Patent Application
20210167295
The present invention relates to electroluminescent display devices and methods of making electroluminescent display devices. More particularly, the present invention relates to electroluminescent display devices which utilize a two-dopant system for fluorescence. More particularly, the present invention relates to electroluminescent display devices which utilize a two-dopant system for fluorescence wherein the two dopants are quantum dots and molecules which exhibit thermally activated delayed fluorescence.
There has been substantial interest in the preparation and characterization of compound semiconductors consisting of particles with dimensions in the order of 2-100 nm, often referred to as quantum dots (QDs) and/or nanoparticles. Studies in this field have focused mainly on the size-tunable electronic, optical and chemical properties of nanoparticles. Semiconductor nanoparticles are gaining interest due to their potential in commercial applications as diverse as biological labeling, solar cells, catalysis, biological imaging, and light-emitting diodes.
Two fundamental factors (both related to the size of the individual semiconductor nanoparticles) are primarily responsible for their unique properties. The first is the large surface-to-volume ratio: as a particle becomes smaller, the ratio of the number of surface atoms to those in the interior increases. This leads to the surface properties playing an important role in the overall properties of the material. The second factor is that, for many materials (including semiconductor nanoparticles), the electronic properties of the material change with particle size. Moreover, because of quantum confinement effects, the band gap typically becomes gradually larger as the size of the nanoparticle decreases. This effect is a consequence of the confinement of an “electron in a box,” giving rise to discrete energy levels similar to those observed in atoms and molecules, rather than a continuous band as observed in the corresponding bulk semiconductor material. Semiconductor nanoparticles tend to exhibit a narrow bandwidth emission that is dependent upon the particle size and composition of the nanoparticle material. The first excitonic transition (band gap) increases in energy with decreasing particle diameter.
Semiconductor nanoparticles of a single semiconductor material, referred to herein as “core nanoparticles,” along with an outer organic passivating layer, tend to have relatively low quantum efficiencies due to electron-hole recombination occurring at defects and dangling bonds situated on the nanoparticle surface that can lead to non-radiative electron-hole recombinations.
One method to eliminate defects and dangling bonds on the inorganic surface of the nanoparticle is to grow a second inorganic material (typically having a wider band-gap and small lattice mismatch to that of the core material) on the surface of the core particle to produce a “core-shell” particle. Core-shell particles separate carriers confined in the core from surface states that would otherwise act as non-radiative, recombination centers. One example is ZnS grown on the surface of CdSe cores. Another approach is to prepare a core-multi shell structure where the “electron-hole” pair is completely confined to a single shell layer consisting of a few monolayers of a specific material such as a quantum dot-quantum well structure. Here, the core is typically a wide bandgap material, followed by a thin shell of narrower bandgap material, and capped with a further wide-bandgap layer. An example is CdS/HgS/CdS grown using substitution of Hg for Cd on the surface of the core nanocrystal to deposit just a few monolayers of HgS that is then overgrown by monolayers of CdS. The resulting structures exhibit clear confinement of photo-excited carriers in the HgS layer.
The most-studied and prepared semiconductor nanoparticles to date have been so-called “II-VI materials,” for example, ZnS, ZnSe, CdS, CdSe, and CdTe, as well as core-shell and core-multi shell structures incorporating these materials. However, cadmium and other restricted heavy metals used in conventional QDs are highly toxic elements and are of major concern in commercial applications.
Other semiconductor nanoparticles that have generated considerable interest include nanoparticles incorporating Group III-V and Group IV-VI materials, such as GaN, GaP, GaAs, InP, and InAs. Due to their increased covalent nature, III-V and IV-VI highly crystalline semiconductor nanoparticles are more difficult to prepare and much longer annealing times are usually required. However, there are now reports of III-VI and IV-VI materials being prepared in a similar manner to that used for the II-VI materials.
In recent years, electroluminescent display devices, specifically organic light-emitting diodes (OLEDs), have been of great interest within the display industry. An OLED is a light-emitting diode (LED) in which a film of organic compounds is placed between two conductors, which film emits light in response to excitation, such as an electric current. OLEDs are useful in displays, such as television screens, computer monitors, mobile phones, and tablets. A problem inherent in OLED displays is the limited lifetime of the organic compounds. OLEDs which emit blue light, in particular, degrade at a significantly increased rate as compared to green or red OLEDs.
OLED materials rely on the radiative decay of molecular excited states (excitons) generated by recombination of electrons and holes in a host transport material. Two types of excited states are created when charge recombines in an OLED—bright singlet excitons (with a total spin of 0) and dark triplet excitons (with a total spin of 1)—but only the singlets directly give light which fundamentally limits external OLED efficiencies. Spin statistics states that one singlet exciton is generated for every three triplet excitons after the recombination of holes and electrons in organic semiconductor materials. The efficiency of OLEDs can therefore be substantially increased if the non-emissive triplets can be utilized.
To date, OLED material design has focused on harvesting the remaining energy from the normally dark triplets. Recent work to create efficient phosphors, which emit light from the normally dark triplet state, have resulted in green and red OLEDs. Other colors, such as blue, however, require higher energy excited states which accelerate the degradation process of the OLED.
The fundamental limiting factor to the triplet-singlet transition rate is a value of the parameter |Hfi/Δ|2, where Hfi is the coupling energy due to hyperfine or spin-orbit interactions, and Δ is the energetic splitting between singlet and triplet states. Traditional phosphorescent OLEDs rely on the mixing of singlet and triplet states due to spin-orbital (SO) interaction, increasing Hfi, and affording a lowest emissive state shared between a heavy metal atom and an organic ligand. This results in energy harvesting from all higher singlet and triplet states, followed by phosphorescence (relatively short-lived emission from the excited triplet). The shortened triplet lifetime reduces triplet exciton annihilation by charges and other excitons. Recent work by others suggests that the limit to the performance of phosphorescent materials has been reached.
It is thought that the solution processability of OLED devices may lead to a low production cost once mass production has been fully established, and can enable the fabrication of devices on flexible substrates, leading to new technologies such as roll-up displays. In an OLED device, the pixels emit directly, enabling a greater contrast ratio and wider viewing angle compared to liquid crystal displays (LCDs). Further, in contrast to LCDs, OLED displays do not require a backlight, allowing a true black when the OLED is switched off. OLEDs also offer faster response times than LCDs. However, OLED devices typically suffer from poor stability and lifetimes, owing to the lifespans of the organic emissive materials. Blue OLEDs currently display much lower external quantum efficiencies than green and red OLEDs. Further, OLEDs often suffer from broad emission; for display applications narrower emission is desirable to provide better colour purity. Thus, there is a need for a solution-processable emissive device with good stability and lifetime and improved blue emission.
It has been discovered that thermally activated delayed fluorescence (TADF), which relies on minimization of A as opposed to maximization of Hfi, can transfer population between singlet levels and triplet sublevels in a relevant timescale, such as, for example, 1-100 μs. OLEDs incorporating TADF molecules can reach higher excitation states without rapid degradation. The devices described herein are capable of luminescing at higher energy excitation states than devices previously described.
OLEDs are typically composed of a layer of organic materials or compounds between two electrodes, an anode and a cathode. The organic molecules are electrically conductive as a result of delocalization of π electronics caused by conjugation over part or all of the molecule. When a voltage is applied, electrons from the highest occupied molecular orbital (HOMO) present at the anode flow into the lowest unoccupied molecular orbital (LUMO) of the organic molecules present at the cathode. Removal of electrons from the HOMO is also referred to as inserting electron holes into the HOMO. Electrostatic forces bring the electrons and the holes towards each other until they recombine and form an exciton (which is the bound state of the electron and the hole). As the excited state decays and the energy levels of the electrons relax, radiation having a frequency in the visible spectrum is emitted. The frequency of this radiation depends on the band gap of the material, which is the difference in energy between the HOMO and the LUMO.
Because electrons and holes are fermions with half integer spin, an exciton may either be in a singlet state or a triplet state depending on how the spins of the electron and hole have been combined. Statistically, three triplet excitons will be formed for each singlet exciton. Decay from triplet states is spin forbidden, which results in increases in the timescale of the transition and limits the internal efficiency of fluorescent devices.
Thermally activated delayed fluorescence (TADF) seeks to minimize energetic splitting between singlet and triplet states (Δ). The reduction in exchange splitting from typical values of 0.4-0.7 eV to a gap of the order of the thermal energy (proportional to kBT, where kB is the Boltzmann constant, and T is temperature) means that thermal agitation can transfer population between singlet levels and triplet sublevels in a relevant timescale even if the coupling between states is small.
TADF molecules consist of donor and acceptor moieties connected directly by a covalent bond or via a conjugated linker (or “bridge”). A “donor” moiety is likely to transfer electrons from its HOMO upon excitation to the “acceptor” moiety. An “acceptor” moiety is likely to accept the electrons from the “donor” moiety into its LUMO. The donor-acceptor nature of TADF molecules results in low-lying excited states with charge-transfer character that exhibit very low A. Since thermal molecular motions can randomly vary the optical properties of donor-acceptor systems, a rigid three-dimensional arrangement of donor and acceptor moieties can be used to limit the non-radiative decay of the charge-transfer state by internal conversion during the lifetime of the excitation.
It is beneficial, therefore, to decrease energetic splitting between singlet and triplet states (Δ), and to create a system with increased reversed intersystem crossing (RISC) capable of exploiting triplet excitons. Such a system may result in decreased emission lifetimes. Systems with these features may be capable of emitting blue light without being subject to the rapid degradation prevalent in blue OLEDs of the prior art.
The following description of the embodiments is merely exemplary in nature and is in no way intended to limit the subject matter of the present disclosure, their application, or uses.
As used throughout, ranges are used as shorthand for describing each and every value that is within the range. Any value within the range can be selected as the terminus of the range. Unless otherwise specified, all percentages and amounts expressed herein and elsewhere in the specification should be understood to refer to percentages by weight.
For the purposes of this specification and appended claims, unless otherwise indicated, all numbers expressing quantities, percentages or proportions, and other numerical values used in the specification and claims, are to be understood as being modified in all instances by the term “about.” The use of the term “about” applies to all numeric values, whether or not explicitly indicated. This term generally refers to a range of numbers that one of ordinary skill in the art would consider as a reasonable amount of deviation to the recited numeric values (i.e., having the equivalent function or result). For example, this term can be construed as including a deviation of ±10 percent, alternatively ±5 percent, and alternatively ±1 percent of the given numeric value provided such a deviation does not alter the end function or result of the value. Accordingly, unless indicated to the contrary, the numerical parameters set forth in this specification and attached claims are approximations that can vary depending upon the desired properties sought to be obtained by the present invention.
It is noted that, as used in this specification and the appended claims, the singular forms “a,” “an,” and “the,” include plural references unless expressly and unequivocally limited to one referent. As used herein, the term “include” and its grammatical variants are intended to be non-limiting, such that recitation of items in a list is not to the exclusion of other like items that can be substituted or added to the listed items. For example, as used in this specification and the following claims, the terms “comprise” (as well as forms, derivatives, or variations thereof, such as “comprising” and “comprises”), “include” (as well as forms, derivatives, or variations thereof, such as “including” and “includes”) and “has” (as well as forms, derivatives, or variations thereof, such as “having” and “have”) are inclusive (i.e., open-ended) and do not exclude additional elements or steps. Accordingly, these terms are intended to not only cover the recited element(s) or step(s), but may also include other elements or steps not expressly recited. Furthermore, as used herein, the use of the terms “a” or “an” when used in conjunction with an element may mean “one,” but it is also consistent with the meaning of “one or more,” “at least one,” and “one or more than one.” Therefore, an element preceded by “a” or “an” does not, without more constraints, preclude the existence of additional identical elements.
In some instances, the emitting layer 50 of the QD-LED 100 can include a population of quantum dots and a population of TADF molecules dispersed in a host matrix. In other instances, the emitting layer 50 of the QD-LED 100 can include a population of quantum dots and a population of TADF molecules without the use of a host matrix. In some instances, the emitting layer 50 of the QD-LED 100 can include a population of quantum dots dispersed in a host matrix, while an adjacent layer can include a population of TADF molecules dispersed in a different host matrix. In other instances, the emitting layer 50 of the QD-LED 100 can include a population of quantum dots, while an adjacent layer can include a population of TADF molecules, with neither layer utilizing a host matrix.
In some instances, the ETL 70 and the EIL 80 are made of different materials. In some instances, a single composition can serve as both the ETL 70 and the EIL 80. In some instances, the ETL 70 and the EIL 80 are made of ZnO nanoparticles. In some instances, the ETL 70 and the EIL 80 are made of doped ZnO nanoparticles having the general formula Zn1-xMxO, where M=Al, Li, Mg, Ca, Y, Cs, or Ga. In some instances, x ranges between about 0.01 and about 0.5, alternatively between 0.025 and about 0.4, alternatively between about 0.05 and 0.3, alternatively between about 0.075 and 0.2, and alternatively between about 0.075 and about 0.15.
In accordance with various aspects of the present disclosure, a two-dopant system comprising a quantum dot fluorescent emitter dopant a TADF-assistant dopant is provided for use in electroluminescent display devices such as QD-LED devices. QDs may provide advantages over organic fluorophores as fluorescent emitters for TADF-assisted light-emitting devices. Embodiments of the present disclosure are designed to combine the exciton harvesting capabilities of TADF molecules to achieve near unity internal quantum efficiency, with energy transfer of harvested excitons to QDs with high photoluminescence quantum yield, to achieve hyperfluorescent, narrow emission quantum dot devices. The narrow, pseudo-Gaussian emission of QDs may lead to better colour purity and efficiency as compared to organic fluorophores. QD fluorescence emission is tuneable by tuning the particle size and composition, whereas organic fluorophores generally exhibit broad and specific emission profiles. Additionally, the fluorescence quantum yields (QYs) of QDs are typically higher than those of organic fluorophores.
In some instances, an emitting layer of a QD-LED device can include a population of quantum dots and a population of TADF molecules dispersed in a host matrix. In some instances, an emitting layer of a QD-LED device can include a population of quantum dots and a population of TADF molecules and be free of a host matrix. In either instance, emitting layers having both a population of quantum dots and a population of TADF molecules can have a thickness ranging from about 5 nm to about 100 nm, alternatively about 7.5 nm to about 80 nm, alternatively about 10 nm to about 60 nm, alternatively about 12.5 nm to about 40 nm, alternatively about 15 nm to about 20 nm, alternatively about 17.5 nm to about 25 nm, and alternatively about 20 nm. Additionally the emissive layer can have a QD:TADF ratio of about 10:1 to about 1:10 by weight, alternatively about 9:1 to about 1:6 by weight, alternatively about 8:1 to about 1:3 by weight, alternatively about 7:1 to about 1:2 by weight, alternatively about 6:1 to about 1:1 by weight; alternatively about 5:1 to about 2:1 by weight; alternatively about 4.5:1 to about 3.5:1 by weight, and alternatively about 4:1 by weight.
In some instances, the emitting layer of a QD-LED can include a population of quantum dots dispersed in a host matrix, while an adjacent layer can include a population of TADF molecules dispersed in a different host matrix. In some instances, the emitting layer of a QD-LED can include a population of quantum dots free of a host matrix, while an adjacent layer can include a population of TADF molecules dispersed in a host matrix. The emitting layer, having QDs with or without a host matrix, can have a thickness ranging from about 2.5 nm to about 100 nm, alternatively about 5 nm to about 80 nm, alternatively about 7.5 nm to about 60 nm, alternatively about 10 nm to about 40 nm, alternatively about 10 nm to about 20 nm, alternatively about 12.5 nm to about 17.5 nm, and alternatively about 15 nm. The adjacent layer, having TADF molecules dispersed in a host matrix, can have a thickness ranging from about 1 nm to about 120 nm, alternatively about 1.5 nm to about 100 nm, alternatively about 2 nm to about 80 nm, alternatively about 2.5 nm to about 60 nm, alternatively about 3 nm to about 40 nm, alternatively about 3.5 nm to about 20 nm, alternatively from about 4 nm to about 10 nm, and alternatively from about 4 nm to about 8 nm. In some instances, the TADF molecules-containing adjacent layer is a hole transport layer (HTL). In some instances, the TADF molecules-containing adjacent layer is a layer serving as both of an electron blocking layer (EBL) and an HTL.
In some instances, TADF molecules are dispersed throughout the entirety of the adjacent layer. In other instances, TADF molecules are dispersed throughout only a portion of the adjacent layer. In other instances, TADF molecules are dispersed throughout only a portion of the adjacent layer, wherein the portion having TADF molecules is situated next to the emissive layer and the portion not having TADF molecules is situated away from the emissive layer. For example, an adjacent layer having a thickness of 40 nm, where the contact point of the emissive layer and the adjacent layer corresponds to an adjacent layer thickness of 0 nm and the portion of the adjacent layer further from the emissive layer corresponds to an adjacent layer thickness of 40 nm, can have TADF molecules dispersed throughout the 0-30 nm portion of the adjacent layer, alternatively TADF molecules dispersed throughout the 0-20 nm portion of the adjacent layer, alternatively TADF molecules dispersed throughout the 0-10 nm portion of the adjacent layer, alternatively TADF molecules dispersed throughout the 0-9 nm portion of the adjacent layer, alternatively TADF molecules dispersed throughout the 0-7 nm portion of the adjacent layer, alternatively TADF molecules dispersed throughout the 0-5 nm portion of the adjacent layer, alternatively TADF molecules dispersed throughout the 0-3 nm portion of the adjacent layer, and alternatively TADF molecules dispersed throughout the 0-2 nm portion of the adjacent layer.
The concentration (in wt % of the layer) of the TADF-molecules within the adjacent layer, when the TADF molecules are dispersed throughout the entire adjacent layer, can range from about 1 wt % to about 50 wt %, alternatively about from about 5 wt % to about 40 wt %, from about 10 wt % to about 30 wt %, alternatively from about 15 wt % to about 25 wt %, and alternatively about 20 wt %. When the TADF molecules are dispersed throughout only a portion adjacent layer, the concentration of the TADF-molecules within that portion can range from about 1 wt % to about 50 wt %, alternatively about from about 5 wt % to about 40 wt %, from about 10 wt % to about 30 wt %, alternatively from about 15 wt % to about 25 wt %, and alternatively about 20 wt %.
In some instances, the QDs can be blue-emitting QDs. In other instances, the QDs can be green-emitting QDs. In yet other instances, the QDs can be red-emitting QDs. In yet other instances, the QDs can be any combination of blue-, green- and red-emitting QDs. In yet other instances, the QDs can be UV-emitting QDs. In yet other instances, the QDs can be IR-emitting QDs. In yet other instances, the QDs can be tuned to emit at any wavelength ranging from the UV to the IR regions of the electromagnetic spectrum, depending on the application. The particular TADF molecule is not limiting. TADF molecules used in accordance with various aspects of the present disclosure can include, for example, those described in U.S. Pat. Nos. 9,502,668, 9,634,262, 9,660,198, 9,685,615, U.S. Patent Application Publication No. 2016/0372682, U.S. Patent Application Publication No. 2016/0380205, and U.S. Patent Application Publication No. 2017/0229658, the entire contents of which are incorporated by reference herein.
To optimize the performance of two-dopant systems in electroluminescent devices, such as OLED devices, it may be advantageous to design QDs having various qualities. First, the QDs should have high oscillator strength. Second, the QDs should be fabricated to have high FRET with the TADF molecule. Third, the QDs should be fabricated to be strong absorbers. Finally, the QDs should be fabricated to exhibit a short excited state lifetime. One of ordinary skill in the art that the above are not necessarily the only qualities that may be optimized in systems according to the present disclosure.
In accordance with various aspects of the present disclosure, singlet excitons of the TADF molecule are resonantly transferred to a singlet state of the QDs via FRET. A critical distance for the near-field dipole-dipole coupling mechanism, FRET, can be calculated from the spectral overlap of a TADF molecule (a “fluorescence donor”) and a QD (an “absorbance acceptor”) according to the well-known Forster mechanism [Forster, Th., Ann. Phys. 437, 55 (1948)]. To maximize the efficiency of FRET between the TADF molecule and the QD, the critical distance should be determined. The critical distance, r0, between the TADF molecule and the QD is the distance at which the FRET efficiency is 50% and is defined Equation 1:
where c is the speed of light in a vacuum, n is the refractive index of the material, κ2 is an orientation factor, ηD is the photoluminescence (PL) quantum efficiency of the TADF molecule, SD is the normalised PL spectrum of the TADF molecule, and σA is the QD absorption cross-section. [Y. Q. Zhang and X. A. Cao, Appl. Phys. Lett., 2010, 97, 253115]. The critical distance, r0, can thus be manipulated by, for example, altering the PL properties of the TADF molecule (photoluminescence maximum (PLmax)), full-width at half-maximum (FWHM) and PL quantum efficiency, and σA, which may be influenced by factors such as the shape, composition and architecture of the QDs. The better the spectral overlap between the TADF emission and the QD absorption, the better the transfer efficiency and thus the longer the distance over which the energy can be carried.
While the TADF molecule is shown in
In some instances, TADF molecules used in accordance with varying aspects of the present disclosure can be, for example,
(2,3,5,6-tetra(9H-carbazol-9-yl)isonicotinonitrile,
(2,3,5,6-tetra(9H-carbazol-9-yl)benzonitrile),
(2,3,4,5,6-penta(9H-carbazol-9-yl)benzonitrile),
(2,3,5,6-tetrakis(3,6-di-tert-butyl-9H-carbazol-9-yl)benzonitrile),
(2,3,4,5,6-pentakis(3,6-di-tert-butyl-9H-carbazol-9-yl)benzonitrile), or any suitable structural analogs or homologs thereof.
In some instances, TADF molecules used in accordance with varying aspects of the present disclosure can be, for example,
(4,5-di(9H-carbazol-9-yl)phthalonitrile),
(3,4,5,6-tetra(9H-carbazol-9-yl)phthalonitrile),
(4,4″-bis(9,9-dimethylacridin-10(9H)-yl)-[1,1′:2′,1″-terphenyl]-4′,5′-dicarbonitrile), or any suitable structural analogs or homologs thereof.
In some instances, TADF molecules used in accordance with varying aspects of the present disclosure can be, for example,
(2,4,5,6-tetra(9H-carbazol-9-yl)isophthalonitrile),
(2,4,5,6-tetrakis(3,6-dimethyl-9H-carbazol-9-yl)isophthalonitrile),
(2,6-di(9H-carbazol-9-yl)-4-phenylpyridine-3,5-dicarbonitrile), or any suitable structural analogs or homologs thereof.
In some instances, TADF molecules used in accordance with varying aspects of the present disclosure can be, for example,
(2,3,5,6-tetra(9H-carbazol-9-yl)terephthalonitrile),
(2,3,5,6-tetrakis(3,6-diphenyl-9H-carbazol-9-yl)terephthalonitrile), or any suitable structural analogs or homologs thereof.
In some instances, TADF molecules used in accordance with varying aspects of the present disclosure can be, for example,
(12-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-phenyl-5,12-dihydroindolo[3,2-a]carbazole),
(9-(4,6-diphenyl-1,3,5-triazin-2-yl)-9′-phenyl-9H,9′H-3,3′-bicarbazole),
(9-(4-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)-9′-phenyl-9H,9′H-3,3′-bicarbazole),
(9-(4-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)-9H-3,9′-bicarbazole,
(9′-(4-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)-9′H-9,3′:6′,9″-tercarbazole),
(9′-(4-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)-3,3″,6,6″-tetraphenyl-9′H-9,3′:6′,9″-tercarbazole),
(10-(4-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)-10H-phenoxazine),
(10-(4-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)-10H-phenothiazine),
(9-(4-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)-1,3,6,8-tetramethyl-9H-carbazole),
(9-(4-(4,6-diphenyl-1,3,5-triazin-2-yl)-2,6-dimethylphenyl)-3,6-dimethyl-9H-carbazole),
(10-(4-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)-9,9-dimethyl-9,10-dihydroacridine),
(10-(4-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)-10H-spiro[acridine-9,9′-fluorene]),
(9-(4-(4,6-diphenyl-1,3,5-trilazin-2-yl)phenyl)-N3,N3,N6,N6-tetraphenyl-9H-carbazole-3,6-diamine),
(10-(4-(2-(4-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl)phenyl)-9,9-dimethyl-9,10-dihydroacridine), or any suitable structural analogs or homologs thereof.
In some instances, TADF molecules used in accordance with varying aspects of the present disclosure can be, for example,
(10,10′-((6-phenyl-1,3,5-triazine-2,4-diyl)bis(4,1-phenylene))bis(10H-phenoxazine)),
(2,4,6-tris(4-(9,9-dimethylacridin-10(9H)-yl)phenyl)-1,3,5-triazine)),
(2,4,6-tris(4-(10H-phenoxazin-10-yl)phenyl)-1,3,5-triazine), or any suitable structural analogs or homologs thereof.
In some instances, TADF molecules used in accordance with varying aspects of the present disclosure can be, for example,
(9,9′,9″-(5-(4,6-diphenyl-1,3,5-triazin-2-yl)benzene-1,2,3-triyl)tris(9H-carbazole),
(9,9′,9″-(5-(4,6-diphenyl-1,3,5-triazin-2-yl)benzene-1,2,3-triyl)tris(3,6-dimethyl-9H-carbazole)), or any suitable structural analogs or homologs thereof.
In some instances, TADF molecules used in accordance with varying aspects of the present disclosure can be, for example,
(10-(4-(benzo[d]oxazol-2-yl)phenyl)-10H-phenoxazine),
(2,6-bis(4-(10H-phenoxazin-10-yl)phenyl)benzo[1,2-d:5,4-d′]bis(oxazole)), or any suitable structural analogs or homologs thereof.
In some instances, TADF molecules used in accordance with varying aspects of the present disclosure can be, for example,
(2,6-bis(diphenylamino)anthracene-9,10-dione),
(2,6-bis(4-(bis(4-(tert-butyl)phenyl)amino)phenyl)anthracene-9,10-dione), or any suitable structural analogs or homologs thereof.
In some instances, TADF molecules used in accordance with varying aspects of the present disclosure can be, for example,
(3-(9,9-dimethylacridin-10(9H)-yl)-9H-xanthen-9-one),
(3-(9′H-[9,3′:6′,9″-tercarbazol]-9′-yl)-9H-xanthen-9-one), or any suitable structural analogs or homologs thereof.
In some instances, TADF molecules used in accordance with varying aspects of the present disclosure can be, for example,
(5,9-diphenyl-5,9-dihydro-5,9-diaza-13b-boranaphtho[3,2,1-de]anthracene),
(9-([1,1′-biphenyl]-3-yl)-N,N,5,11-tetraphenyl-5,9-dihydro-5,9-diaza-13b-boranaphtho[3,2,1-de]anthracen-3-amine), or any suitable structural analogs or homologs thereof.
In some instances, TADF molecules used in accordance with varying aspects of the present disclosure can be, for example,
(9,9-dimethyl-10-(10-(2,4,6-triisopropylphenyl)-10H-dibenzo[b,e][1,4]oxaborinin-3-yl)-9,10-dihydroacridine), or any suitable structural analog or homolog thereof.
In some instances, TADF molecules used in accordance with varying aspects of the present disclosure can be, for example,
(9-(4-(dimesitylboraneyl)-3,5-dimethylphenyl)-N3,N3,N6,N6-tetraphenyl-9H-carbazole-3,6-diamine), or any suitable structural analog or homolog thereof.
In some instances, TADF molecules used in accordance with varying aspects of the present disclosure can be, for example,
(4,4′,4″-(1,3,3a1,4,6,7,9-heptaazaphenalene-2,5,8-triyl)tris(N,N-bis(4-(tert-butyl)phenyl)aniline)), or any suitable structural analog or homolog thereof.
In some instances, TADF molecules used in accordance with varying aspects of the present disclosure can be, for example,
(7,10-bis(4-(diphenylamino)phenyl)dibenzo[f,h]quinoxaline-2,3-dicarbonitrile)), or any suitable structural analog or homolog thereof.
In some instances, TADF molecules used in accordance with varying aspects of the present disclosure can be, for example,
(12,12′-(6-([1,1′-biphenyl]-4-yl)-1,3,5-triazine-2,4-diyl)bis(11-phenyl-11,12-dihydroindolo[2,3-a]carbazole)), or any suitable structural analog or homolog thereof.
In some instances, TADF molecules used in accordance with varying aspects of the present disclosure can be, for example,
(bis(4-(9H-[3,9′-bicarbazol]-9-yl)phenyl)methanone), or any suitable structural analog or homolog thereof.
In some instances, TADF molecules used in accordance with varying aspects of the present disclosure can be, for example,
(10,10′-(sulfonylbis(4,1-phenylene))bis(9,9-dimethyl-9,10-dihydroacridine)), or any suitable structural analog or homolog thereof.
In some instances, TADF molecules used in accordance with varying aspects of the present disclosure can be, for example,
(10-phenyl-10H,10′H-spiro[acridine-9,9′-anthracen]-10′-one), or any suitable structural analog or homolog thereof.
QDs used in accordance with varying aspects of the present disclosure can have a size ranging from 2-100 nm and include core material comprising:
IIA-VIA (2-16) material, consisting of a first element from group 2 of the periodic table and a second element from group 16 of the periodic table and also including ternary and quaternary materials and doped materials. Nanoparticle material includes but is not restricted to: MgS, MgSe, MgTe, CaS, CaSe, CaTe, SrS, SrSe, SrTe, BaS, BaSe, BaTe;
IIB-VIA (12-16) material consisting of a first element from group 12 of the periodic table and a second element from group 16 of the periodic table and also including ternary and quaternary materials and doped materials. Nanoparticle material includes but is not restricted to: ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, HgS, HgSe, HgTe;
II-V material, consisting of a first element from group 12 of the periodic table and a second element from group 15 of the periodic table and also including ternary and quaternary materials and doped materials. Nanoparticle material includes but is not restricted to: Zn3P2, Zn3As2, Cd3P2, Cd3As2, Cd3N2, Zn3N2;
III-V material, consisting of a first element from group 13 of the periodic table and a second element from group 15 of the periodic table and also including ternary and quaternary materials and doped materials. Nanoparticle material includes but is not restricted to: BP, AlP, AlAs, AlSb; GaN, GaP, GaAs, GaSb; InN, InP, InAs, InSb, AlN, BN;
III-IV material, consisting of a first element from group 13 of the periodic table and a second element from group 14 of the periodic table and also including ternary and quaternary materials and doped materials. Nanoparticle material includes but is not restricted to: B4C, Al4C3, Ga4C;
III-VI material, consisting of a first element from group 13 of the periodic table and a second element from group 16 of the periodic table and also including ternary and quaternary materials. Nanoparticle material includes but is not restricted to: Al2S3, Al2Se3, Al2Te3, Ga2S3, Ga2Se3, GeTe; In2S3, In2Se3, Ga2Te3, In2Te3, InTe;
IV-VI material, consisting of a first element from group 14 of the periodic table and a second element from group 16 of the periodic table, and also including ternary and quaternary materials and doped materials. Nanoparticle material includes but is not restricted to: PbS, PbSe, PbTe, SnS, SnSe, SnTe;
V-VI material, consisting of a first element from group 15 of the periodic table and a second element from group 16 of the periodic table, and also including ternary and quaternary materials and doped materials. Nanoparticle material includes but is not restricted to: Bi2Te3, Bi2Se3, Sb2Se3, Sb2Te3; and
Nanoparticle material, consisting of a first element from any group in the transition metal of the periodic table, and a second element from group 16 of the periodic table and also including ternary and quaternary materials and doped materials. Nanoparticle material includes but is not restricted to: NiS, CrS, CuInS2, CuInSe2, CuGaS2, CuGaSe2, CuInxGa1-xSySe2-y (where 0≤x≤1 and 0≤y≤2), AgInS2.
By the term doped nanoparticle for the purposes of specifications and claims, refers to nanoparticles of the above and a dopant comprised of one or more main group or rare earth elements, this most often is a transition metal or rare earth element, such as but not limited to zinc sulfide with manganese, such as ZnS nanoparticles doped with Mn2+.
The term “ternary material,” for the purposes of specifications and claims, refers to QDs of the above but a three-component material. The three components are usually compositions of elements from the as mentioned groups Example being (ZnxCd1-xS)mLn nanocrystal (where L is a capping agent).
The term “quaternary material,” for the purposes of specifications and claims, refers to nanoparticles of the above but a four-component material. The four components are usually compositions of elements from the as mentioned groups Example being (ZnxCd1-xSySe1-y)mLn nanocrystal (where L is a capping agent).
The material used on any shell or subsequent numbers of shells grown onto the core particle in most cases will be of a similar lattice type material to the core material i.e. have close lattice match to the core material so that it can be epitaxially grown on to the core, but is not necessarily restricted to materials of this compatibility. The material used on any shell or subsequent numbers of shells grown on to the core present in most cases will have a wider bandgap than the core material but is not necessarily restricted to materials of this compatibility. The materials of any shell or subsequent numbers of shells grown on to the core can include material comprising:
IIA-VIA (2-16) material, consisting of a first element from group 2 of the periodic table and a second element from group 16 of the periodic table and also including ternary and quaternary materials and doped materials. Nanoparticle material includes but is not restricted to: MgS, MgSe, MgTe, CaS, CaSe, CaTe, SrS, SrSe, SrTe;
IIB-VIA (12-16) material, consisting of a first element from group 12 of the periodic table and a second element from group 16 of the periodic table and also including ternary and quaternary materials and doped materials. Nanoparticle material includes but is not restricted to: ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, HgS, HgSe, HgTe;
II-V material, consisting of a first element from group 12 of the periodic table and a second element from group 15 of the periodic table and also including ternary and quaternary materials and doped materials. Nanoparticle material includes but is not restricted to: Zn3P2, Zn3As2, Cd3P2, Cd3As2, Cd3N2, Zn3N2;
III-V material, consisting of a first element from group 13 of the periodic table and a second element from group 15 of the periodic table and also including ternary and quaternary materials and doped materials. Nanoparticle material includes but is not restricted to: BP, AlP, AlAs, AlSb; GaN, GaP, GaAs, GaSb; InN, InP, InAs, InSb, AlN, BN;
III-IV material, consisting of a first element from group 13 of the periodic table and a second element from group 14 of the periodic table and also including ternary and quaternary materials and doped materials. Nanoparticle material includes but is not restricted to: B4C, Al4C3, Ga4C;
III-VI material, consisting of a first element from group 13 of the periodic table and a second element from group 16 of the periodic table and also including ternary and quaternary materials. Nanoparticle material includes but is not restricted to: Al2S3, Al2Se3, Al2Te3, Ga2S3, Ga2Se3, In2S3, In2Se3, Ga2Te3, In2Te3;
IV-VI material, consisting of a first element from group 14 of the periodic table and a second element from group 16 of the periodic table and also including ternary and quaternary materials and doped materials. Nanoparticle material includes but is not restricted to: PbS, PbSe, PbTe, SnS, SnSe, SnTe;
V-VI material, consisting of a first element from group 15 of the periodic table and a second element from group 16 of the periodic table, and also including ternary and quaternary materials and doped materials. Nanoparticle material includes but is not restricted to: Bi2Te3, Bi2Se3, Sb2Se3, Sb2Te3; and
Nanoparticle material, consisting of a first element from any group in the transition metal of the periodic table, and a second element from group 16 of the periodic table and also including ternary and quaternary materials and doped materials. Nanoparticle material includes but is not restricted to: NiS, CrS, CuInS2, CuInSe2, CuGaS2, CuGaSe2, CuInxGa1-xSySe2-y (where 0≤x≤1 and 0≤y≤2), AgInS2.
As illustrated in
To maximise FRET, smaller QDs emitting at a given wavelength may be desirable. For example, QDs based on InP, which has a narrower bulk band gap and larger Bohr radius than core QDs such as CdSe, may be advantageous. An InP QD core emitting at, for example, 620 nm, will typically have a smaller diameter than a CdSe QD core emitting at the same wavelength.
For example, the overlap along with the values used to estimate the critical distance for a system having a QD, exhibiting a maximum photoluminescence (PLmax) of 528 nm and a full-width at half maximum (FWHM) of 39 nm, and a TADF molecule, exhibiting a PLmax of 548 nm and a FWHM of 92 nm, are presented in
From the above, a critical distance of 4.7 nm is obtained for a QD, exhibiting a maximum photoluminescence (PLmax) of 528 nm and a full-width at half maximum (FWHM) of 39 nm, and a TADF molecule, exhibiting a PLmax of 548 nm and a FWHM of 92 nm. One of ordinary skill in the art will readily understand the critical distance is a function of the particular QD and TADF molecule used in a system.
The oscillator strength of the band gap transition of a QD, fgap, describes the probability of fluorescence. Thus, for two-dopant system applications it may be desirable to incorporate QDs having a high oscillator strength. In the strong quantum confinement regime, oscillator strength varies only weakly of with QD size, since the electron and hole wave functions overlap completely, independently of particle size, [M. D. Leistikow, J. Johansen, A. J. Kettelarij, P. Lodahl and W. L. Vos, Phys. Rev. B, 2009, 79, 045301] whereas for QDs beyond the strong quantum confinement regime the oscillator strength should increase with increasing particle size. [K. E. Gong, Y. Zeng and D. F. Kelley, J. Phys. Chem. C, 2013, 117, 20268].
QDs comprising a core comprising, for example, InP and emitting within the visible spectrum would have a radius well within the strong confinement regime and the oscillator strength would therefore largely be independent of particle size. In some instances, the shape of the QD may influence oscillator strength. In some instances, the QDs can be substantially spherical or ovoid. In other instances, the QDs can be substantially conical. In yet other instances, the QDs can be substantially cylindrical. In yet other instances, the QDs can be substantially rod-shaped. In yet other instances, the QDs can be in the form or nanorods, nanotubes, nanofibers, nanosheets, dendrimers, stars, tetrapods, disks, or similar physical configurations.
A high QD absorption cross-section is desirable to maximise the FRET process. In quantum rods, for example the emission wavelength is controlled by the length of the short axis, and the absorption cross-section depends predominantly on volume. The absorption cross-section of a nanoparticle, αa, is defined in Equation 2:
where nb and αb are the refractive index and the absorption coefficient of the bulk semiconductor, respectively, n is the refractive index of the surrounding medium, |f(hω)|2 is the local-field factor, and Vis the volume. Htoon et al. investigated the absorption cross-section of spherical (radius=2.3 nm) QDs compared with that of elongated nanoparticles, quantum rods, with the same radius but lengths of 22, 36 and 44 nm. [H. Htoon, J. A. Hollingworth, A. V. Malko, R. Dickerson and V. I. Klimov, Appl. Phys. Lett., 2003, 82, 4776]. As well as the nanorods having a larger volume, |f(hω)|2 was found to almost twice as high for randomly oriented nanorods compared to the spherical nanoparticles. |f(hω)|2 can be increased yet further for aligned nanorods. Thus, a quantum rod architecture may be advantageous over a spherical QD geometry, in terms of increasing the QD absorption cross-section.
For efficient FRET, it is advantageous to minimize the excited state lifetime of QDs. Fundamentally, the excited state lifetime of a QD relates to the degree of confinement. The higher the overlap between the electron and hole, the stronger the confinement and the shorter the radiative lifetime. QD architectures that maximise the electron-hole overlap may be beneficial for two-dopant systems in electroluminescent devices. In some instances, for a given core size, increasing the shell thickness on said core decreases the excited state lifetime of the QD. However, as previously discussed, a core-shell quantum dot having a relatively thick shell may not be desirable, the distance between the TADF molecule and the QD increases with increasing shell thickness. Thus, alternative methods to manipulate the degree of confinement in the QD may be required.
In a Type I core-shell QD, an abrupt offset of the energy levels may result in strong confinement, whereas compositional grading may lead to some delocalisation of the electrons and holes. For example, the confinement in an InP/ZnS QD, consisting of an InP core (bulk band gap, Eg, =1.34 eV) overcoated with a ZnS shell (Eg=3.54 eV (cubic); 3.91 eV (hexagonal)), will be stronger than that in an InP/ZnSe core-shell QD (ZnSe Eg=2.82 eV). An example of a compositionally graded Type I QD would be In1-xP1-yZnxSy, wherein x and y increase gradually from 0, at the centre of the QD, to 1, at the outer surface of the QD.
Where core-multishell architectures are used, the relative thicknesses of the shells may influence the degree of confinement.
For core QDs of a particular material, the smaller the QD, the higher the overlap between the electron and hole and thus the shorter the radiative lifetime. Therefore, strategies to reduce the diameter of the QD core while maintaining a specific emission wavelength may be employed. This could include alloying a first semiconductor material with a second material having a smaller band gap at a similar lattice constant. For example, an InAsP nanoparticle, made by alloying InP with InAs, can emit at 630 nm and will have a smaller diameter than an InP nanoparticle emitting at the same wavelength. Also, for example, a CdSeS nanoparticle, made by alloying CdS with CdSe, can emit at 480 nm and will have a smaller diameter than a CdS nanoparticle emitting at the same wavelength.
In some instances, nanoparticle shape can affect the excited state lifetime. For example, the radiative lifetime of prolate CdSe QDs may be slightly shorter than that of spherical CdSe nanoparticles. [K. Gong, Y. Zang and D. F. Kelley, J. Phys. Chem. C, 2013, 117, 20268] Thus, rod-shaped QDs, i.e. quantum rods, may offer a shorter excited state lifetime than spherical QDs. Herein, “quantum rod” is used to describe a quantum dot having lateral dimensions, x and y, and a length, z, wherein z>x,y. Alternatively, a shorter excited state lifetime may be provided by a 2-dimensional QD, wherein the quantum dot has lateral dimensions in the quantum confinement regime and a thickness between 1-5 monolayers.
In this example an exemplary electroluminescent QD-LED device was constructed according to the energy level diagram of
Example 2 is the same as Example 1 except a TADF molecule (TADF-1; shown below; PLmax=548 nm, FWHM=92 nm) was doped into the first 3 nm of the HTL adjacent to the emissive layer at a doping concentration of about 20 wt %. Therefore the first 3 nm of TCTA adjacent to the emissive layer had approximately 20 wt %. TADF while the remaining 37 nm not adjacent to the emissive layer was pure TCTA.
Example 3 is the same as Example 2 except the TADF-1 molecule was doped into the first 5 nm of the HTL adjacent to the emissive layer at a doping concentration of about 20 wt %. Therefore the first 5 nm of TCTA adjacent to the emissive layer had approximately 20 wt %. TADF while the remaining 35 nm not adjacent to the emissive layer was pure TCTA.
Example 4 is the same as Example 2 except the TADF-1 molecule was doped into the first 7 nm of the HTL adjacent to the emissive layer at a doping concentration of about 20 wt %. Therefore the first 7 nm of TCTA adjacent to the emissive layer had approximately 20 wt %. TADF while the remaining 33 nm not adjacent to the emissive layer was pure TCTA.
Example 5 is the same as Example 2 except the TADF-1 molecule was doped into the first 9 nm of the HTL adjacent to the emissive layer at a doping concentration of about 20 wt %. Therefore the first 9 nm of TCTA adjacent to the emissive layer had approximately 20 wt %. TADF while the remaining 31 nm not adjacent to the emissive layer was pure TCTA.
It has been shown that TADF molecules and TCTA can form an exciplex excited state and so the photoluminescence quantum yield (PLQY) of such films can be diminished. The host material 3,3-di(9H-carbazol-9-yl)biphenyl (mCBP) has been used in TADF devices with great success, maintaining PLQY for films in the region of 90%. As such, another example device is presented whereby an mCBP HTL buffer is placed between the quantum dot emissive layer and the TCTA HTL.
In this example another exemplary electroluminescent QD-LED device was constructed according to the energy level diagram of
Example 7 is the same as Example 6 except the TADF-1 molecule was doped into about the first 2 nm of the HTL buffer adjacent to the emissive layer at a doping concentration of about 20 wt %. Therefore the first 2 nm of the HTL buffer adjacent to the emissive layer had approximately 20 wt %. TADF while the remaining 6 nm not adjacent to the emissive layer was pure mCBP.
Example 8 is the same as Example 7 except the TADF-1 molecule was doped into about the first 4 nm of the HTL buffer adjacent to the emissive layer at a doping concentration of about 20 wt %. Therefore the first 4 nm of the HTL buffer adjacent to the emissive layer had approximately 20 wt %. TADF while the remaining 4 nm not adjacent to the emissive layer was pure mCBP.
Example 9 is the same as Example 7 except the TADF-1 molecule was doped into about the first 6 nm of the HTL buffer adjacent to the emissive layer at a doping concentration of about 20 wt %. Therefore the first 6 nm of the HTL buffer adjacent to the emissive layer had approximately 20 wt %. TADF while the remaining 2 nm not adjacent to the emissive layer was pure mCBP.
Example 10 is the same as Example 7 except the TADF-1 molecule was doped into the entire HTL buffer layer adjacent to the emissive layer at a doping concentration of about 20 wt %.
In this example an electroluminescent QD-LED device was constructed according to the energy level diagram of
In this example, an emissive film comprising TADF molecules and QDs was prepared. A solution of green-emitting CFQD® quantum dots [Nanoco Technologies Limited, Manchester, UK] comprising indium and phosphorus (PLmax=527 nm, FWHM=40 nm) in toluene was prepared at a concentration of 2 mg/mL. A solution of sky blue-emitting TADF molecules (TADF-2 (shown below; PLmax=486 nm, FWHM=81 nm when deposited as a film) in toluene was prepared at a concentration of 10 mg/mL.
0.25 mL of the TADF solution and 5 mL of the QD solution were combined and spin-coated onto a quartz glass substrate at a rate of 2,000 rpm for 60 seconds to form a 20 nm film.
The PL spectrum and transient PL characteristics were measured. As can be seen in
In this example, an exemplary electroluminescent QD-LED device was constructed according to the energy level diagram of
Example 14 is the same as Example 13 except that the QD layer thickness was increased to 15 nm and a TADF molecule (TADF-2; PLmax=486 nm, FWHM=81 nm) was doped into the mCPB HTL buffer layer adjacent to the emissive layer at a doping concentration of about 30 wt %.
Example 15 is the same as Example 14, except that the QD layer thickness was reduced to 10 nm.
Example 16 is the same as Example 14, except that the TADF molecule was doped into the mCPB HTL buffer layer adjacent to the emissive layer at a doping concentration of about 40 wt %.
Example 17 was the same as Example 16, except that the QD layer thickness was reduced to 10 nm.
The optical properties of the devices prepared in Examples 13-17 are summarized in Table 2 and illustrated in
In accordance with various aspects of the present disclosure, electroluminescent (EL) devices comprising QDs and TADF molecules, as described herein, may be used to create a multi-element display device. For example, a display panel may comprise red, green and blue (RGB) pixels. One, two, or all three of the RGB pixels may comprise an electroluminescent device comprising QDs and TADF molecules. Where only one or two of the RGB pixels comprise an electroluminescent device comprising QDs and TADF molecules, the remaining pixel(s) may comprise one or more of the following: a QD-EL device (i.e., an EL device comprising QDs but no TADF molecules), a TADF-EL device (i.e., an EL device comprising TADF molecules but no QDs), a TADF hyperfluorescent device (i.e., a device where TADF molecules are used in conjunction with another type of emissive material such as, for example, an organic molecule, to achieve hyperflourescence), or an OLED device (i.e., an organic light emitting diode with neither QDs nor TADF molecules). For example, a blue pixel comprising QDs and TADF molecules may be used in combination with a green QD-EL pixel and a red OLED pixel. Also for example, a blue pixel comprising QDs and TADF molecules may be used in combination with a green QD-EL pixel and a pixel having red-emitting QDs and TADF molecules. These devices can have none, one or multiples of charge transport layers in common. For example, the ETL may be common across the subpixel or, alternatively, the p-type hole transport layers may be in common.
Although the present invention and its objects, features and advantages have been described in detail, other embodiments are encompassed by the invention. Finally, those skilled in the art should appreciate that they can readily use the disclosed conception and specific embodiments as a basis for designing or modifying other structures for carrying out the same purposes of the present invention without departing from the scope of the invention as defined by the appended claims.
This application claims the benefit of U.S. Provisional Application No. 62/656,074 filed Apr. 11, 2018, U.S. Provisional Application No. 62/673,344 filed May 18, 2018, and U.S. Provisional Application No. 62/703,226 filed Jul. 25, 2018. The contents of each application are incorporated by reference herein in their entirety.
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/IB2019/000393 | 4/4/2019 | WO | 00 |
| Number | Date | Country | |
|---|---|---|---|
| 62656074 | Apr 2018 | US | |
| 62673344 | May 2018 | US | |
| 62703226 | Jul 2018 | US |
