WO2006014591A2 - Permeation barriers for flexible electronics - Google Patents

Permeation barriers for flexible electronics

Info

Publication number
WO2006014591A2
WO2006014591A2 PCT/US2005/024266 US2005024266W WO2006014591A2 WO 2006014591 A2 WO2006014591 A2 WO 2006014591A2 US 2005024266 W US2005024266 W US 2005024266W WO 2006014591 A2 WO2006014591 A2 WO 2006014591A2
Authority
WO
WIPO (PCT)
Prior art keywords
ald
thin film
layer
permeation barrier
permeation
Prior art date
Application number
PCT/US2005/024266
Other languages
French (fr)
Other versions
WO2006014591A3 (en
Inventor
Brian S. Berland
Joseph Armstrong
Russell E. Hollingsworth
Lin J. Simpson
Original Assignee
Itn Energy Systems, Inc.
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 Itn Energy Systems, Inc. filed Critical Itn Energy Systems, Inc.
Publication of WO2006014591A2 publication Critical patent/WO2006014591A2/en
Publication of WO2006014591A3 publication Critical patent/WO2006014591A3/en

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    • H—ELECTRICITY
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    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
    • H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
    • H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
    • H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
    • H01L21/0228—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition deposition by cyclic CVD, e.g. ALD, ALE, pulsed CVD
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/02—Pretreatment of the material to be coated
    • C23C16/0272—Deposition of sub-layers, e.g. to promote the adhesion of the main coating
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C23C16/45525—Atomic layer deposition [ALD]
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C23C16/45525—Atomic layer deposition [ALD]
    • C23C16/45555—Atomic layer deposition [ALD] applied in non-semiconductor technology
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/56—After-treatment
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
    • H01L21/02164—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material being a silicon oxide, e.g. SiO2
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
    • H01L21/0217—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material being a silicon nitride not containing oxygen, e.g. SixNy or SixByNz
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02172—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides
    • H01L21/02175—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal
    • H01L21/02178—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal the material containing aluminium, e.g. Al2O3
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/022—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being a laminate, i.e. composed of sublayers, e.g. stacks of alternating high-k metal oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02205—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition
    • H01L21/02208—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si
    • H01L21/02211—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si the compound being a silane, e.g. disilane, methylsilane or chlorosilane
    • 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
    • H10K59/80—Constructional details
    • H10K59/87—Passivation; Containers; Encapsulations
    • H10K59/873—Encapsulations
    • H10K59/8731—Encapsulations multilayered coatings having a repetitive structure, e.g. having multiple organic-inorganic bilayers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K77/00—Constructional details of devices covered by this subclass and not covered by groups H10K10/80, H10K30/80, H10K50/80 or H10K59/80
    • H10K77/10—Substrates, e.g. flexible substrates
    • H10K77/111—Flexible substrates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
    • H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
    • H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
    • H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
    • H01L21/02274—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition in the presence of a plasma [PECVD]
    • 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
    • H10K2102/311—Flexible OLED
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • Flexible displays and electronics may utilize a permeation barrier that blocks reactive environmental species from contacting sensitive underlying components. This may be done, for example, to eliminate or mitigate damage that is otherwise caused by the action of oxygen and water upon light-emitting polymers and metal cathodes of organic light-emitting diodes (OLEDs).
  • OLEDs organic light-emitting diodes
  • the rate of water and oxygen permeation is directly linked to the lifetime of an electronic device.
  • the most sensitive applications are believed to require ultra-low water vapor transmission rates of about 1E-6 g/m -day or less. Failure to achieve this permeation limit is a significant problem because higher values do not provide adequate protection for sensitive electronic components, which suffer reduced service lives.
  • inorganic materials have essentially zero permeability and may be deposited in thin layers that are suitable as permeation barriers.
  • inorganic films have an unavoidable concentration of microscopic defects, such as pinholes or columnar growth structures. The number of these defects per unit of surface area depends, at least in part, upon the technique that is used to deposit the inorganic material.
  • Conventional film deposition techniques may include sputtering, evaporation, spraying, chemical vapor deposition (CVD), and plasma enhanced chemical vapor deposition (PECVD). As deposition progresses, the deposited layers grow in a directional manner, and according to many of these techniques directional growth progresses from a finite number of nucleation sites on a substrate surface.
  • Defect formation may be compounded in flexible electronics or displays where structural fatigue may exacerbate permeation due to physical cracking of the barrier.
  • the present instrumentalities overcome the problems outlined above and advance the art by providing permeation barriers to protect electronics from the action of environmental species, such as water and oxygen.
  • Applications for these permeation barriers suitably include, without limitation, flexible electronic displays (e.g., OLEDs, electrophoretic displays, electrochromic displays), solar cells, electrochromic coatings for active thermal control (e.g., architectural glass, responsive clothing, space coatings), and packaging.
  • Flexible permeation barriers for flexible electronics and methods of making the flexible permeation barriers are disclosed.
  • a flexible substrate is coated with a thin film that after deposition is over-deposited by atomic layer deposition (ALD) of an inorganic material. This ALD overlayer conforms to and heals defects of the thin film.
  • ALD atomic layer deposition
  • a flexible substrate is coated with an ALD decoupling layer that mitigates defect formation in a subsequently applied thin film.
  • the flexible substrate coated with the ALD decoupling layer and the thin film may also include the ALD overlayer.
  • the permeation barriers form multilayer stacks.
  • the multilayer stack may be a heterostructure formed of alternating ALD and polymer materials.
  • Figure 1 illustrates a cross-section of a permeation barrier having polymer decoupling layers.
  • Figure 2 illustrates a cross-section of a permeation barrier having an ALD defect healing layer according to one embodiment.
  • Figure 3 illustrates a cross-section of a permeation barrier having an ALD decoupling layer according to one embodiment.
  • Figure 4 illustrates a cross-section of a permeation barrier having an ALD decoupling layer and an ALD defect healing layer according to one embodiment.
  • Figure 5 is a flowchart showing steps used to make the permeation barriers of Figures 2-4.
  • Figure 6 illustrates a cross-section of an active device deposited on a substrate having a permeation barrier according to one embodiment.
  • Figure 7 illustrates a cross-section of an active device disposed between two permeation barriers according to one embodiment.
  • FIG. 1 illustrates a cross-section of a substrate 100 having a permeation barrier stack 102.
  • Substrate 100 may be any substrate, such as an electronic device, e.g., a wafer, plastic display base, or printed circuit board, and may be provided with operable solid state components (not shown).
  • Substrate 100 is planarized, for example, by application of a polymer base layer 104.
  • Permeation barrier stack 102 is deposited atop polymer base layer 104 as a heterostructure formed of alternating inorganic layers 106, 108, 110, 112, which are interspersed with polymer decoupling layers 114, 116, 118, 120.
  • Polymer decoupling layers 114, 116, 118, 120 may be made of the same type of polymer material or different polymer materials.
  • Inorganic layers 106, 108, 110, 112 may, for example, form active circuitry or optical components, but are usually present as barrier layers.
  • the inorganic layers have, for example, nucleated, aggregated, agglomerated, coagulated or conglomerated, to form structures 122, 124 with defects 126, 128, through respective layers 112, 110.
  • the heterostructure of permeation barrier stack 102 uses polymer decoupling layers 114, 116, 118, 120 and polymer base layer 104 to prevent the propagation of cracks, pinholes, and other defects 126, 128, between adjacent inorganic layers 106, 108, 110, 112. Nevertheless, the polymer materials are permeable to oxygen. Accordingly, defects 126, 128 provide a permeation pathway 130 that transports oxygen and other harmful environmental gases throughout permeation barrier stack 102 and polymer base layer 104 to substrate 100.
  • Atomic Layer Deposition is a monolayer method where inorganic materials are conformally adsorbed and chemically bound to a substrate.
  • the substrate is loaded into a vacuum chamber and heated to an appropriate temperature.
  • the deposition of an ALD layer includes a series of sequential exposures to reactive precursors. The deposition process starts with the introduction of a first reactant vapor. After a period of time, a saturated exposure is achieved when chemical reactions self-terminate because the gas phase precursors have effectively reacted with all available reactive surface sites. Then excess reactant vapor is flushed from the chamber, leaving a monolayer of the first reactant chemically bound to the substrate. A second reactant is then introduced in an exposure sufficient to again lead to self-terminating reaction with the first monolayer.
  • the second reactant vapor is then flushed from the chamber.
  • Additional ALD layers may be applied by reintroducing the first reactant vapor and repeating the deposition method of sequential saturated exposures. Mixing of the first and second reactant vapors in the gas phase results in chemical vapor deposition (CVD) and should be avoided during ALD; therefore, the surface of the substrate and/or the reaction chamber is typically flushed with an inert gas, such as nitrogen, between introduction of reactant vapors.
  • an aluminum oxide (alumina, Al 2 Os) layer may be deposited on a substrate by alternately exposing the substrate to an aluminum reactant (e.g., trimethyl aluminum, TMA) and an oxygen reactant (e.g., water).
  • an aluminum reactant e.g., trimethyl aluminum, TMA
  • an oxygen reactant e.g., water
  • Substrate, S typically displays reactive functional groups that bind to the aluminum reactant.
  • Aluminum reactants useful in forming ALD layers include alkyl aluminum
  • Oxygen reactants useful in forming ALD layers include water, hydrogen peroxide, ozone, molecular oxygen, nitrous oxide, and metal alkoxides.
  • Metal reactants useful in forming ALD layers include metal acetylacetonates, metal halides, alkyl metal compounds, alkoxy metal compounds, and metallic vapor.
  • Silicon reactants useful in forming ALD layers include silanes (e.g., SiH 4 , Si 2 H 6 , Si 3 H 8 ), dichlorosilane (SiH 2 Cl 2 ), silicon tetrachloride (SiCl 4 ), silicon tetrafluoride (SiF 4 ), methylsilane (SiH 3 CH 3 ), dimethylsilane (SiH 2 (CHs) 2 ), hexamethylsiloxane ([(CH 3 ) 3 Si] 2 O), tetramethylorthosilicate (Si(OCH 3 ) 4 ), and tetraethylorthosilicate (Si(OCH 2 CHa) 4 ).
  • silanes e.g., SiH 4 , Si 2 H 6 , Si 3 H 8
  • dichlorosilane SiH 2 Cl 2
  • silicon tetrachloride SiCl 4
  • silicon tetrafluoride SiF 4
  • Nitrogen reactants useful in forming ALD layers include ammonia and molecular nitrogen.
  • ALD reactants are chosen to promote self-terminating surface chemical reactions that provide control over film thickness and uniformity. The self-limiting nature of the chemical reactions enables the application of conformal coatings in high aspect ratio structures.
  • a combination of a conventionally deposited thin film and an ALD layer as described herein achieves low permeance with the additional advantages of flexibility, scratch resistance, chemical resistance, electrical isolation, minimal weight, transparency, refractive index matching, and hydrophobicity.
  • a thin film of an inorganic material is deposited by a conventional deposition technique (e.g., sputtering, evaporation, CVD, PECVD, etc.) on a flexible substrate. Conventional deposition conditions and materials are chosen to minimize the size and concentration of defects.
  • This thin film serves as a primary barrier layer.
  • a second inorganic layer that hermetically seals or "heals" defects in the primary barrier layer is applied directly over the thin film by ALD.
  • ALD atomic layer deposition
  • An ALD healing layer with water vapor transport rates of 1E-03 g/m -day, employed in conjunction with a PECVD coating with low defect concentrations is sufficient to achieve combined water vapor transport rates of 1E-06 g/m *day or less.
  • Figure 2 illustrates the aforementioned by showing a cross-section of a permeation barrier 200.
  • An inorganic thin film 204 is applied to a substrate 202 by a conventional deposition technique. Thereafter, an ALD defect healing layer 208 is applied.
  • the self-terminating reactions and conformal nature of ALD assure good coverage even on high aspect ratio features, such as cracks or grain boundaries 206, 210.
  • Thin film 204 acts as a primary barrier layer and contains defects 206, 210 that are hermetically sealed or "healed” by application of ALD defect healing layer 208 over thin firm 204.
  • the flowchart of Figure 5 A shows steps used to make permeation barrier 200 of Figure 2.
  • Deposition 510 of conventional thin film 204 Figure 2 precedes step 512 for the deposition of ALD healing layer 208.
  • ALD provides an inorganic decoupling layer, that minimizes defects in subsequently applied layers.
  • a thin film may be applied over the ALD decoupling layer by conventional deposition.
  • the ALD decoupling layer serves to reduce deleterious effects on thin film growth that are related to artifacts of the underlying substrate.
  • the function of the ALD decoupling layer is to provide optimal surface chemistry to promote uniform nucleation of subsequently applied thin films.
  • Figure 3 is a cross-sectional view of a permeation barrier 300 having an ALD decoupling layer 304.
  • ALD decoupling layer 304 is applied directly to substrate 302 to achieve surface energy matching of the thin film material with the substrate to promote uniform wetting of the thin film, and/or to fill surface pores and minimize other defect causing imperfections on the surface of substrate 302.
  • Thin film 306 is applied over ALD decoupling layer 304, which promotes uniformity, density and adhesion for thin film 306.
  • Thin film 306 has a minimal number of defects 308.
  • the flowchart of Figure 5B shows steps used to make permeation barrier 300 of Figure 3. Deposition 508 of ALD decoupling layer 304 ( Figure 3) precedes step 510 for the deposition of conventional thin film 306.
  • a permeation barrier in another embodiment, includes an ALD decoupling layer deposited on a substrate, a thin film deposited on the ALD decoupling layer by conventional deposition techniques, and an ALD healing layer deposited on the thin film.
  • Figure 4 is a cross-sectional view of a permeation barrier 400 having an ALD decoupling layer 404 and an ALD healing layer 410.
  • ALD decoupling layer 404 is applied directly to substrate 402 to achieve surface energy matching of the thin film material with the substrate to promote uniform wetting of the thin film, or to fill surface pores and minimize other defect causing imperfections on the surface of substrate 402.
  • Thin film 406 is applied on ALD decoupling layer 404, which promotes uniformity, density and adhesion for thin film 406.
  • Thin film 406 has a minimal number of defects 408. Defects 408 are hermetically sealed or "healed” by application of ALD defect healing layer 410 atop thin film 406.
  • the flowchart of Figure 5C shows steps used to make permeation barrier 400 of Figure 4. Deposition 508 of ALD decoupling layer 404 ( Figure 4) is followed by deposition 510 of conventional thin film 406 and then deposition 512 of ALD healing layer 410.
  • Permeation barriers such as those described above with reference to Figures 2- 4 may be used in conjunction with active devices (e.g., light emitting polymers, transistors, solar cells, etc.), while preferably but optionally not forming part of the active device circuitry.
  • active devices e.g., light emitting polymers, transistors, solar cells, etc.
  • a thin film forming part of the active device may be an electrode or conductive metal oxide that may or may not coincide to the full areal extent of the ALD layer.
  • the thin film that combines with the ALD may be in electrical contact with this electrode or conductive metal oxide without being configured and arranged to form a necessary party of the active device circuitry.
  • Figure 6 illustrates a cross-section of an active device 600 deposited on a substrate 602 having a permeation barrier 604 according to one embodiment.
  • Permeation barrier 604 includes an ALD decoupling layer 606 and a thin film 608 deposited atop ALD decoupling layer 606.
  • Thin film 608 interfaces with an electrode 610 and may function as a conductor or heat sink; however, in a preferred embodiment, thin film 608 is not an active circuitry component. Active circuitry components undergo time and temperature dependent phenomena, and thin films functioning as both barrier layers and active components may suffer structural fatigue that could cause premature degradation of the permeation barrier.
  • Active device 600 is disposed between electrode 610 and a second electrode 612.
  • a thin film 614 is deposited over active device 600 and electrodes 610, 612, and an ALD layer 616 is deposited over thin film 614 forming a second permeation barrier stack. It will be understood that various sequences of ALD layers and thin films as described herein may be used to create the permeation barriers of Figure 6.
  • FIG. 7 illustrates a cross-section of an active device 700 disposed between two permeation barriers 704 according to one embodiment.
  • Permeation barriers 704 include ALD layers 706 and thin films 708 deposited on substrates 702.
  • Active device 700 is disposed between two electrodes 710,712. Electrodes 710,712 interface with permeation barriers 704.
  • An optional dielectric layer (not shown) may separate electrodes 710,712 from thin films 708.
  • a sealant 714 such as epoxy, secures permeation barriers 704 in proximity to one another and seals the edges of active device 700. It will be understood that various sequences of ALD layers and thin films as described herein may be used to create the permeation barriers of Figure 7.
  • Multilayer stacks including two or more layers, formed by combinations of thin films, deposited by conventional deposition techniques, and ALD layers in various sequences are contemplated.
  • a multilayer stack may include an ALD layer/conventional layer/ALD layer/conventional layer/ALD layer, or a multilayer stack may include a conventional layer/ALD layer/conventional layer, or an ALD layer/conventional layer/conventional layer/ALD layer.
  • the ALD layers may serve as decoupling layers to minimize defects in subsequently applied layers and/or as defect healing layers to seal defects in underlying layers.
  • Each "layer" may be a monolayer or may be formed by multiple monolayer applications where a material is deposited using a single deposition technique.
  • the flowcharts of Figures 5A-C show exemplary steps that may be linked in series to make permeation barriers comprised of multilayer stacks.
  • planarization layer such as an organic polymer
  • a decoupling layer Figure 1 to reduce defect propagation and improve flexibility
  • a stress balancing film deposited on the back side of the flexible substrate to prevent curling from residual stress in the ALD and/or conventional layers.
  • Planarization and decoupling layers e.g., polyimides, poly(methyl methacrylate) (PMMA), novolacs and polyesters
  • PMMA poly(methyl methacrylate)
  • novolacs and polyesters may be applied by spraying or evaporating a UV curable polymer onto the substrate.
  • Suitable permeation barrier materials for both conventional layers and ALD layers include, but are not limited to silicon oxides, silicon nitrides, silicon oxynitrides, silicon oxycarbides, metal oxides, metal nitrides, metal oxynitrides, metal oxycarbides, ultra-thin metallic layers and conductive oxides. Many compounds in these material classes are optically transparent, which is desirable, for example, for electronic displays, photovoltaic cells and architectural glass where visible light must enter and/or exit the material.
  • the thickness of an ALD layer is, for example, in a range of from about 1-200 nm, and more typically in a range of from about 1-10 nm. Thin layers are more tolerant to flexing without cracking and more transparent than thick layers. Thin films, prepared by conventional deposition techniques, typically have a thickness in a range of from about 20-500 nm. However, thicknesses greater than about 150 nm can impact optical transmission. Deposition temperatures for both the ALD process and conventional depositions may be in a range of from about 20-400 0 C, depending on the upper temperature limit of the polymer substrate and/or electronic components.
  • Substrate materials include, but are not limited to polyarylates (PAR), poly(ether ether ketones) (PEEK), polyurethanes, polyesters (e.g., polyethylene terephthalate (PET), polybutylene terephthalate (PBT)), epoxy resins, epoxy-novalac resins, phenolic resins, cellulose ethers and esters, polyvinyl alcohol, polyvinyl chloride, polyamides, polyamines, polyvinylidene chloride, poly(alkenyl aromatic) polymers (e.g., polystyrene, polyethylene naphthalate (PEN)), polyacrylic acids, polyacrylimides, polyimides, polycarbonates, polyolefins, polymers of conjugated dienes (e.g., polybutadiene, isoprene), organosilicone polymers, and mixtures and random or block copolymers thereof.
  • PAR polyarylates
  • PEEK poly(ether ether ketones)
  • Polymers containing functional groups such as halogen, hydroxyl, carbonyl, carboxylic acid, primary amines, secondary amines, and/or sulfonate groups, provide sites at which it is possible to form chemical bonds with permeation barrier materials.
  • functional groups such as halogen, hydroxyl, carbonyl, carboxylic acid, primary amines, secondary amines, and/or sulfonate groups
  • Substrates are usually cleaned to remove particulate matter and minimize surface imperfections prior to application of permeation barrier materials. Methods of cleaning substrates are known and may include, for example ultrasonic soaks in a series of chemical solutions and/or ion/plasma based processes. Features measuring about one micron or greater in size should be removed from the substrate surface.
  • Techniques for characterizing inorganic permeation barriers include gas permeation studies, infrared spectroscopy, transmission electron microscopy, atomic force microscopy (to measure surface roughness), X-ray photoelectron spectroscopy and X-ray diffraction (for depth-profiling and structural analysis), and characterization of electrical properties.
  • electrical leakage current and permeation are both tied to defect density; therefore, a reduction in electrical leakage current relative to a control sample suggests decreased permeation.
  • MULTI-LAYER STACK INCLUDING A DECOUPLING LAYER DEPOSITED BY ALD, CONVENTIONAL LAYER DEPOSITED BY PECVD, AND A DEFECT HEALING LAYER DEPOSITED BY ALD
  • the vacuum chamber is segmented into three zones.
  • the first zone is a drying station having a bank of infrared lamps to remove excess moisture from the substrate.
  • the second zone is an ion cleaning station and the third zone is an ALD deposition chamber.
  • the process environment of each zone is isolated from neighboring zones and from ambient conditions.
  • the roll of PET is pulled from a supply reel to a take up reel at a speed of about 0.1 to 2 m/min. After drying in the first zone, the PET is pulled through an ion cleaning station.
  • the chamber of the second zone contains approximately 1-500 mTorr of gaseous species selected from mixtures of Ar, N 2 , and/or O 2 .
  • a typical mixture contains 50% Ar (g) and 50% O 2 (g).
  • Radio frequency power having a frequency of 13.56 MHz is supplied through an impedance matching network to generate a plasma containing reactive ion species. The substrate is thus cleaned by ion bombardment for a period of about 10 seconds to 1 minute.
  • the PET is then pulled into the third zone containing a traveling wave ALD reactor.
  • the base pressure of the traveling wave ALD reactor is typically below 1E-3 mbar with operating pressures from 1-5 mbar.
  • a stream of inert nitrogen is continuously passed over the substrate at a rate of 1 standard liter per min.
  • the inert carrier gas is periodically and sequentially injected with pulses of trimethyl aluminum (TMA) and water.
  • TMA trimethyl aluminum
  • One such sequence might be, for example, 0.1-0.5 seconds of TMA, 0:1-1.0 second of nitrogen, 0.1-1.0 second of water, and 1-5 seconds of nitrogen. This dosing sequence is repeated for a number of cycles, where each cycle deposits slightly less than 0.1 run of aluminum oxide.
  • TMA, nitrogen, and water are all present in multiple locations over the PET.
  • the system is designed to be in laminar flow such that the reactive species remain isolated until they reach a reactive trap before the vacuum pump.
  • the PET is maintained at a temperature of 100 0 C by techniques such as employing a bank of infrared lamps or pulling the substrate over a heated drum.
  • the thickness of the ALD decoupling layer is established by the residence time of the PET in the traveling wave reactor and the number of TMA/water cycles each region of the substrate is exposed to.
  • a typical decoupling layer is about 1-100 angstroms of deposited alumina.
  • the PET is moved to a similar roll coater equipped with ion cleaning and PECVD capabilities.
  • the PET is pulled through the ion cleaning station where it is cleaned for a second time, as described above.
  • a thin film of silicon oxide is then deposited by PECVD.
  • Silane and nitrous oxide (N 2 O) are simultaneously introduced into the reactor chamber in a 1 :50 ratio.
  • the PET temperature is held at about 100- 15O 0 C.
  • the SiO x thin film thickness is determined by the residence time of the PET in the deposition region. A typical residence time of about 30 seconds will create a thin film about 100-2000 angstroms thick, more typically a thin film about 200-500 angstroms is deposited.
  • the PET roll is then transferred back to the original deposition zone for processing of a defect healing ALD layer by introduction of TMA and water vapors sequentially as described above.
  • the ALD defect healing layer is from about 50-200 angstroms thick.
  • panes of PET may be coated with multilayer permeation barrier stacks.

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Abstract

Permeation barriers having a conventionally deposited layer and a layer applied by atomic layer deposition (ALD) are disclosed for use with flexible substrates. The ALD layers serve as decoupling layers to minimize defects in subsequently applied layers and/or as defect healing layers to seal defects in underlying layers.

Description

PERMEATION BARRIERS FOR FLEXIBLE ELECTRONICS
RELATED APPLICATIONS
This application claims the benefit of priority to U.S. provisional patent application serial no. 60/586,260, filed July 8, 2004, which is incorporated herein by reference.
BACKGROUND
Flexible displays and electronics may utilize a permeation barrier that blocks reactive environmental species from contacting sensitive underlying components. This may be done, for example, to eliminate or mitigate damage that is otherwise caused by the action of oxygen and water upon light-emitting polymers and metal cathodes of organic light-emitting diodes (OLEDs). The rate of water and oxygen permeation is directly linked to the lifetime of an electronic device. The most sensitive applications are believed to require ultra-low water vapor transmission rates of about 1E-6 g/m -day or less. Failure to achieve this permeation limit is a significant problem because higher values do not provide adequate protection for sensitive electronic components, which suffer reduced service lives.
In theory, inorganic materials have essentially zero permeability and may be deposited in thin layers that are suitable as permeation barriers. However, inorganic films have an unavoidable concentration of microscopic defects, such as pinholes or columnar growth structures. The number of these defects per unit of surface area depends, at least in part, upon the technique that is used to deposit the inorganic material. Conventional film deposition techniques may include sputtering, evaporation, spraying, chemical vapor deposition (CVD), and plasma enhanced chemical vapor deposition (PECVD). As deposition progresses, the deposited layers grow in a directional manner, and according to many of these techniques directional growth progresses from a finite number of nucleation sites on a substrate surface. Growth from a point, such as a nucleation site, can lead to columnar growth with boundaries that facilitate transport of gases along the boundaries formed between columns. Even where this type of directional growth does not occur as a direct result of deposition, post-deposition annealing processes may generally form grains. Thus, conventional deposition and/or annealing techniques may propagate defects through multilayer inorganic stacks, so that permeation may not be reduced by applying additional or thicker layers.
Defect formation may be compounded in flexible electronics or displays where structural fatigue may exacerbate permeation due to physical cracking of the barrier.
SUMMARY
The present instrumentalities overcome the problems outlined above and advance the art by providing permeation barriers to protect electronics from the action of environmental species, such as water and oxygen. Applications for these permeation barriers suitably include, without limitation, flexible electronic displays (e.g., OLEDs, electrophoretic displays, electrochromic displays), solar cells, electrochromic coatings for active thermal control (e.g., architectural glass, responsive clothing, space coatings), and packaging. Flexible permeation barriers for flexible electronics and methods of making the flexible permeation barriers are disclosed. In one embodiment, a flexible substrate is coated with a thin film that after deposition is over-deposited by atomic layer deposition (ALD) of an inorganic material. This ALD overlayer conforms to and heals defects of the thin film. In another embodiment, a flexible substrate is coated with an ALD decoupling layer that mitigates defect formation in a subsequently applied thin film. In other embodiments, the flexible substrate coated with the ALD decoupling layer and the thin film may also include the ALD overlayer. In certain embodiments, the permeation barriers form multilayer stacks. In one example, the multilayer stack may be a heterostructure formed of alternating ALD and polymer materials.
BRIEF DESCRIPTION OF THE FIGURES
Figure 1 illustrates a cross-section of a permeation barrier having polymer decoupling layers.
Figure 2 illustrates a cross-section of a permeation barrier having an ALD defect healing layer according to one embodiment.
Figure 3 illustrates a cross-section of a permeation barrier having an ALD decoupling layer according to one embodiment.
Figure 4 illustrates a cross-section of a permeation barrier having an ALD decoupling layer and an ALD defect healing layer according to one embodiment.
Figure 5 is a flowchart showing steps used to make the permeation barriers of Figures 2-4.
Figure 6 illustrates a cross-section of an active device deposited on a substrate having a permeation barrier according to one embodiment.
Figure 7 illustrates a cross-section of an active device disposed between two permeation barriers according to one embodiment.
DETAILED DESCRIPTION
One method that has been used to reduce defect propagation in a multilayer inorganic stack involves applying an organic polymer layer after each inorganic layer. This process is known as planarization or decoupling. However, the transport of gas through thin organic polymer layers is high due to the inherent void spaces of entangled polymer chains. Thus, gas may permeate through polymer decoupled multilayer stacks by moving through the organic layers, which act as conduits, to defects in underlying inorganic layers. Figure 1 illustrates a cross-section of a substrate 100 having a permeation barrier stack 102. Substrate 100 may be any substrate, such as an electronic device, e.g., a wafer, plastic display base, or printed circuit board, and may be provided with operable solid state components (not shown). Substrate 100 is planarized, for example, by application of a polymer base layer 104. Permeation barrier stack 102 is deposited atop polymer base layer 104 as a heterostructure formed of alternating inorganic layers 106, 108, 110, 112, which are interspersed with polymer decoupling layers 114, 116, 118, 120. Polymer decoupling layers 114, 116, 118, 120 may be made of the same type of polymer material or different polymer materials. Inorganic layers 106, 108, 110, 112, may, for example, form active circuitry or optical components, but are usually present as barrier layers. As shown, the inorganic layers have, for example, nucleated, aggregated, agglomerated, coagulated or conglomerated, to form structures 122, 124 with defects 126, 128, through respective layers 112, 110. The heterostructure of permeation barrier stack 102 uses polymer decoupling layers 114, 116, 118, 120 and polymer base layer 104 to prevent the propagation of cracks, pinholes, and other defects 126, 128, between adjacent inorganic layers 106, 108, 110, 112. Nevertheless, the polymer materials are permeable to oxygen. Accordingly, defects 126, 128 provide a permeation pathway 130 that transports oxygen and other harmful environmental gases throughout permeation barrier stack 102 and polymer base layer 104 to substrate 100.
Atomic Layer Deposition (ALD) is a monolayer method where inorganic materials are conformally adsorbed and chemically bound to a substrate. In one such method, the substrate is loaded into a vacuum chamber and heated to an appropriate temperature. The deposition of an ALD layer includes a series of sequential exposures to reactive precursors. The deposition process starts with the introduction of a first reactant vapor. After a period of time, a saturated exposure is achieved when chemical reactions self-terminate because the gas phase precursors have effectively reacted with all available reactive surface sites. Then excess reactant vapor is flushed from the chamber, leaving a monolayer of the first reactant chemically bound to the substrate. A second reactant is then introduced in an exposure sufficient to again lead to self-terminating reaction with the first monolayer. The second reactant vapor is then flushed from the chamber. Additional ALD layers may be applied by reintroducing the first reactant vapor and repeating the deposition method of sequential saturated exposures. Mixing of the first and second reactant vapors in the gas phase results in chemical vapor deposition (CVD) and should be avoided during ALD; therefore, the surface of the substrate and/or the reaction chamber is typically flushed with an inert gas, such as nitrogen, between introduction of reactant vapors. By way of example, an aluminum oxide (alumina, Al2Os) layer may be deposited on a substrate by alternately exposing the substrate to an aluminum reactant (e.g., trimethyl aluminum, TMA) and an oxygen reactant (e.g., water). The ALD method described above is shown in the following illustrative reactions, where stoichiometry has been omitted to highlight chemical changes at an independent reactive site (marked with an asterisk): S* + Al(CHs)3 (g) → S -Al(CH3)* (1)
S-Al(CH3)* + H2O (g) → S-Al(OH)* + CH4 (g) (2)
S Al(OH)* + Al(CHs)3 (g) → S-Al-O-Al(CH3)* + CH4 (g). (3) Substrate, S, typically displays reactive functional groups that bind to the aluminum reactant.
Aluminum reactants useful in forming ALD layers include alkyl aluminum
(e.g., A1(CH3)3, Al(CH2CHs)3), aluminum halides and aluminum with a combination of organic and halide ligands. Oxygen reactants useful in forming ALD layers include water, hydrogen peroxide, ozone, molecular oxygen, nitrous oxide, and metal alkoxides. Metal reactants useful in forming ALD layers include metal acetylacetonates, metal halides, alkyl metal compounds, alkoxy metal compounds, and metallic vapor. Silicon reactants useful in forming ALD layers include silanes (e.g., SiH4, Si2H6, Si3H8), dichlorosilane (SiH2Cl2), silicon tetrachloride (SiCl4), silicon tetrafluoride (SiF4), methylsilane (SiH3CH3), dimethylsilane (SiH2(CHs)2), hexamethylsiloxane ([(CH3)3Si]2O), tetramethylorthosilicate (Si(OCH3)4), and tetraethylorthosilicate (Si(OCH2CHa)4). Nitrogen reactants useful in forming ALD layers include ammonia and molecular nitrogen. ALD reactants are chosen to promote self-terminating surface chemical reactions that provide control over film thickness and uniformity. The self-limiting nature of the chemical reactions enables the application of conformal coatings in high aspect ratio structures.
The speed of ALD limits practical thicknesses achievable in commercial settings and single ALD layers alone may not have sufficient mechanical or structural properties to provide the permeability necessary for electrical applications; single layer ALD coatings have reported water vapor transport rates of about 1E-3 g/m2-day. Numerous publications describe flexible substrates coated with permeation barriers by atomic layer deposition. For example, WO 2004/105149 describes a plastic substrate coated with Al2O3 by an ALD process. The ALD barrier is envisioned for protection of electronic devices from oxygen and water permeation.
However, single layer ALD coatings have not achieved sufficient barrier performance to sufficiently protect the OLED device.
A combination of a conventionally deposited thin film and an ALD layer as described herein achieves low permeance with the additional advantages of flexibility, scratch resistance, chemical resistance, electrical isolation, minimal weight, transparency, refractive index matching, and hydrophobicity. In one embodiment, a thin film of an inorganic material is deposited by a conventional deposition technique (e.g., sputtering, evaporation, CVD, PECVD, etc.) on a flexible substrate. Conventional deposition conditions and materials are chosen to minimize the size and concentration of defects. This thin film serves as a primary barrier layer. A second inorganic layer that hermetically seals or "heals" defects in the primary barrier layer is applied directly over the thin film by ALD. Due to the conformal nature of ALD layers, the ALD material is deposited into the defects of the thin film to heal the defects and block permeation of gases. An ALD healing layer with water vapor transport rates of 1E-03 g/m -day, employed in conjunction with a PECVD coating with low defect concentrations is sufficient to achieve combined water vapor transport rates of 1E-06 g/m *day or less.
According to one embodiment, Figure 2 illustrates the aforementioned by showing a cross-section of a permeation barrier 200. An inorganic thin film 204 is applied to a substrate 202 by a conventional deposition technique. Thereafter, an ALD defect healing layer 208 is applied. The self-terminating reactions and conformal nature of ALD assure good coverage even on high aspect ratio features, such as cracks or grain boundaries 206, 210. Thin film 204 acts as a primary barrier layer and contains defects 206, 210 that are hermetically sealed or "healed" by application of ALD defect healing layer 208 over thin firm 204. The flowchart of Figure 5 A shows steps used to make permeation barrier 200 of Figure 2. Deposition 510 of conventional thin film 204 (Figure 2) precedes step 512 for the deposition of ALD healing layer 208.
In another embodiment, ALD provides an inorganic decoupling layer, that minimizes defects in subsequently applied layers. A thin film may be applied over the ALD decoupling layer by conventional deposition. The ALD decoupling layer serves to reduce deleterious effects on thin film growth that are related to artifacts of the underlying substrate. The function of the ALD decoupling layer is to provide optimal surface chemistry to promote uniform nucleation of subsequently applied thin films. Figure 3 is a cross-sectional view of a permeation barrier 300 having an ALD decoupling layer 304. ALD decoupling layer 304 is applied directly to substrate 302 to achieve surface energy matching of the thin film material with the substrate to promote uniform wetting of the thin film, and/or to fill surface pores and minimize other defect causing imperfections on the surface of substrate 302. Thin film 306 is applied over ALD decoupling layer 304, which promotes uniformity, density and adhesion for thin film 306. Thin film 306 has a minimal number of defects 308. The flowchart of Figure 5B shows steps used to make permeation barrier 300 of Figure 3. Deposition 508 of ALD decoupling layer 304 (Figure 3) precedes step 510 for the deposition of conventional thin film 306.
In another embodiment, a permeation barrier includes an ALD decoupling layer deposited on a substrate, a thin film deposited on the ALD decoupling layer by conventional deposition techniques, and an ALD healing layer deposited on the thin film. Figure 4 is a cross-sectional view of a permeation barrier 400 having an ALD decoupling layer 404 and an ALD healing layer 410. ALD decoupling layer 404 is applied directly to substrate 402 to achieve surface energy matching of the thin film material with the substrate to promote uniform wetting of the thin film, or to fill surface pores and minimize other defect causing imperfections on the surface of substrate 402. Thin film 406 is applied on ALD decoupling layer 404, which promotes uniformity, density and adhesion for thin film 406. Thin film 406 has a minimal number of defects 408. Defects 408 are hermetically sealed or "healed" by application of ALD defect healing layer 410 atop thin film 406. The flowchart of Figure 5C shows steps used to make permeation barrier 400 of Figure 4. Deposition 508 of ALD decoupling layer 404 (Figure 4) is followed by deposition 510 of conventional thin film 406 and then deposition 512 of ALD healing layer 410.
Permeation barriers such as those described above with reference to Figures 2- 4 may be used in conjunction with active devices (e.g., light emitting polymers, transistors, solar cells, etc.), while preferably but optionally not forming part of the active device circuitry. By way of example, a thin film forming part of the active device may be an electrode or conductive metal oxide that may or may not coincide to the full areal extent of the ALD layer. The thin film that combines with the ALD may be in electrical contact with this electrode or conductive metal oxide without being configured and arranged to form a necessary party of the active device circuitry. Figure 6 illustrates a cross-section of an active device 600 deposited on a substrate 602 having a permeation barrier 604 according to one embodiment. Permeation barrier 604 includes an ALD decoupling layer 606 and a thin film 608 deposited atop ALD decoupling layer 606. Thin film 608 interfaces with an electrode 610 and may function as a conductor or heat sink; however, in a preferred embodiment, thin film 608 is not an active circuitry component. Active circuitry components undergo time and temperature dependent phenomena, and thin films functioning as both barrier layers and active components may suffer structural fatigue that could cause premature degradation of the permeation barrier. Active device 600 is disposed between electrode 610 and a second electrode 612. A thin film 614 is deposited over active device 600 and electrodes 610, 612, and an ALD layer 616 is deposited over thin film 614 forming a second permeation barrier stack. It will be understood that various sequences of ALD layers and thin films as described herein may be used to create the permeation barriers of Figure 6.
Figure 7 illustrates a cross-section of an active device 700 disposed between two permeation barriers 704 according to one embodiment. Permeation barriers 704 include ALD layers 706 and thin films 708 deposited on substrates 702. Active device 700 is disposed between two electrodes 710,712. Electrodes 710,712 interface with permeation barriers 704. An optional dielectric layer (not shown) may separate electrodes 710,712 from thin films 708. A sealant 714, such as epoxy, secures permeation barriers 704 in proximity to one another and seals the edges of active device 700. It will be understood that various sequences of ALD layers and thin films as described herein may be used to create the permeation barriers of Figure 7.
Multilayer stacks, including two or more layers, formed by combinations of thin films, deposited by conventional deposition techniques, and ALD layers in various sequences are contemplated. For example, a multilayer stack may include an ALD layer/conventional layer/ALD layer/conventional layer/ALD layer, or a multilayer stack may include a conventional layer/ALD layer/conventional layer, or an ALD layer/conventional layer/conventional layer/ALD layer. In multilayer stacks, the ALD layers may serve as decoupling layers to minimize defects in subsequently applied layers and/or as defect healing layers to seal defects in underlying layers. Each "layer" may be a monolayer or may be formed by multiple monolayer applications where a material is deposited using a single deposition technique. The flowcharts of Figures 5A-C show exemplary steps that may be linked in series to make permeation barriers comprised of multilayer stacks.
The permeation barriers described above may be used in conjunction with, for example, a planarization layer (Figure 1), such as an organic polymer, to create a smooth surface prior to application of the first inorganic layer; a decoupling layer (Figure 1) to reduce defect propagation and improve flexibility; and/or a stress balancing film deposited on the back side of the flexible substrate to prevent curling from residual stress in the ALD and/or conventional layers. Planarization and decoupling layers (e.g., polyimides, poly(methyl methacrylate) (PMMA), novolacs and polyesters) may be applied by spraying or evaporating a UV curable polymer onto the substrate.
Suitable permeation barrier materials for both conventional layers and ALD layers include, but are not limited to silicon oxides, silicon nitrides, silicon oxynitrides, silicon oxycarbides, metal oxides, metal nitrides, metal oxynitrides, metal oxycarbides, ultra-thin metallic layers and conductive oxides. Many compounds in these material classes are optically transparent, which is desirable, for example, for electronic displays, photovoltaic cells and architectural glass where visible light must enter and/or exit the material.
The thickness of an ALD layer is, for example, in a range of from about 1-200 nm, and more typically in a range of from about 1-10 nm. Thin layers are more tolerant to flexing without cracking and more transparent than thick layers. Thin films, prepared by conventional deposition techniques, typically have a thickness in a range of from about 20-500 nm. However, thicknesses greater than about 150 nm can impact optical transmission. Deposition temperatures for both the ALD process and conventional depositions may be in a range of from about 20-4000C, depending on the upper temperature limit of the polymer substrate and/or electronic components.
Substrate materials include, but are not limited to polyarylates (PAR), poly(ether ether ketones) (PEEK), polyurethanes, polyesters (e.g., polyethylene terephthalate (PET), polybutylene terephthalate (PBT)), epoxy resins, epoxy-novalac resins, phenolic resins, cellulose ethers and esters, polyvinyl alcohol, polyvinyl chloride, polyamides, polyamines, polyvinylidene chloride, poly(alkenyl aromatic) polymers (e.g., polystyrene, polyethylene naphthalate (PEN)), polyacrylic acids, polyacrylimides, polyimides, polycarbonates, polyolefins, polymers of conjugated dienes (e.g., polybutadiene, isoprene), organosilicone polymers, and mixtures and random or block copolymers thereof. Polymers containing functional groups, such as halogen, hydroxyl, carbonyl, carboxylic acid, primary amines, secondary amines, and/or sulfonate groups, provide sites at which it is possible to form chemical bonds with permeation barrier materials. For polymers that do not contain functional groups, it is possible to introduce such groups by techniques such as water plasma treatment, ozone treatment, ammonia treatment and hydrogen treatment, for example. Substrates are usually cleaned to remove particulate matter and minimize surface imperfections prior to application of permeation barrier materials. Methods of cleaning substrates are known and may include, for example ultrasonic soaks in a series of chemical solutions and/or ion/plasma based processes. Features measuring about one micron or greater in size should be removed from the substrate surface. Techniques for characterizing inorganic permeation barriers include gas permeation studies, infrared spectroscopy, transmission electron microscopy, atomic force microscopy (to measure surface roughness), X-ray photoelectron spectroscopy and X-ray diffraction (for depth-profiling and structural analysis), and characterization of electrical properties. For example, electrical leakage current and permeation are both tied to defect density; therefore, a reduction in electrical leakage current relative to a control sample suggests decreased permeation.
EXAMPLE l
MULTI-LAYER STACK INCLUDING A DECOUPLING LAYER DEPOSITED BY ALD, CONVENTIONAL LAYER DEPOSITED BY PECVD, AND A DEFECT HEALING LAYER DEPOSITED BY ALD
A roll of polyethylene terephthalate (PET) (substrate), which is approximately 0.3-2 meters wide and 50-250 microns thick, is mounted in a vacuum chamber with roll-to-roll processing, plasma/ion cleaning, and ALD capabilities. The vacuum chamber is segmented into three zones. The first zone is a drying station having a bank of infrared lamps to remove excess moisture from the substrate. The second zone is an ion cleaning station and the third zone is an ALD deposition chamber. The process environment of each zone is isolated from neighboring zones and from ambient conditions.
The roll of PET is pulled from a supply reel to a take up reel at a speed of about 0.1 to 2 m/min. After drying in the first zone, the PET is pulled through an ion cleaning station. The chamber of the second zone contains approximately 1-500 mTorr of gaseous species selected from mixtures of Ar, N2, and/or O2. For example, a typical mixture contains 50% Ar (g) and 50% O2 (g). Radio frequency power having a frequency of 13.56 MHz is supplied through an impedance matching network to generate a plasma containing reactive ion species. The substrate is thus cleaned by ion bombardment for a period of about 10 seconds to 1 minute.
The PET is then pulled into the third zone containing a traveling wave ALD reactor. The base pressure of the traveling wave ALD reactor is typically below 1E-3 mbar with operating pressures from 1-5 mbar. A stream of inert nitrogen is continuously passed over the substrate at a rate of 1 standard liter per min. The inert carrier gas is periodically and sequentially injected with pulses of trimethyl aluminum (TMA) and water. One such sequence might be, for example, 0.1-0.5 seconds of TMA, 0:1-1.0 second of nitrogen, 0.1-1.0 second of water, and 1-5 seconds of nitrogen. This dosing sequence is repeated for a number of cycles, where each cycle deposits slightly less than 0.1 run of aluminum oxide. At any given point in time, TMA, nitrogen, and water are all present in multiple locations over the PET. The system is designed to be in laminar flow such that the reactive species remain isolated until they reach a reactive trap before the vacuum pump. The PET is maintained at a temperature of 1000C by techniques such as employing a bank of infrared lamps or pulling the substrate over a heated drum. The thickness of the ALD decoupling layer is established by the residence time of the PET in the traveling wave reactor and the number of TMA/water cycles each region of the substrate is exposed to. A typical decoupling layer is about 1-100 angstroms of deposited alumina.
The PET is moved to a similar roll coater equipped with ion cleaning and PECVD capabilities. The PET is pulled through the ion cleaning station where it is cleaned for a second time, as described above. A thin film of silicon oxide is then deposited by PECVD. Silane and nitrous oxide (N2O) are simultaneously introduced into the reactor chamber in a 1 :50 ratio. The PET temperature is held at about 100- 15O0C. The SiOx thin film thickness is determined by the residence time of the PET in the deposition region. A typical residence time of about 30 seconds will create a thin film about 100-2000 angstroms thick, more typically a thin film about 200-500 angstroms is deposited. The PET roll is then transferred back to the original deposition zone for processing of a defect healing ALD layer by introduction of TMA and water vapors sequentially as described above. The ALD defect healing layer is from about 50-200 angstroms thick.
Similar process steps may be carried out in batch processes, where panes of PET may be coated with multilayer permeation barrier stacks.
Changes may be made in the above methods and systems without departing from the scope hereof. It should thus be noted that the matter contained in the above description or shown in the accompanying drawings should be interpreted as illustrative and not in a limiting sense. The following claims are intended to cover all generic and specific features described herein, as well as all statements of the scope of the present method and system, which, as a matter of language, might be said to fall there between.

Claims

CLAIMSWhat is claimed is:
1. A flexible permeation barrier for flexible electronics, comprising: a flexible substrate; a thin film deposited over the flexible substrate; and an ALD layer deposited onto the thin film, to conform to and heal defects of the thin film.
2. The permeation barrier of claim 1 , wherein the permeation barrier is disposed within a display.
3. The permeation barrier of claim 1, the thin film comprising one of silicon dioxide or silicon nitride.
4. The permeation barrier of claim 1, the ALD layer comprising aluminum oxide.
5. The permeation barrier of claim 1, further comprising a planarizing layer.
6. The permeation barrier of claim 1, further comprising a decoupling layer.
7. A flexible permeation barrier for flexible electronics, comprising: a flexible substrate; an ALD decoupling layer deposited on the substrate; a thin film, wherein the ALD decoupling layer minimizes formation of defects in the thin film; and wherein the thin film is not an active circuitry component.
8. The permeation barrier of claim 7, further comprising an ALD healing layer deposited on the thin film, to conform to and heal defects of the thin film.
9. The permeation barrier of claim 8, the ALD healing layer comprising aluminum oxide.
10. The permeation barrier of claim 8, further comprising a planarizing layer.
11. The permeation barrier of claim 8, further comprising a decoupling layer.
12. The permeation barrier of claim 7, wherein the permeation barrier is disposed within a display.
13. The permeation barrier of claim 7, the thin film comprising one of silicon dioxide or silicon nitride.
14. The permeation barrier of claim 7, the ALD decoupling layer comprising aluminum oxide.
15. The permeation barrier of claim 7, further comprising a planarizing layer.
16. The permeation barrier of claim 7, further comprising a decoupling layer.
17. A flexible permeation barrier, comprising: a flexible substrate; and a multilayer stack comprised of thin film layers and ALD layers, wherein the thin film layers are not active circuitry components.
18. The permeation barrier of claim 17, further comprising a planarizing layer.
19. The permeation barrier of claim 17, further comprising a decoupling layer.
20. A method of creating a flexible permeation barrier for flexible electronics, comprising: depositing a decoupling layer on a flexible substrate by atomic layer deposition (ALD); depositing a thin film on the decoupling layer using a conventional deposition technique, wherein the decoupling layer minimizes formation of defects in the thin film; and depositing an ALD layer onto the thin film, to conform to and heal defects of the thin film.
21. A method of creating a flexible permeation barrier for flexible electronics, comprising: depositing a thin film on the flexible substrate using a conventional deposition technique; and depositing an ALD layer onto the thin film, to conform to and heal defects of the thin film.
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