US 20190027414A1 ( 19) United States (12 ) Patent Application Publication ( 10) Pub . No. : US 2019 / 0027414 A1 Ramadas et al. (43 ) Pub . Date : Jan . 24 , 2019 ( 54 ) ENCAPSULATION BARRIER STACK HOIL 51 /52 ( 2006 .01 ) B82Y 30 / 00 (2011 . 01 ) ( 71 ) Applicants : Agency for Science , Technology and HOIL 51/ 10 ( 2006 . 01 ) Research , Singapore (SG ) ; HOIL 21/ 56 (2006 . 01 ) Tera - Barrier Films PTE LTD ., (52 ) U . S . CI. Singapore (SG ) CPC HOIL 23 /29 ( 2013 .01 ) ; HOIL 51/ 448 ( 2013 .01 ) ; C23C 28 / 00 ( 2013 .01 ) ; C23C 28 / 42 (72 ) Inventors : Senthil Kumar Ramadas, Singapore (2013 .01 ) ; HO1L 51 /5253 ( 2013 .01 ) ; HOIL ( SG ) ; Saravanan Shanmugavel, 2924 / 0002 ( 2013 . 01 ) ; HOIL 51 / 107 ( 2013 .01 ) ; Singapore (SG ) HOIL 21 /56 ( 2013 . 01 ) ; HOIL 51/ 5256 ( 73 ) Assignees: Agency for Science , Technology and (2013 .01 ) ; HOIL 2251 /5369 ( 2013 .01 ) ; B82Y Research , Singapore ( SG ) ; 30 / 00 ( 2013 .01 ) Tera - Barrier Films PTE LTD . , (57 ) ABSTRACT Singapore ( SG ) Disclosed is an encapsulation barrier stack , capable of encapsulating a moisture and / or oxygen sensitive article and (21 ) Appl . No. : 16 / 140 , 065 comprising a multilayer film , wherein the multilayer film comprises : ( 22 ) Filed : Sep . 24 , 2018 one or more barrier layer ( s ) having low moisture and / or oxygen permeability , and Related U . S . Application Data one or more sealing layer ( s ) arranged to be in contact with (62 ) Division of application No . 14 /354 , 118 , filed on Apr . a surface of the at least one barrier layer , thereby 24 , 2014 , filed as application No. PCT /SG2012 / covering defects present in the barrier layer , 000402 on Oct. 24 , 2012 . wherein the one or more sealing layer ( s ) comprise ( s ) a plurality of encapsulated nanoparticles, the nanoparticles (60 ) Provisional application No . 61/ 550 , 764 , filed on Oct. being reactive in that they are capable of interacting with 24 , 2011. moisture and /or oxygen to retard the permeation ofmoisture and /or oxygen through the defects present in the barrier Publication Classification layer . The encapsulation of the particles can be obtained by (51 ) Int . CI. polymerising a polymerisable compound ( a monomeric or a HOTL 23 /29 ( 2006 . 01 ) polymeric compound with polymerisible groups or ) cross HOIL 51/ 44 ( 2006 .01 ) linking a cross - linkable compound on the surface of the C23C 28 /00 (2006 .01 ) reactive nanoparticles . polymer encapsulated organic species nanoparticle passivated nanoparticle NASSA MX* columnar structure -barrier oxide porous film ( 60 -80 rum } planarised by functional WWW* w XXX mwox Wow M WWW Patent Application Publication Jan . 24 , 2019 Sheet 1 of 13 US 2019 / 0027414 A1 barrier oxide porous polymer film * barrier oxide -. * . * . TAX 28 . te 1: 46 S barrierstack .. ** * * * * 144 porous polymer film barrier oxide . tortuous path. * Fig . 1 (prior art) . % % % % 0 . 4 . 4 . 4 . 4 . 4 . 4 . 4 . 4 . 4 4 . 4 . 4 . 4 . 4 . 4 . 4 . 4 . 4 . 4 . 4 . 4 . 4 . 4 . 4 assess .iiiiii .. 17 H . .. .. barrier oxide . barrierstack . 13 . | barrier oxide . % Fig . 2 ( prior art) Patent Application Publication Jan . 24 , 2019 Sheet 2 of 13 US 2019 /0027414 A1 barrier layer sealing layer Fig . 3A barrier layer sealing layer Fig . 3B polymer encapsulated organic species passivated nanoparticle functional mano layer columnar structure -barrier oxide porous Him (60 -80 anni www planarised by functional Fig . 3C Patent Application Publication Jan . 24 , 2019 Sheet 3 of 13 US 2019 / 0027414 A1 . ... .. * * . 1 . 1 U - . : .IFF 2 . * . 2 . :.9223 . :. ' . .. - . ! . + ! . ' . ' . BANAN . : XXX . w OWOWOWO . wwwwwwwwwwwwwwwwwwwwww wwwwwwwwaminiai Fig . 5 Patent Application Publication Jan . 24 , 2019 Sheet 4 of 13 US 2019 /0027414 A1 piastie film PÉTER Fig . 6 * * * * * * * * * * . * SELS .OkV 420 ,00 204. / FIG . 7 Patent Application Publication Jan . 24 , 2019 Sheet 5 of 13 US 2019 / 0027414 A1 DO TURSEN OB . 20 8 02. 4 41. ** * * * * * M * ** * * FIG . 8 FIG . 9 Patent Application Publication Jan . 24 , 2019 Sheet 6 of 13 US 2019 /0027414 A1 FIG . 10 oooooo IMRE SE 4 .0KV X10 ,000 Tue WD 5 .9mm Fig . 11 Patent Application Publication Jan . 24 , 2019 Sheet 7 of 13 US 2019 /0027414 A1 OW XXXL wo XXX Wow Fig . 12 SEU SOKV 235, 000 100m WD 4 .8m Fig . 13A Patent Application Publication Jan . 24 , 2019 Sheet 8 of 13 US 2019 /0027414 A1 20 Fig . 13B WWW WAAR UNRANNA FIG . 13C Patent Application Publication Jan . 24 , 2019 Sheet 9 of 13 US 2019 /0027414 A1 1 3D YYYYYYYYYYY FIG . 13D FIG . 14A Patent Application Publication Jan . 24 , 2019 Sheet 10 of 13 US 2019 /0027414 A1 OOXXX * * VOOR CS * * * * * * * * * * * * * * * * * * * * ** * * * * * * ** * * * ** ** * ** * * * * * * * * * * * * * * * * FIG . 14B ww freelypemainedand met tower w Det is er popruhy Fig . 15 PatentPatent Application PublicationPublication Jan . 24 , 2019 Sheet 11 of 13 US 2019 /0027414 A1 Plastic substrate Nanoparticle sealing Nanoparticle sealing Al2O3 oxide layer layer- Layer 1 layer - Layer 2 IMRE SEL 5 .0KV X50 ,000 100nm WD 5 .6mm Fig . 16 A Patent Application Publication Jan . 24 , 2019 Sheet 12 of 13 US 2019 /0027414 A1 Nanoparticle sealing Upper A1203 oxide layer layer Layer 2 **** * M IMRE SEI 5 . 0kV X30 ,000 100nm .. WD. 6 .3mm. .. .. .. Fig . 16 B Patent Application Publication Jan . 24 , 2019 Sheet 13 of 13 US 2019 /0027414 A1 Nanoparticle sealing layer - Al2O3 oxide layer eminar Plastic substrate MRE SE 5. 0KV XXO 100m WD 5 , 745 Fig . 17 US 2019 /0027414 A1 Jan . 24 , 2019 ENCAPSULATION BARRIER STACK barrier films comprise 30 % to 35 % , i . e . US $ 25 - 30 . This would include substrates ( top and bottom ) as well as sealants CROSS -REFERENCE TO RELATED and other protective laminates . Since the base substrate APPLICATIONS generally is a lower cost metal film , the barrier film share would be in the range of US $ 15 - 20 /m² maximum . If the PV [ 0001] The present application is a divisional application module price continues to decline ( as expected by many of U . S . patent application Ser. No . 14 /354 , 118 , filed Apr. 24 , industry analysts ), the barrier film share of the total PV 2014 , which is the U . S . national phase application of Inter module product cost would be in the range of US $ 10 /m² . national Application No. PCT/ SG2012 /000402 , filed Oct . Similarly for OLED lighting applications, the cost expecta 24 , 2012 , which designated the U . S . and in turn claims the tion is similar to the PV applications . This invention pro right of priority to U . S . Provisional Application No . 61/ 550 , poses to reduce the production cost of the barrier stack and 764 filed Oct . 24 , 2011 , the entire content of each of which provide additional cost benefits by enhancing the UV block is incorporated herein for all purposes . ing and anti- reflection properties . Therefore, the proposed barrier stack design can provide barrier and optical proper FIELD OF THE INVENTION ties at lower cost for PV and OLED lighting applications. [0002 ] The present invention relates to the field of barrier [0006 ] Manufacturers of flexible solar cells have set their stacks , and more particularly to a barrier stack that includes target at less than US $ 1 /Watt , since their flexible rolls of encapsulated nanoparticles . The encapsulation of the par solar modules are easily transported and installed . Currently , ticles can be obtained by partially or fully encapsulating CIGS manufacturers have achieved more than 12 % effi with an organic material , which includes a polymerising a ciency on their regular roll- to - roll production lines , with polymerisable compound ( a monomeric or a polymeric champion efficiencies of more than 16 % . compound with polymerisible groups or) cross - linking a [ 0007 ] Most of the barrier coating technologies are based cross -linkable compound on the surface of the reactive on the use of oxide barrier films in their barrier stack in order nanoparticles . The encapsulated nanoparticles may be to get high barrier properties . These oxide barrier films are deposited on to inorganic thin oxide (barrier ) films. A deposited on the plastic substrates by Sputtering (Physical respective barrier stack can be arranged on a substrate , for Vapour Deposition ) processes and PECVD methods . How example in an electronic device . ever , the most preferred method is the sputtering process , which can provide high packing density of oxide films, BACKGROUND OF THE INVENTION which has lower density of defects such as pinholes , cracks [0003 ] Flexible solar cells and flexible plastic or printed and other defects such as grain boundary . The atomic layer electronics are considered as a next generation display deposition can also provide high packing density barrier technology. However, like many new technologies of the films with lower number of defects , but the production future, many technical questions have to be resolved such as throughput is currently lower than sputtering The Roll - to those related to the high gas barrier performance and the cost Roll production systems and efforts in increasing production of the polymeric substrates . Polymer films do not typically throughput are under development stage . However, efforts show high barrier performance (as compared to the require have been taken to increase the production speed by Roll ment of less than 10 - 5 to 10 - 6 g/ m² / day permeability of to -Roll processes, which are currently being developed . The water vapour at 39° C . and 95 % relative humidity ) even if typical barrier properties which can be achieved by Sput they are coated with a metal- oxide coating to improve their tering and ALD techniques are in the order of 0 . 02 g /m² day barrier properties . It is well known that high barrier thin film to 0 .006 g /m² .day at 38° C . and 90 % relative humidity . oxides , coated onto plastic films, have imperfections such as Nevertheless , the sputtering technology has already reached pinholes , cracks, grain boundaries , etc . which vastly affect a matured stage , and Roll - to - Roll coating manufacturing the performance of barrier films.