Electrically- and chemically-active adlayers for plasma electrodes

• US 9,133,546 B1
• Filed: 03/05/2014
• Issued: 09/15/2015
• Est. Priority Date: 03/05/2014
• Status: Active Grant

• Current Assignee: Lotus Applied Technology LLC, Toppan Printing Co., Ltd. (TOPPAN Holdings, Inc.)
• Original Assignee: Lotus Applied Technology LLC
• Inventors: Dickey, Eric R., Danforth, Bryan Larson, Kon, Masato
• Primary Examiner(s): KUSUMAKAR, KAREN M
• Application Number:
  US14/198,429
• Publication Number:
  US 20150252478A1
• Time in Patent Office: 559 Days
• Field of Search: 438478-509, 438597-688, 427/248.1, 427/539, 427/569, 427/575, 118/718, 118/719, 118/723.R
• US Class Current: 1/1
• CPC Class Codes: C23C 16/405 of refractory metals or yttrium
• CPC Class Codes: C23C 16/45534 Use of auxiliary reactants other than used for contributing to the composition of the main film, e.g. catalysts, activators or scavengers
• CPC Class Codes: C23C 16/45536 Use of plasma, radiation or electromagnetic fields
• CPC Class Codes: C23C 16/45551 for relative movement of the substrate and the gas injectors or half-reaction reactor compartments
• CPC Class Codes: H01J 37/32357 Generation remote from the workpiece, e.g. down-stream
• CPC Class Codes: H01J 37/32422 Arrangement for selecting ions or species in the plasma
• CPC Class Codes: H01J 37/32532 Electrodes
• CPC Class Codes: H01J 37/3255 Material
• CPC Class Codes: H01J 37/32559 Protection means, e.g. coatings
• CPC Class Codes: H01J 37/3277 of continuous material

Abstract

A system for forming a thin film on a substrate uses a plasma to activate at least one gaseous precursor in a plasma generator fluidly coupled with a reaction space. The plasma generator is operative to generate a plasma from at least a portion of the precursor gas with at least one pair of plasma electrodes, one plasma electrode having a non-native electrically conductive adlayer exhibiting property characteristics that cause the adlayer to be substantially conserved and chemically active with at least one of the gases present within the plasma generation region.

Claims

1. A system for forming a thin film on a substrate using a plasma to activate film deposition process from at least one gaseous precursor, the system comprising:

a reaction space which is, when the system is in use, supplied with a precursor gas and provisioned with the substrate; and

a plasma generator fluidly coupled with the reaction space and operative to generate in a plasma generation region a plasma from at least a portion of the precursor gas and having at least one plasma electrode including a non-native electrically conductive adlayer exhibiting property characteristics that cause the adlayer to be substantially conserved and chemically active with at least one of the gases present within the plasma generation region.

2. The system of claim 1, further comprising another plasma electrode that is electrically insulated from the at least one plasma electrode and electrically operative to have a different electrical potential from the at least one plasma electrode.

3. The system of claim 2, wherein the other plasma electrode includes one or more of a dark space shield fluidly coupled with the plasma generation region or a reaction vessel wall fluidly coupled with the plasma generation region.

4. The system of claim 2, wherein the other plasma electrode does not include a non-native electrically conductive adlayer.

5. The system of claim 1, wherein the selected plasma electrode includes an electrode body which supports the adlayer, wherein the electrode body is formed from a first metal, and wherein the adlayer includes a second metal that is different from the first metal.

6. The system of claim 5, wherein a work function of the second metal is different from a work function of the first metal.

7. The system of claim 1, wherein the adlayer consists essentially of a transition metal selected from the group consisting of palladium (Pd), platinum (Pt), cobalt (Co), iridium (Ir), and nickel (Ni).

8. The system of claim 1, wherein the adlayer includes a conductive layer formed by partial reduction of a stable oxide.

9. The system of claim 8, wherein the adlayer includes a reduced mixed oxide including indium and tin.

10. The system of claim 1, wherein the plasma electrode includes an electrode body, and wherein an adhesion layer covers at least a portion of the electrode body to thereby bond the adlayer to the electrode body.

11. The system of claim 10, wherein the adhesion layer includes one or more of titanium (Ti), titanium nitride (TiN), chromium (Cr), or tungsten (W).

12. The system of claim 1, wherein the selected plasma electrode is a cathode.

13. The system of claim 1, wherein the plasma generator is positioned within the reaction space.

14. The system of claim 1, wherein the plasma generator is fluidly coupled with the reaction space via a radical delivery conduit.

15. The system of claim 1, wherein the adlayer includes, in an amount of about 15% or less, a p-type dopant selected from the group consisting of fluorine (F), antimony (Sb), and aluminum (Al).

16. The system of claim 1, wherein the substrate is a flexible substrate and wherein the plasma supplies radicals generated from the precursor gas to a first precursor zone, thereby forming chemisorbed first precursor on the substrate, and further comprising a second precursor zone separated from the first precursor zone by a zone divider, the second precursor zone supplied with a second precursor that is reactive with the chemisorbed first precursor;

and

a transport mechanism adapted to impart relative motion between the flexible substrate and the first and second precursor zones so as to alternate exposure of the flexible substrate to the first and second precursor zones and build up a film on the flexible substrate.

17. A method of depositing a thin film on a substrate, the method comprising:

provisioning a reaction space with a substrate;

forming a layer of a first precursor on an active region of the substrate;

removing non-chemisorbed amounts of the first precursor from the layer until no more than chemisorbed first precursor remains on the active region;

supplying, with a second precursor gas, a plasma generator having a plasma electrode including a non-native electrically conductive adlayer exposed to the second precursor gas, the adlayer exhibiting property characteristics that cause the non-native electrically conductive adlayer to be substantially conserved and chemically active with the second precursor gas present within the plasma generator;

using the plasma generator, generating a plasma using at least a portion of the second precursor gas to thereby form radicals from the second precursor gas; and

after removing non-chemisorbed amounts of the first precursor from the active region, exposing the active region to the radicals to thereby form a thin film on the substrate.

18. The method of claim 17, wherein the plasma electrode is one of at least one pair of plasma electrodes operable at different electrical potentials to generate the plasma.

19. The method of claim 17, further comprising:

supplying the first precursor gas within a first precursor zone;

supplying the second precursor gas within a second precursor zone; and

using a substrate transport mechanism, imparting relative motion between the substrate and the first and second precursor zones.

20. The method of claim 17, wherein the plasma electrode includes an electrode body which supports the adlayer, wherein the electrode body is formed from a first metal, and wherein the adlayer includes a second metal that is different from the first metal.

21. The method of claim 20, wherein a work function of the second metal is different from a work function of the first metal.

22. The method of claim 17, further comprising positioning the plasma generator within the reaction space.

23. The system of claim 17, further comprising fluidly coupling the plasma generator with the reaction space via a radical delivery conduit so that the active region is not exposed to plasma.

24. The method of claim 17, wherein generating the plasma includes catalytically transforming the second precursor gas into radicals using the plasma electrode.

25. The method of claim 17, wherein the non-native electrically conductive adlayer is chemically active with the second precursor gas to substantially maintain the electrical conductivity of the electrode.

26. A system for forming a thin film on a substrate using a plasma to activate a film deposition process from at least one gaseous precursor, the system comprising:

means for forming a layer of a first precursor on an active region of the substrate;

means for removing non-chemisorbed amounts of the first precursor from the layer until no more than chemisorbed first precursor remains on the active region;

means for supplying a plasma generator with a second precursor gas, the plasma generator having a plasma electrode including a non-native electrically conductive adlayer exposed to a second precursor gas, the adlayer exhibiting property characteristics that cause the non-native electrically conductive adlayer to be substantially conserved and chemically active with the second precursor gas present within the plasma generator to thereby form radicals from the second precursor gas; and

means for exposing the active region to the radicals after the non-chemisorbed amounts of the first precursor have been removed from the active region, to thereby form a thin film on the substrate.

27. The method of claim 26, wherein the non-native electrically conductive adlayer catalytically transforms the second precursor gas into radicals.

28. The method of claim 26, wherein the non-native electrically conductive adlayer substantially maintains the electrical conductivity of the plasma electrode.

29. The method of claim 26, wherein the non-native electrically conductive adlayer has a different work function than the plasma electrode.