Dense Plasma Focus as a Novel High Energy Density Pulsed Plasma Facility for Controlled Synthesis of

Variety of Materials

Rajdeep Singh Rawat

Plasma Radiation Sources Lab National Institute of Education

Nanyang Technological University

Project Team from NIE/NTU – S. V. Springham, T.L. Tan & P. Lee

PhD Students: J.J. Lin S. Mahmood Zhenying Pan Wang Ying Tan Kin Seng Bo Ouyang I. A. Khan Z. Umar A. Hussnain Rishi Verma Sabpreet Bhatti

Collaborators: Lee Sing (IPFS, Australia] Riaz Ahmed (GCU, Pakistan] R. V. Ramanujan (Nanyang Technological University, Singapore) M. Jacob (James Cook University, Australia] S. N. Piramanayagam (Nanyang Technological University, Singapore)

Acknowledgement

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Funding: NIE AcRF; MOE Tier 1 grant; RS-SAA Grant; IAEA CRP

Plasma/Laser Activities @ PRSL/NIE/NTU

Dense Plasma Focus

Laser Produced Plasmas

Low-temperature Plasmas

10 Hz Miniature PF Portable Neutron Source

20 kJ PF Neutron Source for Material Irradiation

Short-lived Radioisotopes Production

Coded Aperture Imaging of Fusion Neutron Source

X-ray emission studies for SXR Microlithography

Magnetic Nanopartilces and Hard-Coatings using

Plasma Focus

Nanostructured Carbon using Plasma Focus

Microwave Plasmas for Diamond Synthesis

RF Plasmas + Thermal CVD for Graphene and other Energy Storage

Materials

Atmospheric Microplasma for Nanofabrication

Time – resolved imaging of plasma plume

PLD of Nanophase Magnetic Materials

TM Doped ZnO Based DMS

LPP as EUV and Soft X-ray Source

Spectroscopy of LPP plume

Pulsed Laser Processing of Materials

• Current sheath speed in axial phase: 0.2 ×105 -1.0 ×105 ms-1, • Current sheath speed in radial phase: typically 2 to 2.5 times the axial speed, • Pinch plasma electron/ion densities: 5 ×1024 –1026 m-3, • Pinch plasma electron temperatures: 200 eV – 2 keV, • Ion temperatures of pinch plasmas: 300 eV – 1.5 keV, • Energies of instability accelerated electrons: tens of keV to few hundreds of keV, • Energies of instability accelerated ions: tens of keV to few MeV.

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Dense Plasma Focus – HEDPP Device

A - S. Lee, S. H. Saw, P. Lee, and R. S. Rawat, PPCF, 51(10), 105013 (2009). B - H. Krompholz, et al, Physics Letters A 82, 2 (1981). C - A. J. Toepfer, D. R. Smith and E. H. Beckner, Physics of Fluids 14, 52 (1971). D - V. A. Gribkov, et al, Journal of Physics D-Applied Physics 40(12), 3592-3607 (2007). E - N. Qi, et al, IEEE Transactions on Plasma Science 26(4), 1127 (1998). F - A. Bernard, et al, Physics of Fluids 18, 180 (1975). G - N. J. Peacock, M. G. Hobby and P. D. Morgan, in 5th International Conference on Plasma Physics and Controlled Nuclear Fusion Research, IAEA-CN-28/D-3, Tokyo, (1972). I - T. Zhang, J. Lin, A. Patran, D. Wong, S. M. Hassan, S. Mahmood, T. White, T. L. Tan, S. V. Springham, S. Lee, P. Lee and R. S. Rawat, Plas. Sour. Sci. Technol. 16, 250 (2007). J - P. Choi, C. Deeney, H. Herold, C.S. Wong, Laser and Particle Beams 8, 469 (1990). K - H. Bhuyan, S.R. Mohanty, T.K. Borathakur, R.S. Rawat, Indian Journal of Pure and Applied Physics 39, 698 (2001). L - M V Roshan, S V Springham, A Talebitaher, R S Rawat and P Lee ,Plasma Physics and Controlled Fusion 52 ,085007 (2010). M - R. L. Gullickson, J. S. Luce and H. L. Shalin, Journal of Applied Physics 48, 3718 (1977).

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Plasma Type Low –temp, Non-equilib., Low-pressure

Thermal Plasma

Low-temp, Non-equilib., High Pressure

High-pressure Microplasma

Plasmas in Liquids

High Energy Density Pinch Plasma

Te Few to tens of eV

0.1 – 5 eV 2 – 5 eV > 10 eV 1 – 2 eV 200 – 2000 eV

Ne 109 – 1014 m-3 1019 – 1023 m-3 1016 -1020 m-3 1018 m-3 1021 - 1023 m-3 1025 - 1026 m-3

Non-equilibrium Equilibrium Non-equilibrium Non-equilibrium Non-equilibrium Non-equilibrium

Ion-beam Electron-beam Shock wave

Plasmas of Interest for Materials Research

K. Ostrikov et al . JPD:AP 44 (2011) 17400

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T S

Various DPF Deposition Setups

Ablation of target by energetic ion beam and hot dense decaying fast plasma stream

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Various DPF Deposition Setups

T S

Ablation of target by energetic electron beam

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T

Various DPF Deposition Setups Processing of metal target surface by suitable gas plasma to convert top layer into different film.

I.A. Khan*, M. Hassan, T. Hussain, R. Ahmad, M. Zakaullah and R.S. Rawat, Synthesis of nano-crystalline zirconium aluminium oxynitride (ZrAlON) composite films by dense plasma focus device, Applied Surface Science 255(12) 6132-6140 (2009).

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Various DPF Deposition Setups

T

S T

S

Ablation of anode top material or anode insert material by hot dense plasma and backward moving electron beam.

R.S. Rawat, W.M. Chew, P. Lee, T. White and S. Lee, Deposition of titanium nitride thin films on 304-stainless steel substrates at room temperature using a plasma focus device, Surface and Coating Technology 173 (2-3), 276-284 (2003).

L.Y. Soh, P. Lee, X. Shuyan, S. Lee, and R.S. Rawat, Shadowgraphic Studies of DLC film deposition process in Dense Plasma Focus Device, IEEE Transactions on Plasma Science 32 (2), 448-455 (2004)

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Advantages of DPF based Depositions High material flux High deposition rates

High energy flux Dense films

Insitu processing of material Phase transition

Insitu processing of material Superior material properties

Insitu processing of material Surface reconstruction

Advantages High deposition rates

Z Y Pan, R S Rawat, M V Roshan, J J Lin, R Verma, P Lee, S V Springham and T L Tan, J. Phys. D: Appl. Phys. 42 (2009) 175001

CoPt deposition rate in 6 mbar 880 J NX 2 PF

Plasma process Growth rate Growth Temperature, ° C

Conventional CVD 1.5 µm/min 950

RF sputtering 0.1 µm/min RT

Plasma-assisted mist-CVD 0.1 µm/min RT

RF magnetron sputtering 5 nm/min 250

DPF Device (10 Hz) 60 µm/min RT

K.S. Tan, R.J. Mah and R.S. Rawat*, Dense Plasma Focus Device Based High Growth Rate Room Temperature Synthesis of Nanostructured Zinc Oxide Thin Films, Plasma Science, IEEE Transactions on Plasma Science 43(8), 2539-2546 (2015)

FESEM cross sectional images of ZnO samples. 20 Shots, 15 cm 20 Shots, 21 cm

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Advantages Dense films

FESEM cross sectional image highlighting dense columnar growth for ZnO

K.S. Tan, R.J. Mah and R.S. Rawat*, Dense Plasma Focus Device Based High Growth Rate Room Temperature Synthesis of Nanostructured Zinc Oxide Thin Films, Plasma Science, IEEE Transactions on Plasma Science 43(8), 2539-2546 (2015)

Z. Y. Pan, R. S. Rawat*, M.V. Roshan, J. J. Lin, R. Verma, P. Lee, S. V. Springham and T. L. Tan, Nanostructured magnetic CoPt thin films synthesis using dense plasma focus device operating at sub-kilojoule range, Journal of Physics D: Applied Physics 42(17), 175001 (2009)

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Advantages Phase transition

[R.S.Rawat, M.P.Srivastava, S.Tandon and A.Mansingh, Phys. Rev B 47, 4858 (1993)] Amorphous Crystalline

Crystalline Amorphous R. Sagar and M. P. Srivastava, "Amorphization of thin film of CdS due to ion irradiation by dense plasma focus," Physics Letters A 183, 209-213 (1993). M. Sadiq, M. Shafiq, A. Waheed, R. Ahmad, and M. Zakaullah, "Amorphization of silicon by ion irradiation in dense plasma focus," Physics Letters A 352 (1-2), 150-154 (2006).

Other examples: [M.P.Srivastava, S.R.Mohanty, S.Annapoorni and R.S.Rawat, Phys. Lett. A 215, 63 (1996)] – N-type doping on PA for Diode formation

[P.Aggarwala, S.Annapoorni, M.P.Srivastava, R.S.Rawat & P.Chauhan, Phys. Lett. A 231, 434 (1997)] – Change of Magnetic Phase – Haemetite to Magnetite

[R.S.Rawat, P.Arun, A.G.Videshwar, Y.L.Lam, P.Lee, M.H.Liu, S.Lee and A.C.H.Huan, Bull. Mat. Res. 35, 477 (2000)] – Sb2Te3 - non-stoichiometric to fully stoichiometric

[R.S.Rawat, P.Arun, A.G.Videshwar, P.Lee and S.Lee, Journal of Applied Physics 95 (12), 7725 (2004)] – Band gap modification of CdI2 thin films

[A. Lepone, H. Kelly, D. Lamas, and A. Marquez, Applied Surface Science 143 (1-4), 124 (1999).] – austenitic to martensitic

Advantages – Surface Reconstruction

J.J. Lin, M.V. Roshan, Z.Y. Pan, R.Verma, P. Lee, S.V. Springham, T.L. Tan, R.S. Rawat, FePt nanoparticle formation with lower phase transition temperature by single shot plasma focus ion irradiation, Journal of Physics D: Applied Physics 41, 135213 (2008)

Single shot irradiation Two shot irradiation

H+ irradiation 14 kV, 2.94 kJ Z=5.0 cm Thickness=67 nm 35 keV to 1.5 MeV Mean E – 124 keV

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SEM micrographs of (a) the Ti substrate surface, (b-d) N+ irradiated surface at different magnifications. N=30 shots, z=5.0 cm and Theta = 10 degree

Rakesh Malik, S Annapoorni*, S Lamba, S Mahmood, and R S Rawat, Dispersion of laser droplets using H+ ions and annealing effect on pulsed laser deposited nickel ferrite thin films, Applied Physics A: Materials Science and Processing, 105(1), 233-238 (2011) 15

Advantages – Surface Reconstruction

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Advantages – Superior Properties

I. A. Khan*, M. Hassan, R. Ahmad, A. Qayyum, G. Murtaza, M. Zakaullah and R.S. Rawat, Nitridation of zirconium using ion beam delivered by plasma focus discharges, Thin Solid Films 516 (23), 8255-8263 (2008)

K.S. Tan, R.J. Mah and R.S. Rawat, DPF based High Growth Rate Room RT Synthesis of Nanostructured ZnO Thin Films, IEEE Transactions on Plasma Science 43(8), 2539-2546 (2015)

R.S. Rawat, W.M. Chew, P. Lee, T. White and S. Lee, Deposition of TiN thin films on 304-SS substrates at RT using a PF, Surface and Coating Technology 173, 276 (2003).

M. Valipour*, M. A. Mohammadi, S. Sobhanian, and R. S. Rawat, Increasing of Hardness of Ti using Energetic N Ions from Sahand PF Facility, Journal of Fusion Energy 31(1), 65-72 (2012)

Advantage – Superior properties

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J.J. Lin, L.S. Loh, P. Lee, T.L. Tan, S.V. Springham and R.S. Rawat, ASS 255 (8), 4372-4377 (2009).

PLD

Z.Y. Pan, J. J. Lin, T. Zhang, S. Karamat, R.Verma, M.V. Roshan, S. Mahmood, P. Lee, S.V. Springham, T.L. Tan, R.S. Rawat, Lower phase transition temperature and two order of coercivity enhancement, Thin Solid Films, 517, 2753-2757 (2009),

H+ irradiation; 4 kV, 2.94 kJ Z=5, 6 and 7 cm; Thick=100 nm Annealing – 400 Deg C

DPF

Z Y Pan, R S Rawat, M V Roshan, J J Lin, R Verma, P Lee, S V Springham and T L Tan, J. Phys. D: Appl. Phys. 42 (2009) 175001

R.S. Rawat and J.J. Lin, Synthesis and Characterization of Magnetic Nanoparticles, Book Chapter in “Nanoparticles: Synthesis, Characterization and Applications” Editors: Ramesh Chaughule and R.V.Ramanujan, American Scientific Publishers, USA (2010). R. S. Rawat, High Energy Density Pulsed Plasmas in Plasma Focus: Novel Plasma Processing Tool for Nanophase Hard Magnetic Material Synthesis, Nanoscience and Nanotechnology Letters 4, 251-274 (2012)

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Advantage – Superior properties

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Key Criticism of DPF based Synthesis However DPF devices have been used on very limited basis for material synthesis as it faces criticism of lack of controlled deposition with desired features.

The criticisms include

(i) limited type of deposition, e.g. mostly nanoparticle morphology,

(ii) Lack of uniformity in deposition – small area uniformity,

(iii) limited metal anode based deposition only and

(iv) shot to shot variation in operation leading to uncertainty in deposition

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Criticism 1 – Limited 0-D NP Morphology

R.S. Rawat, P. Lee, T. White, Li Ying and S. Lee, RT deposition of TiC thin film, SCT 138, 159, (2001).

I.A. Khan, R.S. Rawat, R. Verma, G. Macharaga, R. Ahmad*, AlN films using PF, Journal of Crystal Growth 317(1), 98-103 (2011).

RS Rawat, T Zhang, KS Thomas Gan, P Lee, RV Ramanujan, Nano Fe thin film deposition using PF, Applied Surface Science 253, 1611 (2006).

K.S. Tan, R.J. Mah and R.S. Rawat, Nanostructured ZnO Thin Films, IEEE TPS 43(8), 2539-2546 (2015)

T. Zhang, et al, PF as electron beam source for thin film deposition, PSST 16 (2), 250-256 (2007)

I. A. Khan*, M. Hassan, R. Ahmad, A. Qayyum, G. Murtaza, M. Zakaullah and R.S. Rawat, Nitridation of zirconium using ion beam delivered by plasma focus discharges, Thin Solid Films 516 (23), 8255-8263 (2008)

I.A. Khan, S. Jabbar, T. Hussain, M. Hassan, R. Ahmad*, M. Zakaullah, R.S. Rawat, ZrCN films using PF, Nucl. Inst. Meth. Phys. Res. B 268, 2228 (2010)

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Not True: 1-D NW/NT Morphologies

T Zhang, K S Thomas Gan, P Lee, R V Ramanujan, and R S Rawat, Characteristics of FeCo nano-particles synthesized using plasma focus device, Journal of Physics D: Applied Physics 39, 2212–2219, 2006.

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Not True: 1-D NW/NT Morphologies J.J. Lin, M.V. Roshan, Z.Y. Pan, R.Verma, P. Lee, S.V. Springham, T.L. Tan, R.S. Rawat, FePt nanoparticle formation with lower phase transition temperature by single shot plasma focus ion irradiation, Journal of Physics D: Applied Physics 41, 135213 (2008)

S.R. Mohanty*, N.K. Neog, R.S. Rawat, P. Lee, B.B. Nayak, and B.S. Acharya, Room temperature fabrication of polyaniline nanowires in nanosecond timescale using electron beam of a plasma focus device, Physics Letters A 373, 1962-1966 (2009)

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NOT Convinced Yet 1-, 2- and 3- Dimensional Nanostructured

Carbon Synthesis Using DPF

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Properties and Applications of CNT and Graphene

http://www.meijo-nano.com/en/applications/use.html

Synthesize carbon nanostructures (CNT, graphene and graphene quantum dots) and carbon films • Pulsed Laser Plasmas,

• High Energy Density Pulsed Plasma Focus device plasma and

• RF – PECVD system

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1. Mohan V. Jacoba, Dai Taguchi, Mitsumasa Iwamotob, Kateryna Bazakaa, and Rajdeep Singh Rawat, Resistive switching in graphene-–organic device: Charge transport properties of graphene-organic device through electric field induced optical second harmonic generation and charge modulation spectroscopy, Carbon 112, 111-116 (2017).

2. Bo Ouyang, Yongqi Zhang, Ying Wang, Zheng Zhang, Hong Jin Fan*, and Rajdeep Singh Rawat*, Plasma surface functionalization induces nanostructure and nitrogen-doping in carbon cloth with enhanced energy storage performance, Journal of Material Chemistry A 4, 17801–17808 (2016).

3. Yongqi Zhang, Guichong Jia, Huanwen Wang, Bo Ouyang, Rajdeep Singh Rawat, and Hong Jin Fan*, Ultrathin CNTs@FeOOH nanoflakes core/shell networks as efficient electrocatalysts for oxygen evolution reaction, Materials Chemistry Frontiers, In Press (2016).

4. Bo Ouyang, Yongqi Zhang, Zheng Zhang, Hong Jin Fan and R.S. Rawat*, Green synthesis of vertical graphene nanosheets and their application in high-performance supercapacitors, RSC Advances 6, 23968-23973 (2016).

5. Bo Ouyang, Ying Wang, Zheng Zhang, and R.S. Rawat*, MoS2 anchored free-standing three dimensional vertical graphene foam based binder-free electrodes for enhanced lithium-ion storage, Electrochimica Acta 194, 151-160 (2016):

6. Bo Ouyang, M.V. Jacob, and R.S. Rawat*, Free standing 3D graphene nano-mesh synthesis by RF plasma CVD using non-synthetic precursor, Material Research Bulletin 71, 61-66 (2015):

7. M.V. Jacob, R.S. Rawat, Bo Ouyang, K. Bazaka, D. Sakthi Kumar, Dai Taguchi, Mitsumasa Iwamoto, Ram Neupane, and Oomman K. Varghese, Catalyst-Free Plasma Enhanced Growth of Graphene from Sustainable Sources, Nano Letters 15 (9), 5702–5708 (2015).

Our Interest in Carbon

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CNT using Plasma Focus

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CNT Synthesis Using HEDPP-PF Device

Silicon Subs Silicon Subs PLD ~10 nm Fe layer Heat

Silicon Subs

Fe Nanoparticles PF Silicon Subs

Heat

VA - CNT

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CNT Synthesis Using HEDPP-PF Device

Number of Shots

Cross Sectional FESEM

Average Tube Diameter, nm and Histogram Material Characteristics

5 14.5 ± 3.7

Compressed and non-uniform surface.

Anisotropy: 103.8

2 12.9 ± 3.7 Highly dense and uniform. Vertically aligned MWCNT.

Anisotropy: 233.5

1 8.5 ± 1.5 Highly dense and uniform. Vertically aligned MWCNT.

Anisotropy: 224.0

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CNT Synthesis Using HEDPP-PF Device Catalyst FESEM Material Characteristics

Fe Highly dense growth of CNT.

FePt Dense growth of CNT, substrate surface is visible.

Ni Distinguishable filaments of CNT covering surface.

Ag Well separated nanoparticles of catalyst, no growth of CNT present.

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CNT Synthesis Using HEDPP-PF Device

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CNTs

CNT Synthesis Using HEDPP-PF Device

Number of walls in MWCNT can be tuned.

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Direct Synthesis of CNT on Bulk Target

Silicon Subs Silicon Subs PLD ~10 nm Fe layer Heat

Silicon Subs

Fe Nanoparticles PF Silicon Subs

Heat

VA - CNT

Stainless-Steel Subs PF

SS Subs Heat

VA - CNT

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Gas Phase Synthesis of CNT Using PF Device

CNTs

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Probably the highest ever instantaneous growth rate of about 2µm/100µs ⇒ IGR of 2cm/s

Ultrafast CNT Growth using HEDPP-PF Device

Bulk Catalyst Synthesis of Graphene Nanoflakes Films using Dense Plasma Focus Device Effect of substrate type.

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High magnification FESEM of GNF synthesize on a) SS and b) Si substrate.

3-D Graphene

Bulk Catalyst Synthesis of Graphene Nanoflakes Films using Dense Plasma Focus Device Effect of substrate type.

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Raman spectra of GNF synthesize in different pressure.

3-D Graphene

Bulk Catalyst Synthesis of Graphene Nanoflakes Films using Dense Plasma Focus Device Effect of gas pressure and substrate type.

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Gas pressure,

mbar 1.0 1.5 1.8 2.5 4.0

SS

Si

3-D Graphene

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Large Area Synthesis is

Possible

Single shot vertically aligned Carbon Nanotubes synthesis

X1 mbar X2 mbar X3 mbar

Criticism 1 – small area uniformity

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Criticism 3 – Limited Metal/Graphite Anode Based depositions

Stage 1: until year 2000 Metal/Graphite Ablation Physical Vapor Deposition (PVD) Stage 2: year 2000 onwards Anode Metal Ablation + Background reactive gas PVD + PECVD Stage 3: Year 2012 onwards We have started doing purely gas phase based deposition – CNT and Graphene were using carbon containing gas precursor PECVD or more appropriately HED-PECVD

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Criticism 4 – Shot to shot variation Reproducibility Issue

R S Rawat, T Zhang, K S Thomas Gan, P Lee, RV Ramanujan, Fe thin film, Appl Surf Sci 253, 1611 (2006).

CoPt using 50, 100 and 200 PF Shots Z Y Pan, R S Rawat1, M V Roshan, J J Lin, R Verma, P Lee, S V Springham and T L Tan, J. Phys. D: Appl. Phys. 42 (2009) 175001

Conclusion Plasma Focus is versatile device and is maturing for its remarkable

usefulness as NOVEL Material Processing and Synthesis Facility

0-D 1-D 2-D 3-D

MX M= Metal; X=N/C/O/ON/CN

Bi-metals FePt, CoPt

Carbon DLC, CNT, G

High deposition rates Dense films

Phase transition Superior material properties

Surface reconstruction Large Area Uniform Deposition

Reproducibility