WO2015015113A1 - Fabrication d'une electrode grille par demouillage d'argent - Google Patents
Fabrication d'une electrode grille par demouillage d'argent Download PDFInfo
- Publication number
- WO2015015113A1 WO2015015113A1 PCT/FR2014/051962 FR2014051962W WO2015015113A1 WO 2015015113 A1 WO2015015113 A1 WO 2015015113A1 FR 2014051962 W FR2014051962 W FR 2014051962W WO 2015015113 A1 WO2015015113 A1 WO 2015015113A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- silver
- transparent conductive
- metal
- dewetting
- grid
- Prior art date
Links
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 32
- 239000004332 silver Substances 0.000 title claims abstract description 32
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 40
- 239000002184 metal Substances 0.000 claims abstract description 40
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000000758 substrate Substances 0.000 claims abstract description 30
- 238000000151 deposition Methods 0.000 claims abstract description 13
- 239000004020 conductor Substances 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 229910001316 Ag alloy Inorganic materials 0.000 claims abstract description 8
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 22
- 230000008021 deposition Effects 0.000 claims description 10
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 10
- 238000000137 annealing Methods 0.000 claims description 7
- 230000001788 irregular Effects 0.000 claims description 2
- 238000005240 physical vapour deposition Methods 0.000 claims description 2
- 238000005498 polishing Methods 0.000 claims description 2
- 239000012808 vapor phase Substances 0.000 claims description 2
- 239000010408 film Substances 0.000 description 27
- 239000010410 layer Substances 0.000 description 13
- 230000005540 biological transmission Effects 0.000 description 5
- 239000011521 glass Substances 0.000 description 4
- 238000005530 etching Methods 0.000 description 3
- 230000005525 hole transport Effects 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 230000000873 masking effect Effects 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 206010073306 Exposure to radiation Diseases 0.000 description 1
- HEFNNWSXXWATRW-UHFFFAOYSA-N Ibuprofen Chemical compound CC(C)CC1=CC=C(C(C)C(O)=O)C=C1 HEFNNWSXXWATRW-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 238000004049 embossing Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 238000005289 physical deposition Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000307 polymer substrate Polymers 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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
- H10K71/60—Forming conductive regions or layers, e.g. electrodes
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/805—Electrodes
- H10K50/81—Anodes
- H10K50/813—Anodes characterised by their shape
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/805—Electrodes
- H10K50/81—Anodes
- H10K50/814—Anodes combined with auxiliary electrodes, e.g. ITO layer combined with metal lines
-
- 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
- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
- H10K2102/10—Transparent electrodes, e.g. using graphene
- H10K2102/101—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO]
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
- H10K2102/301—Details of OLEDs
- H10K2102/351—Thickness
Definitions
- the present invention relates to a method of manufacturing a gate-shaped electrode supported for OLED using a silver dewetting step. It also relates to the electrode obtained by this method.
- TCO transparent conductive oxides
- Such metal networks can be manufactured by complex photolithography processes comprising several steps of masking, etching, exposure to radiation, washing, deposition etc.
- the object of the present invention is to provide a considerably simpler method of forming an OLED transparent electrode comprising, on a mineral glass substrate, a transparent conductive layer and a continuous metal network in contact with the transparent conductive layer.
- the method of the present invention unlike the photolithographic methods usually used for forming metal grids, does not require any masking, printing, ablating or selective etching step.
- the key steps of the method of the present invention are likely to be implemented on a magnetron sputtering line, which greatly facilitates the industrialization of this method of producing supported electrodes for OLED.
- the physical phenomenon underlying the present invention is the dewetting of thin films of solid silver. It is known that certain solid metal films, when heated to a much lower temperature than their melting temperature, do not remain in the form of continuous films but dewax to form metallic "droplets" having a smaller contact area. with the substrate.
- the present invention takes advantage of the relatively slow dynamics of this dewetting phenomenon to freeze the film being dewaxed before the individualization of the metal droplets. A metallic network is thus spontaneously formed which, when sufficiently continuous, allows the passage of an electric current.
- the Applicant has discovered that the conductivity and the transparency in the visible light of such a "dewaxed" metal network could easily be adjusted by modifying the initial film thickness, the temperature and the heating time.
- the geometry of the formed metal network may further be adjusted by performing the dewetting of the silver not on a perfectly smooth substrate, but on a substrate comprising a relief.
- This transparent conductive material can act as anode, output work adaptation layer or hole transport layer of the OLED organic stack. In all cases it will serve as a protective layer against oxidation of the silver grid during a possible storage and / or transport.
- the subject of the present invention is therefore a method for manufacturing an electrode for OLED, comprising the following successive steps:
- the present invention also relates to an electrode that can be obtained by such a method and which successively comprises a transparent substrate, a silver grid or random silver alloy obtained by dewetting a metal film, and a continuous layer of transparent conductive material covering said silver or silver alloy grid.
- any transparent heat-resistant substrate of step (b) can be used in principle. It is of course preferably inorganic glass substrates, especially thin or ultrathin glasses having a thickness of less than 1 mm, but one could also consider the use of polymer substrates.
- the substrate may be perfectly smooth, that is to say have a roughness of less than a few nanometers.
- the dewetting of the metal film will then be governed primarily by the surface and interfacial tensions of the metal.
- the substrate is not smooth but has a roughness or a sufficiently deep relief to guide or guide the dewetting.
- Such relief must be formed of juxtaposed individualized patterns of regular or irregular shape, formed for example by etching or embossing.
- the metal When a silver metallic film is deposited on such a relief formed of juxtaposed individualized patterns (pyramids, mounds, islets), the metal will fill, after dewaxing, preferentially the valleys. If the valleys form a continuous network, the metal network obtained should have good electrical conductivity while having an opening rate ensuring good transparency to the electrode.
- the silver or silver alloy film may be deposited by any known method for controlling its thickness. Examples of such methods include vacuum evaporation deposition, magnetron sputter deposition and chemical silver plating (reduction of silver salt). It is particularly interesting to deposit the silver film by magnetron sputtering because this technique also allows the deposition of a transparent conductive oxide, the process thus being able to be implemented on the same magnetron cathode sputtering line.
- the deposition of the metal film (step (a)) and the deposition of the transparent conductive oxide (step (c)) are both implemented by physical deposition in vapor phase (PVD), preferably by magnetron sputtering, on the same magnetron sputtering line.
- PVD physical deposition in vapor phase
- the step (b) of heating the substrate carrying the silver film is preferably carried out very shortly after the end of step (a) in order to avoid the oxidation of silver.
- the heating of the silver-coated substrate is carried out under vacuum, on the magnetron sputtering line, between step (a) and step (c).
- the heating temperatures indicated above are understood as the temperatures of the substrate carrying the metal film.
- the temperature of the heating elements is of course considerably higher than the temperature of the substrate, typically greater than 200 ° C to 300 ° C at the temperature at which it is desired to heat the substrate.
- the random metal grid formed after dewetting has a greater thickness than the initially deposited silver film. This thickness is however generally less than about 150 nm.
- the transparent electroconductive material deposited in step (c) may be a transparent conductive oxide (TCO). When it is deposited in a sufficient quantity, for example at a rate of 1 to 3 g / m 2 , it plays both the role of a planarization layer of the metal grid obtained by dewetting and the role of anode in the OLED final. The amount of transparent conductive oxide deposited must be sufficient to completely cover the grid.
- Deposition of the TCO is preferably by magnetron sputtering using a ceramic target. Reactive cathode sputtering from a metal target should be avoided as oxygen may oxidize the silver gate.
- the transparent conductive material may also be formed of an organic polymer, such as a PEDOTPSS polymer which has the same function as a TCO.
- an organic polymer such as a PEDOTPSS polymer which has the same function as a TCO.
- Such an organic polymer has the advantage of being liquid deposited and planarize perfectly the metal grid.
- the transparent conductive material may be the first layer, that is to say the hole transport layer (HTL) of the organic stack of the OLED.
- HTL hole transport layer
- the process of the present invention preferably comprises, after step (c), a second annealing step (d) at a temperature between 150 and 350 ° C for a period of 5 and 60 minutes.
- This second annealing essentially has the function of increasing the crystallinity and the conductivity of the partially amorphous TCO after deposition.
- the TCO layer deposited on the relief created by the metal grid generally has a large surface roughness, incompatible with the deposition of the stack of organic layers which requires a perfectly flat surface, otherwise leakage currents due to short circuits in the final OLED.
- the TCO layer is subjected, before or after annealing, to a step of polishing the transparent conductive oxide layer.
- Influence of the thickness of the silver film on the properties of the grid formed after dewetting Magnetron sputtering films of different thicknesses are deposited on a mineral glass substrate.
- the substrates carrying the films are immediately annealed in a radiation oven.
- the temperature at the substrate is 300 ° C and the heating time 30 and 45 minutes.
- the table below shows the resistances per square (Ra) and transmissions of silver films of different thicknesses, dewaxed by heating at a temperature of 300 ° C for 30 and 45 minutes.
- Dewetting a film 40 nm thick leads to an electroconductive network after 45 minutes of annealing.
- the lack of conductivity of the sample obtained after 30 minutes annealing is probably due to a lack of reproducibility.
- the optimum film thickness is 50 nm.
- the two samples obtained after 30 and 45 minutes of annealing have a resistance per square less than 3 ⁇ / ⁇ and have a transmission of between 29 and 41%. As the thickness of the silver film increases further, a decrease in square resistance accompanied by a decrease in transmission is observed.
- Figure 1 shows two electron microscopy snapshots of a silver grid obtained by dewetting (30 minutes at 300 ° C) of a silver film having a thickness of 40 nm.
Landscapes
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Electroluminescent Light Sources (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Physical Vapour Deposition (AREA)
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020167002359A KR20160037918A (ko) | 2013-08-01 | 2014-07-29 | 은의 디웨팅에 의한 게이트 전극의 제조 |
US14/908,427 US20160163984A1 (en) | 2013-08-01 | 2014-07-29 | Production of a gate electrode by dewetting silver |
JP2016530585A JP2016527688A (ja) | 2013-08-01 | 2014-07-29 | 銀をディウェッティングさせることによるゲート電極の製造 |
CN201480043463.4A CN105409029A (zh) | 2013-08-01 | 2014-07-29 | 通过使银反润湿来制备栅电极 |
EP14750596.0A EP3028321A1 (fr) | 2013-08-01 | 2014-07-29 | Fabrication d'une electrode grille par demouillage d'argent |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR1357665A FR3009436B1 (fr) | 2013-08-01 | 2013-08-01 | Fabrication d'une electrode grille par demouillage d'argent |
FR1357665 | 2013-08-01 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2015015113A1 true WO2015015113A1 (fr) | 2015-02-05 |
Family
ID=49212959
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/FR2014/051962 WO2015015113A1 (fr) | 2013-08-01 | 2014-07-29 | Fabrication d'une electrode grille par demouillage d'argent |
Country Status (8)
Country | Link |
---|---|
US (1) | US20160163984A1 (fr) |
EP (1) | EP3028321A1 (fr) |
JP (1) | JP2016527688A (fr) |
KR (1) | KR20160037918A (fr) |
CN (1) | CN105409029A (fr) |
FR (1) | FR3009436B1 (fr) |
TW (1) | TW201521263A (fr) |
WO (1) | WO2015015113A1 (fr) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20180190984A1 (en) * | 2016-12-30 | 2018-07-05 | Guardian Glass, LLC | Silver nano-metal mesh inclusive electrode, touch panel with silver nano-metal mesh inclusive electrode, and/or method of making the same |
EP3580644A1 (fr) * | 2017-02-08 | 2019-12-18 | Guardian Glass, LLC | Électrode comprenant un maillage nano-métallique d'argent, panneau tactile avec électrode comprenant un maillage nano-métallique d'argent, et/ou son procédé de fabrication |
CN109119332B (zh) * | 2018-07-30 | 2022-07-22 | 长春理工大学 | 一种采用退火方法制备图案化有序双金属纳米粒子阵列的方法 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1548852A2 (fr) * | 2003-12-22 | 2005-06-29 | Samsung Electronics Co., Ltd. | Dispositif électroluminescent d'un composant de nitrure à l'émission par la surface et procédé de sa manufacture |
WO2007123355A1 (fr) * | 2006-04-25 | 2007-11-01 | Seoul Opto-Device Co., Ltd. | Procédé pour former une électrode métallique, procédé pour fabriquer des éléments luminescents à semi-conducteur et éléments luminescents à semi-conducteur à base de nitrure |
FR2924274A1 (fr) * | 2007-11-22 | 2009-05-29 | Saint Gobain | Substrat porteur d'une electrode, dispositif electroluminescent organique l'incorporant, et sa fabrication |
US20120187821A1 (en) * | 2009-07-16 | 2012-07-26 | Lg Chem, Ltd. | Electrical conductor and a production method therefor |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5806653B2 (ja) * | 2011-12-27 | 2015-11-10 | 株式会社神戸製鋼所 | 反射電極用Ag合金膜、反射電極、およびAg合金スパッタリングターゲット |
US9237646B2 (en) * | 2012-05-14 | 2016-01-12 | The Hong Kong University Of Science And Technology | Electrical and thermal conductive thin film with double layer structure provided as a one-dimensional nanomaterial network with graphene/graphene oxide coating |
JP2015525430A (ja) * | 2012-05-18 | 2015-09-03 | スリーエム イノベイティブ プロパティズ カンパニー | オーバーコートされたナノワイヤ透明導電コーティングのコロナによるパターニング |
-
2013
- 2013-08-01 FR FR1357665A patent/FR3009436B1/fr not_active Expired - Fee Related
-
2014
- 2014-07-29 KR KR1020167002359A patent/KR20160037918A/ko not_active Application Discontinuation
- 2014-07-29 EP EP14750596.0A patent/EP3028321A1/fr not_active Withdrawn
- 2014-07-29 JP JP2016530585A patent/JP2016527688A/ja active Pending
- 2014-07-29 US US14/908,427 patent/US20160163984A1/en not_active Abandoned
- 2014-07-29 WO PCT/FR2014/051962 patent/WO2015015113A1/fr active Application Filing
- 2014-07-29 CN CN201480043463.4A patent/CN105409029A/zh active Pending
- 2014-07-30 TW TW103126007A patent/TW201521263A/zh unknown
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1548852A2 (fr) * | 2003-12-22 | 2005-06-29 | Samsung Electronics Co., Ltd. | Dispositif électroluminescent d'un composant de nitrure à l'émission par la surface et procédé de sa manufacture |
WO2007123355A1 (fr) * | 2006-04-25 | 2007-11-01 | Seoul Opto-Device Co., Ltd. | Procédé pour former une électrode métallique, procédé pour fabriquer des éléments luminescents à semi-conducteur et éléments luminescents à semi-conducteur à base de nitrure |
FR2924274A1 (fr) * | 2007-11-22 | 2009-05-29 | Saint Gobain | Substrat porteur d'une electrode, dispositif electroluminescent organique l'incorporant, et sa fabrication |
US20120187821A1 (en) * | 2009-07-16 | 2012-07-26 | Lg Chem, Ltd. | Electrical conductor and a production method therefor |
Also Published As
Publication number | Publication date |
---|---|
KR20160037918A (ko) | 2016-04-06 |
FR3009436B1 (fr) | 2015-07-24 |
EP3028321A1 (fr) | 2016-06-08 |
FR3009436A1 (fr) | 2015-02-06 |
TW201521263A (zh) | 2015-06-01 |
JP2016527688A (ja) | 2016-09-08 |
CN105409029A (zh) | 2016-03-16 |
US20160163984A1 (en) | 2016-06-09 |
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