Element, method for manufacturing the same, and organic semiconductor laser diode

Abstract

Disclosed are devices and methods for fabricating the same, including a substrate and at least two distinct optoelectronic devices monolithically fabricated on the substrate. Also disclosed are organic semiconductor laser diodes including, in order, a substrate, an insulating grating, a first electrode, an organic layer, and a second electrode.

Description

Technical Field

[0001] The present invention relates to an element including a substrate and at least two different optoelectronic devices, wherein the at least two different optoelectronic devices are monolithically fabricated on the substrate. The present invention also relates to a method for manufacturing the element, and an organic semiconductor laser diode including a substrate, a dielectric diffraction grating, a first electrode, an organic layer, and a second electrode in this order.

Background Art

[0002] In conventional inorganic electronics, devices with different functions require different crystalline semiconductor materials and different manufacturing processes. For example, to incorporate different devices (such as light-emitting diodes, laser diodes, transistors, etc.) on the same substrate, it is necessary to grow different crystalline inorganic materials on the same substrate. Growing different crystalline materials on the same substrate is difficult because they have individual lattice constants. Such problems limit the use of highly versatile substrates and the chip integration density, and increase the manufacturing cost.

[0003] Furthermore, the technology of RGB laser diodes using conventional inorganic light-emitting semiconductors has significant problems regarding miniaturization and mass production. In fact, the gain materials of red, green, and blue laser diodes are GaN, GaInN, and AlGaInP, respectively. The lattice constants of these crystalline semiconductors are not the same. Therefore, it is very difficult to grow three different laser diodes on the same substrate. Such problems also limit the use of highly versatile substrates such as glass, plastic, and paper. Furthermore, even when trying to incorporate conventional RGB laser diodes to create a compact system, the use of connectors and various driving conditions impose limitations, thereby significantly restricting the integration density of chips and microdisplays that require high resolution. For example, to monolithically integrate two materials for green and red light emission with different bandgap energies, an adhesive bonding and chemical wet etching process are used to integrate both AlGaInP-based and InGaN-based LDs on one substrate. To move forward towards ultimate chip miniaturization, it is important to monolithically incorporate each optoelectronic device using a common fabrication process.

[0004] On the other hand, recently, a current-injected semiconductor laser diode using an organic material has been demonstrated. Patent Document 1 discloses a current-injected organic semiconductor laser diode including a pair of electrodes, an optical resonator structure, and one or more organic layers. The one or more organic layers include an optical amplification layer composed of an organic semiconductor. This optical amplification layer has sufficient overlap between the exciton density distribution and the electric field strength distribution of the resonant optical mode while current is injected and laser light is emitted.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0006] In view of these circumstances, the present inventors have conducted intensive research with the aim of providing an element including at least two different optoelectronic devices that solves the above problems caused by the use of inorganic semiconductor materials.

Means for Solving the Problems

[0007] As a result of intensive research, the present inventors have made the following inventions. (1) An element including a substrate and at least two different optoelectronic devices, wherein the at least two different optoelectronic devices are monolithically fabricated on the substrate. (2) The element according to (1), wherein the at least two different optoelectronic devices are at least two photoexcited organic solid-state lasers that emit light at different wavelengths. (3) The element according to (1), wherein the at least two different optoelectronic devices are at least two organic semiconductor laser diodes that emit light at different wavelengths. (4) The element according to (1), wherein the at least two different optoelectronic devices are an organic solid-state laser and an organic light-emitting diode. (5) The element according to (1), wherein the at least two different optoelectronic devices include an organic solid-state laser diode, and the organic solid-state laser diode includes a substrate, an insulating diffraction grating, a first electrode, an organic layer, and a second electrode in this order. (6) The element according to any one of (1) to (5), wherein the at least two different optoelectronic devices include an organic solid-state laser diode, and the element emits light from the lower surface. (7) The element according to any one of (1) to (5), wherein the at least two different optoelectronic devices include an organic solid-state laser diode, and the element emits light from the upper surface. (8) An organic semiconductor laser diode including a substrate, an insulating diffraction grating, a first electrode, an organic layer, and a second electrode in this order. A method for manufacturing an element comprising a substrate and at least two different optoelectronic devices, the method comprising monolithically fabricating the at least two different optoelectronic devices on the substrate. (10) The method according to (9), wherein the element comprises a substrate and at least two different optoelectronic devices, and the at least two different optoelectronic devices include an organic solid-state laser diode, the method comprising forming a dielectric diffraction grating on the substrate and then forming an organic layer for the at least two different optoelectronic devices.

Brief Description of the Drawings

[0008]

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Embodiments for Carrying Out the Invention

[0009] The content of the present invention will be described in detail below. Each component can be described below with reference to representative embodiments and specific examples of the present invention, but the present invention is not limited to these embodiments and examples. In the description of this specification, a numerical range expressed as "~" means a range including the upper limit and / or the lower limit.

[0010] The device of the present invention includes a substrate and at least two different optoelectronic devices. These at least two different optoelectronic devices are fabricated monolithically on the above substrate. An optoelectronic device has a function of converting electricity into light or light into electricity. Examples of optoelectronic devices include a photoexcitation type organic solid laser (OSL), an organic semiconductor laser diode (OSLD), an organic light-emitting diode (OLED), an organic photodetector, and an organic solar cell. At least two optoelectronic devices in the device of the present invention are different from each other, but may belong to the same optoelectronic device type. In some embodiments of the present invention, the at least two optoelectronic devices are at least two photoexcitation type organic solid lasers that emit light at different wavelengths. In some embodiments of the present invention, the at least two optoelectronic devices are at least two organic semiconductor laser diodes that emit light at different wavelengths. In some embodiments of the present invention, the at least two optoelectronic devices are an organic solid laser and an organic light-emitting diode. As long as the device of the present invention includes at least two different optoelectronic devices, it can additionally include at least one optoelectronic device that is the same as either of the at least two optoelectronic devices. The device of the present invention can also include an organic photodetector, an organic field effect transistor, an organic thermoelectric generator, etc.

[0011] At least two different optoelectronic devices are fabricated monolithically on a single substrate. In some embodiments of the present invention, at least two different optoelectronic devices are fabricated monolithically on a single substrate. In some embodiments of the present invention, the at least two different optoelectronic devices are encapsulated together. In some embodiments of the present invention, the at least two different optoelectronic devices include at least one common organic layer of the same composition. The common organic layer of each device may be of the same thickness. In some embodiments of the present invention, the number of the common organic layers may be at least two, at least three, or at least four. In some embodiments, the distance between the at least two different optoelectronic devices is less than 1 mm. The distance may be less than 10 micrometers, less than 1 micrometer, or less than 100 nanometers. The present invention includes the following four aspects.

[0012] (1) The first aspect of the invention (Background) Instead of conventional technologies such as light-emitting diodes (LEDs) and organic light-emitting diodes (OLEDs), using RGB lasers for displays is very attractive. By using a laser light source, high color purity due to a very narrow spectral linewidth (~0.2 nm), high brightness, and high power efficiency are achieved, and they contribute to the miniaturization of display systems.

[0013] The technology of RGB laser diodes using conventional inorganic light-emitting semiconductors has significant problems regarding miniaturization and mass production. In fact, the gain materials of red, green, and blue laser diodes are GaN, GaInN, and AlGaInP, respectively. The lattice constants of these crystalline semiconductors are not the same. Therefore, it is very difficult to grow three different laser diodes on the same substrate. Such problems also limit the use of highly versatile substrates such as glass, plastic, and paper. Furthermore, even when trying to incorporate conventional RGB laser diodes to create a compact system, the use of connectors and various driving conditions impose limitations, thereby significantly restricting the integration density of chips and microdisplays that require high resolution. For example, to monolithically integrate two materials for green and red light emission with different bandgap energies, an adhesive bonding and chemical wet etching process are used to integrate both AlGaInP-based and InGaN-based LDs on one substrate. To move forward towards ultimate chip miniaturization, it is important to monolithically incorporate each optoelectronic device using a common fabrication process.

[0014] (Invention) Using organic semiconductors can solve the problems inherent in inorganic semiconductors. In fact, using organic semiconductors makes it possible to fabricate high-density monolithic circuits on various substrates such as glass, plastic, and even paper. This interesting feature is brought about by the fact that organic semiconductors are amorphous and do not need to be crystalline. Furthermore, organic semiconductors can be formed into films using various simple techniques suitable for mass production such as inkjet printing and thermal evaporation.

[0015] The first aspect of the present invention provides an element comprising a substrate and at least two optically pumped organic solid-state lasers (OSLs) that emit light at different wavelengths, wherein the at least two organic solid-state lasers are monolithically fabricated on the substrate.

[0016] More specifically, it is proposed here to monolithically integrate each light-excited type OSL of RGB using the same manufacturing process on the same substrate. It is possible to integrate two colors, three colors, or more colors (wavelengths). Instead of, or in addition to, red, green, and blue, other colors may be used.

[0017] The first aspect of the present invention includes the following embodiments. [Embodiment 1-1] Organic solid-state lasers that emit light at different wavelengths (for example, red, green, and blue) are fabricated (monolithically integrated) on the same substrate. [Embodiment 1-2] Monolithic integration onto a substrate having flexibility and / or transparency. [Embodiment 1-3] Manufacturing method: solution process (inkjet, spin coating) and thermal evaporation.

[0018] In some embodiments of the present invention, the structure of the OSL is composed of the following. 1. Excitation light source 2. Substrate 3. Diffraction grating 4. Organic gain material (semiconductor) 5. Encapsulant

[0019] The diffraction grating may be located above the organic gain material, or above the substrate and below the organic gain material. In one embodiment of the present invention, the substrate, diffraction grating, and organic gain material are formed in this order from the bottom. In one embodiment of the present invention, the substrate, organic gain material, and diffraction grating are formed in this order from the bottom. In one embodiment of the present invention, the diffraction grating is in contact with the organic gain material. In one embodiment of the present invention, the diffraction grating is in contact with the substrate. In one embodiment, the organic material is in contact with the diffraction grating, and the diffraction grating is in contact with the substrate.

[0020] The advantages of the present invention are as follows. - Improvement in device integration density towards ultimate chip miniaturization by monolithic integration, - Use of a substrate having flexibility and transparency, - A simple fabrication process suitable for mass production such as inkjet printing and thermal evaporation, - A major advancement towards an all-organic electronic platform.

[0021] Figure 1 shows a photoexcited, monolithically integrated RGB organic solid-state laser according to the present invention.

[0022] (Example: Monolithic integration of red, green, and blue organic solid-state lasers) Red, green, and blue surface-emitting organic solid-state lasers (Figure 1) were fabricated on the same substrate glass using a thermal evaporation process for the above three colors. This OSL includes an emitter formed by thermal evaporation on a second-order distributed feedback (DFB) diffraction grating and then sealed using a lid of Cytop (registered trademark) and sapphire. The above DFB diffraction grating was directly etched on the surface of silicon dioxide using electron beam lithography and reactive ion etching. Figure 7 shows the laser spectra of monolithically integrated red, green, and blue organic solid-state lasers. The periods of the blue, green, and red organic solid-state lasers are Λ = 270, 310, 380 nm respectively, and emit laser emissions at λ = 470, 511, 601 nm.

[0023] (2) The second aspect of the invention (Background) With the miniaturization of electronic components, it has become possible to execute almost all the functions of a smartphone in wearable small smart devices such as smartwatches, medical handheld monitors, and head-mounted displays. To move forward towards ultimate chip miniaturization, it is important to monolithically integrate each optoelectronic device using a common fabrication process.

[0024] In conventional inorganic electronics, different crystalline semiconductor materials and different manufacturing processes are required for devices with different functions. For example, to incorporate different devices (such as light-emitting diodes, laser diodes, transistors, etc.) on the same substrate, it is necessary to grow different crystalline inorganic materials on the same substrate. Growing different crystalline materials on the same substrate is difficult because they have individual lattice constants. These problems limit the use of highly versatile substrates and the chip integration density, increasing the manufacturing cost.

[0025] Using innovative materials such as organic semiconductors can solve problems inherent in inorganic semiconductors. In fact, using organic semiconductors makes it possible to fabricate monolithic circuits on various substrates such as glass, plastic, and even paper. This interesting feature is brought about by the fact that organic semiconductors are amorphous and do not need to be crystalline. Therefore, organic semiconductors can be film-formed using various simple techniques such as spin coating, inkjet printing, and thermal evaporation. Furthermore, monolithic integration of multiple organic semiconductor devices is a very important feature for the early realization of an all-organic electronic platform.

[0026] Today, many electronic devices such as organic solar cells, organic sensors, organic field-effect transistors (OFETs), organic light-emitting diodes (OLEDs), organic memories, and organic lasers can be fabricated with organic materials. OLEDs and organic optical sensors have been commercialized and are surpassing the inorganic device market. By integrating OSL into an all-organic electronic platform, the device functions for applications such as sensing and display can be added and improved.

[0027] (Invention) The second aspect of the present invention provides an element comprising a substrate, a photoexcited organic solid laser, and an organic light-emitting diode, wherein the organic solid laser and the organic light-emitting diode are monolithically fabricated on the substrate.

[0028] In some embodiments, for the purpose of demonstrating a photoexcited OSL monolithically integrated on an all-organic electronic platform, an OSL, an OLED, and an organic photodetector are fabricated on the same substrate.

[0029] Here, it is proposed to monolithically integrate an OSL on an all-organic electronic platform. This all-organic optoelectronic system may be composed of a photoexcited OSL, an OLED, an organic solar cell, an optical photodetector, an organic field-effect transistor, an organic memory, and an organic thermoelectric generator.

[0030] Figure 2 shows the integration of a photoexcited OSL, an OLED, and an organic photodetector fabricated in the same area. In this embodiment, these devices are fabricated on the same substrate. The OLED is composed of an organic light-emitting layer sandwiched between pairs of a transport layer (TL) and an electrode. The OLED can emit light from the upper or lower surface. The OSL is composed of a distributed feedback (DFB) diffraction grating and an organic gain material. The DFB can be disposed on the substrate or on the upper surface of the organic gain material. The photodetector is composed of an organic active layer sandwiched between pairs of a transport layer (TL) and an electrode. The three devices are fabricated on a common substrate.

[0031] The second aspect of the present invention includes the following embodiments. [Embodiment 2-1] An organic solid laser, an organic light-emitting diode, and an optical photodetector are monolithically integrated (fabricated on the same substrate). [Embodiment 2-2] Monolithic integration on a flexible and / or transparent substrate. [Embodiment 2-3] The present invention includes the following combinations. [Embodiment 2-4] OLED + OSL [Embodiment 2-5] OLED + OSL + organic solar cell [Embodiment 2-6] OLED + OSL + organic photodetector [Embodiment 2-7] OLED + OSL + organic field-effect transistor [Embodiment 2-8] OLED + OSL + organic thermoelectric generator [Embodiment 2-9] OLED + OSL + Organic Solar Cell + Organic Photodetector + Organic Field-Effect Transistor + Organic Thermoelectric Generator Figure 2 is a diagram of an OLED, OSL, and organic photodetector monolithically integrated.

[0032] (Example: Monolithic Integration of Organic Laser and OLED) The fabrication of these devices was performed by vacuum deposition. First, a glass substrate coated with ITO patterned to a thickness of 100 nm was ultrasonically treated using a neutral detergent, pure water, acetone, and isopropanol, and then cleaned by UV-ozone treatment. The OLED region was protected using a mask, and SiO2 was deposited by sputtering. A DFB diffraction grating was formed in the non-ITO portion on the SiO2 layer using electron beam lithography and reactive ion etching. Next, the organic layer, injection layer, and metal electrode layer were vacuum deposited using a mask. This metal mask protects the DFB diffraction grating region (no metal is deposited in the DFB diffraction grating region). These devices were sealed in a glove box filled with nitrogen using a glass lid and UV-curable epoxy. Figures 8 (a, b, c, d) show the laser spectrum of a blue organic solid laser, the current-voltage curve of the OLED, the external quantum efficiency (EQE)-current curve of the OLED, and the electroluminescence spectrum of the OLED, respectively.

[0033] (3) The Third Aspect of the Invention (Background) Using red, green, and blue (RGB) lasers in displays instead of conventional technologies such as light-emitting diodes (LEDs) and organic light-emitting diodes (OLEDs) is very attractive. By using a laser light source, high color purity due to a very narrow spectral linewidth (~0.2 nm), high brightness, and high power efficiency are achieved, and they contribute to the miniaturization of the display system.

[0034] The technology of RGB laser diodes using conventional inorganic light-emitting semiconductors has significant problems regarding miniaturization and mass production. In fact, the gain materials of red, green, and blue laser diodes are GaN, GaInN, and AlGaInP, respectively. The lattice constants of these crystalline semiconductors are not the same. Therefore, it is very difficult to grow three different laser diodes on the same substrate. These problems also limit the use of highly versatile substrates such as glass, plastic, and paper. Furthermore, even when trying to incorporate conventional RGB laser diodes to create a compact system, the use of connectors and various driving conditions impose limitations, thereby significantly restricting the integration density of chips and microdisplays that require high resolution. For example, to monolithically integrate two materials for green and red light emission with different bandgap energies, an adhesive bonding and chemical wet etching process are used to integrate both AlGaInP-based and InGaN-based LDs on one substrate. To move forward towards ultimate chip miniaturization, it is important to monolithically incorporate each optoelectronic device using a common fabrication process.

[0035] (Invention) Using organic semiconductors can solve the problems inherent in inorganic semiconductors. In fact, using organic semiconductors makes it possible to fabricate high-density monolithic circuits on various substrates such as glass, plastic, and even paper. This interesting feature is brought about by the fact that organic semiconductors are amorphous and do not need to be crystalline. Furthermore, organic semiconductors can be formed into films using various simple techniques suitable for mass production such as inkjet printing and thermal evaporation.

[0036] The third aspect of the present invention provides an organic semiconductor laser diode including a substrate, an insulating diffraction grating, a first electrode, an organic layer, and a second electrode in this order, and the monolithic integration of two or more different organic semiconductor laser diodes.

[0037] The third aspect of the present invention includes the following embodiments. [Embodiment 3-1] Organic semiconductor laser diodes that emit light at different wavelengths (red, green, and blue) are fabricated in the same region. In this embodiment, these devices are fabricated on the same substrate (monolithic integration). The distributed feedback resonator is formed on the substrate and under the electrode. The monolithically integrated organic semiconductor laser diode can emit light from the top surface or the bottom surface. [Embodiment 3-2] The monolithically integrated organic semiconductor laser diode can be flexible. [Embodiment 3-3] The monolithically integrated organic semiconductor laser diode can be transparent.

[0038] The third aspect of the present invention provides the following two invention concepts. <1> A novel OSLD design including a transparent electrode above the diffraction grating In the first demonstration of OSLD (Patent Document 1), an insulating diffraction grating is used above the ITO electrode (the top surface in Patent Document 1). The role of the diffraction grating is to generate optical feedback. As shown in Fig. 3(a), in order to enable charge injection from the electrode to the light-emitting layer, it is necessary to completely remove the insulator on the electrode, so the formation of the insulating diffraction grating on the electrode becomes complicated. In the novel OSLD design proposed in the present invention, as shown in Fig. 3(b), the diffraction grating is located below the electrode (the bottom surface in this embodiment). When the electrode is above the insulating diffraction grating, charge carriers are injected from the entire device region. Therefore, excitons can be generated uniformly within the device. Thereby, the gain increases due to an increase in the overlapping portion between the exciton density and the distribution of the optical resonance mode.

[0039] Optical simulations were performed to design the OSLD structure shown in Figs. 4(a - d). For the purpose of adjusting the resonance wavelength λ0 and increasing the Q value and the confinement factor Γ, the thickness d of the ITO electrode ITO and the thickness d of the organic film FILMEach has been optimized. The results of the optical optimization are shown in Table 1. Figure 4 shows the electric field distributions of the DFB resonant cavities at the resonant wavelengths of a) OSLD1, b) OSLD2, c) OSLD3, and d) OSLD4. In OSLD1-4, the DFB diffraction grating is fabricated on the substrate and under the ITO electrode. In OSLD-ref, the DFB diffraction grating is fabricated on the ITO electrode (previously patented OSLD, Patent Document 1). All of OSLD1-4 showed higher Q values and confinement factors than OSLD-ref. The resonant cavity of OSLD4 showed the best optical performance.

[0040]

Table 1

[0041] <2>Monolithic integration of two or more different organic semiconductor laser diodes Figure 5 shows, as a preferred embodiment, the monolithic integration of RGB colors. It is possible to integrate two colors, three colors, or more colors (wavelengths). Instead of, or in addition to, red, green, and blue, other colors can be used.

[0042] The structure of the OSLD can be as follows. 1. An upper surface emitting OSLD structure composed in the order of a substrate, an electrode, a distributed feedback (DFB) diffraction grating made of a low refractive index material, an electron transport layer, an organic gain layer, a hole transport layer, and a transparent or semi-transparent electrode. 2. A lower surface emitting OSLD structure composed in the order of a substrate, an electrode, a DFB diffraction grating made of a low refractive index material, a hole transport layer, an organic gain layer, an electron transport layer, and a transparent or semi-transparent electrode.

[0043] In either structure, the DFB diffraction grating can be formed in the same region of the substrate (in this embodiment, on the substrate) and on one side of the ITO electrode (in this embodiment, under the electrode). For example, the present invention includes the following OSLD structures. 1. An upper surface emitting OSLD structure composed of a substrate, a distributed feedback (DFB) diffraction grating made of a low refractive index material, a transparent or translucent electrode, an electron transport layer, an organic gain layer, a hole transport layer, and a transparent or translucent electrode in this order. 2. A lower surface emitting OSLD structure composed of a substrate, a DFB diffraction grating made of a low refractive index material, a transparent or translucent electrode, a hole transport layer, an organic gain layer, an electron transport layer, and a transparent or translucent electrode in this order.

[0044] The advantages of the third aspect of the present invention are as follows. - Improvement in device integration density towards ultimate chip miniaturization by monolithic integration, - Use of a flexible substrate, - A simple manufacturing process suitable for mass production such as inkjet printing and thermal evaporation, - A major advancement towards an all-organic electronics platform.

[0045] (4) The fourth aspect of the invention (Background) Due to the miniaturization of electronic components, it has become possible to execute almost all functions of a smartphone in small, wearable smart devices such as smartwatches and medical handheld monitors. To move forward towards ultimate chip miniaturization, it is important to monolithically integrate each optoelectronic device using a common manufacturing process.

[0046] Compared with conventional electronics, in organic electronics, a manufacturing process with low manufacturing cost, high speed, simplicity, and suitability for mass production is carried out, and the possibility of creating devices with super flexibility, foldability, stretchability, and biocompatibility is opened up. Through molecular design, highly versatile molecules with various characteristics and various emission wavelengths can be easily realized. In inorganic electronics, different crystalline semiconductor materials and different manufacturing process chambers are required for light-emitting diodes (LEDs) and laser diodes (LDs) of different colors. Therefore, monolithic integration of inorganic LEDs and LDs cannot be performed on a common substrate.

[0047] On the other hand, when using organic materials, due to their rich application characteristics, it becomes possible to fabricate several devices with various optoelectronic functions, such as organic lasers, OLEDs, organic solar cells, and optical sensors. In fact, the architecture of organic electronic devices is composed of an organic active layer stacked between pairs of interface layers and electrodes. This device architecture is a common feature of various organic electronic devices. Therefore, when using organic semiconductors, it becomes possible to fabricate monolithic circuits on various substrates such as glass, plastic, and even paper. This interesting feature is brought about by the fact that organic semiconductors are amorphous and do not need to be crystalline. Therefore, organic semiconductors can be film-formed using various simple techniques such as spin coating, inkjet printing, and thermal evaporation. Monolithic integration of multiple organic semiconductor devices becomes a very important feature for the early realization of all-organic electronic platforms. Today, many electronic devices, such as organic solar cells, organic sensors, organic field-effect transistors (OFETs), organic light-emitting diodes (OLEDs), organic memories, and organic lasers, can be fabricated with organic materials. OLEDs and organic optical sensors have been commercialized and are outperforming the inorganic device market.

[0048] (Invention) Recently, the demonstration of an organic semiconductor laser diode (OSLD) has been carried out. Interestingly, the OSLD has the same structure as the OLED. The main difference is that in the OSLD, a resonant cavity is required to provide optical feedback. Therefore, the fabrication method of the OSLD has an affinity with the technology of the OLED.

[0049] The fourth aspect of the present invention provides an element including a substrate and at least two organic semiconductor laser diodes that emit light at different wavelengths, wherein the at least two organic semiconductor laser diodes are monolithically fabricated on the substrate. The fourth aspect of the present invention further provides an element including a substrate, an organic semiconductor laser diode, and an organic light emitting diode, wherein the organic semiconductor laser diode and the organic light emitting diode are monolithically fabricated on the substrate.

[0050] In some embodiments, for the purpose of demonstrating OSLD, OLED, and optical photodetectors monolithically integrated, the OSLD, OLED, and organic photodetector are fabricated on the same substrate.

[0051] The fourth aspect of the present invention includes the following embodiments. [Embodiment 4-1] An organic semiconductor laser diode, an organic light emitting diode, and an optical photodetector are monolithically integrated (fabricated on the same substrate). A system for bottom emission detection and top emission detection is proposed here. A distributed feedback resonator can be fabricated on the upper side of the substrate (e.g., the upper surface of the substrate) and under the electrode (e.g., the lower surface of the electrode). [Embodiment 4-2] Monolithic integration onto a flexible and / or transparent substrate Figures 6(a - d) show an organic optoelectronic system composed of an OSLD, an OLED, and an optical photodetector in the same region of the substrate using the same technology. These figures show a top emission detection configuration and a bottom emission detection configuration with a diffraction grating on one side of the ITO electrode (in this embodiment, on the surface). Figures 6(c, d) show a top emission detection configuration and a bottom emission detection configuration with a diffraction grating under the ITO electrode (in this embodiment, on the bottom surface). By forming a diffraction grating under the ITO electrode (in this embodiment, on the bottom surface), injection is enhanced.

[0052] 1. The top emission detection configuration includes the following (Figure 6(a)). a. A top-emitting OLED structure composed in the order of a substrate, an electrode, an electron transport layer, an organic light-emitting layer, a hole transport layer, and a transparent or semi-transparent electrode. b. A top-emitting OSLD structure composed in the order of a substrate, an electrode, a distributed feedback (DFB) diffraction grating made of a low refractive index material, an electron transport layer, an organic gain layer, a hole transport layer, and a transparent or semi-transparent electrode. c. A top-detection organic photodetector composed in the order of a substrate, an electrode, an electron transport layer, an organic active (absorbing) layer, a hole transport layer, and a transparent or semi-transparent electrode.

[0053] 2. The bottom-emitting detection configuration includes the following (Fig. 6(b)). a. A bottom-emitting OLED structure composed in the order of a transparent or semi-transparent substrate, a transparent or semi-transparent electrode, a hole transport layer, an organic light-emitting layer, an electron transport layer, and an electrode. b. A bottom-emitting OSLD structure composed in the order of a transparent or semi-transparent substrate, a transparent or semi-transparent electrode, a DFB diffraction grating made of a low refractive index material, a hole transport layer, an organic gain layer, an electron transport layer, and an electrode. c. A bottom-detection organic photodetector composed in the order of a transparent or semi-transparent substrate, a transparent or semi-transparent electrode, a hole transport layer, an organic active (absorbing) layer, an electron transport layer, and an electrode.

[0054] 3. The top-emitting detection configuration includes the following (Fig. 6(c)). a. A top-emitting OLED structure composed in the order of a substrate, an electrode, an electron transport layer, an organic light-emitting layer, a hole transport layer, and a transparent or semi-transparent electrode. b. A top-emitting OSLD structure composed in the order of a substrate, a DFB diffraction grating made of a low refractive index material, an electrode, an electron transport layer, an organic gain layer, a hole transport layer, and a transparent or semi-transparent electrode. c. A top-detection organic photodetector composed in the order of a substrate, an electrode, an electron transport layer, an organic active (absorbing) layer, a hole transport layer, and a transparent or semi-transparent electrode.

[0055] 4. The bottom-emitting detection configuration includes the following (Fig. 6(d)). a. A bottom-emitting OLED structure composed in the order of a transparent or semi-transparent substrate, a transparent or semi-transparent electrode, a hole transport layer, an organic light-emitting layer, an electron transport layer, and an electrode. b. A bottom-emitting OSLD structure composed of a transparent or translucent substrate, a DFB diffraction grating made of a low refractive index material, a transparent or translucent electrode, a hole transport layer, an organic gain layer, an electron transport layer, and an electrode in this order. c. A bottom-detection organic photodetector composed of a transparent or translucent substrate, a transparent or translucent electrode, a hole transport layer, an organic active (absorbing) layer, an electron transport layer, and an electrode in this order.

[0056] The present invention includes the following combinations. OLED + OSLD OLED + OSLD + organic solar cell OLED + OSLD + organic photodetector OLED + OSLD + organic field effect transistor OLED + OSLD + organic thermoelectric generator OLED + OSLD + organic solar cell + organic photodetector + organic field effect transistor + organic thermoelectric generator

[0057] The present invention includes the following embodiments. [1] An element comprising a substrate and at least two photoexcited organic solid-state lasers that emit light at different wavelengths, wherein the at least two organic solid-state lasers are monolithically fabricated on the substrate. [2] The element according to [1], comprising at least three organic solid-state lasers that emit light at different wavelengths. [3] The element according to [2], comprising an organic solid-state laser that emits blue light, an organic solid-state laser that emits green light, and an organic solid-state laser that emits red light. [4] The element according to any one of [1] to [3], wherein the substrate is flexible. [5] The element according to any one of [1] to [4], wherein the substrate is transparent. (Note) The term "transparent" in this application includes both transparent and translucent. The transmittance of the "transparent" substrate or "transparent" electrode in this application is preferably at least 70%, more preferably at least 90%, still more preferably at least 95%, and even more preferably at least 99%. [6] A method for manufacturing an element including a substrate and at least two optically pumped organic solid-state lasers that emit light at different wavelengths, the method including monolithically fabricating the organic solid-state lasers on the substrate. [7] The method for manufacturing an element according to [6], wherein the element includes at least three organic solid-state lasers that emit light at different wavelengths. [8] The method for manufacturing an element according to [7], wherein the element includes an organic solid-state laser that emits blue light, an organic solid-state laser that emits green light, and an organic solid-state laser that emits red light. [9] The method for manufacturing an element according to any one of [6] to [8], wherein the substrate is flexible.

[10] The method for manufacturing an element according to any one of [6] to [9], wherein the substrate is transparent.

[11] The method for manufacturing an element according to any one of [6] to

[10] , including monolithically fabricating the organic solid-state lasers on the substrate by a solution process.

[12] The method for manufacturing an element according to any one of [6] to

[10] , including monolithically fabricating the organic solid-state lasers on the substrate by an inkjet process.

[13] The method for manufacturing an element according to any one of [6] to

[10] , including monolithically fabricating the organic solid-state lasers on the substrate by a spin coating process.

[14] The method for manufacturing an element according to any one of [6] to

[10] , including monolithically fabricating the organic solid-state lasers on the substrate by a thermal evaporation process.

[0058]

[15] An element including a substrate, an optically pumped organic solid-state laser, and an organic light-emitting diode, wherein the organic solid-state laser and the organic light-emitting diode are monolithically fabricated on the substrate.

[16] The element according to

[15] , including the substrate, the organic solid-state laser, the organic light-emitting diode, and an optical photodetector, wherein the organic solid-state laser, the organic light-emitting diode, and the optical photodetector are monolithically fabricated on the substrate.

[17] The device according to

[15] , comprising the above-mentioned substrate, the above-mentioned organic solid laser, the above-mentioned organic light-emitting diode, and the organic solar cell, wherein the above-mentioned organic solid laser, the above-mentioned organic light-emitting diode, and the above-mentioned organic solar cell are monolithically fabricated on the above-mentioned substrate.

[18] The device according to

[15] , comprising the above-mentioned substrate, the above-mentioned organic solid laser, the above-mentioned organic light-emitting diode, and the organic field-effect transistor, wherein the above-mentioned organic solid laser, the above-mentioned organic light-emitting diode, and the above-mentioned organic field-effect transistor are monolithically fabricated on the above-mentioned substrate.

[19] The device according to

[15] , comprising the above-mentioned substrate, the above-mentioned organic solid laser, the above-mentioned organic light-emitting diode, and the organic thermoelectric generator, wherein the above-mentioned organic solid laser, the above-mentioned organic light-emitting diode, and the above-mentioned organic thermoelectric generator are monolithically fabricated on the above-mentioned substrate.

[20] The device according to any one of

[15] to

[19] , wherein the above-mentioned substrate has flexibility.

[21] The device according to any one of

[15] to

[19] , wherein the above-mentioned substrate has transparency.

[22] A method for manufacturing a device comprising a substrate, a photoexcited organic solid laser, and an organic light-emitting diode, the method including monolithically fabricating the above-mentioned organic solid laser and the above-mentioned organic light-emitting diode on the above-mentioned substrate.

[23] The method for manufacturing a device according to

[22] , including monolithically fabricating the above-mentioned organic solid laser, the above-mentioned organic light-emitting diode, and the organic photodetector on the above-mentioned substrate.

[24] The method for manufacturing a device according to

[22] or

[23] , including monolithically fabricating the above-mentioned organic solid laser, the above-mentioned organic light-emitting diode, and the organic solar cell on the above-mentioned substrate.

[25] The method for manufacturing a device according to any one of

[22] to

[24] , including monolithically fabricating the above-mentioned organic solid laser, the above-mentioned organic light-emitting diode, and the organic field-effect transistor on the above-mentioned substrate.

[26] The method for manufacturing a device according to any one of

[22] to

[25] , including monolithically fabricating the above-mentioned organic solid laser, the above-mentioned organic light-emitting diode, and the organic thermoelectric generator on the above-mentioned substrate.

[27] The device manufacturing method according to any one of

[22] to

[26] , wherein the above manufacturing is performed monolithically by a solution process.

[28] The device manufacturing method according to any one of

[22] to

[26] , wherein the above manufacturing is performed monolithically by an inkjet process.

[29] The device manufacturing method according to any one of

[22] to

[26] , wherein the above manufacturing is performed monolithically by a spin coating process.

[30] The device manufacturing method according to any one of

[22] to

[26] , wherein the above manufacturing is performed monolithically by a thermal evaporation process.

[0059]

[31] An organic semiconductor laser diode including a substrate, an insulating diffraction grating, a first electrode, an organic layer, and a second electrode in this order.

[32] The organic semiconductor laser diode according to

[31] , wherein the insulating diffraction grating is in contact with the first electrode.

[33] The organic semiconductor laser diode according to

[31] or

[32] , wherein the insulating diffraction grating is in contact with the substrate.

[34] The organic semiconductor laser diode according to any one of

[31] to

[33] , wherein the first electrode and the substrate have transparency.

[35] The organic semiconductor laser diode according to

[34] , which emits light from the bottom surface (from the side of the first electrode).

[36] The organic semiconductor laser diode according to any one of

[31] to

[35] , wherein the second electrode has transparency.

[37] The organic semiconductor laser diode according to

[36] , which emits light from the top surface (from the side of the second electrode).

[38] The organic semiconductor laser diode according to any one of

[31] to

[37] , wherein a diffraction grating is not formed on the surface of the first electrode on the organic layer side.

[39] The organic semiconductor laser diode according to any one of

[31] to

[38] , wherein charge carriers are injected into the organic layer from the surface of the first electrode without being hindered by the diffraction grating. The organic semiconductor laser diode according to any one of

[31] to

[39] , wherein the thickness of the first electrode and the thickness of the organic film are optimized by adjusting the resonance wavelength and increasing the Q value and the confinement factor. The organic semiconductor laser diode according to any one of

[31] to

[39] , having a Q value of at least 450. The organic semiconductor laser diode according to any one of

[31] to

[39] , having a confinement factor of at least 60%.

[43] Forming an insulating diffraction grating on or above a substrate, Forming a first electrode on or above the insulating diffraction grating, Forming an organic layer on or above the first electrode, Forming a second electrode on or above the organic layer, A method for manufacturing an organic semiconductor laser diode, comprising:

[44] The method for manufacturing an organic semiconductor laser diode according to

[43] , wherein the first electrode is directly formed on the insulating diffraction grating so as to completely cover the insulating diffraction grating.

[45] The method for manufacturing an organic semiconductor laser diode according to

[43] or

[44] , wherein the insulating diffraction grating is directly formed on the substrate.

[46] The method for manufacturing an organic semiconductor laser diode according to any one of

[43] to

[45] , wherein the first electrode and the substrate are transparent.

[47] The method for manufacturing an organic semiconductor laser diode according to any one of

[43] to

[46] , wherein the second electrode is transparent.

[48] The method for manufacturing an organic semiconductor laser diode according to any one of

[43] to

[47] , wherein no diffraction grating is formed on the surface of the first electrode on the organic layer side.

[49] The method for manufacturing an organic semiconductor laser diode according to any one of

[43] to

[48] , wherein the thickness of the first electrode and the thickness of the organic layer are optimized by adjusting the resonance wavelength and increasing the Q value and the confinement factor. An organic semiconductor laser diode fabricated by the method according to any one of

[43] to

[49] of

[50] .

[0060]

[51] An element comprising a substrate and at least two organic semiconductor laser diodes that emit light at different wavelengths, wherein the at least two organic semiconductor laser diodes are monolithically fabricated on the substrate.

[52] The element according to

[51] , comprising at least three organic semiconductor laser diodes that emit light at different wavelengths.

[53] The element according to

[52] , comprising an organic semiconductor laser diode that emits blue light, an organic semiconductor laser diode that emits green light, and an organic semiconductor laser diode that emits red light.

[54] The element according to any one of

[51] to

[53] , wherein the substrate is flexible.

[55] The element according to any one of

[51] to

[54] , wherein the substrate is transparent.

[56] The element according to

[55] , wherein the at least two organic semiconductor laser diodes emit light from the bottom surface.

[57] The element according to

[56] , wherein the at least two organic semiconductor laser diodes include a transparent substrate, a first electrode having transparency, a distributed feedback (DFB) diffraction grating, a hole transport layer, an organic gain layer, an electron transport layer, and a second electrode in this order.

[58] The element according to

[56] , wherein the at least two organic semiconductor laser diodes include a transparent substrate, a distributed feedback (DFB) diffraction grating, a first electrode having transparency, a hole transport layer, an organic gain layer, an electron transport layer, and a second electrode in this order.

[59] The element according to any one of

[51] to

[55] , wherein the at least two organic semiconductor laser diodes emit light from the top surface.

[60] The element according to

[59] , wherein the at least two organic semiconductor laser diodes include a substrate, a first electrode, a distributed feedback (DFB) diffraction grating, an electron transport layer, an organic gain layer, a hole transport layer, and a second electrode having transparency in this order.

[61] The device according to

[59] , wherein the at least two organic semiconductor laser diodes include a substrate, a distributed feedback (DFB) diffraction grating, a first electrode, an electron transport layer, an organic gain layer, a hole transport layer, and a transparent second electrode in this order.

[62] The device according to any one of

[51] to

[61] , wherein one or more of the at least two organic semiconductor laser diodes are the organic semiconductor laser diodes according to any one of

[31] to

[42] and

[50] .

[63] The device according to any one of

[51] to

[61] , wherein all of the at least two organic semiconductor laser diodes are the organic semiconductor laser diodes according to any one of

[31] to

[42] and

[50] .

[0061]

[64] A method for manufacturing a device including a substrate and at least two organic semiconductor laser diodes that emit light at different wavelengths, the method including monolithically fabricating the organic semiconductor laser diodes on the substrate.

[65] The method for manufacturing a device according to

[64] , wherein the device includes at least three organic semiconductor laser diodes that emit light at different wavelengths.

[66] The method for manufacturing a device according to

[65] , wherein the device includes an organic semiconductor laser diode that emits blue light, an organic semiconductor laser diode that emits green light, and an organic semiconductor laser diode that emits red light.

[67] The method for manufacturing a device according to any one of

[64] to

[66] , wherein the substrate is flexible.

[68] The method for manufacturing a device according to any one of

[64] to

[67] , wherein the substrate is transparent.

[69] The fabrication of the at least two organic semiconductor laser diodes includes forming an insulating diffraction grating on or above the substrate, forming a first electrode on or above the insulating diffraction grating, forming an organic layer on or above the first electrode, forming a second electrode on or above the organic layer, The device manufacturing method according to any one of

[64] to

[68] , which is performed by

[70] The device manufacturing method according to

[69] , wherein at least two of the organic semiconductor laser diodes are manufactured by the method according to any one of

[44] to

[49] .

[71] The manufacturing of at least two of the organic semiconductor laser diodes is forming a first electrode on or above the substrate, forming an insulating diffraction grating on or above the first electrode, forming an organic layer on or above the insulating diffraction grating, forming a second electrode on or above the organic layer, The device manufacturing method according to any one of

[64] to

[68] , which is performed by

[72] The device manufacturing method according to any one of

[64] to

[71] , including monolithically manufacturing the organic semiconductor laser diode on the substrate by a solution process.

[73] The device manufacturing method according to any one of

[64] to

[71] , including monolithically manufacturing the organic semiconductor laser diode on the substrate by an inkjet process.

[74] The device manufacturing method according to any one of

[64] to

[71] , including monolithically manufacturing the organic semiconductor laser diode on the substrate by a spin coating process.

[75] The device manufacturing method according to any one of

[64] to

[71] , including monolithically manufacturing the organic semiconductor laser diode on the substrate by a thermal evaporation process.

[0062]

[76] A device comprising a substrate, an organic semiconductor laser diode, and an organic light emitting diode, wherein the organic semiconductor laser diode and the organic light emitting diode are monolithically manufactured on the substrate.

[77] The device according to

[76] , including the above-mentioned substrate, the above-mentioned organic semiconductor laser diode, the above-mentioned organic light-emitting diode, and the optical photodetector, wherein the above-mentioned organic semiconductor laser diode, the above-mentioned organic light-emitting diode, and the above-mentioned optical photodetector are monolithically fabricated on the above-mentioned substrate.

[78] The device according to

[76] , including the above-mentioned substrate, the above-mentioned organic semiconductor laser diode, the above-mentioned organic light-emitting diode, and the organic solar cell, wherein the above-mentioned organic semiconductor laser diode, the above-mentioned organic light-emitting diode, and the above-mentioned organic solar cell are monolithically fabricated on the above-mentioned substrate.

[79] The device according to

[76] , including the above-mentioned substrate, the above-mentioned organic semiconductor laser diode, the above-mentioned organic light-emitting diode, and the organic field-effect transistor, wherein the above-mentioned organic semiconductor laser diode, the above-mentioned organic light-emitting diode, and the above-mentioned organic field-effect transistor are monolithically fabricated on the above-mentioned substrate.

[80] The device according to

[76] , including the above-mentioned substrate, the above-mentioned organic semiconductor laser diode, the above-mentioned organic light-emitting diode, and the organic thermoelectric generator, wherein the above-mentioned organic semiconductor laser diode, the above-mentioned organic light-emitting diode, and the above-mentioned organic thermoelectric generator are monolithically fabricated on the above-mentioned substrate.

[81] The device according to any one of

[76] to

[80] , wherein the above-mentioned substrate has flexibility.

[82] The device according to any one of

[76] to

[80] , wherein the above-mentioned substrate has transparency.

[83] The device according to

[82] , wherein the above-mentioned organic semiconductor laser diode and the above-mentioned organic light-emitting diode emit light from the bottom surface.

[84] The device according to

[83] , wherein the above-mentioned organic semiconductor laser diode includes a transparent substrate, a first electrode having transparency, a distributed feedback (DFB) diffraction grating, a hole transport layer, an organic gain layer, an electron transport layer, and a second electrode in this order.

[85] The device according to

[83] , wherein the above-mentioned organic semiconductor laser diode includes a transparent substrate, a distributed feedback (DFB) diffraction grating, a first electrode having transparency, a hole transport layer, an organic gain layer, an electron transport layer, and a second electrode in this order. The device according to any one of

[77] to

[82] , wherein the organic semiconductor laser diode emits light from the upper surface. The device according to

[86] , wherein the organic semiconductor laser diode includes a substrate, a first electrode, a distributed feedback (DFB) diffraction grating, an electron transport layer, an organic gain layer, a hole transport layer, and a second transparent electrode in this order. The device according to

[86] , wherein the organic semiconductor laser diode includes a substrate, a distributed feedback (DFB) diffraction grating, a first electrode, an electron transport layer, an organic gain layer, a hole transport layer, and a second transparent electrode in this order. The device according to any one of

[77] to

[88] , wherein the organic semiconductor laser diode is the organic semiconductor laser diode according to any one of

[31] to

[42] and

[50] .

[0063] A method for manufacturing a device including a substrate, an organic semiconductor laser diode, and an organic light-emitting diode, the method including monolithically fabricating the organic semiconductor laser diode and the organic light-emitting diode on the substrate. The device manufacturing method according to

[90] , including monolithically fabricating the organic semiconductor laser diode, the organic light-emitting diode, and an organic photodetector on the substrate. The device manufacturing method according to

[90] or

[91] , including monolithically fabricating the organic semiconductor laser diode, the organic light-emitting diode, and an organic solar cell on the substrate. The device manufacturing method according to any one of

[90] to

[92] , including monolithically fabricating the organic semiconductor laser diode, the organic light-emitting diode, and an organic field-effect transistor on the substrate. The device manufacturing method according to any one of

[90] to

[93] , including monolithically fabricating the organic semiconductor laser diode, the organic light-emitting diode, and an organic thermoelectric generator on the substrate. The device manufacturing method according to any one of

[90] to

[94] , wherein the substrate has flexibility. The device manufacturing method according to any one of

[90] to

[95] , wherein the substrate has transparency.

[97] The fabrication of the organic semiconductor laser diode is forming an insulating diffraction grating on or above the substrate; forming a first electrode on or above the insulating diffraction grating; forming an organic layer on or above the first electrode; forming a second electrode on or above the organic layer; The device manufacturing method according to any one of

[90] to

[96] , which is performed by

[98] The device manufacturing method according to

[97] , wherein the organic semiconductor laser diode is fabricated by the method according to any one of

[44] to

[49] .

[99] The fabrication of the organic semiconductor laser diode is forming a first electrode on or above the substrate; forming an insulating diffraction grating on or above the first electrode; forming an organic layer on or above the insulating diffraction grating; forming a second electrode on or above the organic layer; The device manufacturing method according to any one of

[90] to

[96] , which is performed by

[0100] The device manufacturing method according to any one of

[90] to

[99] , wherein the above fabrication is performed monolithically by a solution process.

[0101] The device manufacturing method according to any one of

[90] to

[99] , wherein the above fabrication is performed monolithically by an inkjet process.

[0102] The device manufacturing method according to any one of

[90] to

[99] , wherein the above fabrication is performed monolithically by a spin coating process.

[0103] The device manufacturing method according to any one of

[90] to

[99] , wherein the above fabrication is performed monolithically by a thermal evaporation process.

Claims

1. An element comprising a substrate and at least two different optoelectronic devices, wherein the at least two different optoelectronic devices are monolithically fabricated on the substrate, and the element satisfies at least one of the following (1) and (2). (1) The at least two different optoelectronic devices have different diffraction gratings and organic gain materials from each other. (2) The at least two different optoelectronic devices include an organic solid-state laser diode, and the organic solid-state laser diode includes an insulating diffraction grating, a first electrode, an organic layer, and a second electrode on the substrate in this order.

2. The element according to claim 1, wherein the at least two different optoelectronic devices are three different optoelectronic devices.

3. The element according to claim 2, wherein the three different optoelectronic devices are a red light-emitting optoelectronic device, a green light-emitting optoelectronic device, and a blue light-emitting optoelectronic device, respectively.

4. The element according to claim 1, which satisfies (1), and the at least two different optoelectronic devices are at least two optically pumped organic solid-state lasers that emit light at different wavelengths.

5. The element according to claim 1, wherein the at least two different optoelectronic devices are at least two organic semiconductor laser diodes that emit light at different wavelengths.

6. The element according to claim 1, wherein the at least two different optoelectronic devices are an organic solid-state laser and an organic light-emitting diode.

7. The element according to claim 1, which satisfies (2).

8. The element according to claim 7, wherein the element emits light from the bottom surface.

9. The element according to claim 7, wherein the element emits light from the top surface.

10. An organic semiconductor laser diode including a substrate, an insulating diffraction grating, a first electrode, an organic layer, and a second electrode in this order.

11. A method for manufacturing an element comprising a substrate and at least two different optoelectronic devices, the method including monolithically fabricating the at least two different optoelectronic devices on the substrate, and satisfying at least one of the following (1) and (2). (1) The at least two different optoelectronic devices have different diffraction gratings and organic gain materials from each other. (2) The at least two different optoelectronic devices include an organic solid-state laser diode, and the organic solid-state laser diode includes a dielectric diffraction grating, a first electrode, an organic layer, and a second electrode on the substrate in this order.

12. The method according to claim 11, wherein the at least two different optoelectronic devices are three different optoelectronic devices.

13. The method according to claim 12, wherein the three different optoelectronic devices are a red light-emitting optoelectronic device, a green light-emitting optoelectronic device, and a blue light-emitting optoelectronic device, respectively.

14. The method satisfying (2), the method including forming a dielectric diffraction grating on the substrate and then forming an organic layer for the at least two different optoelectronic devices, according to claim 11.

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