Ferroelectric Ceramic Technology for Sensors. Jim McIntosh Ceramic Operations Manager PCB Piezotronics

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1 Ferroelectric Ceramic Technology for Sensors Jim McIntosh Ceramic Operations Manager PCB Piezotronics

2 Overview Ferroelectricity versus Piezoelectricity Historical Background Ferroelectric Ceramic Composition Engineering Ceramic Manufacturing Process

3 Ferro- vs. Piezoelectricity PIEZO PYRO FERRO Piezoelectrics no center of symmetry in crystal structure Pyroelectrics Piezo with spontaneous dipole moment Ferroelectrics Pyro with spontaneous dipoles that are reversible

4 Historical Background Piezoelectricity - Quartz J. & P. Curie, 1880 Pyroelectricity - Tourmaline Greeks, ca. 315 B.C. Ferroelectricity - Rochelle Salt Valasek, 1921

5 FE Hysteresis Loop

6 Ferroelectric Ceramics Barium Titanate - first FE ceramic High dielectric constant determined to be due to ferroelectricity Lead Zirconate Titanates (PZT) Most widely used FE ceramics Bismuth Titanates High temperature application (T C ~680 C) Many others Lead metaniobate Lead titanate, and various combinations with PT

7 Typical Sensor Crystal Properties Quartz PZT-5A Charge Output 2.3 (d 11 ) 380 (d 33 ) Diel. Constant Voltage Output 62 (g 11 ) 25 (g 33 ) Temp Stability Stable Pyro Time Stability Stable Aging Effects Polar Axis Fixed Determined by processing

8 Ferroelectric Ceramics (Import unit cell sketch here) PZT ceramics are based on the perovskite (ABO 3 ) crystal structure, Pb(Zr/Ti)O 3

9 Ferroelectric Ceramics High temperature bismuth titanates form in layer structures (Bi 2 O 2 ) (Bi 2 Ti 3 O 10 )

10 PZT Ceramics PbZrO 3 PbTiO 3 phase diagram ABO 3, where A=Pb, B=Zr/Ti Morphotropic phase boundary exists at specific Zr/Ti ratio, results in maximum PE properties

11 PZT Ceramics Major advantage is the ability to slightly modify the composition to tailor the properties Small adjustments to Zr:Ti ratio alter properties GLAC ZrO2 Ratio Study d31 vs Temp for GLAC ZrO d K % Change F 75F 230F 350F 500F % Zr d33 K -15.0

12 PZT Ceramics Properties can also be tailored by substitutions doping Doping changes oxygen vacancy concentration Soft and Hard PZT s, depending on dopant type Dopant Replaces Type Effects Nb 5+ Zr,Ti 4+ Donor Soft PZT; Increased I.R., K T, d 33 ; dielectric losses increase; lower Q m Fe 3+ Zr,Ti 4+ Acceptor Hard PZT; Decreased I.R., K T, d 33 ; dielectric losses decrease; higher Q m

13 Specialty Raw Materials Electronic grade raw materials are used Each new raw material lot requires qualification

14 Powder Preparation Weighing Calcining

15 Powder Preparation Milling Granulating

16 Powder Characterization Particle size distribution analysis is used to verify process conditions

17 Batch Qualification Testing Sample crystals from each batch are processed and tested Properties measured at room temp and over extended temp range

18 Tablet Processing Dry Pressing

19 Tablet Processing Loading Crucibles Ceramic Firing

20 Preparing Ceramics for Polarization Lapping Silver Plating

21 Polarization Poling d 33 Test

22 Polarization (Import picture) Left: Unpoled material has randomly oriented domains Right: Application of DC field reorients the domains

23 Machining of Polarized Pieces Core Drilling OD Grinding

24 Plating Crystals Electroless Nickel Plating Gold Plating

25 Final Shaping Finish Lapping Slotting

26 Testing and Inspection Cap Test I.R. Test

27 Testing and Inspection Visual Inspection Mechanical Inspection

28 Finished Ceramic Crystals (Import pictures: various crystals, by mode)

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