PREPARATION AND LAYER

Abstract

Described is a flowable preparation for depositing a passivation layer on an organic electronic (OE) device containing an organic layer; the organic layer is selected from an organic semiconductor (OSC) layer and an organic gate insulator (OGI) layer; the preparation comprises a passivating material and a solvent; the solvent includes lactate and/or derivatives thereof. Further described are an OE device and a manufacture method therefor.

Claims

1. A flowable formulation for depositing a passivation layer on an organic electronic (OE) device comprising an organic layer, wherein the organic layer is selected from an organic semiconductor (OSC) layer and an organic gate insulator (OGI) layer, wherein the formulation comprises a passivation material and a solvent; wherein the solvent comprises lactate and/or a derivative thereof.

2. The formulation according to claim 1, wherein the derivative has Hansen solubility parameters that are within 6 MPa.sup.1/2 of those for ethyl lactate.

3. The formulation according to claim 1, wherein the passivation material comprises a cross-linkable composition.

4. The formulation according to claim 3, wherein the cross-linkable composition comprises monomeric, oligomeric and/or polymeric precursors.

5. The formulation according to claim 4, wherein the monomeric, oligomeric and/or polymeric precursors comprise an epoxy group.

6. The formulation according to claim 5, wherein the passivation material comprises at least one of a crosslinking agent, a photoacid generator, a hardener and an antioxidant.

7. The formulation according to claim 4, wherein the monomeric, oligomeric and/or polymeric precursors comprise (alkyl)acrylate repeating units.

8. The formulation according to claim 4, wherein the monomeric, oligomeric and/or polymeric precursors are cross-linkable via a thiol-ene or a thiol (alkyl)acrylate reaction.

9. The formulation according to claim 4, wherein the monomeric, oligomeric and/or polymeric precursors are cross-linkable via a thermal azide alkyne cycloaddition reaction.

10. The formulation according to claim 3, wherein the cross-linkable composition comprises a polyimide.

11. The formulation according to claim 3, wherein the cross-linkable composition comprises a cycloolefinic polymer.

12. The formulation according to claim 3, wherein the cross-linkable composition comprises a substituted poly(vinylphenol) derivative.

13. The formulation according to claim 1, comprising at least one of a crosslinking agent, a photoacid generator, a hardener, an antioxidant, a surfactant and a filler.

14. The formulation according to claim 1, further comprising a cosolvent.

15. A method of fabricating an organic electronic (OE) device comprising an organic layer, wherein the organic layer is selected from an organic semiconductor (OSC) layer and an organic gate insulator (OGI) layer, and wherein the method comprises: providing a passivation layer on at least a part of the organic layer by depositing a formulation according to claim 1 thereon and removing the solvent.

16. An organic electronic (OE) device comprising an organic layer and a passivation layer directly thereon, wherein the organic layer is selected from an organic semiconductor (OSC) layer and an organic gate insulator (OGI) layer, and wherein the passivation layer is made from the formulation according to claim 1.

17. The organic electronic (OE) device according to claim 16, wherein the organic electronic (OE) device is selected from an organic field effect transistor (OFET) device, wherein one of the source or drain electrodes does not completely surround the other.

18. The organic electronic (OE) device according to claim 16, wherein overlap of a gate metal with source and drain electrodes is less than 5 microns.

19. A product comprising an organic electronic (OE) device according to claim 16.

20. A flowable formulation comprising a photopatterning material and a solvent; wherein the solvent comprises lactate and/or a derivative thereof.

Description

BRIEF DESCRIPTION OF DRAWINGS

[0030] To enhance the understanding of the present application, and to show how exemplary embodiments of the same may be brought into effect, referencing to the accompanying drawings will be made, by examples only, in which:

[0031] FIGS. 1A and 1B show schematically a method of fabrication of an OE device using conventional solution processible passivation materials;

[0032] FIGS. 2A to 2C depict schematically a 2D Hansen solubility parameter map of lactate solvents and other solvents;

[0033] FIGS. 3A and 3B show schematically a method of fabrication of an OE device according to an embodiment of aspects of the present application;

[0034] FIG. 4 shows schematically another method of fabrication of an OE device according to an embodiment of aspects of the present application;

[0035] FIGS. 5A to 5F show a series of designs for transistor source-drain electrodes. These include (FIG. 5A) Corbino structure, (FIG. 5B) C-shape, (FIG. 5C) W-shape, (FIG. 5D) linear, (FIG. 5E) linear cross design of source and drain electrodes. In (FIG. 5F), a gate metal layer associated with the source and the drain electrodes is also shown. If the solvent of the passivation layer is selected inappropriately, the conductive channel in OTFT will be sensitive to erosion by the solvent because the edge of the gate metal is very close to the conductive channel. The conductive channel region is not affected by the lactate solvents of the present application, as shown by the electrical results in the section of the examples.

[0036] FIGS. 6A and 6B show the transfer characteristics and the mobility curve data for a linear OE device with W/L of 9800/12 (microns) after deposition of a passivation layer of ethyl lactate and deposition and patterning of a metal interconnection layer. A high on/off ratio and a subthreshold swing as low as 0.3 V/decade can be seen in the transfer curve. FIGS. 6C and 6D show the transmission characteristics and the mobility curve data for the linear OE device, respectively, with W/L of 200/12 (microns) and a subthreshold swing of 1V/decade.

[0037] FIGS. 7A and 7B show the transfer characteristics and the mobility curve data for a linear OE device with W/L of 200/12 (microns) after deposition of the passivation layer from Cyrene and deposition and patterning of a metal interconnection layer, respectively. A low on/off ratio and a subthreshold swing as high as 15 V/decade can be clearly seen in the transfer curve.

DETAILED DESCRIPTION

[0038] Hereinafter, the embodiments of the present application will be described in detail. It should be noted that the embodiments in the present application and the features in the embodiments can be arbitrarily combined with each other without conflict.

[0039] According to the present application, there are provided formulations, methods and organic electronic (OE) device as described above. Other features of the present application will be apparent from the description that follows.

[0040] Throughout this application, the term “comprising” or “comprises” means including the component(s) specified, but not excluding the presence of other components. The term “consisting essentially of” or “consists essentially of” means including the components specified but excluding other components except for materials present as impurities, unavoidable materials present because of the processes used to provide the components, and components added for a purpose other than achieving the technical effect of the present application.

[0041] The term “consisting of” or “consists of” means including the components specified but excluding other components.

[0042] Where appropriate, depending on the context, the use of the term “comprises” or “comprising” may also be taken to include the meanings of “consists essentially of” or “consisting essentially of”, and may also be taken to include the meanings of “consists of” or “consisting of”.

[0043] The optional features set out herein may be used either individually or in combination with each other where appropriate and particularly in the combinations as set out in the appended claims. The optional features for each aspect or exemplary embodiment of the present application, as set out herein are also applicable to all other aspects or exemplary embodiments of the present application, where appropriate. In other words, a skilled person reading this specification should consider the optional features for each aspect or exemplary embodiment of the present application as interchangeable and combinable between different aspects and exemplary embodiments.

[0044] Development of SPPMs is challenged by conflicting requirements, as outlined above.

[0045] The SPPMs and/or formulations should preferably be compatible with (i.e., orthogonal to) organic layers, such as the OSC layers and/or OGI layers, and OE device architectures. However, the organic layers may be soluble in organic solvents, and hence exposure of these organic layers to such solvents should be avoided. In addition, inter-layer adhesion, such as an adhesion between overlapping OSC and/or OGI layers, is important for functioning of OE devices. Since different organic layers, such as the OSC and/or OGI layers, have typically different surface energies, solvents that may not dissolve a particular layer may penetrate via the inter-layer interfaces, and thereby also degrade or destroy functioning of OE devices.

[0046] Furthermore, the SPPMs should preferably provide environmental, physical and/or chemical resistance, for example against materials and conditions applied in the subsequent fabrication steps during OE device manufacture, for example photolithography. Typically, photolithography includes one or more of the following processing steps, which may involve chemical and/or physical exposure of the underlying layer: deposition of photoresist resin, typically in an organic solvent; UV exposure; development of the photoresist, typically using bases; etching of metal, typically using aggressive acid and redox reactions; and/or removal of the photoresist, typically using aggressive organic solvents.

[0047] Hence, the deposited passivation material should preferably be resistant to organic solvents and/or aqueous solutions. However, as a conflicting requirement, deposition of a passivation material generally requires the passivation material to preferably be soluble and/or dispersible in an organic solvent or in an aqueous solution. Thus, the passivation material may be cross-linked after deposition, for example, to meet these conflicting requirements.

[0048] The deposited passivation layer should preferably exhibit at least one of the following properies: mechanical flexibility, good scratch resistance, thermal stability, optical transparency, uniformity, pinhole free, good adhesion to other layers, good barrier properties with respect to water and/or oxygen, non-hygroscopic and good dielectric breakdown strength.

[0049] Formulation

[0050] The first aspect of the present application provides a flowable formulation for depositing a passivation layer on an organic electronic (OE) device comprising an organic layer, wherein the organic layer is selected from an organic semiconductor (OSC) layer and an organic gate insulator (OGI) layer, wherein the formulation comprises a passivation material and a solvent;

[0051] wherein the solvent comprises lactate and/or a derivative thereof.

[0052] One aspect of the present application provides a flowable formulation comprising a passivation material and a solvent;

[0053] wherein the solvent comprises lactate and/or a derivative thereof.

[0054] For example, the flowable formulation according to the first aspect of the present application may also be suitable for providing layers in other devices, such as microelectromechanical systems (MEMs), microfluidic devices and/or conventional (for example, a non-organic thin film transistor (OTFT)) electronics.

[0055] According to an aspect of the present application, there is also provided a flowable formulation comprising a photopatterning material and a solvent;

[0056] wherein the solvent comprises lactate and/or a derivative thereof.

[0057] In this way, direct photopatterning on an organic electronic (OE) device comprising an organic layer, wherein the organic layer is selected from an organic semiconductor (OSC) layer and an organic gate insulator (OGI) layer, may be provided. In this way, RIE etching may be avoided, thereby, for example, reducing the cost and/or complexity of fabrication of OE devices.

[0058] According to an aspect of the present application, there is also provided a flowable formulation comprising a cross-linkable composition and a solvent;

[0059] wherein the solvent comprises lactate and/or a derivative thereof.

[0060] Generally, the flowable formulation may be applied for spin coating and/or printing directly and/or subsequent addition of additional solvents. Generally, flowable formulations, for example, for spin coating, may have dynamic or absolute viscosities in a range from 1 to 10,000 centipoises or more, as known to the person skilled in the art. In one example, a dynamic viscosity of the flowable formulation is in a range from 1 to 10,000 centipoises, preferably 1 to 1,000 centipoises, and more preferably 1 to 20 centipoises. A dynamic viscosity of the flowable formulation may depend, at least in part, on an amount of the solvent in the flowable formulation in such a way that an increased amount of the solvent may decrease the dynamic viscosity.

[0061] In the present application, the lactate and/or derivatives thereof include L-lactate and/or derivatives thereof, or D-lactate and/or derivatives thereof, or a mixture of L-lactate and/or derivatives thereof and D-lactate and/or derivatives thereof, preferably a mixture of L-lactate and/or a derivative thereof and D-lactate and/or a derivative thereof in a ratio of 1:1 (also known as a racemic mixture).

[0062] The inventors have determined that lactate and/or a derivative thereof may substitute for conventional organic solvents, such as cyclopentanone, GBL or PGMEA, for example, in SU-8, as described above in relation to the second passivation layer.

[0063] Surprisingly, the inventors have determined that lactate and/or derivatives thereof may also be orthogonal solvents, unlike the conventional organic solvents, such as cyclopentanone, GBL or PGMEA, as described above.

[0064] Namely, the inventors have determined that lactate and/or a derivative thereof may be used as solvents for solutions containing robust cross-linkable polymers dissolved and/or dispersed therein and that these solutions may be applied, for example, directly, on organic layers, such as on an OSC layer and/or on an OGI layer and/or a stack comprising one or more of these layers.

[0065] Preferably, the formulation may be applied directly on the OGI layer, which may, for example, be part of the stack. Alternatively, the formulation may be preferably applied directly on a protective layer, for example fluoropolymer protection layer, on the OSC layer. Typically, such protection layers are provided on the OSC layer for patterning, such as by dry etching as described previously.

[0066] In this way, only a single passivation layer may be required, in contrast with the conventional double passivation layer, as described above. Namely, the single passivation layer provided by the first formulation replaces the first passivation layer and the second passivation layer, as conventionally provided.

[0067] In this way, OE device fabrication complexity and/or cost may be reduced, since fewer steps and materials are required. Furthermore, since utilization of water-soluble polymers, such as PVA, is avoided, long-term stability of OE devices may be improved.

[0068] In one example, the solvent comprises lactate and/or a derivative thereof in an amount of at least 20%, at least 25%, at least 30%, at least 35%, at least 40%, at least 45%, at least 50%, at least 55%, at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 97.5%, or at least 99%, where the amount of lactate and/or a derivative thereof is a percentage by weight of total amount of solvent in the formulation.

[0069] In one example, the solvent comprises lactate and/or a derivative thereof in an amount of at most 25%, at most 30%, at most 35%, at most 40%, at most 45%, at most 50%, at most 55%, at most 60%, at most 65%, at most 70%, at most 75%, at most 80%, at most 85%, at most 90%, at most 95%, at most 97.5%, at most 99%, or at most 100%, where the amount of lactate and/or a derivative thereof is a percentage by weight of total amount of solvent in the formulation.

[0070] In one example, the solvent comprises a mixture of lactate and/or one or more derivatives thereof.

[0071] In one example, the solvent comprises a cosolvent for example, organic and/or aqueous solvents. Examples of the cosolvents may include cyclopentanone, GBL and PGMEA, propylene carbonate, diethylene glycol, isopropyl alcohol (IPA), 2-propanol and/or ethanol. In one example, the solvent comprises the cosolvent in an amount of at most 50%, at most 45%, at most 40%, at most 35%, at most 30%, at most 25%, at most 20%, at most 15%, at most 10%, at most 5%, at most 2.5%, or at most 1%, where the amount of the cosolvent is a percentage by weight of total amount of solvent in the formulation. In one example, the solvent comprises the cosolvent in an amount of at least 50%, at least 45%, at least 40%, at least 35%, at least 30%, at least 25%, at least 20%, at least 15%, at least 10%, at least 5%, at least 2.5%, or at least 1%, wherein the amount of the cosolvent is a percentage by weight of total amount of solvent in the formulation.

[0072] In one example, the solvent comprises a plurality of cosolvents. In one example, the solvent comprises the plurality of cosolvents in an amount of at most 50%, at most 45%, at most 40%, at most 35%, at most 30%, at most 25%, at most 20%, at most 15%, at most 10%, at most 5%, at most 2.5%, or at most 1%, where the amount of the plurality of cosolvents is a percentage by weight of total amount of solvent in the formulation. In one example, the solvent comprises the plurality of cosolvents in an amount of at least 50%, at least 45%, at least 40%, at least 35%, at least 30%, at least 25%, at least 20%, at least 15%, at least 10%, at least 5%, at least 2.5% or at least 1%, where the amount of the plurality of cosolvents is a percentage by weight of total amount of solvent in the formulation.

[0073] In one example, the formulation comprises the solvent in an amount of at least 20%, at least 25%, at least 30%, at least 35%, at least 40%, at least 45%, at least 50%, at least 55%, at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 97.5%, or at least 99%, where the amount of solvent is a percentage by weight of the formulation.

[0074] In one example, the formulation comprises the solvent in an amount of at most 25%, at most 30%, at most 35%, at most 40%, at most 45%, at most 50%, at most 55%, at most 60%, at most 65%, at most 70%, at most 75%, at most 80%, at most 85%, at most 90%, at most 95%, at most 97.5%, or at most 99%, where the amount of solvent is a percentage by weight of the formulation.

[0075] In one example, the formulation comprises the passivation material in an amount of at least 20%, at least 25%, at least 30%, at least 35%, at least 40%, at least 45%, at least 50%, at least 55%, at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at most 95%, at most 97.5%, or at most 99%, where the amount of passivation material is a percentage by weight of the formulation.

[0076] In one example, the formulation comprises the passivation material in an amount of at most 80%, at most 75%, at most 70%, at most 65%, at most 60%, at most 55%, at most 50%, at most 45%, at most 40%, at most 35%, at most 30%, at most 25%, at most 20%, at most 15%, at most 10%, at most 5%, at most 2.5%, or at most 1%, where the amount of the passivation material is a percentage by weight of the formulation.

[0077] Hansen Solubility Parameters

[0078] Generally, Hansen solubility parameters may be used to characterize polarity of solvents in terms of their dispersion forces δ.sub.d, the degree of polarity that arises from any dipole δ.sub.p, and their capacity for hydrogen bonding δ.sub.h. The solvents may be thus located in Hansen space with a three-dimensional (3D) representation of δ.sub.d, δ.sub.p and δ.sub.h. The closer two solvents are in the Hansen space, the more likely they are to exhibit the same solubilising properties. The Hansen dispersion forces δ.sub.d expressed by solvents may be similar and therefore, for a simpler representation of the Hansen solubility parameters, δ.sub.p may be plotted against δ.sub.h to represent different types of solvents in a two-dimensional (2D) graph.

[0079] In one example, the derivative has Hansen solubility parameters that are within 6 MPa.sup.1/2 of those for ethyl lactate. In one example, the derivative has Hansen solubility parameters that are within 3 MPa.sup.1/2 of those for ethyl lactate. In one example, the derivative has Hansen solubility parameters that are within 1.5 MPa.sup.1/2 of those for ethyl lactate.

[0080] Table 1 details Hansen solubility parameters of various solvents, including ethyl lactate and conventional solvents such as cyclopentanone, GBL and PGMEA, as described above.

TABLE-US-00001 TABLE 1 Hanson solubility parameters of ethyl lactate and conventional solvents cyclopentanone, GBL and PGMEA, as described above, were compiled from HSPiP software, Version 2 (https://www.hansen-solubility.com/). δ.sub.d δ.sub.p δ.sub.h Solvents Mpa.sup.0.5 Mpa.sup.0.5 Mpa.sup.0.5 Butyl lactate 15.8 6.1 16.4 Ethyl lactate 16.0 7.6 12.5 Methyl lactate 17.6 8.59 12.95 2-Ethylhexyl lactate 16.0 2.15 8.27 Cyclopentanone 17.9 11.9 5.2 GBL 18 16.6 7.4 PGMEA 15.6 5.9 9.8 NMP 18.0 12.3 7.2 cyclohexanone 17.8 8.4 5.1 Dimethylformamide (DMF) 17.4 13.7 11.3 Dimethylacetamide (DMAc 16.8 11.5 10.2 or DMA) Dimethyl sulfoxide (DMSO) 18.4 16.4 10.2

[0081] Ethyl Lactate

[0082] While the Hansen solubility parameters may suggest that lactate and/or a derivative thereof may substitute for conventional organic solvents, such as cyclopentanone, GBL or PGMEA, in, for example, SU-8, as described above, the Hansen solubility parameters provide no indication that these conventional solvents may also be orthogonal solvents.

[0083] Surprisingly, as described above, the inventors have determined that lactate and/or a derivative thereof may also be orthogonal solvents, unlike the conventional organic solvents, such as cyclopentanone, GBL or PGMEA, as described above. Namely, lactate and/or a derivative thereof may both substitute for conventional organic solvents, such as cyclopentanone, GBL or PGMEA, in, for example, SU-8, and may be orthogonal solvents, unlike the conventional organic solvents, such as cyclopentanone, GBL or PGMEA.

[0084] FIGS. 2A, 2B and 2C schematically depict 2D Hansen solubility parameter map of lactate and other commonly used solvents, some of which are used for SU8 passivation.

[0085] Cross-Linkable Composition

[0086] In one example, the passivation material comprises a cross-linkable composition. In this way, the passivation material may be dissolved and/or dispersed in the solvent for deposition and subsequently cross-linked after deposition, with the passivation material may be resistant to organic solvents and/or aqueous solutions. Therefore, the passivation material may meet at least some of the conflicting requirements, as described above.

[0087] In one example, the passivation material comprises a cross-linkable composition in an amount of at least 50%, at least 55%, at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 97.5% or at least 99%, wherein the amount of cross-linkable composition is a percentage by weight of the passivation material.

[0088] In one example, the passivation material comprises the cross-linkable composition in an amount of at most 50%, at most 55%, at most 60%, at most 65%, at most 70%, at most 75%, at most 80%, at most 85%, at most 90%, at most 95%, at most 97.5%, at most 99% or at most 99.5%, wherein the amount of cross-linkable composition is a percentage by weight of the passivation material.

[0089] In one example, the cross-linkable composition comprises monomeric, oligomeric and/or polymeric precursors. Examples of cross-linkable compositions comprising monomeric, oligomeric and/or polymeric precursors include monomeric, oligomeric and/or polymeric precursors comprising, for example, cross-linkable epoxy groups, siloxane-organic hybrid frameworks comprising cross-linkable epoxy groups and/or cross-linkable acrylate or (alkyl)acrylate repeat units. Examples of cross-linking initiation include, for example, thermal initiation, photochemical initiation, via free radical reaction, via a thiol-ene or a thiol (alkyl)acrylate reaction, and/or via thermal azide alkyne cycloaddition reaction.

[0090] In one example, the monomeric, oligomeric and/or polymeric precursors comprise epoxy groups, which may be cross-linked.

[0091] A passivation layer may be formed by thermal or photochemical crosslinking of monomeric, oligomeric or polymeric precursors comprising epoxy groups. Typically, the passivation formulation may be coated onto a surface and then subjected to thermal or photochemical crosslinking conditions. An example of a suitable oligomeric precursor comprising epoxy groups is the commercial product EPON™ SU-8 resin (also known as EPIKOTE™ 157) available from Hexion. EPON™ resin SU-8 is a polymeric solid epoxy novolac resin, which possesses an average epoxy group functionality about 8.

[0092] Suitable monomeric, oligomeric or polymeric precursors may also comprise siloxane-organic hybrid frameworks comprising epoxy groups.

[0093] Table 2 details examples of commercially available epoxy siloxane monomeric and oligomeric precursors including products PC-1000, PC-1035, PC-2000, PC-2004, PC-2011, PC-2021 and PC-2026 available from Polyset Inc (Mechanicville, N.Y., USA). Other epoxy siloxane monomeric and oligomeric precursors are known.

TABLE-US-00002 TABLE 2 Epoxy siloxane monomeric and oligomeric precursors commercially available from Polyset Inc. Descriptions Monomer products PC-1000 Bifunctional Epoxy Terminated PC-1035 Bifunctional Epoxy Terminated Oligomer products PC-2000 Multifunctional 20,000 g/mol resin PC-2004 Multifunctional 1,000 g/mol resin PC-2011 Aromatic-Epoxy Copolymer PC-2021 High EEW Copolymer PC-2026 Fluoroalkyl-Epoxy Copolymer

[0094] An example of a crosslinked material prepared from epoxy siloxane precursors is described in J Appl Polymer Sci 2013, 39968, 1-7.

[0095] In one example, the formulation comprises at least one of a cross-linking agent, a photoacid generator, a hardener, an antioxidant, a surfactant and a filler.

[0096] The cross-linkable composition, which, for example, comprises epoxy type monomers, oligomers or polymers, may also comprise crosslinking reagent and/or catalysts. A chemical reaction used, which provides a crosslinked, insoluble layer, may be thermally or photochemically driven. An example of a thermally driven crosslinking reaction of a thin film precursor comprising a polymer substituted with epoxy groups is described in ACS Applied Materials Interfaces 2009, 1, 7, 1585. In that example, methyl tetrahydrophthalic anhydride (MeTHPA) was used as a thermal curing agent and N,N-dimethylbenzylamine (BDMA) as a catalyst to promote thermal curing.

[0097] For photochemically driven crosslinking of thin films comprising precursors, for example functionalized with epoxy groups, the passivation formulation may comprise a photoacid generator (PAG). Generally, PAGs are reagents which generate active acid catalysts on exposure to visible or ultraviolet radiation, typically ultraviolet radiation. Many different types of PAGs are known in the art. Suitable PAGs include materials in Irgacure® series, commercially available from BASF (Germany). PAG reagents may be ionic or non-ionic in nature, and within different PAGs the chemical structures may be designed to operate at different UV wavelengths. PAGs, which are commercially available, are used for operation at I-line (365 nm) and g/h-line (405 nm, 436 nm) UV wavelengths, and are widely used in microelectronics fabrication processes.

[0098] The cross-linkable composition, which, for example, comprises epoxy type monomers, oligomers or polymers as described above, may also comprise a hardener (also known as a hardening reagent or agent) which may be used to adjust the curing time and/or the mechanical properties of the resulting crosslinked passivation layer. Examples of suitable hardeners include the ARON series of oxetane hardeners available from Toagosei (Japan).

[0099] The cross-linkable composition, for example comprising epoxy type monomers, oligomers or polymers as described above, may also comprise an antioxidant. The antioxidant may be used to suppress discoloration (yellowing) in the cross-linkable or crosslinked films, for example due to side reactions with the PAG or its chemical by-products. Examples of suitable antioxidants are described in US 2013/225711 A1.

[0100] In one example, the monomeric, oligomeric and/or polymeric precursors comprise (alkyl)acrylate repeating units, for example acrylate or methacrylate repeating units.

[0101] The crosslinkable monomer, oligomer, or polymer comprising acrylate or methacrylate repeating units, herein described collectively as (alkyl)acrylates, may be highly useful for the formation of crosslinked passivation layers. A wide variety of (alkyl)acrylate thin film coating precursors are commercially available, for example under the SARTOMER brand produced by Arkema (France). It is known in the art that (alkyl)acrylate precursors may be selected and formulated in different proportions to provide different properties in crosslinked thin film coatings.

[0102] The (alkyl)acrylate precursor used to produce crosslinked thin film coatings, such as a passivation layer, may be monofunctional, bifunctional, or multifunctional, and may optionally be substituted with additional non(alkyl)acrylate reactive functional groups, thereby allowing further crosslinking by alternative chemical methods other than those used to polymerize the (alkyl)acrylate groups. Examples of additional non(alkyl)acrylate reactive functional groups described in WO 2013/119717 A1 are epoxy groups, or cinnamylidene groups.

[0103] The crosslinkable (alkyl)acrylate precursors suitable for use in the cross-linkable composition may themselves be oligomeric or polymeric in nature. An example of such a material is SIRIUS-501, a dendritic acrylate produced by Osaka Organic Chemical Industry Ltd (Japan).

[0104] (Alkyl)acrylate precursors suitable for use in thermally or photochemically crosslinkable films, such as passivation layers, may optionally be substituted with partially or fully fluorinated side chains. Thin films comprising polymers prepared from these precursors, and, therefore, bearing such side chain substituents, may have usefully altered properties, such as chemical resistance, hydrophobicity or surface energy.

[0105] Table 3 details a range of fluorinated (alkyl)acrylate precursors commercially available from Sigma Aldrich, a subsidiary of Merck KGaA (Germany). Other fluorinated (alkyl)acrylate precursors are known.

TABLE-US-00003 TABLE 3 Fluorinated (alkyl)acrylate precursors that are commercially available from Sigma Aldrich. Sigma Aldrich Molecular Products # Structures Descriptions Formula 367656 [00001] 1,1,1,3,3,3-Hexafluoroisopropyl acrylate 99% C.sub.6H.sub.4F.sub.6O.sub.2 367664 [00002] 1,1,1,3,3,3-Hexafluoroisopropyl methacrylate 99% C.sub.7H.sub.6F.sub.6O.sub.2 371971 [00003] 2,2,3,4,4,4-Hexafluorobutyl methacrylate 98% C.sub.8H.sub.8F.sub.6O.sub.2 371998 [00004] 2,2,3,3-Tetrafluoropropyl methacrylate 99% C.sub.7H.sub.8F.sub.4O.sub.2 373761 [00005] 2,2,2-Trifluoroethyl methacrylate containing 50-200 ppm MEHQ as inhibitor, 99% C.sub.6H.sub.7F.sub.3O.sub.2 443751 [00006] 2,2,3,3,4,4,4-Heptafluorobutyl acrylate 97% C.sub.7H.sub.5F.sub.7O.sub.2 444006 [00007] 2,2,3,3,4,4,4-Heptafluorobutyl methacrylate 97% C.sub.8H.sub.7F.sub.7O.sub.2 470961 [00008] 2,2,3,3,3-Pentafluoropropyl acrylate 98%, containing 100 ppm 4-tert-butylcatechol as inhibitor C.sub.6H.sub.5F.sub.5O.sub.2 470988 [00009] 2,2,3,3,4,4,5,5-Octafluoropentyl methacrylate, containing 100 ppm MEHQ as inhibitor, 98% C.sub.9H.sub.8F.sub.8O.sub.2 474193 [00010] 2,2,3,3,3-Pentafluoropropyl methacrylate 97%, containing 100 ppm 4-tert-butylcatechol as inhibitor C.sub.7H.sub.7F.sub.5O.sub.2 474215 [00011] 3,3,4,4,5,5,6,6,7,7,8,8,8-Tridecafluorooctyl methacrylate, containing 100 ppm 4-tert-butylcatechol as inhibitor, 97% C.sub.12H.sub.9F.sub.13O.sub.2 474223 [00012] 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-Heptadecafluorodecyl methacrylate containing MEHQ as inhibitor, 97% C.sub.14H.sub.9F.sub.17O.sub.2 474231 [00013] 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-Heneicosafluorododecyl methacrylate 97% C.sub.16H.sub.9F.sub.21O.sub.2 474282 [00014] 4,4,5,5,6,6,7,7,8,9,9,9-Dodecafluoro-2-hydroxy-8-(trifluoromethyl) nonyl methacrylate 97% C.sub.14H.sub.11F.sub.15O.sub.3 474347 [00015] 3,3,4,4,5,5,6,6,7,7,8,8,8-Tridecafluorooctyl acrylate containing inhibitor, 97% C.sub.11H.sub.7F.sub.13O.sub.2 474355 [00016] 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-Heneicosafluorododecyl acrylate 96% C.sub.15H.sub.7F.sub.21O.sub.2 474401 [00017] 2,2,3,3,4,4,5,5-Octafluoropentyl acrylate 97%, containing 100 ppm monomethyl ether hydroquinone as inhibitor C.sub.8H.sub.6F.sub.8O.sub.2 474428 [00018] 2,2,3,34,4,5,5,6,6,7,7-Dodecafluoroheptyl acrylate 95% C.sub.10H.sub.6F.sub.12O.sub.2 474452 [00019] 2,2,3,4,4,4-Hexafluorobutyl acrylate 95% C.sub.7H.sub.6F.sub.6O.sub.2 474487 [00020] 1H,1H,2H,2H-Perfluorodecyl acrylate containing 100 ppm tert-butylcatechol as inhibitor, 97% C.sub.13H.sub.7F.sub.17O.sub.2 733660 [00021] 2-[(1′,1′,1′-Trifluoro-2′-(trifluoromethyl)-2′-hydroxy)propyl]-3-norbornyl methacrylate >97% C.sub.15H.sub.18F.sub.6O.sub.3 733695 [00022] 1,1,1-Trifluoro-2-(trifluoromethyl)-2-hydroxy-4-methyl-5-pentyl methacrylate >97% C.sub.11H.sub.14F.sub.6O.sub.3 [00023]

[0106] Suitable monomeric, oligomeric or polymeric precursors may also comprise siloxane-organic hybrid frameworks comprising (alkyl)acrylate groups. An examples of such hybrid precursor is described in J Sol Gel Sci Technol 2012, 61, 2, 321.

[0107] The cross-linkable composition comprising monomeric, oligomeric or polymeric (alkyl)acrylate precursors may be crosslinked using free radical reactions. The cross-linkable composition used to form crosslinkable films may additionally comprise a free radical initiator. Typically, the free radical initiator is initiated under thermal or photochemical conditions. Many examples of free radical initiators, suitable for thermal or photochemical initiation, are known in the art.

[0108] Table 4 details free radical thermal initiators commercially available from Sigma Aldrich, a subsidiary of Merck KGaA (Germany).

TABLE-US-00004 TABLE 4 Free radical thermal initiators available from Sigma Aldrich. Sigma Aldrich Catalogue Number Free radical thermal initiator 441465 tert-Amyl peroxybenzoate 118168 4,4-Azobis (4-cyanovaleric acid) 380210 1,1′-Azobis (cyclohexanecarbonitrile) 441090 2,2′-Azobisisobutyronitrile (AIBN) 179981 Benzoyl peroxide 441694 2,2-Bis(tert-butylperoxy)butane 388149 1,1-Bis(tert-butylperoxy)cyclohexane 388092 2,5-Bis(tert-butylperoxy)-2,5-dimethylhexane 329533 2,5-Bis(tert-butylperoxy)-2,5-dimethyl-3-hexyne 441716 Bis(1-(tert-butylperoxy)-1-methylethyl)benzene 388084 1,1-Bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane 416665 tert-Butyl hydroperoxide 388076 tert-Butyl peracetate 168521 tert-Butyl peroxide 159042 tert-Butyl peroxybenzoate 441473 tert-Butylperoxy isopropyl carbonate 247502 Cumene hydroperoxide 289086 Cyclohexanone peroxide 329541 Dicumyl peroxide 290785 Lauroyl peroxide 441821 2,4-Pentanedione peroxide 269336 Peracetic acid 216224 Potassium persulfate

[0109] Table 5 details free radical photoinitiators commercially available from Sigma Aldrich, a subsidiary of Merck KGaA (Germany).

TABLE-US-00005 TABLE 5 Free radical photoinitiators available from Sigma Aldrich. Sigma Aldrich Catalogue Number Free radical photoinitiator A1,070-1 Acetophenone, 99% A8,840-9 Anisoin, 95% A9,000-4 Anthraquinone, 97% 12,324-2 Anthraquinone-2-sulfonic acid, sodium salt monohydrate, 97% 11,931-8 (Benzene) tricarbonylchromium, 98% B515-1 Benzil, 98% 39,939-6 Benzoin, sublimated, 99.5+% 17,200-6 Benzoin ethyl ether, 99% 19,578-2 Benzoin isobutyl ether, tech., 90% B870-3 Benzoin methyl ether, 96% B930-0 Benzophenone, 99% 40,562-0 Benzophenone/l-Hydroxycyclohexyl phenyl ketone, 50/50 blend 26,246-3 3,3′,4,4′-Benzophenonetetracarboxylic dianhydride, sublimated, 98% B1,260-1 4-Benzoylbiphenyl, 99% 40,564-7 2-Benzyl-2-(dimethylamino)-4′-morpholinobutyrophenone, 97% 16,032-6 4,4′-Bis(diethylamino)benzophenone, 99+% 14,783-4 4,4′-Bis(dimethylamino)benzophenone, 98% 12,489-3 Camphorquinone, 98% C7,240-4 2-Chlorothioxanthen-9-one, 98% 40,807-7 (Cumene)cyclopentadienyliron (II) hexafluorophosphate, 98% D3,173-7 Dibenzosuberenone, 97% 22,710-2 2,2-Diethoxyacetophenone, 95% D11,050-7 4,4′-Dihydroxybenzophenone, 99% 19,611-8 2,2-dimethoxy-2-phenylacetophenone, 99% 14,934-9 4-(Dimethylamino)benzophenone, 98% 14,670-6 4,4′-Dimethylbenzil, 97% D14,966-7 2,5-Dimethylbenzophenone, tech., 95% D14,967-5 3,4-Dimethylbenzophenone, 99% 40,566-3 Diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide/2- hydroxy-2-methylphenylacetone, 50/50 blend 27,571-9 4′-Ethoxyacetophenone, 98% E1,220-6 2-Ethylanthraquinone, 97+% F40-8 Ferrocene, 98% 32,810-3 3′-Hydroxyacetophenone, 99+% 27,856-4 4′-Hydroxyacetophenone, 99% 22,043-4 3-Hydroxybenzophenone, 99% H2,020-2 4-Hydroxybenzophenone, 98% 40,561-2 1-Hydroxycyclohexyl phenyl ketone, 99% 40,565-5 2-Hydroxy-2-methylpropiophenone, 97% 15,753-8 2-Methylbenzophenone, 98% 19,805-6 3-Methylbenzophenone, 99% M3,050-7 Methybenzoylformate, 98% 40563-9 2-Methyl-4′-(methylthio)-2-morpholinopropiophenone, 98% 15,650-7 Phenanthrenequinone, 99+% 29,074-2 4′-Phenoxyacetophenone, 98% T3,400-2 Thioxanthen-9-one, 98%

[0110] In analogy to PAGs used for epoxy group polymerization, a variety of photochemical free radical initiators are available, allowing the operation of the photochemical crosslinking process at different wavelengths, including i line (365 nm) and g/h line (405 nm, 436 nm).

[0111] Certain types of commercially available photochemical free radical initiators are known as Type II initiators. These photoinitiators typically require the presence of a further reagent, known as co-initiator. Commonly used examples of co-initiators for Type II systems are alcohols or amines.

[0112] In one example, the monomeric, oligomeric and/or polymeric precursors are cross-linkable via thiol-ene or thiol (alkyl)acrylate reaction for example, as described below.

[0113] A further type of a useful chemical reaction, which is suitable for the preparation of crosslinked thin films, such as a passivation layer, is the thiol-ene reaction. The thiol-ene reaction involves the reaction of an unsaturated double bond with a separate precursor bearing a thiol (—SH) group. The unsaturated double bond may be a (alkyl)acrylate, in which case the process may be described as thiol-(alkyl)acrylate reaction. The thiol-ene or thiol-(alkyl)acrylate reaction is typically a radical reaction, which may be initiated thermally or photochemically as described above for polymerization processes using only (alkyl)acrylate precursors.

[0114] A useful property of the thiol-ene or thiol-(alkyl)acrylate reaction, as used in the preparation of crosslinked thin film coatings, such as a passivation layer, is that the reaction process is less sensitive to the inhibition from atmospheric oxygen, allowing the crosslinking process to be carried out in air rather than under an inert gas blanket.

[0115] Suitable precursors for thermal or photochemical crosslinking processes using thiol-ene or thiol-(alkyl)acrylate reactions may be monomeric, oligomeric or polymeric in nature. An example of the use of thiol-ene reaction to provide crosslinked films suitable for use as insulating layers in organic electronic devices is described in Chem Mater 2013, 25, 4806.

[0116] In one example, the monomeric, oligomeric and/or polymeric precursors are cross-linkable via a thermal azide alkyne cycloaddition reaction, for example, as described below.

[0117] An example of cross-linking via a thermal azide alkyne cycloaddition reaction is described in Shengxia Li, Wei Tang, Weimin Zhang, Xiaojun Guo and Qing Zhang, Cross-linked Polymer-Blend Gate Dielectrics through Thermal Click Chemistry, Chem. Eur. J. 2015, 21, 17762-17768 DOI: 10.1002/chem.201502825.

[0118] Another example of cross-linking via a thermal azide alkyne cycloaddition reaction is described in Sheng-Xia Li, Lin-Run Feng, Xiao-Jun Guo, Qing Zhang, Application of thermal azide-alkyne cycloaddition (TAAC) reaction as a low temperature cross-linking method in polymer gate dielectrics for organic field effect transistors, J. Mater. Chem. C, 2014, DOI: 10.1039/C4TC00116H.

[0119] In one example, the cross-linkable composition comprises a polyimide. Typically, polyimides are examples of oligomer precursors.

[0120] Polyimides are useful materials for the formation of protective films. The chemistry and properties of polyimides are usefully reviewed in the Handbook of Polymer Coatings for Electronics: Chemistry, Technology and Applications (2.sup.nd Edition), pages 55-65. Efforts have been made to improve the solubility and solution processability of polyimides, and solvent soluble polyimides are known in the art.

[0121] A suitable class of polyimides for use in the present application is soluble polyimide oligomers. Soluble polyimide oligomers may be further functionalized with suitable groups for thermal or photochemical crosslinking reactions, other than the backbone polyimide functional groups. The polyimide oligomers have good solvent solubility due to their low average molecular weights, and they may be conveniently coated by solution processing methods. The resultant film can then be subjected to thermal or photochemical crosslinking processes, depending on the nature of the further functionalized crosslinkable groups. This results in a highly insoluble crosslinked film. Examples of thermally crosslinked films produced from polyimide oligomers are described in EP 2524947 A1.

[0122] In one example, the cross-linkable composition comprises a cycloolefinic polymer. Typically, cycloolefinic polymers are examples of oligomeric or polymeric precursors.

[0123] A further class of material useful for passivation layers in organic electronic devices are cycloolefinic polymers. Cycloolefinic polymers bearing chemical substituents that allow further thermal or photochemical crosslinking, after deposition of the non-crosslinked film, are known in the art. Examples of suitable cycloolefinic polymers with cross-linkable side groups are described in U.S. Pat. No. 9,082,981 and WO 2013/120581.

[0124] In one example, the cross-linkable composition comprises a substituted poly(vinylphenol) derivative, for example, as described below. For example, the poly(vinylphenol) may be substituted at the phenolic group (e.g., alkyl, aryl, aralkyl with optional further substituents). Chem Mater 2015, 25, 4806 shows one possible type of substituent (O-allyl).

[0125] Suitably substituted poly(vinylphenol) derivatives are a further class of crosslinked thin film coating precursors suitable for use in the cross-linkable composition.

[0126] Chem Mater 2015, 25, 4806 describes a composition that comprises an O-allyl derivative of poly(vinyl phenol) and pentaerythritol tetra(3-mercaptopropionate) for formation of a soluble thin film, which is then thermally crosslinked by thiol-ene reaction using AIBN as a radical initiator.

[0127] WO 2013/119717 describes derivatives of poly(vinylphenol) that may be crosslinked under photochemical conditions to provide insoluble films, such as a passivation layer.

[0128] In one example, the formulation comprises a surfactant, to improve coating properties, such as surface wettability, leveling and flow.

[0129] Formulations of the present application may optionally comprise surfactants, for example fluorinated surfactants and/or siloxane solvents, to improve coating properties, such as surface wettability, leveling and flow. An amount of a surfactant, such as fluorosurfactant, in the formulation may be in a range from 0% to 5% by weight of the formulation, preferably in a range from 0% to 2% by weight of the formulation. The amount of the surfactant may be at least 0.001%, at least 0.01% or at least 0.1% by weight of the formulation.

[0130] An example fluorosurfactant is commercially available from AGC Seimi Chemical Co., Ltd. (Japan) as SURFLON.

[0131] Table 6 details fluorosurfactants commercially available from Cytonix LLC, Maryland (USA) as FluorN.

TABLE-US-00006 TABLE 6 Fluorosurfactants available from Cytonix. FluorN Chemical description 561 Fluorinated Ethylene Glycol 562 Fluorinated Ethylene Glycol 659 Perfluoroalkyl Stearate 1740G Fluoro-acrylate Copolymer S83 Fluoro-acrylate Copolymer 20158 Fluoro-acrylate Copolymer 2900N PFPE polyethylene glycol 1788 PFPE-diisocyanate

[0132] Table 7 details fluorosurfactants commercially available from DIC Corporation, Tokyo (Japan) as MEGAFACE. Preferred fluorosurfactants include MEGAFACE R-41, R-40, R-40-LM, R-43, F-556, F-557, F-554, F-559, RS-72-K, F-567, F-563, F-560, F-444, F-553, F-477, F-554, F-556, F-557, F-568, F-563 and F-560.

TABLE-US-00007 TABLE 7 Fluorosurfactants available from DIC Corporation. MEGAFACE product number Description F-114 Perfluoro butane sulfonate F-251 Oligomer with fluoro and lipophilic groups F-253 Oligomer with fluoro and lipophilic groups F-281 Oligomer with fluoro and lipophilic groups F-410 Carboxylate with perfluoroalkyl group F-430 Oligomer with fluoro and hydrophilic groups F-444 Perfluoroalkyl ethylene oxide adduct F-477 Oligomer with fluoro, hydrophilic and lipophilic groups F-510 Phosphoric ester with fluoro group F-511 Ammonium phosphate with fluoro group F-551 Oligomer with fluoro and lipophilic groups F-552 Oligomer with fluoro and lipophilic groups F-553 Oligomer with fluoro, hydrophilic and lipophilic groups F-554 Oligomer with fluoro and lipophilic groups F-555 Oligomer with fluoro, hydrophilic and lipophilic groups F-556 Oligomer with fluoro, hydrophilic and lipophilic groups F-557 Oligomer with fluoro, hydrophilic and lipophilic groups F-558 Oligomer with fluoro and lipophilic groups F-559 Oligomer with fluoro, hydrophilic and lipophilic groups F-560 Oligomer with fluoro and lipophilic groups F-561 Oligomer with fluoro and lipophilic groups F-562 Oligomer with fluoro, hydrophilic and lipophilic groups F-563 Oligomer with fluoro and lipophilic groups F-565 Oligomer with fluoro, hydrophilic and lipophilic groups F-568 Oligomer with fluoro, hydrophilic and lipophilic groups F-569 Oligomer with fluoro and hydrophilic groups F-570 Oligomer with fluoro, hydrophilic, lipophilic and carboxyl groups F-571 Oligomer with fluoro, hydrophilic and lipophilic groups F-572 Oligomer with fluoro and lipophilic groups R-40 Oligomer with fluoro, hydrophilic and lipophilic groups R-40-LM Oligomer with fluoro, hydrophilic and lipophilic groups R-41 Oligomer with fluoro and lipophilic groups R-43 Oligomer with fluoro and lipophilic groups R-94 Oligomer with fluoro, hydrophilic and lipophilic groups RS-55 Oligomer with fluoro, hydrophilic, lipophilic and UV reactive groups RS-56 Oligomer with fluoro, hydrophilic, lipophilic and UV reactive groups RS-72-K Oligomer with fluoro, hydrophilic, lipophilic and UV reactive groups RS-75 Oligomer with fluoro, hydrophilic, lipophilic and UV reactive groups RS-76-E Oligomer with fluoro, hydrophilic, lipophilic and UV reactive groups RS-76-NS Oligomer with fluoro, hydrophilic, lipophilic and UV reactive groups RS-78 Oligomer with fluoro, hydrophilic, lipophilic and UV reactive groups RS-90 Oligomer with fluoro, hydrophilic, lipophilic and UV reactive groups

[0133] Formulations of the present application may optionally comprise a siloxane solvent, particularly a cyclic siloxane solvent. The siloxane solvent may be used to alter the wettability, leveling and flow properties of the formulation. Examples of suitable siloxane solvent additives include octamethylcyclotetrasiloxane (BP 175° C.), decamethylcyclopentasiloxane (BP 210° C.) and dodecamethylcyclohexasiloxane (BP 245° C.). The loading of siloxane solvent in the composition would be 0 to 10% by weight of the passivation material, preferably 0 to 5% by weight of the passivation material, and more preferably 0 to 2% by weight of the passivation material.

[0134] An amount of siloxane solvent in the formulation may be in a range from 0 to 10% by weight of the formulation, preferably in a range from 0 to 5% by weight of the passivation material, and more preferably in a range from 0 to 2% by weight of the passivation material. The amount of surfactant may be at least 0.001%, at least 0.01% or at least 0.1% by weight of the passivation material.

[0135] In one example, the formulation comprises a filler, to alter the physical and/or electrical properties of the crosslinked layer.

[0136] Suitable compositions for utilisation in the present application may optionally also comprise a filler. Fillers may usefully alter the physical and/or electrical properties of the crosslinked thin film coating, for example, dielectric constant, mechanical strength or dielectric breakdown strength. Suitable fillers include inorganic nanoparticles, in which case the resulting crosslinked film may be described as a polymer nanocomposite. Examples of suitable fillers are described in Materials 2009, 2, 1697-1733; doi:10.3390/ma2041697. Such described fillers include inorganic fillers, for example, BaTiO.sub.3, PMN-PT (65/35), PbNb.sub.2O.sub.6, PLZT (7/60/40), SiO.sub.2, Al.sub.2O.sub.3, Ta.sub.2O.sub.5, TiO.sub.2, SrTiO.sub.3, ZrO.sub.2, HfO.sub.2, HfSiO.sub.4, La.sub.2O.sub.3, Y.sub.2O.sub.3, α-LaAlO.sub.3, CaCu.sub.3Ti.sub.4O.sub.12 and La.sub.1.8Sr.sub.0.2NiO.sub.4. These inorganic fillers may be provided as particles, for example microparticles and/or nanoparticles.

[0137] Organic Semiconductor (OSC) Materials

[0138] The organic semiconductor material (OSC) layer comprises a single component or multicomponent blend of materials, which may be evaporated or solution processed. The OSC layer is preferably solution processable and it can be polymeric, but preferably comprises a semiconducting non-polymeric polycyclic compound, such as a semiconducting non-polymeric organic polycyclic compound, which is OSC (also known as a small molecule organic semiconductor).

[0139] Preferably, the semiconducting non-polymeric polycyclic compounds have carrier mobilities of 10.sup.−1 cm.sup.2/Vs or more, more preferably 0.5 cm.sup.2/Vs or more, and even more preferably 2 cm.sup.2/Vs or more. Preferably, the semiconducting non-polymeric polycyclic compounds have carrier mobilities of less than 100 cm.sup.2/Vs. The charge mobility of the semiconducting non-polymeric polycyclic compound can be determined through field effect transistor measurements on drop cast films or thermally evaporated single crystal films.

[0140] Any suitable semiconducting non-polymeric polycyclic compound may be used. These may be p-type or n-type OSC materials.

[0141] Examples of suitable semiconducting non-polymeric polycyclic compounds include polyacenes. Suitable polyacenes are disclosed in WO 2012/164282. For example, suitable polyacenes may have the structural formula shown in Formula (III):

##STR00024##

[0142] wherein each of R.sup.54, R.sup.56, R.sup.32 and R.sup.34 is hydrogen; R.sup.55 and R.sup.33 are each —C≡C—SiR.sup.35R.sup.36R.sup.37, wherein R.sup.35, R.sup.36 and R.sup.37 are each independently selected from C.sub.1-C.sub.4 alkyl, C.sub.2-C.sub.4 alkenyl and C.sub.3-C.sub.6 cycloalkyl; R.sup.50, R.sup.51, R.sup.52, R.sup.53, R.sup.57, R.sup.29, R.sup.30 and R.sup.31 are each independently selected from hydrogen, C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.6 alkoxy and C.sub.6-C.sub.12 aryloxy; or wherein independently each pair of R.sup.51 and R.sup.52 and/or R.sup.29 and R.sup.30 may be cross-bridged to form a C.sub.4-C.sub.10 saturated or unsaturated ring, which saturated or unsaturated ring may be intervened by an oxygen atom, a sulfur atom or a group shown by formula —N(R.sup.49)— (wherein R.sup.49 is a hydrogen atom, a C.sub.1-C.sub.6 alkyl group or a C.sub.1-C.sub.10 perfluoroalkyl group; and

[0143] wherein k and 1 are independently 0 or 1, preferably both k and 1 are 1, or both k and I are 0.

[0144] Suitably, in compounds of Formula (III), k and 1 are both 1; R.sup.55 and R.sup.33 are —C≡C—SiR.sup.35R.sup.36R.sup.37, wherein R.sup.35, R.sup.36 and R.sup.37 are each independently selected from ethyl, n-propyl, isopropyl, 1-propenyl, 2-propenyl and C.sub.3-C.sub.6 cycloalkyl; and R.sup.50, R.sup.51, R.sup.52, R.sup.53, R.sup.57, R.sup.29, R.sup.30 and R.sup.31 are each independently selected from hydrogen, methyl, ethyl and methoxy.

[0145] Suitably, in compounds of Formula (III), k and 1 are both 0; R.sup.55 and R.sup.33 are —C≡C—SiR.sup.35R.sup.36R.sup.37, wherein R.sup.35, R.sup.36 and R.sup.37 are each independently selected from ethyl, n-propyl, isopropyl, 1-propenyl, 2-propenyl and C.sub.3-C.sub.6 cycloalkyl; R.sup.50, R.sup.53, R.sup.57 and R.sup.31 are hydrogen; and R.sup.51 and R.sup.52 together, and R.sup.29 and R.sup.30 together, form 5-membered heterocyclic rings containing 1 or 2 nitrogen atoms, 1 or 2 sulfur atoms or 1 or 2 oxygen atoms, wherein the heterocyclic rings may be optionally substituted, for example by C.sub.1-C.sub.6 alkyl and halogen.

[0146] Especially preferred polyacene compounds are those of Formulae (IV) and (V):

##STR00025##

[0147] wherein R.sup.50, R.sup.53, R.sup.57 and R.sup.31 are each independently selected from hydrogen, C.sub.1-C.sub.6 alkyl and C.sub.1-C.sub.6 alkoxy (preferably R.sup.50, R.sup.53, R.sup.57 and R.sup.31 are each independently selected from hydrogen, methyl, ethyl, propyl, n-butyl, isobutyl, tert-butyl, methoxy, ethoxy, propoxy and butoxy, more preferably hydrogen, methyl, propyl and methoxy);

[0148] R.sup.51, R.sup.52, R.sup.29 and R.sup.30 are each independently selected from hydrogen, C.sub.1-C.sub.6 alkyl and C.sub.1-C.sub.6 alkoxy, or each pair of R.sup.51 and R.sup.52 and/or R.sup.29 and R.sup.30, are cross-bridged to form a C.sub.4-C.sub.10 saturated or unsaturated ring, which saturated or unsaturated ring may be intervened by an oxygen atom, a sulfur atom or a group shown by Formula —N(R.sup.38)— (wherein R.sup.38 is hydrogen or C.sub.1-C.sub.10 alkyl); and wherein one or more of the carbon atoms of the polyacene skeleton may optionally be substituted by a heteroatom selected from N, P, As, O, S, Se and Te (preferably, R.sup.51, R.sup.52, R.sup.29 and R.sup.30 are each independently selected from hydrogen, methyl, ethyl, propyl, n-butyl, isobutyl, tert-butyl, methoxy, ethoxy, propoxy and butoxy, more preferably hydrogen, methyl, ethyl, propyl and methoxy); and R.sup.39, R.sup.40 and R.sup.41 are each independently selected from C.sub.1-C.sub.6 alkyl and C.sub.2-C.sub.6 alkenyl (preferably R.sup.39, R.sup.40 and R.sup.41 are each independently selected from methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, 1-propenyl and 2-propenyl, more preferably ethyl, n-propyl and isopropyl).

##STR00026##

[0149] wherein R.sup.39, R.sup.40 and R.sup.41 are each independently selected from C.sub.1-C.sub.6 alkyl and C.sub.2-C.sub.6 alkenyl (preferably R.sup.39, R.sup.40 and R.sup.41 are each independently selected from methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, 1-propenyl and 2-propenyl, more preferably ethyl, n-propyl and isopropyl);

[0150] R.sup.42 and R.sup.43 are each independently selected from hydrogen, halogen, cyano, optionally fluorinated or perfluorinated C.sub.1-C.sub.20 alkyl, fluorinated or perfluorinated C.sub.1-C.sub.20 alkoxy, fluorinated or perfluorinated C.sub.6-C.sub.30 aryl and CO.sub.2R.sup.44, wherein R.sup.44 is hydrogen, fluorinated or perfluorinated C.sub.1-C.sub.20 alkyl, or fluorinated or perfluorinated C.sub.6-C.sub.30 aryl (preferably R.sup.42 and R.sup.43 are each independently selected from fluorinated or perfluorinated C.sub.1-C.sub.8 alkyl, fluorinated or perfluorinated C.sub.1-C.sub.8 alkoxy and C.sub.6F.sub.5); and

[0151] Y.sup.1, Y.sup.2, Y.sup.3 and Y.sup.4 are each independently selected from —CH═, ═CH—, O, S, Se or NR.sup.45 (wherein R.sup.45 is hydrogen or C.sub.1-C.sub.10 alkyl).

[0152] In yet another preferred embodiment, the polyacene compounds of the present application are those of Formulae (VI) and (VII):

##STR00027##

[0153] wherein R.sup.39, R and R.sup.41 are each independently selected from methyl, ethyl and isopropyl;

[0154] wherein R.sup.50, R.sup.51, R.sup.52, R.sup.53, R.sup.57, R.sup.29, R.sup.30 and R.sup.31 are each independently selected from C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 alkoxy and C.sub.6-C.sub.20 aryloxy. Preferably R.sup.50, R.sup.51, R.sup.52, R.sup.53, R.sup.57, R.sup.29, R.sup.30 and R.sup.31 are each independently selected from methyl, ethyl, propyl, n-butyl, isobutyl, tert-butyl, methoxy, ethoxy, propoxy and butoxy.

[0155] Polyacene compounds may be synthesized by any known method within the common general knowledge of a person skilled in the art. In a preferred embodiment, the methods disclosed in US 2003/01 16755 A, U.S. Pat. Nos. 3,557,233, 6,690,029, WO 2007/078993, WO 2008/128618 and Organic Letters, 2004, Volume 6, number 10, pages 1609-1612 can be employed for the synthesis of polyacene compounds.

[0156] Preferably, the polyacene compounds have carrier mobilities of 10.sup.−1 cm.sup.2/Vs or more, more preferably of 0.5 cm.sup.2/Vs or more, and even more preferably of 2 cm.sup.2/Vs or more. Preferably, the polyacene compounds have carrier mobilities of less than 100 cm.sup.2/Vs. The charge mobility of polyacene can be determined through field effect transistor measurements on drop cast films or thermally evaporated single crystal films.

[0157] For example, a suitable polyacene is 1,4,8,11-tetramethyl-6,13-bis(triethylsilylethynyl) pentacene (TMTES).

[0158] Alternative semiconductor non-polymeric polycyclic compounds used in the present application may include the following materials, either applied via solution processing or evaporation: pentacene, 2,7-dioctyl[1]benzothieno[3,2-b][1]benzothiophene (C8-BTBT), 2,9-didecyldinaphtho[2,3-b:2′,3′-f]thieno[3,2-b]thiophene (C10-DNTT), 3,11-didecyl-dinaphtho[2,3-d:2′,3′-d′]benzo[1,2-b:4,5-b′]dithiophene (C10-DNBDT), 8,17-bis((triisopropylsilyl)ethynyl)tetraceno[2,1,12-qra]tetracene (Formula (VIII)), 8,17-bis((diisopropyl(octyl) silyl)ethynyl)tetraceno[2,1,12-qra]tetracene (Formula (IX)).

##STR00028##

[0159] Suitable n-type small molecules could include naphthalene diimides (NTCDI) or perylene tetracarboxylic diimides (PTCDA), [6,6]-phenyl-C61-butyric acid ester ([60]PCBM) and [6,6]-phenyl-C71-butyric acid methyl ester ([70]PCBM).

[0160] The OSC layer may optionally comprise a polymeric binder material to aid film forming and uniformity. Suitable binder materials can be found in WO2012160383 which discloses high-k (permittivity >3.4) binders in combination with small molecule semiconductors, or WO2005055248 which discloses low-k binders (1.1<k<3.3) in combination with small molecule semiconductors.

[0161] Organic Gate Insulator (OGI) Materials

[0162] Suitable OGI materials are polymers that can be crosslinked such that they are solvent resistant or based on polymers that are not soluble in lactate and/or a derivative thereof. Examples of preferred polymers include polymers that have more than 30% of fluorine by weight and are soluble in fluorinated or perfluorinated solvents. Examples of preferred soluble amorphous fluoropolymers include Cytop (Asahi), Teflon AF (DuPont), Hyflon AD (Solvay), Fluoropel (Cytonix). Suitable solvents for the fluorinated OGI layer include Fluorinert (trade name) FC43, or Hydrofluoroethers Novec (3M) HFE7500 or HFE7700.

[0163] The OGI material may be vapor deposited through chemical vapor deposition, such as parylene, or thermal evaporation, but it is especially preferred that the OGI is deposited by solution processing.

[0164] In one example, the passivation layer provides an interlayer dielectric, arranged to isolate, for example electrically isolate, metal layers, such as a metal gate electrode from a source and/or drain electrode, on the OE device.

[0165] Ethyl Lactate

[0166] For the avoidance of doubt, statements of the invention below explicitly recite ethyl lactate, as described above in detail. The formulation, the solvent and/or the passivation material, together with the OE device and organic layer, may be as described above with respect to the first aspect.

[0167] In one example, the solvent comprises lactate and/or a derivative thereof.

[0168] In one example, the solvent comprises lactate and/or a derivative thereof, and the passivation material comprises the cross-linkable composition.

[0169] In one example, the solvent comprises lactate and/or a derivative thereof, and the cross-linkable composition comprises monomeric, oligomeric and/or polymeric precursors.

[0170] In one example, the solvent comprises lactate and/or a derivative thereof, and the monomeric, oligomeric and/or polymeric precursors comprise an epoxy group.

[0171] In one example, the solvent comprises lactate and/or a derivative thereof, and the monomeric, oligomeric and/or polymeric precursors comprise acrylate or methacrylate repeating units.

[0172] In one example, the solvent comprises lactate and/or derivatives thereof, and the monomeric, oligomeric and/or polymeric precursors are cross-linkable via a thiol-ene or a thio (alkyl)acrylate reaction.

[0173] In one example, the solvent comprises lactate and/or a derivative thereof, and the monomeric, oligomeric and/or polymeric precursors are cross-linkable via a thermal azide alkyne cycloaddition reaction.

[0174] In one example, the solvent comprises lactate and/or a derivative thereof, and the cross-linkable composition comprises a polyimide.

[0175] In one example, the solvent comprises lactate and/or a derivative thereof, and the cross-linkable composition comprises a cycloolefinic polymer.

[0176] In one example, the solvent comprises lactate and/or a derivative thereof, and the cross-linkable composition comprises a substituted poly(vinylphenol) derivative.

[0177] In one example, the solvent comprises lactate and/or a derivative thereof, and the formulation comprises at least one of a crosslinking agent, a photoacid generator, a hardener, an antioxidant, a surfactant and a filler.

[0178] In one example, the solvent comprises lactate and/or a derivative thereof and a cosolvent.

[0179] The second aspect of the present application provides a method of fabricating an organic electronic (OE) device comprising an organic layer, wherein the organic layer is selected from an organic semiconductor (OSC) layer and an organic gate insulator (OGI) layer, wherein the method comprises:

[0180] providing a passivation layer on at least a part of the organic layer by depositing a formulation according to the first aspect and removing the solvent, for example, at least a part of the solvent, substantially all of the solvent and/or all of the solvent.

[0181] In one example, the method comprises providing a substrate. The substrate may comprise, for example, glass, metal, a polymer or an IC. The substrate may include an optional buffer layer (also known as a sublayer) provided on the surface of the substrate. The buffer layer, which may also be known as a polarization layer, is provided by a crosslinkable polymer that may improve surface uniformity and/or homogeneity by smoothing defects in the surface of the substrate and may provide a chemically inert surface upon which an OE device is fabricated. The buffer layer may comprise, for example, SU-8, crosslinked acrylate polymers or polycycloolefinic polymers. Alternatively, the substrate may comprise, for example, polyethylene terephthalate (PET) or polyethylene naphthalate (PEN), and the substrate can be processed without a buffer layer.

[0182] In one example, the method comprises providing a source and/or a drain electrode on the surface of the substrate, for example by sputtering and photolithography. The source and drain electrodes are typically metal, such as silver or gold or alloys thereof, or non-metal. The source and drain electrodes can be constructed in various potential geometries with respect to each other. One construction manner is Corbino structure, in which the source electrode surrounds the drain electrode, and the other is C-shaped or W-shaped. Alternatively, the electrodes may be linear. Examples of possible arrangements are shown in FIGS. 5A to 5F. In an example, the electrodes are arranged in a non-Corbino arrangement because this is more space-saving in a small area such as a display panel pixel. Non-corbino electrodes are preferred due to the more compact arrangement of electrodes in electronic circuits, such as display panel pixels. The source and drain electrodes may be treated with a thiol solution, to adjust work functions of the source and drain electrodes. In this way, injection of charges into an overlapping OSC layer can be improved. Excess thiol solution can be washed away, with thiol being bound only to the source and drain electrodes.

[0183] In one example, the method comprises providing an OSC layer on the source and drain electrodes and the exposed surface of the substrate, for example, by spin coating or printing. The OSC layer has typically a thickness of 30 nm. In one example, the method comprises providing an OGI layer on the OSC layer, for example by spin coating or printing. The OGI layer has typically a thickness of 300 nm. A metal layer, which is, for example, silver or gold or alloys thereof, can be subsequently deposited on the OGI layer, for example, by evaporation. A photoresist can be subsequently patterned (e.g., by photolithography) on the metal layer, and portions of the metal layer exposed through the patterned photoresist may be removed by wet etching. The patterned metal layer may provide a gate, such as a thin film transistor (TFT) gate. The geometry of the gate is defined according to the geometries of the source and drain. The width of gate size is the same as that of transistor channel, and the length of the gate is the same as that of transistor channel, with the overlap value of each end of channel counted in. The overlapping range is 0 to 50 microns, preferably 0 to 10 microns, more preferably 0 to 2 microns, and most preferably 0 to 0.5 microns. Patterned metal layers may provide a hardmask against reactive ion etching (RIE) (also known as dry etching, using, for example O.sub.2 and/or Ar), thereby masking the underlying OGI layer, the OSC layer, and the source and the drain electrodes. Subsequently, RIE can remove portions of the OGI layer and the OSC layer, that are not masked by the patterned metal layer. In this way, a stack comprising the patterned metal layer, the OGI layer, the OSC layer and the source and the drain electrodes can be provided on the substrate. It should be understood that the stack generally describes a multilayered structure, and thus may comprise more or fewer and/or different layers. For example, the stack may comprise those layers at an intermediate stage of fabrication of the OE device. For example, the stack may comprise all layers of the completed OE device. Thus, layers included in the stack can change during fabrication, by addition and/or by removal of layers. Sides of the OGI layer and sides of the OSC layer may be thus exposed to, for example, RIE, and may be adversely affected by unsuitable solvents. Further, inter-layer interfaces, for example, those between the substrate and the OSC layer, between the OSC layer and the OGI layer, and/or between the OGI layer and the metal layer, may also be exposed. These inter-layer interfaces may be subject to solvent permeation, as described previously, thereby providing another vector of attack by unsuitable solvent. Other surfaces of the OGI layer and/or the OSC layer may be additionally and/or alternatively exposed.

[0184] In one example, the method comprises providing the passivation layer on the stack and the exposed surface of the substrate, for example, by coating with a formulation according to an exemplary embodiment of the present application.

[0185] In one example, the method comprises providing a positive photoresist mask on the passivation layer.

[0186] In one example, the method comprises forming a first hole or via through the passivation layer to reach the patterned metal layer, by RIE through the positive photoresist mask, thereby exposing at least a part of the surface of the metal layer.

[0187] In one example, the method comprises removing residual photoresist mask.

[0188] In one example, the method comprises providing a metal gate interconnect through the first hole to reach the patterned metal layer, for example, by sputtering, masking and etching.

[0189] The third aspect of the present application provides an organic electronic (OE) device comprising an organic layer and a passivation layer directly thereon, wherein the organic layer is selected from an organic semiconductor (OSC) layer and an organic gate insulator (OGI) layer, and wherein the passivation layer comprises a cross-linked product of a cross-linkable composition according to the first aspect.

[0190] In one example, the OE device is selected from a group consisting of an Organic Field Effect Transistor (OFET) such as a bottom gate OFET or preferably a top gate OFET, including Organic Thin Film Transistor (OTFT), an Organic Light Emitting Diode (OLED), an Organic Photovoltaic (OPV) device and an Organic Photodetector (OPD).

[0191] In one example, the organic field effect transistor (OFET) device is configurated such that, preferably, one of the source or drain electrodes does not completely surround the other, and more preferably, the overlap between the gate metal and the source and drain electrodes is less than 5 microns.

[0192] The fourth aspect of the present application provides a product comprising an organic electronic (OE) device fabricated according to the second aspect and/or an OE device according to the third aspect.

[0193] In one example, the product is selected from a group consisting of an Integrated Circuit (IC), a Radio Frequency Identification (RFID) tag, a security marking or security device containing an RFID tag, a Flat Panel Display (FPD), a backplane of an FPD, a backlight of an FPD, an electrophotographic device, an electrophotographic recording device, an organic storage device, a sensor, a biosensor and a biochip.

[0194] The fifth aspect of the present application provides a flowable formulation comprising a photopatterning material and a solvent; wherein the solvent comprises lactate and/or a derivative thereof.

[0195] The solvent may be as described with respect to the first aspect. The photopatterning material may be similar to the passivation material described with respect to the first aspect.

[0196] The sixth aspect of the present application provides use of a solvent comprising lactate and/or a derivative thereof in a method of fabricating an organic electronic (OE) device comprising an organic layer, wherein the organic layer is selected from an organic semiconductor (OSC) layer and an organic gate insulator (OGI) layer.

[0197] The solvent may be as described with respect to the first aspect. The method of fabricating may be as described with respect to the second aspect.

[0198] FIGS. 3A and 3B show schematically a method of fabrication of an OE device, specifically, a top gate OFET, according to an embodiment of various aspects of the present application. Typically, such a method of fabrication may be achieved practically by photolithographic processing, as known to the person skilled in the art.

[0199] In contrast to the method of fabrication described above with reference to FIGS. 1A and 1B, a formulation according to an exemplary embodiment of the present application is used, thereby eliminating at least one step of the prior art method. In this way, OE device fabrication complexity and/or cost can be reduced. Furthermore, water-soluble polymers, such as PVA, which may be hygroscopic, are avoided, thereby improving long-term stability of OE devices fabricated according to exemplary embodiments of the present application. In addition, the formulation used comprises a “green” solvent, thereby improving the environmental profile of the formulation.

[0200] At S301, as described previously with reference to S101, a substrate 310 is provided. The substrate 310 may comprise, for example, glass, metal, a polymer or an IC. The substrate 310 may comprise an optional buffer layer (also known as a sublayer) provided on the surface of the substrate 310. The buffer layer, which may also be known as a planarization layer, is provided by a crosslinkable polymer that may improve surface uniformity and/or homogeneity by smoothing defects in the surface of the substrate and may provide a chemically inert surface upon which the OE device is fabricated. The buffer layer may comprise, for example, crosslinked acrylate polymers or polycycloolefinic polymers. Alternatively, the substrate 310 may comprise polyethylene terephthalate (PET) or polyethylene naphthalate (PEN), for example, and may be processed without a buffer layer.

[0201] At S302, as described previously with reference to S102, source and drain electrodes 320 are provided on the surface of the substrate 310, for example, by sputtering and photolithography (using mask 1). The source and the drain electrodes 320 are typically metal, such as silver or gold or alloys thereof, or non-metal. The source and the drain electrodes 320 may be treated with a thiol solution, to adjust work functions of the source and drain electrodes 320. In this way, injection of charges into an overlapping OSC layer can be improved. Excess thiol solution can be washed away, with thiol being bound only to the source and drain electrodes 320.

[0202] At S303, as described previously with reference to S103, firstly, an OSC layer 330 is provided on the source and drain electrodes 320 and the exposed surface of the substrate 310, for example, by spin coating or printing. The OSC layer 330 has typically a thickness of 30 nm. An OGI layer 340 is subsequently provided on the OSC layer 330, for example, by spin coating or printing. The OGI layer 340 has typically a thickness of 300 nm. A metal layer 350, which is, for example, silver or gold or alloys thereof, is subsequently deposited on the OGI layer 340, for example, by evaporation. A photoresist (not shown) is subsequently patterned (e.g., by photolithography) on the metal layer 350, and portions of the metal layer 350 exposed through the patterned photoresist are removed by wet etching. The patterned metal layer 350 provides a gate, such as a thin film transistor (TFT) gate. The patterned metal layer 350 also provides a hardmask (mask 2) against reactive ion etching (RIE) (also known as dry etching, using, for example O.sub.2 and/or Ar), thereby masking the underlying OGI layer 340, the OSC layer 330 and the source and the drain electrodes 320. Subsequently, RIE removes portions of the OGI layer 340 and the OSC layer 330 that are not masked by the patterned metal layer 350. In this way, a stack 300 comprising the patterned metal layer 350, the OGI layer 340, the OSC layer 330 and the source and the drain electrodes 320 is provided on the substrate 310. It should be understood that the stack 300 generally describes a multilayered structure, and thus may comprise more or fewer and/or different layers. For example, the stack 300 may comprise those layers at an intermediate stage of fabrication of the OE device. For example, the stack 300 may comprise all the layers of the completed OE device. Thus, layers included in the stack 300 may change during fabrication, by addition and/or by removal of layers. Sides 341 of the OGI layer 340 and sides 331 of the OSC layer 330 may be thus exposed to, for example, RIE, and may be adversely affected by unsuitable solvents. Further, inter-layer interfaces, for example, those between the substrate 310 and the OSC layer 330, between the OSC layer 330 and the OGI layer 340, and/or between the OGI layer 340 and the metal layer 150, may also be exposed. These inter-layer interfaces may be subject to solvent permeation, as described previously, thereby providing another vector of attack by unsuitable solvents. Other surfaces of the OGI layer 340 and/or the OSC layer 330 may be additionally and/or alternatively exposed.

[0203] At S304, in contrast to as described previously with reference to S104, a passivation layer 360 is provided on the stack 300 and the exposed surface of the substrate 310, for example, by coating with a formulation according to an exemplary embodiment of the present application.

[0204] Specifically, the formulation comprises a passivation material and a solvent, wherein the solvent comprises lactate and/or a derivative thereof. In this example, the passivation material comprises a cross-linkable composition, such as bisphenol A novolac epoxy, and the solvent comprises ethyl lactate. In this example, the passivation material is dissolved in the solvent.

[0205] In contrast the conventional method of fabrication described above with reference to FIGS. 1A and 1B, in which the first passivation layer 180 and the second passivation layer 190 are required for reasons as described above, only the single passivation layer 360 is required, according to an exemplary embodiment of the present application. The single passivation layer 360 provides the robustness required to ensure environmental, chemical and/or physical protection of the fabricated OE device, similar to the second passivation layer 190 described above, that required also the first passivation layer 180. In this way, OE device fabrication complexity and/or cost can be reduced. Furthermore, water-soluble polymers, such as PVA, which may be hygroscopic, are avoided, thereby improving long-term stability of OE devices fabricated according to exemplary embodiments of the present application.

[0206] In this example, the passivation material is crosslinked by UV. The passivation layer 360 has typically a thickness of between 300 nm and 2000 nm.

[0207] At S305, a positive photoresist mask 361 (mask 3) is provided on the passivation layer 360, similarly to as described previously at S105 with reference to FIGS. 1A and 1B.

[0208] At S306, a first hole or via is formed through the passivation layer 360 to reach the patterned metal layer 350, by RIE through the positive photoresist mask 361, thereby exposing at least a part of the surface of the metal layer 350, similarly to as described previously at S106 with reference to FIGS. 1A and 1B.

[0209] At S307, residual photoresist mask 381 is removed, similarly to as described previously at S107 with reference to FIGS. 1A and 1B.

[0210] Since only the single passivation layer 360 may be required, provision of a second passivation layer, such as described previously at S108 with reference to FIGS. 1A and 1B, is not required. In this way, OE device fabrication complexity and/or cost can be reduced. Furthermore, water-soluble polymers, such as PVA, which may be hygroscopic, are avoided, thereby improving long-term stability of the OE device fabricated according to exemplary embodiments of the present application. In addition, the formulation used comprises a “green” solvent, thereby improving the environmental profile of the formulation.

[0211] At S309, a metal gate interconnect 370 is provided through the first hole to reach the patterned metal layer 350, for example, by sputtering, masking (mask 4) and etching, similarly to as described previously at S107 with reference to FIGS. 1A and 1B.

[0212] In this way, the OE device having a single passivation layer 360 may be provided.

[0213] Therefore, in contrast with the conventional process described with reference to FIGS. 1A and 1B, only the single passivation layer 360 may be required. Furthermore, water-soluble polymers are avoided. In addition, the formulation used comprises a “green” solvent. In addition, according to this method of fabrication of OE device, only four masks (mask 1 to mask 4) are required, unlike the conventional process which requires five masks.

[0214] FIG. 4 shows schematically a method of fabrication of another OE device, according to an embodiment of aspects of the present application. Typically, such a method of fabrication may be achieved practically by photolithographic processing, as known to the person skilled in the art.

[0215] In contrast to the method of fabrication described above with reference to FIGS. 1A and 1B, a formulation according to an exemplary embodiment of the present application is used, thereby eliminating at least one step of the prior art method. In this way, OE device fabrication complexity and/or cost can be reduced. Furthermore, water-soluble polymers, such as PVA, which may be hygroscopic, are avoided, thereby improving long-term stability of the OE device fabricated according to exemplary embodiments of the present application.

[0216] At S401, as described previously with reference to S101, a substrate 410 is provided. The substrate 410 may comprise, for example, glass, metal, a polymer or an IC. The substrate 410 may include an optional buffer layer provided on the surface of the substrate 410. The buffer layer, which can also be known as a planarization layer, is provided by a cross-linkable polymer that may improve surface uniformity and/or homogeneity by smoothing defects in the surface of the substrate and may provide a chemically inert surface upon which the OE device is fabricated.

[0217] At S402, as described previously with reference to S103, firstly, an OSC layer 430 is provided on the exposed surface of the substrate 410, for example, by spin coating or printing. The OSC layer 430 has typically a thickness of 30 nm.

[0218] At S403, an OGI layer 440 is subsequently provided on the OSC layer 430, for example, by spin coating or printing. The OGI layer 440 has typically a thickness of 300 nm. In this way, a stack 400 comprising the OGI layer 440 and the OSC layer 430 is provided on the substrate 410. It should be understood that the stack 400 generally describes a multilayered structure, and thus may comprise more or fewer and/or different layers. For example, the stack 400 may comprise those layers at an intermediate stage of fabrication of the OE device. For example, the stack 400 may comprise all layers of the completed OE device. Thus, layers included in the stack 400 may change during fabrication, by addition and/or by removal of layers. Sides 441 of the OGI layer 440 and sides 431 of the OSC layer 430 may be thus exposed to, for example, RIE, and may be adversely affected by unsuitable solvents. Further, inter-layer interfaces, for example those between the substrate 410 and the OSC layer 430 and/or between the OSC layer 430 and the OGI layer 440, may also be exposed. These inter-layer interfaces may be subject to solvent permeation, as described previously, thereby providing another vector of attack by unsuitable solvents. Other surfaces of the OGI layer 440 and/or the OSC layer 430 may be additionally and/or alternatively exposed.

[0219] At S404, a passivation layer 460 is provided on the stack 400 and the exposed surface of the substrate 410, for example, by coating with a formulation according to an exemplary embodiment of the present application.

[0220] The passivation layer 460 may be provided as described previously with reference to S304.

[0221] Specifically, the formulation comprises a passivation material and a solvent, wherein the solvent comprises lactate and/or a derivative thereof.

[0222] In contrast the conventional method of fabrication described above with reference to FIGS. 1A and 1B, in which the first passivation layer 180 and the second passivation layer 190 are required for reasons as described above, only the single passivation layer 460 is required, according to an exemplary embodiment of the present application. The single passivation layer 460 provides the robustness required to ensure environmental, chemical and/or physical protection of the fabricated OE device, similar to the second passivation layer 190 described above, that required also the first passivation layer 180. In this way, OE device fabrication complexity and/or cost can be reduced. Furthermore, water-soluble polymers, such as PVA, which may be hygroscopic, are avoided, thereby improving long-term stability of OE devices fabricated according to exemplary embodiments of the present application.

[0223] Since only the single passivation layer 460 may be required, provision of a second passivation layer, such as described previously at S108 with reference to FIGS. 1A and 1B, is not required. In this way, OE device fabrication complexity and/or cost can be reduced. Furthermore, water-soluble polymers, such as PVA, which may be hygroscopic, are avoided, thereby improving long-term stability of the OE device fabricated according to exemplary embodiments of the present application.

[0224] In this way, the OE device having a single passivation layer 460 can be provided.

[0225] FIGS. 5A to 5F show a series of different structures of source and drain electrodes of an organic thin film transistor (OTFT). FIG. 5A shows the design of a Corbino structure, in which the drain electrode 502 is surrounded by the source electrode 501 with the OTFT channel 503 therebetween. After the organic gate insulator (OGI) layer and the organic semiconductor (OSC) layer are dry etched, this special OTFT design does not expose a part of the channel to the passivation layer solvent, and thus is less sensitive to the type of the passivation layer solvent. However, the overall size of the smallest OTFT that can be achieved is limited due to the need to form a via down to the drain electrode. FIGS. 5B to 5F are all designs of linear OTFTs having the source electrode 501, the drain electrode 502 and the channel 503. In FIG. 5F, a gate metal 504 is shown. It can be seen that when the organic gate insulator (OGI) layer and the organic semiconductor (OSC) layer are patterned using the gate metal, there is a region at the end of each OTFT channel finger pattern in an interdigital device that will be in direct contact with the passivation layer solvent. This region, which is marked as 505, is one of OTFT channel finger patterns. In this particular design, there are a total of 12 regions marking the finger ends of OTFT channels.

Example 1

[0226] Example 1 relates to fabrication of an OTFT device, including a passivation formulation of SU-8 polymer in ethyl lactate solvent.

[0227] 10 cm×10 cm glass substrate (Corning Eagle XG) was treated using ultrasound for 20 minutes in Deconex (3% w/w in water) followed by rinsing in ultrapure water, and dried using compressed air. The substrate was baked at 70° C. for 30 minutes in a convection furnace. The substrate was then spin-coated with a thermally cross-linkable polymer (P11) (available to the public from NeuDrive Ltd) as a buffer layer (also known as a sublayer). After spin coating, the substrate was first placed on a hotplate at 95° C. for 2 minutes to softbake, and then baked at 150° C. for 60 minutes. The final thickness of P11 layer was measured to be 1 micron.

[0228] After the preparation of the P11 sublayer, the substrate was sputter coated with 50 nm of Au, and then source and drain electrodes were prepared with a combination of photolithographic and wet etching techniques (etchant composition: potassium iodide and iodine in water). A linear interdigital design was applied to source and drain electrodes, and had different transistor channel widths and lengths. After removal of the residual photoresist from the source and drain contacts by UV flash exposure and spin-coating development, the substrates were inspected under an optical microscope, and channel length features were measured in several areas of the substrate.

[0229] Before proceeding with the organic thin-film transistor (OTFT) fabrication, the substrate was treated in a Plasma Etch Inc. PE100 surface treatment system, using Ar/O.sub.2 plasma. Each gas was supplied at a concentration of 50 sccm and a RF power of 250 W for 65 s.

[0230] Prior to spin coating of the organic semiconductor (OSC), a 10 mM solution of 3-fluoro-4-methoxythiophenol in 2-propanol was applied to the surface of the electrodes for 1 minute followed by rinsing in 2-propanol (2 times), followed by drying on a hotplate at 100° C. for 1 minute. An OSC formulation of 1,4,8,11-tetramethyl bis-triethylsilylethynyl pentacene (TM-TES) and 30:70 4-isopropylcyano-polytriarylamine (PTAA): 2,4-dimethyl polytriarylamine copolymer (binder) was formulated at ratio of 1 part of TM-TES to 2 parts of binder by weight in 1,2,3,4 tetrahydronaphthalene in a mixed solvent system, composed of 1,2,3,4-tetrahydronaphthalene and isopropanol at a ratio of 9:1 (by weight), as for example, described in Example 5 in WO 2012/160383. The OSC formulation was then coated by spin coating at 1250 rpm for 60 seconds onto the SD electrodes using a Suss RC12 spinner set at 1250 rpm for 1 minute, followed by baking on a hotplate for 60 seconds at 100° C. For the organic gate insulator (OGI) layer, a solution of 1 part Cytop 809M (Asahi Glass) and 2 parts FC43 solvent (Acros Organics) was spin-coated at 1500 rpm for 20 seconds, and the sample was baked on a hotplate for 60 seconds at 100° C. The thickness of the organic gate insulator (OGI) layer was 160 nm.

[0231] The substrates were then coated with 50 nm of Au by thermal evaporation, and the gate electrodes were patterned by a combination of photolithography and wet etching as described above. Thereafter, the photoresist on the Au was removed by UV flash exposure and development.

[0232] Dry Etching to Pattern the OSC Layer

[0233] An example passivation layer formulation was here provided containing 2.5 g of EPON-SU-8 base polymer (i.e., a passivation material comprising a cross-linkable composition, wherein the cross-linkable composition comprises polymeric precursors comprising epoxy groups) and 17 g of ethyl lactate. The passivation layer further contains 0.5 g of triarylsulfonium hexafluoroantimonate solution (50% solution by weight in propylene carbonate) as a cross-linking agent. That is, the solvent of this passivation formulation comprises 17 g of ethyl lactate together with 0.25 g of propylene carbonate as a cosolvent.

[0234] The formulation of SU-8 and photoinitiator in ethyl lactate was spin-coated at 500 rpm for 10 seconds followed by 1250 rpm for 30 seconds, and then baked on a hotplate at 95° C. for 2 minutes to form a dry film. The sample was inspected under the microscope to ensure that the solvent of passivation layer does not affect OSC/OGI/gate layers. The film layer was exposed to UV (broadband g, h, I lines, exposure amount of 1000 mJ) with a Tamarack mask alignment exposure machine to expose the film to UV light. It was then baked at 115° C. for 5 minutes. 1.8 micron Shipley S1805 photoresist was spin coated on the surface and baked at 115° C. for 1 minute. The via mask (VIA MASK, which is a dark field mask) was aligned with the first metal layer (using EVG6200 mask alignment exposure machine) to ensure that the via is patterned on the underlying metal pattern, with an exposure amount of 84 mJ. After exposure, the photoresist development was performed and the feature pattern was inspected. The via shape in the photoresist was transferred to SU8 film by reactive ion etching (RIE) using Aurion RIE system. The dry etching process was performed at a pressure of 0.07 hPa, a power of 730 W, a process time of 260 s, a O.sub.2 flow rate of 100 sccm, a Ar flow rate of 40 sccm, and a CF.sub.4 flow rate of 10 sccm. After the via was inspected under an optical microscope, the residual photoresist was removed by flood exposure and development.

[0235] Then, 50 nm of Au was deposited onto the above surface by metal sputtering, and the metal layer was patterned by photolithography and wet etching to form the top metal pattern of the via structure.

Comparative Example—Passivation Layer Using SU8 in Cyrene Solvent

[0236] A SU8 formulation was prepared comprising 2.5 g EPON-SU-8 base polymer (i.e., passivation material comprising a cross-linkable composition, wherein the cross-linkable composition comprises polymeric precursors comprising epoxy groups) and 15.3 g Cyrene and 1.7 g hexanol. The passivation formulation further comprised 0.5 g triarylsulfonium hexafluoroantimonate solution (50% solution by weight in propylene carbonate) as a crosslinking agent.

[0237] OTFT Characterization

[0238] OTFTs were tested using a Wentworth Pegasus 300S semi-automatic probe station in conjunction with a Keithley S4200 semiconductor parameter analyzer. This allowed a statistically significant number of OTFT device measurements to be made on each substrate. The Keithley system calculated the linear mobility according to the equation shown below:

[00001]$\mu =\frac{\partial I_{\mathrm{DS}}}{\partial V_{\mathrm{GS}}}\frac{L}{{\mathrm{WC}}_i{V}_{\mathrm{DS}}}$

[0239] wherein L is the transistor length, W is the transistor width, I.sub.DS is the drain to source current, and C.sub.i is the dielectric capacitance per unit area. V.sub.DS (drain-source voltage) was set at −2V, and V.sub.GS (gate voltage) was varied from depletion to accumulation (+20 V to −29 V in 1V steps). The mobility values reported are an average of the 5 highest points in accumulation for each transistor. The data is reported for the channel lengths shown below and is displayed as an average of the devices measured. To exclude devices with gate leakage, a ratio of the gate current to the source-drain current was set at the highest V.sub.GS value for a V.sub.DS of −2V. If this ratio was below 10 (i.e. the gate current was more than 10% of the source-drain current), then the device was excluded from the results. The standard deviation of the mobility values is reported as a percentage of the mean. Turn on voltage of the transistor (V.sub.to) is defined as the gate voltage point at which the derivative of the logarithm of the drain current with respect to gate voltage is a maximum. It represents the transition point where the device starts to switch from the off state towards the on state. On/off ratio is defined as the maximum current in accumulation (at V.sub.g=−29V) divided by the off current in depletion. The subthreshold swing S is defined as the numerical value of the gate voltage required to change the drain current by one order of magnitude.

[0240] Results

[0241] The electrical test results of OTFT prepared using ethyl lactate as the solvent of SU8 passivation layer are shown in the table below. Four groups of transistors of the same design were fabricated on a 4″ square substrate and tested. The transistors use a linear cross channel design.

TABLE-US-00008 Current Mobility on/off Channel Channel Average standard ratio Counted length width mobility deviation I.sub.on/off number [microns] [microns] [cm.sup.2/Vs] % (average) of devices 12 9800 4.09 12.4% 7.49E+07 12 12 9800 3.96 10.9% 6.85E+07 11 12 9800 4.15  9.2% 6.33E+07 11 12 9800 4.15  6.2% 6.89E+07 11

[0242] The results show that high performance linear source-drain OTFT with low turn-on voltage can be prepared by using ethyl lactate as the solvent of SU8 passivation layer. FIGS. 6A and 6B show the transfer characteristics and mobility curves of the fourth group of devices from the substrate, respectively (the results of 11 devices are plotted on each graph).

Example 2

[0243] Further device test results were obtained using a series of transistor designs with different channel widths, where ethyl lactate was used as the solvent of SU8 passivation layer. In this group of devices, the thickness of the organic gate insulator (OGI) layer was 300 nm, and the etching time for the organic gate insulator (OGI) layer and the organic semiconductor (OSC) layer was 60 s.

[0244] The results are shown in the table below, and the transfer characteristics and mobility curves are also shown in FIGS. 6C and 6D, respectively.

TABLE-US-00009 Channel Channel Average Mobility Current on/off Counted lengths widths mobility standard ratio I.sub.on/off number of [micron] [micron] [cm.sup.2/Vs] deviation % (average) devices 12 200 3.64 11.5% 5.57E+06 10 12 816 3.66  9.0% 1.94E+07 7 12 2000 3.61  9.6% 3.53E+07 10 12 280 3.37 16.0% 6.53E+06 10

Example 3 (Comparative Experiment)

[0245] The comparative data of the device using the passivation layer coated with the passivation layer formulation containing a solvent mixture of Cyrene and hexanol (9:1 by weight) was obtained, with the same solid content and crosslinking formulation as those in Example 2 being used. Although the mobility shown in the table below is generally comparable to the results in Example 2, the transfer characteristic curve in FIG. 7A shows the significantly reduced performance thereof—subthreshold slope and low current on/off ratio.

TABLE-US-00010 Channel Channel Average Mobility Current on/off Counted lengths widths mobility standard ratio I.sub.on/off number of [micron] [micron] [cm.sup.2/Vs] deviation % (average) devices 12 200 2.89  7.4% 1.61E+04 16 12 816 3.00 17.8% 3.34E+04 16 12 2000 2.81 22.5% 7.64E+04 15 12 280 2.72 26.9% 8.97E+03 15

[0246] In summary, the present application provides a formulation for preparing a passivation and/or photo-patterning layers for use in fabrication of organic electronic devices that may be provided, for example directly, on organic layers, such as an organic gate insulator (OGI) layer and an organic semiconductor (OSC) layer and/or a stack comprising one or more of these layers, without adversely affecting the organic layers. The formulation comprises a solvent of lactate and/or a derivative thereof. Further, the present application provides a method of fabrication of organic electronic devices, using such a formulation, which can reduce the complexity and cost of the device. In addition, the present application provides an organic electronic device, including a passivation layer and/or a photopatterning layer provided by such a formulation, that has better long-term stability.

[0247] Although preferred embodiments have been shown and described, it will be appreciated by those skilled in the art that various changes and modifications might be made without departing from the scope of the application, as defined in the appended claims. For example, the square pad and frame corresponding with the square aperture may be modified to be a circular pad and frame to correspond with a circular aperture. For example, the gap may be provided within the aperture rather than outside and adjacent to the aperture.

[0248] Attention is directed to all papers and documents which are filed concurrently with or previous to this specification in connection with this application and which are open to public inspection with this specification, and the contents of all such papers and documents are incorporated herein by reference.

[0249] All features disclosed in this specification (including any accompanying claims and drawings), and/or all of the steps of any method or process so disclosed, may be combined in any combination, except combinations where at least some of such features and/or steps are mutually exclusive.

[0250] Each feature disclosed in this specification (including any accompanying claims and drawings) may be replaced by alternative features serving the same, equivalent or similar purpose, unless expressly stated otherwise. Thus, each feature disclosed is one example only of a generic series of equivalent or similar features, unless explicitly stated otherwise.

[0251] The present application is not restricted to the details of the foregoing embodiment(s). The present application extends to any novel one or any new combination, of the features disclosed in this specification (including any accompanying claims and drawing), or to any new one, or any new combination, of the steps of any method or process so disclosed.

[0252] This disclosure is an example of the principles of the embodiments of the present application and is not intended to limit the application in any form or substance, or to limit the application to specific embodiments. It will be apparent to those skilled in the art that the elements, methods and systems, etc. of the technical schemes of the embodiments of the present application may be altered, changed, modified and evolved without departing from the principles, spirit and scope as defined in the claims of the embodiments and technical schemes of the present application as described above. These altered, changed, modified and evolved embodiments are all included in the scope of equivalent embodiments of the present application, which are all included within the scope of the present application defined by the claims. Although embodiment of the present application may be embodied in many different forms, some embodiments of the present application are described in detail herein. In addition, any possible combination of some or all of the various embodiments described herein is included in the embodiments of the present application and is also included in the scope of the present application defined by the claims. All patents, patent applications and other cited materials mentioned anywhere in the present application or any of the cited patents, cited patent applications or other cited materials are hereby incorporated by reference in their entirety.

[0253] The above disclosure is provided as illustrative rather than exhaustive. For those skilled in the art, this specification will suggest many variations and alternatives. All such alternatives and variations are intended to be included within the scope of the claims, wherein the term “including” means “including, but not limited to”.

[0254] The description of the alternative embodiments of the present application is completed herein. Those skilled in the art will recognize other equivalent variations of the embodiments described herein, which are also encompassed by the claims appended hereto.