TWI619246B - Inkjet devices - Google Patents
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- TWI619246B TWI619246B TW103116624A TW103116624A TWI619246B TW I619246 B TWI619246 B TW I619246B TW 103116624 A TW103116624 A TW 103116624A TW 103116624 A TW103116624 A TW 103116624A TW I619246 B TWI619246 B TW I619246B
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- 239000010410 layer Substances 0.000 claims abstract description 157
- 239000002344 surface layer Substances 0.000 claims abstract description 86
- 238000000151 deposition Methods 0.000 claims abstract description 25
- 238000004381 surface treatment Methods 0.000 claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- 230000008859 change Effects 0.000 claims abstract description 5
- 239000012777 electrically insulating material Substances 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 82
- 238000000034 method Methods 0.000 claims description 47
- 239000000463 material Substances 0.000 claims description 23
- 239000000758 substrate Substances 0.000 claims description 21
- 229920002120 photoresistant polymer Polymers 0.000 claims description 13
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 10
- 238000002347 injection Methods 0.000 claims description 7
- 239000007924 injection Substances 0.000 claims description 7
- 239000010409 thin film Substances 0.000 claims description 7
- 239000004065 semiconductor Substances 0.000 claims description 6
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 4
- 238000007641 inkjet printing Methods 0.000 claims description 4
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 4
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 4
- 238000000206 photolithography Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 description 21
- 230000002209 hydrophobic effect Effects 0.000 description 15
- 239000000976 ink Substances 0.000 description 15
- 238000000059 patterning Methods 0.000 description 14
- 230000008021 deposition Effects 0.000 description 8
- 238000009736 wetting Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 6
- 238000007639 printing Methods 0.000 description 5
- 230000004888 barrier function Effects 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000005286 illumination Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
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- 230000009977 dual effect Effects 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 3
- 229910010272 inorganic material Inorganic materials 0.000 description 3
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- 239000007789 gas Substances 0.000 description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
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- 238000004528 spin coating Methods 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 2
- YTPFRRRNIYVFFE-UHFFFAOYSA-N 2,2,3,3,5,5-hexamethyl-1,4-dioxane Chemical compound CC1(C)COC(C)(C)C(C)(C)O1 YTPFRRRNIYVFFE-UHFFFAOYSA-N 0.000 description 1
- DGXIWVPFUVBGLB-UHFFFAOYSA-N C(CCCCCCCCCCCCCCCCC)C(C(Cl)(Cl)Cl)CCCCCCCC Chemical compound C(CCCCCCCCCCCCCCCCC)C(C(Cl)(Cl)Cl)CCCCCCCC DGXIWVPFUVBGLB-UHFFFAOYSA-N 0.000 description 1
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000012025 fluorinating agent Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000005525 hole transport Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
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- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000002094 self assembled monolayer Substances 0.000 description 1
- 239000013545 self-assembled monolayer Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000000992 sputter etching Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
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Classifications
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
- H10K71/13—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen printing
- H10K71/135—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen printing using ink-jet printing
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/10—OLED displays
- H10K59/17—Passive-matrix OLED displays
- H10K59/173—Passive-matrix OLED displays comprising banks or shadow masks
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/10—OLED displays
- H10K59/12—Active-matrix OLED [AMOLED] displays
- H10K59/122—Pixel-defining structures or layers, e.g. banks
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/191—Deposition of organic active material characterised by provisions for the orientation or alignment of the layer to be deposited
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Electroluminescent Light Sources (AREA)
- Thin Film Transistor (AREA)
Abstract
本發明係關於一種製造電子裝置之方法，其包括：選擇性地施加表面處理，以改變表面層之第一或第二區域之表面能，以使得第一溶液在沉積於該第一區域上時之接觸角大於該第一溶液在沉積於該第二區域上時之接觸角，該第一區域圍繞並毗鄰該第二區域；及在該表面層上沉積界定井之護堤結構，該護堤結構包括電絕緣材料並圍繞該第一區域；將該第一溶液沉積於該表面層之該第二區域上，並乾燥該沉積的第一溶液，以形成層；及將第二溶液沉積於該由該第一溶液所形成之層上及該第一表面層區域上，其中該沉積的第一溶液在該表面層之該等第一及第二區域間之邊界上具有釘扎點，且該沉積的第二溶液具有不同的釘扎點。 The present invention relates to a method of fabricating an electronic device, comprising: selectively applying a surface treatment to change a surface energy of a first or second region of a surface layer such that a first solution is deposited on the first region a contact angle greater than a contact angle of the first solution when deposited on the second region, the first region surrounding and adjacent to the second region; and depositing a berm structure defining a well on the surface layer, the berm The structure includes an electrically insulating material surrounding the first region; depositing the first solution on the second region of the surface layer, and drying the deposited first solution to form a layer; and depositing a second solution on the a layer formed by the first solution and the first surface layer region, wherein the deposited first solution has a pinning point on a boundary between the first and second regions of the surface layer, and The deposited second solution has different pinning points.
Description
本發明大體上係關於電子裝置如有機發光二極體及有機薄膜電晶體，且更特定言之係關於一種製造包括具有表面層之基板及位於該表面層上之界定井的護堤結構之電子裝置之方法，及係關於一種包括基板及界定井的護堤結構之電子裝置，該基板具有表面層。 The present invention relates generally to electronic devices such as organic light-emitting diodes and organic thin film transistors, and more particularly to an electronic device for fabricating a berm structure comprising a substrate having a surface layer and a defined well located on the surface layer A method of apparatus, and an electronic device comprising a substrate and a berm structure defining a well, the substrate having a surface layer.
如本申請者的早期申請案PCT/GB2010/002235(2011年6月16日公開為WO2011/070316 A2，發明者Crankshaw及Dowling)中所指示，已對包括自溶液沉積活性組分(溶液加工)之電子裝置製造方法作了廣泛研究。若自溶液沉積活性組分，一個問題在於如何將活性組分控制在基板之所需區域中。該問題之一解決方案係提供一種包括界定出井之圖案化護堤層之基板，在該等井中可自溶液沉積活性組分。該等井在溶液乾燥時容納該溶液，以使得活性組分留在由該等井所界定之基板區域內。 As indicated in the applicant's earlier application PCT/GB2010/002235 (published as Jun. 16, 2011, WO 2011/070316 A2, inventor Crankshaw and Dowling), it has been included to include active components from solution deposition (solution processing). The electronic device manufacturing method has been extensively studied. If the active component is deposited from the solution, one problem is how to control the active component in the desired region of the substrate. One solution to this problem is to provide a substrate comprising a patterned banknote layer defining a well in which active components can be deposited from solution. The wells hold the solution as it dries to leave the active component in the area of the substrate defined by the wells.
已發現，此等方法尤其可用於自溶液沉積有機材料。該等有機材料可具有導電性、半導電性及/或光電活性，以使得其等在有電流通過時發光，或在光衝擊其等時藉由產生電流而檢測光。使用此等材料之裝置被稱為有機電子裝置。若該有機材料係發光材料，則該裝置被稱為有機發光裝置(OLED)。此外，溶液加工容許以低成本低溫製造薄膜電晶體(TFT)，及特定言之有機薄膜電晶體(OTFT)。在此等裝 置中，尤其重要的是將有機半導體(OSC)容納在該裝置之恰當區域及特定言之通道內，且已知可提供界定井之護堤以容納該OSC。 These methods have been found to be particularly useful for depositing organic materials from solution. The organic materials may have electrical conductivity, semiconductivity, and/or photoelectric activity such that they emit light when current is passed through, or when current is generated by light impact or the like. Devices that use such materials are referred to as organic electronic devices. If the organic material is a luminescent material, the device is referred to as an organic light-emitting device (OLED). In addition, solution processing allows thin film transistors (TFTs), and in particular organic thin film transistors (OTFTs), to be produced at low cost at low cost. In this loading Centrally, it is especially important to house an organic semiconductor (OSC) in the proper area of the device and in particular channels, and it is known to provide a berm defining the well to accommodate the OSC.
一些裝置可能需要不止單一溶液沉積層。典型的OLED(如用於顯示器中者)可具有兩層有機半導體材料-一層可係發光材料層(諸如發光聚合物(LEP))，且另一層可係電洞傳輸材料(諸如聚噻吩衍生物或聚苯胺衍生物)層。 Some devices may require more than a single solution deposition layer. A typical OLED (such as used in a display) can have two layers of organic semiconductor material - one layer of luminescent material (such as a light emitting polymer (LEP)), and another layer can be a hole transport material (such as a polythiophene derivative) Or a layer of polyaniline derivative).
簡單的護堤結構具有設計成用於容納所有依次沉積液體之單一材料/層。在此裝置中，所有層延伸至(大約)相同的釘扎點可導致在該點上引起邊緣效應，及/或護堤材料可能無法針對所有使用的液體呈現最佳性質(例如潤濕行為)。此外，若裝置針對所有沉積液體具有單一護堤材料及單一釘扎點，則存在產生漏電路徑或溶液沉積層任一側電極間發生短路之風險。如圖1a及1b中所示，在包括HIL-IL-EL-陰極結構之OLED結構中，該洩漏路徑可由該陰極直接接觸護堤上之電洞注入層(HIL)(圖1a)、在護堤上形成極薄裝置堆疊物(圖1b)或在釘扎點處產生點接觸而引起。此可見於圖2a及2b之相應裝置結果中，其中完全印刷裝置(虛線曲線)之JV曲線(電流密度-電壓；圖2a)在反向驅動(例如在-4V下)時及在接通(例如在1V下)之前顯示高洩漏(高電流)。在具有旋塗中間層(IL)及電致發光層(EL)(加粗實線曲線)時，洩漏係低得多，因為HIL之頂部完全被旋塗膜覆蓋。相應的效率曲線(圖2b)反映此結果，其中完全印刷情形顯示低得多的效率。 A simple berm structure has a single material/layer designed to accommodate all of the sequentially deposited liquid. In this device, the extension of all layers to (approximately) the same pinning point may result in edge effects at this point, and/or the berm material may not exhibit optimal properties for all liquids used (eg, wetting behavior). . In addition, if the device has a single berm material and a single pinning point for all of the deposited liquid, there is a risk of creating a short circuit between the leakage path or the electrode on either side of the solution deposition layer. As shown in FIGS. 1a and 1b, in an OLED structure including a HIL-IL-EL-cathode structure, the leakage path can be directly contacted by the cathode to a hole injection layer (HIL) on the berm (Fig. 1a). The formation of a very thin device stack on the bank (Fig. 1b) or caused by point contact at the pinning point. This can be seen in the corresponding device results of Figures 2a and 2b, where the JV curve (current density-voltage; Figure 2a) of the full printing device (dashed curve) is reverse driven (e.g., at -4V) and on ( High leakage (high current) is shown before, for example, at 1V. In the case of a spin-on intermediate layer (IL) and an electroluminescent layer (EL) (bold solid line curve), the leakage system is much lower because the top of the HIL is completely covered by the spin coating film. The corresponding efficiency curve (Fig. 2b) reflects this result, with the full printing situation showing much lower efficiency.
根據上文，針對沉積於井中之不同液體提供兩個不同釘扎點之雙護堤結構在某些情形下可係有利。圖3a及3b顯示具有單釘扎點之雙護堤配置(圖3a)與具有雙釘扎點之雙護堤配置(圖3b)間之比較結果。 In accordance with the above, a dual berm structure that provides two different pinning points for different liquids deposited in the well may be advantageous in certain circumstances. Figures 3a and 3b show the comparison between a double berm configuration with a single pinning point (Figure 3a) and a double berm configuration with double pinning points (Figure 3b).
WO 2009/077738(2009年6月25日公開之PCT/GB2008/004135，發明者Burroughes及Dowling，申請者Cambridge Display Technology Ltd.)揭示一種針對沉積於井中之不同液體提供兩個不同釘扎點之雙護 堤結構，其中一者位於井周圍之第一層之邊緣，且另一者位於退離該井之第二層之邊緣。 WO 2009/077738 (PCT/GB2008/004135, published on Jun. 25, 2009, the inventor Burroughes and Dowling, Applicant Cambridge Display Technology Ltd.) discloses a method of providing two different pinning points for different liquids deposited in a well. Double guard A bank structure, one of which is located at the edge of the first layer around the well and the other is located at the edge of the second layer that exits the well.
WO2011/070316(上述)揭示一種製造包括界定井的雙護堤結構之電子裝置之方法，且旨在容許不同流體分別釘扎至兩個護堤並容納於其中。然而，WO2011/070316之方法需要光圖案化步驟，以移除第一絕緣層之部份。 WO 2011/070316 (described above) discloses a method of manufacturing an electronic device comprising a dual berm structure defining a well, and is intended to allow different fluids to be pinned separately to and contained in the two berms. However, the method of WO 2011/070316 requires a photo patterning step to remove portions of the first insulating layer.
因此，希望提供一種容許不同液體分別釘扎並容納在井內之改良結構及/或一種製造此結構之方法。該改良結構尤其可具有諸如以下優勢：裝置更為緊湊、結構複雜性低及/或可以更少加工步驟進行製造，其中任一者均可提高裝置製造之時間或成本效益及/或提高裝置產率及/或可重複性，及/或減少關於組成材料體積及數量之要求，其可(例如)降低成本。 Accordingly, it is desirable to provide an improved structure that allows different liquids to be pinned separately and housed in a well and/or a method of making the structure. The improved structure may have, inter alia, advantages such as a device that is more compact, has a lower structural complexity, and/or can be manufactured with fewer processing steps, either of which can increase the time or cost effectiveness of device manufacture and/or increase the yield of the device. Rate and/or repeatability, and/or reduced requirements regarding the volume and quantity of constituent materials, which may, for example, reduce costs.
根據本發明之第一態樣，提供一種製造電子裝置之方法，該電子裝置包括具有表面層之基板及該表面層上之界定井的護堤結構，該方法包括：選擇性地對該表面層施加表面處理，以改變該表面層之第一或第二區域之表面能，以使得第一溶液在沉積於該第一區域上時之接觸角大於該第一溶液在沉積於該第二區域上時之接觸角，該第一區域圍繞並毗鄰該第二區域；及在該表面層上沉積界定井之護堤結構，該護堤結構包括電絕緣材料並圍繞該第一區域；將該第一溶液沉積於該表面層之該第二區域上，並乾燥該沉積的第一溶液，以形成層；及將第二溶液沉積於該由該第一溶液所形成之層上及該第一表面層區域上，其中該沉積的第一溶液在該表面層之該等第一及第二區域間之邊界上具有釘扎點，且該沉積的第二溶液具有另一不同的釘扎點。 According to a first aspect of the present invention, there is provided a method of fabricating an electronic device comprising a substrate having a surface layer and a berm structure defining a well on the surface layer, the method comprising: selectively: the surface layer Applying a surface treatment to change the surface energy of the first or second region of the surface layer such that a contact angle of the first solution when deposited on the first region is greater than deposition of the first solution on the second region a contact angle of the time, the first region surrounding and adjacent to the second region; and depositing a berm structure defining a well on the surface layer, the berm structure comprising an electrically insulating material and surrounding the first region; Depositing a solution on the second region of the surface layer, and drying the deposited first solution to form a layer; and depositing a second solution on the layer formed by the first solution and the first surface layer The region wherein the deposited first solution has a pinning point on a boundary between the first and second regions of the surface layer, and the deposited second solution has a different pinning point.
因此，在一實施例中，第一外表面層區域相對於第二內表面層區域具有低潤濕性，且此可在該等第一及第二區域間之邊界上產生釘 扎點。(在一實施例中，釘扎點可視為用於組織溶液流過該釘扎點之間斷處，該釘扎點有效地為此流體提供能量障壁。此釘扎點可相當於(例如)沿著該第二表面層區域之週長之二維(例如，線性)間斷處)。 Thus, in an embodiment, the first outer surface layer region has a low wettability relative to the second inner surface layer region, and this may create a staple on the boundary between the first and second regions Pick up. (In one embodiment, the pinning point can be considered to be used for tissue solution flow through the break between the pinning points, the pinning point effectively providing an energy barrier for the fluid. This pinning point can be equivalent to, for example, along A two-dimensional (eg, linear) discontinuity of the perimeter of the second surface layer region).
因此，沉積於更濕潤的內表面層區域上液體微滴在表面層(例如，裝置陽極)之展開可由此受到限制。有利地，與該第一溶液具有更大接觸角之表面層區域可由此充當內部護堤，所以一實施例可無需超過一個物理護堤層。換言之，該實施例可提供具有雙釘扎點之的單一物理護堤。在至少該第一溶液係利用噴墨技術進行沉積之情形下，此可具有獨特優勢。 Thus, the deployment of liquid droplets on the surface layer (e.g., device anode) deposited on the more wet inner surface layer region can thereby be limited. Advantageously, the surface layer region having a greater contact angle with the first solution may thus serve as an internal berm, so an embodiment may not require more than one physical barrier layer. In other words, this embodiment can provide a single physical berm with double pinning points. This may have a unique advantage in situations where at least the first solution is deposited using ink jet technology.
在一實施例中，內部區域與外部區域間之表面能差異可提供第一溶液之釘扎點，而第一表面層區域與護堤結構之井界定壁間之邊界(其可具有類似表面能差異)可為第二溶液提供釘扎點。 In one embodiment, the difference in surface energy between the inner region and the outer region provides a pinning point for the first solution, and the boundary between the first surface layer region and the well defining wall of the bank structure (which may have similar surface energy) The difference) provides a pinning point for the second solution.
該界定井的護堤結構較佳包括至少一個界定用於限制第二溶液之至少部份之橫向範圍的井之物理護堤層(「橫向範圍」係在實質上平行於表面層之平面內)。 Preferably, the berm structure defining the well includes at least one physical barrier layer defining a well for limiting a lateral extent of at least a portion of the second solution ("lateral extent" is in a plane substantially parallel to the surface layer) .
就加工步驟之任何順序而言，護堤結構可在表面處理之前或之後沉積，且可存在介入步驟。第一溶液較佳係在沉積該護堤結構後沉積。 In any order of processing steps, the berm structure can be deposited before or after surface treatment and there can be an intervention step. The first solution is preferably deposited after depositing the berm structure.
可另外提供該方法，其中該表面處理增加第一溶液在該第一區域上之接觸角(亦即，該表面處理降低該第一區域之潤濕性)。(另外或或者，該處理可減小第一溶液在第二區域上之接觸角)。較佳地，該表面層在進行該表面處理之前係實質上親水，與第一溶液具有該較大接觸角之第一區域在進行該表面處理之後係實質上疏水，及/或第二區域在被該與第一溶液具有該較大接觸角之第一區域圍繞時，在進行該表面處理之後保持實質上親水。該等第一及第二區域與第一溶液之不同接觸角較佳係在平坦的該表面層上提供。 The method may additionally be provided wherein the surface treatment increases the contact angle of the first solution on the first region (i.e., the surface treatment reduces the wettability of the first region). (Additionally or alternatively, the treatment may reduce the contact angle of the first solution on the second region). Preferably, the surface layer is substantially hydrophilic prior to performing the surface treatment, the first region having the larger contact angle with the first solution is substantially hydrophobic after performing the surface treatment, and/or the second region is When surrounded by the first region having the larger contact angle with the first solution, it remains substantially hydrophilic after the surface treatment. The different contact angles of the first and second regions with the first solution are preferably provided on the flat surface layer.
可另外提供該方法，其包括：在該表面層之該第一或該第二區域上提供犧牲層區域，以防止該等第一及第二區域中之另一者之表面能在該表面處理期間發生該變化；施加該表面處理；及至少部份移除該犧牲層區域。然而，吾人注意到，此移除無法在該表面處理後立即進行。 The method may be additionally provided, comprising: providing a sacrificial layer region on the first or second region of the surface layer to prevent surface treatment of the other of the first and second regions from being processed at the surface The change occurs during the application; the surface treatment is applied; and the sacrificial layer region is at least partially removed. However, we have noticed that this removal cannot be performed immediately after the surface treatment.
可另外提供該方法，其中該提供該犧牲層區域包括：在該表面層上沉積犧牲層；進行光微影術，以用光阻劑選擇性地覆蓋該犧牲層之該犧牲層區域及選擇性地曝露該犧牲層之其他區域；移除該犧牲層之該曝露區域，以藉助該選擇性覆蓋光阻劑防止移除該犧牲層區域；在移除該犧牲層之該曝露區域後，移除該選擇性覆蓋光阻劑。較佳地，在該表面處理後實質上(較佳完全)移除該犧牲層區域。較佳地，該曝露的其他區域係在該表面層之第一區域上及/或覆蓋該表面層之第一區域。 The method may be further provided, wherein the providing the sacrificial layer region comprises: depositing a sacrificial layer on the surface layer; performing photolithography to selectively cover the sacrificial layer region and the selectivity of the sacrificial layer with a photoresist Exposing other regions of the sacrificial layer; removing the exposed region of the sacrificial layer to prevent removal of the sacrificial layer region by the selective overlying photoresist; removing the exposed region of the sacrificial layer, removing This selective coverage of the photoresist. Preferably, the sacrificial layer region is substantially (preferably completely) removed after the surface treatment. Preferably, the exposed other regions are on the first region of the surface layer and/or cover the first region of the surface layer.
注意，移除犧牲層之曝露區域可進一步移除至少一些剩餘的光阻劑。此外，「之後」並不排除介入步驟，例如，移除選擇性覆蓋光阻劑可能並非在移除犧牲層之曝露區域後立即進行，及/或移除犧牲層區域可能並非在表面處理後立即進行。 Note that removing the exposed area of the sacrificial layer may further remove at least some of the remaining photoresist. In addition, "after" does not exclude the intervention step. For example, removing the selective overlying photoresist may not be performed immediately after removing the exposed area of the sacrificial layer, and/or removing the sacrificial layer area may not be immediately after surface treatment. get on.
可另外提供該方法，其中該部份移除該犧牲層區域係藉由至少一個加工步驟進行，該至少一個加工步驟係在該表面處理之後在實質上移除剩餘的該犧牲層區域之前進行。部份移除犧牲層區域可(例如)移除犧牲層厚度之薄層(例如，10-20nm)。 The method may additionally be provided wherein the partial removal of the sacrificial layer region is performed by at least one processing step performed prior to the surface treatment to substantially remove the remaining sacrificial layer region. Partial removal of the sacrificial layer region may, for example, remove a thin layer of sacrificial layer thickness (eg, 10-20 nm).
可另外提供該方法，其中該犧牲層的初始沉積厚度係在10-50nm之範圍內。 The method may additionally be provided wherein the initial deposited thickness of the sacrificial layer is in the range of 10-50 nm.
可另外提供該方法，其中該表面處理包括蒸氣曝露，較佳矽烷蒸氣曝露。 The method may additionally be provided wherein the surface treatment comprises vapor exposure, preferably decane vapor exposure.
可另外提供該方法，其中該犧牲層區域包括氧化鎢。此氧化鎢 可稱為WOx，且可包括(例如)三氧化鎢。或者，可使用其他金屬氧化合物，諸如氧化鉬。 The method may additionally be provided wherein the sacrificial layer region comprises tungsten oxide. This tungsten oxide It may be referred to as WOx and may include, for example, tungsten trioxide. Alternatively, other metal oxygen compounds such as molybdenum oxide can be used.
可另外提供該方法，其中該表面層包括無機材料，諸如氧化銦錫(例如，ITO)或摻雜錫之銦氧化物(例如氧化銦(III)(In2O3)及氧化錫(IV)(SnO2)(例如，90% In2O3，10% SnO2，以重量計)之固溶體)。 The method may additionally be provided wherein the surface layer comprises an inorganic material such as indium tin oxide (eg, ITO) or tin-doped indium oxide (eg, indium (III) oxide (In 2 O 3 ) and tin (IV) oxide) (SnO 2 ) (for example, 90% In 2 O 3 , 10% SnO 2 , by weight) solid solution).
可另外提供該方法，其中該電子裝置係發光裝置，較佳有機發光裝置，諸如OLED，且其中第一溶液包括第一有機半導體材料，且係用於提供電洞注入層(HIL)，及/或其中第二溶液包括第二有機半導體材料，且係用於提供中間層(IL)或發光層(EL)，或者，該裝置可係吸光層，諸如光伏打裝置。其中該電子裝置係發光裝置，該方法可用於製造包括複數個此等裝置之電致發光顯示器。 The method may additionally be provided, wherein the electronic device is a light emitting device, preferably an organic light emitting device such as an OLED, and wherein the first solution comprises a first organic semiconductor material and is used to provide a hole injection layer (HIL), and/ Or wherein the second solution comprises a second organic semiconductor material and is used to provide an intermediate layer (IL) or an illuminating layer (EL), or the device may be a light absorbing layer, such as a photovoltaic device. Wherein the electronic device is a light emitting device that can be used to fabricate an electroluminescent display comprising a plurality of such devices.
可另外提供該方法，其中在該表面處理後(例如，在即將沉積第二溶液之前)，該第一溶液在沉積於該表面層之第一區域上時之接觸角係約50°或更大(更佳大於約100°或約150°)。另外或或者，在該表面處理後(例如，在即將沉積第一溶液之前)，該第一溶液在沉積於該表面層之第二區域上時之接觸角係約10°或更小。在一具體實施例中，該表面層(例如，ITO)上之第一溶液(例如，HIL)在「內部護堤」(例如，經第一表面區域圍繞之第二表面區域)上之接觸角<10°及/或在「外部護堤」(例如，物理護堤結構)上之接觸角>80°(然而，應注意：HIL可能不會達到所謂的外部護堤)。該第二溶液(例如，IL)較佳在乾燥第一溶液(例如，HIL)上之接觸角<20°，在內部護堤上之接觸角<25°(例如當該內部護堤係疏水但親油而使得IL潤濕越過內部護堤區域時，此係可能出現)及/或在第一表面層區域及/或外部護堤上之接觸角>60°。 The method may additionally be provided, wherein after the surface treatment (for example, just prior to deposition of the second solution), the contact angle of the first solution when deposited on the first region of the surface layer is about 50° or greater (More preferably greater than about 100° or about 150°). Additionally or alternatively, after the surface treatment (e.g., immediately prior to deposition of the first solution), the first solution has a contact angle of about 10 or less when deposited on the second region of the surface layer. In a specific embodiment, the contact angle of the first solution (eg, HIL) on the surface layer (eg, ITO) on the "internal berm" (eg, the second surface region surrounded by the first surface region) <10° and/or contact angles on the "external berm" (for example, physical berm structure) > 80° (however, it should be noted that the HIL may not reach the so-called external berm). The second solution (eg, IL) preferably has a contact angle <20° on the dried first solution (eg, HIL) and a contact angle <25° on the inner berm (eg, when the inner berm is hydrophobic but When the oleophilic oil causes the IL to wet over the inner berm area, this may occur) and/or the contact angle on the first surface layer region and/or the outer berm is >60°.
較佳地，毗鄰並圍繞第一表面層區域之護堤結構之至少一區域與第二溶液之接觸角大於約90°，更佳係100°或更大。 Preferably, at least one region of the berm structure adjacent and surrounding the first surface layer region has a contact angle with the second solution of greater than about 90, more preferably 100 or greater.
較佳地，在該沉積該第二溶液期間，該第二溶液在該第一區域上之接觸角小於該第二溶液在該護堤結構上(例如至少在該護堤結構沿著該第一區域之週長之區域上)之接觸角。此可藉由對該第一區域或該護堤結構進行選擇性表面處理及/或藉由適當選擇材料(諸如護堤結構材料)而實現。 Preferably, during the depositing the second solution, the contact angle of the second solution on the first region is smaller than the second solution on the berm structure (eg, at least the berm structure is along the first The contact angle of the area of the perimeter of the area. This can be achieved by selective surface treatment of the first region or the berm structure and/or by appropriate selection of materials such as berm structure materials.
可另外提供該方法，其中該第二溶液之釘扎點係位於該表面層之該第一區域與該護堤結構間之邊界上。 The method may additionally be provided wherein the pinning point of the second solution is on the boundary between the first region of the surface layer and the bank structure.
根據本發明之第二態樣，提供一種包括基板及界定井的護堤結構之電子裝置，該基板具有表面層，其中該界定井的護堤結構係置於該表面層上，該界定井的護堤結構包括電絕緣材料並圍繞該表面層之第一及第二區域，該裝置包括：置於該表面層之該第二區域上之第一溶液可加工層；及置於該表面層之該第一區域上及該第一溶液可加工層上之第二溶液可加工層，其中該第一區域係在該第二區域與該護堤結構之間，且圍繞並毗鄰該第二區域。 According to a second aspect of the present invention, there is provided an electronic device comprising a substrate and a berm structure defining a well, the substrate having a surface layer, wherein the berm structure defining the well is placed on the surface layer, the well defining The berm structure includes an electrically insulating material and surrounding the first and second regions of the surface layer, the device comprising: a first solution processable layer disposed on the second region of the surface layer; and disposed on the surface layer a second solution processable layer on the first region and on the first solution processable layer, wherein the first region is between the second region and the berm structure and surrounds and abuts the second region.
在一實施例中，該護堤結構可圍繞但不會直接接觸該第一區域，例如可存在(例如)約10μm或更大之間隔。 In an embodiment, the berm structure may surround but not directly contact the first region, for example, there may be an interval of, for example, about 10 [mu]m or more.
可另外提供該電子裝置，其中第一及第二區域間之邊界界定第一層與第二層間之界面。在沉積期間，用於形成該第一層之溶液較佳釘扎在該等第一及第二區域間之邊界上，且在溶液可加工的第一層乾燥後，沉積用於形成該第二層之溶液並釘扎在不同邊界上。在一實施例中，該第一區域上之該第二層可進一步置於該護堤結構之至少一部份上；然而，該第一區域與該護堤結構間之邊界較佳可為用於形成該第二層之溶液提供釘扎點。 The electronic device can be additionally provided, wherein a boundary between the first and second regions defines an interface between the first layer and the second layer. During deposition, the solution for forming the first layer is preferably pinned at the boundary between the first and second regions, and after the first layer of the solution processable is dried, deposited for forming the second The solution of the layers is pinned to different boundaries. In an embodiment, the second layer on the first region may be further disposed on at least a portion of the berm structure; however, the boundary between the first region and the berm structure may preferably be used A pinning point is provided for the solution forming the second layer.
較佳地，一實施例之內部釘扎點(該等第一及第二區域間之邊界)與外部(第二)釘扎點(例如，在該第一區域與該護堤結構之間)間之最小間隔係至少約10μm，較佳大於約20μm。然而，該間隔在同一裝 置內及不同裝置間可有所變化，例如端視該第一區域與該護堤結構之配向而定。 Preferably, an internal pinning point (the boundary between the first and second regions) and an outer (second) pinning point (for example, between the first region and the berm structure) of an embodiment The minimum spacing between them is at least about 10 μm, preferably greater than about 20 μm. However, the interval is in the same package There may be variations between the interior and the different devices, for example depending on the alignment of the first region and the berm structure.
可另外提供該電子裝置，其中該表面層包括氧化銦錫。 The electronic device may additionally be provided wherein the surface layer comprises indium tin oxide.
可另外提供該電子裝置，其中至少用於形成該第一溶液可加工層之溶液可藉由噴墨印刷沉積。(溶液可加工層通常係可藉由沉積隨後乾燥形成該層之溶液而形成之層)。 The electronic device can additionally be provided wherein at least a solution for forming the first solution processable layer can be deposited by ink jet printing. (The solution processable layer is usually a layer which can be formed by depositing a solution which is subsequently dried to form the layer).
可另外提供該電子裝置，其中該電子裝置係發光裝置(諸如OLED)，且表面層包括該發光裝置之電極。可另外提供該電子裝置，其中第一層係電洞注入層(HIL)，及/或其中第二層係中間層(IL)或(例如)包括發光聚合物(LEP)之發光層(EL)。(作為發光裝置之替代，該裝置可係吸光層，諸如光伏打裝置)。 The electronic device may be additionally provided, wherein the electronic device is a light emitting device such as an OLED, and the surface layer includes electrodes of the light emitting device. The electronic device may be additionally provided, wherein the first layer is a hole injection layer (HIL), and/or wherein the second layer is an intermediate layer (IL) or, for example, a light-emitting layer (EL) including a light-emitting polymer (LEP) . (Alternatively, as a light-emitting device, the device may be a light absorbing layer, such as a photovoltaic device).
可另外提供包括複數個此等發光裝置之電致發光顯示器。 An electroluminescent display comprising a plurality of such illumination devices can be additionally provided.
可另外提供該電子裝置，其中該電子裝置係包括其上配置護堤結構之源極及汲極之薄膜電晶體，諸如有機薄膜電晶體(OTFT)，其中該電晶體之通道區域係界定在該源極及汲極之間。較佳地，表面層包括基板表面或該表面層包括該源極及汲極。 The electronic device may be additionally provided, wherein the electronic device comprises a thin film transistor having a source and a drain on which a berm structure is disposed, such as an organic thin film transistor (OTFT), wherein a channel region of the transistor is defined Between the source and the bungee. Preferably, the surface layer comprises a substrate surface or the surface layer comprises the source and the drain.
可另外提供該電子裝置，其中用於形成第一層之第一溶液在該表面層之第二區域上之接觸角係大於用於形成第二層之第二溶液在該表面層之第一區域上之接觸角。 The electronic device may be additionally provided, wherein a first solution for forming the first layer has a contact angle on a second region of the surface layer greater than a first solution for forming a second layer in the first region of the surface layer The contact angle on the top.
較佳實施例係定義在附屬項中。 The preferred embodiment is defined in the dependent items.
以上態樣之任何一者或多者及/或較佳實施例之以上可選特徵之任何一者或多者可以任何排列組合。 Any one or more of the above aspects and/or any one or more of the above optional features of the preferred embodiment may be combined in any permutation.
A1‧‧‧表面層 A1‧‧‧ surface layer
A1i‧‧‧第二表面層區域 A1i‧‧‧Second surface layer area
A1o‧‧‧第一表面層區域 A1o‧‧‧ first surface layer area
B1‧‧‧護堤結構 B1‧‧‧Belt structure
B2‧‧‧內部物理護堤 B2‧‧‧Internal physical berm
D1‧‧‧裝置實施例 D1‧‧‧ device example
PP1‧‧‧內部釘扎點 PP1‧‧‧ internal pinning point
PP2‧‧‧釘扎點 PP2‧‧‧ pinning point
PR1‧‧‧光阻劑圖案 PR1‧‧‧ photoresist pattern
S1‧‧‧第一溶液 S1‧‧‧ first solution
S2‧‧‧第二溶液 S2‧‧‧Second solution
SL1‧‧‧犧牲層 SL1‧‧‧ sacrificial layer
SR1‧‧‧犧牲層區域 SR1‧‧‧ sacrificial layer area
301‧‧‧極少重疊產生到達HIL之洩漏路徑 301‧‧‧very overlap creates a leak path to the HIL
302‧‧‧長得多的重疊延長到達HIL之洩漏路徑 302‧‧‧A much longer overlap extends the leak path to the HIL
701‧‧‧陽極表面 701‧‧‧Anode surface
702‧‧‧疏水ITO 702‧‧‧Hydrophilic ITO
703‧‧‧外部護堤 703‧‧‧External berm
為更好地理解本發明及顯示如何實現本發明，現將以實例方式參考附圖，其中：圖1a及1b顯示已知單一護堤基板在製成裝置時之橫截面；陰極可 直接接觸護堤上之電洞注入層(HIL)(圖1a，曝露PEDOT)、在護堤上具有極薄裝置堆疊物(圖1b，護堤上之薄裝置堆疊物)或點接觸於釘扎點；圖2a及2b顯示圖1a及1b之裝置之結果。完全印刷裝置(虛線曲線)之JV曲線(圖2a)在反向驅動(例如在-4V下)時及在接通(例如在1V下)之前顯示高洩漏(高電流)。在具有旋塗中間層(IL)及電致發光層(EL)(加粗實線)時，洩漏係低得多，因為HIL之頂部完全被該等旋塗膜覆蓋。效率曲線(圖2b)反映此結果，其中完全印刷情形(虛線)顯示低得多的效率；圖3a及3b比較具有單釘扎點之雙護堤配置(圖3a顯示極少重疊產生到達HIL之洩漏路徑；301)及具有雙釘扎點之雙護堤配置(圖3b顯示長得多的重疊延長到達HIL之洩漏路徑；302)；圖4a及4b顯示用於進行比較之雙護堤雙釘扎點裝置結構(圖4a)及一實施例之單護堤雙釘扎點結構(圖4b)；圖5顯示一實施例之製造方法，其中使犧牲內部像素圖案化係用以保持ITO層清潔及潤濕，且然後以最後沖洗步驟加以移除；圖6顯示包括犧牲無機材料(無機犧牲SR1)之一實施例之像素，其中弧形箭頭表示作為最後沖洗步驟沖洗掉；圖7a及7b顯示一實施例之雙釘扎點結構之實例，其中圖7a顯示在最後沖洗犧牲WOx前之平面圖(未印刷，圖7a包含：在最後沖洗之前的陽極表面701(ITO上具有10nm Sac-WOx)；疏水ITO 702(「內部」護堤區域或HIL釘扎點)；及「外部」護堤B1 703)，且圖7b顯示平面圖(單滴HIL)，其顯示移除犧牲WOx後之極佳潤濕性；且圖8顯示包括雙護堤雙釘扎點結構之裝置之結果(虛線曲線)及包括單護堤雙釘扎點結構之實施例裝置之結果(實線曲線)。 For a better understanding of the present invention and how the present invention can be implemented, reference will now be made to the accompanying drawings, in which FIGS. 1a and 1b show a cross section of a known single bank substrate in the fabrication of the device; Direct contact with the hole injection layer (HIL) on the berm (Fig. 1a, exposed PEDOT), with a very thin stack of devices on the berm (Fig. 1b, thin stack of devices on the berm) or point contact with pinning Points; Figures 2a and 2b show the results of the apparatus of Figures 1a and 1b. The JV curve of the full printing device (dashed curve) (Fig. 2a) shows high leakage (high current) when driven in reverse (for example at -4 V) and before switching on (for example at 1 V). In the case of a spin-on intermediate layer (IL) and an electroluminescent layer (EL) (bold solid line), the leakage is much lower because the top of the HIL is completely covered by the spin coating. The efficiency curve (Fig. 2b) reflects this result, where the full printing situation (dashed line) shows much lower efficiency; Figures 3a and 3b compare the double berm configuration with a single pinning point (Fig. 3a shows very little overlap to produce a leak to the HIL) Path; 301) and double berm configuration with double pinning points (Fig. 3b shows a much longer overlap extending the leak path to the HIL; 302); Figures 4a and 4b show double pinning for the double berm for comparison Point device structure (Fig. 4a) and a single bevel double pinning point structure of an embodiment (Fig. 4b); Fig. 5 shows a manufacturing method of an embodiment in which a sacrificial internal pixel patterning system is used to keep the ITO layer clean and Wetting, and then removing it in the final rinsing step; Figure 6 shows a pixel comprising an embodiment of a sacrificial inorganic material (inorganic sacrificial SR1), wherein the curved arrows indicate flushing as a final rinsing step; Figures 7a and 7b show one An example of a double pinning point structure of an embodiment, wherein Figure 7a shows a plan view prior to final rinsing of the sacrificial WOx (unprinted, Figure 7a includes: anode surface 701 (10 nm Sac-WOx on ITO) prior to final rinsing; hydrophobic ITO 702 ("internal" berm area HIL pinning point); and "outer" berm B1 703), and Figure 7b shows a plan view (single drop HIL) showing excellent wettability after sacrificial WOx removal; and Figure 8 shows double berm double The result of the device of the pinning point structure (dashed curve) and the result of the embodiment device including the single bead double pinning point structure (solid curve).
可描述在概念上至少包含單護堤雙釘扎點結構之一實施例。此實施例之雙釘扎點配置包括「內部」釘扎點，其邊緣設定在「外部」護堤內並與之分離。例如，一噴墨裝置實施例包括物理護堤結構，以在噴墨印刷期間容納墨水，該裝置在單一物理護堤層內具有複數個對應於各別墨水之液體釘扎點(但僅出於完整性考慮應指出的是，可(例如) 提供一或多個其他物理護堤層以獲得其他釘扎點)。有利地，使用兩個此種物理分離的液體釘扎點，以使得後續的沉積或印刷層不與下伏的第一層共用相同的液體釘扎點，且因而完全覆蓋該下伏的第一層。因此，此護堤系統對第一層之漏電性可係較低(較佳經減小、最小化或消除)，其進而有利於裝置性能。 One embodiment that conceptually includes at least a single berm double pinning point structure can be described. The double pinning point configuration of this embodiment includes an "internal" pinning point with its edge disposed within and separated from the "outer" berm. For example, an inkjet device embodiment includes a physical berm structure to contain ink during inkjet printing, the device having a plurality of liquid pinning points corresponding to individual inks within a single physical berm layer (but only for Integrity considerations should be noted that, for example, One or more other physical berm layers are provided to obtain other pinning points). Advantageously, two such physically separated liquid pinning points are used such that the subsequent deposited or printed layer does not share the same liquid pinning point with the underlying first layer, and thus completely covers the underlying first Floor. Thus, the bermage system can have a lower leakage (preferably reduced, minimized, or eliminated) to the first layer, which in turn facilitates device performance.
為進行比較，圖4a顯示雙護堤雙釘扎點裝置結構，而圖4b顯示裝置實施例(D1)之單護堤雙釘扎點裝置結構。圖4a及4b各顯示包括陽極(表面層A1)之OLED結構。圖4a顯示呈物理護堤層B2形式之第一(「內部」)護堤，而圖4b具有第一表面層區域A1o。在兩個圖中，第一墨水層((例如)電洞注入層(HIL)之第一溶液S1)均接觸陽極(在圖4b實施例中，其至少包括內部第二表面層區域A1i)。在各圖4a及4b中，「外部」護堤係以物理護堤B1之形式提供，且第二墨水層((例如)發光層(EL)(諸如發光聚合物(LEP)層之第二溶液S2，其中EL與HIL間較佳具有中間層(IL))接觸第一墨水層。陰極(未顯示)較佳係提供在第二墨水層上，且可具有介入層，諸如電子傳輸層(ETL)及/或電子注入層(EIL)。(然而，應注意：圖4b中所示的墨水層在乾燥時可變平)。希望藉由(例如)確保陽極及/或HIL與陰極保持充分物理及/或電學分離而使陰極與陽極間具有低電洩漏。(就未在圖4b中顯示之陰極而言，當藉由(例如)真空蒸鍍沉積時，此可敷形於下一最低層。另外，就此而言，一實施例由於(例如)僅具有單一物理護堤而可具有更平坦輪廓。此可提高井內層厚度之均一性；相應地，此可提高發光裝置之發光均勻性及/或提高產率、可靠性及/或壽命))。 For comparison, Figure 4a shows the double berm double pinning point device structure, while Figure 4b shows the single berm double pinning point device structure of the device embodiment (D1). 4a and 4b each show an OLED structure including an anode (surface layer A1). Figure 4a shows the first ("inside") berm in the form of a physical barrier layer B2, while Figure 4b has a first surface layer region A1o. In both figures, the first ink layer (for example, the first solution S1 of the hole injection layer (HIL)) is in contact with the anode (in the embodiment of Fig. 4b, which includes at least the inner second surface layer region A1i). In each of Figures 4a and 4b, the "outer" berm is provided in the form of a physical berm B1 and a second ink layer (for example a light-emitting layer (EL) such as a second solution of a layer of luminescent polymer (LEP) S2, wherein preferably an intermediate layer (IL) between the EL and the HIL contacts the first ink layer. A cathode (not shown) is preferably provided on the second ink layer, and may have an intervening layer such as an electron transport layer (ETL) And/or an electron injecting layer (EIL). (However, it should be noted that the ink layer shown in Figure 4b can be flattened when dry.) It is desirable to ensure sufficient physics of the anode and/or HIL and cathode by, for example, And/or electrically separated to provide low electrical leakage between the cathode and the anode. (For the cathode not shown in Figure 4b, this can be applied to the next lowest layer when deposited by, for example, vacuum evaporation. In addition, in this regard, an embodiment may have a flatter profile due to, for example, having only a single physical berm. This may increase the uniformity of the thickness of the inner layer; accordingly, this may improve the uniformity of illumination of the illumination device. And/or improve yield, reliability and/or lifetime)).
與圖4a相比，一實施例略去內部物理護堤(B2)，以使得無需用於製造物理內部護堤之光圖案化步驟。否則，此光圖案化可導致噴墨印刷法之非潤濕像素區域及/或需要以反應性離子蝕刻(RIE)進行額外光遮罩步驟來界定內部護堤。 In contrast to Figure 4a, an embodiment omits the internal physical berm (B2) such that a light patterning step for making a physical internal berm is not required. Otherwise, this photopatterning can result in non-wetting pixel regions of the inkjet printing process and/or require additional photomasking steps with reactive ion etching (RIE) to define the inner berm.
儘管如此，此實施例可藉由選擇性地改變下伏表面(例如位於井底部之陽極表面)之表面性質得到雙釘扎點(參見(例如)，圖4b配置之釘扎點PP1及PP2)。此可導致潤濕性陽極主動像素區域(A1i)被陽極非潤濕區域(A1o)圍繞(例如，就第一液體(諸如HIL溶液)之潤濕性而言)。此沉積於該潤濕區域上之液體之液滴在陽極表面上之展開可由此受到限制。(該等墨水層中之任一者或多者可包括用於在液態沉積後於乾燥期間交聯成固態之聚合物)。該潤濕性質可確保陽極主動像素區域被第一液體(S1，其可為HIL溶液，例如，極性水基溶劑)完全覆蓋，亦即使得不存在第一液體厚度為零之區域。 Nonetheless, this embodiment can achieve a double pinning point by selectively changing the surface properties of the underlying surface (e.g., the anode surface at the bottom of the well) (see, for example, pinning points PP1 and PP2 of Figure 4b configuration). . This can result in the wetted anode active pixel region (A1i) being surrounded by the anode non-wetting region (A1o) (eg, in terms of wettability of the first liquid (such as a HIL solution)). The unfolding of the droplets of liquid deposited on the wetted area on the surface of the anode can thereby be limited. (Either or more of the ink layers may include a polymer for crosslinking into a solid during drying after liquid deposition). This wetting property ensures that the anode active pixel region is completely covered by the first liquid (S1, which may be a HIL solution, for example, a polar water-based solvent), that is, there is no region where the first liquid thickness is zero.
或者，圖4b之裝置實施例D1可描述為包括基板(未顯示)、界定井的護堤結構(B1)、表面層(A1)；該界定井的護堤結構係經配置以圍繞並部份覆蓋該表面層之第一區域(A1o)，其進而圍繞該表面層之第二區域(A1i)，該裝置另外包括分別由溶液S1及S2所形成之第一及第二墨水層。 Alternatively, device embodiment D1 of Figure 4b can be described as comprising a substrate (not shown), a berm structure (B1) defining a well, a surface layer (A1); the berm structure defining the well is configured to surround and partially Covering a first region (A1o) of the surface layer, which in turn surrounds a second region (A1i) of the surface layer, the device additionally includes first and second ink layers formed by solutions S1 and S2, respectively.
圖5顯示一種製造裝置實施例(D1)(諸如OLED)之方法。使較佳的透明陽極層(A1，例如，ITO，其可藉由在玻璃基板(未顯示)上真空沉積而形成；然而，替代性陽極層材料亦可係適宜)圖案化，然後清潔基板，以使該基板實質上無缺陷及污染物。然後沉積犧牲層(SL1)(其較佳係無機及/或水溶性層(且因此可藉由在水中清洗而移除))，以覆蓋陽極(步驟St1)。沉積技術可包括(例如)濺鍍或蒸鍍。在此實例中，該犧牲層包括WOx(氧化鎢)，且因此用術語Sac-WOx指代；然而，該犧牲層可包括一或多種替代性或其他材料。 Figure 5 shows a method of manufacturing device embodiment (D1), such as an OLED. A preferred transparent anode layer (A1, such as ITO, which may be formed by vacuum deposition on a glass substrate (not shown); however, an alternative anode layer material may be suitably patterned) and then the substrate is cleaned, So that the substrate is substantially free of defects and contaminants. A sacrificial layer (SL1), which is preferably an inorganic and/or water-soluble layer (and thus removable by washing in water), is then deposited to cover the anode (step St1). Deposition techniques can include, for example, sputtering or evaporation. In this example, the sacrificial layer comprises WOx (tungsten oxide) and is therefore referred to by the term Sac-WOx; however, the sacrificial layer may comprise one or more alternative or other materials.
較佳地，該犧牲層耐受光微影圖案化方法，然而，應注意，光微影圖案化方法通常實際上係水性，且因此可移除Sac-WOx之某一部份。就此而言，該犧牲層之初始厚度可在10-50nm之範圍內，及更佳係大於20nm，端視後續圖案化步驟之侵蝕性如何。藉由使沉積的犧 牲層具有足夠初始厚度，可在最後移除犧牲層之前以一或多個中間加工步驟移除薄層(例如，10-20nm)，例如，在光微影方法期間。然而，中間移除此等薄層可係有利，因為可防止犧牲層表面受到過度污染，且因此容許該犧牲層保持足夠溶解性，以在最後的Sac-WOx移除步驟中被移除。 Preferably, the sacrificial layer is resistant to photolithographic patterning methods, however, it should be noted that the photolithographic patterning process is typically aqueous in nature and thus a portion of the Sac-WOx can be removed. In this regard, the initial thickness of the sacrificial layer can be in the range of 10-50 nm, and more preferably greater than 20 nm, depending on how aggressive the subsequent patterning step is. By making the sacrifice of sediment The layer has a sufficient initial thickness to remove the thin layer (e.g., 10-20 nm) in one or more intermediate processing steps prior to the final removal of the sacrificial layer, for example, during the photolithography method. However, the intermediate removal of such thin layers can be advantageous because the sacrificial layer surface can be prevented from being overly contaminated, and thus the sacrificial layer is allowed to remain sufficiently soluble to be removed in the final Sac-WOx removal step.
使用標準光阻劑圖案化方法(通常係正型)界定像素(加工步驟St2)，該光阻劑像素(PR1)係充當犧牲層之遮罩。然後經由水性沖洗(例如，稀TMAH(氫氧化四甲銨)、熱DI(去離子)水)移除較佳水溶性無機犧牲層之一部份，然後以標準方式剝離光阻劑圖案PR1，但僅使用冷Cold-DI沖洗(例如，室溫或更低溫，以使得光阻劑下部的待剝離犧牲層不被移除)(步驟St3)。以上加工形成犧牲無機材料之像素(犧牲層區域SR1)，此顯示在圖6之區域A1i中。 The pixel is defined using a standard photoresist patterning method (typically positive) (processing step St2), which acts as a mask for the sacrificial layer. The portion of the preferred water-soluble inorganic sacrificial layer is then removed via an aqueous rinse (eg, dilute TMAH (tetramethylammonium hydroxide), hot DI (deionized) water), and then the photoresist pattern PR1 is stripped in a standard manner, However, only cold Cold-DI rinsing is used (for example, room temperature or lower temperature so that the sacrificial layer to be peeled off at the lower portion of the photoresist is not removed) (step St3). The above processing forms a pixel of the sacrificial inorganic material (sacrificial layer region SR1), which is shown in the area A1i of FIG.
然後，利用製劑(例如包含矽烷及/或包含具有(i)疏水頭部及附接點或(ii)親液或疏液頭部及附接點之分子之製劑)將區域A1o及較佳亦將A1i(參見圖6)曝露於蒸氣底塗步驟(St4)，其可使得A1o(ITO)之表面疏水，原因係(例如)該製劑與區域A1o中之羥基結合。 Then, using a formulation (eg, a formulation comprising decane and/or a molecule comprising (i) a hydrophobic head and attachment point or (ii) a lyophilic or lyophobic head and attachment point), the region A1o and preferably also A1i (see Figure 6) is exposed to a vapor undercoating step (St4) which can make the surface of A1o (ITO) hydrophobic because, for example, the formulation binds to the hydroxyl groups in the region A1o.
然後在水溶液中沖洗該基板，以容許移除(但非完全移除)WOx層(犧牲層區域SR1)之一部份(St4續)。此使WOx保持清潔，從而容許在隨後的最後移除Sac-WOx的步驟中進行更快速更均勻移除。 The substrate is then rinsed in an aqueous solution to allow removal (but not complete removal) of a portion of the WOx layer (sacrificial layer region SR1) (St4 continued). This keeps the WOx clean, allowing for faster and more uniform removal in the subsequent final step of removing the Sac-WOx.
然後使所有區域固化(例如200-250℃，持續30-60分鐘)，以強化疏水ITO表面A1o上之鍵結(St4續)。 All areas are then cured (eg, 200-250 ° C for 30-60 minutes) to strengthen the bond on the hydrophobic ITO surface A1o (St. 4).
然後使區域A1o之部份光圖案化，以形成疏水及/或疏油護堤，其可稱為單一(物理)「外部」護堤(B1)(步驟St5)。該圖案化過程及該單一護堤之後續顯影可進一步移除更多的Sac-WOx材料，以在烘烤該物理護堤之最後固化步驟之前使其再次清潔。 Part of the light of area A1o is then patterned to form a hydrophobic and/or oleophobic berm, which may be referred to as a single (physical) "outer" berm (B1) (step St5). The patterning process and subsequent development of the single berm can further remove more Sac-WOx material to clean it again prior to the final curing step of baking the physical berm.
在該物理護堤B1固化後，則可藉助最後的水性沖洗實質上(較佳 完全)移除最後的Sac-WOx層(St6)。ITO之內部像素(區域A1i)較佳極易被水基墨水(諸如HIL溶液)潤濕。 After the physical berm B1 is cured, the final aqueous rinse can be used substantially (preferably Completely remove the last Sac-WOx layer (St6). The internal pixels of the ITO (area A1i) are preferably highly wettable by water-based inks such as HIL solutions.
就使物理護堤B1之表面變得疏水之方法而言，應指出的是，可使用諸如SU-8之光阻劑來使此表面變得疏水。另外應指出的是，蒸氣底塗步驟可使用HMDS(六甲基二矽氮烷)，其可被視為黏著促進劑及/或表面改性劑(此改性降低表面能)。或者，可沉積包含OTS(十八烷基-三氯矽烷)之表面改性劑。而且，可自(例如)氣態或溶液態沉積自組裝單層，以提供一組附著至該表面且因此使該表面變得疏水之自組裝分子。 In the method of making the surface of the physical berm B1 hydrophobic, it should be noted that a photoresist such as SU-8 can be used to make the surface hydrophobic. It should also be noted that the vapor undercoating step may use HMDS (hexamethyldioxane), which may be considered an adhesion promoter and/or a surface modifier (this modification reduces surface energy). Alternatively, a surface modifier comprising OTS (octadecyl-trichlorodecane) can be deposited. Moreover, the self-assembled monolayer can be deposited, for example, from a gaseous or solution state to provide a set of self-assembling molecules attached to the surface and thereby rendering the surface hydrophobic.
應指出的是，一方法實施例可包括上文所述之一些或所有加工步驟及/或圖5中所示之一些或所有步驟。例如，除上述使A1o表面變得疏水之方法以外或作為其替代方法，可簡單地使在即將進入該階段之前存在之裝置靜置一段時間(例如2週)，而無需進行任何加工步驟，以使ITO區域A1o之表面經時自然變得疏水。因此，使A1o(ITO)表面變得疏水之加工在一實施例中可係不必要。 It should be noted that a method embodiment may include some or all of the processing steps described above and/or some or all of the steps illustrated in FIG. For example, in addition to or as an alternative to the above-described method of rendering the A1o surface hydrophobic, the device present prior to entering the stage can be simply left to stand for a period of time (eg, 2 weeks) without any processing steps, The surface of the ITO region A1o is naturally made hydrophobic over time. Therefore, the process of making the A1o (ITO) surface hydrophobic may not be necessary in one embodiment.
諸如上述之方法較佳使物理護堤B1內之陽極材料(例如ITO)之內部A1i及外部A1o區域上及/或該物理護堤上之相關液體產生適宜的液體接觸角(且因此產生適宜的表面能)。例如，然後HIL可潤濕ITO區域A1i，但不會潤濕疏水的「內部釘扎點區域」A1o，以便被容納。IL可潤濕「內部釘扎點區域」A1o，但不會潤濕物理護堤B1，以便填充至物理護堤B1，但為其所容納。因此，ITO可提供相對於外部物理護堤B1充當內部護堤之「內部釘扎點區域」A1o。 Preferably, the method described above preferably produces a suitable liquid contact angle on the interior A1i and the outer A1o region of the anode material (e.g., ITO) within the physical berm B1 and/or the associated liquid on the physical berm (and thus produces a suitable Surface energy). For example, the HIL can then wet the ITO region A1i, but does not wet the hydrophobic "internal pinning point region" A1o to be accommodated. IL wets the "internal pinning point area" A1o, but does not wet the physical berm B1 to fill the physical berm B1 but is accommodated. Therefore, the ITO can provide an "internal pinning point region" A1o serving as an inner berm with respect to the outer physical berm B1.
此可藉由選擇用於陽極(ITO)之單一蒸氣處理及單一護堤之材料及在用以使其等圖案化之加工順序中實現。就上述具體裝置實例而言，已使用氣相矽烷(例如，HMDS)方法來界定內部釘扎點PP1，因為其使所用HIL產生大接觸角，但使IL產生小接觸角。迄今為止，兩種 物理護堤材料已顯示獲得成功-具有來自Solvay之氟化劑之Zeon聚丙烯酸酯及來自Nissan之氟化護堤材料，因為此兩種護堤材料均與IL及LEP墨水產生大接觸角。 This can be achieved by selecting the material for the single vapor treatment of the anode (ITO) and the single berm and in the processing sequence used to pattern it. For the specific device examples described above, the gas phase decane (e.g., HMDS) method has been used to define the internal pinning point PP1 because it produces a large contact angle for the HIL used, but produces a small contact angle for the IL. So far, two Physical berm material has been shown to be successful - Zeon polyacrylate with Solvay's fluorinating agent and fluorinated berm material from Nissan, as both berming materials produce large contact angles with IL and LEP inks.
一實施例中之加工步驟包括使犧牲內部像素圖案化以保持ITO清潔及潤濕，及然後移除該犧牲內部像素作為最後沖洗步驟(如圖5中所示)。根據雙護堤系統之開發可理解此等實施例之優勢，其中前者難以實現使HIL在ITO上保持極小接觸角及使HIL在護堤上保持大接觸角但使IL在護堤上保持小接觸角之加工步驟。 The processing steps in an embodiment include patterning the sacrificial internal pixels to keep the ITO clean and wet, and then removing the sacrificial internal pixels as a final rinse step (as shown in Figure 5). The advantages of these embodiments can be understood from the development of a dual berm system in which it is difficult for the former to maintain a very small contact angle of the HIL on the ITO and to maintain a large contact angle of the HIL on the berm but keep the IL in small contact on the berm The processing steps of the corners.
圖5之圖案化方法容許ITO表面藉助光圖案化方法(其優勢係(例如)與RIE(快速離子蝕刻)方法相比具有低成本)及藉助一些保護陽極(ITO)像素免受將在護堤固化期間結合至該層中之污染物污染之簡單沖洗而變得潤濕或保持潤濕。此係有利的，因為ITO潤濕對噴墨法而言通常成問題，且使ITO保持親水之能力有時需要曝露至UV-臭氧或O2-電漿圖案化。此等處理很複雜(就O2-電漿圖案化而言)或使得ITO及護堤均潤濕，且因此無法容納墨水(如在UV-臭氧之情形下)。 The patterning method of Figure 5 allows the ITO surface to be protected from the bevel by means of a photo patterning process (which has advantages such as low cost compared to RIE (fast ion etching) methods) and with some protective anode (ITO) pixels The simple flushing of contaminant contamination incorporated into the layer during curing becomes wetted or remains wet. This system is advantageous, because ITO wetting for the ink jet method is generally problematic, and hydrophilicity retention of the ITO exposed to UV- ozone is sometimes necessary or O 2 - plasma patterning. Such process is complex (it O 2 - plasma patterning purposes) or such are ITO berm and wetting, and thus the ink can not be accommodated (as in the case of UV- ozone).
以犧牲層使ITO圖案化可保護ITO像素在後續步驟期間免受污染，其使得雙釘扎區域變得疏水，此等步驟係(例如)ITO之氣相矽烷蒸氣曝露及/或護堤固化步驟。在最後沖洗移除Sac-WOx後，ITO可持續許多小時呈現極潤濕狀態。如本實例中之情形，若犧牲層本身係電洞注入材料，則無需擔心在印刷HIL時有一定量殘留在該裝置中，只要像素(ITO)表面潤濕即可。 Patterning the ITO with a sacrificial layer protects the ITO pixel from contamination during subsequent steps, which causes the double pinned region to become hydrophobic, such as a gas phase decane vapor exposure and/or a berm curing step of, for example, ITO . After the final rinse to remove Sac-WOx, the ITO can be extremely wetted for many hours. As in the case of this example, if the sacrificial layer itself is a hole injecting material, there is no need to worry that a certain amount remains in the device when printing the HIL as long as the surface of the pixel (ITO) is wetted.
利用上述加工步驟製得之此單護堤雙釘扎點結構之影像係顯示於圖7a及7b中，其中圖7a顯示最後Sac-WOx沖洗前之平面圖(未印刷)，且圖7b顯示平面圖(單滴HIL)，其顯示移除Sac-WOx後之極佳潤濕性。此雙釘扎點配置較佳在護堤配置及液體下具有表面層，該表面層較佳包括ITO。該表面層之最內部區域較佳被第一液體(諸如HIL溶 液)潤濕。該最內部區域可係親水及/或疏油。將一或多個其他層印刷於由該第一液體所形成之第一層上，較佳在該表面層上延伸至物理護堤結構。因此，該第一層可被該(等)其他層完全覆蓋，此對於如上所述之低電洩漏而言係有利。 The image of the single bead double pinning point structure obtained by the above processing steps is shown in Figures 7a and 7b, wherein Figure 7a shows the plan view (unprinted) before the final Sac-WOx rinse, and Figure 7b shows the plan view ( A single drop of HIL) showed excellent wettability after removal of Sac-WOx. The double pinning point arrangement preferably has a surface layer in the bank configuration and liquid, the surface layer preferably comprising ITO. The innermost region of the surface layer is preferably dissolved by the first liquid (such as HIL Liquid) wetting. The innermost region can be hydrophilic and/or oleophobic. One or more other layers are printed on the first layer formed from the first liquid, preferably on the surface layer to the physical berm structure. Thus, the first layer can be completely covered by the (other) layers, which is advantageous for low electrical leakage as described above.
圖8顯示利用雙護堤雙釘扎點結構(虛線曲線)及單護堤雙釘扎點結構(實線)(例如，如圖7a及7b中所示的結構)所製得之裝置之JV(電流密度對電壓)結果。如圖所示，單護堤雙釘扎點實施例之實線曲線通常指示較低漏電性。 Figure 8 shows the JV of the device made with a double bead double pinning point structure (dashed curve) and a single bevel double pinning point structure (solid line) (for example, the structure shown in Figures 7a and 7b). (current density versus voltage) results. As shown, the solid curve of the single bevel double pinning embodiment generally indicates lower leakage.
如參照圖5所述之以上加工步驟可類似地應用於薄膜電晶體(例如，有機(OTFT))，以將墨水容納在此裝置之源極與汲極之間。本發明之一裝置實施例可係TFT(例如，OTFT)。 The above processing steps as described with reference to Figure 5 can be similarly applied to a thin film transistor (e.g., organic (OTFT)) to accommodate ink between the source and the drain of the device. An embodiment of the device of the present invention may be a TFT (e.g., an OTFT).
如參照圖5所述之類似加工步驟可用以製造結構大體上類似於上述發光裝置(例如，OLED)之光伏打裝置。本發明之一裝置實施例可係光伏打裝置。 A similar processing step as described with reference to Figure 5 can be used to fabricate a photovoltaic device that is substantially similar in structure to the illumination device described above (e.g., OLED). An embodiment of the apparatus of the present invention may be a photovoltaic device.
毫無疑問，技藝熟練人士將思及許多其他有效替代物。應瞭解，本發明並不限於所述實施例，且涵蓋位於所附申請專利範圍之精髓及範圍內並為熟習此項技術者所知曉之修飾。 There is no doubt that skilled artisans will consider many other effective alternatives. It is to be understood that the invention is not limited to the embodiments described, and is intended to be included within the scope and scope of the appended claims.
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