Organic light-emitting diode

The present invention relates to a light-emitting diode, and specifically to an organic light-emitting diode.

A conventional organic light-emitting diode (OLED) is formed of several stacked nano-size layers including an anode, a hole transport layer (HTL), a luminescent layer, an electron transport layer (ETL) and a cathode in spatial order. When a voltage is applied to an OLED, a current of holes flows from the anode to the highest occupied molecular orbitals (HOMO) of the HTL, thus generating positive polarons, and at the same time a current of electrons flows from the cathode to the lowest unoccupied molecular orbitals (LUMO) of the ETL, thus generating negative polarons. The positive polarons and the negative polarons recombine in the luminescent layer, thereby generating singlet excitons and triplet excitons. Thereafter, the singlet excitons return to the ground state, upon which light is emitted.

In the evolution of OLEDs, extending the lifetime of blue OLEDs has been a key issue, the reason being that the energy of blue photons is relatively high, which results in the property of rapid degradation. To be specific, active exciton-polaron annihilation exists in blue OLEDs since excitons possess long lifespan and thus tend to react with excitons and form high energy polarons that break molecular bonds in the luminescent material and consequently reduce the lifetime of blue OLEDs.

In addition, light is emitted when singlet excitons return to the ground state, while triplet excitons in fluorescent materials cannot return to the ground state with photon emission. That is to say, a considerable amount of energy is wasted taking into consideration of the fact that triplet excitons account for 75 percent of excited excitons as a result of the recombination between the positive polarons and the negative polarons.

Therefore, in light of the above-mentioned drawbacks, OLEDs of the prior art still have room for improvement.

One of the objectives of the present invention is to provide an organic light-emitting diode which emits light utilizing the triplet energy thereof, thereby extending the lifetime of the organic light-emitting diode.

One embodiment of the present embodiment provides an organic light emitting diode including an anode, a cathode and a luminescent layered structure. The luminescent layered structure is disposed between the anode and the cathode. The luminescent layered structure has a luminescent layer and a sensitizer layer. The luminescent layer has a luminescent-layer ground state, a luminescent-layer singlet state and a luminescent-layer triplet state, in which two times of the luminescent-layer triplet state is higher than the luminescent-layer singlet state. The sensitizer layer has a sensitizer-layer triplet state, which is between the luminescent-layer singlet state and the luminescent-layer triplet state. The molecules of the sensitizer layer at the sensitizer layer triplet state transfer energy to the molecules of the luminescent layer at the luminescent-layer triplet state and triggers triplet-triplet annihilation upconversion in the luminescent layer such that the luminescent layer emits light of a first color.

To further understand the features and technical content of the present invention, please refer to the following detailed descriptions and drawings related to the present invention. However, the provided drawings are used only for providing reference and descriptions, and are not intended to limit the present invention.

FIG. 1 is a schematic view illustrating an organic light-emitting diode according to a first embodiment of the present invention.

FIG. 2 illustrates a variant embodiment of the organic light-emitting diode according to the first embodiment of the present invention.

FIG. 3 illustrates another variant embodiment of the organic light-emitting diode according to the first embodiment of the present invention.

FIG. 4 is an energy level diagram of the luminescent layered structure of a first experimental example according to the first embodiment of the present invention.

FIG. 5 is a diagram illustrating the transient electroluminescence of the first experimental example according to the first embodiment of the present invention.

FIG. 6 illustrates the transient electroluminescence of the luminescent layer of the first experimental example according to the first embodiment of the present invention.

FIG. 7 is a diagram illustrating the external quantum efficiency of the first experimental example according to the first embodiment and those of comparative examples.

FIG. 8 illustrates an energy level diagram of the luminescent layered structure of a second experimental example according to the first embodiment of the present invention.

FIG. 9 illustrates the transient electroluminescence of the luminescent layer of the second experimental example according to the first embodiment of the present invention.

FIG. 10 is a diagram illustrating the external quantum efficiency of the second experimental example according to the first embodiment and those of the comparative examples.

FIG. 11A is a schematic view of the organic light-emitting diode according to the second embodiment of the present invention.

FIG. 11B illustrates an energy level diagram of the luminescent layered structure according to the second embodiment of the present invention.

FIG. 12 is a diagram illustrating the external quantum efficiency of a first experimental example, a second experimental example and a third experimental example according to the second embodiment of the present invention.

Embodiments of the present invention are described below with reference to FIG. 1 to FIG. 12 . A person skilled in the art can understand the advantages and effects of the present invention from the description disclosed below. However, the content disclosed below is not intended to limit the protection scope of the present invention. The present invention can be implemented by a person skilled in the art based on different perspectives and applications without departing from the concept and spirit of the present invention. In addition, it should be stated in advance that the accompanying drawings of the present invention are merely used for illustration, and are not drawn according to actual dimensions for sake of clear illustration. Moreover, the same reference number corresponds to the same component. It should also be understood that expressions such as one component is “connected to” or “disposed on” another may mean that the former is either directly or indirectly connected to or disposed on the latter, wherein “connected” may refer to either physical or electrical connection.

First Embodiment

The organic light-emitting diode Z according to the first embodiment of the present invention is described between with reference to FIG. 1 to FIG. 7 . First of all, referring to FIG. 1 , the organic light-emitting diode Z provided by the first embodiment of the present invention includes an anode 1 , a cathode 2 , a luminescent layered structure 3 , a hole transport layer 4 and an electron transport layer 5 . The hole transport layer 4 is disposed between the anode 1 and the luminescent layered structure 3 , and the electron transport layer 5 is disposed between the cathode 2 and the luminescent layered structure 3 .

As shown in FIG. 1 , the luminescent layered structure 3 has a luminescent layer 31 and a sensitizer layer 32 . The luminescent layer 31 includes a luminescent-layer ground state, a luminescent-layer singlet state and a luminescent-layer triplet state. Specifically, in the present embodiment, the luminescent layer 31 is a TTA material layer, that is to say, two times of the luminescent-layer triplet state is higher than the luminescent-layer singlet state. More specifically, the luminescent layer 31 is preferably made of an anthracene derivative, a pyrene derivative or a perylene derivative; however, the present invention is not limited thereto. The anthracene derivative may be but not limited to 9,10-Di(2-naphthyl)anthracene (ADN), 2-methyl-9,1-D(2-naphthyl)anthracene, 2-tert-butyl-9,10-Di(2-naphthyl)anthracene, or 9,9′-dianthracene.

In the embodiment shown in FIG. 1 , the sensitizer layer 32 is disposed between the luminescent layer 31 and the hole transport layer 4 . However, the present invention is not limited thereto. In other embodiments, the position of the luminescent layer 31 and that of the sensitizer layer 32 are interchangeable. That is to say, in other embodiments, the sensitizer layer 32 can be disposed between the luminescent layer 31 and the electron transport layer 5 . The sensitizer layer 32 has a sensitizer-layer triplet state, which is between the luminescent-layer singlet state and the luminescent-layer triplet state. In the present embodiment, the material of the sensitizer layer 32 is preferably a (8-hydroxyquinoline) metal complex or a 10-hydroxybenzo [h]quinoline-metal complex. More specifically, examples of the (8-hydroxyquinoline) metal complex may include but not limited to tris(8-hydroxyquinoline)-aluminium (Alq 3 ) and tris-(8-hydroxyquinoline)gallium (Gaq 3 ), and examples of 10-hydroxybenzo [h]quinoline-metal complex may include but not limited to bis(10-hydroxybenzo[h]quinolinato)beryllium.

In a variant embodiment of the present embodiment, the sensitizer layer 32 can transport electron holes and acts as a hole transport layer disposed between the luminescent layer 31 and the anode 1 , as shown in FIG. 2 . In another variant embodiment, the sensitizer layer 32 can transport electrons and serve as an electron transport layer disposed between the luminescent layer 31 and the cathode 2 , as shown in FIG. 3 . Furthermore, in other embodiments, the sensitizer layer 32 can be added to the luminescent layer 31 as a dopant. It should be noted that the present invention is not limited to any of the above examples.

The light emitting mechanism of the organic light-emitting diode of a first experimental example according to the present embodiment is described below with reference to FIG. 4 , which shows an energy level diagram of the luminescent layered structure 3 of the first experimental example. In FIG. 4 , the luminescent-layer singlet state S 1 , the sensitizer-layer triplet state T 1 and the sensitizer-layer ground state G 1 of sensitizer layer 32 and the luminescent-layer singlet state S 2 , the luminescent-layer triplet state T 2 , and the luminescent-layer ground state G 2 of the luminescent layer 31 are shown. As shown in FIG. 4 , the triplet state T 1 of the sensitizer layer 32 is between the luminescent-layer singlet state S 2 and the luminescent-layer triplet state T 2 . To be specific, the material of the luminescent layer 31 of the first experimental example is ADN, and that of the sensitizer layer 32 is Alq 3 , in which the energy level of the luminescent layered structure 3 is shown in Table 1 below.

In the present embodiment, through the technical solution that the sensitizer layer 32 is disposed next to the luminescent layer 31 such that triplet-triplet energy transfer mechanism (TTET) between the sensitizer layer 32 and the luminescent layer 31 can occur, i.e. the molecules of the sensitizer layer 32 at the sensitizer-layer triplet state T 1 transfer energy to the molecules of the luminescent layer 31 at the luminescent-layer triplet state T 2 in a manner such that triplet-triplet annihilation upconversion mechanism (TTAUC) is triggered in the luminescent layer 31 thereafter.

Specifically, the aforementioned TTAUC mechanism occurs among excited triplet state molecules, wherein one excited triplet state molecule transfers energy to another excited triplet state molecule and returns to the ground state, and the excited triplet state molecule that receives the energy is raised to the singlet state. Next, molecules of the luminescent layer 31 that arc raised to the singlet state return to the luminescent-layer ground state G 2 , thereby emitting light of a first color L 1 .

Referring to FIG. 4 , in the present embodiment, molecules of the sensitizer layer 32 at the sensitizer-layer singlet state S 1 emit light of a second color L 2 when returning to the sensitizer-layer ground state G 1 . Furthermore, in the present embodiment, white light can be generated by mixing the first color light L 1 , the second color light L 2 , and light of a third color. For example, when using Alq 3 as the sensitizer layer 32 and ADN as the luminescent layer 31 , then with an added light-emitting material that emits red light, a white light can be obtained by mixing the blue light emitted by ADN, the green light emitted by Alq 3 and the red light. However, the present invention is not limited thereto. For instance, in other embodiments, the material of the luminescent layer 31 and that of the sensitizer layer 32 are selected based on a predetermined color of light emitted by the organic light-emitting diode Z, thereby generating light of the predetermined color by mixing the first color light L 1 and the second color light L 2 .

Please refer to FIG. 5 and FIG. 6 , wherein FIG. 5 shows a diagram illustrating the electroluminescent property of the first experimental example according to the present embodiment, and FIG. 6 shows a diagram illustrating the transient electroluminescence of the luminescent layer of the first experimental example according to the present embodiment. Specifically, in the first experimental example, indium tin oxide (ITO) is used as the anode 1 , and LiF/Al is used as the cathode 2 . The thickness of the hole transport layer 4 is 50 nm, and the material thereof is N,N′-di(1-naphthyl)-N,N′-diphenyl benzidine (NPB). The thickness of the electron transport layer 5 is 65 nm, and the material thereof is 4,7-diphenyl-1,10-phenanthroline (Bphen). The thickness of the sensitizer layer 32 is 5 nm, and the material thereof is Alq 3 . The thickness of the luminescent layer 31 is 10 nm, and the material thereof is ADN. It should be noted that the above description regarding the materials used and the specifications thereof are the exemplary embodiment of the present invention; the present invention is not limited thereto.

In the experimental example shown in FIG. 5 and FIG. 6 , the transient electroluminescence of the organic light-emitting diode Z is measured by first applying an electro-pulse to the organic light-emitting diode Z, and the light emitted by the organic light-emitting diode Z in response to the electro-pulse is gauged and converted into electric output with a photomultiplier. The curves shown in FIG. 5 respectively represent the electric signals outputted by the organic light-emitting diode Z in response to an input voltage of 5 V, 4.6 V, 4.2 V, 3.8 V and 3.4 V. As shown in FIG. 5 , when each applied voltage is turned off at 0 second, the speed at which the organic light-emitting diode Z of the first experimental example emits light is of microsecond-scale. In general, the speed at which singlet excitons emit light is of nanosecond-scale, and that of triplet excitons is of microsecond-scale since triplet excitons decay slower owing to the spin conservation. That is to say, FIG. 5 shows that in the first experimental example the triplet excitons contribute to a larger percentage of total emission than organic light-emitting diodes in the prior art. The curves shown in FIG. 6 respectively represent the electric signals outputted by the luminescent layer 31 corresponding to an input electro-pulse of 5 V, 4.6 V, 4.2 V, 3.8 V and 3.4 V. It can be seen from FIG. 6 that in the first experimental example of the present embodiment, the first color light L 1 emitted by the luminescent layer 31 (ADN) is mainly from the triplet excitons thereof.

FIG. 7 illustrates the external quantum efficiency of the first experimental example (shown with the curve marked as Alq 3 /ADN) according to the present embodiment and those of a first comparative example (shown with the curve marked as ADN) and a second comparative example (shown with the curve marked as Alq 3 ). The difference between the first experimental example and the first and second comparative examples lies in that the first experimental example has a sensitizer layer and a luminescent layer, whereas the first comparative example has only ADN as the luminescent layer and does not have a sensitizer layer; the second comparative example has only Alq 3 as the luminescent layer and does not have a sensitizer layer. As shown in FIG. 7 , the first experimental example exhibits higher external quantum efficiency than the first comparative example and the second comparative example do within most part of the operational current density. As stated in the background of the invention, 75% of recombined positive polarons and negative polarons transform into triplet excitons, which means the waste in energy in the prior art. In the present embodiment, by adding the sensitizer layer 32 in the organic light-emitting diode Z and adjusting the thicknesses of the hole transport layer 4 and the electron transport layer 5 , the negative polarons and the positive polarons recombine in the sensitizer layer 32 instead of the luminescent layer 31 so that singlet excitons and triplet excitons can be generated in the sensitizer layer 32 , which triggers triplet-triplet energy transfer mechanism (TTET) between the luminescent layer 31 and the sensitizer layer 32 and then triplet-triplet annihilation upconversion mechanism (TTAUC) in the luminescent layer 31 thereafter. In this way, most of the triplet energy in the sensitizer layer 32 and the triplet energy in the luminescent layer 31 are converted to light emitted by the organic light-emitting diode Z, thereby increasing the external quantum efficiency of the organic light-emitting diode Z.

The second experimental example of the organic light-emitting diode Z of the present embodiment is described below with reference to FIG. 8 to FIG. 10 . The second experimental example has a structure that is similar to that of the first experimental example with the main difference being that the material of the sensitizer layer 32 of the second experimental example is 1-(2, 5-dimethyl-4-(1-pyrenyl)phenyl)pyrene (DMPPP). FIG. 8 shows the energy level diagram of the luminescent layered structure 3 of the second experimental example. As shown in the figure, the sensitizer-layer triplet state T 3 of the sensitizer layer 32 (DMPPP) is higher than the luminescent-layer triplet state T 2 of the luminescent layer 31 , and the sensitizer-layer singlet state S 3 of the sensitizer layer 32 is higher than the luminescent-layer singlet state S 2 of the luminescent layer 31 . More specifically, the energy level of the luminescent layered structure 3 is shown in Table 2 below.

Please refer to FIG. 9 . FIG. 9 illustrates the transient electroluminescence of the luminescent layer of the first experimental example according to the present embodiment. The curves shown in FIG. 9 respectively represent the electric signals outputted by the luminescent layer 31 (ADN) in response to an input voltage of 5.5 V-6 V, 5.5 V, 5.0 V, 4.5 V, and 4.0 V. As shown in FIG. 9 , when each applied voltage is turned off at 0 second, the speed at which the organic light-emitting diode Z of the second experimental example emits light is of microsecond-scale, which indicates that a larger percentage of the total emission of the second experimental example is converted from the triplet energy as compared to a conventional organic light-emitting diode.

FIG. 10 illustrates the external quantum efficiency of the second experimental example (shown with the curve marked as DMPPP/ADN) according to the present embodiment and those of a third comparative example (shown with the curve marked as ADN) and a fourth comparative example (shown with the curve marked as DMPPP). The difference between the second experimental example and the third and fourth comparative examples lies in that the second experimental example has a sensitizer layer 32 and a luminescent layer 31 , whereas the third comparative example has only ADN has only the luminescent layer and does not have a sensitizer layer; the fourth comparative example has only DMPPP as the luminescent layer and does not have a sensitizer layer either. As shown in FIG. 10 , the second experimental example, which includes DMPPP as the sensitizer layer 32 and ADN as the luminescent layer 31 , exhibits higher external quantum efficiency than the third comparative example and the fourth comparative example.

It should be noted that the relative difference between the sensitizer-layer singlet state and the luminescent-layer singlet state is not limited in the present invention. A person skilled in the art can select the material of the sensitizer layer and that of the luminescent layer according to actual needs. For instance, when in a condition that ADN which emits blue light has been determined to be the material of the luminescent layer 31 , the material of the sensitizer layer 32 can be decided based on the predetermined light color of the organic light-emitting diode Z. Specifically, when in one embodiment the predetermined light color is white, a material that has a singlet state lower than the luminescent-layer singlet state S 2 can be selected as the material of the sensitizer layer 32 , as in the case of the first experimental example, so that the second color light L 2 is green. In this way, with a doped red light-emitting material the organic light-emitting diode Z can emit white light. When in another embodiment the predetermined light color of the organic light-emitting diode Z is blue, then a material that has a singlet state higher than the luminescent-layer singlet state S 2 can be chosen to be the material of the sensitizer layer 32 , as in the case of the second experimental example, so that the second color light L 2 and the first light color L 1 are both blue light.

In summary, the first embodiment of the present invention uses mainly the triplet energy thereof to emit light utilizing the technical solution of the sensitizer layer 32 , which serves as the place the recombination between the positive polarons and the negative polarons takes place such that triplet-triplet annihilation upconversion mechanism can be triggered in the luminescent layer 31 by the triplet excitons in the sensitizer layer 32 generated from the recombination. Since the sensitizer layer 32 acts as the recombination zone in the present embodiment, high energy polarons are prevented from reacting with the excitons in the luminescent layer 31 . Therefore, the triplet energy in the sensitizer layer 32 can be utilized to emit light by being transferred to the luminescent layer 31 and converted through TTAUC mechanism, thereby enhancing the illumination efficiency of the organic light-emitting diode Z and extending the lifetime thereof.

Second Embodiment

Referring to FIG. 11A , the main difference between the present embodiment and the first embodiment lies in that the organic light-emitting diode Z of the second embodiment further includes a blocking layer 33 between the luminescent layer 31 and the sensitizer layer 32 . With reference to FIG. 11B , the blocking layer 33 has a blocking-layer singlet state S 4 and a blocking-layer triplet state T 4 , in which the blocking-layer singlet state S 4 is higher than the luminescent-layer singlet state S 2 , and the blocking-layer triplet state T 4 is higher than the luminescent-layer triplet state T 2 .

With the blocking layer 33 , the triplet energy of the sensitizer layer 32 can be transferred to the triplet state of the luminescent layer 31 . At the same time, the quenching effects between the sensitizer layer 32 and the luminescent layer 31 can be reduced. In this way, the illumination efficiency of the organic light-emitting diode Z can be further improved.

Furthermore, the material of the blocking layer 33 can be 1-(2, 5-dimethyl-4-(1-pyrenyl)phenyl)pyrene (DMPPP) or 1,3,5-Tri(1-pyrenyl)benzene (TPB3). However, the present invention is not limited thereto. Specifically, the blocking layer 33 of the present embodiment is DMPPP, whose energy level is shown in Table 3 below.

Please refer to FIG. 12 , which shows a diagram illustrating the external quantum efficiency of a first experimental example, a second experimental example and a third experimental example according to the second embodiment of the present invention. The first experimental example of the present embodiment uses ADN as the luminescent layer, Alq 3 as the sensitizer layer, and the first experimental example has no blocking layer. The second experimental example is shown with a curve marked as 5 nm in FIG. 12 . The difference between the first experimental example and the second experimental example is that the second experimental example has a blocking layer 33 with a thickness of 5 nm between the luminescent layer 31 and the sensitizer layer 32 . The material of the blocking layer 33 is DMPPP. The third experimental example is shown with a curve marked as 10 nm in FIG. 12 . The difference between the first experimental example and the third experimental example is that the third experimental example has a blocking layer 33 with a thickness of 10 nm between the luminescent layer 31 and the sensitizer layer 32 . The material of the blocking layer 33 of the third experimental example is DMPPP. As shown in FIG. 12 , the third experimental example exhibits higher external quantum efficiency than the second experimental example, which in turn offers higher external quantum efficiency than the first experimental example. Therefore, the present embodiment shows that adding a blocking layer 33 to the organic light-emitting diode Z (as in the second experimental example and third experimental example of the present embodiment compared to the first experimental example) can effectively enhance the efficiency of the organic light-emitting diode Z.

In summary, the embodiments of the present invention achieves “the molecules of the sensitizer layer at the sensitizer-layer triplet state transfer energy to the molecules of the luminescent layer at the luminescent-layer triplet state and triggers triplet-triplet annihilation upconversion in the luminescent layer such that the luminescent layer emits light of a first color” through the technical solutions that “two times of the luminescent-layer triplet state is higher than the luminescent-layer singlet state” and “the sensitizer-layer triplet state is between the luminescent-layer singlet state and the luminescent-layer triplet state”.

Through the aforementioned technical solutions, the organic light-emitting diode Z of the present embodiments utilizes the sensitizer layer 32 to perform triplet-triplet energy transfer between the sensitizer layer 32 and the luminescent layer 31 , thereby triggering triplet-triplet annihilation upconversion mechanism in the luminescent layer 31 . In this way, triplet energy of the luminescent layer 31 and that of the sensitizer layer 32 can be converted into light emitted by the organic light-emitting diode Z, thereby effectively enhancing the illumination efficiency and the lifespan of the organic light-emitting diode Z.

In addition, in some embodiments, a blocking layer can be added to the organic light-emitting diode Z, in which the singlet state of the blocking layer is higher than the singlet state of the luminescent layer, and the triplet state of the blocking layer is higher than the triplet state of the luminescent layer. In this way, the illumination efficiency of the organic light-emitting diode can be further increased.

The present invention has been described with reference to the above embodiments, but the above embodiments are merely examples for implementing the present invention. It should be noted that the disclosed embodiments are not intended to limit the scope of the present invention. On the contrary, any modification and equivalent configuration within the spirit and scope of the appended claims shall fall within the scope of the present invention.