

itta

nce (

%)

Wavelength (nm)

(a)

340 360 380 400 420

0.0

1.5

3.0

4.5

6.0

Der

ivat

ive

Tra

nsm

itta

nce

(%

/nm

)

Wavelength (nm)

(b)

Single-layer

Multi-layer

X-ray diffraction patterns of the undoped single- (a) and multi-layer (b) films. The table shows the data

obtained from these patterns.

DIFFRACTOMETRY

Property

Film TypeRelative Intensity of (002)

Crystal OrientationAverage Crystallite Size (nm)

Single-layer 0.62 37

Multi-layer 0.94 46

25 30 35 40 45 50

0

100

200

300

400

500

(10

1)

(10

0)

(00

2)

Inte

nsi

ty

2 (o)

(a)

25 30 35 40 45 50

0

2

4

6

8

10

Inte

nsi

ty x

10

-3

2 (o)

(b)

(00

2)

(10

0)

(10

1)

Crystallite size calculation

DIFFRACTOMETRY

Scherrer’s equation:

BBt

cos

9.0

t: thickness of the crystal,

B: actual full width at half maximum of the peak centred at 2θB.

λ: wavelength of the incident light (X-ray)

Current-voltage plots of the single-layer film before and after FGP. The table shows the data obtained

from these plots.

ELECTRICAL CHARACTERISATION

Measurement Stage Minimum Electrical Resistivity (Ω m)

Before FGP 4.5

After FGP 0.14

-60 -40 -20 0 20 40 60-100

-80

-60

-40

-20

0

20

40

60

80

100

Before FGP

After FGP

Cu

rren

t (

A)

Voltage (V)

Measured by 4-point

probe method

IMAGING

SEM images of the single- (1st and 3rd row) and multi-layer (2nd and 4th row) films. (From left to right: Day-1 to Day-5; the

width of the scale bars corresponds to 500 nm)

Av.

106 nm

Av.

307 nm

M. Çopuroğlu, S. O’Brien, G. M. Crean, Applied Surface Science 256 (2009) 737.

SPECTROSCOPY

UV/vis spectra of the single- (a) and multi-layer (b) films and their first derivatives ((c) and (d),

respectively).

300 400 500 600 700 80040

50

60

70

80

90

100

Day-1

Day-2

Day-3

Day-4

Day-5Tra

nsm

itta

nce (

%)

Wavelength (nm)

(a)

300 400 500 600 700 8000

20

40

60

80

100

Day-1

Day-2

Day-3

Day-4

Day-5Tra

nsm

itta

nce (

%)

Wavelength (nm)

(b)

340 360 380 400 420

0

1

2

3

4

Wavelength (nm)

(c)

Day-1

Day-2

Day-3

Day-4

Day-5

Der

ivat

ive

Tra

nsm

itta

nce

(%

/nm

)

340 360 380 400 420

0

1

2

3

4

5

6

Wavelength (nm)

(d)

Day-1

Day-2

Day-3

Day-4

Day-5

Der

ivat

ive

Tra

nsm

itta

nce

(%

/nm

)

X-ray diffraction patterns of the single- (a) and multi-layer (b) films.

25 30 35 40 45 50

Day-4

Day-1

Day-2

Day-3

Day-5

Inte

nsi

ty (

No

t to

Scale

)

(10

1)(0

02

)

(10

0)

2 (o)

(a)

25 30 35 40 45 50

Day-1

Day-2

Day-3

Day-4

Day-5

Inte

nsi

ty (

No

t to

Scale

)

(10

1)

(10

0)

(00

2)

2 (o)

(b)

DIFFRACTOMETRY

Current-voltage plots of the single-layer film before and after FGP. (From (a) to (b): Day-1 to Day-5)


-60 -40 -20 0 20 40 60-150

-100

-50

0

50

100

150

Before FGP

After FGP

Curr

ent

(A

)

Voltage (V)

(a)

-60 -40 -20 0 20 40 60-150

-100

-50

0

50

100

150

Before FGP

After FGP

Curr

ent

(A

)Voltage (V)

(b)

-60 -40 -20 0 20 40 60-150

-100

-50

0

50

100

150

Before FGP

After FGP

Cu

rren

t (

A)

Voltage (V)

(c)

-60 -40 -20 0 20 40 60-150

-100

-50

0

50

100

150

Before FGP

After FGP

Cu

rren

t (

A)

Voltage (V)

(d)

-60 -40 -20 0 20 40 60-150

-100

-50

0

50

100

150

Before FGP

After FGP

Cu

rren

t (

A)

Voltage (V)

(e)

Average Electrical

Resistivity (Ω m)

23 18

1.5 1.3

OUTLINE

Zinc oxide-

dopedZinc oxide-

undopedORMOSIL with

aryl groups

ORMOSIL with

transition metal

Materials

Inorganic/organic

hybridCeramic

25 30 35 40 45 50

Inte

nsi

ty (

No

t to

Scale

)

Undoped

Al-doped

2 (o)

(a)

(00

2)

(10

0)

(10

1)

25 30 35 40 45 50

Inte

nsi

ty (

No

t to

Sca

le)

Al-doped

Undoped

2 (o)

(b)

(00

2)

(10

0)

(10

1)

DIFFRACTOMETRY

Property

Film TypeRelative Intensity of (002)

Crystal OrientationAverage Crystallite Size (nm)

Single-layer 1 24

Multi-layer 1 22

X-ray diffraction patterns of the single- (a) and multi-layer (b) films. The table shows the data obtained from these patterns.

M. Çopuroğlu, S. O’Brien, G. M. Crean, Thin Solid Films 517 (2009) 6323.

IMAGING

Top-view ((a) and (b)) and cross-sectional ((c) and (d)) SEM images of the Al-doped single- ((a) and (c))

and multi-layer ((b) and (d)) films.

500 nm

(a)

500 nm

(b)

500 nm

(c) (d)

500 nm

92 nm 266 nm

SPECTROSCOPY

UV/vis spectra of the single- (a) and multi-layer (b) films, and their first derivatives ((c) and (d),

respectively).

300 400 500 600 700 80040

50

60

70

80

90

100T

ran

smit

tan

ce (

%)

Wavelength (nm)

(a)

Undoped

Al-doped

300 400 500 600 700 8000

15

30

45

60

75

90

105

Tra

nsm

itta

nce (

%)

Wavelength (nm)

(b)

Undoped

Al-doped

340 360 380 400 420

0

1

2

3

4

Deri

vati

ve T

ran

smit

tan

ce (

%/n

m)

Wavelength (nm)

(c)

Undoped

Al-doped

340 360 380 400 420

0

1

2

3

4

5

6

Der

ivat

ive

Tra

nsm

itta

nce

(%

/nm

)

Wavelength (nm)

(d)

Undoped

Al-doped

Current-voltage plots of the undoped and the Al-doped single-layer films.


-60 -40 -20 0 20 40 60

-60

-40

-20

0

20

40

60

Cu

rren

t (

A)

Voltage (V)

Undoped

Al-doped

Measurement Stage Minimum Electrical Resistivity (Ω m)

Undoped 4.5

Al-doped 0.34

RELIABILITY ANALYSIS

Top-view ((a), (b) and (e)) and cross-sectional ((c), (d) and (f)) SEM images of the undoped single- ((a)

and (c)) and multi-layer ((b) and (d)), and the Al-doped multi-layer ((e) and (f)) films after the temperature

cycling test (-40-65 C) (100 cycles).

500 nm

(e)

(f)

500 nm

500 nm

(a)

500 nm

(b)

500 nm

(c)

500 nm

(d)

CONCLUSIONS-ZINC OXIDE

Both undoped and Al-doped ZnO systems

synthesised by the sol-gel method

Thin-films deposited by the spin-coating technique

Reproducible desired properties obtained

Electrical conductivity improved by Al-doping

High degree of reliability demonstrated

POSTDOC-SUMMARY

Development of perovskite-type lead-magnesium-niobium titanate

(PMNT)-based material systems for monolithic above-IC ultra-high-

value capacitors for mobile and wireless communication systems.

Involves

• sol-gel synthesis under controlled environment (atmosphere,

temperature, etc.)

• nanoparticle seeding

• various thin-film processing techniques including rapid

thermal annealing (RTA), UV-irradiation, and laser-activation

• characterisation

Mg(C2H5O)2 + Nb(C2H5O)5

in 2ME

Ti(n-C3H7O)4in 2ME

Pb(C2H3O2)2

in 2ME

Refluxing @ 125-126 °Cfor ~15 h under N2

Refluxing @ 125-126 °Cfor ~4 h under N2

Mg-Nb-Ti complex

Formamide

Refluxing and distillationunder N2

PMNT sol

SYNTHESIS

Flowchart of synthesis. (2ME: 2-Methoxyethanol)

M. Çopuroğlu, S. O’Brien, B. Malič, B. Kužnik, M. Kosec, X. Zhu, E. Defaÿ, R. Winfield, IOP Con. Ser.: Mat. Sci. Eng. 8

(2010) 012007.

W. Chen, K. G. McCarthy, M. Çopuroğlu, H. Doyle, B. Malic, B. Kuznik, M. Kosec, S. O’Brien, R. Winfield, A. Mathewson,

Thin Solid Films (2011), doi:10.1016/j.tsf.2010.12.194.

W. Chen, K. G. McCarthy, A. Mathewson, M. Çopuroğlu, S. O’Brien, R. Winfield, IEEE Electron Device Letters 31 (2010)

996.


Outline of film preparation and processing, and RTA time-temperature profile and conditions.

λ = 222 nm

0-3 times

PreparedPMNT sol

Spin-coating@ 3000 rpm for 30 s

Heating@ 300 °C for ~1 min

RTA

1HPK

UV-irradiation@ RT for 4 min

Substrate:Pt/TiO2/SiO2/Si

RTA t ime- temperature pro f ile:

X = 350-750 in O2; 750 in N2

RT RT

1 min ~10 min

X °C, 5 min

M. Çopuroğlu, S. O’Brien, B. Malič, B. Kužnik, M. Kosec, X. Zhu, E. Defaÿ, H. Doyle, R. Winfield, Physica Status Solidi

A, under review.

W. Chen, K. G. McCarthy, M. Çopuroğlu, S. O’Brien, R. Winfield, A. Mathewson, IOP Con. Ser.: Mat. Sci. Eng. 8 (2010)

012020.

W. Chen, K. G. McCarthy, M. Çopuroğlu, S. O’Brien, R. Winfield, A. Mathewson, IEEE Int. Con. Microelec. Test Struc.

(2010) 98.

(a) (b)

FILM CHARACTERISATION-SEM

Planar (a) and cross-sectional (b) SEM images of two representative films annealed at 750 (unexposed) and 550 (UV-exposed) C, respectively.

750/1/O2 750/2/O2 750/3/O2 750/4/O20

50

100

150

200

250

300

350

400

Thic

kn

ess (

nm

)

Annealing temperature (°C)/No of layer/Annealing atmosphere

(a)

550/4/O2 650/4/O2 700/4/O2 750/4/O2 750/4/N20

100

200

300

400

500

Thic

kness (

nm

)

Annealing temperature (°C)/No of layer/Annealing atmposphere

(b)

FILM CHARACTERISATION-THICKNESS EVALN.

Thickness profiles of the films.

350

400

450

500

550

650 700550 750

Th

ickn

ess (

nm

)

Annealing Temperature (°C)

Unexposed

UV-exposed

FILM CHARACTERISATION-THICKNESS EVALN.

Thickness values of the films.

M. Çopuroğlu, S. O’Brien, B. Malič, B. Kužnik, M. Kosec, X. Zhu, E. Defaÿ, R. Winfield, Thin Solid Films 518 (2010)

4503.

10 20 30 40 50 60

x

2 (o)

(a)

750 °C

700 °C

650 °C

550 °C

Inte

nsity (

Arb

itra

ry u

nits)

x o x s x

o

s o x

o: perovskite

x: pyrochlore

s: substrate

10 20 30 40 50 60

750 °C

700 °C

650 °C

550 °C

2 (o)

(b)

Inte

nsity (

Arb

itra

ry u

nits)

x o

x

os

x

o

s o x x

o: perovskite

x: pyrochlore

s: substrate

FILM CHARACTERISATION-XRD

XRD patterns of the unexposed (a) and the UV-exposed (b) films that were annealed at various temperatures.

% perovskite phase = 97 (750 C) % perovskite phase = 61 (750 °C)

-10 -8 -6 -4 -2 0 2 4 6 8 10200

400

600

800

1000

1200

1400

1600

k

tan

DC bias voltage (V)

(a)

k

0.00

0.04

0.08

0.12

0.16

0.20

tan

k = 1425!

-10 -8 -6 -4 -2 0 2 4 6 8 10

81.2

81.6

82.0

82.4

82.8

k

tan

DC bias voltage (V)

(b)

k

0.00

0.04

0.08

0.12

0.16

0.20

tan

k = 82.66

FILM CHARACTERISATION-ELECTRICAL MEAS.

DC bias dependence of k and tan δ of the films composed of 4-layer, and annealed at 750 C in O2 (a) and (c), and N2 (b) atmosphere. (a) and (b) unexposed, (c) UV-exposed.

-10 -8 -6 -4 -2 0 2 4 6 8 10

48

50

52

54

56 k

tan

DC bias voltage (V)

(c)

k

0.025

0.030

0.035

0.040

tan

k = 55.71

-10 -8 -6 -4 -2 0 2 4 6 8 10-30

-20

-10

0

10

20

P (

C/c

m2)

DC bias voltage (V)

2.5 V

4 V

5 V

6 V

7.5 V

10 V

Remnant polarisation = 7 μC cm-2 Coercive field = 35.8 kV cm-1

FILM CHARACTERISATION-ELECTRICAL MEAS.

Polarisation (P) hysteresis loops of the film composed of 4-layer, and annealed at 750 C in O2

atmosphere.

Delamination upon Cr/Au electrode deposition (by

sputtering)

Observed even if cleaning step (H2O2/NH3 aq. soln.)

skipped

Rows mJ/cm2

1 57

2 47

3 38

4 28

5 19

6 9

Columns No of shots

1 2 3 4 5 6 7 8 9

100 80 65 50 35 25 10 5 1

LASER PROCESSING

Crack-free films with tunable thickness obtained

Unexposed film annealed at 750 °C in O2 atm (4-

layer) exhibited a considerably high k value (1425)

Use of gentle-UV-irradiation could facilitate the

lattice formation-initiation at lower temperatures, and

play a role in modifying the microstructure

This PMNT thin film system appeared potentially

suitable for ultrahigh-value capacitor applications

CONCLUSION

Synthesis and preparation:

Avail of

• sol-gel method-based approaches

• polymerisation/crosslinking regimes

Employ combinations of precursors

• polyfunctional silicon and/or metal alkoxides

• optionally containing polymerisable/crosslinkable functional moieties

• other oligomers/polymers

Make use of various techniques

• thermal processing

• photon-assisted processing

Tailor desired properties

DİŞ DOLGU MALZEMELERİ İÇİN YENİ POLİMER

NANOKOMPOZİTLERİN GELİŞTİRİLMESİ (AKRONİM: “DİP”)



Si

O O

OO

TEOS Ti(OPr)4

O

Ti

OO

O

O

OH

MAA

GDPTMS

O OSi

OO

O

Si

O

O

DMDEOS

Foto-basla tici

S S+S+ SbF6-SbF6

- S S+ SbF6-

Skeletal formulae of the chemicals used, and outline of the synthesis. GDPTMS: (3-

glycidyloxypropyl)trimethoxysilane; DMDEOS: dimethyldiethoxysilane; Ti(OPrn)4: titanium(IV) iso-

propoxide; MAA: methacrylic acid.



Takip edilen sentez rotasının şeması.

(damla damla)H2O/H3O+

GDPTMS + DMDEOS + TEOS

IPA

Ti:MAA

15 dakika oda sicakligindakaristirma

5 dakika oda sicakligindakaristirma

1 saat oda sicakligindakaristirma

Sol yaslanmasi

Foto-baslatici

2.5 saat oda sicakligindakaristirma



Takip edilen işlem rotasının şeması.

Kaliplama

60 °C'de 30 dakikakurutma

Sol-jel karisimi

UV-kür islemi



Örneklerin isimlendirilmesinde kullanılan kodlama sistemi.

Kod Ti bileşimi (mol %) Sol yaşlanma süresi Kür süresi (dakika)

Ti0 0 0 saat 0

Ti1 5 1 saat 1

Ti2 10 3 saat 2

Ti3 15 6 saat 5

Ti4 20 12 saat 10

Ti5 25 1 gün 20

Ti6 30 2 gün 30

Ti7 40 3 gün 60

Ti8 50 6 gün 120

Ti9 75 10 gün 300



1400 1200 1000 800 600

Ab

sorb

ance

(A

rbit

rary

un

its) Ti09

Ti00

Ti07

Ti06

Ti02

Ti01

Ti05

Ti03

Wavenumber (cm-1

)

(a)

Ti08

Si-O-Si

Epoxy ring

1400 1200 1000 800 600

Ab

sorb

ance

(A

rbit

rary

un

its)

Ti59

Ti50

Ti57

Ti56

Ti52

Ti51

Ti55

Ti53

Wavenumber (cm-1

)

(b)

Ti58

Si-O-Si

Epoxy ring

Polyether

Si-O-Ti

Molce % 0 (a) ve 25 (b) Ti başlangıç maddesi içeren örnekler için sol yaşlanma süresi FT-IR profili.



Molce % 0 (a) ve 25 (b) Ti başlangıç maddesi içeren örnekler için UV kür süresi FT-IR profili.

1400 1200 1000 800 600

Ab

sorb

ance

(A

rbit

rary

un

its)

Ti050

Ti056

Ti055

Ti052

Ti051

Ti054

Ti053

Wavenumber (cm-1

)

(a)

Ti057

Si-O-Si

Epoxy ring

Polyether

1400 1200 1000 800 600

Si-O-SiSi-O-Ti

Ab

sorb

ance

(A

rbit

rary

un

its)

Ti550

Epoxy ring

Polyether

Ti556

Ti555

Ti552

Ti551

Ti554

Ti553

Wavenumber (cm-1

)

(b)

Ti557



Molce % 0 (a) ve 25 (b) Ti başlangıç maddesi içeren örnekler için UV kür süresi TGA profili.

100 200 300 400 500 600

40

50

60

70

80

90

100 Ti550

Ti551

Ti552

Ti553

Ti557

Mass

(%

)

Temperature (°C)

(b)

100 200 300 400 500 600

40

50

60

70

80

90

100 Ti050

Ti051

Ti054

Ti057

Mass

(%

)

Temperature (°C)

(a)



Polimer nanokompozitler ve potansiyel uygulamaları. (Sertlik testi ve hesaplamaları)

Shore-A hardness & elastic modulus

t: sample thickness;

r: radius of truncated cone of the indenter of device;

d: depth of penetration;

d’: corrected depth of penetration;

s: Shore hardness

E: elastik (Young’s) modulus

• Siddiqui, A., Braden, M., Patel, M. P., Parker, S., “An experimental and theoretical study of the effect of

sample thickness on the Shore hardness of elastomers.” Dent. Mater. 26 (2010) 560.

• Meththananda, I. M., Parker, S., Patel, M. P., Braden, M., “The relationship between Shore hardness of

elastomeric dental materials and Young’s modulus.” Dent. Mater. 25 (2009) 956.



Polimer nanokompozitler ve potansiyel uygulamaları. (Sertlik testi ve hesaplamaları-sonuçlar)

Shore-A hardness & elastic modulus:

Shore-A hardness and elastic (Young’s) modulus (E) values for particular samples.

Sample

0 mol % Ti

UV-irrad. 10 min. 0 mol % Ti



UV-irrad. 60 min.

Shore-A hardness 46 70 71 81

E (MPa) ~ 0 0.5 4 3



Polimer nanokompozitler ve potansiyel uygulamaları (adesiv). (Mekanik test)

polymer nanocomposites/ ceramics systems · variation of refractive index (633 nm) and Δn with zr...

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