ageing resistance (12 years) of hard and oxidation...

Ageing Resistance (12 years) of Hard and Oxidation Resistant SiBCN Coatings

Jiri HouskaDepartment of Physics and NTIS - European Centre of Excellence,

University of West Bohemia, Czech Republic

Acknowledgment

Grant Agency of the Czech Republic through Project No. 15-00859Y

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SiBCN coatingsin as-deposited state studied for years

Pulsed reactive magnetron sputtering of high-temperature Si-B-C-N films with high optical transparency2013Surf. Coat. Technol. 226, 34J. Vlcek et al.

Development of a new generation of amorphous hard coatings based on the Si-B-C-N-O system for ...2013Surf. Coat. Technol. 223, 52H. Abu Samra et al.

Amorphous boron containing silicon carbo-nitridescreated by ion sputtering2011Surf. Coat. Technol. 206, 149V.M. Vishnyakov et al.

Amorphous-SiCBN-based metal-semiconductor-metal photodetector for high-temperature applications2007IEEE Electron Device Lett. 28, 713A. Vijayakumar et al.

Silicoboron–carbonitride ceramics: A class of high-temperature, dopable electronic materials2001Appl. Phys. Lett. 78, 3076P.A. Ramakrishnan et al.

PACVD-Derived Thin Films in the System Si-B-C-N1999Chem. Vap. Deposition 5, 61D. Hegemann et al.

Surface Studies of Potentially Oxidation Protective Si-B-N-C Films for Carbon Fibers1997Chem. Mater. 9, 285M.A. Rooke et al.

Other labs (examples)

Ageing resistance of SiBCN ceramics2015Ceram. Int. 41, 7921J. Houska et al.

Microstructure characterization of high-temperature, oxidation-resistant Si-B-C-N films2013Thin Solid Films 542, 167J. He et al.

Thermal conductivity of high-temperature Si-B-C-N thin films2011Surf. Coat. Technol. 206, 2030J.J. Gengler et al.

Effect of nitrogen content on electronic structure and properties of SiBCN materials2011Acta Materialia 59, 2341V. Petrman et al.

Thermal stability of magnetron sputtered Si-B-C-N materials at temperatures up to 1700 °C2010Thin Solid Films 519, 306P. Zeman et al.

SiBCN materials for high-temperature applications: Atomistic origin of electrical conductivity2010J. Appl. Phys. 108, 083711J. Houska et al.

High-temperature stability of the mechanical and optical properties of Si-B-C-N films prepared by ...2009Thin Solid Films 518, 174J. Kalas et al.

Effect of the gas mixture composition on high temperature behavior of magnetron suttered Si-B-C-N ...2008Surf. Coat. Technol. 203, 466J. Capek et al.

Magnetron sputtered Si-B-C-N films with high oxidation resistance and thermal stability in ...2008J. Vac. Sci. Technol. A26, 1101J. Vlcek et al.

Mechanical and optical properties of quaternary Si-B-C-N films prepared by reactive magnetron sputtering2008Thin Solid Films 516, 7286J. Cizek et al.

Effect of implanted argon on hardness of novel magnetron sputtered Si-B-C-N materials: ...2007J. Phys.: Condens. Matter 19, 196228J. Houska et al.

Bonding statistics and electronic structure of novel Si-B-C-N materials: ab-initio calculations and ...2007J. Vac. Sci. Technol. A 25, 1411J. Houska et al.

Influence of substrate bias voltage on structure and properties of hard Si-B-C-N films prepared by ...2007Diamond Relat. Mater. 16, 29J. Houska et al.

Effect of B and the Si/C ratio on high-temperature stability of novel Si-B-C-N materials2006Europhys. Lett. 76, 512J. Houska et al.

New quaternary Si-B-C-N films prepared by reactive magnetron sputtering2006Trans. Mater. Res. Soc. Jpn 31, 447J. Vlcek et al.

The effect of argon on the structure of amorphous SiBCN materials: an experimental and ab initio study2006J. Phys.: Condens. Matter 18, 2337J. Houska et al.

Ab initio simulations of nitrogen evolution in quenched CNx and SiBCN amorphous materials2005Phys. Rev. B 72, 054204J. Houska et al.

Reactive magnetron sputtering of hard Si-B-C-N films with a high-temperature oxidation resistance2005J. Vac. Sci. Technol. A 23, 1513J. Vlcek et al.

University of West Bohemia

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This workageing resistance (12yr) of coatings prepared in 2002-3


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This workageing resistance (12yr) of coatings prepared in 2002-3

Important (for obvious reasons) but rarely studied (also for obvious reasons)

Motivation: examples of as-deposited propeties of S iBCN

Si-Ta-NSi-Zr-NSi-Mo-N

Musil et al.

500 700 900 1100 1300 1500 1700-0.1

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

nc-TiN/a-Si3N

4

Veprek et al. Si-Al-N Musil et al.

1900

Si-B-C-N Vlcek et al.

Si-Ti-N Musil et al.

Temperature (°C)

Mas

s ch

ange

(m

g/cm

2)

TiAlN/CrNWadsworth et al.

TiAlCrYNDonohue et al.

TiAlZrNMünz et al.

TiCMünz et al.

TiAlNMünz et al.TiN

Donohue et al.

1900

300 700 1100 1500 1900

calorimetry in Ar

Hea

t flo

w (

a.u.

)

Temperature (°C)

50% N2

25% N2

Thermal stability and oxidation resistance up to ~1 500 °C (thin surf. oxide at 1700 °C)

3/14



Musil et al.

500 700 900 1100 1300 1500 1700-0.1

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

nc-TiN/a-Si3N

4


1900



Temperature (°C)

Mas

s ch

ange

(m

g/cm

2)



TiAlZrNMünz et al.

TiCMünz et al.


Donohue et al.

1900

300 700 1100 1500 1900

calorimetry in Ar

Hea

t flo

w (

a.u.

)

Temperature (°C)

50% N2

25% N2

0 10 20 30 100

0

1

2

3

4

N2 fraction in the gas mixture

Opt

ical

gap

(eV

)

Si83

B14

C3

(108Ωm)


10152025303540455055

50mN

30mN

Har

dnes

s (G

Pa)

-3

-2

-1

0

Str

ess

(GP

a)

0 100 200 300 400 500

150

200

250

300

350

400

E/(

1-ν2

) (G

Pa)

0 100 200 300 400 50030

40

50

60

70

80

90

100

Ela

stic

rec

over

y (%

)

Negative substrate bias (V)

0 100 200 300 400 500

30mN100

Tailored mechanical properties(H up to ~35 GPa, E >300 GPa, ...)

Tailored electronic structure ⇒ optical & electrical prop.

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Musil et al.

500 700 900 1100 1300 1500 1700-0.1

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

nc-TiN/a-Si3N

4


1900



Temperature (°C)

Mas

s ch

ange

(m

g/cm

2)



TiAlZrNMünz et al.

TiCMünz et al.


Donohue et al.

1900

300 700 1100 1500 1900

calorimetry in Ar

Hea

t flo

w (

a.u.

)

Temperature (°C)

50% N2

25% N2

0 10 20 30 100

0

1

2

3

4


Opt

ical

gap

(eV

)

Si83

B14

C3

(108Ωm)

0 500 1000 150010

20

30

40

50 20 mN 30 mN 50 mN

Har

dnes

s (G

Pa)

Temperature (°C)

400 600 800 1000 1200 1400 1600

10-4

10-3

10-2

10-1

1150°C in He

Ext

inct

ion

coef

ficie

nt

Wavelength (nm)

1400°C in He

asdeposited


10152025303540455055

50mN

30mN

Har

dnes

s (G

Pa)

-3

-2

-1

0

Str

ess

(GP

a)

0 100 200 300 400 500

150

200

250

300

350

400

E/(

1-ν2

) (G

Pa)

0 100 200 300 400 50030

40

50

60

70

80

90

100

Ela

stic

rec

over

y (%

)


0 100 200 300 400 500

30mN100



High-temperature stability of mechanical propertiesand optical properties

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Musil et al.

500 700 900 1100 1300 1500 1700-0.1

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

nc-TiN/a-Si3N

4


1900



Temperature (°C)

Mas

s ch

ange

(m

g/cm

2)



TiAlZrNMünz et al.

TiCMünz et al.


Donohue et al.

1900

300 700 1100 1500 1900

calorimetry in Ar

Hea

t flo

w (

a.u.

)

Temperature (°C)

50% N2

25% N2

0 10 20 30 100

0

1

2

3

4


Opt

ical

gap

(eV

)

Si83

B14

C3

(108Ωm)

0 500 1000 150010

20

30

40

50 20 mN 30 mN 50 mN

Har

dnes

s (G

Pa)

Temperature (°C)

400 600 800 1000 1200 1400 1600

10-4

10-3

10-2

10-1

1150°C in He

Ext

inct

ion

coef

ficie

nt

Wavelength (nm)

1400°C in He

asdeposited

0 1 2 3 4 5 6 70

1

2

3

0

1

2

3

0

1

2

3

0

1

2

3

40 % Si

Com

pres

sive

str

ess

(GP

a)

Ar content (%)

20 % Si

5 % Si

0 % Si


10152025303540455055

50mN

30mN

Har

dnes

s (G

Pa)

-3

-2

-1

0

Str

ess

(GP

a)

0 100 200 300 400 500

150

200

250

300

350

400

E/(

1-ν2

) (G

Pa)

0 100 200 300 400 50030

40

50

60

70

80

90

100

Ela

stic

rec

over

y (%

)


0 100 200 300 400 500

30mN100



Si relaxes stress caused (in BCN) by implanted Ar


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Musil et al.

500 700 900 1100 1300 1500 1700-0.1

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

nc-TiN/a-Si3N

4


1900



Temperature (°C)

Mas

s ch

ange

(m

g/cm

2)



TiAlZrNMünz et al.

TiCMünz et al.


Donohue et al.

1900

300 700 1100 1500 1900

calorimetry in Ar

Hea

t flo

w (

a.u.

)

Temperature (°C)

50% N2

25% N2

0 10 20 30 100

0

1

2

3

4


Opt

ical

gap

(eV

)

Si83

B14

C3

(108Ωm)

0 500 1000 150010

20

30

40

50 20 mN 30 mN 50 mN

Har

dnes

s (G

Pa)

Temperature (°C)

400 600 800 1000 1200 1400 1600

10-4

10-3

10-2

10-1

1150°C in He

Ext

inct

ion

coef

ficie

nt

Wavelength (nm)

1400°C in He

asdeposited

0 1 2 3 4 5 6 70

1

2

3

0

1

2

3

0

1

2

3

0

1

2

3

40 % Si

Com

pres

sive

str

ess

(GP

a)

Ar content (%)

20 % Si

5 % Si

0 % Si


10152025303540455055

50mN

30mN

Har

dnes

s (G

Pa)

-3

-2

-1

0

Str

ess

(GP

a)

0 100 200 300 400 500

150

200

250

300

350

400

E/(

1-ν2

) (G

Pa)

0 100 200 300 400 50030

40

50

60

70

80

90

100

Ela

stic

rec

over

y (%

)


0 100 200 300 400 500

30mN100



Si relaxes stress caused (in BCN) by implanted Ar


Explanations by ab-initio calculation of structures and electronic structures

(clustering of Si around Ar, doping role of C atoms and CC bonds, ...) 500 1000 1500 2000

0.0

0.5

1.0

1.5

C=C

C-C

cBN

B-CN-N

Wavenumber (cm-1)

cBN

Si-Si

hBN

C-N

C=N

Si-C

hBN

Si-N

Abs

orpt

ion

coef

. (10

4 cm

-1)

Experiment (IR)

500 1000 1500 2000

0

20

40

60

80

100

120

Wavenumber (cm-1)

Simulation

N

umbe

r of

bon

ds

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Deposition technique

DC magnetron sputtering of Six(B4C)1-x in N2+Ar at 350 °C(selected compositions: cross-check using dc pulsed magnetron sputtering)

Three main control parameters� sputter target composition� discharge gas mixture compositon� substrate bias voltage

DCMagnetron

Gas inlet MatchingNetwork

13.56 MHzGenerator

Heater

Thermocouple

Cryopump

Substrateholder

Ub

Ts

ImS

N

N

4/14

Main characterization technique

Ageing resistance expressed in terms of the thickness of the surface oxide layer measured by spectroscopic ellipsometry

Example of measured and fitted raw ellipsometric data: (change of light polarization after its reflection from the coating)

clear optical boundary between thin surface oxide (low n) and thick bulk nitride (high n) 1 2 3 4

0

20

40

60

80

Energy (eV)

Exp. Fit

Ψ (

°)

2200 nm bulk 214 nm oxide

5/14

SiBCN coatings studied

5 Six(B4C)1-x sputter target comp.[Si target ] = 5, 20, 40, 60, 75%

×4 N2+Ar gas mixture comp.

[Ar plasma ] = 0, 25, 50, 75%×

2 substrate bias valuesUb = -100 or -500 V

×2 storage conditions (open air

or in polyethylene bags)⇓

80 coatings studied

6/14


controlling elementalcomposition

controlling ion bombardment (densification)

5 Six(B4C)1-x sputter target comp.[Sitarget] = 5, 20, 40, 60, 75%


[Arplasma] = 0, 25, 50, 75%×




80 coatings studied

6/14


5 Six(B4C)1-x sputter target comp.[Sitarget] = 5, 20, 40, 60, 75%


[Arplasma] = 0, 25, 50, 75%×




80 coatings studied

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(a) ≤50% Ar + ≥50% N2

(b) 75% Ar + 25% N 2


2002-2003 : 80 coatings deposited, as-deposited properties measured

↓

2005+ : as-deposited properties published

↓

2003-2015 : storage of 40 coatings under open air + 40 coatings in polyethylene bags

↓

2015 : ageing resistance (surface oxide thickness) studied

DCMagnetron

Gas inlet MatchingNetwork

13.56 MHzGenerator

Heater

Thermocouple

Cryopump

Substrateholder

Ub

Ts

ImS

N

N

7/14

Ageing resistance for Si 5(B4C)95 target

� oxidation barrier formed in all cases� effect of gas mixture composition qualitatively depends on Ub� perfect ageing resistance at high |Ub| and low [Arplasma]

Si5(B4C)95

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Si5(B4C)95 Si20(B4C)80

------ : complete oxidation (down to substrate)


� least optimum target composition: frequent complete oxidation down to a substrate

� ageing resistance at strong Ar+ bomb. (highest [Arplasma])

8/14

Si5(B4C)95 Si20(B4C)80 Si40(B4C)60 Si60-75(B4C)25-40

resistant(no oxidation beyond surf. roughness)



� overall improvement compared to Si20(B4C)80 target� perfect ageing resistance at high [Arplasma]� even higher Si content: even better (only resistant samples)

8/14


100% N2 + 0% Ar

Ageing resistance for 100% N 2 + 0% Ar plasma(⇒ "saturation" N content in SiBCN)

� ageing at medium [Sitarget] = 20-40%� stronger dependence on [Sitarget] at high |Ub| = 500 V

9/14


100% N2 + 0% Ar 25% N2 + 75% Ar

Ageing resistance for 25% N 2 + 75% Ar plasma(⇒ "sub-saturation" N content in SiBCN)

� better - or even perfect - ageing resistance at higher [Sitarget] � again, stronger dependence on [Sitarget] at high |Ub| = 500 V

9/14

SiBCN ageing resistance maptwo information in one box: effect of substrate bias

Six(B4C)1-xsputter target composition

N2+Ar discharge gas mixture composition10/14



N2+Ar discharge gas mixture composition

SiO2 can protect bulk material

B2O3 can protect bulk material

SixByOz(silicon constitutes impurities, not oxide in its own right) can NOT protect bulk material

10/14



N2+Ar discharge gas mixture composition

best high-temperature (~1500 °C) stability and oxidation resistance

10/14

SiBCN ageing resistance mapsubstrate bias leading to better performance


N2+Ar discharge gas mixture composition11/14

Explanation of some trends shown: densification

Densification expressed(despite compositional changes with [Arplasma])

in terms of hardnessin terms of refractive index

� Higher [Arplasma]: densification of SiBCN coatings(steeper trends at higher [Sitarget] and lower |Ub|)

� Other words: transition from Ub = -500 V to -100 V is more beneficial / less harmful at higher [Arplasma]

� Yet other words: do not combine high |Ub| + high [Arplasma]

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ageingresistance

(densification in terms of)hardness

(densificationin terms of)refractive index

Performance of Si-rich films- steeply dependent on [Arplasma]

- the best at high [Arplasma] and low |Ub|

13/14


ageingresistance

(densification in terms of)hardness

(densificationin terms of)refractive index

Performance of Si-rich films- steeply dependent on [Arplasma]

- the best at high[Arplasma] and low |Ub|

Performance of Si-poor films- more weakly dependent on [Arplasma]

- the best at low [Arplasma] and high |Ub|

13/14

Conclusions

14/14

SiBCN coatings prepared in a wide range of compositions (⇒ properties)

Ageing expressed in terms of surface oxide thickness (ellipsometry) after 12 yr

Optimization of process parameters for each composition ⇒ ageing resistance(and densification)

Si-rich compositions resistant, prefered preparation in Ar-rich plasma at low |Ub|

B4C-rich compositions resistant, prefered preparation in Ar-poor plasma at high |Ub|

[ J. Houska, Ceram. Int. 41, 7921 (2015) ]

ageing resistance (12 years) of hard and oxidation...

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