1. Limits of low-temperature ALD Tapani Alasaarela

2. Outline Low temperature? How ALD works? Plasma enhanced or thermal? Possible thermal processes –TiO 2 –Al 2 O 3 –ZnO –Ta 2 O 5 Conclusions

3. What is low temperature? ALD processes are usually ran at around 200-300°C, which is low for CVD My definition for low temperature ALD: less than 150°C –Allows use of wider range of substrates, e.g. silver, many polymer films, etc.

4. How ALD works? Source: Cambridge NanoTech In low temperature, there will likely be some excess water condensation on the surface

5. How ALD works? Source: Cambridge NanoTech The resulting film will be less dense in low temperature

6. Plasma enhanced or thermal ALD PEALD enables lower growth temperatures for many processes –Energy for growth brought via plasma instead of thermal Plasma processes difficult to optimize

7. Low temperature thermal processes TiO 2 from TiCl 4 + H 2 O Al 2 O 3 from TMA + H 2 O ZnO from DEZn + H 2 O Ta 2 O 5 (or TaO x ) from TaCl 5 and H 2 O Many others, area not too well studied

8. General features of low temperature ALD When temperature is lowered –the density (and the refractive index of films) usually goes down –with TiO 2, growth rate gets higher and is more dependent of temperature Many materials are amorphous At least TiCl 4 + H 2 O and TMA + H 2 O processes work at room temperature –uniformity is still okay –adhesion and durability not good

9. TiO 2 from TiCl 4 and H 2 O Amorphous < ~150°C Good optical properties Resistant against many liquids –good barrier

10. TiO 2 from TiCl 4 and H 2 O At 120°C

11. TiO 2 from TiCl 4 and H 2 O At 120°C, grown on resonance waveguide gratings Pictures courtesy of the University of Eastern Finland

12. TiO 2 from TiCl 4 and H 2 O Chlorine content increases as temperature gets lower Aarik et al. Effect of crystal structure on optical properties of TiO2 films grown by atomic layer deposition. Thin Solid Films (1997) vol. 305 pp. 270-273

13. TiO 2 from TiCl 4 and H 2 O Growth rates not saturating very well –pulsing time dependency G. Triani et al., “Low temperature atomic layer deposition of titania thin films”, Thin Solid Films, Volume 518, Issue 12, 2 April 2010, Pages 3182-3189

14. TiO 2 from TiCl 4 and H 2 O Growth rates not saturating very well –strong temperature dependency

15. Al 2 O 3 from TMA and H 2 O M. D. Groner et al., Low-Temperature Al2O3 Atomic Layer Deposition, Chemistry of Materials 2004 16 (4), 639-645

16. ZnO from DEZ and H 2 O E. Guziewicz et al., Extremely low temperature growth of ZnO by atomic layer deposition, J. Appl. Phys. 103, 033515

17. TaO x from TaCl 5 and H 2 O Kukli et al. Properties of tantalum oxide thin films grown by atomic layer deposition. Thin Solid Films (1995)

18. Conclusions Low temperature (< 150°C) growth enables many new substrate materials and applications Plasma enables many new low temperature ALD processes, lots of research going on Thermal processes nicer –TiO 2, Al 2 O 3, ZnO, and Ta 2 O 5 were shown Films can be done even in room temperature Often high impurity content in low temperatures –Cl in TiO 2