Lecture 3 Properties of diamond films ● Thermal conductivity ● Isotopic effect ● Impurities ● Optical properties ● Stress ● Fracture strength Thermal conductivity of diamond and some optical and electronic materials at room temperature bulk materials Thermal conductivity (W/m*K) 2000 CVD Diamond 1500 3 GHz, 50 W transistor on CVD diamond heat spreader. “Pulsar” company, Moscow 1000 500 4H-SiC Cu BeO 0 AlN Si GaN GaAs Al O 2 3 ● thermal conductivity of diamond: 5 times higher than for copper, and 50 times higher than for sapphire. ● ultimate bulk material for thermal management and high power optics. Anisotropy of thermal conductivity in polycrystalline CVD diamond Phonon scattering on grain boundaries. Columnar grain structure TC anisotropy. Depth inhomogeneity due to crystal size variation. Perpendicular values k should higher than the in-plane values k. J. Graebner, et al., J. Appl. Phys. 71 (1992) 5353. Measurements of thermal diffusivity by Laser Flash Technique (LFT) Method: heating of the front side by short laser pulse and tracing the T(t) on rear side. ● Delivery of laser pulse through an optical fiber to improve uniformity of irradiation on the sample. ● Software for automatic evaluation of thermal diffusivity and TC. ● Vacuum Cryostat. Measurements thermal diffusivity in the temperature range 180 – 430 К. IR detector laser beam sample metal film (absorber) Temperature evolution (T(t) on rear side of the film ● LFT measures perpendicular thermal diffusivity D. Transient thermal grating technique measures parallel thermal diffusivity D He - Ne 0 ,0 8 D iffraction intensity, a.u. Nd:YAG 0 ,1 0 0 ,0 6 0 ,0 4 1 0 6 4 nm 0 ,0 2 0 ,0 0 -2 -1 0 1 2 3 4 5 T im e, m icroseconds ● thermal grating formation due to refraction coefficient modulation by two interfering laser (Nd:YAG) beams. ● diffraction of probe He-Ne laser beam on the transient grating with period Λ. Diffraction signal decay due to thermal dissipation 2 4 D II 2 Set-up for DII measurement using thermal grating technique A custo-op tic g ate 63 3 nm H e-N e laser H arm on ics g en erator YA G :N d laser 10 64, 532 , 35 5, 26 6, 2 13 nm 1 Trigg errin g D iffractio nal beam sp litter S patial filter PM T S am ple Period of thermal grating 30-120 µm S patial filter D igital osciloscope and P C O ptical fiber E.V. Ivakin, Quantum Electronics (Moscow), 32 (2002) 367. Thermal conductivity at room temperature sensitive to content of hydrogen impurity in diamond ● Bonded hydrogen (C-H) decorates defects and grain boundaries. ● Hydrogen concentration as an indicator the defect abundance in CVD diamond. 22 K II 20 K k , W /c m К 18 K┴ 16 14 12 10 K║ 8 0 200 400 600 800 1000 H yd ro g e n co n ce n tra tio n in d ia m o n d , p p m ● Thermal conductivity as high as 2100 W/mK. ● anisotropy: k (perpendicular ) > k (in-plane); Δk/k=10-15%. A.V. Sukhadolau et al. Diamond Relat. Mater. 14 (2005) 589 Thermal conductivity k┴ vs hydrogen impurity in diamond T h e rm a l c o n d u c tiv ity, W /c m K 25 20 15 10 5 10 100 1000 H yd ro g e n c o n c e n tra tio n , p p m Open squares – samples from Element Six [S.E. Coe, Diamond Relat. Mater. 9 (2000) 1726]; full squares – GPI samples. V. Ralchenko, in Hydrogen Materials Science and Chemistry of Metal Hydrides, Kluwer, 2002, p. 203. Thermal conductivity along diamond wafer as measured by LFT at room temperature disk diameter 63 mm, thickness 1.28 mm k, W/cmK Distance along disk diameter, mm Correlation of optical absorption and parallel thermal conductivity = 18 5 0 0 nm T h e rm a l c o n d u c tiv ity W c m -1 K -1 Absorption spectra in the visible 100 , cm -1 75 50 7 . 9 W cm -1 K -1 1 1 .3 16 14 12 10 8 0 5 10 15 20 1 2 .4 A b s o rp tio n , c m 25 30 35 1 2 .5 1 5 .3 1 7 .4 200 25 -1 300 400 500 600 700 In agreement with the correlation found by J. Graebner, DRM, 4 (1995) 1196 for white light absorption and k. W av el en g t h , n m At least a part of defects contribute both in enhanced absorption and in thermal resistance. A.V. Sukhadolau et al. Diamond Relat. Mater. 14 (2005) 589 Thermal conductivity kII at elevated temperatures The decrease of thermal conductivity with T is mostly due to phonon-phonon scattering mechanism (phonon population increases with T). Well fitted with the relationship k ~ T –n (solid lines). T h erm al c o n d u c tiv ity, W /c m K 22 ty pe IIa B -d op e C V D u nd op ed C V D 20 18 16 14 Samples compared: - undoped diamond film (poly), -B-doped film poly); - type IIa single crystal diamond [T.D. Ositinskaya, Superhard Materials (Kiev), No. 4 (1980) 13]. 12 10 8 6 2 50 30 0 35 0 40 0 45 0 50 0 550 Te m p e ratu re , K 60 0 65 0 k(T) : general form for an insulator Heat is transferred by phonons k = ⅓ C(T)· v· λ(T) C is the heat capacity per unit volume, v is the average phonon velocity, λ is the mean free path of phonons between collisions. Any phonon scattering mechanism reducing λ decreases the thermal conductivity. scattering on boundary defects phonon-phonon scattering ● The peak in k occurs at a temperature about 10% of Debye temperature, D. ● At low T: λ is constant, and k ~ C(T) ~ T3. ● Phonon-phonon scattering dominates at high T (k ~ T-1). ● Scattering on defects is essential at intermediate temperatures. Temperature dependence of thermal conductivity for certain crystals k, W/mK Occurrence a maximum in k(T) at low temperatures (80-100 K). Diamond – not the champion in the value of maximum TC, but its k is uniquely high at high temperatures (T>70K), particularly at room temperature. This is the consequence of record high Debye temperature θD =1860K for diamond (very high phonon frequencies are excited). R. Berman, Diamond. Res. (1976) Thermal conductivity kII at elevated temperatures T = 293-460 K Exponent n = 0.17 – 1.02 increases with diamond quality Approximation k ~ T –n 36 is o to p ic a lly p u re [O ls o n , 1 9 9 3 ] 32 28 22 20 20 [H ] = 1 5 0 p p m 16 50 18 CVD 16 K II (W c m /K ) K II (W c m /K ) 24 250 12 690 10 14 12 10 8 8 620 6 T yp e Ia [5 ] 4 300 360 420 480 T e m p e ra tu re (K ) 0 .2 0 .4 0 .6 0 .8 1 .0 1 .2 1 .4 n ● Concentration of H impurity (in ppm) is indicated for each sample. ● Comparison with data for single crystal natural diamonds [ Burgemeister, Physica, 1978]. ● The data for isotopically pure (12C) synthetic HPHT single crystal diamond [Olson PB’1993] give n=1.36, the highest slope for any diamond. ● Weak temperature dependence for highly defective CVD diamond. A.V. Sukhadolau et al. Diamond Relat. Mater. 14 (2005) 589 Defects in transparent CVD diamond (poly) GB - grain boundaries T - twins SF - stacking faults D - dislocations L. Nistor et al, Phys. Stat. Sol.(a), 174 (1999) 5. Typical dimensions of defects Defects present in polycrystalline CVD diamond and their scale K.J. Gray, Diamond Relat. Mater. (1999) Point defects are atomic scale defects: - isolated foreign atoms; - different isotopes; - vacancies Nitrogen ~ 1 ppm or less Boron << 1ppm Hydrogen 20 -1000 ppm (poly) Vacancies - few ppm (?) Isotope 13C ~10,000 ppm (main impurity!) Scattering rate of phonons with frequency ω on isotopic atom with mass m +Δm: 1/τiso = Ãisoω4 Ãiso = Ciso(V0/4πv3)[Δm/m]2 Ciso is isotope concentration, V0 is atomic volume, v is sound velocity. For diamond Δm=1 : Aiso (nat) = 4.045 × 10-3 c-1K-1. Thermal conductivity of isotopically “pure” diamond Is it possible to increase K for diamond above 2400 W/mK at room temperature? Natural and synthetic diamonds (and any carbon material) contain 1.1% of isotope 13C. The 13C atoms are scattering centers for phonons – carriers of heat, thus restricting the thermal conductivity of diamond. Concentration of 13C isotope is much higher than other impurities–point defects. Solution – eliminate 13C isotope from CVD diamond. Isotopic composition of C, Si and Ge Element C Si Ge Isotopes content, % 12C 13C 98.93 1.07 28Si 29Si 30Si 92.23 4.68 3.09 70Ge 72Ge 73Ge 74Ge 76Ge 20.38 27.31 7.76 36.72 7.83 Isotopic effect on thermal conductivity of diamond The ultimate opportunity to achieve TC values > 2400 W/mK relays on purification of isotopic composition of diamond. The natural isotope content in diamond is 98.93% 12C and 1.07% 13C. Phonon scattering on 13C atoms results in thermal resistance. Previous works Si diamond Isotopically modified 12C (99.90%) single crystal HPHT diamond, General Electric (1990-1993) k=33.2 W/cmK 50% increase vs “normal” diamond. L. Wei, PRL, 70 (1993) 3764 28Si. Highly enriched (99.98%) At room temperature: thermal conductivity enhancement of 10% compared to k = 140 W/mK for natural Si. In the maximum at 26K the TC gain is 8 times. R.K. Kremer et al. Sol. State Comm. 131 (2004) 499. 12C-enriched polycrystalline CVD diamond films: k = 21,8 W/cmK; k = 26 W/cmK G.E. Graebner, Appl. Phys. Lett. 64 (1994) 2549. Growth of isotopically enriched poly 12C CVD diamond 12 45 C 1 1 Thermal conductivity (W cm K ) ● production of 12CO with purity 12C 99.96% ● conversion to 12CH4 ● diamond deposition by MPCVD (purity is preserved) ● cutting to 12x2x0.46 mm3 bar ● TC measurements, steady state method CO isotope separation by diffusion. “Colonna” system, Kourchatov Institute, Moscow. 40 35 25.1 W/cm K 30 25 20 natur C (poly) 15 19.0 W/cm K 10 100 200 300 400 Temperature (K) k = 2510 W/mK at 298K for 12C diamond (higher than for type IIa single crystals) - isotopic effect of 32%. k = 1900 W/mK for 0.5 mm thick film with natural isotope abundance. k=2600 W/mK - perpendicularly to the film plane. The isotopic effect increases with temperature decrease - the maximum TC of 4700 W/mK at T=160K. A. Inyushkin et al. Bull. Lebedev Phys. Inst. 34 (2007) 329 The further increase in TC for 12C diamond is limited by defects, impurities, grain boundaries. ► single crystals Measurement cell to determine thermal conductivity at T = 4 - 450K Steady state method of constant thermal gradient. Sample – polycrystalline CVD diamond. The cryostat in vacuum lower 10-5 Torr. Multilayer thermal radiation shield (at T>200K). Copper block Diamond bar 14x2x0.5 mm3 Measurement accuracy of k is better 3% (primarily due to an error in distance between thermometers). Resistor thermometer (Cernox, LakeShore Cryotronics) Heater (resistor) Kourchatov Institute, Moscow Applications of isotopically modified diamonds with extraordinary thermal conductivity ● Heat spreaders for high power electronic devices ● Single crystals and nanocrystals with nitrogen-vacancy (NV) fluorescent color centers for quantum computing and cryptography isotope 13C with nuclear spin should be eliminated to increase spin relaxation (coherence) time of NV centers to µs level. ● Reflecting and transmission X-ray optics for high intensity beams (synchrotron sources) a combination of high TC, low atomic number Z and structure perfection is required. ● Laser optics (including diamond Raman lasers) with increased damage threshold. Thermal conductivity of UNCD measured by a laser flash technique 0 ,0 7 0 0.12 0.11 2 T h e rm a l d iffu s iv ity, c m /s 0 ,0 6 0 0 ,0 5 5 0.1 0 ,0 5 0 0.09 0 ,0 4 5 0.08 0 ,0 4 0 0.07 0 ,0 3 5 0.06 0 ,0 3 0 0.05 0 5 10 15 20 25 N 2, % Thermal conductivity vs N2% T h e rm a l c o n d u c tiv ity, W /c m *К 0 ,0 6 5 ● k = 0.06-0.10 W/cmK at RT is 200 times lower than for single crystal diamond, but still higher than for amorphous sp3 carbon ta-C ka-C = 0.035 W/cmK. ● Thermal conductivity decreases with nitrogen “doping”. ● k = 1/3 C*V*L, where C – heat capacity, V – sound velocity, L – phonon free path. For single crystal L=240 nm; for NCD L2 nm (of the order of grain size). V. Ralchenko, et al. DRM, 16 (2007) 2067 Thermal conductivity of UNCD Temperature dependences measured by “3 Omega” method W.L. Liu et al. APL 89 (2006) 171915 2 Thermal Conductivity (W/cmK) 10 Bulk Diamond: Callaway Model 1 10 Poly NCD_25 NCD_0 Hopping Model (2m, t=0.9) 0 10 Hopping Model (22nm, t=0.32) -1 10 Hopping Model (26nm, t=0.2) a-C -2 10 Minimum K for Carbon -3 10 200 400 Temperature (K) ● kNCD is between polycrystalline diamond and amorphous carbon; ● slow and monotonic temperature dependence; ● in a phonon-hopping model (PHM) the reduction in thermal conductivity is due to decrease in phonon transparency parameter (t) through grain boundaries: t=0.2-0.32 for UNCD, t=0.9 for polycrystalline film. Nitrogen and hydrogen impurities in CVD diamond N and H content evaluation from optical absorption spectra N-induced UV absorption 270 nm 25 A 600 C-H stretch absorption bands 2800-3100 cm-1 150 A 500 -1 A b so rb a n ce , cm 400 50 70 60 0 250 300 300 350 400 W a v ele n g th, n m 50 B T, % A b s o rb a n c e , c m -1 , cm -1 100 20 200 D C 40 30 E 2-phonon absorptio n 20 100 10 200 300 400 500 W a ve le n g th , n m 600 700 4000 3500 3000 2500 2000 1500 Wavenumber, cm 1000 500 -1 15 10 D 5 B E C 2800 2900 3000 W a ve n u m b e r, cm Diamond samples of different qualities A - E S. Nistor et al. J. Appl. Phys. 87 (2000) 8741. -1 3100 Correlation of (bonded) H and N impurities B o n d e d h yd ro g e n co n ce n tra tio n , p p m Hydrogen and nitrogen concentrations are determined from IR and UV absorption 600 500 400 300 200 100 0 2 4 6 8 10 12 14 16 18 S u b stitu tio n a l n itro g e n co n ce n tra tio n , p p m V. Ralchenko et al. in Hydrogen Materials Science and Chemistry of Metal Hydrides, Kluwer, 2002, p. 203; A.V. Sukhadolau et al. Diamond Relat. Mater. 14 (2005) 589. Luminescent nitrogen-vacancy (N-V) and nitrogen-vacancy (Si-V) color centers in diamond 350 (N-V) 575 nm (N-V) 637 nm 200 150 2-nd order 250 daimond Intensity, arb. units - 0 300 Si-V 738 nm PL spectrum on moderate quality of polycrystalline diamond film. 100 ● Bright PL lines на 637 nm (1,945 эВ) from NV- and 575 nm from NV0. 50 0 500 600 700 Wavelenght, nm 800 ● PL lines на 738 nm from SiV. ● All these centers are stable at room temperature. ● Doping during growth process Si impurity in CVD diamond: depth mapping V. Ralchenko, in Nanostructured Thin Films and Nanodispersion Strengthened Coatings, 2004, p. 209. Mapping PL in cross section 50 Intensity, a.u. 40 30 o Si, 800 C 20 o Si, 700 C 10 o M o, 700 C 0 0 10 20 30 40 50 60 distance from substrate surface, m Si-diamond interface The diamond films were deposited on Si substrate at temperature 700ºC (squares) and 800ºC (triangles), and on Mo substrate at 700ºC (circles). Si impurity extends to 20-60 μm in depth. Optical transmission Extremely broad transparency window: from UV to RF, including THz range 1 80 Window 27_02_2009 # 109 1 5 0 m t hick 40 Transmittance T ra n s m itta n c e , % 60 20 1 10 0 10 W a ve le n g th , m ● Cut-off wavelength 225 nm. ● 2-phonon absorption band at 2.5- 6.3 µm ● Loss tangent 10-5 at 170 GHz. 100 Wavenumber, cm 1000 -1 Optical transmission in UV and visible range for natural IIa type single crystal diamond and poly CVD film 80 S in g le crysta l 70 C V D d ia m o n d T ra n s m is s io n , % 60 50 40 absorption and scattering on defects and grain boundaries 30 20 10 0 200 300 400 500 600 W a v e le n g th , n m 700 800 Polycrystalline CVD diamond as material for high power CO2 laser windows Non-contact phase photothermal method to absolute measurements of optical absorption coefficient The absorption of heating CO2 laser (λ=10.6 μm) leads to local variable (at the modulation frequency) heating and to changes in the refractive index, which, in turn, caused the change in the phase difference between two probe beams of He-Ne laser (633 nm) detected by the probe interferometer. Diamond type HPHT single crystal (yellow) Natural single crystal (white) CVD polydiamond (GPI) CVD polydiamond (Element Six) Theoretical limit (due to two phonon absorption tail) α, cm-1 (10.6 μm) 0.09 – 0.50 0.086 0.057 0.03 0.03 Simulation and experiment show that the level of low absorption achieved is enough for use of CVD diamond as window of multi-kilowatt cw CO2 lasers. A.Yu. Luk’yanov, Quantum Electronics (Moscow) 38 (2008) 1171 Dielectric losses in CVD diamond (170 GHz) ● Far infrared (Microwave) absorption of dielectrics is due to lattice absorption owing to unharmonism (two phonon absorption - TPA). Diamond has very low TPA, hence low loss tangent. ● Theory: tgδ ~109 for λ=2 mm (150 GHz) [B. Garin, JTP Lett. 1994, No. 21, p.56] – record low for any material. Compare with tgδ ~105 for Si. ● Experiment: best result tgδ ~ 3106 @ 140 GHz for Element Six polydiamond. Sample: GPI 0.74 mm thick diamond film tgδ ~105 stable up to 400ºC 6 ta n [1 0 ] 35 ta n [1 0 30 5 ] 5 25 4 20 3 1 15 2 2 10 1 50 5 100 150 200 f [G H z] 0 100 200 300 400 500 600 o T e m p e ra tu re , C B. Garin et al. Techn. Phys. Lett. 25 (1999) 288 MicroRaman mapping of stress in diamond films The confocal optical scheme – high spatial resolution 1 3 3 2 .5 c m -1 ◄ no stress a Intensity, a.u. b 1320 c 1330 R am an shift, cm d ◄ compressive stress e ◄ tensile stress 1340 -1 Raman spectra taken at 5 different locations on the surface of diamond film within one grain (≈100x100 µm). The shift of the peak from 1332. 5 cm-1 position is the evidence of stress. MicroRaman stress mapping on a surface over a selected 160x160 μm grain in the diamond film local stress regions E Ki Ks Ei {1 1 0 } [1 10 -1 4 , c m A D 6 C ] 2 _ [0 0 1 ] [110] {110} [001] [cm-1] = -2.2 [GPa] stress along (111); [cm-1] = -0,7 [GPa] stress along (100). max ≈ 6 cm-1 S plitting [1 1 0 ] B 0 max ≈ 3 GPa I.I. Vlasov, Appl. Phys. Lett. 71 (1997) 1789. MicroRaman Stress mapping around grain boundary laser beam scanning in depth and along the surface 1332.5 cm tension (-) in-depth, grain B in-depth, grain A lateral, from A to B -1 1332.5 c m com pression (+ ) tens ion (-) 1332.5 cm -1 c om pres s ion (+ ) tension (-) -1 com pression (+ ) -60 m 0 m -40 m 0 m 20 m Intensity, a.u. -20 m Intensity, a.u. Intensity, a.u. 0 m 20 m 40 m 20 m 1320 1330 1340 R a m a n s hift, c m 40 m 60 m 40 m 1320 1330 1340 -1 R a m a n s h ift, c m -1 1320 1330 1340 R a m a n s h ift, c m -1 I. Vlasov, Physica Status Solidi (a), 174 (1999) 11. Fracture strength by 3-point measurement techniques Advantage of 3 point method: ability to handle with small size samples Observation: the fracture happens close to the central part of the bars (in locations of maximum stress) Testing apparatus at Fraunhofer Institute IAF, Friburg Fracture strength Young’s modulus E 3 l 2 h b 2 l F frac (1) 3 4 b h 3 F (2) D b and h are the specimen width and thickness, Fс is critical load value, l = 7.8 mm is distance between supports, D is displacement of the bar under load (measured by an inductive sensor with a resolution ~ 1µm). two supporting cylinders 3mm diameter. Similar principle at USTB (Beijing) DF-100 test unit bar thickness of 0.5 mm only L = 8 mm, loading rate 0.5 N/s V.G. Ralchenko et al. Diamond and Related Materials 23 (2012) 172. Fracture strength vs film thickness white diamond 2500 300 Grain Size, m Fracture strength f, MPa 250 2000 200 150 100 50 1500 0 0 500 1000 1500 Film Thickness, m 2000 Grain size ranges with thickness from 10 µm to ~ 200 µm substrate side 1000 σfr = 400 - 1400 MPa for 0.5 mm thick plate 500 growth side 0 0 300 600 900 1200 Film thickness, m ● Rapid increase in strength towards small thickness h: σ = 600 MPa @ h ≈ 1000 µm ► 2.2 GPa @ h = 60 µm (nucleation side in tension). ● Similar tendency for growth side. ● Compatible with Hall-Petch relation if the length of critical cracks is proportional to grain size. ● Results similar to Element Six data. ● The Young’ modulus of Е=1072 ± 153 GPa measured from the bending tests is only 10% lower compared to therotetical Young’ modulus of polycrystalline diamond. Fracture strength vs grain size Hall-Petch relation σf = σ0 +Kd-1/2 400 Fracture strength f , MPa 2400 Grain size d, m 100 44 25 16 11 substrate side 2000 1600 1200 800 400 0 growth side 0 0.05 0.10 0.15 (Grain size d) 0.20 - 1/2 , m 0.25 0.30 - 1/2 Growth side and substrate side are under tensile load. White diamond. The plate side under 0, MPa K, MPa·cm1/2 41±36 3900±270 197±105 6910±780 tension growth side (21 samples) substrate side (21 samples) Fracture patterns close to growth and nucleation sides white diamond Growth side, top view – evidence of transgrain fracture Growth side Cleavage steps Nucleation side ●Transcrystallite fracture over entire film thickness ● Strong grain boundaries Fractures statistics. Weibull analysis for white diamond P(σ) = 1 – exp[– (σ)/σN)m] m is Weibull modulus, can found from slope of eq. or ln[–ln(1 – P)] = – mln(σN) + mln(σ) High m value means more narrow strength interval (more predictable behavior). 2 ln (-ln(1-P)) 1 growth side 0 m = 6.4 -1 substrate side -2 m = 4.5 -3 -4 5.7 (a) Failure Probability 1.0 0.8 0.6 0.4 6.3 6.6 6.9 7.2 substrate side 0.2 0 6.0 growth side (b) 0 ln , MPa Nominal strength σN = 550 MPa for growth side in tension σN =1060 MPa for substrate side in tension Higher modulus m for growth side 300 600 900 , MPa 1200 1500 Comparison of fracture strength of white and black diamond film thickness 0.5 mm diamond grade black white thickness t, grain size, μm μm 538±39 490±10 10 60 σfg, MPa σfn, MPa 141±10 312±33 316±109 812±86 Independent on what side is under tension, a factor of 2 – 2.5 lower σ for opaque material in spite of the smaller grain size. Black diamond. Fracture surface Cleavage along GB ►smooth surface planes along boundaries of columnar grains ► reduced bending strength intergranular fracture transgranular fracture Growth side Nucleation side Area in the middle of the cross- section Columnar structure is seen even in a few microns thin layer adjacent to the substrate.