QuickTime et un décompresseur TIFF (non compressé) sont requis pour visionner cette image. Preparation and characterization of nanostructured thermoelectric materials Laboratoire de Physique des Matériaux, UMR 7556 Ecole Nationale Supérieure des Mines de Nancy, France A. Dauscher, B. Lenoir, D. Colceag, V. Kosalathip, C. Candolfi, V. Da Ros Ca x Co 4 Sb 12 /substrate films, BiSbTe nano-powders Bi/PbTe/substrate films
Film specifications high quality films well-known thickness high density large grains smooth surfaces sharp interfaces - no interdiffusion no oxygen contamination Pulsed laser deposition (PLD) for the synthesis of thermoelectric films Stoichiometry of target restored Lower deposition temperature
Experimental: pulsed laser deposition set-up substrate heater & holder electrical feedthrough thermocouple feedthrough gauge multiple target holder rotation: 9 r.p.m. gas inlet 10-7 -10-8 mbar Target PbTe Substrate molecular pump fast opening door 30 heating lamp Nd : YAG LASER (5 Hz, 10 ns) λ = 532 nm ionic pump focusing lens Motorized tables allowing the laser beam scanning along X,Y,Z
Experimental: pulsed laser deposition set-up Laser beam Nd:YAG laser Focusing lens x,y,z motorized tables
Adjustable parameters Laser Wavelength: 266, 532, 1064 nm (absorption) Frequency: 2, 5 or 10 Hz (overlapping) Output energy/focalisataion (fluence) Number of shots (thickness) Chamber Vacuum (static or dynamic) Gas (static or dynamic) Target Substrate Polycrystalline self-made ingots Diameter (12-19 mm) Rotation speed Nature (amorphous, oriented) Temperature (20-500 C) Target-substrate distance (2-5 cm) Scanning Rate
Preparation of skutterudite thin films AIM: Synthesis of high quality n- and p-type skutterudites films for their use in thermoelectric micro-devices. Study of the influence of many deposition parameters to achieve a single phase film having the skutterudite structure. MATERIAL: Ca x Co 4 Sb 12 (n-type), Ce x Fe 3.5 Co 0.5 Sb 12 (p-type) PARAMETER STUDIED: wavelength: 266, 355 or 532 nm, density of energy: 2-5 J/cm 2, deposition temperature: 25-300 C, SUBSTRATE: SiO 2 (20 nm)/si(100), quartz, glass
Influence of the deposition temperature (532 nm) X: CoSb 3, * : CoSb 2?, #: Sb x x x x x x x x x x x x ** * * * Thickness: 520 nm Grain: ~ 100 nm RMS = 38.4 nm # 300 C 240 C 220 C 25 C Thickness: 670 nm Grain: > 500 nm RMS = 16.1 nm 20 30 40 50 60 70 80 2 theta ( ) 300 C: textured CoSb 3 +? 240 C: CoSb 3 single phase 220 C: CoSb 3 +? 25 C : amorphous Decrease of film thickness and grain size when Ts
Influence of the deposition temperature (266 nm) X: CoSb 3, * : CoSb 2?, #: Sb x x x x x x x x x x x x # ** * * * 300C 270C 240C 220C 200C 20 30 40 50 60 70 80 2 theta () Thickness: 70 nm Grain size: < 80 nm RMS: 12.7 nm Comparison with 532 nm: No achievement of the skutterudite phase, whatever T s or fluence ( from the literature) No reduction of the droplet density Deposition rate about 10 times lower
Influence of wavelength and substrate / 240 C The nature of the substrate is not significative. The deposition temperature differs strongly according to the wavelength (150 C at 266 nm (UV) and 240 C at 532 nm (visible)).
Topography of n-type skutterudite films (AFM) Quartz substrate: influence of wavelength The films exhibit a low amount of droplets, especially when made from 532 nm, and are smooth (RMS ~ 10 nm). The surface shows a well defined morphology. Grain sizes are about 100 to 200 nm. RMS does not depend on substrate nature. Quartz substrate: influence of thickness 50 000 pulses: influence of substrate
Electrical resistivity of skutterudite films n-type p-type 0.0017 0.00052 0.0016 0.00050 Resistivity (Ohm.cm) 0.0015 0.0014 0.0013 0.0012 0.0011 0.001 Resistivity (Ohm.cm) 0.00048 0.00046 0.00044 0.00042 0.0009 0 50 100 150 200 250 300 350 T(K) 0.00040 0 50 100 150 200 250 300 350 T(K) Both n- and p-type materials show typical behaviours of semi-conductors. The values of the p-type film are much lower than those of the n-type film, in agreement with the differences observed for the bulk materials.
Carrier mobility of skutterudite films n-type p-type 5.0 0.0100 0.0 4.5 Mobility (cm 2 /Vs) -0.010-0.020-0.030 Mobility (cm 2 /Vs) 4.0 3.5 3.0-0.040 0 50 100 150 200 250 300 350 T(K) 2.5 0 50 100 150 200 250 300 350 T(K) The films exhibit the same type of conductivity as the target materials they are made from. The preliminary results show that the carrier mobilities are as high as in bulk materials for the p-type films and much smaller than in bulk materials for the n-type films.
Skutterudite films: conclusions The synthesis of skutterudite films revealed to be particularly sensitive to quite all deposition parameters we tested, but feasability to make both n- and p-type materials by PLD has been proven. The skutterudite phase could be achieved for the first time with the 532 nm wavelength, for a given density of energy (4 J/cm 2 ), deposition temperature (240 C), and base pressure (10-4 mbar). These films exhibit less droplets and a smoother surface than films prepared in the UV range (for equivalent film thickness), contrarily to many materials. The first transport property measurements showed that the films behaves similarly with temperature than the bulk materials. Further work: Try to realise a thermoelectric micro-generator made from both the n and p- type skutterudites synthesized.
Nanostuctured bulk materials : Aim Nano-structured bulk materials with enhanced thermoelectric performance High yield production of nano-particles of thermoelectric materials size as small as possible narrow particle size distribution composition close to that of the starting material Pulsed laser ablation in a liquid media (simple, versatile, no chemical reagents) Materials: n- and p-type (Bi 1-x Sb x ) 2 (Te 1-y Se y ) 3 Physico-chemical characterization of the produced powders
Pulsed laser ablation in a liquid media: principle Laser beam Focusing lens Glass vessel Liquid media Nano-particles target
Experimental set-up Focusing lens Nd:YAG laser Laser beam Target + Liquid Magnetic strirring x,y motorized tables (crenel-like scanning) (agglomeration avoiding, less particles-beam interactions)
Experimental parameters laser target 532 or 1064 nm 2, 5 or 10 Hz 1-20 J/cm 2 1-36 000 shots polycrystalline n (Bi 0.95 Sb 0.05 ) 2 (Te 0.95 Se 0.05 ) 3 p (Bi 0.2 Sb 0.8 ) 2 Te 3 liquid water, ethanol, n-heptane 1 or 2 cm height scanning rate 0.5 or 2 mm/s
Yield optimization: influence of the laser frequency n-type, 532 nm, water, 2.6 J/cm 2, 1 hour Mass ablated (mg) 6 5 4 3 2 1 2 Hz (2 mm/s) 5 Hz (2 mm/s) 10 Hz (2 mm/s) 10 Hz (0.5 mm/s) 0 0 5000 10000 15000 20000 25000 30000 35000 40000 Number of laser shots Strong influence of the laser frequency 2 Hz: no overlapping between 2 consecutive shots 5 Hz: 50 % overlapping 5 Hz, 2 mm/s 10 Hz: 80 % overlapping (2 mm/s) 10 Hz: 90 % overlapping (0.5 mm/s) Saturation limit: ~ 3 mg 70 µg/cm 3
Yield optimization: influence of the fluence 1064 nm, water, 5 Hz 25 20 Mass ablated (mg) 15 10 5 5.3 J/cm 2 (100 mj) n 10.4 J/cm 2 (200 mj) n 15.8 J/cm 2 (300 mj) n 5.3 J/cm 2 (100 mj) p 0 0 10 20 30 40 50 60 70 Duration (min) Density of energy mass ablated (limitation 300 mj) Saturation limit: ~ 10 mg 220 µg/cm 3 IR p-type n-type
Cristallographic structure: influence of the fluence 1064 nm, 18000 shots, 2 mm/s n-type p-type 0,1,5 1,0,10 Intensity (AU) 1,1,0 2,0,5 0,1,5 1,0,10 1,1,0 2,0,5 300 mj 200 mj 100 mj Intensity (AU) 200 mj 100 mj 60 mj target 20 30 40 50 60 70 2θ () 60 mj target 20 30 40 50 60 70 2θ () Achievement of the same phase as the target Achievement of a single phase but different from the target or Presence of multiple phases
Chemical composition (EPMA) 1064 nm, 18000 shots, 2 mm/s Bi Te Sb Se n-target 36.5 59.4 2.2 1.9 n-powders water, 100 mj n-powders water, 300 mj 38.2 58.2 1.8 1.8 38.7 57.8 1.6 1.9 p-target 7.6 60.7 31.7 - p-powders water, 60 mj 8.0 60.8 31.3 -
Morphology 1064 nm, 18000 shots, 60 mj, 2 mm/s n-type p-type Mean particle size TEM: 28 nm (200 shots) XRD: 35 nm (18000 shots)
Summary Proof-of-principle: pulsed laser ablation in a liquid media is efficient to synthesize nano-powders of complex materials. n-type (Bi 0.95 Sb 0.05 ) 2 (Te 0.95 Se 0.05 ) 3 can be synthesized in water. p-type (Bi 0.2 Sb 0.8 ) 2 Te 3 is more difficult to synthesize. (different absorption coefficient, different interaction with the solvent). Each parameter studied has an influence (tailor as a function of we want): - wavelength saturation limit of particles in the solution, size, composition - solvent height: yield, nature: crystallographic phase, size, agglomeration aptitude - energy yield, size, crystallographic phase Problems: low ablation yield, no p-type, large particle size distribution (laser-powder interaction?), inflammability and recuperation of the solvent, oxidation.
New process diagram crushing n-type or p-type ingot Lens sieving Counts (AU) 20000 18000 16000 14000 200 mj 12000 anneal at 180 O C 10000 8000 200 mj 6000 4000 2000 initial powder 0 20 40 60 80 Angle, 2θ XRD analyses SEM analyses 10 Hz 532 nm 36000 shots TEM analyses
New experimental Initial powders in distilled water (small diameter vessel, 10 Hz) 3 magnets Guiding beam for adjusting the laser beam position (excentered position)
Influence of the number of shots: sedimentation test p-type, 532 nm, 300 mj, 30 min test a b c d e a: initial powders b: 9 000 shots c: 18 000 shots d: 27 000 shots e: 36 000 shots Duration of sedimentation increases as a function of the number of shots: the weight and therefore the size of the generated particles become lower, more and more initial particles are broken.
Effect of the laser beam on the particles morphology p-type, 532 nm, 300 mj, 36 000 shots Initial sieved powders: diameter is in the range of 1-17 µm and 2.5 µm in average After laser treatment: nanopowders of size less than 30 nm
Influence of the composition on the particle size 532 nm, 200 mj, 36 000 shots 20 50 20 50 100 100 100 50 n-type nano-powders p-type nano-powders
Influence of the composition on the particle size 532 nm, 200 mj, 36 000 shots n-type: diameter in the range of 2.5-22.5 nm and 6 nm in average Number of particles 350 300 250 200 150 100 50 0 5 10 15 20 25 30 35 40 45 50 Diameter (nm) % cummulative less than size 100 80 60 40 20 0 0 10 20 30 40 50 Particle size (nm) p-type: diameter in the range of 2.5 47.5 nm and 10 nm in average 350 100 Number of particles 300 250 200 150 100 50 0 5 10 15 20 25 30 35 40 45 50 Diameter (nm) % cummulative less than size 80 60 40 20 0 0 10 20 30 40 50 Particle size (nm)
Crystallographic structure 532 nm, 36 000 shots n-type (Bi 0.95 Sb 0.05 ) 2 (Te 0.95 Se 0.05 ) 3 p-type (Bi 0.2 Sb 0.8 ) 2 Te 3 N type nano-powder P type nano- powder 300mJ Counts (AU) 200 mj Counts (AU) 200 mj anneal at 180 O C 200 mj inital powder initial powder 20 40 60 80 20 40 60 80 Angle, 2θ Angle, 2θ no significant difference as a function of output energy for both type n-type: single phase p-type: unknown phase, disappearing after annealing at 180 C
Conclusion By comparison to the production of nano-powders from a bulk target, the use of initial micro-sized powders leads to: smaller particles, improved production yield, improved crystalline quality of the p-type nano-powders (annealing), no inflammability problem (use of water).
Now Acrylic box with powder circulation in water Use of a new fabrication cell to produce nano-powders with high yield to make: nano-structured bulk materials (SPS) to test the thermoelectric performance (electrical and thermal conductivities, thermopower, improvment?) thin films directly from the solution by electrophoresis and test their thermoelectric performance (use in micro-devices: µ-generators or µ-refrigerators)
PbTe-Bi nano-composites: influence of bi-layers number (BaF 2, 150 C) Smoothening of the surface as the number of bi-layers increases Obtaining of the (111) texture
Transport properties of PbTe films and Bi/PbTe nano-composites (T s = 150 C, F = 4 J/cm 2 ) Resistivity [µω.m] Seebeck [µv.k -1 ] Power factor [µw.m -1.K -2 ] PbTe/BaF 2 45-247 20 (PbTe/Bi/BaF 2 ) 32-223 PbTe/glass 14-156 1355 (n=4.9x10 17 cm -3 ) 1554 (n=2.3x10 18 cm -3 ) 1760 (n=2.0x10 20 cm -3 ) 20(PbTe/Bi/glass) 8-118 1780
Thermal cycling of PbTe films and Bi/PbTe nanocomposites The PbTe films do not withstand thermal cycling... Resistivity [µω.m] 60 50 40 30 20 10 Cycle 2 Cycle 1 0 50 100 150 200 250 300 Temperature[K] Seebeck coefficient [µv.k -1 ] 0-20 -40-60 -80-100 -120-140 -160-180 -200 50 100 150 200 250 300 Temperature [K] but the Bi/PbTe nanocomposites do! Resistivity [µω.m] 10 8 6 4 2 0 50 100 150 200 250 300 Temperature [K] Seebeck coefficient [µv.k -1 ] 0-20 -40-60 -80-100 -120 50 100 150 200 250 300 Temperature [K]