Classifications

• • 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
  • H10K50/8445—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
  • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
  • H10K2102/301—Details of OLEDs
  • H10K2102/351—Thickness
• • 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
  • H10K50/85—Arrangements for extracting light from the devices
  • H10K50/858—Arrangements for extracting light from the devices comprising refractive means, e.g. lenses

Definitions

• Embodiments of the present disclosure relate to a barrier layer stack, a method for manufacturing a barrier layer stack, and an ultra-high barrier layer and antireflection system.
• OLEDs Organic light emitting devices
• barrier systems have been used to protect OLED devices from such water vapor or oxygen.
• glass is used to encapsulate OLED devices, a structural stability of the OLED device is compromised, since glass lacks flexibility.
• barrier system e.g. on a substrate such as a flexible polymer substrate, that overcomes at least some of the above aspects.
• barrier system that exhibits enhanced optical performance compared to conventional structures.
• a barrier layer stack In light of the above, a barrier layer stack, a method for manufacturing a barrier layer stack, and an ultra-high barrier layer and antireflection system are provided. Further aspects, advantages, and features of the present disclosure are apparent from the claims, the description, and the accompanying drawings.
• a barrier layer stack includes a first layer, a second layer, a third layer and a fourth layer arranged in this order.
• the first layer and the third layer have a refractive index of at least 1.9, and the second layer and the fourth layer have a refractive index of less than 1.7.
• Each of the layers has a thickness of at least 70 nm.
• a method for manufacturing a barrier layer stack includes: alternately depositing a first layer material and a second layer material on a substrate to form at least four layers, wherein the first layer material has a refractive index of at least 1.9, wherein the second layer material has a refractive index of less than 1.7, and wherein each of the layers has a thickness of at least 70 nm.
• an ultrahigh barrier layer and antireflection system includes a substrate and a layer stack over the substrate.
• the layer stack includes a first layer, a second layer, a third layer and a fourth layer arranged in this order.
• the first layer and the third layer have a refractive index of at least 1.9
• the second layer and the fourth layer have a refractive index of less than 1.7.
• Each of the layers has a thickness of at least 70 nm.
• Embodiments are also directed at apparatuses for carrying out the disclosed methods and include apparatus parts for performing each described method step. These method steps may be performed by way of hardware components, a computer programmed by appropriate software, by any combination of the two or in any other manner. Furthermore, embodiments according to the disclosure are also directed at methods by which the described apparatus operates. It includes method steps for carrying out every function of the apparatus. BRIEF DESCRIPTION OF THE DRAWINGS
• Figures 1A-C show cross sectional views of barrier layer stacks according to embodiments described herein;
• Figure 2 shows a cross sectional view of a barrier layer stack according to further embodiments described herein;
• Figure 3 shows a graph of a reflectance of barrier layer stacks according to embodiments described herein;
• Figure 4 shows a schematic view of a deposition apparatus used for manufacturing a barrier layer stack according to embodiments described herein;
• Figure 5 shows a flow chart of a method for manufacturing a barrier layer stack according to embodiments described herein.
• Layer stacks can be used in optical applications (for instance protection of OLEDs), but they can reduce the transmittance particularly in the visible spectrum and may create undesired colors.
• the present disclosure overcomes this drawback by providing a barrier layer stack having combined barrier and antireflection properties.
• the barrier layer stack according to embodiments described herein can have color neutrality, the color neutrality providing improved optical characteristics of the barrier layer stack.
• the barrier layer stack of the present disclosure can also be used in different applications.
• the barrier layer stack of the present disclosures can be used in the field of packaging for instance of food that requires high oxygen protection, for example fresh pasta, sliced meat, dried fruit, or snacks.
• the barrier layer stack may provide a gas barrier and transparent properties in order provide a product' s visibility.
• the disclosure is related to barrier layer systems with low water vapor and oxygen transmission, and is particularly related to ultra-high barrier layer systems (UHB).
• the barrier layer stacks of the present disclosure include alternating layers (diades), and particularly include at least four layers.
• a thickness of the individual layers is at least 70 nm, and is particularly in the range of 70 nm to 300 nm, and more particularly in the range of 100 nm to 150 nm. Thicknesses and/or optical properties of the individual layers can be different.
• the barrier layer stack can include at least two materials with a low and a high refractive index. At least some of the layers of the barrier layer stack can be dielectric layers.
• the first layer, the second layer, the third layer and the further layer are dielectric layers. In some implementations, all of the layers of the barrier layer stack are dielectric layers.
• the uppermost layer i.e., the last layer arranged e.g. over the substrate such as the fourth layer, has the low refractive index.
• the barrier layer stack having the uppermost layer with the low refractive index provides improved optical characteristics.
• An aspect of the present disclosure is to provide layer thicknesses of the individual layers in order to provide a transmittance, which is for instance higher than a transmittance of a (uncoated) substrate on which the layer stack is disposed. Particularly, an aspect of the present disclosure is to provide a transmittance, which is higher than a transmittance of a (uncoated) substrate in the visible region.
• a barrier layer stack with four layers may be referred to as NONO
• a barrier layer stack with five layers may be referred to as NONON
• a barrier layer stack with six layers may be referred to as NONONO.
• the symbols N and O may denote a material of the layers.
• the symbol N denotes the material or layer with high refractive index (e.g., SiNx)
• the symbol O denotes the material or layer with low refractive index (e.g., SiOx).
• the present disclosure is not limited to SiNx and SiOx, and that any suitable materials having the high refractive index of at least 1.9 and the low refractive index of less than 1.7 could be used for the layers with the high refractive index and the layers with the low refractive index, respectively.
• Some examples can be insulating materials with high and low refractive indexes, for example SiOx, TiOx, NbOx, SiNx, SiOxNy, AlOx, AlOxNy, TaOx, an organic material such as a polymer material, and combinations thereof.
• an extinction coefficient of the materials with the high refractive index and the low refractive index can be small.
• the index of refraction and the extinction coefficient are the real part and the imaginary part, respectively, of the complex index of refraction. Particularly, when light passes through a medium, some part of it will be absorbed. This can be described by defining the complex index of refraction as being equal to n+ik.
• the real part "n” indicates the phase velocity, while the imaginary part “ik” indicates the amount of absorption loss when the electromagnetic wave propagates through the material.
• the transmittance of a NONO/NONONO design can be enhanced above the transmittance for instance of uncoated PET.
• the (absolute) transmittance gain can be in the range of about 4% to about 6% (e.g., increasing a transmittance (Ty) from about 88% to about 92-94%).
• the contrast/color difference may be b* ⁇ 0.3 (b* value as defined by the International Commission on Illumination (CIE) in 1976).
• Figures 1A-C show barrier layer stacks according to embodiments described herein.
• the layer stack of the present embodiments is constituted by a number of films formed (e.g., by deposition) one atop of another.
• FIG 1A a barrier layer stack 10 according to embodiments of the present disclosure is depicted.
• the barrier layer stack 10 includes a first layer 11, a second layer 12, a third layer 13 and a fourth layer 14 arranged in this order.
• the first layer 11 and the third layer 13 have a refractive index of at least 1.9
• the second layer 12 and the fourth layer 14 have a refractive index of less than 1.7.
• Each of the layers 11-14 has a thickness of at least 70 nm.
• the first layer 11 and the third layer 13 having a refractive index of at least 1.9, the second layer 12 and the fourth layer 14 having a refractive index of less than 1.7, and each of the layers 11- 14 having a thickness of at least 70 nm provide a barrier layer stack having combined barrier and antireflection functions.
• the barrier layer stack can include one or more further layers over the fourth layer 14, particularly a fifth or a fifth and a sixth layer as it is shown in figures IB and 1C, respectively.
• FIG. IB a barrier layer stack 20 according to embodiments of the present disclosure is depicted.
• the barrier layer stack 20 is similar to the barrier layer stack 10 of figure 1 with the difference being that a fifth layer 15 is arranged over the fourth layer 14.
• FIG 1C a barrier layer stack 30 according to embodiments of the present disclosure is depicted.
• the barrier layer stack 30 is similar to the barrier layer stack 20 of figure 2 with the difference being that a sixth layer 16 is arranged over the fifth layer 15.
• the odd numbered layers have the refractive index of at least 1.9, and the even numbered layers have the refractive index of less than 1.7.
• the terms "odd” and “even” as used throughout this application refer to parity in mathematics, i.e. that an integer is even if it is evenly divisible by two and odd if it is not even.
• the odd numbered layers can be the first, third, fifth etc. layers
• the even numbered layers can be the second, fourth, sixth, etc. layers.
• the odd numbered layers having a refractive index of at least 1.9, the even numbered layers having a refractive index of less than 1.7, and each of the layers having a thickness of at least 70 nm provide a barrier layer stack having combined barrier and antireflection functions.
• the first to sixth layers, the odd numbers layers and the even numbered layers as referred to in this application are the layers providing the barrier and antireflection functions, i.e., the layers having the refractive index of at least 1.9 or the refractive index of less than 1.7, and the thickness of at least 70 nm.
• the numbering excludes any other layers that could additionally be provided, such as seed layers, hard coatings, adhesive layers and the like.
• a water vapor transmission rate (WVTR; in units of g per cm 2 and day) and/or an oxygen transmission rate (OTR) of the barrier layer stack is less than 10 "4 , specifically less than 10 "5 , and more specifically about 10 "6 .
• a transmittance of the barrier layer stack can be at least 85%, and particularly more than 90%.
• the barrier layer stack including the at least four layers and the substrate may have a transmittance in the range of 87 to 95%, specifically 88% or 89%, and more specifically 93% or 94%.
• the odd numbered layers can have a refractive index of about at least 1.9, and specifically about 2.
• the even numbered layers can have a refractive index of less than 1.7, specifically a refractive index of less than 1.5, and particularly of about 1.46.
• the odd numbered layers of the barrier layer stack include at least one of SiNx, NbOx, SiN, SiOxNy, AlOx, AlOxNy, TiOx TaOx, an organic material such as a polymer material, and/or combinations thereof, and/or the even numbered layers of the barrier layer stack include at least one of SiOx, MgFx, SiOxNy, an organic material such as a polymer material, and/or combinations thereof.
• the first layer 11, e.g. a first dielectric layer can have a high refractive index.
• a barrier layer stack that also has antireflection characteristics can be provided.
• layers having the lower refractive indexes e.g. the even numbered layers
• layers having the higher refractive indexes can be provided by layers containing SiOx, MgFx, SiOxNy, an organic material such as a polymer material, and/or combinations thereof, or the like.
• layers having the higher refractive indexes e.g.
• the odd numbered layers can be provided by films containing NbOx, SiNx, SiN, SiOxNy, AlOx, AlOxNy, TiOx TaOx, an organic material such as a polymer material, and/or combinations thereof, or the like.
• the layers can be manufactured by chemical vapor deposition or physical vapor deposition, for example sputtering or evaporation.
• Some examples can be insulating materials with high and low refractive indexes, for example SiOx, SiN, TiOx, NbOx, SiNx, SiOxNy, AlOx, AlOxNy, TaOx, an organic material such as a polymer material, and/or combinations thereof.
• At least one of the layers has a thickness of more than 100 nm.
• the thickness of each of the odd numbered layers is less than the thickness of each of the even numbered layers.
• a barrier layer stack having four layers is provided, as it is for instance shown in figure 1A.
• the first layer 11 may have a thickness of 139 nm to 143 nm, e.g. about 141 nm
• the second layer 12 may have a thickness of 169 nm to 173 nm, e.g. about 171
• the third layer 13 may have a thickness of 92 nm to 96 nm, e.g. about 94 nm
• the fourth layer 14 may have a thickness of 76 nm to 80 nm, e.g. about 78 nm.
• the first layer 11 and the third layer 13 may include or be made of SiNx, and the second layer 12 and the fourth layer 14 may include or be made of Si0 2 .
• a water vapor transmission rate (WVTR) of the barrier layer stack can be less than 10 "5 , and specifically about 10 ⁇ 6 .
• a transmittance of the barrier layer stack can be about 94%, particularly in a wavelength range of about 400nm to 700nm.
• a barrier layer stack having five layers is provided, as it is for instance shown in figure IB.
• the first layer 11 may have a thickness of 138 nm to 142 nm, e.g. about 140 nm
• the second layer 12 may have a thickness of 163 nm to 167 nm, e.g. about 165 nm
• the third layer 13 may have a thickness of 120 nm to 124 nm, e.g. about 122 nm
• the fourth layer 14 may have a thickness of 155 nm to 159 nm, e.g.
• the fifth layer 15 may have a thickness of 114 nm to 118 nm, e.g. about 116 nm.
• the first layer 11, the third layer 13 and the fifth layer 15 may include or be made of SiNx, and the second layer 12 and the fourth layer 14 may include or be made of Si0 2 .
• a water vapor transmission rate (WVTR) of the barrier layer stack can be less than 10 "5 , and specifically about 10 "6 .
• a transmittance of the barrier layer stack can be about 88%, particularly in a wavelength range of about 400 nm to 700 nm.
• the first layer 11 may have a thickness of 140 nm to 144 nm, e.g. about 142 nm
• the second layer 12 may have a thickness of 169 nm to 173 nm, e.g. about 171 nm
• the third layer 13 may have a thickness of 126 nm to 130 nm, e.g. about 128 nm
• the fourth layer 14 may have a thickness of 160 nm to 164 nm, e.g. about 162 nm
• the fifth layer 15 may have a thickness of 137 nm to 141 nm, e.g. about 139 nm.
• the first layer 11, the third layer 13 and the fifth layer 15 may include or be made of SiNx, and the second layer 12 and the fourth layer 14 may include or be made of Si0 2 .
• a water vapor transmission rate (WVTR) of the barrier layer stack can be less than 10 "5 , and specifically about 10 "6 .
• a transmittance of the barrier layer stack can be in the range of about 88% to about 92%, particularly in a wavelength range of about 400 nm to 700 nm.
• a barrier layer stack having six layers is provided, as it is for instance shown in figure 1C.
• the first layer 11 may have a thickness of 137 nm to 141 nm, e.g. about 139 nm
• the second layer 12 may have a thickness of 160 nm to 164 nm, e.g. about 162 nm
• the third layer 13 may have a thickness of 114 nm to 118 nm, e.g. about 116 nm
• the fourth layer 14 may have a thickness of 154 nm to 158 nm, e.g. about 156 nm
• the fifth layer 15 may have a thickness of 85 nm to 89 nm, e.g.
• the sixth layer 16 may have a thickness of 75 nm to 79 nm, e.g. about 77 nm.
• the first layer 11, the third layer 13 and the fifth layer 15 may include or be made of SiNx
• the second layer 12, the fourth layer 14 and the sixth layer 16 may include or be made of Si0 2 .
• a water vapor transmission rate (WVTR) of the barrier layer stack can be less than 10 ⁇ 5 , and specifically about 10 ⁇ 6 .
• a transmittance of the barrier layer stack can be about 94%, particularly in a wavelength range of about 400nm to 700nm.
• the layers are formed or arranged over each other.
• the second layer 12 is formed or arranged over the first layer 11
• the third layer 13 is formed or arranged over the second layer 12
• the fourth layer 14 is formed or arranged over the third layer 13.
• the term "over” i.e. one layer being over the other, it is understood that, starting from the first layer 11, the second layer 12 is deposited over the first layer 11, and a further layer, deposited after the second layer 12, is thus over the second layer 12 and over the first layer 11.
• the term "over” is used to define an order of layers, layer stacks, and/or films wherein the starting point is the substrate. This is irrespective of whether the barrier layer stack is depicted upside down or not.
• the layers 11- 14 are directly disposed on each other.
• the second layer 12 is formed or arranged on the first layer 11
• the third layer 13 is formed or arranged on the second layer 12
• the fourth layer 14 is formed or arranged on the third layer 13.
• no further layers or films are present between the layers of the barrier layer stack.
• further layers can be provided between at least some of the layers of the barrier layer stack.
• Figure 2 shows a barrier layer stack 40 according to further embodiments described herein.
• the barrier layer stack 40 further includes a substrate 41, and particularly a transparent substrate.
• substrate as used herein can particularly embrace flexible substrates such as a web or a foil.
• substrate may also embrace inflexible substrates, e.g., a wafer, slices of transparent crystal such as sapphire or the like, or a glass plate.
• the term "transparent" as used herein can particularly include the capability of a structure to transmit light with relatively low scattering, so that, for example, light transmitted therethrough can be seen in a substantially clearly manner.
• the substrate includes a transparent polymer material selected from the group including polycarbonate (PC), polyethylene terephthalate (PET), poly(methacrylic acid methyl ester) (PMMA), triacetyl cellulose (TAC), cyclo olefin polymer (COP), poly(ethylene naphthalate) (PEN), and combinations thereof.
• the substrate includes polyethylene terephthalate (PET). PET can have a transmittance of about 90%.
• the layers 11-14 are provided on or over the substrate 41.
• an ultra high barrier (UHB) layer and antireflection system is provided.
• the ultra high barrier (UHB) layer and antireflection system includes a substrate and a layer stack over or on the substrate.
• the layer stack may be anyone of the barrier layer stacks described above with reference to figures 1A-C and 2.
• the layer stack may particularly include a first layer, a second layer, a third layer and a fourth layer arranged in this order, wherein the first layer and the third layer have a refractive index of at least 1.9, wherein the second layer and the fourth layer have a refractive index of less than 1.7, and wherein each of the layers has a thickness of at least 70 nm.
• Figure 3 shows a graph of a reflectance of barrier layer stacks according to embodiments described herein.
• the term “reflectance” as used herein is the fraction of incident electromagnetic power that is reflected.
• the term “reflectance” may be synonymously used with the term “reflectivity”.
• the y-axis of the graph denotes a reflectance in % (percent), and the x-axis denotes a wavelength ⁇ (lambda) in units of nanometer (nm).
• Denoted with reference numeral 50 is a reflectance of an uncoated PET substrate (about 5%).
• Denoted with reference numeral 51 is a reflectance of a barrier layer stack according to embodiments described herein with four layers (NONO), which is less than 1 percent in a range from about 420 nm to about 680 nm.
• Reference numeral 52 indicates a reflectance of a barrier layer stack according to embodiments described herein with six layers (NONONO), which is also less than 1 percent in a range from about 420 nm to about 680 nm.
• Methods for depositing a material for instance on a substrate may include a physical vapor deposition (PVD) process, a chemical vapor deposition (CVD) process, a plasma enhanced chemical vapor deposition (PECVD) process etc.
• PVD physical vapor deposition
• CVD chemical vapor deposition
• PECVD plasma enhanced chemical vapor deposition
• the process is performed in a process apparatus or process chamber, where the substrate to be coated is located.
• a deposition material is provided in the apparatus.
• a plurality of materials such as oxides, nitrides or carbides thereof may be used for deposition.
• other processing steps like etching, structuring, annealing, or the like can be conducted in processing chambers.
• Figure 4 shows a schematic view of an apparatus 100, e.g. a roll- to-roll deposition apparatus, for depositing or coating the layers according to embodiments described herein, and particularly for manufacturing a barrier layer stack according to embodiments described herein.
• apparatus 100 e.g. a roll- to-roll deposition apparatus, for depositing or coating the layers according to embodiments described herein, and particularly for manufacturing a barrier layer stack according to embodiments described herein.
• the apparatus 100 can include at least three chamber portions 102A, 102B and 102C. At chamber portion 102C one or more deposition sources 630 and optionally an etching station 430 can be provided as processing tools.
• a substrate 41 e.g. a flexible substrate, is provided on a first roll 764, e.g. having a winding shaft. The flexible substrate is unwound from the roll 764 as indicated by the substrate movement direction shown by arrow 108.
• a separation wall 401 is provided for separation of chamber portions 102A and 102B. The separation wall 401 can further be provided with gap sluices 140 for having the substrate 41 pass therethrough.
• a vacuum flange 112 provided between the chamber portions 102B and 102C can be provided with openings to take up at last some processing tools.
• the substrate 41 is moved through the deposition areas provided at a coating drum 110 and corresponding to positions of the deposition sources 630. During operation, the coating drum 110 rotates around an axis such that the substrate 41 moves in direction of arrow 108. According to some embodiments, the substrate 41 is guided via one, two or more rollers from the roll 764 to the coating drum 110 and from the coating drum 110 to the second roll 764', e.g. having a winding shaft, on which the substrate 41 is wound after processing thereof.
• the deposition sources 630 can be configured for depositing the layers of the layer stack.
• at least one deposition source 630 can be adapted for deposition of the layer material having the refractive index of at least 1.9, and at least one deposition source 630 can be adapted for deposition of the layer material having the refractive index of less than 1.7.
• a first deposition source can be configured for depositing the first layer
• a second deposition source can be configured for depositing the second layer
• a third deposition source can be configured for depositing the third layer
• a fourth deposition source can be configured for depositing the fourth layer.
• the first chamber portion 102A is separated in an interleaf chamber portion unit 102A1 and a substrate chamber portion unit 102A2.
• interleaf rolls 766/766' and interleaf rollers 105 can be provided as a modular element of the apparatus 100.
• the apparatus 100 can further include a pre-heating unit 194 to heat the flexible substrate.
• a pre-treatment plasma source 192 e.g. an RF (radio frequency) plasma source can be provided to treat the substrate with a plasma prior to entering chamber portion 102C.
• an optical measurement unit 494 for evaluating the result of the substrate processing and/or one or more ionization units 492 for adapting the charge on the substrate can be provided.
• the deposition material may be chosen according to the deposition process and the later application of the coated substrate.
• the deposition material of the deposition sources 630 may be silicon.
• oxide-, nitride- or carbide- layers, which can include such materials, can be deposited by providing the material from the source or by reactive deposition, i.e. the material from the source reacts with elements like oxygen, nitride, or carbon from a processing gas.
• a method 700 for manufacturing a barrier layer stack is provided. The method may include alternately depositing a first layer material and a second layer material on a substrate to form at least four layers.
• the first layer material has a refractive index of at least 1.9
• the second layer material has a refractive index of less than 1.7
• each of the layers has a thickness of at least 70 nm.
• a first layer may be deposited for instance on a substrate (block 701). Then, a second layer may be deposited on or over the first layer (block 702). Afterwards a third layer may be deposited on or over the second layer (block 703). A fourth layer may be deposited on or over the third layer (block 704).

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