KR20140064656A - Hydrophobic and oleophobic encapsulation material with alternating layers - Google Patents

Abstract

An encapsulation material for preventing the permeation of water or oily materials into a protection area or apparatus is explained. The encapsulation material includes alternating layers including hydrophobic and oleophobic first layers and hydrophilic second layers. The second hydrophilic layer holds water molecules and prevents the movement thereof. Through the alternating the hydrophobic and oleophobic layers and the hydrophilic layers (including hydrophobic layers having a thickness almost the same as the thickness of a water molecule or a hydroxyl ion), the encapsulation material forms multiple and limited active wells in the hydrophilic layers. The potential wells confine water molecules, oxygen molecules and hydroxyl ions and prevents the movement thereof through the encapsulation material.

Description

[0001] HYDROPHOBIC AND OLEOPHOBIC ENCAPSULATION MATERIAL WITH ALTERNATING LAYERS [0002]

The present disclosure generally relates to encapsulating materials. In particular, the present specification relates to hydrophobic and oleophobic encapsulating materials having alternating layers.

Various products benefit from, for example, encapsulation or protection from contamination from moisture or oily materials. Exemplary products that benefit from encapsulation include electronic devices (e.g., components of a display device or solar cell) and food or other perishable products.

By forming an encapsulating material on the product itself or by using an encapsulating material as an element to package the product, the moisture and / or oily materials would otherwise be damaged or poor in quality when exposed to the contaminants. . For example, the encapsulating material can be used to protect the product by attaching it to the substrate to act as a protective layer. Alternatively, the encapsulating material may be used with a more durable material located on the encapsulating material.

Perfluoropolymers are chemically stable, resistant to chemicals and weather, have oil repellency and water repellency, have low surface tension, low refractive index, low coefficient of friction, reduced surface adhesion , It can be used as a hydrophobic encapsulating material. However, perfluoropolymers do not have good adhesion properties. Therefore, when a perfluoropolymer is used as a coating material, the perfluoropolymer tends to delaminate from the substrate or other elements of the attached product or package.

Embodiments include the steps of providing a bottom layer of inorganic material, forming a hydrophobic first layer deposited on the bottom layer and comprising at least one metal or an inorganic compound of semi-metal, oxygen and fluorine, and a water- forming a first alternating-layer laminate by forming an inorganic hydrophilic second layer on the first layer to provide an energetic well that retains the first hydroxyl-hydroxyl ion.

In one embodiment, the bottom layer is provided by adsorbing a metal-organic precursor layer on a substrate using atomic layer deposition and exposing the metal-organic precursor layer to a radical species derived from the plasma, The plasma converts the surface portion of the metal-organic precursor layer to the inorganic compound of the first layer.

In one embodiment, a bottom layer is further provided by exposing the bottom layer of inorganic material to a plasma containing fluorine to form an inorganic layer comprising the elements of the inorganic material and fluorine as the first layer.

In one embodiment, a bottom layer is further provided by exposing the bottom layer of inorganic material to a plasma comprising fluorine and silane to form an inorganic layer comprising elements of inorganic material, silicon, carbon and fluorine as a first layer do.

In one embodiment, a bottom layer is further provided by exposing the bottom layer of inorganic material to a plasma comprising fluorine with a precursor comprising titanium to form an inorganic layer comprising elements of inorganic material, titanium, carbon and fluorine Is formed as a first layer.

In one embodiment, the hydrophobic first layer is provided by depositing a polymer, a plasma polymer (i.e., a polymer polymerized using a plasma), or a polymer of aluminum, oxygen, carbon, and fluorine on the bottom layer.

In one embodiment, the hydrophobic first layer has a thickness of from 1 angstrom to 100 angstroms.

In one embodiment, a method for fabricating an encapsulating material comprises forming a bottom layer of tridecafluoro-1,1,2,2-tetrahydrooctyl (meth) acrylate as a first layer to form an Al-Si-OCF polymer on the bottom layer A solution of tridecafluoro-1,1,2,2-tetrahydrooctylmethylbis (dimethylamino) silane, which is exposed to tetrahydrooctylmethylbis (dimethylamino) silane, silane to react with trimethylaluminum in the bottom layer to provide a hydrophobic first layer.

In one embodiment, the inorganic hydrophilic second layer is formed by exposing the first layer to a metal-organic precursor whose molecules are adsorbed on the first layer, adsorbing the adsorbed metal-organic precursor to convert the adsorbed metal- By exposing molecules to the radicals of the plasma.

In one embodiment, at least one additional alternating-layer stack is formed on the first alternating-layer stack.

In one embodiment, the bottom layer is formed by exposing the substrate to a metal-organic precursor, injecting an inert gas onto the substrate to remove the physically adsorbed metal-organic precursor from the substrate, and removing the remaining metal- Is exposed by exposing the radicals generated from the plasma and by providing an organic precursor to the metal-organic molecules that remain on the substrate and are exposed to radicals.

In one embodiment, the inorganic hydrophilic second layer has a thickness from 1 Angstrom to 5 Angstroms.

Other embodiments relate to an encapsulating material comprising a bottom layer of inorganic material and a first alternating-layer laminate. The first alternating-layer laminate comprises a hydrophobic first layer and an inorganic hydrophilic second layer deposited on the first layer. The second layer provides an active well holding water molecules and hydroxyl ions.

In one embodiment, the bottom layer is one of Al ₂ O ₃ , ZrO ₂ , HfO ₂ , SiO ₂ , TiO _2, and combinations thereof.

In one embodiment, the first hydrophobic layer is a polymer.

In one embodiment, the second layer has a thickness approximately equal to the molecular diameter of the water molecule.

In one embodiment, the hydrophobic first layer is an organoaluminum-oxygen-carbon-fluorine compound.

In one embodiment, the hydrophobic first layer is an inorganic aluminum-oxygen-fluorine compound.

In one embodiment, the hydrophobic first layer is made by exposing the bottom layer to a fluorine-containing plasma to convert the surface of the bottom layer to an inorganic aluminum-oxygen-fluorine compound of the first hydrophobic layer.

In one embodiment, the first hydrophobic layer is a polymer.

In one embodiment, the first layer is formed by exposing the substrate to glycidylmethacrylate to deposit a glycidyl methacrylate layer and exposing to a deposited glycidyl methacrylate layer N ₂ O plasma And converting the deposited layer to poly (glycidyl methacrylate).

In one embodiment, the encapsulating material comprises at least one additional alternating-layer stack on the first alternating-layer stack.

Other embodiments relate to an apparatus comprising at least one active layer and an encapsulation layer protecting at least one active layer from contaminants. The encapsulation layer may comprise an inorganic material and a first alternating-layer laminate. The first alternating-layer laminate comprises a hydrophobic first layer compound deposited on the bottom layer and an inorganic hydrophilic second layer deposited on the hydrophobic first layer. The second layer provides an active well holding water molecules and hydroxyl ions.

Subsequently, other embodiments relate to an apparatus comprising at least one active layer, wherein the encapsulation layer protects at least one active layer from contaminants. The encapsulation layer comprises a bottom layer of inorganic material and a first alternating-layer laminate. The first alternating-layer laminate comprises a hydrophobic first layer deposited on the bottom layer, and an inorganic hydrophilic second layer is deposited on the hydrophobic first layer. The second layer provides an active well holding the water molecules and hydroxyl ions, and at least one additional alternating-layer stack on the first alternating-layer stack.

1 is a cross-sectional view of a linear deposition apparatus according to one embodiment.
2 is a perspective view of a linear deposition apparatus according to one embodiment.
3 is a perspective view of a rotary evaporator according to one embodiment.
4 is a perspective view of reactors in a deposition apparatus, according to one embodiment.
5 is a cross-sectional view of an encapsulating material, according to one embodiment.
6 is a flow chart illustrating an encapsulating material forming process, according to one embodiment.
7 is a block diagram of a display device including an organic light emitting diode that is protected from contaminants by an encapsulating material, according to one embodiment.

Embodiments will now be described with reference to the accompanying drawings. It should be understood, however, that the principles set forth herein may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. In the present specification, detailed description of well-known features and techniques may be omitted so as to avoid unnecessarily obscuring the features of the embodiments.

In the drawings, like reference numerals in the drawings represent like elements. The shape, size and area of the drawings, and the like, may be exaggerated for clarity.

Embodiments relate to forming an encapsulating material that prevents water or oily materials from penetrating into a protected area or device. The encapsulating material herein includes hydrophobic and oleophobic first layers and alternating layers of a second layer that are hydrophilic and hold moisture molecules to prevent moisture molecules from diffusing into the first layer surrounding the second layer do. By alternating the first layer and the second layer (e.g., a hydrophobic layer having a thickness substantially equal to the thickness of a water molecule or a hydroxyl ion), the encapsulating material may have multiple, finite potential wells potential well. Potential wells trap water molecules and oxygen molecules to prevent or reduce the transfer of water and / or oxygen through the encapsulating material.

In one or more embodiments, the first and second layers are formed from the same material. In some instances, the first layer is formed by partially exposing the same material to a fluorine plasma. The remaining material that is not exposed to the fluorine plasma becomes the second layer.

In other embodiments, the second layer may be deposited on the first layer using chemical vapor deposition (CVD), atomic layer deposition (ALD), or molecular layer deposition (MLD) Can be deposited. For example, TriMethylAluminium (TMA) can be used as a source precursor followed by a N ₂ O plasma as a reaction precursor to deposit aluminum oxide as a second layer.

Exemplary deposition apparatus

1 is a cross-sectional view of a linear deposition apparatus 100, according to one embodiment. 2 is a perspective view of a linear deposition apparatus 100 (with the chamber walls removed for clarity) according to one embodiment. Linear deposition apparatus 100 may include support columns 104, process chambers 108 and one or more reactors 136 among other components. Reactors 136 may include one or more injectors and radical reactors to perform MLD, ALD, and / or CVD. The injectors inject a source precursor, a reactant precursor, a purge gas, or a combination thereof into the substrate 120. The spacing between the injector and the substrate 120 may be between 0.5 mm and 1.5 mm.

The process chamber 108 is surrounded by walls and can be maintained in a vacuum to prevent contaminants from affecting the deposition process by providing an inert environment for performing the deposition process. The process chamber 108 includes a susceptor 128 that receives the substrate 120. The susceptor 128 may be located above the support plate 124 for slidable motion. The support plate 124 may include a temperature controller (e.g., a heater or a cooler) for controlling the temperature of the substrate 120. Conventionally, depending on the material deposited on the substrate 120 or the precursor used, the substrate 120 has been heated to a temperature of at least 500 캜 and sometimes above 500 캜. Embodiments, however, allow the temperature of the substrate 120 to be maintained at a low temperature by heating the precursor instead of the substrate 120.

The linear deposition apparatus 100 also includes lift pins (not shown) that facilitate loading the substrate 120 onto the susceptor 128 or lowering the substrate 120 from the susceptor 128 can do.

2 is a perspective view of a linear deposition apparatus 100 (with the chamber walls removed for ease of illustration), the embodiment of which is described above with respect to FIG. In one embodiment, the susceptor 128 is secured to a bracket 210 that moves across an extension bar 138 formed with a screw. The pedestal 210 has corresponding screws formed in the holes that receive the extension bar 138. The extension bar 138 is fixed to the spindle of the motor 114, so that the extension bar 138 rotates as the shaft of the motor 114 rotates. The rotation of the extension bar 138 causes the pedestal 210 (and hence the susceptor 128) to move linearly above the support plate 124. By controlling the speed and direction of rotation of the electric motor 114, the speed and direction of the linear motion of the susceptor 128 can be controlled. The use of the electric motor 114 and the extension bar 138 is merely an example of how the susceptor 128 is moved. There may be various other methods of moving the susceptor 128 (e.g., using a gear and pinion or linear motor at the bottom, top or side of the susceptor 128) . Moreover, instead of movement of the susceptor 128, the susceptor 128 can remain stationary and the reactors 136 can move.

3 is a perspective view of a rotary evaporator 300 according to an embodiment. Instead of using the linear deposition apparatus 100 of FIG. 1, the rotary deposition apparatus 300 may be used to perform the deposition process according to another embodiment. Rotary deposition apparatus 300 may include reactors 320, 334, 364 and 368 among other elements, susceptor 318 and a container 324 surrounding such elements. As described above with reference to FIG. 1, the reactor (for example, 320) of the rotary evaporator 300 corresponds to the reactor 136 of the linear deposition apparatus 100. The susceptor 318 holds the substrate 314 in place. The reactors 320, 334, 364, and 368 may be spaced from the substrate 314 and the susceptor 318 with an interval of 0.5 mm to 1.5 mm. The susceptor 318 or reactors 320, 334, 364, and 368 rotate so that the substrate undergoes other processes.

One or more of the reactors 320, 334, 364, 368 are connected to a gas pipe (not shown) to provide a raw precursor, reaction precursor, purge gas, or other materials. The materials supplied by the gas pipe are either (i) mixed in a chamber inside the reactors 320, 334, 364, 368, or (ii) after being mixed with the plasma generated inside the reactors 320, 334, 364, (Iii) may be injected directly into the substrate 314 by the reactors 320, 334, 364, and 368 after being converted into radicals by the radicals. After the materials are injected into the substrate 314, the excess material may be exhausted through the outlets 330, 338. The inside of the rotary evaporator 300 can also be kept in a vacuum state.

The rotary evaporator 300 may also be equipped with one or more heaters to raise the temperature of the substrate 314.

Although the following exemplary embodiments are mainly described with reference to the reactors in the linear deposition apparatus 100, the same principle and operation can be applied to the rotary evaporation apparatus 300 or other types of evaporation apparatuses.

4 is a perspective view of reactors 136A-136D (collectively referred to as " reactors 136 ") within deposition apparatus 100 of FIG. 1, according to one embodiment. The reactors 136A-136D are positioned adjacent to one another. In another embodiment, the reactors 136A-136D may be located at a distance from each other. The substrate 120 is moved by the reactors 136a through 136d to form a deposition layer on the substrate 120 when the susceptor 128 on which the substrate 120 is mounted moves from left to right or from right to left. Are sequentially injected with materials or radicals. Instead of movement of the substrate 120, the reactors 136A-136D may move from right to left while injecting the precursor materials or radicals onto the substrate 120. [

In one or more embodiments, the reactors 136A, 136B, and 136C are gas injectors that inject precursor material, purge gas, or a combination thereof onto the substrate 120. Each of the injectors 136A, 136B, 136C is connected to pipes 412A, 412B, 416, 420 to receive precursors, purge gas, or combinations thereof from one or more sources. Valves and other pipes may be installed between the pipes 412, 416, 420 and the sources to control the amount of gas and gas provided to the gas injectors 136a, 136b, 136c. The excess precursor and purge gas molecules are exhausted through the exhaust portions 440, 442, 448.

The reactor 136D may be a radical reactor that produces radicals of a gas or gas mixture received from one or more sources. The radicals of the gas or gas mixture function as purge gas, reaction precursor, surface treatment mediator, or a combination thereof on the substrate. Gaseous or gas mixtures are injected into the reactor 136D via a pipe 428 and a voltage is applied across the electrodes (e.g., the electrode 422 and the body of the reactor 136C) Lt; RTI ID = 0.0 > 136D. ≪ / RTI > Electrode 422 is connected to the body of a supply voltage source and reactor 136, a coaxial capacitive-type plasma reactor through line 432, (Not shown) to the supply voltage source. The resulting radicals are injected onto the substrate 120 by moving a distance no greater than 50 millimeters (mm) and the remaining radicals and / or gases returned from the radicals to the inactive state are passed through the exhaust portion 448, (136D). By exposing the substrate 120 to the radicals, the surface of the substrate remains reactive until the next precursor is implanted on the surface of the substrate.

In one example of the foregoing process, the oxygen-containing gas or gas mixture is reacted with oxygen radicals (O *), hydrogen radicals (H *), and / or hydroxyl radicals by a method of exposing an input gas to a high pressure source and thereby forming a plasma Is used to generate the radical ((OH) *). In the example of an oxygen plasma, the lifetime of the oxygen radical is in the range of about 1 millisecond to 10 milliseconds at 1 Torr pressure (compared to the life of the hydroxyl radical is about 200 microseconds) . Under these conditions, the rate of oxygen radicals is approximately 10 meters per second (meters / second), so that an oxygen radical range of about 10 centimeters (cm) is given before it reacts to form a more stable species. In this regard, in order to effectively treat a substrate with an oxygen plasma, the substrate must be placed in this range (which is adjusted as a function of the plasma pressure and / or the velocity of the radicals and / or the lifetime).

Exemplary structure of the encapsulating material

5 is a cross-sectional view of an encapsulating material 500, according to one embodiment. The encapsulating material 500 includes a substrate 522 and a bottom layer 518 on which other layers are deposited or formed. The substrate 522 may be flexible. The bottom layer 518 is deposited on the substrate 522. The first layer 515, in this example, the hydrophobic layer, is formed on the bottom layer 518 by exposing the bottom layer 518 to a precursor or by converting a portion of the bottom layer 518.

In one embodiment, the bottom layer 518 is formed by ALD using trimethylaluminium (TMA) as the source precursor and N ₂ O plasma as the reaction precursor. The thickness of the bottom layer 518 is between 1 angstrom and 500 angstroms. Although not being limited in theory, it is believed that the reaction between the oxygen radicals generated from the TMA and the N ₂ O plasma involves the reaction shown in equation (1).

In this example, injector 136A injects TMA through pipe 412A and injects purge gas (e.g., argon gas) through pipe 412B. Oxygen radicals (O *) can be generated from the N ₂ O plasma and injected by the reactor 136D. In other examples, oxygen radicals may also be generated using O ₂ plasma, O ₃ plasma, (O ₂ + H ₂ ) mixed plasma, and (O ₃ + H ₂ ) mixed plasma. Injectors 136B and 136C are left unused during the deposition of aluminum oxide. The process of implanting TMA, purge gas and oxygen radicals can be repeated until a bottom layer 518 of desired thickness is deposited on the substrate 522.

The first layer 514 can be formed by, for example, converting aluminum oxide (i.e., bottom layer 518) to a C ₂ F ₆ plasma or (C ₂ F ₆ + H ₂ ) plasma by converting aluminum oxide to a layer of Al- And then exposed. This plasma produces fluorine radicals (F *) that are used to add fluorine to the first layer 514. In this intention, the reactor 136D may be provided with a mixture of C ₂ F ₆ gas or C ₂ F ₆ gas and H ₂ gas. The radicals produced in the reactor 136D are injected onto the substrate 522. [

Alternatively, the first layer 514 may be a polymer layer such as a plasma polymer, polyglycidyl methacrylate (PGMA), an epoxy-containing polymer layer, an Al-OF compound, or an Al-OCF polymer. In some instances, these configurations of the first layer 514 are deposited on aluminum oxide using atomic layer deposition. In the examples using PGMA, glycidyl methacrylate is used as a reaction precursor in the performance of atomic layer deposition with N ₂ O remote-plasma. In the examples using Al-OCF polymer (or Al-OF compound), TMA is used as a raw material precursor and nonafluorohexyltrimethoxysilane (C9H13F9O3) is used as a reaction precursor. Injects TMA through pipe 412A and injects purge gas (e.g., argon gas) through pipe 412B. The injector 136B injects nonafluorohexyltrimethoxysilane provided through the pipe 416. [ The first layer 514 is hydrophobic as well as possessive. The thickness of the first layer 514 may be between 1 Angstrom and 100 Angstroms in some instances while maintaining the flexibility of the first layer 514 while preventing defect formation in the first layer 514 during deposition The thickness may be between 2 Angstroms and 10 Angstroms.

A hydrophilic second layer 510 of an inorganic material, such as aluminum oxide (Al ₂ O ₃ ), is deposited on the first layer 514. The second layer 510 may be formed by ALD that does not contain fluorine or contains only low concentrations of fluorine, using trimethylaluminum (TMA) as the source precursor and an N ₂ O plasma as the reaction precursor. In this intention, injector 136A injects TMA through pipe 412A and injects purge gas (e.g., argon gas) through pipe 412B. The oxygen radicals can be generated and injected by the reactor 136D. The reactors 136B and 136C are left unused during the deposition of aluminum oxide.

The aluminum oxide layer is hydrophilic and, therefore, catches or holds any water molecules and hydroxyl radicals that have penetrated the second layer 510. Preferably, the aluminum oxide layer has a thickness of from about 1 to about 5 angstroms that is about the size of one water molecule (more specifically, one water molecule duplex). In order to prevent the formation and growth of defects such as pin-holes larger than the size of water molecules, the thickness of the aluminum oxide layer is not greater than 5 angstroms. To prevent migration of other gas molecules through the encapsulation layer, the aluminum oxide used to form the first layer 514 has a thickness between about 1 angstrom and 8 angstroms. Among other reasons, it is advantageous to minimize the thickness of the film, since the size of defects such as pinholes increases as the film thickness increases, and thus the movement path of water or gas molecules is provided. The aluminum oxide layer may contain a low concentration of fluorine due to residues of fluorine radicals after deposition of the first layer 514.

On the second layer 510, another first layer 514 of polymer or fluorine-added material (e.g., Al-O-F compound or Al-O-C-F polymer) is formed. As shown in FIG. 5, the first layer 514 and the second layer 510 are deposited in an alternating manner on the bottom layer 518. The total number of first and second layers 514, 510 may be from 5 to 10 layers, but more layers may be deposited on the bottom layer 518. By maintaining each of the first and second layers 514 and 510 below a particular thickness, the ductility of the encapsulating material 500 can be maintained. After depositing the first and second layers 514 and 510 another bottom layer 518 is deposited and alternate first and second layers 514 and 510 of another set . The overall thickness of the bottom layer 518, the first layer 514, and the second layer 510 may be between 10 Angstroms and 500 Angstroms. By depositing a very thin aluminum oxide or other hydrophilic inorganic material as the first bottom layer 518 and the second layer 514 in one example, the lamination of these very thin layers with the polymer first layer 510 can be from 2 millimeters Allowing the substrate and / or article to bend to a bending radius of 5 millimeters. This bending radius is possible because very thin layers (i.e., between 1 angstrom and 5 angstroms) can deform aluminum oxide and other inorganic materials without micro-cracks or discrepancies that typically occur during deformation of large materials.

In another embodiment, bottom layer 518 is aluminum oxide formed on substrate 522 by ALD using trimethylaluminum (TMA) as source precursor and N ₂ O plasma as reaction precursor. In this intention, injector 136A injects TMA through pipe 412A and injects purge gas (e.g., argon gas) through pipe 412B. N ₂ O radicals can be generated and injected by reactor 136D. The reactors 136A and 136B are left unused during the deposition of aluminum oxide. The thickness of the bottom layer 518 is between 10 and 50 angstroms. By exposing the bottom layer 518 to a (C ₂ F ₆ + SiH ₄ ) plasma, a layer of Al-Si-OCF polymer or Al-Si-OF compound wherein Si can be replaced with another semiconductor or a semi- Is formed as a first layer 514 on the bottom layer 518. [ In this intention, injector 136A injects TMA through pipe 412A and injects purge gas (e.g., argon gas) through pipe 412B. A mixture of C ₂ F ₆ gas and SiH ₄ gas is provided to reactor 136D to produce radicals where TMA is injected onto the pre-implanted bottom layer.

Alternatively, instead of using TMA as a starting material precursor and tridecafluoro-1,1,2,2-tetrahydrooctylmethylbis (dimethylamino) silane (FOMB) as a reaction precursor, _{(DMA) S, C 8 F} 13 H 4 (CH 3) Si (N (CH 3) 2) by performing the ALD using _2, Al-Si-OCF polymer or Al-Si-oF compound layer is a first layer The injector 136A injects the TMA through the pipe 412A and enters the purge gas (e.g., argon gas) via the pipe 412B, The injector 136B injects tridicafluoro-1,1,2,2-tetrahydrooctylmethylbis (dimethylamino) silane onto the TMA pre-implanted bottom layer 518. The first The thickness of layer 514 is between 2 and 10 angstroms.

As in the previous example, the aluminum oxide layer was deposited as a second layer 510 on the first layer 514 by ALD using trimethyl aluminum (TMA) as the source precursor and N ₂ O plasma as the reaction precursor Lt; / RTI > The aluminum oxide layer is hydrophilic. Preferably, the aluminum oxide layer has a thickness between approximately 1 and 5 angstroms, which is approximately the size of the water molecule. The second layer 510 holds the water molecules and prevents hydroxyl radicals and / or water molecules from passing through the subsequent first layer.

On the second layer 510, another first layer 514 of Al-Si-O-C-F polymer or Al-Si-O-F compound is formed. The first layers 514 and the second layers 510 are deposited on the bottom layer 518 in an alternating manner. The total number of first and second layers 514, 510 may be from 5 to 10 layers, but more layers may be deposited on the bottom layer 518. After depositing the first and second layers 514 and 510, another bottom layer 518 may be deposited and another set of alternating first and second layers 514 and 510 may be followed.

_{(C 2 F 6 + SiH 4} ) can instead _{to, (C 2 F 6 + TiCl} 4) plasma containing titanium can be used for depositing an Al-Ti-OCF polymer as the first layer 514 using a plasma. Further, TiCl ₄ or tetradimethylammono titanium (TDMAT) is used as a raw precursor instead of TMA to form a TiO ₂ layer as a bottom layer 522 or a second layer 510 and a Ti-OCF Layer can be formed. TiF ₄ is formed on the TiO ₂ layer by reacting TiCl ₄ with F ₂ . TiOF ₂ can be formed by reacting TiCl ₄ with O ₂ and F ₂ . By combining and controlling the thickness of the TiO ₂ layer, TiO ₂ F layer and TiF ₄ layer, an antireflection layer can be obtained.

Subsequently, in another embodiment, molecular layer deposition (MLD) may be performed to form an alucone (Al-O- (CH) _x ) layer as the bottom layer 518. Specifically, the alu- minone is injected with TMA, the TMA molecules physically adsorbed on the substrate 522 are removed by argon gas, the substrate 522 is exposed to argon radicals, and the butanediol glycol or glycidyl By injecting glycidol, performing removal by argon gas, and repeating these processes until an alu- minum of the desired thickness is obtained. Alternatively, the aluncon can be made by injecting TMA, removing the TMA molecules physically adsorbed on the substrate 522 by argon gas, injecting butanediol glycol or glycidol, removing with argon gas, , And repeating these processes until an alu- minum of the desired thickness is obtained. The thickness of the aluncon layer used as the bottom layer 518 may be between 10 and 500 angstroms.

The first layer 514 is formed by exposing aluminum oxide to a C ₂ F ₆ plasma or (C ₂ F ₆ + H ₂ ) plasma, for example, by converting aluminum oxide to an Al-OF compound or Al- . Alternatively, the first layer 514 may comprise Al-OF deposited on aluminum oxide by performing atomic layer deposition using TMA as the source precursor and nonafluorohexyltrimethoxysilane (C9H13F9O3) as the reaction precursor Compound or an Al-OCF polymer layer. The first layer 514 is hydrophobic as well as possessive. The thickness of the first layer 514 may be between 2 and 10 angstroms to maintain the ductility of the first layer 514 while preventing defect formation in the first layer 514.

A second layer 510 of alu- minic is deposited on the first layer 514 using the same process as the deposition of the bottomconic layer 518. [ Preferably, the second layer 510 has a thickness between approximately 1 and 5 angstroms, approximately the size of the water molecule. Alucon is relatively hydrophilic compared to F-doped oxide, and for this reason, second layer 510 catches water molecules and prevents water molecules from passing through subsequent first layers. In order to prevent the formation and growth of defects such as pin-holes, the thickness of the alucon is less than 5 angstroms.

On the second layer 510, another first layer 514 of Al-O-F compound or Al-O-C-F polymer is formed. As shown in FIG. 5, the first layer 514 and the second layer 510 are deposited in an alternating manner on the bottom layer 518. The total number of first and second layers 510, 514 may be five to ten layers, but more layers may be deposited on bottom layer 518. After depositing the first and second layers 514 and 510, another bottom layer 518 may be deposited and another set of alternating first and second layers 514 and 510 may be followed.

Although the first and second layers 514 and 510 have been described above as being conveniently identifiable boundaries, these layers do not progressively change from one type of layer to another type of layer without overlapping or delimited boundaries . The deposition or conversion process may progressively increase or decrease the fluorine concentration in the encapsulating material 500 as the layers are deposited. As a result, the fluorine concentration in the encapsulating material 500 may fluctuate as the depth of the encapsulating material 500 increases. During the ALD, CVD, or MLD process, the fluorine-containing compounds may be gradually increased to form the first layers 514 or may be slowly reduced to form the second layers 510. The regions or layers of the encapsulating material 500 having a relatively high fluorine content correspond to the first layers 514 while the encapsulating material 500 having a relatively low fluorine content compared to the first layers 514 ) ≪ / RTI > correspond to the second layers (510). The periodic lamination of repeatedly laminated hydrophilic layers or fluorine-containing layers each having a thickness of approximately water molecule size forms multiple finite potential wells and consequently water molecules. Finite potential wells also exhibit proprietary tendencies according to alternating - layer structures.

6 is a flow chart showing the process of forming an encapsulating material. First, a bottom layer 518 is deposited (602) on the substrate 522 by ALD, CVD, or MLD. The bottom layer 518 is, for example, aluminum oxide, alucone or titanium oxide. Substrate 522 is exposed (606) to materials and / or radicals, and hydrophobic and oleophobic first layer (514) is formed or deposited. The first layer 514 may be a hydrophobic layer such as an Al-OF compound, an Al-Si-OCF polymer, an Al-Si-OF compound, an Al-OCF polymer, an Al- Or a polymer or a material having hydrophobic properties such as an Al-OCH compound or an organic compound containing a metal atom and / or a metal atom such as a Si-OCH compound.

A hydrophilic second layer 510 is formed or deposited 610 on the first layer 514. The second layer 510 may be aluminum oxide, silicon oxide, silicon nitride, zirconium oxide, titanium oxide, or oxynitrides thereof. It is then determined 618 whether a predetermined number of layers or materials of a predetermined thickness have been deposited or formed on the substrate 522. If the number of layers or the thickness of the material has not reached the desired degree, the process returns to the step of forming or depositing the first layer (606) by exposing the substrate 522 to materials or radicals. If the number of layers or the thickness of the material has reached the desired degree, the next process is terminated.

In one embodiment, the process returns to depositing the bottom layer 518 after a predetermined number of first and second layers 514, 510 have been deposited. That is, after it is determined that a predetermined number of layers have been deposited, the process returns to step 602 of depositing the bottom layer and repeats the subsequent processes until an encapsulating material of the desired configuration and thickness is obtained.

Exemplary applications of encapsulating materials

Figure 7 illustrates one application of the encapsulating material described above, in accordance with one embodiment. 7 shows a schematic representation of a display device 700 that includes a processor 704, an organic light emitting diode (" OLED ") device 708, a display interface 712, and an encapsulating material 716 do. Processor 704 generates signals and transmits signals to OLED 708 via display interface 712 to display images on OLED 708. [ The encapsulation material 500 is formed across the OLED 708 and the display interface 712 to prevent moisture or other contaminants from damaging the OLED 708 or components of the display interface 712.

In another example, the encapsulating material 500 may be a flexible photovoltaic solar material (e.g., copper indium gallium di (selenide) or " CIGS "), Dye-sensitized solar cells (" DSSC "). In this application, the encapsulating material 500 prevents oxidation of the electrically active material in the solar material by the environment by preventing water (in the form of atmospheric moisture) or hydroxyl radicals from reacting with the electroactive material.

Although the present invention has been described above with reference to certain embodiments, various modifications may be made within the scope of the invention. Therefore, the contents of the present invention are not intended to be limiting, but are intended to be illustrative.

Claims (23)

Providing a bottom layer of inorganic material;
Forming a hydrophobic first layer of at least one metal or an inorganic compound of at least one of a semi-metallic, oxygen, and fluorine, wherein the hydrophobic first layer is deposited on the bottom layer to form the hydrophobic first layer ; And
Forming a first alternating-layer laminate by forming an inorganic hydrophilic second layer on said first layer, said second layer providing an energetic well holding water molecules and hydroxyl ions, Lt; RTI ID = 0.0 > 1, < / RTI > forming a first alternating-layer laminate.
The method according to claim 1,
Wherein providing the bottom layer comprises:
Depositing a metal-organic precursor layer on the substrate using atomic layer deposition; And
Exposing the metal-organic precursor layer to a radical species derived from the plasma, wherein the plasma converts the surface portion of the metal-organic precursor layer to an inorganic compound of the first layer, ≪ / RTI >
3. The method of claim 2,
Further comprising the step of exposing the inorganic material of the bottom layer to a fluorine containing plasma to form an inorganic layer comprising the inorganic material and the elements of fluorine as the first layer.
3. The method of claim 2,
Further comprising the step of exposing the inorganic material of the bottom layer to a plasma containing fluorine and silane to form an inorganic layer comprising elements of the inorganic material, silicon, carbon and fluorine as the first layer , ≪ / RTI >
3. The method of claim 2,
Further comprising the step of exposing the inorganic material of the bottom layer to a fluorine containing plasma to form an inorganic layer comprising elements of the inorganic material, titanium, carbon and fluorine as the first layer .
The method according to claim 1,
Wherein forming the hydrophobic first layer comprises:
Depositing a polymer, a plasma polymer, or a polymer of aluminum, oxygen, carbon and fluorine on the bottom layer.
The method according to claim 1,
Wherein the hydrophobic first layer is between about 1 angstrom and 100 angstroms thick.
The method according to claim 1,
Wherein forming the hydrophobic first layer comprises:
Exposing the bottom layer to tridecafluoro-1,1,2,2-tetrahydrooctylmethylbis (dimethylamino) silane; And
The deposition of the deposited tridecafluoro-1,1,2,2-tetrahydrooctylmethylbis (dimethylamino) silane to form an Al-Si-OCF polymer as the first layer on the bottom layer (dimethylamino) silane) reacts with trimethylaluminum in the bottom layer.
The method according to claim 1,
The formation of the inorganic hydrophilic second layer may be performed,
Exposing the first layer to a metal-organic precursor, wherein molecules of the metal-organic precursor are adsorbed onto the first layer; And
And exposing the adsorbed metal-organic molecules to radicals of the plasma to convert the adsorbed metal-organic molecules to an inorganic layer.
The method according to claim 1,
Further comprising forming at least one second alternating-layer stack on the first alternating-layer stack,
Wherein the second alternating-layer laminate comprises a second hydrophobic first layer and a second inorganic hydrophilic second layer.
The method according to claim 1,
Wherein providing the bottom layer comprises:
Exposing the substrate to a metal-organic precursor;
Removing the physically adsorbed metal-organic precursor from the substrate by injecting an inert gas onto the substrate;
Exposing the metal-organic molecules remaining on the substrate to radicals generated in the plasma after the removal; And
Providing organic precursors to the metal-organic molecules that remain on the substrate and are exposed to the radicals.
The method according to claim 1,
Wherein the inorganic hydrophilic second layer is between about 1 angstrom and about 5 angstroms thick.
Bottom layer of inorganic material; And
A first alternating-layer stack,
The first alternating-
A hydrophobic first layer; And
And an inorganic hydrophilic second layer deposited on the first layer,
Said second layer providing an energetic well that retains water molecules and hydroxyl ions.
14. The method of claim 13,
, An encapsulating material wherein the bottom layer is _{Al 2 O 3, ZrO 2,} HfO 2, SiO 2, TiO 2 and is selected from the group consisting of a combination thereof.
14. The method of claim 13,
Wherein the hydrophobic first layer is a polymer.
14. The method of claim 13,
Said second layer having a thickness equal to the molecular diameter of the water molecule.
14. The method of claim 13,
Wherein the hydrophobic first layer is an organoaluminum-oxygen-carbon-fluorine compound.
14. The method of claim 13,
Wherein the hydrophobic first layer is an inorganic aluminum-oxygen-fluorine compound.
19. The method of claim 18,
The hydrophobic first layer may comprise,
Exposing the bottom layer to a fluorine-containing plasma to convert the surface of the bottom layer to the inorganic aluminum-oxygen-fluorine compound of the hydrophobic first layer.
14. The method of claim 13,
Wherein the first layer comprises:
Exposing the substrate to glycidyl methacrylate to deposit a layer of glycidylmethacrylate; And
And exposing the deposited glycidyl methacrylate layer to a N ₂ O plasma to convert the deposited layer to poly (glycidyl methacrylate).
14. The method of claim 13,
Further comprising at least one second alternating-layer stack on the first alternating-layer stack.
At least one active layer; And
And an encapsulation layer protecting the at least one active layer from contaminants,
Wherein the encapsulation layer comprises:
Bottom layer of inorganic material; And
A first alternating-layer stack,
The first alternating-
A hydrophobic first layer deposited on the bottom layer; And
And an inorganic hydrophilic second layer deposited on the hydrophobic first layer,
Said second layer providing an energetic well that retains water molecules and hydroxyl ions.
23. The method of claim 22,
Further comprising a second alternating-layer stack deposited on the first alternating-layer stack,
Wherein the second alternating-layer laminate comprises a second hydrophobic first layer and a second inorganic hydrophilic second layer.

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