KR100923197B1 - Two Side Emission White Organic Light Emitting Diodes and their Fabrication Methods - Google Patents

Abstract

The present invention relates to a technique for fabricating a new white organic light emitting device (WOLED), which selectively emits yellow or red dopants in a middle portion of a single blue host and emits light on both sides.

This technique selectively dope one type of dopant capable of energy transfer to a single blue host, thereby reducing the " undoped layer / doped layer / undoped layer "

By constructing a symmetrical two-wavelength light emitting layer in a state, it is characterized in that a two-sided light emitting white OLED having a simple manufacturing process and stable operation characteristics can be manufactured.

Conventional white OLEDs mostly obtain white light mixed downward through a blue / yellow 2-wavelength light emitting structure. In this structure, the emission wavelengths are asymmetrically mixed so that the color of the light exiting in the lower (anode) direction and the light exiting in the upper (cathode) direction are different. In addition, since the upper electrode must use an opaque metal, light cannot penetrate the electrode upward.

In order to develop OLEDs emitting pure white light on both sides, the light emitting layer must be manufactured in a symmetrical structure of blue, yellow, and blue, and a transparent electrode having a small work function is used as a cathode. However, when the blue and yellow host and dopant materials are different in the light emitting layer structure of blue, yellow, and blue, the number of fluorescent materials used to form the light emitting layer increases, and the configuration and process of the deposition system are complicated. In addition, since a transparent electrode material having a low work function that can be easily deposited cannot be found, a double-side emission white OLED has not been developed and reported.

In the present invention, one dopant in one host is " undoped layer / dope

Selective doping in the state of "doped layer / undoped layer" to form a symmetric light emitting layer of blue, yellow, and blue, which makes it possible to manufacture a double-sided light emitting white OLED with a simple manufacturing process and stable operation characteristics at low cost. Is getting.

In addition, the upper electrode is realized in a comb structure using Al metal, thereby enabling double-sided light emission without using a transparent electrode material having a particularly low work function.

The technology claimed in the present invention is a novel device technology for double-sided light-emitting WOLEDs, and it is practically utilized in the development of double-sided lighting and double-sided display by enabling the implementation of pure white high-performance white organic light-emitting device at low cost.

OLED, WOLED, white organic light emitting device, double-sided emission, emission spectrum

Description

Two side emission white organic light emitting diodes and their fabrication methods

The present invention relates to a proposal of white organic light emitting diodes (WOLEDs) having a simple structure and showing double-sided light emission characteristics by using a selective doping technique on a single blue host and a device fabrication technology using the same.

Development reports of white organic light emitting diodes showing double-sided emission characteristics have not been found yet. This is because white light emission is obtained by mixing light of various wavelengths, the structure of the light emitting layer appears asymmetrically, and there is a problem of forming a transparent cathode. This is because it is difficult to obtain pure white double-sided light emission.

As is well known, an organic light emitting diode (OLED) is a display device that electrically excites light emitting organic materials to emit light, and has advantages such as low power driving, self-emission, wide viewing angle, high resolution and natural colors, and fast response speed. Have As OLED is widely used as information display window of cell phone exterior window, PDA, camera, watch, office container, automobile, etc., the related parts material market is growing rapidly, and OLED related parts material market has averaged about 70% annually since 2004. It is growing fast. In particular, White Organic Light Emitting Diodes (WOLEDs) have a broad market with various light sources in addition to display applications, and the development value of new WOLED technology that can innovate manufacturing technology in terms of price and performance is unpredictable. Huge enough to be difficult

Currently commercialized OLED has a multi-layered structure composed of low molecular materials. The OLED emits unique light corresponding to the band gap of the light emitting material by injection and movement of electrons and holes through the multilayer thin film from the electrode to the light emitting layer, and formation and recombination of excitons in the light emitting layer. In particular, WOLED is being used to develop full color displays due to the advantage that color filters can easily make R / G / B pixels without going through a complicated process, and are used for liquid crystal display (LCD). It is also being used as a surface light source of a backlight unit (BLU).

 The light emitting layer of an OLED is usually composed of a host-dopant system and the emission color is determined by the host-dopant combination. In general, the host has a high energy gap and the excitons formed in the host undergo energy transfer to dopants having a lower energy gap. In order to achieve white light emission, two-wavelength or more color mixing should be performed. In order to implement each emission color required for mixing, a host according to each color and a dopant according to each host have been used separately.

In order to realize white light, it is ideal to mix three-wavelength light of blue, green, and red, but it is difficult to balance the three colors and change the characteristics and degradation of R / G / B light emitting materials for long time use. Different levels of color mixing do not remain stable.

Recently, as shown in FIG. 1, a WOLED has been studied to mix two wavelengths of blue and yellow (or red) light. Two-wavelength WOLEDs basically reduce the number of fluorescent materials used in device fabrication, and because the number of emitting colors is small, it is possible to solve the difficulty of color mixing and the effects over time, and the light emitting layer is simpler than the three-wavelength method. It has the advantage of easy manufacturing. However, in the two-wavelength WOLED, when the fluorescent material of the light emitting layer emitting blue and yellow is different from each other, for example, the host-1 and the dopant-1 are used in the blue light emitting layer 11 and the host-2 and the dopant- in the yellow light emitting layer 12. When 2 is used, it does not greatly improve from the problems of the three-wavelength method in the ease of the process, the stability of the operation, and the like.

In addition, when looking at the WOLED of the general two-wave stack structure as shown in FIG. 1, as shown in FIG. 2, the light mixture appears as a vertical asymmetric structure, so that the light 21 coming out in the direction of the lower anode and the light 22 exiting the upper cathode are shown. The spectral distribution and the emission color of are different. This is because the light generation position and the propagation path of the light are different, and thus the light absorption and the light mixing intensity of each material are different. Furthermore, since the upper electrode is covered with an opaque metal, light cannot penetrate the electrode upward.

If high-performance WOLED emitting pure white on both sides can be realized at low cost, the application can be made in the development of double-sided lighting and double-sided display. However, for this purpose, the structure of the light emitting layer should be manufactured in a symmetrical structure of blue, yellow, and blue, and a transparent electrode having a small work function as a cathode should be used. When the number of fluorescent materials used to form the light emitting layer increases, As such, the transparent electrode material having a low work function capable of low temperature deposition has not been found yet.

The present invention constitutes a white light emitting layer using only one host and one dopant material, makes the light mixture appear up and down symmetrically so that the spectrum of light exiting from both sides is the same, and also the light is used even if an opaque metal cathode is used. The present invention provides a double-sided light emitting white organic light emitting diode that is easy to manufacture and stable in operating characteristics by being able to come out in the direction of the cathode.

In order to achieve the above object, the present invention provides a known organic light emitting diode in which an ITO, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a metal electrode are sequentially stacked on a glass. Or to provide a double-sided light emitting white organic light emitting diode in which a red dopant is distributed in a "doped / doped / undoped" state to implement a light emitting layer, or using a blue and yellow dopant in a single blue host to "dope / yellow a blue dopant. The light emitting layer is formed by distributing the dopant / doped blue dopant, or by using blue and red dopants in a single blue host, and distributing it in the “doped blue dopant / red dopant / doped blue dopant” state. It provides a double-sided light emitting white organic light emitting diode by implementing a light emitting layer.

In addition, the aforementioned single host and the dopant may be an organic light emitting polymer material or an organic light emitting low molecular material or an organic light emitting oligomer or a copolymer of an organic light emitting low molecular material or a copolymer of an organic light emitting polymer material or a copolymer of an organic light emitting oligomeric material. It is a blue phosphor or a blue phosphor, and the dopant is a yellow phosphor or a red phosphor or a yellow phosphor or a red phosphor.

In addition, the light emitting layer may be formed by vacuum deposition, spin coating, inkjet printing, or solution casting.

In addition, in order to achieve the above object, in the known organic light emitting diode in which ITO, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a metal electrode are sequentially stacked on a glass, a comb-shaped pattern or a mesh is formed. It provides a double-sided light emitting white organic light emitting diode having a cathode electrode structure for emitting light in the direction of the cathode using a metal electrode of.

Thus, in the present invention, by selectively doping one type of yellow dopant capable of energy transfer to a single blue host, the symmetrical blue, symmetrical state with the yellow dopant-doped layer / doped layer / undoped layer sequentially stacked is provided. By constructing the sulfur 2 wavelength light emitting layer, and constructing the structure of the cathode electrode in the shape of a comb-tooth, it is possible to manufacture a double-sided light-emitting WOLED of a new structure by using a method of drawing light to the open part of the electrode, the proposed structure is a material to be mixed This simplicity improves complex color changes and unstable operating characteristics resulting from mixing, resulting in high color stability and high efficiency. Furthermore, the device of the present invention has a practicality because the structure is simple and the process is simplified to enable mass production at low cost.

Referring to the present invention in more detail with reference to the accompanying drawings as follows.

A representative example of the double-sided light emitting WOLED light emitting layer in the present invention is shown in FIG. 3. In FIG. 3, the white light emitting layers 31, 32, and 33 selectively dope a yellow dopant capable of energy transfer to a single blue host in the state of "undoped layer / doped layer / undoped layer". Is made. Since the structure of the light emitting layer is vertically symmetrical, the mixing of yellow light emitted from the dope region 32 and blue light emitted from the undoped regions 31 and 33 is almost similar in the vertical direction. Therefore, the spectrum and intensity of the light 34 and 35 traveling in both the up and down directions are given in almost the same state.

The light emitting layer of FIG. 3 may be made by vacuum deposition. In the manufacturing process, only the host is first deposited (31), and the dopant is deposited with the host (32). Then, when the appropriate thickness is obtained, the dopant is turned off again and only the host is released. Deposition (33) yields a white light emitting layer in which the host is selectively doped with " undoped / doped " This manufacturing technique minimizes the composition of the luminescent material by using one dopant in one host, and forms a blue, yellow, and blue three-layer light emitting region for white mixing in a vertically symmetric manner without changing the evaporation source. You can make it as simple as forming a layer.

The cathode of the OLED is a metal (Al, etc.) having a low work function is used to smoothly inject electrons into the phosphor. Since the metal electrode is opaque, the light traveling upwards is reflected from the metal surface so that no light is transmitted. In order to solve this problem, the structure of the cathode electrode 41 has a comb-pattern or mesh shape 41 to draw light to the open part of the electrode. A representative structural example using this invention is shown in FIG. 4. In the method of FIG. 4, light loss occurs 43 in the metal covered portion, but by using the proper design of the metal pattern and the light scattering well, most of the light emitted in the direction of the cathode can be extracted.

An example of the structure of a double-sided light-emitting WOLED fabricated using the present invention is shown in FIG. 5. Hereinafter, the structure and operation principle shown in FIG. 5 will be described in detail.

 First, an indium tin oxide (ITO) thin film must be formed on a glass plate through which light is transmitted and emitted to the outside. It is used as an anode electrode, and injects holes at the highest Occupied Molecular Orbital (HOMO) level of the hole injection layer 51 (HIL) formed on the transparent, high conductivity, large work function in the visible region. (50). The hole injection layer 51 serves as a medium layer for efficiently injecting holes from the anode to the hole transport layer 52 (HTL). The holes injected into the hole transport layer 52 are transferred to an emissive layer including a lower blue light emitting layer 53, a middle yellow light emitting layer 54, and an upper blue light emitting layer 55, and block a flow of electrons. Have

On the other hand, electrons to be combined with the holes are supplied from the cathode. The cathode is made of aluminum (Aluminum, Al), high conductivity, and reflects incident light. The electron injection layer 58 (EIL) has a function of an intermediate layer for efficiently injecting electrons from the cathode to the electron transport layer (ETL), and the electrons from the cathode are electrons. The injection layer 58 is injected 59 into the Low Unoccupied Molecular Orbital (LUMO) level of the electron transport layer 57. As a result, the electron transport layer 57 transfers electrons injected from the cathode to the light emitting layer. Accordingly, the light emitting layers 53, 54, and 55 emit light inherent to the fluorescent material by the formation of excitons and recombination 56.

 In the light emitting layers 53, 54 and 55 of FIG. 5, the light emitting layer region emits blue light, which is inherent to the light emitting host when there is no dopant (53, 55), and the energy between the host and the dopant in the doped light emitting layer 54 region. The transition gives off yellow, which is a complementary color. At this time, pure white light emission is obtained when the two-wavelength emission colors of complementary colors are mixed at an appropriate intensity. In some cases, new blue dopants may be added to the regions 53 and 55 to increase the blue light emission efficiency of the blue light emitting layers 53 and 55. In this case, it has a white light emitting layer in which two dopants are used in one host.

 Using the principle shown in Figures 4 and 5 specifically from below Glass / ITO /

6 illustrates a specific example of WOLED in which 2-TNATA / NPB / GDI-602 (Rb) / Alq 3 / LiF / Al is stacked. In the GDI-602 (Rb) light emitting layers 64, 65, and 66 of FIG. 6, rubrene (Rb) dopant, which is a yellow light emitting material, is dope 64 / dope 65 / dope to a GDI-602 fluorescent host. It is selectively distributed in the state (66). GDI-602 itself is usually used as a host material for blue light emission, but yellow light can be emitted when rubrene is doped, so rubene is dope (64) / dope 65 / midop (66) to the GDI-602 phosphor. Selective doping with) allows the fabrication of WOLEDs with a single fluorescent host.

In order to manufacture the WOLED according to the present invention, as shown in the flowchart of FIG. 10, first, an ITO electrode 61 is formed on a glass plate, and the surface of the ITO electrode is appropriately plasma treated. Prior plasma treatment must be carried out before organic deposition, and the plasma process contributes to lowering the hole injection barrier from the anode, decontaminating the surface and improving adhesion between the ITO and the organic film. After the plasma treatment, the organic thin film and the metal are deposited in the in-situ method under high vacuum. The first step of forming the organic material is 2-TNATA 62 as the hole injection layer and NPB 63 as the hole transport layer. Deposit.

Next, in the step of depositing the light emitting layer, first, GDI602 is deposited in a thickness of 50 to 150Å in a dope state (64), and then GDI602 and rubrene are simultaneously deposited at a growth ratio of 50: 3 to have a thickness of 100 to 300Å. GDI602: Rubene (6%) layer 65 is formed, and then again blocked rubrene and only GDI602 is deposited in the undoped state 66 to a thickness in the range of 50-150 kV.

The light emitting layer may be formed by vacuum deposition, spin coating, inkjet printing, or solution casting.

Subsequently, after forming Alq ₃ (67) as an electron transporting layer, the basic process of element manufacture is completed by forming the LiF 68 as an electron injection layer and forming Al (69) as a cathode by covering the comb-shaped metal mask.

The spectrum of the light emitted to the upper and lower parts of the device fabricated by this invention is shown in FIG. 7. As shown in FIG. 7, the spectrum 72 of white light emitting upwards at 10V voltage and the spectrum 71 of white light emitting downwards coincide with central wavelengths such as a wavelength of 440 nm of blue and a wavelength of 560 nm of yellow. Similarly, it can be seen that the characteristics of light emitted to both sides are similar. In the WOLED fabricated according to the present invention, even when the applied voltage is changed, the center wavelength position of the emitted light is constant regardless of the voltage, and the relative intensity ratio of blue and yellow is also constant in the wide operating voltage range (6-12V). appear.

8 illustrates changes in the Commission Internationale de I'Eclairage (CIE) color coordinates according to an applied voltage of 6V to 10V for the light emitted to the bottom of the WOLED manufactured by the present invention. As shown in FIG. 8, the emission color was slightly yellowish white at low applied voltage, but as the voltage was increased, the emission color of the device shifted to the blue direction, and pure white light emission was obtained with the CIE color coordinate of (0.33,0.33) near 10V. . The luminescence properties are the same for the light emitted to the top, and the change in the CIE color coordinates according to the applied voltage to the light emitted to the top is shown in FIG. 9.

In addition, the aforementioned single host and dopant may be an organic light emitting polymer material, an organic light emitting low molecular material, or an organic light emitting oligomeric material, and may be a copolymer of these materials. The host may be a blue phosphor or a phosphor, and the dopant may be a yellow or red phosphor or a phosphor.

1 is an explanatory view showing a white light emitting structure by a conventional blue / yellow two-wavelength light emitting layer.

2 is an explanatory view showing a structure in which light is asymmetrically mixed and emitted from both the upper and lower sides of a conventional blue / yellow 2-wavelength light emitting layer.

FIG. 3 is an explanatory view showing a double-sided white light emitting structure using a blue, yellow, and blue symmetric structure formed by selectively doping one yellow dopant in a dope / dope / undoped state to a single blue host in the present invention.

Figure 4 is an explanatory view showing a comb-tooth-shaped metal electrode structure used for light emission to the cathode in the present invention.

5 is an explanatory diagram showing the formation of excitons by the flow of electrons and holes through the energy band structure and the double-sided light emission process;

6 is an explanatory diagram of a specific embodiment produced by the present invention using the principle of FIG.

7 is a diagram of the emission spectrum emitted to the top and bottom of the double-sided white organic light emitting device manufactured by the present invention.

8 is a change in the CIE color coordinates of the lower emission according to the applied voltage of the double-sided white organic light emitting device manufactured by the present invention.

9 is a CIE color coordinate change diagram of the upper emission according to the applied voltage of the double-sided white organic light emitting device manufactured by the present invention.

10 is a flow diagram illustrating a method of manufacturing a double-sided white organic light emitting device according to the present invention.

* Explanation of symbols for the main parts of the drawings

   11: blue light emitting layer

   12: yellow light emitting layer

   21: Mixing of light in the downward direction in blue / yellow 2-wavelength white light emission

   22: Mixing of light in the upward direction in blue / yellow 2-wave white light emission

   31: Undoped lower blue light emitting layer in the dope / dope / undoped symmetric light emitting structure

   32: doped yellow light emitting layer in the dope / dope / dope symmetric light emitting structure

   33: Undoped top in mid-doped / doped symmetric light emitting structure

       Blue light emitting layer

   34: Mixing light downward in a dope / dope / dope symmetric light emitting structure

   35: Light mixing upwards in a dope / dope / dope symmetric light emitting structure

   41: comb-shaped cathode structure

   42: Emission of light to parts not covered with metal

   43: Reflection of light in areas covered with metal

   50: Injection of holes from the anode (ITO)

   51: hole injection layer

   52: hole transport layer

   53: lower blue light emitting layer

   54: intermediate yellow light emitting layer

   55: top blue light emitting layer

   56: Exciton Formation and Recombination

   57: electron transport layer

   58: electron injection layer

   59: Injection of electrons from the cathode to the electron transport layer through the electron injection layer

   61: ITO as anode

   62: 2-TNATA as a hole injection layer

   63: NPB as a hole transport layer

   64: Undoped GDI-602 as a lower blue light emitting layer.

   65: GDI-602 doped with rubrene as a medium yellow light emitting layer 6%

   66: undoped GDI-602 as top blue light emitting layer

   67: Alq3 as the electron transport layer

   68: LiF as an electron injection layer

   69: Al as cathode

   71: spectrum of white light emitting downwards at a voltage of 10 V

   72: spectrum of white light emitting upwards at a voltage of 10 V

Claims (25)

In a known organic light emitting diode in which an ITO, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a metal electrode are sequentially stacked on glass, Yellow dopant is distributed in a "blue light" state in a single blue host to form a light emitting layer, A double-sided light emitting white organic light emitting diode, characterized in that it has an electrode structure for emitting light toward the cathode using a metal electrode having a transmission hole. In a known organic light emitting diode in which an ITO, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a metal electrode are sequentially stacked on glass, The red dopant is distributed in a "mid-doped / doped-doped" state on a single blue host to realize a light emitting layer, A double-sided light emitting white organic light emitting diode, characterized in that it has an electrode structure for emitting light toward the cathode using a metal electrode having a transmission hole. In a known organic light emitting diode in which an ITO, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a metal electrode are sequentially stacked on glass, A light emitting layer is implemented by distributing blue and yellow dopants in a single blue host in a "dope of a blue dopant / dope of a yellow dopant / dope of a blue dopant". A double-sided light emitting white organic light emitting diode, characterized in that it has an electrode structure for emitting light toward the cathode using a metal electrode having a transmission hole. In a known organic light emitting diode in which an ITO, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a metal electrode are sequentially stacked on glass, A light emitting layer is implemented by distributing blue and red dopants in a single blue host in a "dope of blue dopant / dope of red dopant / dope of blue dopant" state, A double-sided light emitting white organic light emitting diode, characterized in that it has an electrode structure for emitting light toward the cathode using a metal electrode having a transmission hole. The method according to any one of claims 1 to 4, A double-sided white organic light emitting diode, wherein the single host and the dopant are organic light emitting low molecular weight materials. The method according to any one of claims 1 to 4, A double-sided light emitting white organic light emitting diode, wherein the single host and the dopant are organic light emitting polymers. The method according to any one of claims 1 to 4, A double-sided white organic light emitting diode, wherein the single host and the dopant are organic light emitting oligomers. The method according to any one of claims 1 to 4, A double-sided white organic light emitting diode, wherein the single host and the dopant are copolymers of organic light emitting low molecular weight materials. The method according to any one of claims 1 to 4, A double-sided light emitting white organic light emitting diode, wherein the single host and the dopant are a copolymer of an organic light emitting polymer material. The method according to any one of claims 1 to 4, A double-sided white organic light emitting diode, wherein the single host and the dopant are a copolymer of an organic light emitting oligomeric material. The method according to any one of claims 1 to 4, A double-sided white organic light emitting diode, wherein the host is a blue phosphor. The method according to any one of claims 1 to 4, A double-sided light emitting white organic light emitting diode, wherein the host is a blue phosphor. The method according to any one of claims 1 to 4, A double-sided white organic light emitting diode, wherein the dopant is a yellow phosphor. The method according to any one of claims 1 to 4, A double-sided white organic light emitting diode, wherein the dopant is a red phosphor. The method according to any one of claims 1 to 4, A double-sided white organic light emitting diode, wherein the dopant is a yellow phosphor. The method according to any one of claims 1 to 4, A double-sided white organic light emitting diode, wherein the dopant is a red phosphor. The method according to any one of claims 1 to 4, A double-sided light emitting white organic light emitting diode, characterized in that the light emitting layer is formed by a vacuum deposition method. The method according to any one of claims 1 to 4, A double-sided light emitting white organic light emitting diode, characterized in that the light emitting layer is formed by spin coating. The method according to any one of claims 1 to 4, A double-sided light emitting white organic light emitting diode, wherein the light emitting layer is formed by an inkjet printing method. The method according to any one of claims 1 to 4, A double-sided light emitting white organic light emitting diode, characterized in that the light emitting layer is formed by a solution casting method. The method according to any one of claims 1 to 4, The above-mentioned transmission hole is a double-sided light emitting white organic light emitting diode, characterized in that the shape of the comb. The method according to any one of claims 1 to 4, The above-mentioned transmission hole is a double-sided light emitting white organic light emitting diode, characterized in that the net shape. The method according to any one of claims 1 to 4, The above-described electrode structure is a double-sided light emitting white organic light emitting diode, characterized in that using the cathode electrode structure. In the known method of manufacturing an organic light emitting diode, the ITO electrode is formed on a glass plate, the surface of the electrode is plasma treated, and an organic thin film and a metal are deposited. In the organic thin film deposition process, a hole injection layer and a hole transporting layer are deposited, and a lower wavelength blue light emitting layer, a middle light emitting layer made of any one of a yellow light emitting layer or a red light emitting layer, and a top of the two wavelength symmetric light emitting layer symmetrically stacked with a blue light emitting layer are vacuum deposited and spinned. It is deposited by any one of coating method, inkjet printing method, and solution casting method, and forms an electron transporting layer, and forms an electron injection layer and LiF / Al as a cathode by covering a comb-patterned or grating-shaped metal mask. A method for producing a double-sided light emitting white organic light emitting diode. The method of claim 24, In the step of depositing the two-wavelength symmetric light emitting layer described above, the first blue light emitting layer is deposited to a thickness in a range of 50 to 150 microns, and then either one of the following yellow or red light emitting layers is formed to a thickness in a range of 100 to 300 microns, and the last blue light emitting layer is 50 to A method for producing a double-sided light emitting white organic light emitting diode, characterized in that the deposition in the 150 Å thickness range.

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