1. Invention of ALD and protection of knowledge Tuomo Suntola Winter-School 09 - 12, January 2012 University of Helsinki, Department of Chemistry

2. Invention of ALD and protection of knowledge 1.Background 2.Identification of the goal and the problem 3.The solution 4.Patents / Confidential knowhow / Presentation 5.From the idea to a major processing technology

3. Environment for ALD innovation 1973 Confidence for industrial success Technology background - thin film technologies - semiconductor devices 1.1.1974 Proposal for EL-flat panel development, March 1974 Instrumentarium Oy - Search for new challenges Late 1973

4. Invention of ALD State of the art: -High performance demonstrated -Major problems with stability due to the high operational voltage Proposal for EL-flat panel development, March 1974 Buildup of ordered film structure requires ordered processing condition Novel thin film processing technique is needed Idea of sequential buildup of compounds, June 1974

5. 1. ALD processing of ZnS, September 1974 From idea to demonstration Idea of sequential buildup of compounds, June 1974 Construction of test equipment 10  torr 360  C 4x10  torr 3x10  torr 2x10  torr 2 c/s Zn S 320  C 100  C 0.4 mm 0.6 0.2 0 0 10 20 minutes Hexagonal ZnS: monolayer 3.13 Å n=2.36 1/3 x monolayer

6. From idea to patents 1977-11-15, US 4.058.430 Demonstration, September 1974 Idea, June 1974 1. ALD patent, November 1974 Method for producing compound thin films: Definition of conditions for ALD reaction to occur Invention or a law of nature? Oral hearing at - US P.O., Washington - Soviet P.O., Moscow - Japan P.O., Tokyo - Germany P.O., Munich

7. From idea to patents Idea, June 1974 1. ALD patent, November 19742. ALD patent, February 1979 Method for performing growth of compound thin films: A method and an apparatus are provided for performing growth of compound thin films by alternately repeating separate surface reactions of the substances comprising the compound. A carrier gas affects a diffusion barrier between the surface reaction steps to be separated from each other. The gas phase diffusion barrier is also applied to separate the source regions of different reacting vapors both from each other and from the surface reaction zone. Method for producing compound thin films: Definition of conditions for ALD reaction to occur Invention or a law of nature? Oral hearing at - US P.O., Washington - Soviet P.O., Moscow - Japan P.O., Tokyo - Germany P.O., Munich 1977-11-15, US 4.058.4301983-11-01, US 4.413.022 Demonstration, September 1974 Project moved to Lohja Corporation 1978

8. Method for performing growth of compound thin films

10. Activation of academic work and conferences on ALD Steps in publicity First public presentation of ALE for the growth of thin material layers: 5. International Conference on Vapor Growth and Epitaxy 1981 First public presentation of ALD-EL devices: SID 1980 conference in San Diego Atomic Layer Epitaxy in Semiconductor Devices Applications, MRS Boston 1994 Commercial interest in EL displays III-V ALD Activity in Japan Commercial ALD-reactors by Microchemistry Ltd. ALE, Atomic Layer Epitaxy: Greek language: ”epi - taxis” => ”On arrangement”

11. 2004 Picosun Oy 2005 Beneq Oy From the Idea to a Major Processing Technology Need, solution, demonstration, basic patents Product prototypes, reactors for EL production Commercial production of EL panels, Lohja / Planar 19701980199020002010 Research for ALD chemistry and new applications Microchemistry Ltd 1999 ASM Microchemistry Explosive increase in ALD activity - research & industrial

12. Thank you for your attention! Winter-School 09 - 12, January 2012 University of Helsinki, Department of Chemistry