Transparent Conducting Oxides - from and industrial perspective
- 2. 2 Wednesday 12th November 2014 TCO Workshop, University of Liverpool Transparent Conducting Oxides – from an industrial perspective •How are TCO’s made on an Industrial Scale? •How are TCO’s used in Industry? Liam Palmer, NSG Group
- 3. 3 Liam Palmer – Liam.Palmer@nsg.com Advanced Technologist, On-line Coatings NSG European Technical Centre Lathom, Lancs. UK. European Technical Centre, Lathom Wednesday 12th November 2014 TCO Workshop, University of Liverpool NSG Group R&D Facility
- 4. Wednesday 12th November 2014 TCO Workshop, University of Liverpool 4 Global Flat Glass Market •Global market for flat glass in calendar year 2011 was approximately 59 million tonnes. •At the level of primary manufacture, this represents a value of around €24 billion. •Most of the world’s float glass goes into buildings. Automotive applications account for around 10 percent.
- 5. Wednesday 12th November 2014 TCO Workshop, University of Liverpool 5 NSG Group • Principal operations in 30 countries • Ownership/interests in 48 float lines • Employs around 28,000 people • Sales in 130+ countries • €54million investment in R&D in FY2013 • The NSG Group is one of four glass groups producing around 50 percent of the world’s high quality glass. World-leading supplier of ultra-thin glass for smart phones and tablet devices. Our Ultra Fine Flat Glass (UFF) is produced in thicknesses as low as 0.3-1.1mm. NSG annual report 2013 ‘Making a Difference to our World through Glass Technology’
- 6. Global Operations Wednesday 12th November 2014 TCO Workshop, University of Liverpool 6
- 7. Expansion of Value-Added Business Wednesday 12th November 2014 TCO Workshop, University of Liverpool 7 High value-added products will drive future growth
- 8. The Float Glass Process •Pilkington float process is at the heart of the worldwide industry. •Operates non-stop for 10-15 years •6000 km/year •0.3 mm-25 mm thick, up to 3 m wide Wednesday 12th November 2014 TCO Workshop, University of Liverpool 8 Melting furnace Float bath Cooling lehr Continuos ribbon of glass Cross cutters Large plate lift- off devices Small plate lift- off devices Raw material feed
- 9. Wednesday 12th November 2014 TCO Workshop, University of Liverpool 9 Transparent Conducting Oxides •TCOs are used wherever electrical conductivity and transparency are required •Different applications use different aspects of the TCO properities •Thin film solar cells make use of the electrical conductivity to collect electrons generated by the photoactive materials •Glazing applications make use of the high reflectance at long wavelengths
- 10. Wednesday 12th November 2014 TCO Workshop, University of Liverpool 10 •Low-Emissivity and Solar Control Coatings •In a double glazed unit, a low-emissivity coating on the inner pane blocks radiative heat trying to escape into the cavity Low-Emissivity and Solar Control Coatings
- 11. Wednesday 12th November 2014 TCO Workshop, University of Liverpool 11 •A wide variety of coating technologies are utilised by the glass industry –Spray Pyrolysis –Powder Spray –Chemical Vapour Deposition –Sputter Coating –Thermal Evaporation Coatings –Sol Gel Coatings •These are applied –On Line i.e. as the glass is produced on the float line –Off Line i.e. coating not necessarily produced at the same location Manufacturing a Functional Coating
- 12. Wednesday 12th November 2014 TCO Workshop, University of Liverpool 12 Variations of CVD •Atmospheric Pressure – APCVD •Low Pressure - LPCVD •Metalorganic – MOCVD •Aerosol Assisted – AACVD •Combustion/Flame – CCVD •Hot Wire/Filament – HWCVD/HFCVD •Plasma Enhanced - PECVD •Laser Assisted – LACVD •Microwave Assisted – MWCVD •Atomic Layer Deposition – ALD Broadly termed thermal CVD methods Broadly termed activated CVD methods
- 13. 3 Main TCO’s •FTO – Fluorine doped Tin Oxide •Manufactured by Atmospheric Pressure Chemical Vapour Deposition (APCVD) •ITO – Indium doped Tin Oxide •Manufactured by Sputtering, Physical Vapour Deposition (PVD) •AZO – Aluminium doped Zinc Oxide •Manufactured by Low Pressure Chemical Vapour Deposition (LPCVD), Plasma Enhanced Chemical Vapour Deposition (PECVD) or Atomic Layer Deposition (ALD) Wednesday 12th November 2014 TCO Workshop, University of Liverpool 13
- 14. Wednesday 12th November 2014 TCO Workshop, University of Liverpool 14 Chemical Vapour Deposition Animation kindly supplied by Dr. Warren Cross, University of Leicester
- 15. Wednesday 12th November 2014 TCO Workshop, University of Liverpool 15 Chemical Vapour Deposition Main gas flow region Gas Phase Reactions Surface Diffusion Desorption of Film Precursor By Products Diffusion to surface
- 16. Wednesday 12th November 2014 TCO Workshop, University of Liverpool 16 CVD on Glass For on-line coating of glass we require: •High growth rates – required thickness in <2 s •Stable chemistry – uniform coatings for continuous operation for many days •Good adhesion to glass •High efficiency – reduce costs
- 17. Wednesday 12th November 2014 TCO Workshop, University of Liverpool 17 APCVD Strengths and Weaknesses Strengths Weaknesses Result On-line coating possible Reduced flexibility Reduced labour costs, high volume manufacture Fresh substrate surfaces No washing step, enhanced adhesion High deposition rates Need to match line speed Thick films possible with high throughput Hard films Improved processability and performance Structure control possible e.g. crystallinity Rough surface Improved functional properties and durability Volatile precursors required Limited range of materials
- 18. Wednesday 12th November 2014 TCO Workshop, University of Liverpool 18 Float Glass Plant
- 19. Wednesday 12th November 2014 TCO Workshop, University of Liverpool 19 Float Glass Plant
- 20. Wednesday 12th November 2014 TCO Workshop, University of Liverpool 20 Float Glass Plant
- 21. Wednesday 12th November 2014 TCO Workshop, University of Liverpool 21 Float Glass Plant
- 22. Wednesday 12th November 2014 TCO Workshop, University of Liverpool 22 On-Line Coating Position Load raw materials Float line Process TCO Coated glass supply chain On-line APCVD T 650°C 1500 oC Melting 600 oC 1050 oC Floating Cooling
- 23. Turbulent Flow CVD Coater Wednesday 12th November 2014 TCO Workshop, University of Liverpool 23 Topcoat Beam RHS Section ViewTunnelSkirtAir curtainSkirtAdjustAir curtaininlet pipeWater coolingInoutSlot1Slot2Glass flowExhaust manifoldassemblyExtraction slotDownstreamwater box
- 24. Wednesday 12th November 2014 TCO Workshop, University of Liverpool 24 •SnCl4 + H2O + HF SnO2:F + HCl (~1.5 at% F) •Much gas phase reaction •Gases introduced separately in turbulent flow regime •Very high growth rates >100 nm/s possible •Low precursor efficiency <10% SiCxOy (70 nm) SnO2:F (350 nm) Glass •SiH4 + C2H4 + CO2 SiCxOy + H2O + other by-products •Used as colour suppression and barrier layer CVD of SnO2:F – Pilkington K Glass™ a Low-E Coating
- 25. Wednesday 12th November 2014 TCO Workshop, University of Liverpool 25 Low Emissivity Coating – Pilkington K Glass™ •SiCO under layer used as a blocking layer and colour suppressant
- 26. Wednesday 12th November 2014 TCO Workshop, University of Liverpool 26 Laminar Flow CVD Coater Glass Glass Ribbon Flow Up-Stream Exhaust Down-Stream Exhaust Precursor gases Outside Atmosphere
- 27. CVD of SnO2:F – Common Precursors •Tin Oxide Precursors •Dimethyl Tin Dichloride (DMT) •Monobutyl Tin Trichloride (MBTC) •Stannic Chloride (SnCl4) •Fluorine Dopant Precursors •Hydrogen Fluoride (HF) •Trifluoro Acetic Acid (TFA / TFAA) Wednesday 12th November 2014 TCO Workshop, University of Liverpool 27
- 28. Challenges Facing On-Line Coatings •Delivering precursors at a constant temperature and flow. •Maintaining a constant uniformity across a 3 metre ribbon at a speed of up to 15 m/min for as long as possible. •Longest coatings run time is currently ~60 hours. •Quality Control – Continuously Inspecting and Monitoring the product being produced. •Warehouse and other ‘cold-end’ activities. Wednesday 12th November 2014 TCO Workshop, University of Liverpool 28
- 29. 3 Main TCO’s •FTO – Fluorine doped Tin Oxide •Manufactured by Atmospheric Pressure Chemical Vapour Deposition (APCVD) •ITO – Indium doped Tin Oxide •Manufactured by Sputtering, Physical Vapour Deposition (PVD) •AZO – Aluminium doped Zinc Oxide •Manufactured by Sputtering, Low Pressure Chemical Vapour Deposition (LPCVD), Plasma Enhanced Chemical Vapour Deposition (PECVD) or Atomic Layer Deposition (ALD) Wednesday 12th November 2014 TCO Workshop, University of Liverpool 29
- 30. The Sputtering Process + - Ar Ar+ e- Pumps Process Gas Wednesday 12th November 2014 TCO Workshop, University of Liverpool 30
- 31. In-Line Production Coater Wednesday 12th November 2014 TCO Workshop, University of Liverpool 31
- 32. Typical Plant Layout – for Continuous Coating Coating Zone Transfer Chamber Transfer Chamber Load Lock Washing Machine Inspection Room Exit Lock Glass Transport Direction Vacuum Plant Speed Position Leading Edge Speed Wednesday 12th November 2014 TCO Workshop, University of Liverpool 32
- 33. Sputtering Plant – OLC1 Wednesday 12th November 2014 TCO Workshop, University of Liverpool 33
- 34. Sputtering Plant – OLC1 Wednesday 12th November 2014 TCO Workshop, University of Liverpool 34
- 35. Sputtering Plant – OLC1 •£16 million cost for the coater •£40 million cost for the entire site installation. •Able to coat ‘Jumbo’ sized plates (6m x 3.21m). •Able to coat ~10 million m2 a year. •Ability to produce single and double silver coatings. •Single silver coatings for Low-E products. •Double silver coatings for Solar Control products. •No TCO’s are made at this coater, due to RTP process. •Able to make TCO’s but not viable as produce FTO. Wednesday 12th November 2014 TCO Workshop, University of Liverpool 35
- 36. Comparison – SnO2:F vs ZnO:Al •ZnO:Al offers better optical and electronic properties over SnO2:F •After etching AZO significantly enhances light scattering (for silicon devices) •SnO2:F is more stable than AZO in chemical durability tests. •SnO2:F is cheaper and more durable than ZnO:Al Wednesday 12th November 2014 TCO Workshop, University of Liverpool 36
- 37. NSG Products Wednesday 12th November 2014 TCO Workshop, University of Liverpool 37
- 38. Coated Products •Coated Products Divided into 3 groups; Wednesday 12th November 2014 TCO Workshop, University of Liverpool 38 Building Products • Low Emissivity • Solar Control • Functional Products NSG TEC™ Products • Electronic display apps. • White goods market (freezer lids, etc.) • OFC Substrates Solar Products •Conductive substrates for solar cell fabrication.
- 39. Pilkington Energy Advantage™ •Pilkington Energy Advantage™ is a low emissivity coating sold predominantly into colder areas of the United States and is basically Pilkington K Glass™ made using oil cooled beams. •Different precursor chemistry, same end result. Main difference for the end user is slightly more hazy than Pilkington K Glass™ – though we can’t sell Pilkington Energy Advantage™ as Pilkington K Glass™ . •Low emissivity feature reduces heat loss from a building by reflecting heat back into the building. •Emissivity is the measure of how efficient the coating is at reflecting heat. •Clear glass allows ~89% of heat to escape, Pilkington Energy Advantage™ only ~15%. Wednesday 12th November 2014 TCO Workshop, University of Liverpool 39
- 40. Pilkington Energy Advantage™ •Pilkington Energy Advantage™ / NSG TEC™ 15 coating is made up of three layers. Wednesday 12th November 2014 TCO Workshop, University of Liverpool 40
- 41. Pilkington Energy Advantage™ Wednesday 12th November 2014 TCO Workshop, University of Liverpool 41 Pilkington Energy Advantage™ coating
- 42. Pilkington Eclipse Advantage™ •Product is a Solar Control coating designed to reduce solar heat from entering a building. •Designed for commercial building applications and produced on a range of tints to provide aesthetic performance. •Tint colour is seen from outside of building and not obscured by coating. •Solar control performance changes with tint. •Predominantly used on surface #2 of an IGU though can be used as a single pane. •Glass side reflection dictates how the product looks from the outside. Wednesday 12th November 2014 TCO Workshop, University of Liverpool 42
- 43. Pilkington Eclipse Advantage™ •Pilkington Eclipse Advantage™ is made up of four layers. Wednesday 12th November 2014 TCO Workshop, University of Liverpool 43
- 44. Pilkington Eclipse Advantage™ Wednesday 12th November 2014 TCO Workshop, University of Liverpool 44 Pilkington Eclipse Advantage™ Coating on #2 Surface
- 45. NSG TEC™ Products •NSG TEC™ products developed as a spin off from Pilkington Energy Advantage™ for electronic applications. •Currently used as; •Transparent, electrically conductive articles - i.e. heated freezer cabinets. •TCO Substrates for additional devices – i.e. LCD displays. •TCO products are basically a variation of top F:SnO2 layer to give different sheet resistance values or morphology. •Originally made to order products for specific customers but formed the basis of the Solar Energy portfolio. Wednesday 12th November 2014 TCO Workshop, University of Liverpool 45
- 46. NSG TEC™ Glass Applications •Thin Film Photovoltaics •Electrochromic Mirrors •Commercial Refrigeration •Oven Windows/White Goods •Heated Glass •Displays •Sodium blocking for sputter coating processors •Thermochromics •Lighting •Numerous other specialty applications Wednesday 12th November 2014 TCO Workshop, University of Liverpool 46
- 47. NSG TEC™ Glass Properties Wednesday 12th November 2014 TCO Workshop, University of Liverpool 47 NSG TEC™ Product Available Thickness (mm) Sheet Resistance (Ohms/square) Visible Transmittance (%) Haze (%) Hemispherical Emittance NSG TEC™ 7 2.2, 3.0, 3.2 6 - 8 80 – 82 5 0.12 NSG TEC™ 8 2.2, 3.2 6 - 9 80 – 81.5 12 0.12 NSG TEC™ 15 2.2, 3.0, 3.2 12-14 82 – 83 ≤0.35 0.15 4.0, 5.0, 6.0, 8, 10 12-14 83 – 84.5 ≤0.75 0.15 NSG TEC™ 20 4.0 19 - 25 80 – 85 ≤0.8 0.21 NSG TEC™ 35 3.2, 6.0 32 - 48 82 – 84 ≤0.65 0.34 NSG TEC™ 50 6.0 43 - 53 80 – 85 ≤0.55 0.38 NSG TEC™ 70 3.2, 4.0 58 - 72 82 – 84 0.5 0.45 NSG TEC™ 250 3.2, 4.0 260 - 325 84– 85 0.7 0.67 NSG TEC™ 1000 3.2 1000 - 3000 88 0.5 0.78
- 48. NSG TEC™ Products for Solar Applications •Solar products are based around the Pilkington Energy Advantage™ system with variation in either layer thickness or chemistry. •Products tend to be manufactured for a single customer rather than same product for multiple customers. •Products generally form the base plate for solar cells with customers then adding further coatings on top of our materials. •Solar customers are very strict in terms of specifications and defects – need to qualify the product with each customer. •Also need products to be exactly the same across each of the manufacturing sites to improve logistics. Wednesday 12th November 2014 TCO Workshop, University of Liverpool 48
- 49. NSG TEC™ Glass Properties •NSG TEC™ products used in the majority of thin film PV technologies. •TCO properties, optimised for each PV technology. •Light transmission. •Coating conductivity. •Haze. Wednesday 12th November 2014 TCO Workshop, University of Liverpool 49 Thin film silicon NSG TEC™A8 High haze, rough coating TCO coating Surface roughness CdTe NSG TEC™C15 Low haze, smooth coating TCO coating Surface roughness
- 50. NSG TEC™ Glass Appliance Applications Wednesday 12th November 2014 TCO Workshop, University of Liverpool 50 Commercial Refrigeration and Freezer Applications Passive Active Curved
- 51. NSG TEC™ Glass Appliance Applications Wednesday 12th November 2014 TCO Workshop, University of Liverpool 51 Commercial Food Warmers Oven Door Glass
- 52. Touch Panel Technology - Resistive • Resistive touchscreens use a flexible outer membrane that, upon user touch, forms an electrical circuit with the glass substrate. Wednesday 12th November 2014 TCO Workshop, University of Liverpool 52 Glass TEC 1100 – High Resistance Coating Resistive Coating Protective Coating Flexible Membrane Insulating Spacers NSG TEC™
- 53. Touch Panel Technology - Capacitive • Capacitive coupling between a conducting surface and the users finger draws current from the surface to determine the touch-point in capacitive screens. Wednesday 12th November 2014 TCO Workshop, University of Liverpool 53 Glass TEC SB - Silica Layer Conductive Coating – TCO (ITO or other) sodium Protective Coating NSG TEC™
- 54. Touch Panel Applications Wednesday 12th November 2014 TCO Workshop, University of Liverpool 54 Video Gaming Systems Airport Check-In Terminals GPS Systems
- 55. NSG TEC™ Glass in Heated Windows •The use of NSG TEC™ Glass for other heated applications is increasing •Restaurants and residences in cold climates are increasing the comfort level surrounding picture windows. •Eliminates the cold-shoulder effect with radiant heat. •Reduces heat loss through the windows and the need to over-heat the entire room to compensate. •Maintains window clarity and preserves spectacular views. •Eliminates condensation. Wednesday 12th November 2014 TCO Workshop, University of Liverpool 55
- 56. Heated Window Applications •Residential Application – Exterior •Photo and Application – Courtesy of Radiant Glass Industries LLC Wednesday 12th November 2014 TCO Workshop, University of Liverpool 56
- 57. Heated Window Applications •Residential Application – Interior •Photo and Application – Courtesy of Radiant Glass Industries LLC Wednesday 12th November 2014 TCO Workshop, University of Liverpool 57
- 58. Heated Window Applications •Restaurant Application - Mahogany Grille, Durango Colorado •Photos and Application – Courtesy of thermique™ Wednesday 12th November 2014 TCO Workshop, University of Liverpool 58
- 59. Industrial Transportation •Can incorporate active or passive defrosting capability in many applications; •Military vehicles •Tank Turrets •Humvees •Marine Glazing •Military •Private Yacht •Locomotive glass •Siemens & General Electric (GE) Wednesday 12th November 2014 TCO Workshop, University of Liverpool 59
- 60. Industrial Transportation Wednesday 12th November 2014 TCO Workshop, University of Liverpool 60
- 61. NSG TEC™ Glass in Electrochromics •Increasing activity in large area commercial electrochromic development •Much more difficult application than EC mirrors •Smart window systems are in development for increased energy management •Layered film solutions are also in development •Large scale producers: •Sage •View Inc. Wednesday 12th November 2014 TCO Workshop, University of Liverpool 61
- 62. Electrochromic Applications •Photo and Application – Courtesy of Sage Electrochromics, Inc. Wednesday 12th November 2014 TCO Workshop, University of Liverpool 62 •Club Porticello - Oconomowac, Wisconsin •Overlooks scenic lake •Windows face west into setting sun •Need to preserve view while keeping diners comfortable
- 63. Electrochromic Applications •Photo and Application – Courtesy of Sage Electrochromics, Inc. Wednesday 12th November 2014 TCO Workshop, University of Liverpool 63
- 64. Summary •Shown common manufacturing methods for 3 of the main TCO materials; •Fluorine doped Tin Oxide (FTO) – manufactured by APCVD. •Indium doped Tin Oxide (ITO) – manufactured by Sputtering. •Aluminium doped Zinc Oxide (AZO) – manufactured by Sputtering, LPCVD, PECVD or ALD. •Shown an incite into industrial applications of Transparent Conductive Oxides; •Low-E, Solar Control and Technical Applications. •Shown some of the products offered by NSG that use TCO’s. Wednesday 12th November 2014 TCO Workshop, University of Liverpool 64 Thank you for you attention