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Carbon-Based Nanostructured Composite and Nanolaminated Films. Carbon-based nanocomposite thin films – deposition , structure and properties. W itold Gulbiński Institute of Mechatronics, Nanotechnology and Vacuum Technique Koszalin University of Technology, PL.
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Carbon-BasedNanostructuredComposite and NanolaminatedFilms Carbon-basednanocompositethinfilms – deposition, structure and properties Witold GulbińskiInstitute of Mechatronics, Nanotechnology and Vacuum Technique Koszalin University of Technology, PL
Carbon-based nanocomposite thin films – deposition, structure and properties • OUTLINE • Carbon films – DLC: taC, aC, aC:H • Carbon-based nanocomposite thin films (CBNTF) – the design concept • Deposition methods • Structure and properties of nanocomposite thin films • Carbide containing MeCx-taC and MeCx-aC:H films (Me = Si, Ti, V, W, Mo…) • Metal containing Me-taC:H and Me-aC:H (Me=Co, Ni, Cu, Ag, Au…) • Comments on applications • Concluding remarks
Carbon-based nanocomposite thin films – deposition, structure and properties The bombardment of energetic carbon species during deposition is critical for the growth of DLCfilms. The ion energy is the most important parameterfor determining the characteristics of DLC films. The ion bombardment tends to result in the highly-dense packing of carbon atoms in the film,yielding a very high compressive stress therein. A very high compressive stress tendsto detach the film from the substrate, when the filmthickness increases above a critical value. The internalstress can be reduced by different mechanisms. A.C. Ferrari, J. Robertson, Interpretation of Raman spectra of disordered and amorphous carbon, Phys. Rev. B 61 (20) (2000)14095.
Carbon-based nanocomposite thin films – deposition, structure and properties A.C. Ferrari, J. Robertson, Interpretation of Raman spectra of disordered and amorphous carbon, Phys. Rev. B 61 (20) (2000)14095. G peak position and I(D)/I(G) ratio vs sp3 fraction foras-deposited a-C:H.
Si Si Al Ni Co Cu Ag, Au Al Ni Co Cu Ag, Au Ti Cr V Mo Ta Zr W Ti Cr V Mo Ta Zr W taC taC:H aC:H Me-taC:H MeCx-taC:H MeCx-taC Me-aC:H MeCx-aC:H Me-taC Carbon-based nanocomposite thin films – deposition, structure and properties
Carbon-based nanocomposite thin films – deposition, structure and properties REQUIREMENTS for tribological coatings • high toughness (high strength + ductility): ability to support high loads in sliding/rolling contact • low friction • high hardness • high adhesion • chemical and tribochemical stability
Carbon-based nanocomposite thin films – deposition, structure and properties Carbon based nanocomposite coatings - the way to increase toughness and wear resistance accompanied by low friction How to do that? - Embed grains of hard phase (TM carbides) in a softer matrix (aC or aC:H), allowing for high ductility due to grain boundary sliding
Carbon-based nanocomposite thin films – deposition, structure and properties • Design concepts of tough nanocomposite coatings: • Encapsulation of 3-10 nm sized hard crystallinegrains in an amorphous matrixrestricts dislocation activity,diverts and arrests macro-crackdevelopment. • A large volume fraction of grain boundaries providesductility through grain boundary sliding andnano-cracking along grain/matrix interfaces. • A graded interface layer is usually applied between thesubstrate and crystalline/amorphous composite coatingto enhance adhesion strength and relieve stresses(combination of functional gradient and nanocompositedesign) A.A. Voevodin, Tsinghua Science and Technology, 10 (2005) 665-679
Nanocomposite Nanocomposite Nanocrystalline MeCx MeC-aC;H MeC-aC;H x x crystallites < 20 nm x crystallites < 10 nm crystallites < 4 nm Up to 10 % a-C:H 10- 70 % a-C:H 70- 95 % a-C:H Powłoki nanokompozytowe typu XC/a-C:H aC:H krystality < 10 nm MeC a) x (111) (111) (200) (200) (220) (220) (311) (311) (222) (222) (400) (400) (420) (420) (422) c) d) b) TiC d = 8-10nm TiC-aC:H d = 4-6nm TiC-aC:H d = <4nm H = 32 GPa, μ = 0.35 Ti48C40H9(O,N.Ar)3 H = 42 GPa, μ = 0.26 Ti38C52H6(O,N.Ar)4 H = 15 GPa, μ = 0.06 Ti6C72H21(O,N.Ar)1 Carbon-based nanocomposite thin films – deposition, structure and properties A. Czyżniewski et al., Journal of Materials Processing Technology 157–158 (2004) 274–283
From scratch test Carbon-based nanocomposite thin films – deposition, structure and properties 3-10 nmcrystalline grains (TiC) embedded in an amorphous matrix (aC). The grains are separated by 1-3 nm. TiC-aC Film thickness: 1μm Load: 10N! Indentation depth: 9μm! restriction of dislocation activity, macro-cracking blocked, ductility through grain boundary sliding, nanocracking along grain-matrix interfaces A.A. Voevodin, Tsinghua Science and Technology, 10 (2005) 665-679
Si Al Ni Co Cu Ag, Au Ti Cr V Mo Ta Zr W taC MeCx-taC Me-taC Carbon-based nanocomposite thin films – deposition, structure and properties Deposition of CBNTF MeCx- or Me-taC • Magnetron sputtering (multisource: Me & C or segment targets) • Ion beam sputtering (multitarget) • Filtered cathodic vacuum arc • Pulsed laser (ns, fs) - segment targets or multitarget geometries
Si Al Ni Co Cu Ag, Au Ti Cr V Mo Ta Zr W taC:H aC:H Me-taC:H MeCx-taC:H Me-aC:H MeCx-aC:H Carbon-based nanocomposite thin films – deposition, structure and properties Deposition of CBNTF MeCx- or Me-aC:H • CVD, PECVD (RF, MV-ECR) • Reactive magnetron sputtering (multisource: Me targets) • Other techniques usually linking two or more techniques listed above (DMWECR + Sputtering)
Carbon-based nanocomposite thin films – deposition, structure and properties Si-taC films Filtered vacuum arc of graphite withsimultaneous magnetron sputtering of Si. Churl Seung Lee et al., Diamond and Related Materials 11 (2002) 198–203
Carbon-based nanocomposite thin films – deposition, structure and properties Si incorporated into tetrahedral amorphous carbon (aSiC-taC) sp3/sp2 Churl Seung Lee et al., Diamond and Related Materials 11 (2002) 198–203
ncTiC-taC Al-taC sp3/sp2 Carbon-based nanocomposite thin films – deposition, structure and properties Me-taC, Me =Al, Ti films Carbon films were deposited by the off-planedouble-bend filtered cathodic vacuum arcfrommetal doped graphite target. • B.K. Tay et al., Diamond and Related Materials 10 (2001) 1082-1087 (Al or Ti – taC) • D. Sheeja et al., Diamond and Related Materials 12 (2003) 2032–2036 (Al -taC) • S. Zhang et al., Thin Solid Films 482 (2005) 138– 144 (Ti+Al – taC)
Carbon-based nanocomposite thin films – deposition, structure and properties WCx-WS2-aC adaptive nanocomposite films (for vacuum applications) S - 0 at.% S - 15 at.% S - 29 at.% KrF excimer laser + MS PLD: Graphite + MS: (W, WS2) Andrey A. Voevodin et al., Surface and Coatings Technology 116–119 (1999) 36–45
Carbon-based nanocomposite thin films – deposition, structure and properties WS2 lubrication Graphite lubrication
Carbon-based nanocomposite thin films – deposition, structure and properties Ti, W, Si – aC:H nanocomposite films A. Czyżniewski et al., Journal of Materials Processing Technology 157–158 (2004) 274–283
Ti, W, Si – aC:H nanocomposite films A. Czyżniewski et al., Journal of Materials Processing Technology 157–158 (2004) 274–283 Carbon-based nanocomposite thin films – deposition, structure and properties
C-Ti C1s C-C Carbon-based nanocomposite thin films – deposition, structure and properties TiC– aC:H nanocomposite films W. Gulbiński et al., Applied Surface Science 239 (2005) 302–310
Carbon-based nanocomposite thin films – deposition, structure and properties TiC– aC:H nanocomposite films W. Gulbiński et al., Applied Surface Science 239 (2005) 302–310
aC Hydrophobic Θ>700 Hydrophilic Θ<700 Carbon-based nanocomposite thin films – deposition, structure and properties Me-aC where Me = Al, Ti, Ni, Si, were prepared by the filteredcathodic vacuum arc technique with metal-carbon (5 at.% metal) composite targets. P. Zhang, Diamond and Related Materials 13 (2004) 459–464
Carbon-based nanocomposite thin films – deposition, structure and properties MoCx-aC:H nanocomposite films Q.F. Huang et al., Diamond and Related Materials 9 (2000) 534–538
Carbon-based nanocomposite thin films – deposition, structure and properties Ni-aC films with superparamagnetic properties Ion beam co-sputteringof graphite targethaving a nickel chip attached to its surface. Films were deposited on polished Si wafers heated to350 °C. (above Ni3C decomposition temperature) Ni concentration: 5 to 22 wt % F. C. Fonseca et al., JOURNAL OF APPLIED PHYSICS 97 (2005) 044313
TB = 13K Hc=0 Carbon-based nanocomposite thin films – deposition, structure and properties Normalized magnetization as a function of H/T at temperatures of100, 150, 200, 250 and 300 K Ni grain size distribution F. C. Fonseca et al., JOURNAL OF APPLIED PHYSICS 97 (2005) 044313
Carbon-based nanocomposite thin films – deposition, structure and properties Ni3C-aC films by DC MS of Ni and C 18 at% Ni 30 at% Ni Ts = 200C The films deposited below 400 C showed a columnar structure of hexagonal Ni3C type crystalline grains embedded in a matrix consisting of an amorphous and/or graphite-like carbon. K. Sedlackova, P. Lobotka, I . Vavra, G. Radnoczi, Carbon 43 (2005) 2192–2198
Carbon-based nanocomposite thin films – deposition, structure and properties Ni-aC films 30 at% Ni Ts = 4000C Above TS = 400 Cthe composite consists of globular fcc Ni grains sized between50 and 100 nm that were separated by the Fullerene-like carbon phase. K. Sedlackova, P. Lobotka, I . Vavra, G. Radnoczi, Carbon 43 (2005) 2192–2198
Carbon-based nanocomposite thin films – deposition, structure and properties Co-taC nanocomposite films (Co 65 at.% -taC)with ferromagnetic properties Hao Wang et al., Materials Science and Engineering C 16 (2001) 147–151
As dep. 3500C C1s 4000C Carbon-based nanocomposite thin films – deposition, structure and properties Co-taC nanocomposite films (Co:65 at.%) with ferromagnetic properties The most important advantageof carbon encapsulation is the increase of the effectivedistance of neighbouring magnetic grains so that the exchangecoupling between them is weakened or eliminated. XPS Hao Wang et al., Materials Science and Engineering C 16 (2001) 147–151
Carbon-based nanocomposite thin films – deposition, structure and properties 3000C As deposited Co-taC nanocomposite films 3500C 4000C Magnetic Force Microscopy Magnetization loop Hao Wang et al., Materials Science and Engineering C 16 (2001) 147–151
σ = 2.9 GPa μH = 22 GPa 0 at.% Cu 0.7 GPa 16 GPa 11 at.% Cu Carbon-based nanocomposite thin films – deposition, structure and properties Cu-aC:H nc thin films (RF PECVD + Cu sputtering) • Copperwas used to: • prevent the formation of bondsbetween the nanocrystallite and the carbon matrix, • facilitate grain–matrix interface sliding,whichincreases the film’s ductility. C.-C. Chen, F.C.-N. Hong, Applied Surface Science 242 (2005) 261–269
Carbon-based nanocomposite thin films – deposition, structure and properties Cu-aC:H 16 at.% Cu C.-C. Chen, F.C.-N. Hong, Applied Surface Science 242 (2005) 261–269
Carbon-based nanocomposite thin films – deposition, structure and properties • Ag-aC:H nanocomposite films • Silver within a diamondlike carbon–silver nanocompositefilm may provide antimicrobial functionality to amedical devices. • Silver nanoparticles are highly toxic tomicroorganisms, and demonstrate biocidal effects against: • Staphylococcus aureus, • Escherichia coli, • Pseudomonasaeruginosa, • Listeria monocytogenesand other species ofbacteria. • The exact mechanism of action of silver isunknown, but it is believed that silver ions act by bindingto DNA, interfering with electron transport within cells, andinjuring bacterial enzymes. R.B. Thurman, C.P. Gerba, CRC Crit. Rev.Environ. Control 18(2000) 295
Ag Ti 10 nm Carbon-based nanocomposite thin films – deposition, structure and properties Excimer laser KrF, 248nm, 25ns, 10Hz, 5J/cm2 self-assembled morphology Coalescence of Ag clusters Ag-taC 32 GPa μ = 0.15 TiC-taC 29 GPa μ = 0.10 R.J. Narayan, Diamond & Related Materials 14 (2005) 1319–1330
Carbon-based nanocomposite thin films – deposition, structure and properties Pulsed laser deposition of Ag-taC nanocomposites Laser beam Ag Graphite P.A. Patsalas, ESF Exploratory Workshop, ‘Carbon-based nanostructured composite films’ August 2006, Gdansk, Poland
_ + Ag Carbon-based nanocomposite thin films – deposition, structure and properties Pulsed laser deposition of Ag-taC nanocomposites P.A. Patsalas, ESF Exploratory Workshop, ‘Carbon-based nanostructured composite films’ August 2006, Gdansk, Poland
Carbon-based nanocomposite thin films – deposition, structure and properties Pulsed laser deposition of Ag-taC nanocomposites Ag P.A. Patsalas, ESF Exploratory Workshop, ‘Carbon-based nanostructured composite films’ August 2006, Gdansk, Poland
Carbon-based nanocomposite thin films – deposition, structure and properties Pulsed laser deposition of Ag-taC nanocomposites Ag P.A. Patsalas, ESF Exploratory Workshop, ‘Carbon-based nanostructured composite films’ August 2006, Gdansk, Poland
Carbon-based nanocomposite thin films – deposition, structure and properties IR radiation source or thermostable resistors Mo, Cr Silicon-organic liquid – Plasma Polymerized Methyl Silane (PPMS) was used as a plasma-forming substance of the open plasmatron. (C2H5)3SiO[CH3C6H5SiO]3Si(CH3)3 MeSi-aC:H; Me=Mo, Cr CrSi-aC:H V.K. Dmitriev et al..Diamond and Related Materials 10 (2001) 1007-1010
Carbon-based nanocomposite thin films – deposition, structure and properties MeSi-aC:H; Me=Mo, Cr Mo, Cr Stability test: 1 year at 8000C in air V.K. Dmitriev et al., Diamond and Related Materials 10 (2001) 1007-1010
Carbon-based nanocomposite thin films – deposition, structure and properties Low-k interconnect dielectric a-C:(H+F) R.F. plasma-assisted PACVD in a parallel plate reactor. Films with dielectric constant values between 3.3 and 2.7. ULSI chips ρ = 1016 Ωcm P = CV 2f Incorporation of fluorine in FDLC films produces a material of apparentlyhigher thermal stability and further reduced dielectric constant, to values even lower then 2.4 SEM micrograph of two-level Cu wiring with DLC dielectric A. Grill, Diamond and Related Materials 10 (2001) 234-239
Carbon-based nanocomposite thin films – deposition, structure and properties Co-aC:H filmsdeposited by magnetron sputtering on aramide tissue (20-61 at.% Co) up to percolation threshold. Superparamagnetic state at RT Al2O3 Substrate aramide tissue Co(60 at.%)-aC:H Co-aC:H sputtering on aramide (aromatic polymer - polyamide) tissues provides flexible and durable electromagnetic absorption coverings. Microwave radiation absorption L.V. Lutsev et al., JOURNAL OF APPLIED PHYSICS 97 (2005) 104327
Carbon-based nanocomposite thin films – deposition, structure and properties • Concluding remarks • CBNTF can be deposited by well known PVD (MS, VArc, PLD) and CVD (PACVD) methods • In tribological applications CBNTF show: • friction coefficient below 0.1 - can be achieved in vacuum and under humid conditions, • low wear, • hardness in the range from 10-40GPa, • low residual stresses and good adhesion, • high cohesive toughness. • For CBNTF containing ferromagnetic metals (Ni, Co), superparamagnetic as well as ferromagnetic behaviour is observed dependent on metal cluster size. • Dielectric properties of CBNTF can be tuned form low to high k values. • Surface wetting properties of CBNTF can be modified by metal doping. • Silver conataining CBNTF show a potential for antibacterial applications. • Due to chemical inertness and biocompatibility, CBNTF are candidates for medical applications.
Carbon-based nanocomposite thin films – deposition, structure and properties Thank you for your kind attention