Patent Application
20210017413
The present invention relates to particles, an ink, and a light-emitting device.
Devices that utilize electroluminescence, such as LEDs and organic EL devices, are widely used as light sources for various display apparatuses. In recent years, light-emitting devices that include light-emitting semiconductor nanocrystals, such as quantum dots and quantum rods, as light-emitting materials have attracted attention. Light emitted from semiconductor nanocrystals has good color reproducibility due to its narrower spectral width and wider color gamut than organic EL devices. In general, semiconductor nanocrystals support an organic ligand (dispersant) on their surfaces. In the production of light-emitting devices, the organic ligand is an impurity in the light-emitting layer.
The organic ligand therefore decreases the emission lifetime of the light-emitting layer (light-emitting device). Thus, it has been proposed that the light-emitting layer is selectively heat-treated with laser irradiation heat to remove the organic ligand (see Patent Literature 1, for example). Such a method, however, requires accurate laser beam irradiation of the light-emitting layer, which makes the operation complicated. The laser beam also tends to cause damage to the semiconductor nanocrystals. Thus, a sufficiently improved emission lifetime cannot be expected.
PTL 1: International Publication WO 2011/148791
It is an object of the present invention to provide particles in which a dispersant can be easily removed from semiconductor nanocrystals, an ink with good storage stability, and a light-emitting device with a long emission lifetime.
Such objects of the present invention can be achieved by the following (1) to (6).
(1) Particles containing
light-emitting semiconductor nanocrystals and
a dispersant supported on the semiconductor nanocrystals and having a boiling point of 300° C. or less at atmospheric pressure.
(2) An ink containing
particles described in (1) and
a dispersion medium having a boiling point equal to or higher than the boiling point of the dispersant at atmospheric pressure and containing a polar compound with a polar group.
(3) The ink according to (2), wherein the polar compound has a boiling point of 350° C. or less at atmospheric pressure.
(4) The ink according to (2) or (3), wherein the polar compound constitutes 20% to 80% by mass of the dispersion medium.
(5) The ink according to any one of (2) to (4), wherein the polar group is at least one selected from the group consisting of a hydroxy group and a carbonyl group.
(6) A light-emitting device including
a pair of electrodes,
a light-emitting layer located between the pair of electrodes and containing a dried product of the ink according to any one of (2) to (5), and
a charge-transport layer located between the light-emitting layer and at least one electrode of the pair of electrodes,
wherein the dispersant constitutes 25 ppm or less of the light-emitting layer.
The present invention can provide particles in which a dispersant can be easily removed from semiconductor nanocrystals, an ink with good storage stability, and a light-emitting device with a long emission lifetime.
Particles, an ink, and a light-emitting device according to the present invention are described in detail below with preferred embodiments with reference to accompanying drawings.
An ink according to the present invention contains particles (particles according to the present invention), which contain light-emitting semiconductor nanocrystals and a dispersant supported on the semiconductor nanocrystals, and a dispersion medium for dispersing the particles.
If necessary, an ink according to the present invention may contain a charge-transport material and a surfactant, for example.
The particles contain semiconductor nanocrystals and a dispersant supported on the semiconductor nanocrystals. Semiconductor nanocrystals (hereinafter also referred to simply as “nanocrystals”) are nanoscale crystals (nanocrystal particles) that absorb excitation light and emit fluorescence or phosphorescence, for example, crystals with a maximum particle size of 100 nm or less as measured with a transmission electron microscope or a scanning electron microscope.
For example, nanocrystals can be excited by light energy or electrical energy at a specified wavelength and emit fluorescence or phosphorescence.
The nanocrystals may be red-light-emitting crystals that emit light with an emission peak in the wavelength range of 605 to 665 nm (red light), green-light-emitting crystals that emit light with an emission peak in the wavelength range of 500 to 560 nm (green light), or blue-light-emitting crystals that emit light with an emission peak in the wavelength range of 420 to 480 nm (blue light). In one embodiment, an ink preferably contains at least one type of nanocrystals among these types of nanocrystals.
The emission peak wavelength of nanocrystals can be determined in a fluorescence spectrum or a phosphorescence spectrum measured with an ultraviolet-visible spectrophotometer, for example.
The red-light-emitting nanocrystals preferably have an emission peak in the wavelength range of 665 nm or less, 663 nm or less, 660 nm or less, 658 nm or less, 655 nm or less, 653 nm or less, 651 nm or less, 650 nm or less, 647 nm or less, 645 nm or less, 643 nm or less, 640 nm or less, 637 nm or less, 635 nm or less, 632 nm or less, or 630 nm or less and preferably have an emission peak in the wavelength range of 628 nm or more, 625 nm or more, 623 nm or more, 620 nm or more, 615 nm or more, 610 nm or more, 607 nm or more, or 605 nm or more.
Any of these upper limits and lower limits may be combined. Also in the following similar description, any of each upper limit and each lower limit may be combined.
The green-light-emitting nanocrystals preferably have an emission peak in the wavelength range of 550 nm or less, 557 nm or less, 555 nm or less, 550 nm or less, 547 nm or less, 545 nm or less, 543 nm or less, 540 nm or less, 537 nm or less, 535 nm or less, 532 nm or less, or 530 nm or less and preferably have an emission peak in the wavelength range of 528 nm or more, 525 nm or more, 523 nm or more, 520 nm or more, 515 nm or more, 510 nm or more, 507 nm or more, 505 nm or more, 503 nm or more, or 500 nm or more.
The blue-light-emitting nanocrystals preferably have an emission peak in the wavelength range of 460 nm or less, 477 nm or less, 475 nm or less, 470 nm or less, 467 nm or less, 465 nm or less, 463 nm or less, 460 nm or less, 457 nm or less, 455 nm or less, 452 nm or less, or 450 nm or less and preferably have an emission peak in the wavelength range of 450 nm or more, 445 nm or more, 440 nm or more, 435 nm or more, 430 nm or more, 428 nm or more, 425 nm or more, 422 nm or more, or 420 nm or more.
The wavelength (emission color) of light emitted by nanocrystals depends on the size (for example, particle size) of the nanocrystals according to the solution of the Schrodinger wave equation of a potential well model and also depends on the energy gap of the nanocrystals. Thus, the constituent material and size of nanocrystals can be changed to select (adjust) the emission color.
The nanocrystals may be formed of a semiconductor material and have various structures. For example, the nanocrystals may be composed entirely of a core formed of a first semiconductor material or may be composed of a core formed of the first semiconductor material and a shell covering at least part of the core and formed of a second semiconductor material different from the first semiconductor material. In other words, the nanocrystals may have a structure composed entirely of a core (core structure) or composed of a core and a shell (core/shell structure).
In addition to the shell (first shell) formed of the second semiconductor material, the nanocrystals may further have a shell (second shell) covering at least part of the shell and formed of a third semiconductor material different from the first and second semiconductor materials. In other words, the nanocrystals may have a structure composed of the core, the first shell, and the second shell (core/shell/shell structure).
Each of the core and the shell may be formed of mixed crystals containing two or more semiconductor materials (for example, CdSe+CdS, CIS+ZnS, etc.).
The nanocrystals are preferably formed of at least one semiconductor material selected from the group consisting of group II-VI semiconductors, group III-V semiconductors, group I-III-VI semiconductors, group IV semiconductors, and group I-II-IV-VI semiconductors.
Specific examples of the semiconductor materials include CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, CdHgZnTe, CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, HgZnSTe, CaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, GaNP, GaNAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP, GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, InAlPSb; SnS, SnSe, SnTe, PbS, PbSe, PbTe, SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, SnPbSSe, SnPbSeTe, SnPbSTe, Si, Ge, SiC, SiGe, AgInSe2, CuGaSe2, CuInS2, CuGaS2, CuInSe2, AgInS2, AgGaSe2, AgGaS2, and C.
The semiconductor materials preferably contain at least one selected from the group consisting of CdS, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, InP, InAs, InSb, GaP, GaAs, GaSb, AgInS2, AgInSe2, AgInTe2, AgGaS2, AgGaSe2, AgGaTe2, CuInS2, CuInSe2, CuInTe2, CuGaS2, CuGaSe2, CuGaTe2, Si, C, Ge, and Cu2ZnSnS4.
The nanocrystals formed of these semiconductor materials can have an easily-controlled emission spectrum, high reliability, low production costs, and improved mass productivity.
Examples of the red-light-emitting nanocrystals include CdSe nanocrystals; rod-like CdSe nanocrystals; rod-like nanocrystals with a CdS shell and a CdSe core; rod-like nanocrystals with a CdS shell and a ZnSe core; nanocrystals with a CdS shell and a CdSe core; nanocrystals with a CdS shell and a ZnSe core; nanocrystals with a ZnS shell and an InP core; nanocrystals with a ZnS shell and a CdSe core; CdSe and ZnS mixed nanocrystals; rod-like CdSe and ZnS mixed nanocrystals; InP nanocrystals; rod-like InP nanocrystals; CdSe and CdS mixed nanocrystals; rod-like CdSe and CdS mixed nanocrystals; ZnSe and CdS mixed nanocrystals; and rod-like ZnSe and CdS mixed nanocrystals.
Examples of the green-light-emitting nanocrystals include CdSe nanocrystals; rod-like CdSe nanocrystals; nanocrystals with a ZnS shell and an InP core; nanocrystals with a ZnS shell and a CdSe core; CdSe and ZnS mixed nanocrystals; and rod-like CdSe and ZnS mixed nanocrystals.
Examples of the blue-light-emitting nanocrystals include ZnSe nanocrystals; rod-like ZnSe nanocrystals; ZnS nanocrystals; rod-like ZnS nanocrystals; nanocrystals with a ZnSe shell and a ZnS core; rod-like nanocrystals with a ZnSe shell and a ZnS core; CdS nanocrystals; and rod-like CdS nanocrystals.
The color of light emitted by nanocrystals with a fixed chemical composition can be altered to red or green by adjusting the average particle size of the nanocrystals.
The nanocrystals by themselves preferably have minimal adverse effects on human bodies. Thus, nanocrystals containing minimal amounts of cadmium, selenium, or the like are preferably used alone. When nanocrystals containing these elements (cadmium, selenium, etc.) are used, the nanocrystals are preferably used in combination with other nanocrystals to minimize the amounts of these elements.
The nanocrystals may have any shape, may have any geometrical shape, and may have any irregular shape. For example, the nanocrystals may be spherical, regular tetrahedral, ellipsoidal, pyramid-like, discoid, branched, netlike, or rod-like. The nanocrystals preferably have a less directional shape (for example, spherical, regular tetrahedral, etc.) The use of nanocrystals with such a shape can improve the uniformity and fluidity of the ink.
The nanocrystals preferably have an average particle size (volume-average size) of 40 nm or less, more preferably 30 nm or less, still more preferably 20 nm or less. Nanocrystals with such an average particle size are preferred because such nanocrystals can easily emit light with a desired wavelength.
The nanocrystals preferably have an average particle size (volume-average size) of 1 nm or more, more preferably 1.5 nm or more, still more preferably 2 nm or more. Nanocrystals with such an average particle size are also preferred, because such nanocrystals can easily emit light with a desired wavelength and also have improved dispersibility in the ink and improved storage stability.
The average particle size (volume-average size) of nanocrystals can be measured with a transmission electron microscope or a scanning electron microscope and can be calculated as a volume-average size.
The nanocrystals have surface atoms that can function as coordination sites and therefore have high reactivity. Due to their high reactivity and higher surface area than common pigments, the nanocrystals are more likely to agglomerate.
The nanocrystals emit light due to the quantum size effect. Thus, agglomeration of the nanocrystals causes a quenching phenomenon, decreases the fluorescence quantum yield, and decreases luminance and color reproducibility. Thus, inks in which nanocrystals are dispersed in a dispersion medium as in the present invention tend to cause a degradation in light-emitting properties due to agglomeration, unlike inks in which an organic light-emitting material is dissolved in a solvent. Thus, it is important for an ink according to the present invention to be prepared such that nanocrystals have high dispersion stability.
Accordingly, in the present invention, a dispersant (organic ligand) miscible with a dispersion medium is supported (held) on the surface of nanocrystals, or in other words the surface of nanocrystals is inactivated by the dispersant. The dispersant can improve the dispersion stability of the nanocrystals in the ink.
The dispersant is supported on the surface of the nanocrystals, for example, by a covalent bond, a coordinate bond, an ionic bond, a hydrogen bond, or a van der Waals bond. The term “support”, as used herein, collectively refers to the state in which a dispersant is adsorbed on, adheres to, or is bonded to the surface of nanocrystals. The dispersant can be detached from the surface of the nanocrystals, keep an equilibrium between the support by the nanocrystals and the detachment from the nanocrystals, and repeat these.
The dispersant may be any compound that can improve the dispersion stability of nanocrystals in the ink. The dispersant may be a low-molecular-weight dispersant or a high-molecular-weight dispersant. The term “low-molecular-weight”, as used herein, refers to a molecule with a weight average molecular weight (Mw) of 5,000 or less. The term “high-molecular-weight”, as used herein, refers to a molecule with a weight-average molecular weight (Mw) of more than 5,000.
The term “weight-average molecular weight (Mw)”, as used herein, refers to a molecular weight measured by gel permeation chromatography (GPC) based on polystyrene standards.
Examples of the low-molecular-weight dispersant include oleic acid; compounds containing a phosphorus atom, such as triethyl phosphate, trioctylphosphine (TOP), trioctylphosphine oxide (TOPO), hexylphosphonic acid (HPA), tetradecylphosphonic acid (TDPA), and octylphosphinic acid (OPA); compounds containing a nitrogen atom, such as oleylamine, octylamine, trioctylamine, and hexadecylamine; and compounds containing a sulfur atom, such as 1-decanethiol, octanethiol, 1-tridecanethiol, and amyl sulfide.
Examples of to high-molecular-weight dispersant include high-molecular-weight compounds with a functional group that can be supported on the surface of the nanocrystals.
Examples of such a functional group include a primary amino group, a secondary amino group, a tertiary amino group, a phosphoric acid group, a phosphoric acid ester group, a phosphonic acid croup, a phosphonic acid ester group, a phosphinic acid group, a phosphinic acid ester group, a thiol group, a thioether group, a sulfonic acid group, a sulfonic acid ester group, a carboxylic acid group, a carboxylic acid ester group, a hydroxy group, a ether group, an imidazolyl group, a triazinyl group, a pyrrolidonyl group, an isocyanuric acid group, a boric acid ester group, and a boronic acid group.
Among these, a plurality of functional groups are preferably combined; a primary amino group, a secondary amino group, a tertiary amino group, a carboxylic acid ester group, a hydroxy group, and an ether group are preferred in terms of the ease of synthesis of a high-molecular-weight compound with increased ability be supported on nanocrystals, and a phosphoric acid group, a phosphoric acid ester group, a phosphonic acid group, a phosphonic acid ester group, and a carboxylic acid group are preferred in terms of sufficient ability to be supported on nanocrystals even by itself.
Furthermore, a primary amino group, a secondary amino group, a tertiary amino group, a phosphoric acid group, a phosphonic acid group, and a carboxylic acid group are more preferred in terms of high ability to be supported on nanocrystals in the ink.
Examples of a high-molecular-weight dispersant with a primary amino group include linear amines, such as poly(alkylene glycol) amines, polyester amines, urethane-modified polyester amines, poly(alkylene glycol) diamines, polyester diamines, and urethane-modified polyester diamines, and (meth)acrylic polymers with an amino group on a side chain, that is, comb-like polyamines.
Examples of a high-molecular-weight dispersant with a secondary amino group include comb block copolymers that have a main chain including a linear polyethyleneimine backbone with many secondary amino groups and a side chain, such as a polyester, acrylic resin, or polyurethane.
Examples of a high-molecular-weight dispersant with a tertiary amino group include star-shaped amines, such as tri(poly(alkylene glycol)) amines.
Examples of high-molecular-weight dispersants with a primary amino group, a secondary amino group, and a tertiary amino group include high-molecular-weight compounds with a linear or multi-branched polyethyleneimine block and a poly(ethylene glycol) block described in Japanese Unexamined Patent Application Publication Nos. 2008-037884, 2008-037949, 2008-03818, and 2010-007124.
Examples of a high-molecular-weight dispersant with a phosphoric acid group include poly(alkylene glycol) monophosphates, poly(alkylene glycol) monoalkyl ether monophosphates, perfluoroalkyl polyoxyalkylene phosphates, perfluoroalkyl sulfonamide polyoxyalkylene phosphates, homopolymers of monomers, such as acid phosphoxyethyl mono(meth)acrylate, acid phosphoxypropyl mono(meth)acrylate, and acid phosphoxy polyoxyalkylene glycol mono(meth)acrylates, copolymers of these monomers and other comonomers; and (meth)acrylic polymers with a phosphoric acid group produced by a method described in Japanese Patent No. 4697356.
For a high-molecular-weight dispersant with a phosphoric acid group, an alkali metal hydroxide or an alkaline-earth metal hydroxide may be allowed to react to form a salt and adjust the pH.
Examples of a high-molecular-weight dispersant with a phosphonic acid group include poly(alkylene glycol) monoalkyl phosphonates, poly(alkylene glycol) monoalkyl ether monoalkyl phosphonates, perfluoroalkyl polyoxyalkylene alkyl phosphonates, perfluoroalkyl sulfonamide polyoxyalkylene alkyl phosphonates, polyethylene phosphonic acid; homopolymers of monomers, such as vinylphosphonic acid, (meth)acryloyloxyethylphosphonic acid, (meth)acryloyloxypropylphosphonic acid, and (meth)acryloyloxypolyoxyalkylene glycol phosphonic acid, and copolymers of these monomers and other comonomers.
For a high-molecular-weight dispersant with a phosphonic acid group, an alkali metal hydroxide or an alkaline earth metal hydroxide may be allowed to react to form a salt and adjust the pH.
Examples of a high-molecular-weight dispersant with a phosphinic acid group include poly(alkylene glycol) dialkyl phosphinates, perfluoroalkyl polyoxyalkylene dialkyl phosphinates, perfluoroalkyl sulfonamide polyoxyalkylene dialkyl phosphinates, polyethylenephosphinic acid; homopolymers of monomers, such as vinylphosphinic acid, (meth)acryloyloxydialkylphosphinic acids, and (meth)acryloyloxypolyoxyalkylene glycol dialkylphosphinic acids, and copolymers of these monomers and other comonomers. For a high-molecular-weight dispersant with a phosphinic acid group, an alkali metal hydroxide or an alkaline-earth metal hydroxide may be allowed to react to form a salt and adjust the pH.
Examples of a high-molecular-weight dispersant with a thiol group include polyvinyl thiol and poly(alkylene glycol) ethylenethiols.
Examples of a high-molecular-weight dispersant with a thioether group include poly(alkylene glycol) thioethers produced by a reaction between mercaptopropionic acid and a glycidyl-modified poly(alkylene glycol) described in Japanese Unexamined Patent Application Publication No. 2013-60637.
Examples of a high-molecular-weight dispersant with sulfonic acid group include poly(alkylene glycol) monoalkyl sulfonates, poly(alkylene glycol) monoalkyl ether monoalkyl sulfonates, perfluoroalkyl polyoxyalkylene alkyl sulfonates, perfluoroalkyl sulfonamide polyoxyalkylene alkyl sulfonates, polyethylenesulfonic acid; homopolymers of monomers, such as vinylsulfonic acid, (meth)acryloyloxyalkylsulfonic acids, (meth)acryloyloxypolyoxyalkylene glycol sulfonic acids, and poly(styrene sulfonate), and copolymers of these monomers and other comonomers.
For a high-molecular-weight dispersant with a sulfonic acid group, an alkali metal hydroxide or an alkaline-earth metal. hydroxide may be allowed to react to form a salt and adjust the pH.
Examples of a high-molecular-weight dispersant with a carboxylic acid group include poly(alkylene glycol) carboxylic acids, perfluoroalkyl polyoxyalkylene carboxylic acids, polyethylene carboxylic acid, polyester monocarboxylic acids, polyester dicarboxylic acids, urethane-modified polyester monocarboxylic acids, urethane-modified polyester dicarboxylic acids; homopolymers of monomers, such as vinylcarboxylic acid, (meth)acryloyloxyalkyl carboxylic acids, and (meth)acryloyloxypolyoxyalkylene glycol carboxylic acids, and copolymers of these monomers and other comonomers.
For a high-molecular-weight dispersant with a carboxylic acid group, an alkali metal hydroxide or an alkaline-earth metal hydroxide may be allowed to react to form a salt and adjust the pH.
A high-molecular-weight dispersant with an ester group can be produced by dehydration condensation between the high-molecular-weight dispersant with a carboxylic acid group and, for example, a monoalkyl alcohol.
Examples of a high-molecular-weight dispersant with a pyrrolidonyl group include polyvinylpyrrolidone.
A high-molecular-weight dispersant with a particular functional group may be a synthetic product or a commercial product.
Examples of the commercial product include DISPERBYK series manufactured by BYK-Chemie, such as DISPERBYK-102, DISPERBYK-103, DISPERBYK-108, DISPERBYK-109, DISPERBYK-110, DISPERBYK-111, DISPERBYK-118, DISPERBYK-140, DISPERBYK-145, DISPERBYK-161, DISPERBYK-164, DISPERBYK-168, DISPERBYK-180, DISPERBYK-182, DISPERBYK-184, DISPERBYK-185, DISPERBYK-190, DISPERBYK-191, DISPERBYK-2000, DISPERBYK-2001, DISPERBYK-2008, DISPERBYK-2009, DISPEREYK-2010, DISPERBYK-2012, DISPERBYK-2013, DISPERBYK-2022, DISPERBYK-2025, DISPERBYK-2050, DISPERBYK-2060, DISPERBYK-9070, and DISPERBYK-9077; TEGO Dispers series manufactured by Evonik Industries AG., such as TEGO Dispers 610, TEGO Dispers 630, TEGO Dispers 650, TEGO Dispers 651, TEGO Dispers 652, TEGO Dispers 655, TEGO Dispers 660C, TEGO Dispers 662C, TEGO Dispers 670, TEGO Dispers 685, TEGO Dispers 700, TEGO Dispers 710, TEGO Dispers 715W, TEGO Dispers 740W, TEGO Dispers 750W, TEGO Dispers 752W, TEGO Dispers 755W, and TEGO Dispers 760W; EFKA series manufactured by BASF, such as EFKA-44, EFKA-46, EFKA-47, EFKA-48, EFKA-4010, EFKA-4050, EFKA-4055, EFKA-4020, EFKA-4015, EFKA-4060, EFKA-4300, EFKA-4330, EFKA-4400, EFKA-4406, EFKA-4510, and EFKA-4800; SOLSPERSE series manufactured by Lubrizol Japan Limited, such as SOLSPERS-3000, SOLSPERS-9000, SOLSPERD-16000, SOLSPERS-17000, SOLSPERS-18000, SOLSPERS-13940, SOLSPERS-20000, SOLSPERS-24000, SOLSPERS-32550, and SOLSPERS-71000; Ajisper series manufactured by Ajinomoto Fine-Techno Co., Inc., such as Ajisper (AJISPER) PB-821, Ajisper PB-822, and Ajisper PB-823; DISPARLON series manufactured by Kusumoto Chemicals, Ltd., such as DISPARLON DA325, DISPARLON DA375, DISPARLON DA1800, and DISPARLON DA7301; and Flowlen series manufactured by Kyoeisha Chemical Co., Ltd., such as Flowlen (FLONREN) DOPA-17HF, Flowlen DOPA-15BHF, Flowlen DOPA-33, and Flowlen DOPA-44.
These high-molecular-weight dispersants may be used alone or in combination.
The dispersants used in the present invention have a boiling point of 250° C. or less at atmospheric pressure (1 atm) (hereinafter also referred to simply as “boiling point”). The use of such a dispersant enables a dispersion medium to be sufficiently and reliably removed from a light-emitting layer (nanocrystals) even under mild drying conditions of a coating film in the formation of the light-emitting layer.
This can prevent the nanocrystals from deteriorating and can leave no or little, if any, dispersant as an impurity in the light-emitting layer. Consequently, the resulting light-emitting device can have a long emission lifetime.
In contrast, the use of a dispersant with a boiling point of more than 300° C. requires severe drying conditions of a coating film and may degrade the nanocrystals. Mild drying conditions leave much dispersant in the light-emitting layer. Thus, the light-emitting device has a short emission lifetime.
The dispersant has a boiling point of 250° C. or less, preferably in the range of approximately 80° C. to 250° C. or approximately 100° C. to 250° C. This enables the dispersant to be sufficiently removed from the light-emitting layer even under mild drying conditions. This also prevents the dispersant from being excessively detached from the nanocrystals in the ink and can ensure the dispersion stability of the nanocrystals (particles) in the ink.
The molecules of such a dispersant may be almost entirely or partly supported in contact with the nanocrystals. In both states, the dispersant appropriately performs a dispersive function of stably dispersing the nanocrystals in the dispersion medium.
From this point of view, the dispersant preferably has a weight-average molecular weight (Mw) of 50,000 or less, more preferably approximately 100 to 50,000. Among the low-molecular-weight dispersants, compounds that are not polymers have a mass expressed by “molecular weight” rather than the “weight-average molecular weight”.
A dispersant with a weight average molecular weight equal to or higher than the lower limit has high ability to be supported on nanocrystals and can ensure sufficient dispersion stability of the nanocrystals in the ink. On the other hand, a dispersant with a weight-average molecular weight equal to or lower than the upper limit has a sufficient number of functional groups per unit weight, does not have excessively high crystallinity, and can improve the dispersion stability of nanocrystals in the ink. Such a dispersant does not have an excessively high weight-average molecular weight and can also prevent or reduce the inhibition of charge transfer in the light-emitting layer.
Examples of dispersants that satisfy these conditions include compounds containing a sulfur atom, such as 3-pentanethiol, 3-methyl-1-butanethiol, 2-pentanethiol, cyclopentanethiol, 2-hexanethiol, 1-(methylthio)ethanethiol, 2-methyl-3-tetrafuranthiol, 1,2-ethanedithiol, 1,2-propanedithiol, 2-methyl-3-furanthiol, methylthioisovalerate, cyclohexanethiol, 4-methoxy-2-methylbutanethiol, 2,3-butanedithiol, 1,3-propanedithiol, methyldihydrofuranthiol, 2-heptanethiol, 1,2-butanedithiol, 2, 5-dimethyl-3-furanthiol, 2-thiophenethiol, 1,3-butanedithiol, 1,4-butanedithiol, 2-octanethiol, methylthiophenethiol, 3-(trimethoxysilyl)-1-propanethiol, 1-methoxy-3-heptanethiol, 2-pyridinylmethanethiol, 1-p-methane-8-thiol, 2-decanethiol, 1,6-hexanedithiol, 2,2,4,5,5-pentamethyl-4-heptanethiol, o-aminobenzenethiol, pyrazinylethanethiol, 1-undecanethiol, 2-undecanethiol, 2-dodecanethiol, 1,8-octanedithiol, 1-dodecanethiol, 1,9-nonanethiol, and 1-tridecanethiol; compounds containing a nitrogen atom, such as dimethyl-2,2-dimethylpropylamine, dimethyl-1,1-dimethylpropylamine, ethylisobutylamine, ethylbutylamine, propylisopropylamine, diethylisopropylamine, 3-methoxyisopropylamine, dimethyl-1,2-dimethylpropylamine, dipropylamine, pentylamine, ethylbutylamine, diethylpropylamine, dimethyl-2-methylbutylamine, dimethyl-3-methylbutylamine, cyclopentylamine, methyldiisopropylamine, methylethylbutylamine, dimethylpentylamine, methylpentylamine, tetramethylethylenediamine, N,N-diethylhydroxylamine, 1,2-propanediamine, diethylbutylamine, dimethylethanolamine, cyclohexylamine, ethylpentylamine, hexylamine, aminoethanethiol, diisobutylamine, dimethylhexylamine, methylhexylamine, tripropylamine, 1,3-propanediamine, N-methylcyclohexylamine, N-methyl-2-heptaneamine, heptylamine, 2-ethylhexylamine, methylethanolamine, dibutylamine, 2-ethylhexaneamine, dimethylheptylamine, N,N-diethylpropanediamine, methylheptylamine, 3-methylthiopropylamine, ethanolamine, 1,4-butanediamine, diethylhexylamine, diisopentylamine, 1,2-cyclohexanediamine, ethylheptylamine, octylamine, N,N-dimethylbenzylamine, triisobutylamine, N-methylbenzylamine, isopentylidene, benzylamine, 1-phenylethylamine, dimethyloctylamine, methyloctylamine, methylbenzylamine, dipentylamine, diethylheptylamine, benzylethylamine, 2-phenylethylamine, nonylamine, 3-dimethylaminotoluene, ethyloctylamine, 3-aminopyridine, 4-dimethylaminopyridine, tributylamine, butylcyclohexylamine, diethylenetriamine, hexamethylenediamine, diethyloctylamine, 2-aminopyridine, 2-(methylamino)pyridine, 4-cyclobenzylamine, decylamine, 2-aminothiazole, dimethyldecylamine, dihexylamine, 2-amino-4,6-dimethylpyridine, 2-(2-aminoethylamino)ethanol, N-methyldiethanolamine, undecylamine, methylundecylamine, diethyldecylamine, diisopropanolamine, 2-methoxy-5-methylbenzeneamine, triphenylamine, dicyclohexylamine, dimethyldodecylamine, dodecylamine, o-phenylenediamine, methyldodecylamine, tyramine, diheptylamine, diethanolamine, triethylenetetramine, p-phenylenediamine, m-phenylenediamine, di-2-ethylhexylamine, hexamethylenetetramine, toluenediamine, dimethyltetradecylamine, N,N-dimethyl-1-naphthyleneamine, tetradecylamine, N-methyldiphenylamine, 1-naphthylamine, and 2-naphthylamine; and compounds containing a phosphorus atom, such as methyl methylphosphonate, trimethyl phosphate, triethyl phosphate, methyl diisopropylphospionate, hexamethylphosphoric diamide, tripropyl phosphate, and tributyl phosphate. These compounds may be used alone or in combination. These compounds are preferred because the compounds can be easily detached from nanocrystals even under mild drying conditions.
The amount of dispersant (in particular, high-molecular-weight dispersant) is preferably 50% or less by mass of the amount of nanocrystals. This reduces the amount of unnecessary organic materials left or deposited on the surface of nanocrystals when the nanocrystals support the dispersant. Thus, the dispersant layer is less likely to become an insulating layer to inhibit charge transfer and can prevent degradation in light-emitting properties.
The amount of dispersant is preferably 1% or more by mass, more preferably 3% or more by mass, still more preferably 5% or more by mass, of the amount of nanocrystals. This can ensure sufficient dispersion stability of the nanocrystals in the ink.
Charge-transport materials typically have the function of transporting positive holes and electrons injected into a light-emitting layer.
Any charge-transport materials that have the function of transporting positive holes and electrons may be used. Charge-transport materials are classified into high-molecular-weight charge-transport materials and low-molecular-weight charge-transport materials.
Examples of the high-molecular-weight charge transport materials include, but are not limited to, vinyl polymers, such as poly(9-vinylcarbazole) (PVK) conjugated compound polymers, such as poly[N,N′-bis(4-butylphenyl)-N,N′-bis(phenyl)-benzidine] (poly-TPA), polyfluorene (PF), poly[N,N′-bis(4-butylphenyl)-N,N′-bis(phenyl)-benzidine (Poly-TPD), poly[(9,9-diooctylfluorenyl-2,7-diyl)-co-(4,4′-(N-(4-sec-butylphenyl)diphenylamine)] (TFB), and poly(phenylene vinylene) (PPV), and copolymers containing these monomer units.
Examples of the low-molecular-weight charge-transport materials include, but are not limited to, carbazole derivatives, such as 4,4′-bis(9H-carbazol-9-yl)biphenyl (CBP), 9,9′-(p-tert-butylphenyl)-3,3-biscarbazole, 1,3-dicarbazolylbenzene (mCP), 4,4′-bis(9-carbazolyl)-2,2′-dimethylbiphenyl (CDBP), N,N′-dicarbazolyl-1,4-dimethylbenzene (DCB) , and 5,11-diphenyl-5,11-dihydroindolo[3,2-b]carbazole; aluminum complexes, such as bis(2-methyl-8-quinolinolate)-4-(phenylphenolate) aluminum (BAlq), phosphine oxide derivatives, such as 2,7-bis(diphenylphosphine oxide)-9,9-dimethylfluorene (P06); silane derivatives, such as 3,5-bis(9-carbazolyl)tetraphenylsilane (SimCP) and 1,3-bis(triphenylsilyl)benzene (UGH3); triphenylamine derivatives, such as 4,4′-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (α-NPD), heterocyclic derivatives, such as 9-(4,5-diphenyl-1,3,5-triazin-2-yl)-9H-carbazole and 9-(2,6-diphenylpyrimidine-4-yl)-9H-carbazole, and derivatives of these compounds.
A surfactant, for example, one or two or more of fluorinated surfactants, silicone surfactants, and hydrocarbon surfactants may be used alone or in combination. Among these, silicone surfactants and/or hydrocarbon surfactants are preferred because they are less likely to trap electric charges.
The silicone surfactants and hydrocarbon surfactants may be low-molecular-weight or high-molecular-weight surfactants.
Specific examples of these include BYK series manufactured by BYK-Chemie and Surfynol manufactured by Nissin Chemical Industry Co., Ltd. Among these, silicone surfactants composed of organic modified siloxanes are suitable because a smooth coating film can be formed when an ink is applied.
Particles containing nanocrystals on which such a dispersant is supported are dispersed in a dispersion medium.
Examples of the dispersion medium include, but are not limited to, aromatic hydrocarbon compounds, aromatic ester compounds, aromatic ether compounds, aromatic ketone compounds, aliphatic hydrocarbon compounds, aliphatic ester compounds, aliphatic ether compounds, aliphatic ketone compounds, alcohol compounds, amide compounds, thiol compounds, and other compounds. These may be used alone or in combination.
The aromatic hydrocarbon compounds include toluene, xylene, ethylbenzene, cumene, mesitylene, tert-butylbenzene, indan, diethylbenzene, pentylbenzene, 1,2,3,4-tetrahydronaphthalene, naphthalene, hexylbenzene, heptylbenzene, cyclohexylbenzene, 1-methylnaphthalene, biphenyl, 2-ethylnaphthalene, 1-ethylnaphthalene, octylbenzene, diphenylmethane, 1,4-dimethylnaphthalene, nonylbenzene, isopropylbiphenyl, 3-ethylbiphenyl, and dodecylbenzene.
The aromatic ester compounds include phenyl acetate, methyl benzoate, ethyl benzoate, phenyl propionate, isopropyl benzoate, methyl 4-methylbenzoate, propyl benzoate, butyl benzoate, isopentyl benzoate, ethyl p-anisate, and dimethyl phthalate.
The aromatic ether compounds include dimethoxybenzene, methoxytoluene, ethyl phenyl ether, dibenzyl ether, 4-methylanisole, 2,6-dimethylanisole, ethyl phenyl ether, propyl phenyl ether, 2,5-dimethylanisole, 3,5-dimethylanisole, 4-ethylanisole, 2,3-dimethylanisole, butyl phenyl ether, p-dimethoxybenzene, p-propylanisole, m-dimethoxybenzene, methyl 2-methoxybenzoate, 1,3-dipropoxybenzene, diphenyl ether, 1-methoxynaphthalene, 3-phenoxytoluene, 2-ethoxynaphthalene, and 1-ethoxynaphthalene.
The aromatic ketone compounds include acetophenone, propiophenone, 4′-methylacetophenone, 4′-ethylacetophenone, and butyl phenyl ketone.
The aliphatic hydrocarbon compounds include pentane, hexane, octane, and cyclohexane.
The aliphatic ester compounds include ethyl acetate, butyl acetate, ethyl lactate, hexyl acetate, butyl lactate, isoamyl lactate, amyl valerate, ethyl levulinate, γ-valerolactone, ethyl octanoate, γ-hexalactone, isoamyl hexanate, amyl hexanate, nonyl acetate, methyl decanoate, diethyl glutarate, γ-heptalactone, ε-caprolactone, octalactone, propylene carbonate, γ-nonanolactone, hexyl hexanoate, diisopropyl adipate, δ-nonanolactone, glycerol triacetate, δ-decanolactone, dipropyl adipate, δ-undecalactone, δ-tridecanolactone, δ-dodecalactone, propylene glycol-1-monomethyl ether acetate, propylene glycol diacetate, diethylene glycol diacetate, diethylene glycol monoethyl ether acetate, 1,3-butanediol diacetate, 1,4-butanediol diacetate, and diethylene glycol monobutyl ether acetate.
The aliphatic ether compounds include tetrahydrofuran, dioxane, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol isopropyl methyl ether, diethylene glycol diethyl ether, diethylene glycol butyl methyl ether, dihexyl ether, diethylene glycol dibutyl ether, diheptyl ether, and dioctyl ether.
The aliphatic ketone compounds include diisobutyl ketone, cycloheptanone, isophorone, and 6-undecanone.
The alcohol compounds include methanol, ethanol, isopropyl alcohol, 1-heptanol, 2-ethyl-1-hexanol, propylene glycol, ethylene glycol, diethylene glycol monoethyl ether, triethylene glycol monomethyl ether, diethylene glycol monobutyl ether, ethyl 3-hydroxyhexanate, tripropylene glycol monomethyl ether, diethylene glycol, cyclohexanol, and 2-butoxyethanol.
The amide compounds include N,N-dimethylacetamide, 2-pyrrolidone, N-methylpyrrolidone, and N, N-dimethylacetamide.
The thiol compounds include 2-aminosulfide, 1-undecanethiol, and 1-dodecanethiol.
The other compounds include water, dimethyl sulfoxide, acetone, chloroform, and methylene chloride.
Such a dispersion medium preferably has a viscosity of approximately 1 to 20 mPa·s, more preferably approximately 1.5 to 15 mPa·s, still more preferably approximately 2 to 10 mPa·s, at 25° C. When an ink is ejected by a droplet ejection method, the dispersion medium with a viscosity in this range at normal temperature can prevent or reduce a phenomenon (satellite phenomenon) in which a droplet ejected from a nozzle orifice of a droplet ejection head separates into a main droplet and a small droplet. This can improve the landing accuracy of the droplet on the adherend.
If there is a possibility that particles containing nanocrystals in an ink according to the present invention are inactivated by oxygen, water, or the like and do not function stably, dissolved gas and water in the dispersion medium are preferably minimized before the preparation of the ink, or posttreatment after the preparation of the ink is preferably performed to minimize dissolved oxygen and water in the ink. The posttreatment may be degassing, saturation or supersaturation with an inert gas, heat treatment, or dehydration involving a passage through a drying agent.
The dissolved oxygen and water content of the ink is preferably 200 ppm or less, more preferably 100 ppm or less, still more preferably 10 ppm or less.
The amount of particles in the ink preferably ranges from approximately 0.01% to 20% by mass, more preferably approximately 0.01% to 15% by mass, still more preferably approximately 0.1% to 10% by mass. When the ink is ejected by the droplet ejection method, an amount of particles in the ink in this range results in further improved ejection stability. This can also reduce the agglomeration of the particles (nanocrystals) and improve the luminous efficiency of the light-emitting layer.
The mass of the particles are the total mass of the nanocrystals and the dispersant supported on the nanocrystals.
The phrase “the amount of particles in the ink”, as used herein, refers to the mass percentage of the particles based on the total mass of the particles and a dispersion medium in the ink composed of the particles and the dispersion medium, or the mass percentage of the particles based on the total mass of the particles, a nonvolatile component other than particles, and a dispersion medium in the ink composed of the particles, the nonvolatile component, and the dispersion medium.
As described above, a dispersant with a boiling point of 300° C. or less, that is, a dispersant that can be easily detached from nanocrystals is used in the present invention. Thus, the detachment of a dispersant from nanocrystals during the storage of the ink exposes the surface of the nanocrystals and accelerates the agglomeration of the nanocrystals (particles). Thus, the present inventors have extensively studied to solve such problems and found that it is effective to use a dispersion medium containing a polar compound with a polar group. This is probably because the polar compound solvates the exposed surface of the nanocrystals and thereby prevents the agglomeration of the particles (nanocrystals). Preventing the agglomeration of the particles can improve the dispersion stability of the particles in the ink and sufficiently increase the storage stability of the ink.
In particular, the polar compound is a compound with a boiling point equal to or higher than the boiling point of the dispersant. Thus, when a coating film is dried to form a light-emitting layer, the dispersant is preferentially removed from the coating film before the dispersion medium is removed from the coating film. Thus, in the coating film in the drying process, the polar compound can solvate the surface of the nanocrystals from which the dispersant is detached, and prevent the agglomeration of the nanocrystals (particles). Thus, the nanocrystals are uniformly distributed in the light-emitting layer, and it is possible to prevent or reduce the decrease in the luminous efficiency of the light-emitting layer due to the self-absorption phenomenon of the nanocrystals.
The polar compound has a boiling point equal to or higher than the boiling point of the dispersant, preferably higher by 5° C. or more than the boiling point of the dispersant, more preferably higher by 10° C. or more than the boiling point of the dispersant. The use of the polar compound enables the dispersant to be more reliably removed from the coating film before the polar compound is removed from the coating film while the coating film is dried. This can increase the uniformity of the distribution of the nanocrystals in the light-emitting layer and improve the luminous efficiency of the light-emitting layer.
The polar compound preferably has a boiling point of 350° C. or less, more preferably 330° C. or less, still more preferably 310° C. or less. The polar compound with such a boiling point can be reliably removed from the light-emitting layer even under mild drying conditions of the coating film.
The amount of the polar compound in the dispersion medium preferably ranges from approximately 20% to 80% by mass or approximately 30% to 70% by mass. The use of the dispersion medium containing the polar compound in such an amount can more significantly provide the advantages described above.
Examples of the polar group of the polar compound include a hydroxy group, a carbonyl group, a thiol group, an amino group, a nitro group, and a cyano group. Among these, the polar group is preferably at least one selected from the group consisting of a hydroxy group and a carbonyl group. These polar groups are preferred, because the polar groups ensure sufficient dispersion stability of the nanocrystals in the ink and have a moderate affinity for the nanocrystals such that the polar groups can easily detached from the nanocrystals while the coating film is dried.
Thus, the polar compound is preferably at least one compound selected from the group consisting of aromatic ester compounds, such as phenyl acetate, methyl benzoate, ethyl benzoate, phenyl propionate, isopropyl benzoate, methyl 4-methylbenzoate, propyl benzoate, butyl benzoate, isopentyl benzoate, ethyl p-anisate, and dimethyl phthalate; aromatic ketone compounds, such as acetophenone, propiophenone, 4′-methylacetophenone, 4′-ethylacetophenone, and butyl phenyl ketone; aliphatic ester compounds, such as ethyl lactate, hexyl acetate, butyl lactate, isoamyl lactate, amyl valerate, ethyl levulinate, γ-valerolactone, ethyl octanoate, γ-hexalactone, isoamyl hexanate, amyl hexanate, nonyl acetate, methyl decanoate, diethyl glutarate, γ-heptalactone, ε-caprolactone, octalactone, propylene carbonate, γ-nonanolactone, hexyl hexanoate, diisopropyl adipate, δ-nonanolactone, glycerol triacetate, δ-decanolactone, dipropyl adipate, δ-undecalactone, δ-tridecanolactone, δ-dodecalactone, propylene glycol-1-monomethyl ether acetate, propylene glycol diacetate, diethylene glycol diacetate, diethylene glycol monoethyl ether acetate, 1,3-butanediol diacetate, 1,4-butanediol diacetate, and diethylene glycol monobutyl ether acetate; aliphatic ketone compounds, such as diisobutyl ketone, cycloheptanone, isophorone, and 6-undecanone; alcohol compounds, such as 1-heptanol, 2-ethyl-1-hexanol, propylene glycol, ethylene glycol, diethylene glycol monoethyl ether, triethylene glycol monomethyl ether, diethylene glycol monobutyl ether, ethyl 3-hydroxyhexanate, tripropylene glycol monomethyl ether, diethylene glycol, cyclohexanol, and 2-butoxyethanol; and thiol compounds, such as 2-aminosulfide, 1-undecanethiol, and 1-dodecanethiol. These polar compounds can be used to further improve the emission lifetime of the light-emitting layer (light-emitting device).
A light-emitting device according to the present invention includes an anode and a cathode (a pair of electrodes), a light-emitting layer containing a dried product of an ink according to the present invention located between the electrodes, and a charge-transport layer located between the light-emitting layer and at least one electrode of the anode and the cathode.
The charge-transport layer preferably includes at least one layer selected from the group consisting of a hole-injection layer, a hole-transport layer, an electron-transport layer, and an electron-injection layer. A light-emitting device according to the present invention may further contain a sealing material.
In
For convenience of explanation, the upper side in
A light-emitting device 1 in
Each layer is described below.
The anode 2 has the function of supplying positive holes from an external power supply to the light-emitting layer 6.
The anode 2 may be composed of any material (anode material), for example, a metal, such, as gold (Au), a halogenated metal, such as copper iodide (CuI), or a metal oxide, such as indium tin oxide (ITO), tin oxide (SnO2), or zinc oxide (ZnO). These may be used alone or in combination.
The anode 2 may have any thickness, preferably in the range of approximately 10 to 1,000 nm, more preferably approximately 10 to 200 nm.
The anode 2 can be formed by a dry film formation method, such as a vacuum evaporation method or a sputtering method, for example. The anode 2 in a a predetermined pattern may also be formed by a photolithography method or a method using a mask.
The cathode 3 has the function of supplying electrons from an external power supply to the light-emitting layer 6.
The cathode 3 may be composed of any material (cathode material), for example, lithium, sodium, magnesium, aluminum, silver, a sodium-potassium alloy, a magnesium/aluminum mixture, a magnesium/silver mixture, a magnesium/indium mixture, an aluminum/aluminum oxide (Al2O3) mixture, or a rare-earth metal. These may be used alone or in combination.
The cathode 3 may have any thickness, preferably in the range of approximately 0.1 to 1,000 nm, more preferably approximately 1 to 200 nm.
The cathode 3 can be formed by a dry film formation method, such as an evaporation method or a sputtering method, for example.
The hole-injection layer 4 has the function of receiving positive holes from the anode 2 and injecting the positive holes into the hole-transport layer 5. The hole-injection layer 4 may be formed as required or may be omitted.
The hole-injection layer 4 may be composed of any material (hole-injection material), for example, a phthalocyanine compound, such as copper phthalocyanine; a triphenylamine derivative, such as 4,4′,4″-tris[phenyl(m-tolyl)amino]triphenylamine; a cyano compound, such as 1,4,5,8,9,12-hexaazatriphenylenehexacarbonitrile or 2,3,5,6-tetrafluoro-7,7,8,8-tetracyano-quinodimethane; a metal oxide, such as vanadium oxide or molybdenum oxide; amorphous carbon; or a polymer, such as polyaniline (emeraldine), poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonic acid) (PEDOT-PSS), or polypyrrole.
Among these, the hole-injection material is preferably a polymer, more preferably PEDOT-PSS.
The hole-injection materials may be used alone or in combination.
The hole-injection layer 4 may have any thickness, preferably in the range of approximately 0.1 to 500 nm, more preferably approximately 1 to 300 nm, still more preferably approximately 2 to 200 nm.
The hole-injection layer 4 may have a monolayer structure or a multilayer structure of two or more layers.
The hole-injection layer 4 may be formed by a wet film formation method or a dry film formation method.
In the formation of the hole-injection layer 4 by the wet film formation method, in general, an ink containing the hole-injection material is applied by an application method, and the coating film is dried. The application method may be any method, for example, an ink jet method (a droplet ejection method), a spin coating method, a casting method, a LB method, a letterpress printing method, a gravure printing method, a screen printing method, or a nozzle printing method.
The dry film formation method for the hole-injection layer 4 is preferably a vacuum evaporation method or a sputtering method.
The hole-transport layer 5 has the function of receiving positive holes from the hole-injection layer 4 and efficiently transporting the positive holes to the light-emitting layer 6. The hole-transport layer 5 may have the function of preventing electron transport. The hole-transport layer 5 may be formed as required or may be omitted.
The hole-transport layer 5 may be composed of any material (hole-transport material), for example, a low-molecular-weight triphenylamine derivative, such as N,N′-diphenyl-N,N′-di(3-methylphenyl)-1,1′-biphenyl-4,4′diamine (TPD), 4,4′-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (α-NPD), or 4,4′,4″-tris(3-methylphenylphenylamino)triphenylamine (m-MTDATA); polyvinylcarbazole; a conjugated compound polymer, such as poly[N,N′-bis(4-butylphenyl)-N,N′-bis(phenyl)-benzidine] (poly-TPA), polyfluorene (PF), poly[N,N′-bis(4-butylphenyl)-N,N′-bis(phenyl)-benzidine (Poly-TPD), poly[(9,9-dioctylfluorenyl-2,7-diyl)-co-(4,4′-(N-(sec-butylphenyl)diphenylamine)) (TFB), or poly(phenylene vinylene) (PPV); or a copolymer containing these monomer units.
Among these, the hole-transport material is preferably a triphenylamine derivative or a high-molecular-weight compound produced by polymerization of a triphenylamine derivative with a substituent, more preferably a high-molecular-weight compound produced by polymerization of a triphenylamine derivative with a substituent.
The hole-transport materials may be used alone or in combination.
The hole-transport layer 5 may have any thickness, preferably in the range of approximately 1 to 500 nm, more preferably approximately 5 to 300 nm, still more preferably approximately 10 to 200 nm.
The hole-transport layer 5 may have a monolayer structure or a multilayer structure of two or more layers.
The hole-transport layer 5 may be formed by a wet film formation method or a dry film formation method.
In the formation of the hole-transport layer 5 by the wet film formation method, in general, an ink containing the hole-transport material is applied by an application method, and the coating film is dried. The application method may be any method, for example, an ink jet method (a droplet ejection method), a spin coating method, a casting method, a LB method, a letterpress printing method, a gravure printing method, a screen printing method, or a nozzle printing method.
The dry film formation method for the hole-transport layer 5 is preferably a vacuum evaporation method or a sputtering method.
The electron-injection layer 8 has the function of receiving electrons from the cathode 3 and injecting the electrons into the electron-transport layer 7. The electron-injection layer 8 may be formed as required or may be omitted.
The electron-injection layer 8 may be composed of any material (electron-injection material), for example, an alkali metal chalcogenide, such as Li2O, LiO, Na2S, Na2Se, or NaO; an alkaline-earth metal chalcogenide, such as CaO, BaO, SrO, BeO, BaS, MgO, or CaSe; an alkali metal halide, such as CsF, LiF, NaF, KF, LiCl, KCl, or NaCl; an alkali metal salt, such as 8-hydroxyquinolinolato lithium (Liq); or an alkaline-earth metal halide, such as CaF2, BaF2, SrF2, MgF2, or BeF2.
Among these, preferred is an alkali metal chalcogenide, an alkaline-earth metal halide, or an alkali metal salt.
The electron-injection materials may be used alone or in combination.
The electron-injection layer 8 may have any thickness, preferably in the range of approximately 0.1 to 100 nm, more preferably approximately 0.2 to 50 nm, still more preferably approximately 0.5 to 10 nm.
The electron-injection layer 8 may have a monolayer structure or a multilayer structure of two or more layers.
The electron-injection layer 8 may be formed by a wet film formation method or a dry film formation method.
In the formation of the electron-injection layer 8 by the wet film formation method, in general, an ink containing the electron-injection material is applied by an application method, and the coating film is dried. The application method may be any method, for example, an ink jet method (a droplet ejection method), a spin coating method, a casting method, a LB method, a letterpress printing method, a gravure printing method, a screen printing method, or a nozzle printing method.
The dry film formation method for the electron-injection layer 8 may be a vacuum evaporation method or a sputtering method.
The electron-transport layer 7 has the function of receiving electrons from the electron-injection layer 8 and efficiently transporting the electrons to the light-emitting layer 6. The electron-transport layer 7 may have the function of preventing hole transport. The electron-transport layer 7 may be formed as required or may be omitted.
The electron-transport layer 7 may be composed of any material (electron-transport material), for example, a metal complex with a quinoline or benzoquinoline skeleton, such as tris(8-quinolinolato) aluminum (Alq3), tris(4-methyl-8-quinolinolato) aluminum (Almq3), bis(10-hydroxybenzo[h]-quinolinato) beryllium (BeBq2), bis(2-methyl-8-quinolinolato)(p-phenylphenolate) aluminum (BAlq), or (8-quinolinolato) zinc (Znq); a metal complex with a benzoxazoline skeleton, such as bis[2-(2′-hydroxyphenyl)benzoxozolate] zinc (Zn(BQX)2); a metal complex with a benzothiazoline skeleton, such as bis[2-(2′-hydroxyphenyl)benzothiazolate] zinc (Zn(BTZ)2); a triazole or diazole derivative, such as 2-(4-biphenylyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole (PBD), 3-(4-biphenylyl)-4-phenyl-5-(4-tert-butylphenyl)-1,2,4-triazole (TAZ), 1,3-bis[5-(p-tert-butylphenyl)-1,3,4-oxadiazol-2-yl] benzene (OXD-7), or 9-[4-(5-phenyl-1,3,4-oxadiazol-2-yl)phenyl] carbazole (CO11); an imidazole derivative, such as 2,2′,2″-(1,3,5-benzenetriyl)tris(1-phenyl-1H-benzimidazole) (TPBI) or 2-[3-(dibenzothiophen-4-yl)phenyl]-1-phenyl-1H-benzimidazole (mDBTBIm-II); a quinoline derivative; a perylene derivative; a pyridine derivative, such as 4,7-diphenyl-1,10-phenanthroline (BPhen); a pyrimidine derivative; a triazine derivative; a quinoxaline derivative; a diphenylquinone derivative; a nitro-substituted fluorene derivative; or a metal oxide, such as zinc oxide (ZnO) or titanium oxide (TiO2).
Among these, the electron-transport material is preferably an imidazole derivative, a pyridine derivative, a pyrimidine derivative, a triazine derivative, or a metal oxide (inorganic oxide).
The electron-transport materials may be used alone or in combination.
The electron-transport layer 7 may have any thickness, preferably in the range of approximately 5 to 500 nm, more preferably approximately 5 to 200 nm.
The electron-transport layer 7 may be a monolayer or a multilayer of two or more layers.
The electron-transport layer 7 may be formed by a wet film formation method or a dry film formation method.
In the formation of the electron-transport layer 7 by the wet film formation method, in general, an ink containing the electron-transport material is applied by an application method, and the coating film is dried. The application method may be any method, for example, an ink jet method (a droplet ejection method), a spin coating method, a casting method, a LB method, a letterpress printing method, a gravure printing method, a screen printing method, or a nozzle printing method.
The dry film formation method for the electron-transport layer 7 may be a vacuum evaporation method or a sputtering method.
The light-emitting layer 6 has the function of utilizing energy generated by recombination of positive holes and electrons injected into the light-emitting layer 6 to emit light.
The light-emitting layer 6 is formed of a dried product of an ink according to the present invention. Thus, the light-emitting layer 6 contains uniformly dispersed nanocrystals and has good luminous efficiency.
The light-emitting layer 6 may have any thickness, preferably in the range of approximately 1 to 100 nm, more preferably approximately 1 to 50 nm.
For the light-emitting layer 6, an ink according to the present invention is applied by an application method, and the coating film is dried. The application method may be any method, for example, an ink jet printing method (a piezoelectric or thermal droplet ejection method), a spin coating method, a casting method, a LB method, a letterpress printing method, a gravure printing method, a screen printing method, or a nozzle printing method.
In the nozzle printing method, an ink is applied in a striped pattern as a liquid column through a nozzle orifice.
An ink according to the present invention can be suitably applied by an ink jet printing method. In particular, an ink according to the present invention is preferably applied by a piezoelectric ink jet printing method. This can decrease the heat load in ink ejection and reduce defects in particles (nanocrystals). Thus, an apparatus suitable for the application of an ink according to the present invention is an ink jet printer with a piezoelectric ink jet head.
The light-emitting device 1 may further include a bank (partition) for partitioning the hole-injection layer 4, the hole-transport layer 5, and the light-emitting layer 6, for example.
The bank may have any height, preferably in the range of approximately 0.1 to 5 μm, more preferably approximately 0.2 to 4 μm, still more preferably approximately 0.2 to 3 μm.
The bank preferably has an opening width in the range of approximately 10 to 200 μm, more preferably approximately 30 to 200 μm, still more preferably approximately 50 to 100 μm.
The bank preferably has an opening length in the range of approximately 10 to 400 μm, more preferably approximately 20 to 200 μm, still more preferably approximately 50 to 200 μm.
The bank preferably has a tilt angle in the range of approximately 10 to 100 degrees, more preferably approximately 10 to 90 degrees, still more preferably approximately 10 to 80 degrees.
A method for producing a light-emitting device includes the step of supplying the ink described above to a substrate to form a coating film and drying the coating film to form a light-emitting layer (hereinafter also referred to as a “light-emitting layer forming step”).
Although the substrate is the hole-transport layer 5 or the electron-transport layer 7 in
For example, in the production of a light-emitting device composed of an anode, a hole-transport layer, a light-emitting layer, and a cathode, the substrate is the hole-transport layer or the cathode. In the production of a light-emitting device composed of an anode, a hole-injection layer, a light-emitting layer, an electron-injection layer, and a cathode, the substrate is the hole-injection layer or the electron-injection layer.
Thus, the substrate may be an anode, a hole-injection layer, a hole transport layer, an electron-transport layer, an electron-injection layer, or a cathode. The substrate is preferably an anode, a hole-injection layer, or a hole-transport layer, more preferably a hole-injection layer or a hole-transport layer, still more preferably a hole-transport layer.
The substrate may have a bank, as described above. The formation of the bank enables the light-emitting layer 6 to be formed only in a desired portion on the substrate.
For example, in the droplet ejection method, an ink according to the present invention is applied intermittently to the substrate in a predetermined pattern through a nozzle orifice of a droplet ejection head. The droplet ejection method enables drawing and patterning with a high degree of flexibility. In particular, the piezoelectric droplet ejection method can increase the selectivity of the dispersion medium and decrease the heat load to the ink.
The ink ejection rate is preferably, but not limited to, in the range of 1 to 50 pL, more preferably 1 to 30 pL, still more preferably 1 to 20 pL, at a time.
The opening size of the nozzle orifice preferably ranges from approximately 5 to 50 μm, more preferably approximately 10 to 30 μm. This can prevent clogging of the nozzle orifice and increase ejection accuracy.
The coating film forming temperature is preferably, but not limited to, in the range of approximately 10° C. to 50° C., more preferably approximately 15° C. to 40° C., still more preferably approximately 15° C. to 30° C. Ejection of droplets at such a temperature can reduce the crystallization of various components ((nanocrystals, a dispersant, a charge-transport material, etc.) contained in the ink.
The relative humidity at which a coating film is formed is preferably, but not limited to, in the range of approximately 0.01 ppm to 80%, more preferably approximately 0.05 ppm to 60%, still more preferably approximately 0.1 ppm to 15%, particularly preferably approximately 1 ppm to 1%, most preferably approximately 5 to 100 ppm.
A relative humidity equal to or higher than the lower limit is preferred because the conditions for forming the coating film can be easily controlled. A relative humidity equal to or lower than the upper limit is also preferred because the amount of water that is adsorbed on the coating film and may have adverse effects on the light-emitting layer 6 can be decreased.
The coating film is dried to form the light-emitting layer 6.
The drying may be performed by leaving alone at room temperature (25° C.) or by heating. For drying by heating, the drying temperature is preferably, but not limited to, approximately 40° C. to 150° C., more preferably approximately 40° C. to 120° C.
The drying is preferably performed under reduced pressure, more preferably under a reduced pressure in the range of 0.001 to 100 Pa.
The drying time preferably ranges from 1 to 90 minutes, more preferably 1 to 30 minutes.
Drying the coating film under such drying conditions can reliably remove not only the dispersion medium but also the dispersant from the coating film, and the light-emitting layer 6 is composed substantially of nanocrystals.
The degree of removal can be checked by the amount of dispersant in the light-emitting layer 6. More specifically, the total amount of dispersant in the light-emitting layer 6 is 25 ppm or less, preferably 20 ppm or less, more preferably 10 ppm or less. In such a case, the light-emitting layer 6 is substantially free of the dispersant, which becomes an impurity, and has a long emission lifetime.
Although particles, inks, and light-emitting devices according to the present invention are described above, the present invention is not limited to these embodiments.
For example, the particles, inks, and light-emitting devices according to the embodiments of the present invention may have an additional constituent or may be substituted with a constituent having the same function.
Although the present invention is more specifically described in the following examples, the present invention is not limited to these examples.
First, triethyl phosphate (boiling point: 216° C.) was dissolved in toluene to prepare a solution of triethyl phosphate in toluene.
The solution of triethyl phosphate in toluene was then added dropwise to a toluene solution containing particles (5 mg/mL, manufactured by Aldrich; product No. 776750-5ML; core: InP, shell: ZnS, dispersant: oleylamine) in an argon atmosphere at room temperature (25° C.) to prepare a reaction liquid. The reaction liquid was stirred for 12 hours, and the argon gas atmosphere was then changed to the ambient atmosphere. The same amount of toluene as the evaporation loss was then added to the reaction liquid, and a proper amount of ethanol was then added dropwise to the reaction liquid.
A precipitate was separated from the reaction liquid by centrifugation. The precipitate was mixed with toluene to prepare a dispersion liquid. Ethanol was added dropwise to the dispersion liquid for reprecipitation. Thus, a reprecipitation liquid containing purified precipitate was prepared. The reprecipitation liquid was centrifuged and filtered to prepare nanocrystals (QD-1) on which triethyl phosphate was supported.
Nanocrystals (QD-2) on which amyl sulfide (boiling point: 228° C.) was supported was prepared in the same manner as in the QD-1 except that triethyl phosphate was replaced with amyl sulfide.
Nanocrystals (QD-3) on which 1-decanethiol (boiling point: 241° C.) was supported was prepared in the same manner as in the QD-1 except that triethyl phosphate was replaced with 1-decanethiol.
Nanocrystals (QD-4) on which 1-tridecanethiol (boiling point: 289° C.) was supported was prepared in the same manner as in the QD-1 except that triethyl phosphate was replaced with 1-tridecanethiol.
Samples were taken from each of the QD-1 to QD-4 and were burnt in a pyrolysis mass spectrometer to determine the weight loss. The amount of supported dispersant was approximately 10% to 30% by mass of the nanocrystals.
The QD-1 was dispersed in 2-aminoethylsulfide (a dispersion medium) to prepare an ink containing 1.0% by mass QD-1.
An ink was prepared in the same manner as in the example A1 except that 2-aminoethylsulfide was replaced with triethylene glycol monomethyl ether.
An ink was prepared in the same manner as in the example A1 except that 2-aminoethylsulfide was replaced with 1-undecanethiol.
An ink was prepared in the same manner as in the example A1 except that 2-aminoethylsulfide was replaced with δ-decanolactone.
An ink was prepared in the same manner as in the example A1 except that 2-aminoethylsulfide was replaced with dimethyl phthalate.
An ink was prepared in the same manner as in the example A1 except that 2-aminoethylsulfide was replaced with δ-tridecanolactone.
Inks were prepared in the same manner as in the examples A1 to A6 except that the QD-1 was replaced with the QD-2.
Inks were prepared in the same manner as in the examples A1 to A6 except that the QD-1 was replaced with the QD-3.
The QD-4 was dispersed in δ-dodecalactone (a dispersion medium) to prepare an ink containing 1.0% by mass QD-4.
An ink was prepared in the same manner as in the example A19 except that δ-dodecalactone was replaced with 1,12-dodecanediol.
An ink was prepared in the same manner as in the example A1 except that 2-aminoethylsulfide was replaced with 2-butoxyethanol.
An ink was prepared in the same manner as in the example A1 except that 2-aminoethylsulfide was replaced with γ-valerolactone.
An ink was prepared in the same manner as in the example A1 except that 2-aminoethylsulfide was replaced with ethyl benzoate.
Inks were prepared in the same manner as in the comparative examples A1 to A3 except that the QD-1 was replaced with the QD-9.
Inks were prepared in the same manner as in the comparative examples A1 to A3 except that the QD-1 was replaced with the QD-3.
Hexane was added to the commercial particle toluene solution (5 mg mL, manufactured by Aldrich; product No. 776750-5ML; core: InP, shell: ZnS, dispersant: oleylamine), which was then centrifuged, and a precipitate containing particles was collected with a filter.
Inks were prepared in the same manner as in the examples A2, A4, and A5 except that the QD-1 was replaced with the precipitate.
The ink of each of the examples and comparative examples was spin-coated on a 80 mm×80 mm silicon substrate at 2,000 rpm for 30 seconds to form a coating film. The coating film was then dried at room temperature (25° C.) for 30 minutes under a reduced pressure of 0.003 Pa to form a thin film.
The silicon substrate with the thin film was immersed in 1.5 mL of chloroform for 5 minutes and was then removed from the chloroform. The chloroform was then mixed with trifluoroacetic anhydride for 30 minutes and was analyzed with a gas chromatograph (manufactured by Shimadzu Corporation, GC-2014) to measure the amounts of residual dispersant and dispersion medium in the thin film.
The calibration curves for the dispersant and the dispersion medium were prepared, and the areas obtained by the gas chromatograph analysis were converted to concentrations. The concentrations were rated according to the following criteria.
⊙: 10 ppm or less
◯: more than 10 ppm and 20 ppm or less
Δ: more than 20 ppm and 25 ppm or less
×: more than 25 ppm
Table 1 shows the evaluation results.
First, a positive photoresist to which a fluorinated surfactant was added was spin-coated on a glass substrate (40 mm×70 mm) on which striped ITO was patterned. The positive photoresist was then patterned by photolithography to form a bank that partitioned a pixel 300 μm long and 100 μm wide (vertical pitch: 350 μm, traverse pitch: 150 μm). Thus, the substrate with the bank was prepared.
The thickness of the bank was measured with an optical coherence surface profiler (manufactured by Ryoka Systems Inc.). The bank had a thickness of 2.0 μm.
A 45-nm hole-injection layer, a 30-nm hole-transport layer, and a 30-nm light-emitting layer were successively formed in the pixel of the substrate with the hank using an ink jet printer (DMP2831, cartridge DMC-11610, manufactured by Fujifilm Corporation).
The hole-injection layer was formed from PEDOT/PSS (CLEVIOUS P JET), the hole-transport layer was formed from a solution of 1.0% by mass TFB in tetralin, and the light-emitting layer was formed from the ink described above.
To form the light-emitting layer, the coating film (an ink pattern) was dried under a reduced pressure of 0.003 Pa at 25° C. for 30 minutes.
The substrate on which the layers up to the light-emitting layer were formed was conveyed to a vacuum evaporator, and a 40-nm electron-transport layer, a 0.5-nm electron-injection layer, and a 100-nm cathode were successively formed by evaporation.
The electron-transport layer was formed of TPBI, the electron-injection layer was formed of lithium fluoride, and the cathode was formed of aluminum.
The substrate on which the layers up to the cathode were formed was conveyed to a glove box, and a sealing glass to which an epoxy resin was applied was placed on the substrate. Thus, a light-emitting device was produced.
An electric current of 10 mA/cm2 was applied to the light-emitting device to emit light. The emission lifetime was measured with a photodiode lifetime measuring apparatus (manufactured by System Engineers Co., Ltd.) and was rated according to the following criteria.
The luminance half-life of the light-emitting device according to the comparative example A1 was taken as 1.00. The luminance half-lives of the light-emitting devices according to the examples and comparative examples other than the comparative example A1 were determined as relative values, which were used as measures of the emission lifetime. A higher value is indicative of a longer emission lifetime.
⊙: 2.0 or more
◯: 1.5 or more and less than 2.0
Δ: 1.0 or more and less than 1.5
×: less than 1.0
Table 1 shows the evaluation results.
Table 1 shows that the use of a dispersant with a boiling point of 300° C. or less in combination with a polar compound (dispersion medium) with a boiling point equal to or higher than the boiling point of the dispersant could improve the emission lifetime of the light-emitting device according to each example. This is probably due to small amounts of residual dispersant and dispersion medium and the formation of a light-emitting layer without agglomeration of particles.
Furthermore, the use of a polar compound having a hydroxy or carbonyl group as a polar group and the use of a polar compound with a suitable boiling point could further improve the emission lifetime of the light-emitting device.
In contrast, the light-emitting devices according to the comparative examples A10 to A12, in which the dispersant had a boiling point of more than 300° C., had a short emission lifetime. This is probably because a large amount of dispersant remained in the light-emitting layer due to the excessively high boiling point of the dispersant.
In the comparative examples A1 to A3, the dispersant with a moderate boiling point is less likely to remain in the light-emitting layer. However, the dispersion medium had a lower boiling point than the dispersant and volatilized faster than the dispersant. Thus, the nanocrystals were not solvated and therefore agglomerated, and the emission lifetime of the light-emitting device could not be improved.
In the comparative examples A4 to A6 and A7 to A9, in which the dispersant had a higher boiling point than in the comparative examples A1 to A3, a large amount of dispersant remained in the light-emitting layer, and the emission lifetime of the light-emitting device could not be improved.
An ink was prepared in the same manner as in the example A2 except that the triethylene glycol monomethyl ether was replaced with a mixed dispersion medium containing triethylene glycol monomethyl ether and 1-methoxynaphthalene.
In the examples B1 to B8, the ratio of triethylene glycol monomethyl ether to 1-methoxynaphthalene was changed as shown in Table 2.
An ink was prepared in the same manner as in the example A4 except that the δ-decanolactone was replaced with a mixed dispersion medium containing δ-decanolactone and cyclohexylbenzene.
In the examples B9 to B16, the ratio of δ-decanolactone to cyclohexylbenzene was changed as shown in Table 2.
The luminance half-life of the light-emitting device according to each example was measured in the same manner as described in “4”, and the emission lifetime was rated according to the following evaluation criteria.
The luminance half-life of the light-emitting device according to the example A2 was taken as 1.00, and the luminance half-lives of the light-emitting devices according to the examples B1 to B8 were determined as relative values, which were used as evaluation measures.
The luminance half-life of the light-emitting device according to the example A4 was taken as 1.00, and the luminance half-lives of the light-emitting devices according to the examples B9 to B16 were determined as relative values, which were used as evaluation measures.
A: 1.2 or more
B: 0.8 or more and less than 1.2
C: less than 0.8
Table 2 shows that a polar compound constituting 20% to 80% by mass of the dispersion medium could improve the emission lifetime of the light-emitting device.
Particles according to the present invention contain light-emitting semiconductor nanocrystals and a dispersant supported on the semiconductor nanocrystals and having a boiling point of 300° C. or less at atmospheric pressure. Thus, there are provided particles in which a dispersant can be easily removed from semiconductor nanocrystals, an ink with good storage stability, and a light-emitting device with a long emission lifetime.
1 light-emitting device
2 anode
3 cathode
4 hole-injection layer
5 hole-transport layer
6 light-emitting layer
7 electron-transport layer
8 electron-injection layer
| Number | Date | Country | Kind |
|---|---|---|---|
| 2017-194105 | Oct 2017 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2018/035305 | 9/25/2018 | WO | 00 |
