Patent Application
20230089691
The present invention relates to a method for manufacturing a light-emitting device.
PTL 1 discloses a semiconductor nanoparticle (quantum dot) having a core/shell structure and a ligand that coordinates with the semiconductor nanoparticle.
An improvement in luminous efficiency is desired in a light-emitting device including a quantum dot layer.
In order to solve the problem described above, a method for manufacturing a light-emitting device according to the present invention is a method for manufacturing a light-emitting device including, on a substrate, a light-emitting element including a first electrode, a second electrode, and a quantum dot layer between the first electrode and the second electrode, and the method includes the forming the quantum dot layer, wherein the forming the quantum dot layer includes performing first application of applying, on a position overlapping with the substrate, a first solution including a plurality of quantum dots, a ligand, a first inorganic precursor, and a first solvent, the plurality of quantum dots each including a core and a first shell coating the core, the ligand coordinating with each of the plurality of quantum dots, performing temperature raising of raising a temperature until the ligand melts and the first solvent vaporizes after the performing first application, performing first temperature lowering of lowering a temperature to a melting point of the ligand or lower after the performing temperature raising, and performing first light irradiation of epitaxially growing the first inorganic precursor around the first shell by first light irradiation after the performing first temperature lowering to form a second shell coating the first shell, and the ligand is present around the second shell after the first light irradiation.
According to the configurations described above, luminous efficiency may be further improved in a light-emitting device provided with quantum dots.
As illustrated in
At a position overlapping with the light-emitting face DS in plan view, as illustrated in
The light-emitting element layer 2 includes, on a first electrode 4, a first charge transport layer 6, a light-emitting layer 8 as a quantum dot layer, a second charge transport layer 10, and a second electrode 12, which are sequentially layered from the lower layer. The first electrode 4 of the light-emitting element layer 2 formed in the upper layer of the array substrate 3 is electrically connected to the TFT of the array substrate 3. In the present embodiment, the first electrode 4 is an anode electrode and the second electrode 12 is a cathode electrode, for example.
In the present embodiment, the light-emitting element layer 2 includes a first light-emitting element 2R, a second light-emitting element 2G, and a third light-emitting element 2B. The first light-emitting element 2R, the second light-emitting element 2G, and the third light-emitting element 2B are quantum-dot light emitting diode (QLED) elements in which the light-emitting layer 8 includes a semiconductor nanoparticle material, that is, a quantum dot material, and the quantum dot material is caused to emit light in the light-emitting layer 8.
Each of the first electrode 4, the first charge transport layer 6, and the light-emitting layer 8 is separated by edge covers 14. In particular, in the present embodiment, the first electrode 4 is, by the edge covers 14, separated into a first electrode 4R for the first light-emitting element 2R, a first electrode 4G for the second light-emitting element 2G, and a first electrode 4B for the third light-emitting element 2B. The first charge transport layer 6 is, by the edge covers 14, separated into a first charge transport layer 6R for the first light-emitting element 2R, a first charge transport layer 6G for the second light-emitting element 2G, and a first charge transport layer 6B for the third light-emitting element 2B. Further, the light-emitting layer 8 is, by the edge covers 14, separated into a first light-emitting layer 8R, the second light-emitting layer 8G, and a third light-emitting layer 8B.
The second charge transport layer 10 and the second electrode 12 are not separated by the edge covers 14, and are each formed in a shared manner. As illustrated in
In the present embodiment, the first light-emitting element 2R includes the first electrode 4R, the first charge transport layer 6R, the first light-emitting layer 8R, the second charge transport layer 10, and the second electrode 12. The second light-emitting element 2G includes the first electrode 4G, the first charge transport layer 6G, the second light-emitting layer 8G, the second charge transport layer 10, and the second electrode 12. Furthermore, the third light-emitting element 2B includes the first electrode 4B, the first charge transport layer 6B, the third light-emitting layer 8B, the second charge transport layer 10, and the second electrode 12.
In the present embodiment, the first light-emitting layer 8R, the second light-emitting layer 8G, and the third light-emitting layer 8B emit red light that is light of a first color, green light that is light of a second color, and blue light that is light of a third color, respectively. In other words, the first light-emitting element 2R, the second light-emitting element 2G, and the third light-emitting element 2B are light-emitting elements that emit the red light, the green light, and the blue light, respectively, which are different colors from each other.
Here, the blue light refers to, for example, light having a light emission central wavelength in a wavelength band of equal to or greater than 400 nm and equal to or less than 500 nm. The green light refers to, for example, light having a light emission central wavelength in a wavelength band of greater than 500 nm and equal to or less than 600 nm. The red light refers to, for example, light having a light emission central wavelength in a wavelength band of greater than 600 nm and equal to or less than 780 nm.
The first electrode 4 and the second electrode 12 include conductive materials and are electrically connected to the first charge transport layer 6 and the second charge transport layer 10, respectively. Of the first electrode 4 and the second electrode 12, the electrode closer to the light-emitting face DS is a transparent electrode.
In particular, in the present embodiment, the array substrate 3 is a transparent substrate, and the first electrode 4 is a transparent electrode. The second electrode 12 may be a reflective electrode. Therefore, light from the light-emitting layer 8 passes through the first charge transport layer 6, the first electrode 4, and the array substrate 3, and is emitted from the light-emitting face DS to the outside of the light-emitting device 1. Due to this, the light-emitting device 1 is configured as a bottom-emitting type light-emitting device. Since both the light emitted in the upward direction from the light-emitting layer 8 and the light emitted in the downward direction from the light-emitting layer 8 are available as light emission from the light-emitting device 1, the light-emitting device 1 can improve the usage efficiency of the light emitted from the light-emitting layer 8.
Note that the configuration of the first electrode 4 and the second electrode 12 described above is an example, and may be configured with other materials.
The first charge transport layer 6 is a layer that transports charges from the first electrode 4 to the light-emitting layer 8. The first charge transport layer 6 may have a function of inhibiting the transport of charges from the second electrode 12. In the present embodiment, the first charge transport layer 6 may be a hole transport layer that transports positive holes from the first electrode 4, which is an anode electrode, to the light-emitting layer 8.
The second charge transport layer 10 is a layer that transports the charge from the second electrode 12 to the light-emitting layer 8. The second charge transport layer 10 may have a function of inhibiting the transport of the charges from the first electrode 4. In the present embodiment, the second charge transport layer 10 may be an electron transport layer that transports electrons from the second electrode 12, which is a cathode electrode, to the light-emitting layer 8.
Next, the configuration of the light-emitting layer 8 will be described in detail with reference to
In the present embodiment, the light-emitting layer 8 includes a first quantum dot 16, a second quantum dot 17, and a ligand 18. The first quantum dot 16 includes a quantum dot 20. The quantum dot 20 has a core/shell structure including a core 22 and a first shell 24, with which the periphery of the core 22 is coated. The first quantum dot 16 includes a second shell 26. The second shell 26 coats a periphery of the first shell 24 that is an outer shell of each quantum dot 20.
The quantum dot 20 may have a multi-shell structure in which a plurality of shells are provided around the core 22. In this case, the first shell 24 refers to a shell corresponding to the outermost layer among the plurality of shells.
The ligand 18 coordinates with the first quantum dot 16 on an outer surface of the second shell 26. Further, the ligand 18 also coordinates with the second quantum dot 17 on an outer surface of the second quantum dot 17. The ligand 18 may be, for example, trioctylphosphine oxide (TOPO).
As illustrated in
The core 22 and first shell 24 of the quantum dot 20 may include an inorganic material used for the quantum dots of a known core/shell structure. In other words, the first light-emitting layer 8R, the second light-emitting layer 8G, and the third light-emitting layer 8B may include known quantum dot materials used for light-emitting layers of red, green, and blue QLED elements, respectively.
In addition, similar to the first shell 24, the second shell 26 may include an inorganic shell material used for the quantum dots of a known core/shell structure. The first shell 24 and the second shell 26 may be made of the same material. Note that a specific resistance of the second shell 26 is preferably equal to or greater than a specific resistance of the first shell 24. Further, the size of a band gap of the second shell 26 is preferably greater than the size of a band gap of the first shell 24. With this configuration, the efficiency of charge injection from the second shell 26 to the first shell 24 is improved.
Examples of specific materials for the core 22 include group II-VI semiconductors such as CdSe (band gap 1.73 eV), CdTe (band gap 1.44 eV), ZnTe (band gap 2.25 eV), and CdS (band gap 2.42 eV). Examples of other specific materials for the core 22 include the group III-V such as InP (band gap 1.35 eV) and InGaP (band gap 1.88 eV).
In general, the wavelength emitted by the quantum dot is determined by the particle diameter of the core. Therefore, it is preferable to employ a semiconductor material having an appropriate band gap as a material of the core 22 in order to control the light emitted from the core 22 to be any of red, green, and blue colors, by controlling the particle diameter of the core 22.
The band gap of the material of the core 22 included in the first light-emitting layer 8R is preferably equal to or lower than 1.97 eV in order for the first light-emitting layer 8R serving as a red light-emitting layer to emit red light having a wavelength of 630 nm. In order for the second light-emitting layer 8G serving as a green light-emitting layer to emit green light having a wavelength of 532 nm, the band gap of the material of the core 22 included in the second light-emitting layer 8G is preferably equal to or lower than 2.33 eV. Furthermore, in order for the third light-emitting layer 8B serving as a blue light-emitting layer to emit blue light having a wavelength of 630 nm, the band gap of the material of the core 22 included in the third light-emitting layer 8B is preferably equal to or lower than 2.66 eV. The light-emitting device 1 provided with the first light-emitting layer 8R, the second light-emitting layer 8G, and the third light-emitting layer 8B is preferable from the perspective of satisfying the color space criteria in the International Standard BT 2020 of UHDTV.
Examples of specific materials for the first shell 24 and the second shell 26 include the group II-VI such as ZnSe (band gap 2.7 eV) and ZnS (band gap 3.6 eV), and the group III-V such as GaP (band gap 2.26 eV).
The material of the core 22 preferably has low specific resistance and a less band gap compared to the material of the first shell 24 and the second shell 26. With this configuration, the efficiency of charge injection from the first shell 24 and second shell 26 to the core 22 is improved.
Note that, in the present embodiment, an average film thickness of the first shell 24 from the outer surface of the core 22 is less than a minimum film thickness of the second shell 26. Here, the minimum film thickness of the second shell 26 refers to a film thickness of the second shell 26 between two quantum dots 20 connected to each other via the second shell 26, or the least film thickness of a film thickness from the first shell 24 to the outer surface of the second shell 26.
Here, the shortest distance from the core 22 of one quantum dot 20 to the core 22 of another quantum dot 20 adjacent thereto is preferably equal to or greater than 3 nm when the core 22 is made of InP, and the first shell 24 and second shell 26 are made of ZnS, for example. For example, when the core 22 is made of CdSe, and the first shell 24 and second shell 26 are made of ZnS, the shortest distance is preferably equal to or greater than 1 nm. With this configuration, the electron exudation from the core 22, derived from the electron wave function, may be efficiently reduced by the first shell 24 and the second shell 26.
In the present embodiment, the quantum dot 20 absorbs light having a shorter wavelength than a wavelength of light emitted from itself. In particular, the quantum dot 20 absorbs ultraviolet light. Furthermore, the quantum dot 20 generates heat when absorbing light.
The second quantum dot 17 is formed of the same material as the second shell 26. A part of the charge injected into the light-emitting layer 8 is injected into the first quantum dot 16 via the second quantum dot 17. Thus, the charge injected into the light-emitting layer 8 is easily injected into the first quantum dot 16. As a result, the luminous efficiency in the light-emitting device 1 can be improved.
Next, a method for manufacturing the light-emitting device 1 according to the present embodiment will be described with reference to
First, the array substrate 3 is formed (step S1). Formation of the array substrate 3 may be performed by forming a plurality of TFTs on the substrate to match positions of the subpixels.
Next, the first electrode 4 is formed (step S2). In step S2, for example, after a transparent electrode material having electrical conductivity, such as ITO, is film-formed by sputtering, the first electrode 4 may be formed for each subpixel by patterning while matching a shape of the subpixel. Alternatively, the first electrode 4 may be formed for each subpixel by vapor-depositing a transparent electrode material by using a vapor deposition mask.
Next, the edge covers 14 are formed (step S3). The edge covers 14, after being applied on the array substrate 3 and the first electrode 4, may be obtained by patterning while leaving the positions covering the side surfaces and peripheral end portions of the first electrodes 4 between the adjacent first electrodes 4. The patterning of the edge covers 14 may be performed by photolithography.
Next, the first charge transport layer 6 is formed (step S4). The first charge transport layer 6 may be formed for each subpixel by separately patterning with an ink-jet method, vapor deposition using a mask, or patterning using photolithography.
Next, the light-emitting layer 8 is formed (step S5). The step of forming the light-emitting layer 8 will be described in more detail with reference to
As illustrated in
The first solution 28 is a solution in which the plurality of quantum dots 20 with the ligand 18 being coordinated and a first inorganic precursor 30 are dispersed in a first solvent 32, as illustrated in
The step of the first application is performed at an atmospheric temperature of a temperature T0, as illustrated in
Subsequently, a step of temperature raising is performed in which light irradiation is performed to irradiate the first solution 28 on the array substrate 3 with light such as ultraviolet light so as to heat the quantum dots 20 (step S11). In the step of the temperature raising, the quantum dots 20 are heated until the quantum dots 20 have a first temperature T1 or higher as indicated in
The first temperature T1 is a temperature higher than a melting point of the ligand 18 and a boiling point of the first solvent 32. A temperature TA indicated in
The melting point of TOPO is in a range from 50 degrees Celsius to 54 degrees Celsius, and the boiling point of hexane is in a range from 68.5 degrees Celsius to 69.1 degrees Celsius. Accordingly, in a case where the ligand 18 is TOPO and the first solvent is hexane, the temperature TA is the melting point of the TOPO, and the first temperature T1 is the boiling point of the hexane.
The ambient temperature of the quantum dots 20 follows a rise of the temperature of the quantum dots 20 with a slight delay, as depicted in
By further carrying on the step of the temperature raising, the melting of the ligand 18 ends, and the ambient temperature of the quantum dots 20 begins to rise again. Then, when the ambient temperature of the quantum dots 20 rises up to the temperature TB and the other one of the melting of the ligand 18 and the evaporation of the first solvent 32 begins, the ambient temperature of the quantum dots 20 maintains the first temperature T1 for a while.
Thus, the melting of the ligand 18 and the evaporation of the first solvent 32 are completed by the step of the temperature raising. When the first temperature T1 is the boiling point of the first solvent 32, in the step of the temperature raising, the first solvent 32 vaporizes after the ligand 18 has melted. On the other hand, when the first temperature T1 is the melting point of the ligand 18, in the step of the temperature raising, the ligand 18 melts after the first solvent 32 has vaporized.
In a case where the melting of the ligand 18 is earlier than the vaporization of the first solvent 32, immediately after the vaporization of the first solvent 32, aggregate of the quantum dots 20, around which the solid ligand 18 is attached, is formed in an upper layer relative to the first charge transport layer 6. Since the aggregate is unstable as a film, it is difficult for the first inorganic precursor 30 to be present in some case. Accordingly, in the step of the temperature raising, from the perspective of forming a stable film including the quantum dots 20 and the first inorganic precursor 30, it is preferable that the first solvent 32 vaporize after the melting of the ligand 18.
After the completion of the step of the temperature raising, as illustrated in
Next, a step of first temperature lowering is performed in which the temperature of the array substrate 3 is lowered to the melting point of the ligand 18 or lower (step S12). The step of the first temperature lowering may be performed by storing the array substrate 3 in a cooling environment, or the array substrate 3 may be naturally cooled by stopping the step of the temperature raising.
By carrying on the step of the first temperature lowering, first, the temperature of the quantum dots 20 is lowered from the first temperature T1 to the temperature TA. When the temperature of the quantum dots 20 reaches the temperature TA, solidification of the melted ligand 18 begins. Then, the ambient temperature of the quantum dots 20 maintains the temperature TA until the solidification of the ligand 18 is completed. By further carrying on the step of the first temperature lowering, the solidification of the ligand 18 is completed, and then the ambient temperature of the quantum dots 20 follows a decrease of the temperature of the quantum dots 20 with a slight delay, and reaches the temperature T0.
Subsequently, a step of first light irradiation is performed in which first light irradiation is performed on the position where the first solution 28 has been applied on the array substrate 3 so as to heat the quantum dots 20 (step S13). In the step of the first light irradiation, the first light irradiation is continued until the temperature of the quantum dots 20 reaches a second temperature T2 indicated in
By carrying on the step of the first light irradiation, first, the temperature of the quantum dots 20 reaches the temperature TA. When the temperature TA is reached, the ligand 18 around the quantum dots 20 of the solidified ligand 18 is melted again. Then, the ambient temperature of the quantum dots 20 maintains the temperature TA until the melting of the ligand 18 around the quantum dots 20 is completed, and follows the temperature of the quantum dots 20 with a slight delay. Here, the first solvent 32 has already been evaporated. Thus, the ambient temperature of the quantum dots 20 is not affected by the temperature TB.
Subsequently, in the step of the first light irradiation, the temperature of the quantum dots 20 maintains a temperature at approximately the second temperature T2 from the point in time when the temperature of the quantum dots 20 reaches the second temperature T2. Herein, ultraviolet light may be emitted as in the light irradiation in the step of the temperature raising and the first light irradiation, or light having a less amount of energy per unit time than the light emitted in the first light irradiation may be emitted. Since the temperature of the quantum dots 20 is maintained at the second temperature T2, the ambient temperature of the quantum dots 20 after having reached the second temperature T2 is also maintained at the second temperature T2.
In each of the steps of light irradiation in the present embodiment, when an amount of heat generated in the quantum dots 20 and an amount of heat dissipated toward the peripheral environment of the array substrate 3 are balanced, the temperature around the quantum dots 20 is substantially constant at a certain temperature.
The second temperature T2 is higher than the first temperature T1, and is a temperature at which the first inorganic precursor 30 epitaxially grows around the first shell 24 by thermochemical reaction. Thus, while the ambient temperature of the quantum dots 20 is maintained at the second temperature T2, the first inorganic precursor 30 gradually grows epitaxially around the first shell 24. With this, the second shell 26 is formed around the first shell 24 of each quantum dot 20, as illustrated in
As described above, as illustrated in
Note that in the present embodiment, the step of forming the light-emitting layer 8 is described with reference to the enlarged cross-sectional view of the periphery of the second light-emitting layer 8G. However, a difference in the forming method of each of the first light-emitting layer 8R, second light-emitting layer 8G, and third light-emitting layer 8B is only a difference in the materials contained in the first solution 28. That is, regardless of luminescent colors of the light-emitting layer 8 to be formed, the steps of the first application, the temperature raising, the first temperature lowering, and the first light irradiation may be implemented by the same method.
In the step of the first application, the material contained in the first solution 28 may be changed for each luminescent color of the corresponding light-emitting element, and the first solution 28 may be subjected to separately patterning by an ink-jet method. Specifically, the first solution 28 may be separately applied by an ink-jet method on a position overlapping with each of the first electrodes 4 formed for each light-emitting element. Then, the steps of the temperature raising, the first temperature lowering, and the first light irradiation described above may be performed. As a result, in the step of the first light irradiation, the light-emitting elements having mutually different luminescent colors can be formed by continuous single light irradiation.
Note that the concentration of the first inorganic precursor 30 in the first solution 28 applied in the step of the first application may vary depending on the luminescent color of the corresponding light-emitting element. In particular, the concentration of the first inorganic precursor 30 in the first solution 28 applied on the position corresponding to the second light-emitting element 2G is preferably lower than the concentration of the first inorganic precursor 30 in the first solution 28 applied on the position corresponding to the first light-emitting element 2R. Furthermore, the concentration of the first inorganic precursor 30 in the first solution 28 applied on the position corresponding to the second light-emitting element 2G is preferably higher than the concentration of the first inorganic precursor 30 in the first solution 28 applied on the position corresponding to the third light-emitting element 2B.
In the step of epitaxially growing the second shell 26 around the quantum dot 20, when the amount of light irradiation is the same, the amount of the first inorganic precursor 30 needed for forming the second shell 26 having the same film thickness increases as a particle size of the quantum dot 20 increases. In general, as a wavelength of light emitted from the quantum dot 20 increases, a particle size of the core 22, and thus a particle size of the quantum dot 20 increases.
Therefore, as in the configuration described above, with a longer wavelength of light emitted from the corresponding light-emitting element, a formation condition of each light-emitting layer can be brought closer by increasing the concentration of the first inorganic precursor 30 in the first solution 28. Thus, a variation in film thickness of the second shell 26 can be suppressed between the quantum dots 20 having particle sizes different from each other.
In the step of forming the light-emitting layer, after the first solution 28 is applied on a position overlapping with the first electrode 4 in the step of the first application, partial exposure by laser irradiation may be performed in each of the step of the temperature raising and the step of the first light irradiation. Thereafter, a step of removal may be performed in which the first solution 28 is removed from a position overlapping with a position different from the position where the partial exposure was performed. As a result, the light-emitting layer 8 may be formed only at the position partially exposed by the laser irradiation.
Furthermore, in the step of forming the light-emitting layer, after the first solution 28 is applied on a position overlapping with the first electrode 4 in the step of the first application, partial exposure using a photomask may be performed in each of the step of the temperature raising and the step of the first light irradiation. A method for forming the light-emitting layer 8 by partial exposure using a photomask will be described in more detail with reference to
As illustrated in
The photomask M has a function of shielding light emitted in the step of the temperature raising and the step of the first light irradiation. When the photomask M is installed above the array substrate 3, an opening is formed such that the opening is formed only in a position overlapping with the first electrode 4G. That is, as illustrated in
By performing the step of the temperature raising to the step of the first light irradiation after the photomask M is installed, light irradiation is performed only on the first solution 28 in the position overlapping with the first electrode 4G, as illustrated in
Next, after the photomask M is removed from above the array substrate 3, as illustrated in
Note that, in the step of forming the light-emitting layer, when the partial exposure using laser irradiation or a photomask described above is adopted as a technique for each light irradiation, the step of the first application to the step of the removal described above may be repeatedly performed according to the luminescent color of the corresponding light-emitting element. For example, after the second light-emitting layer 8G illustrated in
Here, according to a kind of the light-emitting layer 8 to be formed, a kind of a solution applied in the step of the first application is changed, and the photomask M installed above the array substrate 3 is also changed. Specifically, in the step of the temperature raising and the step of the first light irradiation, a position of an opening in the photomask M is changed according to a kind of the light-emitting layer 8 such that the light irradiation is performed only on a position overlapping with a position of the light-emitting layer 8 to be formed.
As described above, the light-emitting layer 8 illustrated in
Note that, in the present embodiment, the technique for forming the light-emitting layer 8 partitioned by the edge covers 14 for each light-emitting element has been described. However, when partial exposure using laser irradiation or a photomask is adopted for each light irradiation, light irradiation can be individually performed on a position overlapping with each of the first electrodes 4. Thus, even when the light-emitting layer 8 is not partitioned by the edge covers 14, the light-emitting layer 8 corresponding to each light-emitting element can be formed individually. Therefore, when partial exposure is adopted in each light irradiation, a height of the edge covers 14 may be a height that covers the edge of the first electrode 4.
Note that, in the present embodiment, the method for forming the light-emitting layer 8 in each of the first light-emitting element that emits red light, the second light-emitting element that emits green light, and the third light-emitting element that emits blue light in the step of forming the light-emitting layer described above has been described. However, the step of forming the light-emitting layer described above can be applied to the step of forming the light-emitting layer 8 when a part of the light-emitting element is provided with the light-emitting layer 8 of a kind different from another part of the light-emitting element.
In the present embodiment, the time for performing the first light irradiation on the position corresponding to each of the first light-emitting element 2R, the second light-emitting element 2G, and the third light-emitting element 2B may vary depending on the luminescent color of the light-emitting element. In particular, the irradiation time of the first light irradiation for the position corresponding to the second light-emitting element 2G is preferably shorter than the irradiation time of the first light irradiation for the position corresponding to the first light-emitting element 2R. Furthermore, the irradiation time of the first light irradiation for the position corresponding to the second light-emitting element 2G is preferably longer than the irradiation time of the first light irradiation for the position corresponding to the third light-emitting element 2B.
When the first solution 28 is subjected to separately patterning by an ink-jet method in the step of the first application, and the light irradiation is performed on the entire coating region, the photomask may be installed above the array substrate 3 and the light irradiation may be started again in the middle of the step of the first light irradiation. In this way, the irradiation time of the first light irradiation can be changed according to the luminescent color of the light-emitting element. When the partial exposure described above is performed, the irradiation time of the first light irradiation may be set different in each partial exposure.
In the step of epitaxially growing the second shell 26 around the quantum dot 20, a growing speed of the second shell 26 is slower as a particle size of the quantum dot 20 increases. That is, when the second shell 26 having the same film thickness is formed around the quantum dot 20, time required for the first light irradiation increases as a particle size of the quantum dot 20 increases.
Therefore, as in the configuration described above, a formation condition of each light-emitting layer can be brought closer between the plurality of light-emitting elements by setting different times of the light irradiation according to the luminescent color of the corresponding light-emitting element. Thus, a variation in film thickness of the second shell 26 can be suppressed between the quantum dots 20 having particle sizes different from each other.
Subsequent to the step of forming the light-emitting layer, the second charge transport layer 10 is formed (step S6). The second charge transport layer 10 may be applied and formed in common to all of the subpixels by a spin coat technique or the like.
Finally, the second electrode 12 is formed (step S7). The second electrode 12 may be film-formed in common to all of the subpixels by vapor deposition or the like. As described above, the light-emitting element layer 2 is formed on the array substrate 3, and the light-emitting device 1 is obtained.
In the method for manufacturing the light-emitting device 1 according to the present embodiment, after the quantum dot 20 having the core/shell structure is applied, the second shell 26 epitaxially grows around the first shell 24 of each quantum dot 20. Thus, a film thickness of the shell in each quantum dot 20 can be made thicker than that when the quantum dots 20 having the core/shell structure are simply layered.
For example, in a quantum dot having the core/shell structure, it is conceivable to increase a film thickness of a shell in order to reduce exudation of electrons injected into the core of the quantum dot. However, when quantum dots having a thick film thickness of a shell are layered to form quantum dots, a filling rate of the quantum dots is low with respect to the volume of a light-emitting layer. Thus, it is difficult to achieve sufficient density of the quantum dots in the light-emitting layer, resulting in a decrease in luminous efficiency of a light-emitting element.
In the method for manufacturing the light-emitting device 1 according to the present embodiment, the quantum dot 20 including a thin first shell 24 is applied, and the second shell 26 is then formed on each quantum dot 20. In the light-emitting layer 8 according to the present embodiment, a film thickness of the shell formed around the core 22 can be considered as a total film thickness of the first shell 24 and the second shell 26.
As a result, the density of the quantum dots 20 in the light-emitting layer 8 can be enhanced compared to the case of simply layering the quantum dots provided with the shells having the same film thickness. Thus, while reducing the electron exudation from the quantum dot 20, the density of the quantum dots 20 in the light-emitting layer 8 is improved, thereby resulting in an improvement in luminous efficiency of the light-emitting device 1.
In the present embodiment, since at least one set of quantum dots 20 is connected via the second shell 26, an area of the outer surface of the second shell 26 is smaller in the above one set of quantum dots 20 than that in the case of not being connected. That is, in the present embodiment, an area of the outer surface of the first quantum dot 16 can be reduced compared to the case of simply layering quantum dots.
By reducing the area of the outer surface of the first quantum dot 16, the area of the surface of the second shell 26, through which moisture may infiltrate from the outside, can be reduced. Accordingly, this configuration may reduce damage to the second shell 26 due to the moisture infiltration, and may consequently suppress degradation in a surface protection function of the quantum dot 20 of the second shell 26 due to the damage described above.
When the ligand 18 coordinates on the outer surface of the first quantum dot 16, the reduction of the area of the outer surface makes it possible to reduce the ligand 18 possible to be damaged by the moisture infiltration. Accordingly, the damage to the second shell 26 can be reduced due to the loss of the protection function by the ligand 18 for the second shell 26 due to the damage described above.
By reducing the area of the outer surface of the first quantum dot 16, the surface area of the second shell 26 possible to be damaged can be reduced when the light-emitting device 1 is driven. Thus, the above-discussed configuration may reduce damage to the second shell 26 accompanying the drive of the light-emitting device 1, and may consequently reduce the formation of defects in the second shell 26 due to the damage. As a result, by reducing the area of the outer surface of the first quantum dot 16, the occurrence of a non-emitting process caused by recombination of electrons and holes in the defects is suppressed, and consequently a decrease in luminous efficiency of the light-emitting device 1 is suppressed.
As described above, because of the outer surface of the first quantum dot 16 being small, the area of the outer surface of the first quantum dot 16 possible to be damaged can be reduced, and reduce deactivation of the quantum dot 20 due to damage to the first quantum dot 16.
According to NPL 1, the average value of a random close packing ratio in the packing of rigid spheres is approximately 63.66 percent. Accordingly, in the present embodiment, the proportion of the volume of the first quantum dots 16 in the light-emitting layer 8 is preferably greater than or equal to 63.7 percent. With the above configuration, the density of the quantum dots 20 in the light-emitting layer 8 can be enhanced compared to the case of randomly layering quantum dots each provided with a shell whose film thickness is equal to the total film thickness of the first shell 24 and second shell 26. Furthermore, with the configuration described above, the area of the outer surface of the first quantum dot 16 can more efficiently be decreased compared to the case of randomly layering quantum dots.
In the present embodiment, an average film thickness of the first shell 24 from the outer surface of the core 22 is less than a minimum film thickness of the second shell 26. Thus, the quantum dots 20 can be more densely layered between the step of the temperature raising and the step of the first light irradiation, and the second shell 26 having a relatively thick film thickness can be formed in the subsequent step of the first light irradiation.
Therefore, in the step of the light irradiation, the first shell 24 and the second shell 26 having a film thickness that can sufficiently reduce the electron exudation from the core 22, derived from the electron wave function can be formed, while the quantum dots 20 are densely layered. Thus, according to this configuration, the density of the quantum dots 20 in the first quantum dots 16 can be increased while sufficiently ensuring a film thickness of the first shell 24 and the second shell 26.
In the present embodiment, the light-emitting layer 8 is formed after the formation of the array substrate 3, the first electrode 4, the edge covers 14, and the first charge transport layer 6. However, heating for forming the light-emitting layer 8 is achieved by the heat generation of the quantum dots 20 by light irradiation. Thus, local heating of the light-emitting layer 8 is achieved. Accordingly, the array substrate 3, the first electrode 4, the edge covers 14, and the first charge transport layer 6 do not necessarily need to have high heat resistance with respect to heating in the light irradiation step described above. Therefore, the array substrate 3, the first electrode 4, the edge covers 14, and the first charge transport layer 6 may contain a conventionally known material.
The array substrate 3 may be, for example, a glass substrate containing alkali glass or the like. Further, the array substrate 3 may be an organic substrate containing an organic material such as polyimide. Further, the array substrate 3 may contain a flexible material such as PET, and may achieve a flexible light-emitting device 1.
For example, when the light-emitting element layer 2 forms a bottom-emitting type light-emitting element and the first electrode 4 is an anode electrode, ITO is commonly used for the first electrode 4. When the first charge transport layer 6 is a hole transport layer, an inorganic material such as NiO, MgNiO, Cr2O3, Cu2O, or LiNbO3 may be contained.
In order to achieve a shape having a certain level of height and inclination, an organic material is generally used for the edge cover 14. In the present embodiment, the edge cover 14 may contain polyimide or the like.
For example, the second charge transport layer 10 may contain a material used for a conventionally known electron transport layer, and the second electrode 12 may contain a material used for a conventionally known cathode electrode.
The light-emitting device 1 according to the present embodiment may have the same configuration as that of the light-emitting device 1 according to the previous embodiment except that the layering order of each of the layers in a light-emitting element layer 2 is reversed. In other words, the light-emitting element layer 2 according to the present embodiment includes a second charge transport layer 10, a light-emitting layer 8, a first charge transport layer 6, and a first electrode 4, which are sequentially layered from the lower layer on a second electrode 12.
In comparison with the light-emitting device 1 according to the previous embodiment, each of the second electrode 12 and the second charge transport layer 10 is separated by edge covers 14. In particular, in the present embodiment, the second electrode 12 is, by the edge covers 14, separated into a second electrode 12R for a first light-emitting element 2R, a second electrode 12G for a second light-emitting element 2G, and a second electrode 12B for a third light-emitting element 2B. Further, the second charge transport layer 10 is, by the edge covers 14, separated into a second charge transport layer 10R for the first light-emitting element 2R, a second charge transport layer 10G for the second light-emitting element 2G, and a second charge transport layer 10B for the third light-emitting element 2B.
In comparison with the light-emitting device 1 according to the previous embodiment, the first charge transport layer 6 and the first electrode 4 are not separated by the edge covers 14, and are each formed in a shared manner.
In the present embodiment, the first electrode 4 may be a transparent electrode and the second electrode 12 may be a reflective electrode. Therefore, light from the light-emitting layer 8 passes through the first charge transport layer 6 and the first electrode 4, and is emitted from a light-emitting face DS to the outside of the light-emitting device 1. Due to this, the light-emitting device 1 is configured as a top-emitting type light-emitting device. Because of this, in the present embodiment, an array substrate 3 need not necessarily be a transparent substrate.
The light-emitting device 1 according to the present embodiment can be manufactured by performing each of the steps illustrated in
For example, when the light-emitting element layer 2 forms a top-emitting type light-emitting element and the second electrode 12 is a cathode electrode, the second electrode 12 preferably has a function of also reflecting light emitted in each light irradiation described above. According to the configuration, in each light irradiation described above, not only light directly emitted to the quantum dots 20, but also light that has reached the second electrode 12 once and is reflected by the second electrode 12 can be effectively used as light in each light irradiation. Thus, the step of the light irradiation in the present embodiment can reduce intensity of the light irradiation required to irradiate the quantum dots 20 with sufficient light compared to the step of the light irradiation in the previous embodiment.
From the perspective of enhancing light reflectivity of light emitted in the light irradiation described above, it is preferable to contain a metal material. The second electrode 12 may contain at least a metal thin film having light reflectivity on the surface. For example, the second electrode 12 may contain a metal such as Al or Ag, or an intermetallic compound such as AgMg.
The light-emitting device 1 according to the present embodiment may have the same configuration as that of the light-emitting device 1 of the first embodiment except that a light-emitting layer 8 does not include a ligand 18. As illustrated in
The light-emitting device 1 according to the present embodiment is manufactured by the same method except for step S5, that is, the step of forming the light-emitting layer among the steps illustrated in
In the step of forming the light-emitting layer according to the present embodiment, the same method as that described in the first embodiment is performed from step S10 to step S13. At the point in time of the completion of step S13, the first quantum dot 16, the second quantum dot 17, and the ligand 18 are formed in an upper layer relative to a first charge transport layer 6, as illustrated in
In the present embodiment, subsequent to step S13, a step of second light irradiation is performed in such a manner that second light irradiation is additionally performed to heat the quantum dots 20 so that the temperature of the quantum dots 20 becomes a temperature equal to or higher than a third temperature T3 (step S14). In the second light irradiation, ultraviolet light may be emitted as in the step of the temperature raising and the first light irradiation, or light having a greater amount of energy per unit time than the light emitted in the first light irradiation may be emitted. The third temperature T3 is higher than the second temperature T2, and is equivalent to a boiling point of the ligand 18. For example, in the case where the ligand 18 is the aforementioned TOPO, the third temperature T3 is 411.2 degrees Celsius.
When the ambient temperature of the quantum dots 20 reaches the third temperature T3 by heating the quantum dots 20 in the step of the second light irradiation, evaporation of the ligand 18 begins and the ambient temperature of the quantum dots 20 maintains the third temperature T3 for a while. Thus, in the step of the second light irradiation, the ligand 18 vaporizes, thereby obtaining the light-emitting layer 8 without the ligand 18 as illustrated in
Note that, in the step of the temperature raising and the step of the first light irradiation performed prior to the step of the second light irradiation in the present embodiment, the partial exposure using laser irradiation or a photomask described in the first embodiment may be adopted for each light irradiation. In this case, after the step of the first application to the step of the removal are repeatedly performed according to the luminescent color of the corresponding light-emitting element, the second light irradiation described above may be performed on a position overlapping with a position where the first solution is applied in the step of the first application.
In this way, after the light-emitting layer 8 including the ligand 18 is formed for each luminescent color of the light-emitting element, the ligand 18 in the light-emitting layer 8 can be vaporized at once. Thus, according to the configuration described above, the number of times of performing the second light irradiation can be reduced compared to the case of individually performing the second light irradiation, thereby resulting in a reduction in manufacturing cost.
The light-emitting device 1 according to the present embodiment does not include the ligand 18 in the light-emitting layer 8. Generally, a ligand that coordinates with quantum dots often includes an organic material. Thus, the light-emitting layer 8 according to the present embodiment that does not include the ligand 18 has a low content of an organic material with respect to an inorganic material, and is resistant to deterioration due to moisture permeation or the like. Therefore, the light-emitting device 1 according to the present embodiment can further improve reliability.
Here, from the description of NPL 1 described above, the average value of the proportion of the voids that are not occupied by rigid spheres in the randomly closest packed space of the rigid spheres is approximately 36.34 volume percent. Therefore, for example, a volume ratio of an organic matter to an inorganic matter in the light-emitting layer 8 is preferably equal to or less than 36.3 volume percent. In this case, a proportion of the organic matter in the light-emitting layer 8 can be reduced compared to a case of a light-emitting layer in which conventional quantum dots are randomly closest packed and a void between the quantum dots is filled with an organic ligand. Therefore, with the configuration described above, the reliability of the light-emitting layer 8 can be more efficiently improved.
Note that, in the present specification, expression of “not including a ligand” refers to not substantially including a ligand. For example, the light-emitting layer 8 in the present embodiment may have a residue of impurities or ligands being left to the extent that the reliability of the light-emitting layer 8 is not significantly reduced. Specifically, the light-emitting layer 8 in the present embodiment may have a residue of the impurities or the ligands described above that is approximately 3 volume percent of the entire volume of the light-emitting layer 8.
Also in the present embodiment, similarly to the embodiments described above, the area of the outer surface of the first quantum dot 16 can be reduced. In this way, the surface area of the second shell 26 possible to be damaged by the light irradiation and the heat generation of the quantum dots 20 due to the light irradiation in the step of the second light irradiation in the present embodiment can be reduced. Thus, with this configuration, as described above, formation of a defect in the second shell 26 due to damage to the second shell 26, and thus a decrease in luminous efficiency of the light-emitting device 1 due to the defect can be reduced.
The light-emitting device 1 according to the present embodiment may have the same configuration as that of the light-emitting device 1 according to the previous embodiments except that a light-emitting layer 8 and a first quantum dot 16 are different.
As illustrated in
The third shell 38 is formed around the second shell 26. The third shell 38 may include the same material as the second shell 26, and may include an inorganic shell material used for the quantum dots of a known core/shell structure.
The light-emitting device 1 according to the present embodiment is manufactured by the same method except for step S5, that is, the step of forming the light-emitting layer among the steps illustrated in
In the step of forming the light-emitting layer according to the present embodiment, the same method as that described in the previous embodiment is performed from step S10 to step S14. In the present embodiment, subsequent to step S14, the light irradiation is stopped and a step of second temperature lowering is performed in which the temperature of the quantum dots 20 is lowered to a temperature equal to or lower than the third temperature T3 (step S15).
In the present embodiment, by the step of the second temperature lowering, the cooling is performed until the temperature of the quantum dots 20 becomes a temperature TC, which is lower than a temperature TA. The temperature TC may be higher than a temperature T0 or may be equal to the temperature T0. When the temperature of the quantum dots 20 drops, the temperature around the quantum dots 20 also drops. At the point in time of the completion of the step of the second temperature lowering, the first quantum dot 16 and a second quantum dot 17 are formed in an upper layer relative to a first charge transport layer 6, as illustrated in
After the temperature of the quantum dots 20 has reached the temperature TB by the step of the second temperature lowering, a step of second application is performed in which a second solution 40 is applied on a position overlapping with the array substrate 3 as illustrated in
The second solution 40 contains a second solvent 42, an organic material 44, and a second inorganic precursor 46. The second solvent 42 may be the same as the first solvent 32, and may be hexane. The organic material 44 may be an organic material used for a ligand of conventionally known quantum dots, or may be the same material as that of the ligand 18. The second inorganic precursor 46 contains the same material as the third shell 38 described above. When the material of the third shell 38 is the same as the material of the second shell 26, the second inorganic precursor 46 is the same as the first inorganic precursor 30.
Subsequently, a step of third light irradiation is performed (step S17), in which third light irradiation is performed to irradiate the second solvent 42 above the array substrate 3 with ultraviolet light so as to heat the quantum dots 20 again. In the step of the third light irradiation, the quantum dots 20 are heated until the quantum dots 20 have a fourth temperature T4 or higher as indicated in
The fourth temperature T4 is the higher temperature of a melting point of the organic material 44 and a boiling point of the second solvent 42. A temperature TD indicated in
The ambient temperature of the quantum dots 20 follows a rise of the temperature of the quantum dots 20 with a slight delay, as depicted in
By further carrying on the third light irradiation, one of the melting of the organic material 44 and the evaporation of the second solvent 42 ends, and the ambient temperature of the quantum dots 20 begins to rise again. Then, when the ambient temperature of the quantum dots 20 rises up to the fourth temperature T4 and the other one of the melting of the organic material 44 and the evaporation of the second solvent 42 begins, the ambient temperature of the quantum dots 20 maintains the fourth temperature T4 for a while.
Thus, by the step of the third light irradiation, the melting of the organic material 44 and the evaporation of the second solvent 42 are completed. After the completion of the step of the third light irradiation, as illustrated in
Subsequently, a step of fourth light irradiation is performed in which fourth light irradiation is performed on the position where the second solvent 42 has been applied on the array substrate 3 so as to heat the quantum dots 20 (step S18). In the step of the fourth light irradiation, the fourth light irradiation is continued until the temperature of the quantum dots 20 reaches a fifth temperature T5 indicated in
Subsequently, from the point in time when the temperature of the quantum dots 20 reaches the fifth temperature T5, a step of fifth light irradiation is performed in which fifth light irradiation is performed to maintain the temperature of the quantum dots 20 at approximately the fifth temperature T5 (step S19). In the fifth light irradiation, ultraviolet light may be emitted as in the third light irradiation and the fourth light irradiation, or ultraviolet light having a less amount of energy per unit time than the ultraviolet light emitted in the fourth light irradiation may be emitted. Since the temperature of the quantum dots 20 is maintained at the fifth temperature T5 in the step of the fifth light irradiation, the ambient temperature of the quantum dots 20 after having reached the fifth temperature T5 is also maintained at the fifth temperature T5.
The fifth temperature T5 is higher than the fourth temperature T4, and is a temperature at which the second inorganic precursor 46 epitaxially grows around the second shell 26 by thermochemical reaction. Thus, while the ambient temperature of the quantum dots 20 is maintained at the fifth temperature T5, the second inorganic precursor 46 gradually grows epitaxially around the second shell 26. With this, the third shell 38 is formed around the second shell 26 of each of the first quantum dot 16, as illustrated in
As described above, as illustrated in
Subsequently, a step of sixth light irradiation is performed in which sixth light irradiation is additionally performed to heat the quantum dots 20 so that the temperature of the quantum dots 20 becomes a sixth temperature T6 or higher (step S20). In the sixth light irradiation, ultraviolet light may be emitted as in the third light irradiation, the fourth light irradiation, and the fifth light irradiation, or light having a greater amount of energy per unit time than the light emitted in the fifth light irradiation may be emitted. The sixth temperature T6 is higher than the fifth temperature T5, and is equivalent to the boiling point of the organic material 44.
When the ambient temperature of the quantum dots 20 reaches the sixth temperature T6 by the heating of the quantum dots 20 in the step of the sixth light irradiation, evaporation of the organic material 44 begins and the ambient temperature of the quantum dots 20 maintains the sixth temperature T6 for a while. With this, in the step of the sixth light irradiation, the organic material 44 vaporizes, and as illustrated in
In the light-emitting device 1 according to the present embodiment, the third shell 38 is formed around the second shell 26. The light-emitting layer 8 may include a third quantum dot formed of the same material as the third shell.
Thus, the first quantum dots 16 according the present embodiment have a higher proportion of the volume to the entire volume of the light-emitting layer 8 compared to the first quantum dots 16 in the previous embodiments. That is, the light-emitting layer 8 in the present embodiment has an improvement in filling rate of the shell formed around a core 22 of the quantum dot 20 in the light-emitting layer 8. In other words, after the step of the fifth light irradiation is performed, the density of inorganic matters with respect to the entire volume of the light-emitting layer 8 is higher than that before the step of the fifth light irradiation is performed. Therefore, with the configuration described above, the light-emitting device 1 according to the present embodiment can further improve the reliability of the light-emitting layer 8.
In the present embodiment, after the step of the first light irradiation is performed, the step of the second light irradiation may be omitted, and then the step of the second temperature lowering and the subsequent steps may be performed sequentially. That is, the vaporization of the ligand 18 and the vaporization of the organic material 44 may be carried out collectively in the step of the sixth light irradiation. This decreases the number of steps of the light irradiation, which leads to a reduction in tact time and a reduction in manufacturing cost.
In the present embodiment, although not limited thereto, the step of forming the light-emitting layer is described in the case where the fourth temperature T4 is equal to the first temperature T1, the fifth temperature T5 is equal to the second temperature T2, and the sixth temperature T6 is equal to the third temperature T3. Such a configuration may be realized simply and easily by making the first solvent 32 and the second solvent 42 be the same, the material of the ligand 18 and the organic material 44 be the same, and the first inorganic precursor 30 and the second inorganic precursor 46 be the same.
With this, the temperature as the heating reference for each light irradiation may be adjusted between the steps from the temperature raising to the second light irradiation and the steps from the third light irradiation to the sixth light irradiation. Accordingly, the configuration described above leads to a simplification of the entire step of forming the light-emitting layer.
In each of the embodiments described above, a case has been described in which the quantum dot layer including the quantum dots 20 is the light-emitting layer 8. However, no such limitation is intended, and the first charge transport layer 6 or the second charge transport layer 10 may be the quantum dot layer including the quantum dots 20, for example. In this manner, in the case where each charge transport layer includes the quantum dots 20, these quantum dots 20 may be provided with a function to transport carriers. In this case, in comparison with a charge transport layer including conventional quantum dots, the stability of the quantum dots 20 in each charge transport layer is improved, so that the efficiency of carrier transport in each of the charge transport layers is improved, leading to an improvement in the luminous efficiency of the light-emitting device 1. Each of the charge transport layers including the quantum dots 20 described above may also be formed by the same technique as the step of forming the quantum dot layer in each of the embodiments.
In each of the above-described embodiments, a display device including a plurality of light-emitting elements and having a display face DS is exemplified to describe the configuration of the light-emitting device 1. However, no such limitation is intended, and the light-emitting device 1 in each of the embodiments described above may be a light-emitting device including a single light-emitting element.
The present invention is not limited to each of the embodiments described above, and various modifications may be made within the scope of the claims. Embodiments obtained by appropriately combining technical approaches disclosed in each of the different embodiments also fall within the technical scope of the present invention. Furthermore, novel technical features can be formed by combining the technical approaches disclosed in each of the embodiments.
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2020/004599 | 2/6/2020 | WO |
