Classifications

• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
  • H10K59/80—Constructional details
  • H10K59/87—Passivation; Containers; Encapsulations
  • H10K59/873—Encapsulations
  • H10K59/8731—Encapsulations multilayered coatings having a repetitive structure, e.g. having multiple organic-inorganic bilayers
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
  • H10K30/80—Constructional details
  • H10K30/88—Passivation; Containers; Encapsulations
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K50/00—Organic light-emitting devices
  • H10K50/80—Constructional details
  • H10K50/84—Passivation; Containers; Encapsulations
  • H10K50/844—Encapsulations
  • H10K50/8445—Encapsulations multilayered coatings having a repetitive structure, e.g. having multiple organic-inorganic bilayers
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
  • H10K59/80—Constructional details
  • H10K59/87—Passivation; Containers; Encapsulations
  • H10K59/873—Encapsulations
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E10/00—Energy generation through renewable energy sources
  • Y02E10/50—Photovoltaic [PV] energy
  • Y02E10/549—Organic PV cells

Definitions

• the present invention relates generally to encapsulated devices, and more particularly to barriers for encapsulation, and to methods for making layers for said barriers.
• Many devices are subject to degradation caused by permeation of environmental gases or liquids, such as oxygen and water vapor in the atmosphere or chemicals used in the processing of the electronic product. Some devices are often encapsulated in order to prevent degradation.
• 6,548,912 entitled “Semiconductor Passivation Using Barrier Coatings,” issued April 15, 2003, which is incorporated herein by reference, describes encapsulated microelectronic devices, including integrated circuits, charge coupled devices, light emitting diodes, light emitting polymers, organic light emitting devices, metal sensor pads, micro-disk lasers, electrochromic devices, photochromic devices, microelectromechanical systems, and solar cells.
• One method of making encapsulated devices involves depositing barrier stacks adjacent to one or both sides of the device.
• the barrier stacks typically include at least one barrier layer and at least one decoupling layer. There could be one decoupling layer and one barrier layer, there could be multiple decoupling layers on one side of one or more barrier layers, or there could be one or more decoupling layers on both sides of one or more barrier layers.
• the important feature is that the barrier stack has at least one decoupling layer and at least one barrier layer.
• FIG. 1 One embodiment of an encapsulated display device is shown in Fig. 1.
• the encapsulated display device 100 includes a substrate 105, a display device 110, and a barrier stack 115.
• the barrier stack 115 includes a barrier layer 120 and a decoupling layer 125.
• the barrier stack 115 encapsulates the display device 110, preventing environmental oxygen and water vapor from degrading the display device.
• the barrier layers and decoupling layers in the barrier stack can be made of the same material or of a different material.
• the barrier layers are typically about 100- 1 ,000 A thick, and the decoupling layers are typically about 1,000-10,000 A thick.
• barrier stacks are not limited. The number of barrier stacks needed depends on the level of water vapor and oxygen permeation resistance needed for the particular application. One or two barrier stacks should provide sufficient barrier properties for many applications, while three for four may be sufficient for most. The most stringent applications may require five or more barrier stacks. Another situation in which multiple barrier stacks may be required is where the thickness of the decoupling layer needs to be limited to limit the stress induced by the polymer shrinkage, such as with passive matrix devices.
• the barrier layers can be deposited using a vacuum process, such as sputtering, chemical vapor deposition, plasma enhanced chemical vapor deposition, evaporation, sublimation, electron cyclotron resonance-plasma enhanced vapor deposition (ECR-PECVD), and combinations thereof.
• a vacuum process such as sputtering, chemical vapor deposition, plasma enhanced chemical vapor deposition, evaporation, sublimation, electron cyclotron resonance-plasma enhanced vapor deposition (ECR-PECVD), and combinations thereof.
• Suitable barrier materials include, but are not limited to, metals, metal oxides, metal nitrides, metal carbides, metal oxynitrides, metal oxyborides, and combinations thereof.
• Plasma damage has occurred when a substrate with an environmentally sensitive device on it, such as an OLED, is encapsulated with a multi-layer barrier stack in which a plasma based and/or assisted process is used to deposit a barrier layer or decoupling layer.
• plasma damage has occurred when reactively sputtering a barrier layer of AlO x under conditions suitable for achieving barrier properties, sputtering a barrier layer of AlO x onto the top surface of an environmentally sensitive device, and/or sputtering a barrier layer of AlO x on a vacuum deposited, acrylate based polymeric layer.
• Plasma damage involves a negative impact on the electrical and/or luminescent characteristics of a device resulting from encapsulation. The effects will vary by the type of device, the manufacturer of the device, and the wavelength of the light emitted. It is important to note that plasma damage is dependent on the design of the device to be encapsulated. For example, OLEDs made by some manufacturers show little to no plasma damage, while OLEDs made by other manufacturers show significant plasma damage under -A-
• the decoupling layers can be deposited using a vacuum process, such as flash evaporation with in situ polymerization under vacuum, or plasma deposition and polymerization, or atmospheric processes, such as spin coating, ink jet printing, screen printing, or spraying.
• a vacuum process such as flash evaporation with in situ polymerization under vacuum, or plasma deposition and polymerization, or atmospheric processes, such as spin coating, ink jet printing, screen printing, or spraying.
• Suitable materials for the decoupling layer include, but are not limited to, organic polymers, inorganic polymers, organometallic polymers, hybrid organic/inorganic polymer systems, and silicates.
• U.S. Patent No. 5, 681,666 discusses the importance of the layers of inorganic material being separated by organic material to avoid crack and defect propagation in the inorganic material.
• Treger indicated that cracks, pinholes, or other defects in an inorganic layer tends to be carried into the next inorganic material layer if the next inorganic material layer is deposited directly onto the first layer of inorganic material with no intervening layer of organic material between the two inorganic layers.
• this phenomenon significantly reduces the usefulness of the composite as a moisture barrier, since the defects often propagate through all of the inorganic layers if no organic layer is interposed between them.
• the defects in any particular layer do not tend to propagate into the next layer. This provides a much longer and more tortuous path for the water vapor to go through, even to such an extent that the net result is as though such defects do not exist.
• Graff et al. suggest that lowering the diffusivity and solubility of the polymer layers will improve the barrier performance. This can be accomplished by polymer selection (hydrophobic moieties or organic/inorganic copolymers), physical modifications (such as ion bombardment or crosslinking), or chemical modification (reactive etch or plasma surface treatment). However, they indicate that the range of improvement that is possible with the polymer layer may be insignificant relative to the improvement of the inorganic layer because the effective diffusion of the inorganic layer is at least four orders of magnitude lower than that of the polymer layers.
• the present invention meets this need by providing a method of encapsulating an environmentally sensitive device.
• the method includes providing a substrate; placing at least one environmentally sensitive device adjacent to the substrate; and depositing at least one barrier stack adjacent to the environmentally sensitive device, the at least one barrier stack comprising at least one barrier layer and at least one polymeric decoupling layer, wherein the at least one polymeric decoupling layer comprises a reaction product of at least one polymer precursor comprising at least one reactive functional group bound to a hydrocarbon, and wherein the polymeric decoupling layer has no more than about 8 x 10 20 n/ml of ether linkages, and no more than about 4.0 x 10 21 n/ml side chains.
• the encapsulated display device includes a substrate; at least one environmentally sensitive device adjacent to the substrate; and at least one barrier stack adjacent to the environmentally sensitive device, the at least one barrier stack comprising at least one barrier layer and at least one polymeric decoupling layer, wherein the at least one polymeric decoupling layer is made from at least one polymer precursor, the at least one polymer precursor having a functionalized hydrocarbon backbone, and wherein the polymeric decoupling layer has no more than about 8 x 10 20 n/ml of ether linkages, and no more than about 4.0 x 10 21 n/ml side chains.
• Fig. 1 is a cross-section of a portion of one embodiment of an encapsulated display device.
• Fig. 2 are photographs showing polymer film morphology for different polymer formulations after aging.
• Fig. 3 are photographs showing polymer film discoloration and morphology for different polymer formulations after aging.
• Fig. 4 are photographs showing polymer film morphology for different polymer formulations after aging.
• Fig. 5 are graphs showing interference spectra for different polymer formulations before and after aging.
• Fig.6 are photographs showing calcium tests for different polymer formulations after aging.
• Fig. 7 are photographs showing passive matrix displays for different polymer formulations before and after aging.
• Fig. 8 are photographs showing plasma damage for different polymer formulations after aging.
• Fig. 9 are photographs showing plasma damage for different polymer formulations before and after aging.
• Fig. 10 are photographs showing the electroluminescence and photoluminescence of encapsulated and unencapsulated devices before and after aging.
• Fig. 11 are photographs showing shrinkage for different polymer formulations before and after aging.
• Fig. 12 is a graph of deposition efficiency v. substrate temperature.
• Fig. 13 is a graph showing starting pixel area after encapsulation for different formulations.
• Fig. 14 is a graph showing the shrinkage of the polymer layer as a function of the thickness of the polymer layer for different formulations.
• Fig. 15A is a top plan view of a passive matrix device
• Figs. 15B and 15C are cross-sections of the passive matrix device of Fig. 15A along lines 15B-15B and 15C-15C
• Fig. 16 are photographs showing mechanical damage to the device of Fig. 1OF.
• a number of properties of the polymer films have a significant effect on the performance of the barrier stack as a whole. These properties include polymer film morphology, polymer composition, plasma damage, and mechanical stress induced by polymerization. Some of these properties can be affected by changes to the monomer composition as well as by processing parameters.
• Polymer morphology is a function of the monomer composition and the degree of cure of the polymer.
• the effect of polymer composition on barrier failure depends on monomer composition, layer thickness, and degree of curing.
• Plasma damage is a function of monomer blend composition, monomer structure, degree of cure, and monomer purity (e.g., residual alcohols, acrylic/methacrylic acid, cyclic ether byproducts, and other potential byproducts, etc.)
• the mechanical stress induced by polymerization depends on monomer composition, monomer molecular weight, polymer Tg, layer thickness, and degree of cure. This understanding led to a set of design rules for the formulation of the polymer layer in the barrier stack.
• the polymer layer should have low solubility of the undesirable permeating species within the layer.
• the most important permeating species for environmentally sensitive display devices is water. However, other species might also be important in some circumstances.
• a species which is soluble in a layer will seek to achieve an equilibrium solution/saturation of the layer, which means there is a driving force for the species to enter the layer. This can lead to a weakening and/or reorganization of the structure of the polymeric layer, causing adhesion failures and may, in severe cases, result in swelling (a dimensional change) that induces catastrophic interlayer separations or damage to the barrier layer.
• the undesirable species should have low diffusivity through the polymer layer.
• the polarity or non-polarity of the permeating species, the size of the permeating species, the polarity or non-polarity of the polymeric layer and its conformation (3D dimensions), the packing density of the chains within the polymeric layer, H-bonding, etc. all come into play because a permeating species can interact with the medium it is permeating, and the interaction can impact the rate of permeation. Non-interaction through an open network will obviously result in the highest rates of diffusion. Thus, it is not sufficient for a polymeric layer just to be hydrophobic in order for it to be a good choice for a layer to be a moisture barrier.
• the polymer can be hydrophobic and non-interactive with a water molecule, but if it also has an open structure with widely spaced chains, the water can move through the layer and not be slowed by any interaction with sites on the polymer chains.
• the concentration of water vapor/water molecules will not be high, but the residence time will be short and so a large amount can move through the layer in relatively short periods of time.
• the polymer layer should have resistance to damage when exposed to plasma. Actual experience with the phenomena involves exposure to plasma during reactive sputtering of aluminum oxide using conditions that produce a thin, dense layer that has barrier properties. However, plasma exposure damage to a polymer layer is assumed to be a more general phenomena and may include exposure to plasma used for surface treatments (adhesion promotion, etc.). Finally, the polymer layer should demonstrate low mechanical stress transmitted by the polymeric layer to adjacent surfaces (i.e., low shrinkage). The significant issue is shrinkage/contraction during cure of a precursor blend, but casting from a solvent solution
• the formulations should be designed to have a reduced number of polar regions (e.g., ether linkages), thereby improving the resistance of the resulting film to water.
• polar regions e.g., ether linkages
• Polymer films made from such formulations demonstrate a significant increase in structural stability (i.e., do not swell or significantly change their structural morphology) upon exposure to water.
• An example of these types of materials are those with saturated hydrocarbon backbones.
• the formulations should also be selected to have a high packing density in the resulting film to reduce the migration of moisture though the polymer film.
• Packing density can be controlled by changing the structure of the monomers. For high packing density, materials without branching should be used, as well as materials with minimal branching such as the polybutadiene dimethacrylate.
• One example of low packing density monomers would be those with methyl branches on the backbone. Others include caged materials such as isobornyl acrylate/methacrylate, tricyclodecane dimethanol diacrylate and the norbornene based polymers. Packing density can also be controlled by the number of cross linking site in the system.
• Packing density can also be controlled by changing the UV dose used for curing. Undercured polymer will swell more. These issues are discussed in more detail below.
• the formulations should be designed to have a reduced number of regions that have weaker bond energies than a typical c-c covalent bond (e.g., ether linkages, ester bonds, C-S bonds), thereby improving the resistance of the resulting film to a plasma. Beyond reducing these moieties in the monomer backbone, it can also be advantageous to limit the number of esters moieties in the resulting polymer.
• a typical c-c covalent bond e.g., ether linkages, ester bonds, C-S bonds
• N/(N C -N O ) ratio (where N is the total number of atoms in the monomer unit, N 0 represent the number of oxygen atoms on a monomer unit, and N c is the number of carbon atoms).
• This ratio is termed the Ohnishi parameter in the literature. Ghoken et al., Dry Etch Resistance of Organic Materials, J. Electrochem. Soc; SOLID-STATE SCIENCE AND TECHNOLOGY Vol. 130, No.1 January 1983), which is incorporated herein by reference.
• the formulations should be designed to have reduced cure induced shrinkage stress.
• the materials should have a bulk shrinkage of less than about 15% by volume, less than about 10% by volume, or less than about 5% by volume for multilayer stacks where the polymer layers have thickness in the range of about 1,000 to about 10,000 A.
• shrinkage may not be an issue, but the materials/structure for the OLED maybe very sensitive to the products generated from plasma damage to the poly layer. In that case, the emphasis would be placed on using materials with better plasma damage resistance and not focus as much on the shrinkage.
• the device may not be as sensitive to water, but may be sensitive to shrinkage and plasma damage, and materials would be selected that address those issues.
• Stacks can also be built using multiple types of formulations to address various device issues. For instance, the polymer layer close to the device may have very low shrinkage to protect the device structure but poor moisture resistance, while the rest of the polymer layers in the barrier stack have higher shrinkage but much better moisture resistance. Examples illustrating these design rules follow. Although most, but not all, of the examples relate to acrylate and methacrylate chemistry deposited by vacuum evaporation, the design rules indicate that other types of polymer chemistries could be used.
• Examples of other polymer chemistries that could be used in vacuum evaporation processes include, but are not limited to: urethanes; cationic polymers; acrylate oligomers; thiol-ene systems (step growth polymerization mechanism); thiol-acrylate systems (step growth polymerization mechanism); and epoxide (ring opening) monomers/oligomers.
• U.S. Patent No. 6,506,461 describes flash evaporation and polymerization of urethanes and various reactive groups which can be used as polymer precursors.
• U.S. Patent No. 6,498,595 describes a cationic polymerization approach and various reactive groups which can be used as polymer precursors.
• Alternative deposition techniques can be used to form the polymer layer, including, but not limited to, inkjet, screen printing, spin coating, blade coating, etc.
• Alternative deposition technologies allow chemistries to be used that may not be compatible with vacuum evaporation processes. Examples of these polymer chemistries include, but are not limited to: acrylate and methacrylate oligomer based systems; acrylate monomers with a large molecular weight mismatch, e.g., isobornyl acrylate and ethoxylated (3) trimethylolpropane triacrylate; acrylate oligomers such as polybutadiene diacrylate; thiol-ene systems (step growth polymerization mechanism); thiol-acrylate systems (step growth polymerization mechanism); polymers in solution with a solvent, such as isobornyl based polymers, polybutadiene, etc.; and epoxide (ring opening) monomers/oligomers.
• the polymer film morphology This can be evaluated by aging samples and observing the film for morphology changes, discoloration, and/or spectral shift of transmitted light through a multilayer stack that includes the polymer layers, which are indicators of structural changes in the polymer layer. These changes can have several negative effects on the performance of the barrier stack. Structural changes can damage the integrity of thin barrier layers (e.g., barrier layers less than 100 nm). They can also cause a decrease in the adhesion between layers. In addition, they can alter the optical properties of the barrier stack (e.g., they can lead to a shift in the transmission maxima and minima). This would be particularly important for applications in which the light is emitted through the barrier layer, such as encapsulated top or bottom emitting devices on flexible substrates).
• Polymer films were made using different blends of acrylate monomers.
• the formulations are shown in Table 1.
• Polymer layers made using tripropyleneglycol diacrylate have been described in, for example, "Plasma treatment of PET and acrylic coating surfaces - I. In-situ XPS measurements," Shi, et al., J. Adhesion Sci. Technol., Vol. 14, No. 12, pp 1485- 1498 (2000), which is incorporated herein by reference.
• Formulation 1 which incorporates tripropyleneglycol diacrylate, has been used as a basis for comparison for the other formulations.
• Fig. 2A shows the formation of bumps in the polymer layer of formulation 1.
• Formulation 4 has very few bumps in the film, as shown in Fig. 2B.
• Formulation 1 showed discoloration (Fig. 3A) and surface morphologies (Fig 3B), while formulation 2 did not (Figs. 3C and 3D).
• Fig. 4A shows an image (5Ox magnification) of the surface of a stack made with
• Fig. 4C is a portion of Fig. 4B at a magnification of 20Ox, and it shows that the bumps are formed in different planes within the polymer layer. The formation of the bumps in deeper polymer layers produced by later diffusion of moisture may lead to the loss of adhesion between polymer and oxide layers and/or the introduction of defects in the oxide layers.
• Spectral shift is a change in the interference spectra peak maxima position of more than 5 nm after aging more than 200 hr at 60 0 C and 90% RH for transmitted light through the multilayer stack.
• Formulation 6 contains an esterdiol diacrylate (SR606A available from Sartomer Co. Inc., Exton PA).
• Formulation 3 showed no spectral shift, as shown in Fig. 5B.
• Figs. 5C and 5D show the spectral shift for formulations 1 and 2 after 400 hr aging.
• Formulation 1 shows a spectral shift of 15 nm, while formulation 2 shows no spectral shift.
• Curing conditions can affect the morphology of the polymer.
• Polymer films were cured with different doses, described in the table and aged for more than 300 hr at 60 0 C and 90% RH. The results are shown in Table 2.
• Formulation 1 has a higher spectral shift at all cure levels than formulation 2 does.
• the main component in formulation 1 is tripropyleneglycol diacrylate which has two ether linkages in the backbone, making it a hydrophilic polymer, as well as two methyl groups.
• the hydrophilic polymer reacts with the moisture.
• the main components in formulation 2 are aliphatic hydrocarbons (no ether linkages), making it a hydrophobic polymer, with no methyl groups. The hydrophobic polymer does not react with moisture.
• Example 2 The change in transmission of Ca coupons on glass substrates encapsulated with a multilayer barrier is a good vehicle to test the effectiveness of barrier structures.
• the multilayer structure was constituted by an oxide layer 100 nm thick and 6 polymer/oxide pairs [polymer (0.5 ⁇ m) /oxide (40 nm)].
• Encapsulated Ca coupons were aged for 400 hr at 60 0 C and 90% RH.
• Fig. 6A shows that formulation 4 (5.5 x
• FIG. 6B shows that formulation 1 (3.6 x 10 21 n/ml of ether linkages) has increased transmission at the edges of the calcium area.
• Fig.6C the entire calcium area is fading, indicating extreme barrier failure for formulation 5 (3.2 x 10 21 n/ml of ether linkages).
• Fig. 6D shows a Ca coupon with a multilayer structure constituted by an oxide layer 100 nm thick and only 3 polymer/oxide pairs (polymer (0.7 ⁇ m) /oxide (40 nm)). The polymer layer was made with
• Formulation 7 in Table 1 The formulation is based on polybutadiene dimethacrylate (PBDM) and was deposited by spin-on coating. The sample was aged for 500 hr at 60 0 C and 90% RH.
• PBDM polybutadiene dimethacrylate
• Fig. 6D shows that formulation 7 (0 n/ml of ether linkages) has no increased transmission, and thus, no barrier failure.
• Fig. 7A shows a passive matrix display before aging.
• Fig. 7B shows a display with formulation 1 after 650 hr at 60 0 C and 90% RH.
• Fig. 7C shows a display with formulation 2 after 650 hr at 6O 0 C and 90% RH. Formulation 2 shows much less degradation than formulation 1.
• Another factor that should be considered in selecting a polymer is plasma damage to the polymer layer.
• FIG. 8A shows severe bubbling after exposure to UV/ozone for 15 min for a barrier stack made with formulation 1 (3.6 x 10 21 n/ml of ether linkages; 4.7 - Ohnishi parameter), while there were only two bubbles for the barrier stack made with formulation 2 (0 n/ml of ether linkages; 3.6 Ohnishi parameter), as shown in Fig. 8B.
• Figs. 8C and 8D show that for the barrier stack made with formulation 7 (0 n/ml of ether linkages; 2.6 - Ohnishi parameter) based on PBDM, no bubbles appeared following UV/ozone exposure in the same conditions described above. In this case, the polymer layers were deposited by a spin-on process.
• Plasma damage can also be assessed using OLED test pixels.
• Black spots which are microscopic non-emitting areas, form by diffusion of reactive species produced by plasma damage.
• Barrier stacks were formed on OLED test pixels using various polymer formulations.
• Fig. 9 A shows formulation 1 (3.6 x 10 21 n/ml of ether linkages; 4.7 - Ohnishi parameter) after coating
• Fig. 9B shows the appearance of black spots after storage
• Fig. 9C shows formulation 4 (5. x 10 20 of ether linkages; 4.2 - Ohnishi parameter) after coating
• Fig. 9D shows that no black spots appeared after storage.
• Polymeric decoupling layers can be formed from blends of one or more reactive precursors. These will have one or more reactive groups per unit (molecule) that undergo a linking/cross-linking reaction.
• the reactive groups born by all members of the blend may be the same (e.g., acrylic, methacrylic and vinyl), which self react and/or undergo addition reactions to form chains (e.g. polymethylmethacrylate or polyvinyl acetate).
• a distinction of this approach is that monofunctional precursors (those bearing one reactive group) will form an extended chain via addition, but crosslinking between chains and branching will be minor to absent.
• the reactive groups can also be different (isocyanate mixed with hydroxy, isocyanate mixed with amino, or epoxy mixed with amino), which co-react to form crosslinks between the precursors.
• isocyanate mixed with hydroxy, isocyanate mixed with amino, or epoxy mixed with amino which co-react to form crosslinks between the precursors.
• a distinction here is that formation of polymers requires that each species of reactant bear at least two functional groups; monofunctional versions of either will act as blocks/chain terminators.
• One or more precursors is preferably a hydrocarbon that is typically linear or cyclic. These may be further characterized as saturated, e.g., functionalized linear dodecanes or tricyclodecanes. By saturated, we mean that the hydrocarbon does not include any double or triple bonds. Alternatively, they may be unsaturated, with one or more double (or triple) bonds, e.g., functionalized polybutadienes, or they may be based on aromatics, e.g., functionalized diphenylmethanes. Further, the hydrocarbon is characterized by a limited presence of side chains and pendent, activated methyl groups.
• Another consideration in selecting the precursor blend is to avoid structures based on, or that include, polyethers (carbon - oxygen - carbon linkages, e.g., polyethylene glycol and polypropylene glycol) essentially as the structure bearing the reactive group, or as a portion of a larger structure that may include a hydrocarbon.
• polyethers carbon - oxygen - carbon linkages, e.g., polyethylene glycol and polypropylene glycol
• the latter versions are commonly referred to as ethoxylated or propoxylated versions of the parent hydrocarbon.
• Still another factor that should be considered in selecting a polymer is the mechanical stress induced by polymerization.
• the shrinkage that occurs during the cure of the monomer through the formation of covalent bonds can lead to mechanical and/or structural damage. This has been demonstrated in a photoluminescence study of passive matrix OLED devices.
• the light emitting polymers emit light when stimulated by light (photoluminescence (PL)) or electricity (electroluminescence (EL)).
• a structure emitting light by EL is the basic foundation of OLED devices. Comparing the PL and EL images of a given OLED device shows which areas of the polymer have been degraded and have lost the characteristics that allow them to emit light vs. those that have lost electrical contact.
• Figs. 1 OA- 1 OC show the EL, PL and EL + PL images of a device encapsulated with a high shrinkage process and material (formulation 1).
• a sketch of a passive matrix (PM) device is shown in Fig. 15A-C.
• a glass substrate 205 is covered with a layer of indium tin oxide (ITO) 210.
• ITO indium tin oxide
• the ITO layer 210 is removed from portions of the device.
• ITO layer 210 is removed from portions of the device.
• PLED/PDOT polymer light-emitting diode/polyetliylenedioxythiophene
• the aluminum cathode layer 220 is over the PLED/PDOT layer 215.
• cathode separators 225 which separate the aluminum cathode layer 220.
• the sample was not exposed to moisture after encapsulation or before testing (there was exposure to moisture during shipping before coating).
• the so called “black spots” localized areas where the contact was deteriorated by chemical reaction with a reactive species (mostly water, oxygen, or other species containing oxygen (e.g., CO 2 )) were present before coating and originate from moisture exposure during shipping.
• the EL luminescence image 1OA shows that only a thin central area of the almost square pixels emits light when stimulated by current.
• the thin strip is decorated by the black spots created during shipping.
• Fig. 1 OB shows the PL image of the same area. In this picture, the full area of the pixels emits light.
• FIG. 1OC is an image taken with the two simultaneous stimulations (current and light) and allows an easier comparison of the different features.
• Figure 1 OD shows the PL image of the uniform degradation of a metal canned device at end of life time (EOL). This degradation is due to the loss of efficiency of the light emitting polymer.
• Figs. 1 OE- 1 OH show an unencapsulated device.
• the displays were encapsulated with the same multilayer structure (100 nm oxide/6 polymer/oxide pairs (0.5 ⁇ m polymer/40 nm oxide), and using the same UV conditions (30% UV setting (30 mW/cm 2 , 30 cm/min track speed) (Fusion Systems 10 inch irradiator with an H-type bulb)) for curing the polymer layers.
• TMPTA trimethylolpropane triacrylate
• the stress induced by the polymer shrinkage may be controlled by choosing appropriate curing conditions in order to reduce the conversion of the monomer units and therefore reduce shrinkage.
• This is shown in Fig. 13 for displays coated with Formulation 2.
• the normalized illuminated area of the pixels measured immediately after coating is close to 1 for curing condition 30% UV setting (30 mW/cm 2 , 30 cm/min track speed), about 0.85 when cured at 60% UV setting (100 mW/cm 2 , 75 cm/min track speed) and 0.8 when cured at 90% UV setting (200 mW/cm 2 , 75 cm/min track speed).
• the multilayer structure was 100 nm oxide/6 polymer/oxide pairs (0.5 ⁇ m polymer/40 nm oxide).
• the stress induced by the monomer polymerization depends also on the thickness of the polymer layers used in the structure. This is shown in Fig. 14 where the shrinkage after aging 250 hr at 85 0 C is shown as a function of the thickness of polymer used in the multilayer structure.
• the illuminated area left is about 70% of the initial value. It decreases to 40 % when the polymer thickness increases to 2.2 ⁇ m per layer (only 4 polymer layers in the multilayer structure were used in this case).
• the area left for displays coated with Formulation 1 (bulk shrinkage of 16.0) (all other variables remaining constant) is also shown. In this case, the illuminated area is only 35% for polymer layers 0.5 ⁇ m thick.
• the stress induced by the polymer layers used in multilayer encapsulation to the OLED devices should not increase due to later process steps involving higher temperature or during aging upon accelerated testing conditions or operation.
• High temperature is defined in this context as 80 0 C ⁇ T ⁇ 100 0 C, conditions compatible with the materials used in the fabrication of OLED devices.
• stress may build up at higher temperature if the Tg of the formulation used in multilayer encapsulation is lower than 85 0 C, a typical temperature used for accelerated lifetime testing.
• Tg of the formulation used in multilayer encapsulation is lower than 85 0 C, a typical temperature used for accelerated lifetime testing.
• further conversion reaction may occur due to increased chain mobility for formulations which are not completely cured. As a consequence, the induced stress increases, and therefore the illuminated area may decrease.
• Figs. HA and HB show formulation 1 after coating. The non-uniform light distribution is visible.
• Fig. HB shows substantial shrinkage after aging 100 hr at 85 0 C in nitrogen.
• Figs. HC and 11D show formulation 2 after coating.
• Fig. 11D shows that formulation 2 has significantly reduced shrinkage after aging 100 hr at 85°C compared to formulation 1. Because the samples were aged in nitrogen, the shrinkage is not due to moisture. The large difference in shrinkage is due to continued reaction of the polymer. When formulation 1 is aged at 85°C, it is closer to the T g (62 0 C) of the polymer. The polymer continues to crosslink, and as a result shrinks more. With formulation 2 (Tg of 107 0 C), some reaction occurs, but it is about one half as much as with formulation 1.
• the polymer layer can be deposited using a variety of approaches including vacuum processes and atmospheric processes.
• Vacuum based approaches offer an advantage in that the processes are run in an environment essentially free of moisture, oxygen and other environmental contaminants, and are conveniently combined with vacuum based approaches for OLED deposition used for similar reasons.
• Atmospheric processes involve deposition at atmospheric pressures, but they can employ non-reactive, anhydrous gas (or mixed gases), rather than an ambient atmosphere.
• Vacuum based approaches are disclosed by U.S. Patent Nos. 4,842,893, 4,954,371, and 5,032,461, and they are particularly suited for the application of acrylate functional precursor blends.
• This approach utilizes a precursor deposition station (to supply the acrylate blend) combined with a curing station downstream to cure the deposited blend, and a central process drum that enables thermal control (chilling) of the substrate upon which the deposited blend condenses.
• the deposition station and curing unit are placed adjacent to a station configured to deposit an inorganic layer, such as a metal, an oxide, a nitride, or any of a wide range of other inorganic compounds.
• the inorganic layer can be deposited using thermal evaporation, sputtering, or another suitable process.
• the process allows for deposition and cure of the acrylate blend prior to deposition of an overlying inorganic layer, or deposition of an inorganic layer followed by deposition and cure of an acrylate layer.
• Multiple precursor deposition and curing station pairs and inorganic deposition stations can be used to enable single pass, multilayer stacks.
• the approach is well suited for depositing acrylate functional blends onto web substrates (substrates supplied in roll form) in a vacuum environment. While the approach has developed in detail for acrylate functional precursor blends cured by UV or EB exposure, it is applicable to other chemistries.
• U.S. Patent No. 6,498,595 describes a cationic polymerization approach and uses reactive groups in addition to acrylates as precursors.
• U.S. Application SerialNos. 10/412,133, entitled Apparatus for Depositing a Multilayer Coating on Discrete Sheets, filed April 11, 2003, (VIT-0018 PA) and 11/112,880, entitled Apparatus for Depositing a Multilayer Coating on Discrete Sheets, filed April 22, 2005, (VIT-OO 18 IA) disclose vacuum based approaches using linear and hybrid apparatus combining cluster and linear elements.
• An important feature of these processes is the replacement of a central process drum with a conveying means and/or robotic arms to transport and position sheet substrates. The absence of the central process drum and the process temperature control (thermal management) it enables becomes an important consideration.
• Coating discrete sheets imposes conditions which do not exist for coating continuous webs.
• coating discrete sheets is a start/stop process requiring multiple starts and stops of the precursor feed to the coating chamber. It also requires conveying apparatus and often masking apparatus to limit the coating deposition to the areas in which a coating application is desired.
• the substrate to be coated cannot conveniently be placed in contact with a heat sink, or other thermal regulation equipment, as can be done with web coating by placing the web in contact with a temperature controlled process drum.
• condensation on discrete sheet substrates takes place at higher temperatures than on continuous webs, and continuing deposition of subsequent coatings results in a general rise in the substrate temperatures.
• Deposition efficiency is a characterization of the rate of condensation of a blend of precursors (monomers) on a substrate under a given set of conditions, and how the condensation rate will vary in response to changes in conditions.
• Deposition efficiency is determined by the following formula:
• Monomer flow (ml/min) The thickness of the polymer layer was measured (an n&k Analyzer 1512RT reflectometer available from n&k Technology, Inc. of Santa Clara CA was used, and the measurement was in angstroms). For each sample used in generating the efficiency curve as a function of temperature, the speed of the discrete sheet through the processing chamber and the monomer flow rate were measured, and the deposition efficiency was calculated at the measured substrate temperature.
• the substrates were pre-heated by passing them over the UV curing source prior to monomer deposition.
• the substrate temperature was measured by a thermocouple attached to the deposition surface on the glass plate used as a substrate.
• the substrate temperature during deposition is taken to be the temperature at the bottom of the step in the profile as the thermocouple passed over the monomer slit.
• the deposited polymer thickness varies most strongly with substrate temperature and monomer flux at the substrate surface. Increasing the substrate temperature decreases the deposited thickness. This is believed to be due the reduced sticking coefficient and the increased re-evaporation rate. Increasing the monomer flow to the evaporator increases the vapor pressure of the monomer at the surface which increases the flux impinging on the substrate.
• the deposition efficiency was found to increase with a decrease in substrate temperature.
• one way to improve the deposition efficiency is to decrease the substrate temperature.
• Deposition efficiency is important for processes involving condensation of a vapor, such as a vacuum flash evaporation process, onto discrete sheets. It becomes another consideration in selecting the precursor blend when the polymer layer is deposited using processes in which a vapor is condensed on discrete sheets.
• the deposition efficiency of a precursor blend is in part dependent on the average molecular weight of the blend.
• the precursor blend should generally have an average molecular weight of at least about 275, or at least about 300, or about 275 to about 350, or about 275 to about 325. (As used herein, average molecular weight refers to weight average molecular weight.) Although blends can be used which have lower average molecular weights, polymeric decoupling layers made from such blends may have one or more undesirable characteristics.
• the precursor blend can have a deposition efficiency of at least about 250, or at least about 275, or at least about 300, or at least about 325, or at least about 350, or at least about 375, or at least about 400.
• Deposition efficiency is a function of the molecular weights of the components of the blend, and to a lesser extent, structural considerations that impact volatility. Selecting a precursor blend having a deposition efficiency of at least about 250 provides a polymeric decoupling layer having the stoichiometry of the starting precursor blend, and the precursor blend will condense to form liquid coatings via process conditions obtainable using available encapsulating apparatus.
• the polymeric decoupling layers may have one or more undesirable characteristics.
• a decision can be made to use such blends. The compromise will be adjustment of the overall process parameters, such as speed, dwell time in coating stations, and cleaning requirements, to accommodate the less efficient blend.
• Formulation 1 which had an average molecular weight of 316 and a deposition efficiency of 370, showed low shrinkage and resistance to plasma damage.
• TMPTA is a desirable trifunctional acrylate based on its hydrocarbon backbone, but it is a small molecule known for shrinkage during cure. Therefore, it should be used at a low level.
• Formulation 2 which had an average molecular weight of 300 and a deposition efficiency of 209, which can be used satisfactorily in thin film applications, showed undesirable shrinkage and plasma damage when used for encapsulation (at least with some types of OLEDs). This shows the desirability of avoiding polar backbone precursors and having higher Mw.
• Formulation 3 shows the use of apolycyclic hydrocarbon backbone diacrylate in place of TPGDA, compounds which have similar molecular weights.
• the precursor blend had a similar deposition efficiency (232 v. 209).
• This formulation shows that cyclic or polycyclic hydrocarbon backbone precursors can be used in place of polar backbone precursors to provide blends with similar deposition efficiencies when the resultant average molecular weights are similar.
• Formulation 4 is based on HDODA, a lower molecular weight hydrocarbon backbone diacrylate.
• the polymeric decoupling layer is resistant to plasma damage, but it has poor deposition efficiency corresponding to its lower average molecular weight. It also resulted in poor barrier performance.
• Triethoxy trimethylolpropane triacrylate was used to reduce shrinkage, but its use also results in the introduction of polar ethylene oxide units that increase water vapor permeability. This shows the desirability of avoiding polar backbone precursors.
• Formulation 5 is based on triethoxy trimethylolpropane triacrylate, and has a deposition efficiency of 338 and an average molecular weight of 413. It is included to provide insight into the relationship between deposition efficiency and precursor blends with higher molecular weights. It is essentially a single monomer combined with a photoinitiator, so it is not an ideal comparison with the other formulations because it does not directly address the situation in which the high average molecular weight results from a blend of predominantly lower molecular weight precursors with a much higher molecular weight precursor. However, any differences are not believed to be significant.
• a suitable polymer precursor blend for encapsulation which provides low shrinkage and adequate resistance to plasma damage, includes about 60 to about 90 wt% of a dimethacrylate, such as dodecanediol dimethacrylate, typically about 65 to about 75 wt %. It can include 0 to about 20 wt% of a monoacrylate, such as lauryl acrylate, typically about 10 to about 20 wt %. It can include 0 to about 20 wt% of a triacrylate, such as trimethylolpropane triacrylate, typically about 5 to about 15 wt%. It can also include about 1 to about 10 wt% of a photoinitiator, typically about 1 to about 3 wt %.
• a dimethacrylate such as dodecanediol dimethacrylate
• a monoacrylate such as lauryl acrylate
• triacrylate such as trimethylolpropane triacrylate
• photoinitiator typically about 1
• Suitable photoinitiators are known to those in the art, and include, but are not limited to, diethoxyacetophenone (DEAP) or Esacure TZT (Trimethylbenzophenone based photoinitiator), available from Sartomer.
• DEAP diethoxyacetophenone
• Esacure TZT Trimethylbenzophenone based photoinitiator

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