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High-temperatures in-situ XRD studiesof CrN and TiN films

• Experimental: XRD at high TExperimental: XRD at high T • XRD patterns, lattice parameter evolution and grain XRD patterns, lattice parameter evolution and grain growth of CrN filmsgrowth of CrN films

• XRD patterns, lattice parameter evolution and grain XRD patterns, lattice parameter evolution and grain growth of TiN filmsgrowth of TiN films

• XRD patterns, lattice parameter evolution and grain XRD patterns, lattice parameter evolution and grain growth of CrN and TiN films after the optimization of the growth of CrN and TiN films after the optimization of the HV systemHV system

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PUMP

GAS

X-RAY

1•10-7 mbar

1•10-6 mbar1•10-5 mbar

Optimization• Baking (heating sequence);• Helium streams.

5•10-5 mbar

6•10-7 mbar

5•10-6 mbar

Xpert Philips diffractometer: HV apparatusXpert Philips diffractometer: HV apparatus

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DepositionPVDSubstrate WCThickness 5 - 10 m

XRDTemperature RT - 1000°CPressure 5.6•10-5 - 1.2•10-4 mbar

Experiment 1Experiment 1

RT

400°C

500°C

600°C

700°C

800°C

900°C

1000°C

RT

35 min

5 min - 20°C/min

5 min

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CrCrxxNN1-x1-x phase diagram phase diagram

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CrN →1

2Cr2N +

1

2N2

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2CrN +3

2O2 → Cr2O3 + N2

CrNCrNExperiment 1Experiment 1

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Optical images

Prior tomeasurements

Aftermeasurements

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UnitCell

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Gave =Kλ

β1 2cosθ

Grain growth(Scherrer formula)

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=Ti - hcp =Ti - bcc=TiN =Ti2N‘=Ti2N

TiTixxNN1-x1-x phase diagram phase diagram

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TiN →1

2Ti2N +

1

2N2

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TiN +O2 → TiO 2 +1

2N2

TiNTiNExperiment 1Experiment 1

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Optical images

Prior tomeasurements

Aftermeasurements

Lattice parameter Grain growth

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Experiment 2XRDTemperature RT - 1000°CPressure 1.7 - 7.7 •10-5 mbarHe streamsBaking at 200°C for 1 hour

RT

400°C

500°C

600°C

700°C

800°C

900°C

1000°C

200°C

RT

35 min

5 min - 20°C/min

1 hour

5 min

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CrN →1

2Cr2N +

1

2N2

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2CrN +3

2O2 → Cr2O3 + N2

CrNCrNExperiment 2Experiment 2

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Temperature dependence of lattice parameter and grain sizeExperiment 2

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TiN →1

2Ti2N +

1

2N2

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TiN +O2 → TiO 2 +1

2N2

TiNTiNExperiment 2Experiment 2

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Temperature dependence of lattice parameter and grain sizeExperiment 2

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Performed measurements and Performed measurements and upgradingupgrading

- Optimization of Vacuum systemOptimization of Vacuum system

- XRD at various temperatures on CrN and TiN films- XRD at various temperatures on CrN and TiN films

- Temperature dependence of lattice parametersTemperature dependence of lattice parameters

- Temperature dependence of grain sizesTemperature dependence of grain sizes

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ConclusionsConclusions- CrCrxxNN1-x1-x films exhibit phase stability in the cubic CrN form up to films exhibit phase stability in the cubic CrN form up to

800°C at actual measurement conditions800°C at actual measurement conditions- After 800°C the CrAfter 800°C the CrxxNN1-x1-x samples undergo to oxidation and the samples undergo to oxidation and the

formation of Crformation of Cr22NN- All TiAll TixxNN1-x1-x films exhibit the presence of the cubic TiN phase and films exhibit the presence of the cubic TiN phase and

traces of the traces of the TiTi22N phaseN phase- After 800°C the CrAfter 800°C the CrxxNN1-x1-x samples undergo to oxidation samples undergo to oxidation

at actual measurement conditionsat actual measurement conditions- After 800°C the TiAfter 800°C the TixxNN1-x1-x samples undergo the formation of Cr samples undergo the formation of Cr22N;N;- In general the high temperatures result in an increase of the lattice In general the high temperatures result in an increase of the lattice parametersparameters- In general, the temperature dependence of grain sizes exhibit an In general, the temperature dependence of grain sizes exhibit an upward trendupward trend

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Next StudiesNext Studies- Further optimization of vacuum systemFurther optimization of vacuum system- Control of pOControl of pO22 to perform reproducible measurements to perform reproducible measurements

- Kinetic and thermodynamic studies- Kinetic and thermodynamic studies- Composition (EDX)Composition (EDX)- Phase content quantification (XRD)Phase content quantification (XRD)- XPS studiesXPS studies- Morphology study (SEM)Morphology study (SEM)- Texture evolution study (XRD)Texture evolution study (XRD)- Mechanical propertiesMechanical properties- Stress study using XRD (TEC, oxidation, phase Stress study using XRD (TEC, oxidation, phase transitions, etc)transitions, etc)