The present invention relates to a sealing method for decreasing the time it takes to hermetically seal a device and the resulting hermetically sealed device. Examples of the hermetically sealed device include a light-emitting device (e.g., organic emitting light diode (OLED) device), a photovoltaic device, a thin-film sensor, an evanescent waveguide sensor, a food container and a medicine container.
Transport of oxygen and/or water through laminated or encapsulated materials and their subsequent attack of an inner material within a device represents two of the more common degradation mechanisms associated with many devices including, for example, light-emitting devices (OLED devices), thin-film sensors, evanescent waveguide sensors, food containers and medicine containers. For a detailed discussion about the problems associated with the penetration of oxygen and water into the inner layers (cathode and electro-luminescent materials) of an OLED device, reference is made to the following documents:
It is well known that unless something is done to minimize the penetration of oxygen and water into an OLED device, then their operating lifetime will be severely limited. As a result, much effort has been expended to minimize the penetration of oxygen and water into an OLED device so as to help drive the OLED operation towards a 40 kilo-hour lifetime, the level generally regarded as necessary so OLED devices can overtake older device technologies such as LCD displays as discussed in the following document:
The more prominent efforts to date that have been performed to help extend the lifetime of OLED devices include gettering, encapsulating and using various sealing techniques. In fact, one common way for sealing an OLED device today is to apply and heat-treat (or UV treat) different types of epoxies, inorganic materials and/or organic materials to form a seal on the OLED device. For example, Vitex Systems manufactures and sells a coating under the brand name of Barix™ which is a composite based approach where alternate layers of inorganic materials and organic materials are used to seal the OLED device. Although these types of seals provide some level of hermetic behavior, they can be very expensive and there are still many instances in which they have failed over time to prevent the diffusion of oxygen and water into the OLED device.
To address this sealing problem, the assignee of the present invention has developed several different sealing techniques in which sealing materials (e.g., low liquidus temperature inorganic materials, Sn2+-containing inorganic oxide materials) are used to hermetically seal an OLED device (or other type of device)(see the aforementioned U.S. patent application Ser. Nos. 11/207,691 and 11/803,512). Although these sealing techniques and sealing materials work well to hermetically seal an OLED device (or other types of devices) there is still a desire to improve upon these sealing techniques so that one can decrease the time it takes to hermetically seal an OLED device (or other type of device). This particular need and other needs have been satisfied by the present invention.
The present invention introduces a sealing method for decreasing the time it takes to hermetically seal a device (e.g., an OLED device). The sealing method includes the steps of: (1) cooling an un-encapsulated device; (2) depositing a sealing material over at least a portion of the cooled device to form an encapsulated device; and (3) heat treating the encapsulated device to form a hermetically sealed device. In one embodiment, the sealing material is a low liquidus temperature inorganic (LLT) material such as, for example, tin-fluorophosphate glass, tungsten-doped tin fluorophosphate glass, chalcogenide glass, tellurite glass, borate glass and phosphate glass. In another embodiment, the sealing material is a Sn2+-containing inorganic oxide material such as, for example, SnO, SnO+P2O5 and SnO+BPO4. An advantage of using this sealing method is that by cooling the un-encapsulated device one can then increase the deposition rate that the sealing material (e.g., LLT material, Sn2+-containing inorganic oxide material) is deposited onto the un-encapsulated device which decreases the time it takes to hermetically seal a device (e.g., an OLED device).
A more complete understanding of the present invention may be had by reference to the following detailed description when taken in conjunction with the accompanying drawings wherein:
Referring to
The sealing method 200 has a cooling step 202 in which the substrate 106 and possibly the inner layer(s)/component(s) 104 of an un-encapsulated device 100 are cooled to a temperature which is (for example): preferably <15° C., more preferably <10° C. and even more preferably <1° C. In addition, the sealing method 200 has a deposition step 204 in which the sealing material 102 (e.g., LLT material 102 or Sn2+-containing inorganic oxide material 102) is deposited over the inner layer(s)/component(s) 104 located on top of the cooled support/substrate 106 to form an encapsulated device 100. In one embodiment, the sealing material 102 can be deposited over the cooled inner layer(s)/component(s) 104 and the cooled support/substrate 106 at a deposition rate which is (for example): preferably ˜5 Å/second, more preferably ˜25 Å/second, and even more preferably ˜75 Å/second. Plus, the sealing material 102 can be deposited by using any one of variety of processes including, for example, sputtering, flash evaporation, spraying, pouring, frit-deposition, vapor-deposition, dip-coating, painting, rolling (for example using a film of sealing material 102), spin-coating, a co-evaporation process, a soot gun spraying process, a reactive sputtering process, a laser ablation process, or any combination thereof.
In addition, the sealing method 200 has a heat treatment step 206 in which the encapsulated device 100 is annealed, consolidated or heat-treated (e.g., less than three hours at less than 100° C.) to form the hermetically sealed device 100. The heat treatment step 206 is performed to remove/minimize defects (e.g., pores) within the deposited sealing material 102 which may be formed during the deposition step 204 (note: if Sn2+-containing inorganic oxide material 102 is used and in particular SnO then the sputter-deposition step 204 itself may provide all of the heat necessary for sintering the deposited material 102). In one embodiment, the encapsulated device 100 can be heat treated at a temperature which is (for example): preferably <400° C., more preferably <200° C., even more preferably <100° C. and most preferably <40° C. If desired, the cooling step 202, the deposition step 204 and the heat treatment step 206 can all be performed in an inert atmosphere or in a vacuum to help ensure that a water and an oxygen-free condition is maintained throughout the entire sealing process. This type of processing environment helps to ensure the robust, long-life operation of organic electronics 104 (for example) located within the hermetically sealed device 100.
A main advantage of the sealing method 200 is that by cooling the un-encapsulated device 100 one can then increase the deposition rate that the sealing material 102 is deposited onto the un-encapsulated device 100 which decreases the time it takes to hermetically seal the device 100. This is important when one wants to have a high volume operation and manufacture a large number of hermetically sealed devices 100. Examples of hermetically sealed devices 100 include a light-emitting device (e.g., OLED device), a photovoltaic device, a thin-film sensor, an evanescent waveguide sensor, a food container and a medicine container.
If one is manufacturing an OLED device 100, then the inner layers 104 would include cathode and electro-luminescent materials both of which would be located on the substrate 106. These cathode and electro-luminescent materials 104 can be damaged if they are heated above for example 100-125° C. As such, the heat treatment step 206 would not be possible in this particular application if a traditional material (e.g., soda-lime glass) were deposited on the OLED device 100. Because, the temperature (e.g., 600° C.) needed to remove the defects in a traditional material (e.g., soda-lime glass) would be too high and thus severely damage the OLED device's inner layers 104. However, in the present invention, the heat treatment step 206 can be performed in this particular application because the temperature (e.g., 100° C. or less) needed to remove/minimize the defects if any that may be in the deposited sealing material 102 is relatively low so as to not damage the OLED device's inner layers 104. To accomplish this, the sealing material 102 used to encapsulate the cooled device 100 is preferably a low liquidus temperature (LLT) inorganic material 102 or a Sn2+-containing inorganic oxide material 102. These sealing materials are briefly discussed below but for a more detailed discussion reference is made to the co-pending U.S. patent application Ser. Nos. 11/207,691 and 11/803,512.
The LLT material 102 can make this all possible because this type of material has a relatively low liquidus temperature ≦1000° C. The low liquidus temperature means that the LLT 102 can be heat treated at a relatively low temperature that does not thermally damage the OLED device's inner layer(s) 104 but still results in a pore-free film being formed on the OLED device 100. Again, it should be appreciated that the heat treated LLT material 102 can also be used as a barrier layer on a wide variety of devices 100 in addition to the OLED device 100 such as, for example, a thin-film sensor, a photovoltaic device, an evanescent waveguide sensor, a food container, a medicine container or any type of electronic device that is sensitive to moisture, oxygen or other gases (note: another LLT material 102 namely tungsten-doped tin fluorophosphate glass could also be used herein and this material was disclosed in co-assigned U.S. patent application Ser. No. 11/544,262—the contents of which are incorporated by reference herein).
In one embodiment, the LLT material 102 has a low liquidus temperature ≦1000° C. (and more preferably ≦600° C. and even more preferably ≦400° C.). The LLT material 102 can include, for example, glass such as tin fluorophosphate glass, tungsten-doped tin fluorophosphate glass, chalcogenide glass, tellurite glass, borate glass and phosphate glass (e.g., alkali Zn or SnZn pyrophosphates). For instance, a preferred tin fluorophosphate glass has the following composition: Sn (20-85 wt %), P (2-20 wt %), O (10-36 wt %), F (10-36 wt %), Nb (0-5 wt %) and at least 75% total of Sn+P+O+F (which can be melted powder targets or sputtered pressed powder targets). These LLT materials 102 are desirable for several different reasons including (for example):
In addition, the Sn2+-containing inorganic oxide material 102 can make this all possible because this type of material has the ability, when consolidated at relatively low temperatures, to form hermetic encapsulated coatings which protect the device 100. The Sn2+-containing inorganic oxide materials 102 differ in several respects from the tin fluorophosphate material which was one of the aforementioned LLT materials. First, the Sn2+-containing inorganic oxide materials 102 can be heat-treated at a lower temperature than the tin fluorophosphate material (note: the specific tin fluorophosphate material discussed below with respect to
The Sn2+-containing inorganic oxide materials 102 include compositions such as, for example, SnO powder, blended SnO/P2O5-containing powders (e.g., 80% SnO+20% P2O5), and blended SnO/BPO4 powders (e.g., 90% SnO+10% BPO4). However, the Sn2+-containing inorganic oxide material 102 can also include blended compositions that had been melted to form the appropriate sputtering target (e.g., 80% SnO+20% P2O5). In one embodiment, the Sn2+-containing inorganic oxide materials 102 include: (1) SnO; (2) SnO and a borate material; (3) SnO and a phosphate material; and (4) SnO and a borophosphate material. Typically, the Sn2+-containing inorganic oxide material 102 can contain >50% stannous oxide (and more preferably >70% stannous oxide and even more preferably >80% stannous oxide). Plus, the Sn2+-containing inorganic oxide material 102 can be heat treated at <400° C. (and preferably at <200° C. and more preferably at <100° C. and even more preferably at <40° C.).
Referring to
The RF sputtering vacuum system had a temperature controlled holder which was used to cool the temperatures of the Ca and Al layers 104 and the substrate 106 (note: the three tested device 100 were respectively maintained at 150° C., 44° C. and 14° C.). The tin fluorophosphate material 102 (which in this case had a composition of 39.6 SnF2, 38.7 SnO, 19.9 P2O5, 1.8 Nb2O5 mole percent) was then sputtered onto the Al and Ca layers 104 by an ONYX-3 sputtering gun (Angstrom Sciences, Pa.) under relatively fast RF power deposition conditions (˜70 W forward/1 W reflected RF power) and high argon pressure (˜20 sccm) (see step 204 in
Upon completion of the deposition of the Al and CA layers 104, cooling of the substrate 106 was ceased, and an internal plug-heater was switched on for 2 hours to raise the substrate 106 temperature above 100° C. and consolidate the sputtered tin fluorophosphate material 102 (see step 206 in
Referring to
From the foregoing, it can be readily appreciated by those skilled in the art that the present invention relates to a sealing method 200 for decreasing the time it takes to hermetically seal a device 100 (e.g., an OLED device 100). The sealing method 200 includes the steps of: (1) cooling an un-encapsulated device 100; (2) depositing a sealing material 102 over at least a portion of the cooled device 100 to form an encapsulated device 100; and (3) heat treating the encapsulated device 100 to form a hermetically sealed device 100. The sealing material 102 is a LLT material 102 or a Sn2+-containing inorganic oxide material 102. If desired multiple layers of the same or different types of the sealing materials 102 can be deposited on top of the device 100. As discussed above, the sealing material(s) 102 are specifically suited for inhibiting oxygen or/and moisture degradation which is a common problem to a wide variety of devices 100 including electronic devices, food containers and medicine containers. In addition, the sealing material(s) 102 may be used to reduce, for example, photochemical, hydrolytic, and oxidative damage to a device 100 due to chemically active permeants. Some additional advantages and features of using the sealing material(s) 102 are as follows:
A. The sealing materials 102 may be used to prepare hermetic thin film (˜2 μm) barrier layers that fulfill the most stringent impermeability requirements for OLED long-lived operation (<10−6 water gm/m2 per day), and may be rapidly sputter-deposited and annealed on devices (or substrate materials) and in some cases at extremely low temperatures (<40° C.). The devices 100 include but are not limited to:
The substrate materials include but are not limited to:
B. The sealing of organic electronic devices 100 with these particular sealing materials 102 requires no introduction of oxygen or air into the chamber during the consolidation/heat treatment. The fact that no outside oxidizing source is required to enable the sealing event, especially at low temperatures (˜40° C.), makes this sealing technique an attractive feature for making organic electronic devices. This is especially true since it is well known that oxygen and moisture are the principal degrading reactants associated with the redox and photo-bleaching degradation reactions that adversely affect the organic layers and/or cathode materials located within organic electronic devices like an OLED.
C. Sputter deposition, evaporation, and other thin film deposition processes may be used to deposit the sealing material 102. For example, high rate deposition of Sn2+-containing inorganic oxide films 102 may be produced by evaporation of metallic tin in an oxygen containing environment onto a rolling substrate such as plastic at very high speed. Alternatively, reactive DC sputtering of metallic tin in an oxygen environment may be used to produce the desired high rate deposition of a Sn2+-containing inorganic oxide film onto a device 100. In fact, many different thin film deposition techniques may be used to deposit the Sn2+-containing inorganic oxide film 102 (and the LLT film 102) onto the device 100.
D. The sealing material 102 can be batched with different powders/dopants to create a composition designed to achieve a specific physical-chemical property in the deposited barrier layer. Following is an exemplary list of various dopants that can be mixed with the sealing material 102 to achieve a desired physico-chemical property within the deposited barrier layer:
E. Pattern-Ability: Sputter deposition, or other thin film deposition methods, allow different patterning techniques to be used, such as shadow masking etc., to produce micro-structures having specific dielectric properties to help optimize the operation of the device 100 (e.g., an organic thin film transistor (TFT) device 100 could have insulator gates formed thereon to help achieve a good voltage threshold value).
Although several embodiments of the present invention have been illustrated in the accompanying Drawings and described in the foregoing Detailed Description, it should be understood that the invention is not limited to the embodiments disclosed, but is capable of numerous rearrangements, modifications and substitutions without departing from the spirit of the invention as set forth and defined by the following claims.
This patent application is a continuation application of U.S. patent application Ser. No. 11/820,855, now U.S. Pat. No. 7,722,929, filed Jun. 21, 2007, which is a continuation-in-part application of U.S. patent application Ser. Nos. 11/207,691 filed on Aug. 18, 2005 and entitled “Method for Inhibiting Oxygen and Moisture Degradation of a Device and the Resulting Device”, and 11/803,512 filed on May 15, 2007 now abandoned and entitled “Low Temperature Sintering using Sn2+ Containing Inorganic Materials to Hermetically Seal a Device”. The contents of these documents are hereby incorporated by reference herein.
Number | Name | Date | Kind |
---|---|---|---|
3622439 | Manne et al. | Nov 1971 | A |
3720097 | Kron | Mar 1973 | A |
3795976 | Ikeda | Mar 1974 | A |
3916048 | Walles | Oct 1975 | A |
3932693 | Shaw et al. | Jan 1976 | A |
4040874 | Yerman | Aug 1977 | A |
4077588 | Hurst | Mar 1978 | A |
4314031 | Sanford et al. | Feb 1982 | A |
4374391 | Camlibel et al. | Feb 1983 | A |
4379070 | Tick | Apr 1983 | A |
4702963 | Phillips et al. | Oct 1987 | A |
4740412 | Hocker et al. | Apr 1988 | A |
4802742 | Ichikawa et al. | Feb 1989 | A |
4859513 | Gibbons et al. | Aug 1989 | A |
5084356 | Deak et al. | Jan 1992 | A |
5089446 | Cornelius et al. | Feb 1992 | A |
5110637 | Ando et al. | May 1992 | A |
5110668 | Minnick | May 1992 | A |
5180476 | Ishibashi et al. | Jan 1993 | A |
5183684 | Carpenter | Feb 1993 | A |
5211995 | Kuehnle et al. | May 1993 | A |
5324572 | Kuechler et al. | Jun 1994 | A |
5407713 | Wilfong et al. | Apr 1995 | A |
5462779 | Misiano et al. | Oct 1995 | A |
5478618 | Rosen | Dec 1995 | A |
5567488 | Allen et al. | Oct 1996 | A |
5610742 | Hinata et al. | Mar 1997 | A |
5641559 | Namiki | Jun 1997 | A |
5645923 | Matsuo et al. | Jul 1997 | A |
5736207 | Walther et al. | Apr 1998 | A |
5792550 | Phillips et al. | Aug 1998 | A |
5900285 | Walther et al. | May 1999 | A |
6077928 | Suh et al. | Jun 2000 | A |
6083313 | Venkatraman et al. | Jul 2000 | A |
6162892 | Kobayashi et al. | Dec 2000 | A |
6171703 | Haluska | Jan 2001 | B1 |
6193379 | Tonar et al. | Feb 2001 | B1 |
6207488 | Hwang et al. | Mar 2001 | B1 |
6211560 | Jimenez et al. | Apr 2001 | B1 |
6235579 | Lou | May 2001 | B1 |
6249014 | Bailey | Jun 2001 | B1 |
6268695 | Affinito | Jul 2001 | B1 |
6271150 | Croswell et al. | Aug 2001 | B1 |
6288415 | Leong et al. | Sep 2001 | B1 |
6294420 | Tsu et al. | Sep 2001 | B1 |
6306783 | Yamanaka | Oct 2001 | B1 |
6321571 | Themont et al. | Nov 2001 | B1 |
6350529 | Germain et al. | Feb 2002 | B1 |
6355125 | Tahon et al. | Mar 2002 | B1 |
6403176 | Patouraux et al. | Jun 2002 | B1 |
6413645 | Graff et al. | Jul 2002 | B1 |
6465101 | MacGregor et al. | Oct 2002 | B1 |
6486549 | Chiang | Nov 2002 | B1 |
6492026 | Graff et al. | Dec 2002 | B1 |
6522067 | Graff et al. | Feb 2003 | B1 |
6524698 | Schmoock | Feb 2003 | B1 |
6528442 | Kuwano et al. | Mar 2003 | B1 |
6530477 | Martorano et al. | Mar 2003 | B1 |
6623861 | Martin et al. | Sep 2003 | B2 |
6635989 | Nilsson et al. | Oct 2003 | B1 |
6660409 | Komatsu et al. | Dec 2003 | B1 |
6664730 | Weaver | Dec 2003 | B2 |
6720097 | Ohkawa et al. | Apr 2004 | B2 |
6720203 | Carcia et al. | Apr 2004 | B2 |
6737375 | Buhrmaster et al. | May 2004 | B2 |
6740394 | Jacobsen et al. | May 2004 | B2 |
6866901 | Burrows et al. | Mar 2005 | B2 |
6873101 | Nilsson et al. | Mar 2005 | B2 |
6991506 | Yamada et al. | Jan 2006 | B2 |
7015640 | Schaepkens et al. | Mar 2006 | B2 |
7034457 | Iwase et al. | Apr 2006 | B2 |
7045951 | Kawase et al. | May 2006 | B2 |
7126269 | Yamada et al. | Oct 2006 | B2 |
7169003 | Iwase et al. | Jan 2007 | B2 |
7198832 | Burrows et al. | Apr 2007 | B2 |
7829147 | Aitken et al. | Nov 2010 | B2 |
7923115 | Nagai et al. | Apr 2011 | B2 |
20010005585 | Ashihara et al. | Jun 2001 | A1 |
20010013756 | Mori et al. | Aug 2001 | A1 |
20010033135 | Duggal et al. | Oct 2001 | A1 |
20010038894 | Komada | Nov 2001 | A1 |
20010054436 | Mukai et al. | Dec 2001 | A1 |
20020013042 | Morkoc | Jan 2002 | A1 |
20020037418 | Peiffer et al. | Mar 2002 | A1 |
20020041443 | Varaprasad et al. | Apr 2002 | A1 |
20020074553 | Starikov et al. | Jun 2002 | A1 |
20020076154 | Maisenhoelder et al. | Jun 2002 | A1 |
20020110692 | Suzuki et al. | Aug 2002 | A1 |
20020114937 | Albert et al. | Aug 2002 | A1 |
20020122649 | Shimizu et al. | Sep 2002 | A1 |
20020127341 | Li | Sep 2002 | A1 |
20020140347 | Weaver | Oct 2002 | A1 |
20020142116 | Jud et al. | Oct 2002 | A1 |
20020160137 | Varma | Oct 2002 | A1 |
20020180924 | Sobrinho | Dec 2002 | A1 |
20030000826 | Krempel-Hesse et al. | Jan 2003 | A1 |
20030006697 | Weaver | Jan 2003 | A1 |
20030017297 | Song et al. | Jan 2003 | A1 |
20030019517 | McFarland | Jan 2003 | A1 |
20030020099 | Taylor | Jan 2003 | A1 |
20030022919 | Ayers et al. | Jan 2003 | A1 |
20030032039 | Cunningham et al. | Feb 2003 | A1 |
20030044552 | Komada | Mar 2003 | A1 |
20030047353 | Yamaguchi et al. | Mar 2003 | A1 |
20030049942 | Haukka et al. | Mar 2003 | A1 |
20030068534 | Ohkawa et al. | Apr 2003 | A1 |
20030075753 | Chu | Apr 2003 | A1 |
20030080678 | Kim et al. | May 2003 | A1 |
20030085652 | Weaver | May 2003 | A1 |
20030087513 | Noguchi et al. | May 2003 | A1 |
20030143423 | McCormick et al. | Jul 2003 | A1 |
20030152803 | Acchione | Aug 2003 | A1 |
20030155151 | Hermanns et al. | Aug 2003 | A1 |
20030155860 | Choi et al. | Aug 2003 | A1 |
20030165696 | Namiki et al. | Sep 2003 | A1 |
20030183915 | Scheifers et al. | Oct 2003 | A1 |
20030184219 | Duggal et al. | Oct 2003 | A1 |
20030192587 | Guzman et al. | Oct 2003 | A1 |
20030193057 | Humbs et al. | Oct 2003 | A1 |
20030193286 | Ottermann et al. | Oct 2003 | A1 |
20030197197 | Brown et al. | Oct 2003 | A1 |
20030203210 | Graff | Oct 2003 | A1 |
20030207500 | Pichler et al. | Nov 2003 | A1 |
20030214612 | Freeman | Nov 2003 | A1 |
20030219632 | Schaepkens | Nov 2003 | A1 |
20030234180 | Shimizu et al. | Dec 2003 | A1 |
20040019596 | Taylor et al. | Jan 2004 | A1 |
20040021820 | Sobrinho | Feb 2004 | A1 |
20040033379 | Grunlan et al. | Feb 2004 | A1 |
20040046497 | Schaepkens et al. | Mar 2004 | A1 |
20040046500 | Stegamat | Mar 2004 | A1 |
20040051449 | Klausmann et al. | Mar 2004 | A1 |
20040067604 | Ouellet et al. | Apr 2004 | A1 |
20040075382 | Stegamat et al. | Apr 2004 | A1 |
20040092095 | Nguyen et al. | May 2004 | A1 |
20040097005 | Daniels et al. | May 2004 | A1 |
20040100176 | Pichler | May 2004 | A1 |
20040113542 | Hsiao et al. | Jun 2004 | A1 |
20040113543 | Daniels | Jun 2004 | A1 |
20040115361 | Aegerter et al. | Jun 2004 | A1 |
20040119403 | McCormick et al. | Jun 2004 | A1 |
20040121586 | Abell | Jun 2004 | A1 |
20040132606 | Wolf et al. | Jul 2004 | A1 |
20040135268 | Frischknecht | Jul 2004 | A1 |
20040135503 | Handa et al. | Jul 2004 | A1 |
20040140766 | Nilsson et al. | Jul 2004 | A1 |
20040151934 | Schwark et al. | Aug 2004 | A1 |
20040157426 | Ouellet et al. | Aug 2004 | A1 |
20040166239 | Ohkawa et al. | Aug 2004 | A1 |
20040174115 | Czeremuszkin et al. | Sep 2004 | A1 |
20040195960 | Czeremuszkin et al. | Oct 2004 | A1 |
20040195967 | Padiyath et al. | Oct 2004 | A1 |
20040197489 | Heuser et al. | Oct 2004 | A1 |
20040201027 | Ghosh | Oct 2004 | A1 |
20040201348 | Anandan | Oct 2004 | A1 |
20040206953 | Morena et al. | Oct 2004 | A1 |
20040207314 | Aitken et al. | Oct 2004 | A1 |
20040209126 | Ziegler et al. | Oct 2004 | A1 |
20040229051 | Schaepkens et al. | Nov 2004 | A1 |
20040234797 | Schwark et al. | Nov 2004 | A1 |
20040239241 | Wittmann et al. | Dec 2004 | A1 |
20040245531 | Fuii et al. | Dec 2004 | A1 |
20040258893 | Penttinen et al. | Dec 2004 | A1 |
20050012448 | Ke et al. | Jan 2005 | A1 |
20050051763 | Affinito et al. | Mar 2005 | A1 |
20050153069 | Tapphorn et al. | Jul 2005 | A1 |
20050241815 | Caze et al. | Nov 2005 | A1 |
20070252526 | Aitken et al. | Nov 2007 | A1 |
Number | Date | Country |
---|---|---|
2431917 | Jan 1976 | DE |
0225164 | Jun 1987 | EP |
0135924 | Sep 1987 | EP |
0151462 | Aug 1990 | EP |
0288972 | Sep 1993 | EP |
0394519 | Feb 1994 | EP |
0588667 | Mar 1994 | EP |
0638939 | Feb 1995 | EP |
0494594 | Oct 1995 | EP |
0705757 | Apr 1996 | EP |
0744285 | Dec 1999 | EP |
0701897 | Apr 2001 | EP |
1118459 | Jul 2001 | EP |
1207572 | May 2002 | EP |
1278244 | Feb 2003 | EP |
0895013 | Aug 2003 | EP |
0977469 | Sep 2003 | EP |
0726579 | Nov 2003 | EP |
0775328 | Mar 2004 | EP |
1420041 | May 2004 | EP |
1442067 | Aug 2004 | EP |
0787824 | Sep 2004 | EP |
1410902 | Apr 2006 | EP |
1965453 | Sep 2008 | EP |
2004010843 | Jan 2001 | JP |
2003020235 | Jan 2003 | JP |
2003275575 | Sep 2003 | JP |
2004018335 | Jan 2004 | JP |
2005-306010 | Nov 2005 | JP |
WO9322131 | Nov 1993 | WO |
WO9722536 | Jun 1997 | WO |
WO9919229 | Apr 1999 | WO |
WO 0020536 | Apr 2000 | WO |
WO0066794 | Nov 2000 | WO |
WO 0105205 | Jan 2001 | WO |
WO 0165167 | Sep 2001 | WO |
WO 0183067 | Nov 2001 | WO |
WO 0236647 | May 2002 | WO |
WO03-087427 | Oct 2003 | WO |
WO 2004046767 | Jun 2004 | WO |
WO 2004054010 | Jun 2004 | WO |
WO 2004079781 | Sep 2004 | WO |
WO 2004094321 | Nov 2004 | WO |
WO 2004095597 | Nov 2004 | WO |
WO2004105149 | Dec 2004 | WO |
WO 2007021627 | Feb 2007 | WO |
Entry |
---|
PCT International Search Report for International Application No. PCT/US2006/030670 dated Dec. 19, 2006. |
A. Köhler et al., “Fluorescence and Phosphorescence in Organic Materials”, Advanced Engineering Materials, 2002, vol. 4, No. 7, pp. 453-459. |
R.A. Mathies et al., “Optimization of High-Sensitivity Fluorescence Detection”, Anal. Chem., 1990, vol. 62, pp. 1786-1791. |
P.K.H. Ho et al., “All-Polymer Optoelectronic Devices”, Science, vol. 285, Jul. 9, 1999, pp. 233-236. |
H. Aziz et al., “Degradation Mechanism of Small Molecule-Based Organic Light-Emitting Devices”, Science, Mar. 19, 1999, vol. 283, pp. 1900-1902. |
P.E. Burrows et al., “Reliability and degradation of organic light emitting devices”, Appl. Phys. Lett., vol. 65, No. 23, Dec. 5, 1994, pp. 2922-2924. |
P.A. Tick et al., “Optical Waveguides from Low Melting Temperature Glasses with Organic Dyes”, SPIE, vol. 1775, Nonlinear Optical Properties of Organic Materials V, 1992, pp. 391-401. |
Hood Chatham, “Oxygen Diffusion Barrier Properties of Transparent Oxide Coatings on Polymeric Substrates”, Surface and Coatings Technology, vol. 78, 1996, pp. 1-9. |
D.B. Curliss et al., “Cure Reaction Pathways of Bismaleimide Polymers: A Solid-State 13 N NMR Investigation”, Macromolecules, 1998, vol. 31, pp. 6776-6782. |
N. Regnier et al., “Solid-State 13 C-NMR Study on Bismaleimide/Diamine Polymerization: Structure, Control of Particle Size, and Mechanical Properties”, Journal of Applied Polymer Science, vol. 78, 2000, pp. 2379-2388. |
A. Ashok Kumar et al., “Synthesis and Characterization of Siliconized Epoxy-l, 3-bis(maleimido)benzene Intercrosslinked Matrix Materials”, Polymer, vol. 43, 2002, pp. 693-702. |
M. Sava, “Synthesis of Bismaleimides with Ester Units and Their Polymerization with Diamines”, Journal of Applied Polymer Science, vol. 84, 2002, pp. 750-757. |
MIT Internet Class 6.976, Lecture #7, “Special Topics, in Flat Panel Display”, Spring 2001, http://hackman.mit.edu/6976/LHandouts/Lecture%207.pdf. |
A.C. Misra et at, “Synthesis and properties of octafluoro-benzidine bis-maleimide and of it reaction products with fluorinated diamines”, Polymer, 1992, vol. 33, No. 5, pp. 1083-1089. |
A.C. Misra et al., “Synthesis and properties of some new fluorine-containing polyimides”, Polymer, 1992, vol. 33, No. 5, pp. 1078-1082. |
J.E. White et al., “Polymerization of N,N'-bismaleimide- 4,4'-diphenylmethane with arenedithiols. Syntheis of some new polyimidesulphides”, Polymer, 1984, vol. 25, pp. 850-854. |
Gordon Graff et al. “Barrier Layer Technology for Flexible Displays”, Flexable Flat Panel Displays, p. 55-77. |
Kolosov, D. et al., Direct observation of structural changes in organic light emitting devices during degradation, Journal of Applied Physics, 1001, 90(7). |
Liew, F.Y., et al., Investigation of the sites of dark spots in organic light-emitting devices. Applied Physics Letters, 1000, 77(17). |
Forsythe, Eric, W., Operation of Organic-Based Light-Emitting Devices, in Society for Information Device (SID) 40th anniversary Seminar Lecture Notes, vol. 1, Seminar M5, Hynes Convention Center, Boston, MA, May 20 and 24. (1002). |
Nisato, et al “P-88: Thin Film Encapsulation for OLEDs: Evaluation of Multi-layer Barriers using the Ca Test”, SID 03 Digest, pp. 550-553. |
U.S. Appl. No. 11/509,445, filed Aug. 24, 2006 titled “Tin Phosphate Barrier Film, Method, and Apparatus”. |
Young, R., Flat panel display market outlook, From cyclicality to maturity, in NPD Breakfast with the Experts, D. Ross Young-President, ditor. 2006, DisplaySearch, www.displaysearch.com. |
Nisato, G. et al, Evaluating high performance diffusion barriers: the calcium test. In 8th International Display Workshop 2001. Nagoya, Japan. |
Burrows, P.E., et al., Gas Permeation and Lifetime Tests on Polymer-Based Barrier Coatings, in SPIE Annual Meeting. 2000, SPIE. |
Walther et al; “Multilaycr Barrier Coating System Produced by Plasma-Impulse Chemical Vapor Deposition (PICVD)”; Surface and Coatings Technology, vol. 80, pp. 200-202, 1996. |
Giefers, H. et al; (2005), Kinetics of the disproportionation of SnO1 Solid State Ionics 176, pp. 199-207, Elsevier. |
Titova, Z.P. et al; 1964; Journal of Applied Chemistry USSR, 37 (10-12), pp. 2129. |
Number | Date | Country | |
---|---|---|---|
20100193353 A1 | Aug 2010 | US |
Number | Date | Country | |
---|---|---|---|
Parent | 11820855 | Jun 2007 | US |
Child | 12755023 | US |
Number | Date | Country | |
---|---|---|---|
Parent | 11207691 | Aug 2005 | US |
Child | 11820855 | US | |
Parent | 11803512 | May 2007 | US |
Child | 11207691 | US |