The present application claims priority from Japanese Patent Application No. 2011-081553 filed on Apr. 1, 2011, the content of which is hereby incorporated by reference to this application.
The present invention relates to an optical semiconductor device and a manufacturing method thereof, and in particular, to an encapsulating film of an overall organic EL element and a manufacturing method thereof.
An organic electroluminescence (hereinafter, organic EL) element has many merits such as low power consumption, self-luminescence, and high-speed response, and the development of the organic EL has been pursued for the application to a flat panel display (FPD) or lighting equipment. Further, a bendable display device can be achieved by using a flexible substrate such as a resin substrate (including a resin film), and new added values such as lightness in weight and unbreakability are created, and the application to flexible equipment has also been considered.
Since the organic EL element reduces its luminous efficiency and life when it contacts moisture or oxygen, it is necessary to form an encapsulating film in an environmental atmosphere where moisture and oxygen are eliminated from the manufacturing process. On the other hand, in a flexible substrate such as the resin substrate, a dimension change associated with the absorption of moisture needs to be suppressed, and for this reason, the encapsulating film is formed on the front and back of the resin substrate.
The encapsulating film of the organic EL is required not only to prevent diffusion of moisture and oxygen, but also to have (1) low-temperature film formation (to prevent deterioration of organic EL), (2) low-damage (to prevent deterioration of organic EL), (3) low-stress, low-Young's modulus (to prevent peeling), (4) high transmittance (to prevent deterioration of brightness), and the like. A thin film laminating method has been drawing attention as an encapsulating method. In the thin film laminating method, five to ten layers of a plurality of thin films different in purposes are formed. In general, a thin film with high film density is used as the encapsulating film in order to suppress diffusion of moisture or oxygen and the like. Specifically, a silicon nitride film and an alumina film are the representative films thereof. Since these films are hard (high in Young's modulus) and also high in film stress, there is a problem that the film is peeled off and a crack occurs if a thick film is used. For this reason, the laminated structure with a thin film (buffer film) to reduce the stress of the encapsulating film has been studied. Characteristics required for the buffer film are excellent flattening performance for an underlying material, superior embedding performance to suppress influences of foreign matters adhered on the surface, softness of the film (small in Young' modulus), and small film stress.
Meanwhile, as the manufacturing method of the encapsulating film, various types of film formation methods are proposed such as a plasma CVD (Chemical Vapor Deposition) method, an optical CVD method, a sputtering method and an evaporation method. The representative methods thereof include an optical CVD method using a vacuum ultraviolet light, in which an encapsulating film and a buffer film are continuously formed by using the same technique. Patent Document 1 (Japanese Unexamined Patent Application Publication No. 2005-63850) discloses a manufacturing method of an encapsulating film using the optical CVD method.
Patent Document 1 discloses a top emission type organic EL display panel, in which an encapsulating film including a vacuum ultraviolet light CVD film is formed on a substrate having an anode electrode, an organic EL layer, and a cathode electrode, a transparent electrode is provided on an emission layer (organic EL layer) formed on the substrate, and a light is extracted above the emission layer. Patent Document 1 is characterized in that the vacuum ultraviolet light CVD film includes a silicon oxide film, a silicon nitride film or a laminated film thereof, and a method of forming the encapsulating film directly on the cathode electrode is described therein.
Here, as a source gas which forms a silicon oxide film, the gas containing methyl group, ethyl group, silicon (Si), oxygen (O) and hydrogen (H) is used. For example, TEOS (Tetra ethoxy silane), HMDSO (Hexa methyl disiloxane), TMCTS (Tetra methyl cyclotetrasiloxane) or OMCTS (Octo methyl cyclotetrasiloxane) and the like are used. Further, as a source gas which forms a silicon nitride film, the gas containing methyl group, silicon (Si), nitrogen (N) and hydrogen (H) is used. For example, BTBAS (Bis(tertiary butyl amino)silane) is used.
The organic EL display panel described in Patent Document 1 uses a laminated structure of a silicon oxide film and a silicon nitride film as an encapsulating film. However, since the silicon oxide film and the silicon nitride film are greatly different from each other in terms of refractive index, the laminated film thereof has a problem that a reflection of visible light occurring at the interface between these films constituting the laminated film is large. More specifically, when the encapsulating film composed of a silicon oxide film and a silicon nitride film is adopted for the top emission type organic EL display panel, since an extraction efficiency of the visible light emitted on the organic EL layer is small, there arises a problem that the brightness (light extraction efficiency) of the display is small.
Here,
The lowermost layers of the laminated structures shown in
The laminated structure of
The thicknesses of the silicon nitride films 302b to 304b and 402b to 405b are all 100 nm, the thicknesses of the silicon oxide films 302a and 402a of the lowermost layers are 1000 nm, and the thicknesses of the other silicon oxide films 303a to 305a, 403a and 404a are 500 nm.
In the laminated structure shown in
As is evident from
Further, from a viewpoint of moisture barrier property, that is, an ability of preventing the intrusion of moisture, generally, an inorganic film with a high film density has higher moisture barrier property. In Patent Document 1, at the time of forming the encapsulating film, particularly, the silicon nitride film, an organic silicon source is adopted. In the optical CVD using the organic silicon source, however, since the organic film containing a large amount of carbon (C) is formed, the deposited silicon nitride film has small film density. Hence, from a viewpoint of forming a moisture barrier film (barrier film), it is advantageous in terms of the reliability of the device to use the inorganic barrier film containing no carbon in the film rather than the barrier film containing carbon in the film.
Further, another big problem caused when forming an encapsulating film on the organic EL by using the optical CVD method using a vacuum ultraviolet light is the damage incurred on the organic EL by the vacuum ultraviolet light with a large photon energy. Although not shown in
The cathode electrode is required to have a transmittance of 80% or more with respect to a visible light (400 nm to 700 nm). In a top emission type OLED (Organic Light Emitting Diode) display, an extremely thin metal film, for example, an alloy such as Al—Li or Ag—Mg is generally used. Although it is possible to suppress the vacuum ultraviolet light transmitting through the cathode electrode by increasing the thickness of the cathode electrode, when the cathode electrode is made thick, there arises a problem that a transmittance of visible light is significantly lowered.
Although descriptions have been made with taking the top emission type OLED display in which the light is extracted from the cathode electrode side as an example, the same problem arises also in the structure in which the cathode electrode and the anode electrode are reversely arranged and the light emission is performed from an indium oxide such as ITO (Indium Tin Oxide) based anode electrode and a zinc oxide such as AZO (Aluminum doped Zinc Oxide) based anode electrode. Consequently, to perform the thin-film encapsulation by the optical CVD method using the vacuum ultraviolet light, a technology capable of increasing a transmittance of visible light without giving any optical damage to the organic EL is necessary.
An object of the present invention is to reduce a reflectance of the encapsulating film of the optical semiconductor device and improve light extraction efficiency.
Further, another object of the present invention is to significantly suppress the optical damage to the organic EL by the optical CVD method at the time of forming the encapsulating film of the optical semiconductor device.
The above and other objects and novel characteristics of the present invention will be apparent from the description of the present specification and the accompanying drawings.
The following is a brief description of an outline of the typical invention disclosed in the present application.
An optical semiconductor device according to an invention of the present application is an optical semiconductor device having a first electrode, an organic emission layer, and a second electrode formed on a substrate in this order from a main surface side of the substrate, and an encapsulating film provided on the substrate so as to cover the emission layer, the encapsulating film includes a laminated film obtained by alternately laminating a flattening film and a barrier film, and the flattening film and the barrier film include a silicon oxynitride film.
Also, a manufacturing method of an optical semiconductor device according to an invention of the present application includes the steps of: (a) forming a first electrode on a substrate; (b) forming an organic emission layer electrically connected to the first electrode on the first electrode; (c) forming a second electrode electrically connected to the organic emission layer on the organic emission layer; and (d) forming a silicon oxynitride film on the organic emission layer by an optical CVD method using a vacuum ultraviolet light, and in the step (d), radical irradiation by remote plasma is performed during irradiation of the vacuum ultraviolet light.
The effects obtained by typical embodiments of the invention disclosed in the present application will be briefly described below.
According to the present invention, the light extraction efficiency of the optical semiconductor device can be improved.
Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. Note that components having the same function are denoted by the same reference symbols throughout the drawings for describing the embodiments, and the repetitive description thereof will be omitted. In addition, the description of the same or similar portions is not repeated in principle unless particularly required in the following embodiments.
An embodiment of the present invention will be described below with reference to the drawings.
The bank part 104 mentioned here is an insulating film formed in the shape of a bank, has a bottom surface and an upper surface in parallel to each other, and is a trapezoidal film provided with side walls having a slant tapered angle with respect to the bottom surface and the upper surface.
An organic EL layer 105 is formed on the anode electrode 103 and the bank part 104. The organic EL layer 105 contacts the upper surface of the anode electrode 103 at the bottom of the opening, and is formed so as to cover the upper surface of the anode electrode 103 exposed from the opening, inner walls having the tapered angles of the opening, and a part of the upper surface of the bank part 104. The organic EL layer 105 is an emission layer made up of the laminated film composed of a hole injection layer, a hole transport layer, an emission layer, an electron transport layer, and an electron injection layer which are laminated from the anode electrode 103 side, and the laminated films will be collectively described as the organic EL layer 105 here.
On the organic EL layer 105 and the bank part 104, a cathode electrode 106 and a vacuum ultraviolet light absorption layer 107 are sequentially formed in this order from the glass substrate 101 side so as to cover the organic EL layer 105. The cathode electrode 106 is a conductive layer made of an Ag—Mg alloy having a thickness of about 20 nm. The vacuum ultraviolet light absorption layer 107 is formed so as to cover the cathode electrode 106, and further, is formed so as to overlap with the organic EL layer 105 in a plan view. More specifically, the vacuum ultraviolet light absorption layer 107 is formed right above the organic EL layer 105. Also, the vacuum ultraviolet light absorption layer 107 is formed of a silicon oxynitride film, and has a thickness of about 150 nm.
On the vacuum ultraviolet light absorption layer 107, a buffer film 108, a barrier film 109, a buffer film 110, a barrier film 111, and a buffer film 112 are formed in this order from the glass substrate 101 side. The buffer films 108, 110, and 112, and the barrier films 109 and 111 make up the encapsulating film, and the barrier film mainly functions as a barrier film for moisture. As shown in
The buffer films 108, 110, and 112 have a function of flattening each upper surface and lower surface of a plurality of films which make up the encapsulating film. This is because the buffer films 108, 110, and 112 show a fluidity in the manufacturing process, and even if unevenness is formed on the ground of the buffer film 108 by the opening of the bank part 104, the upper surface of the buffer film 108 has a flat shape. In other words, even if the bottom surface of the buffer film 108 formed at the lowermost layer in the encapsulating film has unevenness, its upper surface is flattened. Further, the buffer films 108, 110, and 112 having lower Young's modulus than the barrier films 109 and 111 are flattening films which have a function of reducing the Young's modulus of the entire encapsulating film and preventing the occurrence of the peeling of the encapsulating film or the occurrence of the cracks of the encapsulating film.
Although not shown in
Although any of the buffer films 108, 110, and 112 and the barrier films 109 and 111 which make up the organic EL element of the present embodiment is formed of a silicon oxynitride film, the organic EL element in which the buffer films 108, 110, and 112 and the barrier films 109 and 111 shown in
The main characteristic of the optical semiconductor device of the present embodiment lies in that the buffer films 108, 110, and 112 contain an inorganic silicon oxynitride film formed by the optical CVD method using vacuum ultraviolet light. The effect of the optical semiconductor device of the present embodiment will be described below.
In the top emission type organic EL element which emits light through the cathode electrode and the encapsulating film on the upper part of the organic EL layer serving as the emission layer, it is considered that the encapsulating film formed on the organic EL layer has a laminated structure. The encapsulating film is required to have a barrier property to prevent moisture and the like from entering the element from the outside of the element. Further, the interface between each of the films constituting the laminated structure of the encapsulating film needs to have a high flatness in order to efficiently extract the light emitted from the organic EL layer. The bank part having the opening in which the upper surface of the organic EL layer is exposed is formed between the anode electrode having the organic EL layer thereon and the encapsulating film, and a large unevenness is formed on the upper surface of the bank part due to the opening. Further, the unevenness is sometimes formed on the bank part due to etching residue and the like. For this reason, it is important that the encapsulating film secures a barrier property of moisture and has a property to improve the flatness of the interface between the films which make up the laminated structure of the encapsulating film at the time of covering to fill the unevenness described above.
Therefore, it is considered that the encapsulating film has a structure in which the silicon nitride film which has good moisture barrier property and the silicon oxide film which is excellent in fluidity in its formation and is easily formed to have a flat upper surface after its formation are laminated. However, in the optical semiconductor device having the encapsulating film formed by laminating the silicon nitride film and the silicon oxide film in this manner, there arises a problem that the brightness of the organic EL element is reduced due to multiple reflection inside the encapsulating film.
The multiple reflection of the visible light emitted from the organic EL layer can be suppressed by reducing as much as possible the refractive index difference between a material of the layer on an incident side (cathode electrode) and the encapsulating film in contact with it, the refractive index difference between a material of the layer on an exit side (adhesion layer) and the encapsulating film in contact with it, and the refractive index difference between the laminated films in the encapsulating film. The incident side and the exit side mentioned here mean that a light emitted upward from the organic EL layer below the cathode electrode enters from the cathode electrode side (incident side) and is emitted to the adhesion layer side (exit side).
Here,
More specifically, since the buffer film has lower Young's modulus than that of the barrier film and has the fluidity during the manufacturing process, even if the ground of the region where the buffer film is formed has unevenness, the buffer film is formed so as to fill the unevenness, and the upper surface of the formed buffer film becomes flat.
The graphs of
For example, as means for setting the refractive indexes of the silicon oxide films constituting the encapsulating film to about 1.7, a method of having nitrogen contained in a silicon oxide film to form a silicon oxynitride film (SiON film) is generally used. However, in the optical CVD method using an organic source containing a large amount of carbon as a source gas, it is difficult to obtain a thin film with a high film density, that is, a moisture barrier film (barrier film) with a high barrier property for moisture. For this reason, it is desirable to use an inorganic film for the moisture barrier film of the laminated encapsulating film in view of the reliability.
Furthermore, when a silicon oxynitride film is formed by the optical CVD method using the vacuum ultraviolet light, a method of making an organic silicon based gas react with a gas serving as an oxidation source or a nitridation source is also available. However, since an ammonium gas (NH3) or a nitrogen gas (N2) serving as a source gas of nitrogen atom (N) and the like have small quenching cross-section area, a degradation efficiency by optical assist is small and it is extremely difficult to obtain the silicon oxynitride film having a desired composition. In other words, when the silicon oxynitride film is formed by the optical CVD method using the vacuum ultraviolet light, there is a problem that a desired amount of nitrogen is not introduced into the formed silicon oxynitride film, and it is difficult to bring the refractive index close to 1.7. Hence, in the present embodiment, in order to obtain excellent moisture barrier property while making use of an advantage of an optical CVD film such as lower stress and lower Young's modulus than a thermal CVD film or a plasma CVD film, the silicon oxynitride film (buffer film and barrier film) is formed by a remote plasma assist. The plasma assist means a film formation method in which a material is pre-degraded by plasma and supplied in a radical state, thereby depositing a film. In the present embodiment, the silicon oxynitride film is formed by using the optical CVD method using the source gas and the plasma assist in combination. Further, the surface to be treated (substrate) is disposed at a position apart from a plasma region (plasma zone) in order to separately use radicals, and this is referred to as remote plasma. Further, the pre-degradation of the material by plasma and the supply of the material in a radical state are referred to as radical irradiation here.
Specifically, in the formation of the buffer film, an organic silicon source containing carbon is used for the source gas of the optical CVD, and a nitrogen radical or a nitrogen radical and an oxygen radical formed by the remote plasma is introduced as a nitridation source. By this means, a SiON (silicon oxynitride) film utilizing the merit of the optical CVD film can be formed. On the other hand, in the formation of the SiON film having high barrier property, an inorganic silicon source not containing carbon such as high order silane is used as the source gas of the optical CVD, and the nitrogen radical or the nitrogen radical and the oxygen radical formed by the remote plasma is introduced as the nitridation source. By this means, an inorganic SiON film having high moisture barrier property can be formed. More specifically, the buffer films 108, 110, and 112 shown in
The buffer films 108, 110, and 112 and the barrier films 109 and 111 are made of the silicon oxynitride films formed by using the optical CVD method using the vacuum ultraviolet light and the plasma CVD method using the remote plasma in combination. The method of forming the silicon oxynitride film by the optical CVD method using the remote plasma assist will be described later in details. The quenching cross-section area means a scale showing the ease of light absorption of a substance, and the substance having larger quenching cross-section area absorbs light more easily and is easily degraded in the optical CVD method.
In the optical semiconductor device of the present embodiment, when the laminated encapsulating film including the buffer film which has small film stress and small Young' modulus and is excellent in filling property and the barrier film having high moisture barrier property is formed, the refractive index difference between the buffer film and the barrier film is reduced as much as possible, and multiple reflection inside the laminated encapsulating film can be suppressed. Further, by reducing the refractive index difference between the films constituting the laminated encapsulating film, a light extraction efficiency of the optical semiconductor device can be significantly improved.
However, in the case where the encapsulating film is formed by the optical CVD method on the organic EL layer via the cathode electrode, there is a problem that the vacuum ultraviolet light irradiated when forming the encapsulating film transmits through the cathode electrode and reaches the organic EL layer to damage the organic EL layer, and the organic EL layer scarcely emits light. Photon energy of the vacuum ultraviolet light used in the film formation process of the optical CVD method is about 7 eV or more, and even if it slightly transmits through the cathode electrode, it gives a great damage to the organic EL layer.
The cathode electrode is required to have a transmittance of 80% or more for the visible light (400 nm to 700 nm). In the top emission type OLED display, it is considered that an extremely thin metal film, for example, such as an Al—Li alloy and an Ag—Mg alloy is used. As a method of suppressing the vacuum ultraviolet light that transmits through the cathode electrode, a method of increasing the thickness of the cathode electrode is considered. However, when the cathode electrode is made thicker, since a transmittance of visible light is significantly reduced, the brightness of the completed organic EL element is lowered.
For this reason, in the optical semiconductor device of the present embodiment, as shown in
As described above, in the present embodiment, in order to suppress the optical damage to the organic EL layer in the film formation process of the optical CVD film, the absorption layer of the vacuum ultraviolet light is formed on the organic EL layer by using the plasma CVD method before performing the optical CVD. By the light absorption layer thus formed, the optical damage to the organic EL layer by the vacuum ultraviolet light when forming the laminated encapsulating film can be significantly suppressed.
The details of the present embodiment will be described below with reference to
Next, as shown in
Thereafter, the organic EL layer 105 electrically connected to the anode electrode 103 is formed on the bottom of the opening of the bank part 104 by using a mask vapor deposition method. The organic EL layer 105 is made up of a hole injection layer, a hole transport layer, an emission layer, an electron transport layer, and an electron injection layer which are sequentially formed in this order from the anode electrode 103 side, and the laminated films will be collectively described as the organic EL layer 105 here. In the present embodiment, though a fluorescent low-molecular material is used for the organic EL layer 105, since the present invention is not an invention related to the organic EL layer, the detailed description of the material of the organic EL layer 105 will be omitted here.
Next, as shown in
Next, by forming an encapsulating film having a laminated structure on the vacuum ultraviolet light absorption layer 107 by using a film formation device shown in
Although the vacuum ultraviolet light absorption layer 107 is formed as a ground on which the buffer film 108 is formed, the surface of the ground has an uneven shape due to the opening of the bank part 104. Since the encapsulating film becomes a path of the light emitted from an organic EL element, diffusion and reflection of the light inside the encapsulating film need to be suppressed, and the encapsulating film is desired to have a flat upper surface parallel to the main surface of the glass substrate 101. Here, when the uneven shape of the ground is filled by forming the buffer film 108 showing the fluidity in its formation, the upper surface of the buffer film 108 can have a flat shape, and therefore, the upper surface and bottom surface of the buffer film and the barrier film formed thereon can be formed to have a flat shape parallel to the main surface of the glass substrate 101.
In addition to the uneven shape due to the opening, foreign matters such as etching residues or dusts formed on the glass substrate 101 before forming the buffer film 108 can be embedded by the buffer film 108. Therefore, it is possible to prevent a decrease of the brightness of the organic EL element due to the deformation of the interfaces between the films constituting the encapsulating film caused by the unevenness formed on the ground of the buffer film 108.
Furthermore, when the barrier film having lower embedding property than the buffer film is directly formed on the ground on which such foreign matters exist, it is considered that gaps where no barrier film is formed are generated on the ground surface directly below the foreign matters and on the side surfaces of the foreign matters. Since the barrier film is a moisture barrier film for preventing the intrusion of moisture, if gaps where the barrier film is not formed are partially generated, a tolerance of the organic EL element for the moisture is reduced, and the reliability of the optical semiconductor device is lowered. In contrast to this, when the buffer film 108 having the fluidity is formed before the barrier film 109 is formed as described above, the buffer film 108 can be formed so as to wrap up the foreign matters even when the foreign matters are formed on the surface of the ground. Therefore, it is possible to prevent the deterioration of the moisture barrier property of the organic EL element due to the gaps generated in the barrier film 109 formed on the buffer film 108.
Here,
Here, as a combination of the film configurations of the buffer film and the barrier film constituting the encapsulating film, combinations of the film configurations A to D in the table of
The film configuration A shown in
Further, the film configuration B shown in
Further, in both the film configuration C and the film configuration D shown in
A manufacturing method in the case where the four film configurations A to D shown in
Each sample (substrate 502) on which the vacuum ultraviolet light absorption layer 107 has been formed through the process described with reference to
In the film configuration A, OMCTS is introduced from the gas inlets 506a and an Xe2 lamp is irradiated from the vacuum ultraviolet light lamp unit 504, thereby forming the buffer film 108 composed of the silicon oxide film on the substrate 502. Subsequently, BTBAS is introduced from the gas inlet 506b and the Xe2 lamp is irradiated from the vacuum ultraviolet light lamp unit 504, thereby forming a barrier film 109 composed of the silicon nitride film on the substrate 502. In the same manner, a buffer film (silicon oxide film) 110, a barrier film (silicon nitride film) 111, and a buffer film (silicon oxide film) 112 are sequentially formed on the substrate 502 in this order.
In the film configuration B, OMCTS is introduced from the gas inlet 506a and the Xe2 lamp is irradiated from the vacuum ultraviolet light lamp unit 504, thereby forming the buffer film 108 composed of the silicon oxide film on the substrate 502. Subsequently, Si2H6 is introduced from the gas inlet 506b, N* is introduced from the remote plasma inlet 505a, O* is introduced from the remote plasma inlet 505b, and the Xe2 lamp is irradiated from the vacuum ultraviolet light lamp unit 504, thereby forming the barrier film 109 composed of the silicon oxynitride film on the substrate 502. In the same manner, the buffer film (silicon oxide film) 110, the barrier film (silicon oxynitride film) 111, and the buffer film (silicon oxide film) 112 are sequentially formed on the substrate 502 in this order.
In the film configuration C, OMCTS is introduced from the gas inlet 506a, N* is introduced from the remote plasma inlet 505a, and the Xe2 lamp is irradiated from the vacuum ultraviolet light lamp unit 504, thereby forming the buffer film 108 composed of the silicon oxynitride film on the substrate 502. Subsequently, Si2H6 is introduced from the gas inlet 506b, N* is introduced from the remote plasma inlet 505a, O* is introduced from the remote plasma inlet 505b, and the Xe2 lamp is irradiated from the vacuum ultraviolet light lamp unit 504, thereby forming the barrier film 109 composed of the silicon oxynitride film on the substrate 502. In the same manner, the buffer film (silicon oxynitride film) 110, the barrier film (silicon oxynitride film) 111, and the buffer film (silicon oxynitride film) 112 are sequentially formed on the substrate 502 in this order. When the buffer films 108, 110, and 112 are formed, O* may be introduced from the remote plasma inlet 505b together with the introduction of N* from the remote plasma inlet 505a.
In the film configuration D, BTBAS is introduced from the gas inlet 506a, O* is introduced from the remote plasma inlet 505b, and the Xe2 lamp is irradiated from the vacuum ultraviolet light lamp unit 504, thereby forming the buffer film 108 composed of the silicon oxynitride film on the substrate 502. Subsequently, Si2H6 is introduced from the gas inlet 506b, N* is introduced from the remote plasma inlet 505a, O* is introduced from the remote plasma inlet 505b, and the Xe2 lamp is irradiated from the vacuum ultraviolet light lamp unit 504, thereby forming the barrier film 109 composed of the silicon oxynitride film on the substrate 502. In the same manner, the buffer film (silicon oxynitride film) 110, the barrier film (silicon oxynitride film) 111, and the buffer film (silicon oxynitride film) 112 are sequentially formed on the substrate 502 in this order. When the buffer films 108, 110, and 112 are formed, O* may be introduced from the remote plasma inlet 505b together with the introduction of N* from the remote plasma inlet 505a.
The refractive index of each layer formed by the above-described method with respect to the light with the wavelength of 632.8 nm is as follows. The refractive indexes of the buffer films (silicon oxide films) of the film configurations A and B are 1.44, and the refractive index of the barrier film (silicon nitride film) of the film configuration A is 1.92. On the other hand, the refractive indexes of the buffer films (silicon oxynitride films) of the film configurations C and D are 1.65, and the refractive indexes of the barrier films (silicon oxynitride films) of the film configurations B, C, and D are 1.7.
From the above-described results, in the optical semiconductor device of the present embodiment, the film configuration C or D is adopted for the configuration of the buffer film and the barrier film shown in
The composition and the refractive index (absorption coefficient) of the silicon oxynitride film in the present embodiment can be adjusted by a flow ratio of the silicon based source gas, the oxygen radical (O*), and the nitrogen radical (N*). Although an example in which an oxidation source is supplied as the oxygen radical has been described in the present embodiment, since oxygen has high degradation efficiency for the vacuum ultraviolet light (large quenching cross-section area), it is possible to form the silicon oxynitride film even if the oxidation source is supplied as oxygen gas instead of the oxygen radical. More specifically, by performing the adjustment of the flow ratio of each gas, the silicon oxynitride film having the desired composition and refractive index (absorption coefficient) can be formed. The method using the oxygen gas instead of the oxygen radical in this manner can be applied to, for example, the formation of the barrier films of the film configurations C and D of
Thereafter, by the known technology, the wirings (not shown) connected to the anode electrode 103 and the cathode electrode 106 shown in
A comparison result of the brightnesses obtained when the current is applied to the four types of organic EL elements having the buffer films and the barrier films of respective film configurations A to D shown in
Furthermore, the sample is left alone for a predetermined time in the environment of the relative humidity of 90% and the temperature of 80° C., and a variation of the brightness with respect to the initial brightness is compared. As a result, the brightness of the film configurations C and D is scarcely changed, but the brightness of the film configuration B is reduced to 90% to 95%, and the brightness of the film configuration A is reduced to 70% to 80%. As shown above, according to the optical semiconductor device of the present embodiment having the encapsulating film of the film configuration C or D, the light extraction efficiency (brightness) of the organic EL element can be improved, and the reliability for moisture can also be improved.
The example in which the moisture barrier film (barrier film) is formed by the optical CVD method using the remote plasma assist has been described in the present embodiment, but the same effect can be obtained even when the other film formation method is used from the viewpoint of the light extraction efficiency (refractive index control) or the moisture barrier property (film density). For example, if the ground, that is, the upper surface of the buffer film 108 is flattened by the formation of the buffer film 108 with high fluidity shown in
Further, although the refractive indexes of the buffer films 108, 110, and 112 formed by the optical CVD method using the remote plasma assist are 1.65 in the present embodiment, it is essential to set up a film composition in consideration of the other characteristics. Specifically, in the film formation by the optical CVD method using the organic silicon source, when the content of nitrogen in the film is increased, the refractive index is increased, but the fluidity of the film is deteriorated, and a film stress and the Young's modulus tend to increase. More specifically, while the buffer film is required to have a good flatness, a low stress for preventing the occurrence of a crack and the peeling of a film, and a low Young's modulus, a contradictory property such as the suppression of multiple reflection inside the laminated encapsulating film is also required. The inventors of the present invention have considered and studied the above-described points and confirmed that an excellent light extraction efficiency (brightness) can be obtained without causing a crack or a peeling of the film if the refractive index difference between the barrier film and the buffer film with respect to the light with the wavelength of 632.8 nm is within the range of 0.25 or less.
Next, a sample in which the vacuum ultraviolet light absorption layer 107 is formed as shown in
Since the encapsulating film has the film configuration A shown in
Although an example using the silicon oxynitride film for the member of the vacuum ultraviolet light absorption layer 107 has been shown in the present embodiment, the vacuum ultraviolet light absorption layer 107 is not always required to be the silicon oxynitride film, and it may be made up of the other members. According to the studies by the inventors of the present invention, if the transmittance of the vacuum ultraviolet light transmitting through the organic EL layer 105 is less than about 10%, the optical deterioration of the organic EL layer is scarcely observed. To be exact, since the cathode electrode on the organic EL layer absorbs 5% of the vacuum ultraviolet light, if the transmittance of the vacuum ultraviolet light transmitting through the organic EL layer becomes 5% or more, the organic EL layer suffers the optical damage, and is optically deteriorated.
Accordingly, if the film is an insulating film which absorbs 90% or more of the vacuum ultraviolet light and does not give the optical damage to the organic EL layer 105, the other type of film other than the silicon oxynitride film can be used. For example, even when aluminum oxide, aluminum nitride, aluminum oxynitride, or the like is used, the same effects can be obtained. However, a necessary film thickness needs to be set in consideration of the light absorption coefficient of the types of films to be used.
Further, the vacuum ultraviolet light absorption layer 107 is formed by the other plasma CVD device in the present embodiment, but it may be formed by the device shown in
As described above, in the organic EL element of the present embodiment, the buffer films 108, 110, and 112 and the barrier films 109 and 111 shown in
As described above, the buffer film and the barrier film can be made of the silicon oxynitride film that is formed by the optical CVD method using the remote plasma assist. As a result, the refractive index difference between the buffer film and the barrier film can be reduced. In the ordinary optical CVD method not using the remote plasma assist, it is difficult to degrade the source gas having small quenching cross-section area such as ammonia gas or a nitrogen gas to take out nitrogen and introduce the nitrogen into a film to be formed. However, by using the film formation device as shown in
In the foregoing, the invention made by the inventors of the present invention has been concretely described based on the embodiments. However, it is needless to say that the present invention is not limited to the foregoing embodiments and various modifications and alterations can be made within the scope of the present invention.
For example, since the encapsulating film is formed by using the optical CVD method in the embodiment described above, it is necessary to prevent the organic EL layer from being damaged by the vacuum ultraviolet light used in the optical CVD method. In the embodiment described above, since the vacuum ultraviolet light absorption layer 107 is formed as shown in
Although the optical semiconductor device in which the organic EL element and the encapsulating film thereof are formed has been shown as an example in the embodiment described above, it is of course possible to apply the encapsulating film to the organic EL display provided with a thin film transistor. For example, the organic EL display can be formed by providing a switching element made up of a thin film transistor between the glass substrate 101 and the insulating film 102 shown in
Further, by forming the encapsulating film of the present invention on the front and back surfaces of the resin film or the resin substrate, dimensional fluctuation due to moisture absorption of the resin film or the resin substrate and the like can be suppressed. In addition, by combining the resin film or the resin substrate having the encapsulating film according to the present invention formed thereon with the organic EL display, a flexible organic EL display can also be formed. In this case, after the structure shown in
Further, although the cathode electrode is disposed on the organic EL layer and the anode electrode is disposed below the organic EL layer in the embodiment described above, it is also possible to inversely dispose the anode electrode on the organic EL layer and dispose the cathode electrode below the organic EL layer.
The manufacturing method of the optical semiconductor device of the present invention is widely utilized for the optical semiconductor device having the encapsulating film through which the visible light transmits.
Number | Date | Country | Kind |
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JP2011-081553 | Apr 2011 | JP | national |