WO2009125177A1 - Thin film device - Google Patents

Thin film device Download PDF

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Publication number
WO2009125177A1
WO2009125177A1 PCT/GB2009/000909 GB2009000909W WO2009125177A1 WO 2009125177 A1 WO2009125177 A1 WO 2009125177A1 GB 2009000909 W GB2009000909 W GB 2009000909W WO 2009125177 A1 WO2009125177 A1 WO 2009125177A1
Authority
WO
WIPO (PCT)
Prior art keywords
film
organic
substrate
electrode
buffer layer
Prior art date
Application number
PCT/GB2009/000909
Other languages
French (fr)
Inventor
Richard Bernard
Bruce Scott
Duncan Nicol
Andrew Jenkins
Christopher Yates
Alastair Robert Buckley
Fiona Marr
Original Assignee
Microemissive Displays Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Microemissive Displays Limited filed Critical Microemissive Displays Limited
Publication of WO2009125177A1 publication Critical patent/WO2009125177A1/en

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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
    • H10K71/20—Changing the shape of the active layer in the devices, e.g. patterning
    • H10K71/231—Changing the shape of the active layer in the devices, e.g. patterning by etching of existing layers
    • H10K71/233—Changing the shape of the active layer in the devices, e.g. patterning by etching of existing layers by photolithographic etching
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/84—Passivation; Containers; Encapsulations
    • H10K50/844—Encapsulations
    • 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
    • H10K59/131—Interconnections, e.g. wiring lines or terminals

Definitions

  • This invention relates to a thin film organic electronic device.
  • any organic electronic device that has material with an electron affinity less than about 4eV is reactive to water and oxygen and will require encapsulating to prevent degradation on storage and operation.
  • the first approach is to fabricate the active device on an impermeable inorganic substrate (typically glass) and then to seal the device, in an inert atmosphere, with a glass or metal can containing a getter material.
  • the seal is made using epoxy adhesive and the getter is typically a Ba based material that is more reactive to water and oxygen than the active device.
  • the getter scavenges any water or oxygen that does leak into the cavity containing the active device.
  • the lifetime of the device is limited by the water vapor and oxygen transmission rate of the epoxy seal, and the volume of wafer and oxygen that the getter can scavenge.
  • the second approach is to seal the active layers with a monolithically deposited thin film of inorganic material or laminate of organic and inorganic materials.
  • This approach has the advantage of having lower form factor (i.e. thinner), requires less space around the outside of the active device, can be transparent, can be fully hermetic and as such does not require a getter.
  • Thin film encapsulation requires hermetic sealing of the active device both over the active area and around the outside of the active area.
  • the polymer will need to be removed for the outside area of the device such that the thin film encapsulation can be deposited onto the underlying substrate.
  • an ion beam method is disclosed that makes such a removal.
  • Other methods of removal include laser ablation.
  • the ion beam method disclosed in WO 2004/088764 uses a contact mask to define the areas where the polymer is removed and the areas where the polymer remains. Sometimes the mask can scratch the polymer and sometimes the mask can deposit a particle on the polymer surface. Both scratching and particle deposition reduce the effectiveness of the seal of the thin film encapsulation to the underlying substrate.
  • the present invention provides a thin film organic device according to claim 1 and a method of forming a thin film organic device according to claim 8.
  • Preferred or optional features of the invention are set out in the dependent claims.
  • Figure 1 is a schematic sectional view of a partly formed device according to an embodiment of the invention.
  • Figure 2 is a schematic sectional view of the formed device.
  • Figure 3 is a schematic sectional view of the device of Figure 2 with an additional encapsulating layer.
  • a substrate 1 is opaque in this example, for example a silicon substrate including CMOS circuitry.
  • the substrate contains substrate electrode portions 2a, 2b and is coated uniformly in organic material 3 by spin coating from solution (or by other methods of forming a uniform coating with thickness controlled within the desired range, such as spray coating, dip coating, doctor blading, etc.)
  • the combination of bottom electrode 2a and top-electrode 4 enable the organic material 3 to be electrically activated by applying a bias voltage between the two electrodes or by passing current from one electrode to the other.
  • the top-electrode of the device 4 is formed by vacuum deposition and may have a thickness between 5 and 50 nm.
  • the top-electrode is formed of one or more alkali or alkaline earth metal elements or compounds.
  • it can comprise a first layer of LiF with thickness between 1 and 4 nm and a second layer of Ca with thickness between 5 and 40 nm.
  • the top-electrode is capped with an evaporated buffer layer 5 such as AI2O3.
  • the buffer layer 5 is patterned using a shadow mask which is aligned to the bottom electrode 2 structure of the underlying substrate 1.
  • the resulting structure is such that the substrate / bottom electrode, organic material, top electrode, and buffer layer are all present, but no electrical connection of the top electrode 4 has been made to the substrate "top” electrode portion 2b.
  • This structure is detailed in figure 1.
  • the buffer layer is deposited to be sufficiently thick that a certain amount (e.g. less than 50%) can be removed by ion beam etching without damaging the underlying organic or top-electrode materials 3, 4 and such that the organic and top-electrode materials are removed from the substrate 1 in the regions where there is no buffer layer.
  • the ion beam can be directed at 90 degrees to the substrate.
  • a reactive ion etch process can be used, the chemistry of which is selected such that the organic material is removed from the substrate, but the buffer layer is not removed, and such that the buffer layer provides protection from the reactive ions for the active layers.
  • the top-electrode In the case of using a reactive etch to remove the organic material the top-electrode must also be patterned using the same shadow mask as the buffer layer and the top-electrode material should not be damaged by the reactive ions.
  • the organic materials can also be deposited in a pattern corresponding to that of the buffer layer so that it does not have to be etched.
  • the organic, top- electrode and buffer layers can all be vacuum evaporated through the same shadow mask.
  • the next process step (as shown in figure 2) is to vacuum deposit a conducting film 6 over the edge of the buffer layer and down onto the substrate and bottom electrode where electrical connection is made.
  • This conducting contact material can be any metal or non-metal conductor but Al metal is a good choice.
  • Electrical contact is made to the top electrode layers due to the combined topographic profile of the deposited buffer layer and the etched layers. A sloping profile is required to achieve reliable contact to the top electrode. Shadow masking and directional deposition of the buffer layer ensures that the edge of the buffer layer is thinner than the centre of the buffer layer, which in turn ensures that a sloping profile is achieved after ion beam etching.
  • Ion beam etching also ensures that the top-electrode material is exposed and un-oxidized before the top-electrode deposition.
  • the shadow mask thickness and the directionality of the buffer layer deposition determine the distance over which the buffer layer thickness reduces and the level of slope in the structure of figure 2.
  • the process of top-electrode deposition, buffer layer deposition, etching and contact deposition is performed without breaking vacuum.
  • the structure of figure 2 fully encapsulates both the planar part of the device as well as the edge of the device while forming reliable electrical contact for the top- electrode. Additional encapsulation can be achieved by depositing further material 7 over the entire structure, for example in a thickness between 50 and 2000 nm. Given that electrical contact has already been made there is no requirement to pattern the further encapsulation layers. The further encapsulation may be required to ensure that particles that are thicker than the buffer layer are covered, pinholes that are present in the buffer layer are filled, and in general a better level of encapsulation is achieved. The choice of materials and deposited techniques for the further encapsulation is wider since the sensitive organic and top-electrode materials are now protected by the buffer layer.
  • Reactively sputtered Aluminum oxy-nitride has been found to perform well as a further encapsulation and is considered a good material along with Silicon oxynitride and Aluminum-Silicon oxynitride, and other such as AI2O3 & SiO 2 .
  • Chemical vapor deposition and atomic layer deposition provide alternatives to reactive sputtering.
  • the incorporation of multiple layers of alternating material properties may provide additional benefit.
  • AI2O3 may alternate with a polymer film.
  • the device of the invention can be an organic light emitting display device, an organic field effect transistor or an organic photovoltaic cell.

Abstract

A thin film organic device comprises a substrate (1) with patterns of conducting material comprising substrate electrode portions (2a, 2b) for the organic device. A continuous film of organic material (3) overlies at least one of the substrate electrode portions. A continuous film of top-electrode material (4) overlies the film of organic material. A film of buffer material (5) overlies said film of top-electrode material. A film of conducting contact material (6) is deposited over an edge of the buffer layer (5) such that electrical contact is made from the top-electrode material (4) to at least one (2b) of the substrate electrode portions that is not covered by said film of organic material (3). A method of forming the device is disclosed.

Description

THIN FILM DEVICE
Background to the Invention
[0001] This invention relates to a thin film organic electronic device.
[0002] In general, any organic electronic device that has material with an electron affinity less than about 4eV is reactive to water and oxygen and will require encapsulating to prevent degradation on storage and operation. This includes most conjugated polymeric and molecular materials that are used in organic electroluminescent diode devices (OLED devices) as well as the cathode materials that are employed to inject electrons into the organic materials used in OLED devices.
[0003] Traditionally there have been two approaches to encapsulation of organic electronic devices.
[0004] The first approach is to fabricate the active device on an impermeable inorganic substrate (typically glass) and then to seal the device, in an inert atmosphere, with a glass or metal can containing a getter material. The seal is made using epoxy adhesive and the getter is typically a Ba based material that is more reactive to water and oxygen than the active device. Although the seal is not perfect, the getter scavenges any water or oxygen that does leak into the cavity containing the active device. The lifetime of the device is limited by the water vapor and oxygen transmission rate of the epoxy seal, and the volume of wafer and oxygen that the getter can scavenge.
[0005] The second approach is to seal the active layers with a monolithically deposited thin film of inorganic material or laminate of organic and inorganic materials. This approach has the advantage of having lower form factor (i.e. thinner), requires less space around the outside of the active device, can be transparent, can be fully hermetic and as such does not require a getter.
[0006] Thin film encapsulation requires hermetic sealing of the active device both over the active area and around the outside of the active area. When fabricating active devices from continuous thin films of, for example, polymer materials, the polymer will need to be removed for the outside area of the device such that the thin film encapsulation can be deposited onto the underlying substrate. In WO 2004/088764 an ion beam method is disclosed that makes such a removal. Other methods of removal include laser ablation.
[0007] An alternative to removal of the active material is to print the active material only in the area that is required. However where the control of the thickness of the active material is extremely stringent the printing technique is not ideal as the thickness of the organic layer can vary from part to part.
[0008] The ion beam method disclosed in WO 2004/088764 uses a contact mask to define the areas where the polymer is removed and the areas where the polymer remains. Sometimes the mask can scratch the polymer and sometimes the mask can deposit a particle on the polymer surface. Both scratching and particle deposition reduce the effectiveness of the seal of the thin film encapsulation to the underlying substrate.
[0009] An additional disadvantage of the use of a mask in the removal of the polymer material is that the mask is required to be aligned to the pattern of the substrate (pixels in the case of a display). The alignment process is time consuming and also requires a tolerance for alignment, taking up space in the footprint of the active device. Summary of the Invention
[0010] The present invention provides a thin film organic device according to claim 1 and a method of forming a thin film organic device according to claim 8. Preferred or optional features of the invention are set out in the dependent claims.
Brief Description o£ the Drawings
[0011 ] The invention will now be described in more detail, by way of example only, with reference to the accompanying drawings, in which:
[0012] Figure 1 is a schematic sectional view of a partly formed device according to an embodiment of the invention;
[0013] Figure 2 is a schematic sectional view of the formed device; and
[0014] Figure 3 is a schematic sectional view of the device of Figure 2 with an additional encapsulating layer.
Detailed Description of Particular Embodiments
[0015] A general description, as detailed in figures 1 to 3, of the disclosed device follows:
[0016] A substrate 1 is opaque in this example, for example a silicon substrate including CMOS circuitry. The substrate contains substrate electrode portions 2a, 2b and is coated uniformly in organic material 3 by spin coating from solution (or by other methods of forming a uniform coating with thickness controlled within the desired range, such as spray coating, dip coating, doctor blading, etc.) The combination of bottom electrode 2a and top-electrode 4 enable the organic material 3 to be electrically activated by applying a bias voltage between the two electrodes or by passing current from one electrode to the other. (In an OLED display device light is generated by the passage of current though an electroluminescent organic layer.) The top-electrode of the device 4 is formed by vacuum deposition and may have a thickness between 5 and 50 nm. In a typical OLED example the top-electrode is formed of one or more alkali or alkaline earth metal elements or compounds. For example, it can comprise a first layer of LiF with thickness between 1 and 4 nm and a second layer of Ca with thickness between 5 and 40 nm. The top-electrode is capped with an evaporated buffer layer 5 such as AI2O3. The buffer layer 5 is patterned using a shadow mask which is aligned to the bottom electrode 2 structure of the underlying substrate 1.
[0017] The resulting structure is such that the substrate/ bottom electrode, organic material, top electrode, and buffer layer are all present, but no electrical connection of the top electrode 4 has been made to the substrate "top" electrode portion 2b. This structure is detailed in figure 1.
[0018] The buffer layer is deposited to be sufficiently thick that a certain amount (e.g. less than 50%) can be removed by ion beam etching without damaging the underlying organic or top-electrode materials 3, 4 and such that the organic and top-electrode materials are removed from the substrate 1 in the regions where there is no buffer layer. The ion beam can be directed at 90 degrees to the substrate. Alternatively, a reactive ion etch process can be used, the chemistry of which is selected such that the organic material is removed from the substrate, but the buffer layer is not removed, and such that the buffer layer provides protection from the reactive ions for the active layers. In the case of using a reactive etch to remove the organic material the top-electrode must also be patterned using the same shadow mask as the buffer layer and the top-electrode material should not be damaged by the reactive ions. [0019] The organic materials can also be deposited in a pattern corresponding to that of the buffer layer so that it does not have to be etched. For example, the organic, top- electrode and buffer layers can all be vacuum evaporated through the same shadow mask.
[0020] The next process step (as shown in figure 2) is to vacuum deposit a conducting film 6 over the edge of the buffer layer and down onto the substrate and bottom electrode where electrical connection is made. This conducting contact material can be any metal or non-metal conductor but Al metal is a good choice. Electrical contact is made to the top electrode layers due to the combined topographic profile of the deposited buffer layer and the etched layers. A sloping profile is required to achieve reliable contact to the top electrode. Shadow masking and directional deposition of the buffer layer ensures that the edge of the buffer layer is thinner than the centre of the buffer layer, which in turn ensures that a sloping profile is achieved after ion beam etching. Ion beam etching also ensures that the top-electrode material is exposed and un-oxidized before the top-electrode deposition. The shadow mask thickness and the directionality of the buffer layer deposition determine the distance over which the buffer layer thickness reduces and the level of slope in the structure of figure 2. In this example, the process of top-electrode deposition, buffer layer deposition, etching and contact deposition is performed without breaking vacuum.
[0021] The structure of figure 2 fully encapsulates both the planar part of the device as well as the edge of the device while forming reliable electrical contact for the top- electrode. Additional encapsulation can be achieved by depositing further material 7 over the entire structure, for example in a thickness between 50 and 2000 nm. Given that electrical contact has already been made there is no requirement to pattern the further encapsulation layers. The further encapsulation may be required to ensure that particles that are thicker than the buffer layer are covered, pinholes that are present in the buffer layer are filled, and in general a better level of encapsulation is achieved. The choice of materials and deposited techniques for the further encapsulation is wider since the sensitive organic and top-electrode materials are now protected by the buffer layer. Reactively sputtered Aluminum oxy-nitride has been found to perform well as a further encapsulation and is considered a good material along with Silicon oxynitride and Aluminum-Silicon oxynitride, and other such as AI2O3 & SiO2. Chemical vapor deposition and atomic layer deposition provide alternatives to reactive sputtering. The incorporation of multiple layers of alternating material properties may provide additional benefit. For example, AI2O3 may alternate with a polymer film.
[0022] The device of the invention can be an organic light emitting display device, an organic field effect transistor or an organic photovoltaic cell.

Claims

Claims
1. A thin film organic device comprising a. A substrate with patterns of conducting material comprising substrate electrode portions for the organic device; b. A continuous film of organic material over-lying at least one of said substrate electrode portions; c. A continuous film of top-electrode material over-lying said film of organic material; d. A film of buffer material, overlying said film of top-electrode material; and e. A film of conducting contact material deposited over an edge of the buffer layer such that electrical contact is made from the top-electrode material to at least one of said substrate electrode portions that is not covered by said film of organic material.
2. A device of claim 1, comprising at least one additional layer of organic material, the device including at least one of a light emitting transistor, a photodiode, or a phototransistor.
3. A device of claim 1 or 2, wherein the top-electrode material comprises one of more layers of the following: Li, Na, K, Rb, Cs, Ca, Mg, Ba, Sr and oxides and halides of the same.
4. A device of claim 1, 2 or 3, wherein the buffer material is an oxide of Al, Si, Ta or another refractory material or metal oxide with a similar or lower sputter rate than the organic material.
5. A device of any preceding claim, wherein the substrate comprises Si and contains active circuitry.
6. A device of any preceding claim, wherein the contact material is a metal such as Al.
7. A device of any preceding claim, wherein the structure is further encapsulated with thin films of one or more of the following: AI2O3, AlON, SiAlON7 SiON, Si3N4, SiO2.
8. A method of forming a thin film organic device, comprising the steps of: a. Providing a substrate with patterns of conducting material comprising substrate electrode portions for the organic device; b. Depositing a film of organic material onto said substrate; c. Depositing a film of top-electrode material onto said film of organic material; d. Forming a patterned buffer layer on said film of organic material; and e. Applying a film of conductive material over an edge of the buffer layer such that electrical contact is made from the top-electrode material to at least one of said substrate electrode portions that is not covered by said film of organic material.
9. A method of claim 8, wherein after step (d) the films of organic material and top- electrode material are removed by ion beam etching except where covered by the buffer material.
10. A method of claim 8, wherein the top-electrode material is formed in a pattern.
11. A method of claim 10, wherein after step (d) the organic material is removed by reactive ion etching using an oxygen or mixed oxygen/ Ar plasma.
12. A method of claim 8, wherein in step (d) the buffer layer is patterned using a shadow mask.
13. A method of claim 12, wherein in steps (b) and (c) the organic material and top- electrode material and buffer layer are vacuum evaporated through the same shadow mask as the buffer layer.
14. A method of any one of claims 8 to 13, comprising a further step of encapsulating the device with a further thin film.
15. A method of claim 14, wherein the further thin film is deposited by one of electron beam evaporation, reactive sputtering, chemical vapor deposition or atomic layer deposition.
PCT/GB2009/000909 2008-04-07 2009-04-07 Thin film device WO2009125177A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB0806293.7 2008-04-07
GBGB0806293.7A GB0806293D0 (en) 2008-04-07 2008-04-07 Thin film device

Publications (1)

Publication Number Publication Date
WO2009125177A1 true WO2009125177A1 (en) 2009-10-15

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109449182A (en) * 2018-10-30 2019-03-08 京东方科技集团股份有限公司 Display base plate and its manufacturing method, display device

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001039287A1 (en) * 1999-11-26 2001-05-31 Cambridge Display Technology Limited Method of producing an organic light-emissive device
US6566156B1 (en) * 1996-06-12 2003-05-20 The Trustees Of Princeton University Patterning of thin films for the fabrication of organic multi-color displays
US20050019977A1 (en) * 2003-07-22 2005-01-27 Shiva Prakash Process for removing an organic layer during fabrication of an organic electronic device and the organic electronic device formed by the process
US20050093439A1 (en) * 2003-09-30 2005-05-05 Gaku Harada Organic electroluminescent device and fabrication method thereof
US20070053202A1 (en) * 2005-09-02 2007-03-08 Seiko Epson Corporation Light-emitting device and method of manufacturing light-emitting device
US20080007163A1 (en) * 2006-07-07 2008-01-10 Toshiyuki Matsuura Organic electroluminescent display device

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6566156B1 (en) * 1996-06-12 2003-05-20 The Trustees Of Princeton University Patterning of thin films for the fabrication of organic multi-color displays
WO2001039287A1 (en) * 1999-11-26 2001-05-31 Cambridge Display Technology Limited Method of producing an organic light-emissive device
US20050019977A1 (en) * 2003-07-22 2005-01-27 Shiva Prakash Process for removing an organic layer during fabrication of an organic electronic device and the organic electronic device formed by the process
US20050093439A1 (en) * 2003-09-30 2005-05-05 Gaku Harada Organic electroluminescent device and fabrication method thereof
US20070053202A1 (en) * 2005-09-02 2007-03-08 Seiko Epson Corporation Light-emitting device and method of manufacturing light-emitting device
US20080007163A1 (en) * 2006-07-07 2008-01-10 Toshiyuki Matsuura Organic electroluminescent display device

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109449182A (en) * 2018-10-30 2019-03-08 京东方科技集团股份有限公司 Display base plate and its manufacturing method, display device

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