QUANTUM DOT, CURABLE COMPOSITION COMPRISING THE SAME, CURED LAYER USING THE COMPOSITION, COLOR FILTER INCLUDING THE CURED LAYER, DISPLAY DEVICE INCLUDING THE CURED LAYER AND METHOD OF MANUFACTURING THE CURED LAYER

Abstract

A quantum dot surface-modified with a ligand, a non-solvent curable composition including the quantum dot, a solvent-based curable composition including the quantum dot, a cured layer manufactured utilizing the curable composition, a color filter including the cured layer, a display device including the color filter, and a method of manufacturing the cured layer are disclosed.

Claims

1. A quantum dot surface-modified with one or more compounds represented by Chemical Formula 1 to Chemical Formula 14: ##STR00026## wherein, in Chemical Formula 1 to Chemical Formula 6, R.sup.1 to R.sup.7 are each independently a substituted or unsubstituted C1 to C10 alkyl group or a substituted or unsubstituted C6 to C20 aryl group, L.sup.1 to L.sup.16 are each independently a substituted or unsubstituted C1 to C10 alkylene group, and n1 to n7 are each independently an integer of 0 to 10, ##STR00027## wherein, in Chemical Formula 7 to Chemical Formula 9, R.sup.8 and R.sup.9 are each independently a substituted or unsubstituted C1 to C10 alkyl group, L.sup.17 to L.sup.23 are each independently a substituted or unsubstituted C1 to C10 alkylene group, and n8 to n10 are each independently an integer of 0 to 10, ##STR00028## wherein, in Chemical Formula 10 to Chemical Formula 13, R.sup.10 to R.sup.15 are each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group, L.sup.24 to L.sup.29 are each independently a substituted or unsubstituted C1 to C10 alkylene group, and n11 to n16 are each independently an integer of 0 to 10, ##STR00029## wherein, in Chemical Formula 14, R.sup.16 to R.sup.18 are each independently a substituted or unsubstituted C1 to C10 alkyl group, L.sup.30 to L.sup.32 are each independently a substituted or unsubstituted C1 to C10 alkylene group, and n17 to n19 are each independently an integer of 0 to 10.

2. The quantum dot of claim 1, wherein the quantum dot has a maximum fluorescence emission wavelength at about 500 nm to about 680 nm.

3. A non-solvent curable composition comprising a quantum dot, and a polymerizable monomer having a carbon-carbon double bond at a terminal end of the polymerizable monomer, wherein the polymerizable monomer is about 40 wt % to about 80 wt % in amount based on a total weight of the non-solvent curable composition, and the non-solvent curable composition does not contain any solvent.

4. The non-solvent curable composition of claim 3, wherein the polymerizable monomer has a molecular weight of about 220 g/mol to about 1,000 g/mol.

5. The non-solvent curable composition of claim 3, wherein the polymerizable monomer is represented by Chemical Formula 15: ##STR00030## wherein, in Chemical Formula 15, R.sup.19 and R.sup.2 are each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group, L.sup.33 and L.sup.35 are each independently a substituted or unsubstituted C1 to C10 alkylene group, and L.sup.34 is a substituted or unsubstituted C1 to C10 alkylene group or an ether group.

6. The non-solvent curable composition of claim 3, wherein the non-solvent curable composition further comprises a polymerization initiator, a light diffusing agent, or a combination thereof.

7. The non-solvent curable composition of claim 6, wherein the light diffusing agent comprises barium sulfate, calcium carbonate, titanium dioxide, zirconia, or a combination thereof.

8. The non-solvent curable composition of claim 6, wherein the non-solvent curable composition further comprises a polymerization inhibitor; malonic acid; 3-amino-1,2-propanediol; a silane-based coupling agent; a leveling agent; a fluorine-based surfactant; or a combination thereof.

9. The non-solvent curable composition of claim 3, wherein the quantum dot is surface-modified with one or more of compounds represented by Chemical Formula 1 to Chemical Formula 14: ##STR00031## wherein, in Chemical Formula 1 to Chemical Formula 6, R.sup.1 to R.sup.7 are each independently a substituted or unsubstituted C1 to C10 alkyl group or a substituted or unsubstituted C6 to C20 aryl group, L.sup.1 to L.sup.16 are each independently a substituted or unsubstituted C1 to C10 alkylene group, and n1 to n7 are each independently an integer of 0 to 10, ##STR00032## wherein, in Chemical Formula 7 to Chemical Formula 9, R.sup.8 and R.sup.9 are each independently a substituted or unsubstituted C1 to C10 alkyl group, L.sup.17 to L.sup.23 are each independently a substituted or unsubstituted C1 to C10 alkylene group, and n8 to n10 are each independently an integer of 0 to 10, ##STR00033## wherein, in Chemical Formula 10 to Chemical Formula 13, R.sup.10 to R.sup.15 are each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group, L.sup.24 to L.sup.29 are each independently a substituted or unsubstituted C1 to C10 alkylene group, and n11 to n16 are each independently an integer of 0 to 10, ##STR00034## wherein, in Chemical Formula 14, R.sup.16 to R.sup.18 are each independently a substituted or unsubstituted C1 to C10 alkyl group, L.sup.3 to L.sup.32 are each independently a substituted or unsubstituted C1 to C10 alkylene group, and n17 to n19 are each independently an integer of 0 to 10.

10. A solvent-based curable composition comprising the quantum dot of claim 1; a binder resin; and a solvent.

11. The solvent-based curable composition of claim 10, wherein the solvent-based curable composition further comprises a polymerizable monomer, a polymerization initiator, a light diffusing agent, or a combination thereof.

12. The solvent-based curable composition of claim 10, wherein the solvent-based curable composition is a photosensitive resin composition.

13. A cured layer manufactured utilizing the composition of claim 3.

14. A cured layer manufactured utilizing the composition of claim 10.

15. A color filter comprising the cured layer of claim 13.

16. A color filter comprising the cured layer of claim 14.

17. A display device comprising the color filter of claim 15.

18. A display device comprising the color filter of claim 16.

19. A method of manufacturing a cured layer, the method comprising: applying the composition of claim 3 onto a substrate by an ink-jet method to form a pattern; and curing the pattern.

20. A method of manufacturing a cured layer, the method comprising: applying the composition of claim 10 onto a substrate by an ink-jet method to form a pattern; and curing the pattern.

21. A method of manufacturing a cured layer, the method comprising: applying the composition of claim 3 onto a substrate by an ink-jet method to form a pattern; developing the pattern; and heat-treating the pattern.

22. A method of manufacturing a cured layer, the method comprising: applying the composition of claim 10 onto a substrate by an ink-jet method to form a pattern; developing the pattern; and heat-treating the pattern.

Description

EXAMPLE 1

[0215] The dispersion according to Preparation Example 1 was weighed and then, mixed and diluted with the monomer represented by Chemical Formula 15-1, and a polymerization inhibitor (methylhydroquinone, Tokyo Chemical Industry Co., Ltd.; 5 wt %) was added thereto and then, stirred for 5 minutes. Subsequently, a photoinitiator (TPO-L, Polynetron) was injected thereinto, and a light diffusing agent (TiO.sub.2; SDT89, Iridos Co., Ltd.) was added thereto. The entire dispersion was stirred for 1 hour to prepare a non-solvent curable composition. 8 wt % of the quantum dots, 80 wt % of the monomer represented by Chemical Formula 15-1, 1 wt % of the polymerization inhibitor, 3 wt % of the photoinitiator, and 8 wt % of the light diffusing agent were included based on a total amount of the non-solvent curable composition.

EXAMPLE 2

[0216] A non-solvent curable composition was prepared according to the same method as Example 1 except that the dispersion according to Preparation Example 2 was utilized instead of the dispersion according to Preparation Example 1.

EXAMPLE 3

[0217] A non-solvent curable composition was prepared according to the same method as Example 1 except that the dispersion according to Preparation Example 3 was utilized instead of the dispersion according to Preparation Example 1.

EXAMPLE 4

[0218] A non-solvent curable composition was prepared according to the same method as Example 1 except that the dispersion according to Preparation Example 4 instead of the dispersion according to Preparation Example 1 and a monomer represented by Chemical Formula 15-3 instead of the monomer represented by Chemical Formula 15-1 were utilized.

EXAMPLE 5

[0219] A non-solvent curable composition was prepared according to the same method as Example 2 except that 48 wt % of the quantum dots, 40 wt % of the monomer represented by Chemical Formula 15-1, 1 wt % of the polymerization inhibitor, 3 wt % of the photoinitiator, and 8 wt % of the light diffusing agent were utilized based on a total amount of the non-solvent curable composition.

COMPARATIVE EXAMPLE 1

[0220] A non-solvent curable composition was prepared according to the same method as Example 1 except that the dispersion of Comparative Preparation Example 1 instead of the dispersion of Preparation Example 1 and a monomer having no carbon-carbon double bond at the terminal end, OXT 221 (Toagosei Co., Ltd.) instead of the monomer represented by Chemical Formula 15-1 were utilized.

COMPARATIVE EXAMPLE 2

[0221] A non-solvent curable composition was prepared according to the same method as Example 2 except that 50 wt % of the quantum dots, 38 wt % of the monomer represented by Chemical Formula 15-1, 1 wt % of the polymerization inhibitor, 3 wt % of the photoinitiator, and 8 wt % of the light diffusing agent were utilized based on a total amount of the non-solvent curable composition.

COMPARATIVE EXAMPLE 3

[0222] A non-solvent curable composition was prepared according to the same method as Example 2 except that 6 wt % of the quantum dots, 82 wt % of the monomer represented by Chemical Formula 15-1, 1 wt % of the polymerization inhibitor, 3 wt % of the photoinitiator, and 8 wt % of the light diffusing agent were utilized based on a total amount of the non-solvent curable composition.

Evaluation 2: Evaluation of Optical Characteristics

[0223] Each composition according to Examples 1 to 5 and Comparative Examples 1 to 3 was coated to be about 15 pm thick on glass substrates (G-1, G-2) or yellow photoresists (YPR) (Y-1, Y-2) with a spin coater (800 rpm, 5 seconds, Opticoat MS-A150, Mikasa Co., Ltd.) and exposed with 5000 mJ/cm.sup.2 (83 C., 10 seconds) with a 395 nm UV exposer under a nitrogen atmosphere to prepare a cured film. Subsequently, a 2 cm2 cm single film specimen of each cured film was loaded in an integrating sphere equipment (QE-2100, Otsuka Electronics, Co., Ltd.) and measured with respect to a light absorption rate and light efficiency, and the results are shown in Tables 2 to 9.

TABLE-US-00002 TABLE 2 Exposure (5 J/cm.sup.2, N.sub.2) Light External Maximum Full width at Example absorption quantum emission half 1 rate efficiency wavelength maximum Thickness (Green) (%) (E.Q.E) (%) (nm) (FWHM) (m) G-1 19.5 16.8 538.5 34.4 15.38 G-2 19.6 16.9 538.4 34.5 15.41 Y-1 100 9.7 538.5 34.5 15.38 Y-2 100 9.8 538.4 34.5 15.41

TABLE-US-00003 TABLE 3 Exposure (5 J/cm.sup.2, N.sub.2) Light External Maximum Full width Example absorption quantum emission at half 2 rate efficiency wavelength maximum Thickness (Green) (%) (E.Q.E) (%) (nm) (FWHM) (m) G-1 20.5 18.8 538.2 34.4 15.2 G-2 20.4 18.7 538.2 34.4 15.3 Y-1 100 10.2 538.1 34.5 15.2 Y-2 100 10.2 538.2 34.5 15.3

TABLE-US-00004 TABLE 4 Exposure (5 J/cm.sup.2, N.sub.2) Light External Maximum Full width Example absorption quantum emission at half 3 rate efficiency wavelength maximum Thickness (Green) (%) (E.Q.E) (%) (nm) (FWHM) (m) G-1 20.3 18.7 538.3 34.5 15.7 G-2 20.4 18.8 538.2 34.5 15.6 Y-1 100 10.1 538.5 34.5 15.7 Y-2 100 10.1 538.4 34.5 15.6

TABLE-US-00005 TABLE 5 Exposure (5 J/cm.sup.2, N.sub.2) Light External Maximum Full width Example absorption quantum emission at half 4 rate efficiency wavelength maximum Thickness (Green) (%) (E.Q.E) (%) (nm) (FWHM) (m) G-1 19.7 18.5 539.3 34.4 15.2 G-2 19.9 18.5 539.4 34.5 15.2 Y-1 100 9.9 539.3 34.5 15.2 Y-2 100 9.9 539.4 34.6 15.2

TABLE-US-00006 TABLE 6 Exposure (5 J/cm.sup.2, N.sub.2) Light External Maximum Full width Example absorption quantum emission at half 5 rate efficiency wavelength maximum Thickness (Green) (%) (E.Q.E) (%) (nm) (FWHM) (m) G-1 97.5 35.5 542.5 35.1 15.4 G-2 97.6 35.4 542.3 35.2 15.3 Y-1 100 33.0 542.1 35.1 15.4 Y-2 100 33.1 542.2 35.2 15.3

TABLE-US-00007 TABLE 7 Exposure (5 J/cm.sup.2, N.sub.2) Comparative Light External Maximum Full width Example absorption quantum emission at half Thick- 1 rate efficiency wavelength maximum ness (Green) (%) (E.Q.E) (%) (nm) (FWHM) (m) G-1 15.3 7.2 538.1 34.4 15.1 G-2 15.5 7.4 538.2 34.3 15.3 Y-1 100 3.8 538.1 34.3 15.1 Y-2 100 3.9 538.2 34.4 15.3

TABLE-US-00008 TABLE 8 Exposure (5 J/cm.sup.2, N.sub.2) Comparative Light External Maximum Full width Example absorption quantum emission at half Thick- 2 rate efficiency wavelength maximum ness (Green) (%) (E.Q.E) (%) (nm) (FWHM) (m) G-1 94.3 31.3 540.8 34.5 15.5 G-2 94.2 31.5 540.9 34.4 15.4 Y-1 100 27.5 540.8 34.5 15.5 Y-2 100 27.4 540.9 34.4 15.4

TABLE-US-00009 TABLE 9 Exposure (5 J/cm.sup.2, N.sub.2) Comparative Light External Maximum Full width Example absorption quantum emission at half Thick- 3 rate efficiency wavelength maximum ness (Green) (%) (E.Q.E) (%) (nm) (FWHM) (m) G-1 15.5% 7.8 539.8 34.3 15.3 G-2 15.6% 7.6 539.8 34.4 15.3 Y-1 100 3.3 539.9 34.3 15.3 Y-2 100 3.5 539.9 34.3 15.3
Evaluation 3: Discharge Rate of Non-solvent curable composition Depending on Latency Time

[0224] Each non-solvent curable composition according to Examples 1 to 5 and Comparative Examples 1 to 3 was evaluated with respect to a discharge rate depending on (e.g., as a function of) latency time in the following method, and the results are shown in Table 10.

[0225] The non-solvent curable compositions were respectively jetted through 100 nozzles on an ink-jet equipment on pixels of a substrate and then, the jetting was stopped and the nozzles were maintained as they were. Subsequently, when the non-solvent curable compositions were jetted by a set or predetermined time (latency time) unit, the number of nozzles not clogged but capable of well discharging the non-solvent curable compositions was counted. That is, after a set or predetermined time (latency time) unit has passed since the time the initial jetting of the non-solvent curable compositions was stopped, the number of nozzles that remain unclogged was counted.

TABLE-US-00010 TABLE 10 (unit: number) Time (Latency time) (hrs.) 0 2 4 8 12 16 20 24 28 Example 1 100 100 100 100 100 100 100 100 90 Example 2 100 100 100 100 100 100 100 100 99 Example 3 100 100 100 100 100 100 100 100 95 Example 4 100 100 100 100 100 100 100 100 92 Example 5 100 100 100 100 100 100 100 100 97 Comparative 100 100 100 90 80 75 35 0 0 Example 1 Comparative 100 100 100 95 87 80 38 5 0 Example 2 Comparative 100 100 100 93 85 78 30 0 0 Example 3

Evaluation 4: Room Temperature (25 C.) Storage Stability of Non-solvent Curable Composition

[0226] The non-solvent curable compositions according to Examples 1 to 5 and Comparative Examples 1 to 3 were evaluated with respect to room temperature storage stability depending on latency time by calculating a viscosity difference from initial viscosity after time went (e.g., as a function of time), and the results are shown in Table 11. That is, the room temperature storage stability is indicated by the change in viscosity from the initial viscosity as a function of storage time.

[0227] The viscosities were measured by utilizing a viscosity meter (RheoStress 6000, HAAKE Technik GmbH) at room temperature at 100 rpm for 2 minutes.

TABLE-US-00011 TABLE 11 (unit: cPs) Time (weeks) 0 1 week 2 weeks 3 weeks 4 weeks Example 1 10.1 10.2 10.1 10.3 10.4 Example 2 11.5 11.4 11.5 11.4 11.5 Example 3 11.7 11.7 11.6 11.8 11.8 Example 4 11.9 11.9 11.8 11.9 11.9 Example 5 24.3 24.4 24.4 24.5 24.5 Comparative 10.3 11.5 12.1 12.5 13.2 Example 1 Comparative 28.5 28.6 28.7 28.9 29.1 Example 2 Comparative 10.8 11.3 12.6 13.0 14.5 Example 3

[0228] Referring to Evaluations 1 to 4, the non-solvent curable composition according to an embodiment had appropriately-adjusted viscosity for ink-jetting as well as exhibited suitable (e.g., very excellent) optical characteristics. Furthermore, storage stability was also suitable (e.g., excellent) at room temperature.

Preparation of Solvent-based Curable Composition

EXAMPLE 6

[0229] The dispersion according to Preparation Example 1 was weighed to disperse quantum dots (23 wt %) in dimethyl adipate (45 wt %) and mixed with a cardo-based binder resin (TSR-TA01, TAKOMA) (8 wt %) to prepare a quantum dot dispersion. Subsequently, OXT-221 (Toagosei Co., Ltd.) (1 wt %) and PFM-02 (SMS) (16.5 wt %) as a thermosetting monomer, a light diffusing agent (TiO.sub.2; SDT89, Iridos Co., Ltd.) (2 wt %), glycol di-3-mercaptopropionate (Bruno Bock Chemische Fabrik GMBH & CO., KG) (4.2 wt %), and methyl hydroquinone (TCI) (0.3 wt %) as a polymerization inhibitor were mixed, and the quantum dot dispersion was added thereto and then, stirred to prepare a solvent-based curable composition.

EXAMPLE 7

[0230] A solvent-based curable composition (photosensitive resin composition) was prepared utilizing the following components in the corresponding amount.

[0231] 1) Quantum dot: 12 wt % of quantum dots obtained from Preparation Example 1

[0232] 2) Binder resin: 25 wt % of a cardo-based binder resin (TSR-TA01, TAKOMA)

[0233] 3) Polymerizable monomer: 5.4 wt % of pentaerythritolhexamethacrylate (DPHA, Nippon Kayaku Co. Ltd.)

[0234] 4) Photopolymerization initiator: 0.7 wt % of diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (TPO, Sigma-Aldrich Corporation)

[0235] 5) Solvent: 39 wt % of dimethyladipate

[0236] 6) Diffusing agent: 39 wt % of titanium dioxide dispersion (a TiO2 solid content: 20 wt %, an average particle diameter: 200 nm, Ditto Technology)

[0237] 7) Thiol additive: 2 wt % of glycol di-3-mercaptopropionate (BRUNO BOCK)

[0238] 8) Other additives: 0.9 wt % of a fluorine-based surfactant (F-554, DIC Co., Ltd.)

[0239] Specifically, the photopolymerization initiator was dissolved in the solvent, and the solution was sufficiently stirred at room temperature for 2 hours. Subsequently, the binder resin along with the photo-conversion material and the dispersing agent (TEGO D685 made by EVONIK) were added thereto, and the obtained mixture was stirred again at room temperature for 2 hours. Then, the diffusing agent and the fluorine-based surfactant were added thereto and then, stirred for 1 hour at room temperature, and the product therein was filtered three times to remove impurities to prepare the photosensitive resin composition.

Evaluation 5: Photo-conversion Rate and Photo-conversion Maintenance Rate of Quantum Dots

[0240] The curable compositions according to Examples 6 and 7 were respectively coated to be 2 m thick on a glass substrate with a spin coater (150 rpm, Opticoat MS-A150, Mikasa Co., Ltd.) and then, dried on a hot-plate at 80 C. for 1 minute to obtain a short film, and an initial blue photo-conversion rate thereof was measured (First Step).

[0241] The obtained film was dried in a forced convection dryer at 220 C. for 40 minutes, and a blue photo-conversion rate thereof was measured (Second Step).

[0242] In the first and second steps, a photo-conversion rate and a photo-conversion maintenance rate of incident blue light from BLU (Backlight Unit) into green were evaluated, and the results are shown in Table 12. Herein, a blue photo conversion rate (Green/Blue) was measured by utilizing a CAS 140 CT spectrometer and specifically, through putting (e.g., loading) a bare glass on blue BLU (455 nm) covered with a diffusing film to first obtain a reference with a detector, putting (e.g., loading) each short film coated with the solvent-based curable compositions according to Examples 6 to 7, and calculating a peak increase converted into green light relative to an absorption peak decrease of blue light. That is, the photo-conversion rate is calculate as the ratio of the amount of increase in the peak height of the green light to the amount of decrease in the peak height of the blue light in the absorption spectrum, each based on the bare glass on blue BLU (455 nm) covered with the diffusing film. In addition, how much the photo-conversion rate in the first step was maintained in the second step, that is, a photo-conversion maintenance rate from the first step to the second step was also measured, and the results are shown in Table 12.

[0243] In addition, as for the solvent-based curable composition of Example 7, a photo-conversion rate was measured with an exposer (ghi broadband, Ushio Inc.) by performing post-baking (POB) in a convection clean oven (Jongro) at 180 C. for 30 minutes after irradiating UV with a power of 100 mJ/cm.sup.2, and the results are shown in

[0244] Table 13.

TABLE-US-00012 TABLE 12 (unit: %) Example 6 Example 7 Photo-conversion rate 28 25 Photo-conversion 95 93 maintenance rate

TABLE-US-00013 TABLE 13 (unit: %) Example 7 Initial photo-conversion rate 25 Photo-conversion rate after POB is once 21.8 performed at 180 C. for 30 min

[0245] As shown in Tables 12 and 13, the solvent-based curable composition prepared by utilizing surface-modified quantum dots according to an embodiment exhibited small deterioration of a blue photo-conversion rate due to a color filter process but exhibited a high photo-conversion maintenance rate.

[0246] Expressions such as at least one of or at least one selected from when preceding a list of elements, modify the entire list of elements and do not modify the individual elements of the list. Further, the use of may when describing embodiments of the present invention refers to one or more embodiments of the present invention. Also, the term exemplary is intended to refer to an example or illustration. As used herein, the term substantially, about, and similar terms are used as terms of approximation and not as terms of degree, and are intended to account for the inherent deviations in measured or calculated values that would be recognized by those of ordinary skill in the art. Moreover, any numerical range recited herein is intended to include all sub-ranges of the same numerical precision subsumed within the recited range. For example, a range of 1.0 to 10.0 is intended to include all subranges between (and including) the recited minimum value of 1.0 and the recited maximum value of 10.0, that is, having a minimum value equal to or greater than 1.0 and a maximum value equal to or less than 10.0, such as, for example, 2.4 to 7.6. Any maximum numerical limitation recited herein is intended to include all lower numerical limitations subsumed therein and any minimum numerical limitation recited in this specification is intended to include all higher numerical limitations subsumed therein. Accordingly, Applicant reserves the right to amend this specification, including the claims, to expressly recite any sub-range subsumed within the ranges expressly recited herein. All such ranges are intended to be inherently described in this specification such that amending to expressly recite any such subranges would comply with the requirements of 35 U.S.C. 112, first paragraph, or 35 U.S.C. 112(a), and 35 U.S.C. 132(a).

[0247] The terminology used herein is for the purpose of describing particular example embodiments only and is not intended to be limiting of the invention. As used herein, the singular forms a, an and the are intended to include the plural forms as well, unless the context clearly indicates otherwise. It will be further understood that the terms comprises and/or comprising, when used in this specification, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof.

[0248] While this disclosure has been described in connection with what is presently considered to be practical example embodiments, it is to be understood that the subject matter of the present disclosure is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims, and equivalents thereof. Therefore, the aforementioned embodiments should be understood to be exemplary but not limiting the subject matter of the present disclosure in any way.