Formation of a lithium comprising structure on a substrate by ALD

Abstract

A method for the formation of lithium includes a layer on a substrate using an atomic layer deposition method. The method includes the sequential pulsing of a lithium precursor through a reaction chamber for deposition upon a substrate. Using further oxidizing pulses and or other metal containing precursor pulses, an electrolyte suitable for use in thin film batteries may be manufactured.

The invention claimed is: 
     
       1. A method for formation of a Li-comprising layer on a substrate by atomic layer deposition comprising the following steps:
 a) providing a substrate in a reaction chamber wherein said reaction chamber is arranged for gas-to-surface reactions,   b) pulsing a lithium precursor through said reaction chamber,   c) reacting said lithium precursor with at least one surface of said substrate,   d) purging of said reaction chamber
 d1) by sending a purge gas through said reaction chamber for the purging of the reaction chamber or 
 d2) by evacuating said chamber, and 
   repeating steps b) to d) a desired number of times in order for the formation of a thin film layer of a lithium comprising material upon said at least one surface of said substrate,   wherein the lithium precursor is selected from among lithium 2,2,6,6-tetramethylheptane-3,5-dionate, lithium alkoxides, lithium alkyls, cyclic lithium compounds, lithium dicyclohexamide, and bimetallic or multimetallic compounds.   
     
     
       2. A method according to  claim 1  wherein steps b) through d) are repeated with independently chosen lithium precursors in step b). 
     
     
       3. A method according to  claim 1 , further comprising the following steps:
 e) pulsing an oxygen precursor through said reaction chamber,   f) reacting said oxygen precursor with said at least one surface of said   substrate,   g) purging of said reaction chamber, where the purging of said chamber may be performed by sending a purge gas through said reaction chamber for the purging of the reaction chamber or by evacuating said chamber, repeating steps b) to g) a desired number of times in order for the formation of a thin film layer of a lithium comprising material upon said at least one surface of said substrate.   
     
     
       4. A method for formation of a Li-comprising layer on a substrate by atomic layer deposition comprising the following steps:
 a) providing a substrate in a reaction chamber wherein said reaction chamber is arranged for gas-to-surface reactions,   b) pulsing a lanthanum precursor through said reaction chamber,   c) reacting said lanthanum precursor with said at least one surface of said substrate,   d) purging of said reaction chamber,   e) pulsing an oxygen precursor through said reaction chamber,   f) reacting said oxygen precursor with said at least one surface of said substrate,   g) purging of said reaction chamber,   h) pulsing a lithium precursor through said reaction chamber,   i) reacting said lithium precursor with a surface layer of the substrate,   j) purging of said reaction chamber,   k) pulsing an oxygen precursor through said reaction chamber,   l) reacting said oxygen precursor with said at least one surface of said substrate,   m) purging of said reaction chamber,   n) repeating steps b) to m) a desired number of times in order for the formation of a thin film layer of a lithium and lanthanum comprising material upon said at least one surface of said substrate,   
       where the purging of said chamber may be performed by sending a purge gas through said reaction chamber for the purging of the reaction chamber or by evacuating said chamber. 
     
     
       5. A method for formation of a Li-comprising layer on a substrate by atomic layer deposition comprising the following steps:
 a) providing a substrate in a reaction chamber wherein said reaction chamber is arranged for gas-to-surface reactions,   b) pulsing a lanthanum precursor through said reaction chamber,   c) reacting said lanthanum precursor with said at least one surface of said substrate,   d) purging of said reaction chamber,   e) pulsing an oxygen precursor through said reaction chamber,   f) reacting said oxygen precursor with said at least one surface of said substrate,   g) purging of said reaction chamber,   h) pulsing a lithium precursor through said reaction chamber,   i) reacting said lithium precursor with a surface layer of the substrate,   j) purging of said reaction chamber,   k) pulsing an oxygen precursor through said reaction chamber,   l) reacting said oxygen precursor with said at least one surface of said substrate,   m) purging of said reaction chamber,   n) pulsing a titanium precursor through said reaction chamber,   o) reacting said titanium precursor with said at least one surface of said substrate,   p) purging of said reaction chamber,   q) pulsing an oxygen precursor through said reaction chamber,   r) reacting said oxygen precursor with said at least one surface of said substrate,   s) purging of said reaction chamber,   t) repeating steps b) to s) a desired number of times in order for the formation of a thin film layer of a lithium, lanthanum and titanium comprising material upon said at least one surface of said substrate,   
       where the purging of said chamber may be performed by sending a purge gas through said reaction chamber for the purging of the reaction chamber or by evacuating said chamber. 
     
     
       6. A method according to  claim 1 , wherein each step of the process is independently repeated a desired number of times. 
     
     
       7. A method according to  claim 3 , where the steps b)-g) are independently repeated one or more times before continuing the sequence. 
     
     
       8. A method according to  claim 1 , where the thin film layer is an oxide or a carbonate layer or a mixture thereof. 
     
     
       9. A method according to  claim 5  for the production of a La—Li—Ti—O layered thin film. 
     
     
       10. A method according to  claim 1  for the production of a lithium-comprising thin film battery. 
     
     
       11. A method according to  claim 1  for the production of a lithium-comprising electrolyte thin film for use in a battery. 
     
     
       12. A method according to  claim 4 , wherein the lithium precursor is selected from among lithium 2,2,6,6-tetramethylheptane-3,5-dionate, lithium alkoxides, lithium alkyls, cyclic lithium compounds, lithium dicyclohexamide, and bimetallic or multimetallic compounds. 
     
     
       13. A method according to  claim 12 , wherein each step of the process is independently repeated a desired number of times. 
     
     
       14. A method according to  claim 12 , where the groups of steps b)-g) and f)-m) respectively are independently repeated one or more times before continuing the sequence. 
     
     
       15. A method according to  claim 12 , where the thin film layer is an oxide or a carbonate layer or a mixture thereof. 
     
     
       16. A method according to  claim 12  for the production of a lithium-comprising thin film battery. 
     
     
       17. A method according to  claim 12  for the production of a lithium-comprising electrolyte thin film for use in a battery. 
     
     
       18. A method according to  claim 5 , wherein the lithium precursor is selected from among lithium 2,2,6,6-tetramethylheptane-3,5-dionate, lithium alkoxides, lithium alkyls, cyclic lithium compounds, lithium dicyclohexamide, and bimetallic or multimetallic compounds. 
     
     
       19. A method according to  claim 18 , wherein each step of the process is independently repeated a desired number of times. 
     
     
       20. A method according to  claim 18 , where the groups of steps b)-g), f)-m) and n)-s) respectively are independently repeated one or more times before continuing the sequence. 
     
     
       21. A method according to  claim 18 , where the thin film layer is an oxide or a carbonate layer or a mixture thereof. 
     
     
       22. A method according to  claim 18  for the production of a lithium-comprising thin film battery. 
     
     
       23. A method according to  claim 18  for the production of a lithium-comprising electrolyte thin film for use in a battery. 
     
     
       24. A composition comprising an electrolyte or electrode material coated with a thickness-controlled lithium-comprising thin film layer, wherein the lithium-comprising layer comprises monolayers of lithium oxide, monolayers of lithium carbonate, or a combination thereof. 
     
     
       25. The composition of claim 24, wherein the material coated with the lithium-comprising layer is an electrolyte material. 
     
     
       26. The composition of claim 24, wherein the material coated with the lithium-comprising layer is an anode material. 
     
     
       27. The composition of claim 24, wherein the lithium-comprising layer saturates exposed surfaces of the electrolyte or electrode material. 
     
     
       28. The composition of claim 24, wherein the lithium-comprising layer further comprises one or more elements from the periodic table. 
     
     
       29. The composition of claim 28, wherein the lithium-comprising layer comprises Li in the form of lithium oxide, together with one or more other metals or metal oxides forming a lithium metal(s) oxide film. 
     
     
       30. The composition of claim 29, wherein the lithium-comprising layer comprises one or more metal elements selected from Titanium, Lanthanum, Niobium, and Tantalum. 
     
     
       31. The composition of claim 28, wherein the lithium-comprising layer comprises one or more lithium metal(s) oxide selected from lithium titanate, lithium lanthanate, lithium niobate, lithium tantalate, and lithium lanthanum titanate. 
     
     
       32. The composition of claim 28, wherein the lithium-comprising layer comprises alternating monolayers of a lithium compound and a non-lithium compound. 
     
     
       33. The composition of claim 24, wherein the lithium-comprising layer is coated onto the electrolyte or electrode material by atomic layer deposition. 
     
     
       34. The composition of claim 33, wherein the lithium-comprising layer has a thickness of 19.2 nm or less. 
     
     
       35. The composition of claim 33, wherein the lithium-comprising layer comprises 3 to 33 atomic percent of lithium. 
     
     
       36. A battery comprising the electrolyte material of claim 25. 
     
     
       37. A battery comprising the anode material of claim 26. 
     
     
       38. A composition comprising a substrate coated with a lithium-comprising thin film layer, wherein the lithium-comprising layer comprises monolayers of lithium oxide, monolayers of lithium carbonate, or a combination thereof, and wherein the lithium-comprising layer is coated by atomic layer deposition. 
     
     
       39. The composition of claim 38, wherein the lithium-comprising layer is an electrolyte layer. 
     
     
       40. The composition of claim 38, wherein the substrate is a barrier or separator. 
     
     
       41. A battery comprising the barrier or separator of claim 40. 
     
     
       42. A device comprising the composition of claim 38, wherein the device is an electro-optical device, a photoelastic device, a piezoelectric device, an acousto-optical device, a pyroelectric device, a sensor, or an optical waveguide. 
     
     
       43. A solid state battery comprising an electrolyte material and an electrode material, wherein the electrolyte material and/or the electrode material is coated with a lithium-comprising thin film layer, wherein the lithium-comprising layer comprises a monolayer of lithium oxide, a monolayer of lithium carbonate, or a combination thereof, and wherein the lithium-comprising layer is coated by atomic layer deposition. 
     
     
       44. The solid state battery of claim 43, wherein the lithium-comprising layer comprises Li in the form of lithium oxide, together with one or more other metals or metal oxides forming a lithium metal(s) oxide film. 
     
     
       45. The solid state battery of claim 44, wherein the lithium-comprising layer comprises one or more lithium metal(s) oxide: of lithium titanate, lithium lanthanate, lithium niobate, lithium tantalate, and lithium lanthanum titanate.