# US 7,407,849 B2 · Self-aligned printing > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 7,407,849 B2 - Document ID: US7407849B2 - Status: Granted - Kind: B2 - Application number: 10/499,665 - Filed: 2002-12-20 - Published: 2005-07-14 - Granted: 2008-08-05 - Earliest claimed: 2001-12-21 - Assignees: Plastic Logic Limited; Cambridge University Technical Services Limited - Inventors: Henning Sirringhaus; Michael J. Banach; Nicholas Jim Stone; David William Joseph Wilson; John Devin Mackenzie; Wilhelmus Theodorus Stefanus Huck; Christoph Wilhelm Sele - Web page: https://patentgrep.com/patent/US7407849B2 ## CPC - H10K 71/611: {using printing deposition, e.g. ink jet printing} - B82Y 30/00: Nanotechnology for materials or surface science, e.g. nanocomposites - H10K 10/464: {Lateral top-gate IGFETs comprising only a single gate} - H10K 10/466: {Lateral bottom-gate IGFETs comprising only a single gate} - H10K 10/468: {characterised by the gate dielectrics} - H10K 71/13: using printing techniques, e.g. ink-jet printing or screen printing - H10K 71/231: {by etching of existing layers} - H10K 85/1135: {Polyethylene dioxythiophene [PEDOT]; Derivatives thereof} - H10K: ORGANIC ELECTRIC SOLID-STATE DEVICES - B82Y: SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES ## Abstract A method for forming an organic or partly organic switching device. The method comprises depositing layers of conducing, semiconducting and/or insulating layers by solution processing and direct printing. Then, high-resolution patterns of electroactive polymers are formed by self-aligned formation of a surface energy barrier around a first pattern that repels the solution of a second material. ## Claims ### Claim 1 A method of forming an electronic device, comprising: forming a first body having a first composition on a first region of a substrate; subsequently depositing a liquid of a second composition in contact with the first body to form a second body not in contact with the first body on a second region of the substrate adjacent the first region; and preparing the surface of the first body prior to the deposition of the liquid of the second composition to repel the liquid of the second composition, wherein the shortest distance between the first and second bodies defines a dimension of a critical feature of the electronic device, and wherein the first body forms an active feature of the electronic device. ### Claim 2 (depends on 1) A method according to claim 1, wherein the step of preparing the surface of the first body includes selecting the composition of the first body such that the surface thereof repels the liquid of the second composition. ### Claim 3 (depends on 1) A method according to claim 1, wherein the electronic device is a field effect transistor and the critical feature is the channel length of the FET. ### Claim 4 (depends on 3) A method as claimed in claim 3, comprising the additional step of depositing a solvent on top of the first and second body, wherein said solvent dissolves a layer on the substrate in the region between the edge of the first and second body. ### Claim 5 (depends on 4) A method as claimed in claim 4, wherein said dissolution opens up a via-hole interconnection to a conducting layer that is part of the substrate layer structure, and further conducting material is deposited into the region between the first and second body to fill the via-hole interconnection. ### Claim 6 (depends on 5) A method as claimed in claim 5, wherein the diameter of said via-hole interconnection is less than 20 μm. ### Claim 7 (depends on 1) A method as claimed in claim 1, wherein the first composition is a solution of at least two components having a tendency to segregate. ### Claim 8 (depends on 7) A method as claimed in claim 7, wherein one of the components is a polymer with a tendency to segregate to the surface of the first composition. ### Claim 9 (depends on 7) A method as claimed in claim 7, wherein one of the components is a diblock copolymer comprising a relatively polar and a relatively non-polar block. ### Claim 10 (depends on 7) A method as claimed in claim 7, wherein one of the components is a surfactant. ### Claim 11 (depends on 1) A method as claimed in claim 1, comprising treating the first body prior to deposition of the liquid of the second composition so as to modify at least one physical or chemical property of the surface of the first body. ### Claim 12 (depends on 11) A method as claimed in claim 11, wherein the property is composition. ### Claim 13 (depends on 11) A method as claimed in claim 11, wherein the property is surface roughness. ### Claim 14 (depends on 11) A method as claimed in claim 11, wherein the property is surface energy. ### Claim 15 (depends on 11) A method as claimed in claim 11, wherein the step of treating the surface of the first body does not modify the surface energy of the substrate in the second region. ### Claim 16 (depends on 11) A method as claimed in claim 11, wherein the contact angle of the liquid of the second composition on said treated surface of the first body is higher by more than 10° than that on the surface of the substrate in the second region. ### Claim 17 (depends on 11) A method as claimed in claim 11, wherein the contact angle of the liquid of the second composition on said treated surface of the first body is higher by more than 40° than that on the surface of the substrate in the second region. ### Claim 18 (depends on 11) A method as claimed in claim 11, wherein the contact angle of the liquid of the second composition on said treated surface of the first body is higher by more than 70° than that on the surface of the substrate in the second region. ### Claim 19 (depends on 11) A method as claimed in claim 11, wherein the step of treating the surface of the first body comprises increasing the density of fluorinated or alkylated chemical groups on the surface of the first body. ### Claim 20 (depends on 11) A method as claimed in claim 11, wherein the step of surface treating the first body comprises applying a surfactant to the surface of the first body. ### Claim 21 (depends on 20) A method as claimed in claim 20, wherein the surface of the first body comprises positively charged ionic species. ### Claim 22 (depends on 21) A method as claimed in claim 21, wherein the surfactant is an anionic surfactant. ### Claim 23 (depends on 20) A method as claimed in claim 20, wherein the surface of the first body comprises negatively charged ionic species. ### Claim 24 (depends on 23) A method as claimed in claim 23, wherein the surfactant is a cationic surfactant. ### Claim 25 (depends on 24) A method as claimed in claim 24, wherein said layer of a different composition is a polymer brush. ### Claim 26 (depends on 23) A method as claimed in claim 23, wherein said layer of a different composition is a polymer layer. ### Claim 27 (depends on 20) A method as claimed in claim 20, wherein the surface of the substrate is subjected to a thermal treatment or exposure to electromagnetic radiation prior to application of said surfactant. ### Claim 28 (depends on 11) A method as claimed in claim 11, wherein the step of treating the surface of the first body comprises growing a layer of a different composition off the surface of the first composition. ### Claim 29 (depends on 11) A method as claimed in claim 11, wherein the step of treating the surface of the first body comprises exposing the substrate to a plasma treatment. ### Claim 30 (depends on 29) A method as claimed in claim 29, wherein said plasma treatment comprises exposure to a plasma containing a fluorinated species. ### Claim 31 (depends on 30) A method as claimed in claim 30, wherein said plasma treatment comprises exposure to CF4 or a radical of CF4. ### Claim 32 (depends on 31) A method as claimed in claim 31, comprising the additional step of removing the material of the first body in the surrounding region after the deposition of the second body. ### Claim 33 (depends on 32) A method as claimed in claim 32, wherein said step of removing the material of the first body in the surrounding region involves etching. ### Claim 34 (depends on 11) A method as claimed in claim 11, wherein the step of surface treating the first body comprises dedoping the surface of the first body or depleting the surface of the first body of charge carriers. ### Claim 35 (depends on 11) A method as claimed in claim 11, wherein the step of surface treating the first body comprises etching the surface of the first body. ### Claim 36 (depends on 1) A method as claimed in claim 1, wherein the first composition comprises a solution of one or more materials in a solvent, which dries to form the first body; and the first body has a bulk region and a surrounding region around the periphery of the bulk region and in contact with the substrate. ### Claim 37 (depends on 36) A method as claimed in claim 36, wherein the width of said surrounding region is less than 20 μm. ### Claim 38 (depends on 36) A method as claimed in claim 36, wherein the surface energy in the surrounding region is different from that of the substrate surface in a region not covered by the first body. ### Claim 39 (depends on 36) A method as claimed in claim 36, wherein the surface roughness in the surrounding region is different from that of the substrate surface in the second region. ### Claim 40 (depends on 36) A method as claimed in claim 36, wherein the thickness of the first body in the surrounding region does not exceed 80% of the greatest thickness of the first body in said bulk region. ### Claim 41 (depends on 36) A method as claimed in claim 36, wherein the solution of the first composition recedes from the surrounding region during the drying of the solution of the first composition. ### Claim 42 (depends on 36) A method as claimed in claim 36, wherein the solution of the first composition comprises a surface modifying component that modifies the surface energy of the substrate in the surrounding region. ### Claim 43 (depends on 42) A method as claimed in claim 42, wherein the surface modifying component modifies the surface energy of the substrate while the solution of the first composition recedes from the surrounding region. ### Claim 44 (depends on 42) A method as claimed in claim 42, wherein the surface modifying component diffuses out of said bulk region into said surrounding region. ### Claim 45 (depends on 36) A method as claimed in claim 36, wherein prior to the deposition of the liquid of the second composition, the substrate is heated to cause the first body to recede from the surrounding region. ### Claim 46 (depends on 36) A method as claimed in claim 36, wherein the method comprises treating the surface of the first body in the surrounding region, so as to increase the contact angle of the solution of the second composition in the surrounding region. ### Claim 47 (depends on 36) A method as claimed in claim 36, wherein the substrate has a surface layer that dissolves into the solution of the first composition during the drying of the solution of the first composition, thereby uncovering the underlying material of the substrate in said surrounding region. ### Claim 48 (depends on 1) A method as claimed in claim 1, wherein the liquid of said second composition comprises a surfactant. ### Claim 49 (depends on 1) A method as claimed in claim 1 in which the first body is in a solid state while the liquid of the second composition is deposited. ### Claim 50 (depends on 1) A method as claimed in claim 1 in which the first body is in a liquid state while the solution of the second composition is deposited. ### Claim 51 (depends on 1) A method as claimed in claim 1, comprising confining the liquid of the second composition after depositing it on the substrate, so as to encourage the liquid of the second composition to contact the first body in a defined region of the first body. ### Claim 52 (depends on 1) A method as claimed in claim 1, wherein the liquid of at least one of the first or second composition is deposited by ink-jet printing. ### Claim 53 (depends on 1) A method as claimed in claim 1, wherein the liquid of at least one of the first or second composition is deposited by spray-coating. ### Claim 54 (depends on 1) A method as claimed in claim 1, wherein the liquid of at least one of the first or second composition is applied to the substrate as a continuous film, and the substrate contains regions of relatively low surface energy, that cause the liquid to dewet from said regions of relatively low surface energy. ### Claim 55 (depends on 1) A method as claimed in claim 1, wherein the liquid of the first composition is deposited by offset printing. ### Claim 56 (depends on 1) A method as claimed in claim 1, wherein the liquid of the second composition dries to form a second body and at least one of the first body and the second body is electrically conductive. ### Claim 57 (depends on 56) A method as claimed in claim 56, wherein both the first body and the second body are electrically conductive. ### Claim 58 (depends on 57) A method as claimed in claim 57, wherein the first and second body form electrodes of an electronic device. ### Claim 59 (depends on 58) A method as claimed in claim 58, wherein the first and second body form source and drain electrodes of an electronic switching device. ### Claim 60 (depends on 58) A method as claimed in claim 58, wherein the first and second body form source and drain electrodes of a thin film transistor. ### Claim 61 (depends on 56) A method as claimed in claim 56, wherein at least one of said first or second body comprises a conducting polymer. ### Claim 62 (depends on 56) A method as claimed in claim 56, wherein the liquid of the second composition dries to form a second body and at least one of the first and second bodies comprises a inorganic conductive material deposited from solution. ### Claim 63 (depends on 1) A method as claimed in claim 1, wherein the liquid of the second composition dries to form a second body and at least one of the first body and the second body is semiconductive. ### Claim 64 (depends on 63) A method as claimed in claim 63, wherein both the first body and the second body are semiconductive. ### Claim 65 (depends on 63) A method as claimed in claim 63, wherein at least one of the first body and the second body comprises a conjugated polymer. ### Claim 66 (depends on 63) A method as claimed in claim 63, comprising forming an electronic device having said semiconductive body as an active semiconducting layer thereof. ### Claim 67 (depends on 1) A method as claimed in claim 1, wherein the liquid of the second composition dries to form a second body and at least one of the first body and the second body is electrically insulating. ### Claim 68 (depends on 67) A method as claimed in claim 67, wherein both the first body and the second body are electrically insulating. ### Claim 69 (depends on 67) A method as claimed in claim 67, wherein at least one of said first or second body comprises an electrically insulating polymer. ### Claim 70 (depends on 1) A method as claimed in claim 1 wherein the distance between the edge of the first and second body is less than 20 μm. ### Claim 71 (depends on 1) A method as claimed in claim 1 wherein the distance between the edge of the first and second body is less than 1 μm. ### Claim 72 (depends on 1) A method as claimed in claim 1 wherein the distance between the edge of the first and second body is less than 100 nm. ### Claim 73 (depends on 1) A method as claimed in claim 1 wherein the distance between the edge of the first and second body is less than 10 nm. ### Claim 74 (depends on 1) A method as claimed in claim 1, comprising the additional step of depositing a solution of a third composition on top of the first and second body to form a third body in contact with the first and second body. ### Claim 75 (depends on 74) A method as claimed in claim 74, wherein the solution of said third composition is repelled by the surface of both the first and second body. ### Claim 76 (depends on 75) A method as claimed in claim 75, wherein the third body is confined to a region on the substrate between the edge of the first and second body. ### Claim 77 (depends on 74) A method as claimed in claim 74, wherein said third body is semiconducting. ### Claim 78 (depends on 74) A method as claimed in claim 74, wherein said third body is electrically conducting. ### Claim 79 (depends on 74) A method as claimed in claim 74, wherein said third body is electrically insulating. ### Claim 80 (depends on 1) An electronic device formed by a method as claimed in claim 1. ### Claim 81 (depends on 1) A logic circuit, display memory or sensor device formed by a method as claimed in claim 1. ### Claim 82 A method of forming an electronic device, comprising: forming a first body on a first region of the substrate; and subsequently depositing a liquid of a second composition in contact with the first body to form a second body in contact with the first body on a second region of the substrate adjacent the first region, wherein the first body has a non-conducting or semiconducting surface region whose thickness defines a dimension of a critical feature of the electronic device, and a conductive region underlying the non-conducting or semiconducting surface region. ### Claim 83 (depends on 3, 82) A method as claimed in claim 3 or 82, wherein the liquid of the second composition is deposited in such a way that it comes in contact with the first body only at the periphery of the first region of the substrate. ### Claim 84 (depends on 1, 82) A method as claimed in claim 1 or claim 82, wherein the first and second body consist essentially of the same material. ### Claim 85 (depends on 1, 82) A method as claimed in claim 1 or claim 82, wherein the first composition has a tendency to segregate to form a surface region and an interior region of the first body, the surface region having a different composition from the interior region. ### Claim 86 (depends on 85) A method as claimed in claim 85, wherein the contact angle of the liquid of the second composition on said surface region is higher by more than 10° than that on the surface of the substrate in the second region. ### Claim 87 (depends on 86) A method as claimed in claim 86, wherein the contact angle of the liquid of the second composition on said surface region is higher by more than 40° than that on the surface of the substrate in the second region. ### Claim 88 (depends on 87) A method as claimed in claim 87, wherein the contact angle of the liquid of the second composition on said surface region is higher by more than 70° than that on the surface of the substrate in the second region. ### Claim 89 (depends on 86) A method as claimed in claim 86, wherein the liquid of a second composition comprises a solvent and said surface region is insoluble in the solvent. ### Claim 90 (depends on 85) A method as claimed in claim 85, wherein said surface region contains alkylated or fluorinated chemical groups. ### Claim 91 (depends on 85) A method, as claimed in claim 85, wherein said surface region of the first body is electrically insulating. ### Claim 92 (depends on 91) A method as claimed in claim 91, comprising forming an electronic device having said electrically insulating surface region as a dielectric layer thereof. ### Claim 93 (depends on 92) A method as claimed in claim 92, comprising forming a thin film transistor device having said electrically insulating surface region as a dielectric layer thereof. ### Claim 94 (depends on 85) A method as claimed in claim 85, wherein said surface region of the first body is electrically conducting. ### Claim 95 (depends on 94) A method as claimed in claim 94, comprising forming an electronic device having said electrically conducting surface region as an electrode therefor. ### Claim 96 (depends on 95) A method as claimed in claim 95, wherein said electrically conducting surface region forms an electrical injection layer for injecting charge into a semiconductive layer. ### Claim 97 (depends on 85) A method, as claimed in claim 85, wherein said surface region of the first body is semiconducting. ### Claim 98 (depends on 97) A method as claimed in claim 97, comprising forming an electronic device having said semiconductive surface region as an active semiconducting layer thereof. ### Claim 99 (depends on 98) A method as claimed in claim 98, wherein the electronic device is an electronic switching device. ### Claim 100 (depends on 99) A method as claimed in claim 99, wherein the electronic device is a thin film transistor. ### Claim 101 (depends on 85) A method as claimed in claim 85, comprising the step of removing the surface region of the first body after the deposition of the second body. ### Claim 102 An electronic switching device comprising a source electrode, a drain electrode, a gate electrode, a semiconductor region electrically between the source electrode and the drain electrode and a dielectric region electrically between the semiconductor region and the gate electrode, the semiconductor region being in the form of a layer of substantially uniform thickness located over at least one of the source electrode and the drain electrode and being located physically between and adjacent to the source electrode and the drain electrode so as to separate the source electrode and the drain electrode such that at their closest proximity the source electrode and the drain electrode are spaced apart by the thickness of the said layer. ### Claim 103 An electronic switching device comprising a source electrode, a drain electrode, a gate electrode, a semiconductor region electrically between the source electrode and the drain electrode and a dielectric region electrically between the semiconductor region and the gate electrode, the dielectric region being in the form of a layer of substantially uniform thickness and being: located physically between and adjacent to the gate electrode and at least one of the source electrode and the drain electrode, so as to separate the gate electrode and the said one of the source electrode and the drain electrode such that at their closest proximity the gate electrode and the said one of the source electrode and the drain electrode are spaced apart by the thickness of the said layer; and located physically between and adjacent to the source electrode and the drain electrode, so as to separate the source electrode and the drain electrode such that at their closest proximity the source electrode and the drain electrode are spaced apart by the thickness of the said layer.