CN117693277A - Light emitting device and method of manufacturing the same - Google Patents
Light emitting device and method of manufacturing the same Download PDFInfo
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- CN117693277A CN117693277A CN202211372288.6A CN202211372288A CN117693277A CN 117693277 A CN117693277 A CN 117693277A CN 202211372288 A CN202211372288 A CN 202211372288A CN 117693277 A CN117693277 A CN 117693277A
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- Electroluminescent Light Sources (AREA)
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Abstract
The invention relates to a light emitting device and a manufacturing method thereof. The light-emitting device comprises an anode layer, a light-emitting layer and a cathode layer which are sequentially stacked. The light-emitting layer contains quantum dot light-emitting material, the electron transport layer contains electron transport material and first additive, and the hole injection layer contains airA hole injecting material and a second additive; the molecular structure of the first additive and the second additive is thatThe additive can reduce the LUMO energy level of the electron transport material, prevent electron injection from the cathode layer to the electron transport layer, establish interface dipoles at the interface between the electron transport layer and the light-emitting layer, and further prevent electron injection from the electron transport layer to the light-emitting layer, so that unbalance of the number of holes and electrons in the light-emitting layer is reduced, and the efficiency and stability of the device are improved. The additive can reduce the HOMO energy level of the hole injection material and promote the injection of holes, thereby reducing the unbalance of the number of the holes and the electrons in the luminescent layer and improving the efficiency and the stability of the device.
Description
Technical Field
The present invention relates to the field of photoelectric technology, and in particular, to a light emitting device and a method for manufacturing the same.
Background
Display technology has realized a number of qualitative leaps from early Cathode Ray Tube (CRT) display, to Liquid Crystal Display (LCD) in the 80 th century, plasma flat Panel Display (PDP), to Organic Light Emitting Diode (OLED), quantum dot light emitting diode (QLED) display, which are currently mainstream.
OLED devices have become the dominant technology in the display technology field due to their advantages of self-luminescence, simple structure, light weight, fast response, wide viewing angle, low power consumption, flexible display, etc. QLED devices have the advantages of saturated color of emitted light, wavelength adjustability, high quantum yield of emitted light, and the like, and have become a powerful competitor for OLEDs in recent years.
In conventional QLED devices, carrier functional layers such as a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), and an Electron Transport Layer (ETL) are generally disposed on both sides of a quantum dot light emitting layer to regulate and control the transport of holes and electrons. For example, one QLED device has the structure: anode/hole injection layer/hole transport layer/quantum dot light emitting layer/electron transport layer/cathode.
The electron transport layer of a QLED device typically uses inorganic nanoparticle oxides, such as ZnO, baO, tiO 2 And the LUMO energy level of the quantum dot luminescent material is about 4eV, and the difference between the quantum dot luminescent material and the LUMO energy level of the quantum dot luminescent material is small. Therefore, the energy level barrier that needs to be crossed when electrons are transferred from the electron transport layer to the quantum dot light emitting layer is small. The hole mobility of the hole transmission layer is several orders of magnitude smaller than the electron mobility of the electron transmission layer, so that the quantity of holes and electrons transmitted to the quantum dot luminescent layer is unbalanced, and the quantum dot material is charged, thereby generating non-radiative luminescence such as Auger recombination and the like, and reducing the efficiency and stability of the device.
Disclosure of Invention
Based on this, it is necessary to provide a light emitting device and a method of fabricating the same to solve the problem of unbalance in the number of holes and electrons transferred to the quantum dot light emitting layer.
An object of the present invention is to provide a light emitting device, which has the following configuration:
the light-emitting device is characterized by comprising an anode layer, a light-emitting layer and a cathode layer which are sequentially stacked, wherein the light-emitting layer contains quantum dot light-emitting materials;
the light emitting device further includes an electron transport layer disposed between the light emitting layer and the cathode layer, the electron transport layer containing an electron transport material and a first additive; and/or
The light emitting device further includes a hole injection layer disposed between the light emitting layer and the anode layer, the hole injection layer containing a hole injection material and a second additive;
the first additive and the second additive are each independently selected from at least one of the following compounds: :
wherein R11 is selected from: hydrogen, substituted or unsubstituted C6-C18 aryl, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C1-C18 heteroaryl;
r12 and R13 are each independently selected from: hydrogen, halogen, substituted or unsubstituted C1-C20 alkyl;
R21 is selected from: hydrogen, substituted or unsubstituted C6-C18 aryl, substituted or unsubstituted C1-C20 alkyl;
r22 is selected from: hydrogen, halogen, carboxyl, hydroxyl, substituted or unsubstituted C1-C20 alkyl;
the substituent is independently selected from one or more of C1-C10 ester group, C1-C10 amide group, C1-C10 alkoxy group, C1-C10 alkylthio group, C1-C10 alkyl group, C6-C10 aryl group, carboxyl group, sulfhydryl group, phosphino group, phosphonic acid group, amino group, nitro group, cyano group, halogen, hydroxyl group and vinyl group.
In one embodiment, R11 is selected from: substituted or unsubstituted C6-C18 aryl, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C1-C18 heteroaryl, preferably substituted or unsubstituted C6-C10 aryl, such as phenyl, naphthyl, 2-methylphenyl, 2-methylnaphthyl;
r12 and R13 are each independently selected from: hydrogen, halogen, substituted or unsubstituted C1-C10 alkyl, preferably C1-C10 alkyl, such as methyl, ethyl, n-propyl, isopropyl;
r21 is selected from: substituted or unsubstituted C6-C18 aryl, substituted or unsubstituted C1-C10 alkyl, preferably substituted or unsubstituted C6-C10 aryl, such as phenyl, naphthyl, 2-methylphenyl, 2-methylnaphthyl;
R22 is selected from: hydrogen, halogen, carboxyl, hydroxyl, substituted or unsubstituted C1-C10 alkyl, preferably carboxyl.
In one embodiment, the first additive and the second additive are each independently selected from at least one of the following compounds:
in one embodiment, the electron transport material is selected from at least one of a metal oxide or a doped metal oxide, preferably the metal oxide is selected from ZnO, baO, tiO 2 And SnO 2 At least one of them.
In one embodiment, the doped metal oxide is selected from ZnO, baO, tiO 2 And SnO 2 The doping element is at least one selected from Al, mg and Li.
In one embodiment, the mass fraction of the electron transport material in the electron transport layer is 90-99%, and the mass fraction of the first additive in the electron transport layer is 1-10%;
preferably, the mass fraction of the electron transport material in the electron transport layer is 93% -97%, and the mass fraction of the first additive in the electron transport layer is 3% -7%.
In one embodiment, the hole injection layer is formed of a material selected from at least one of TFB, cuPc, PVK, poly-TPD, DNTPD, TCATA, TCCA, CBP, TPD, NPB, NPD, PEDOT: PSS, TAPC, MCC, F4-TCNQ, HATCN, 4' -tris (N-3-methylphenyl-N-phenylamino) triphenylamine, polyaniline, a transition metal oxide, a transition metal sulfide, a transition metal stannate, doped graphene, undoped graphene, and C60.
In one embodiment, the mass fraction of the hole injection material in the hole injection layer is 60% -99%, and the mass fraction of the second additive in the hole injection layer is 1% -40%;
preferably, the mass fraction of the hole injection material in the hole injection layer is 65% -90%, and the mass fraction of the second additive in the hole injection layer is 10% -35%.
In one embodiment, the light emitting device further comprises a hole transport layer disposed between the hole injection layer and the light emitting layer, the hole transport layer having a material selected from one or more of TPD, poly-TPD, PVK, CBP, NPB, TCTA, mCP, TAPC, and TFB.
In one embodiment, the quantum dot luminescent material is selected from at least one of single-structure quantum dots and core-shell structure quantum dots, the material of the single-structure quantum dots is selected from at least one of II-VI compounds, IV-VI compounds, III-V compounds and I-III-VI compounds, wherein the II-VI compounds are selected from 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, hgZnTe, cdZnSeS, cdZnSeTe At least one of CdZnSTe, cdHgSeS, cdHgSeTe, cdHgSTe, hgZnSeS, hgZnSeTe and HgZnSTe, wherein the IV-VI compound is at least one of SnS, snSe, snTe, pbS, pbSe, pbTe, snSeS, snSeTe, snSTe, pbSeS, pbSeTe, pbSTe, snPbS, snPbSe, snPbTe, snPbSSe, snPbSeTe and SnPbSTe, the III-V compound is at least one of GaN, 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 or InAlPSb, and the I-III-VI compound is at least one of CuInS 2 、CuInSe 2 AgInS 2 At least one of (a) and (b); the core of the quantum dot with the core-shell structure comprises any one of the quantum dots with the single structure, and the shell material of the quantum dot with the core-shell structure comprises CdS, cdTe, cdSeTe, cdZnSe, cdZnS, cdSeS, znSe, znSeS, znS and at least one of the quantum dots with the single structure.
An object of the present invention is to provide a method for manufacturing a light emitting device, which comprises the following steps:
A method of fabricating a light emitting device, comprising the steps of:
a method of fabricating a light emitting device, comprising the steps of:
manufacturing a cathode layer on a substrate;
manufacturing an electron transport layer on the cathode layer;
manufacturing a light-emitting layer on the electron transport layer;
a hole injection layer is manufactured on the light-emitting layer;
preparing a light emitting layer on the hole injection layer;
manufacturing an anode layer on the light-emitting layer to obtain the light-emitting device;
or,
manufacturing an anode layer on a substrate;
manufacturing a hole injection layer on the anode layer;
manufacturing a light-emitting layer on the hole injection layer;
manufacturing an electron transport layer on the light-emitting layer;
manufacturing a cathode layer on the electron transport layer to obtain the light-emitting device;
wherein the light emitting layer contains a quantum dot light emitting material;
preferably, the electron transport layer contains an electron transport material and a first additive,
and/or the hole injection layer contains a hole injection material and a second additive;
the first additive and the second additive are each independently selected from at least one of the following compounds:
wherein R11 is selected from: hydrogen, substituted or unsubstituted C6-C18 aryl, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C1-C18 heteroaryl;
R12 and R13 are each independently selected from: hydrogen, halogen, substituted or unsubstituted C1-C20 alkyl;
r21 is selected from: hydrogen, substituted or unsubstituted C6-C18 aryl, substituted or unsubstituted C1-C20 alkyl;
r22 is selected from: hydrogen, halogen, carboxyl, hydroxyl, substituted or unsubstituted C1-C20 alkyl;
the substituent is independently selected from one or more of C1-C10 ester group, C1-C10 amide group, C1-C10 alkoxy group, C1-C10 alkylthio group, C1-C10 alkyl group, C6-C10 aryl group, carboxyl group, sulfhydryl group, phosphino group, phosphonic acid group, amino group, nitro group, cyano group, halogen, hydroxyl group and vinyl group.
In one embodiment, the electron transport material is selected from at least one of a metal oxide or a doped metal oxide, preferably the metal oxide is selected from ZnO, baO, tiO 2 And SnO 2 At least one of (a) and (b);
preferably, the method comprises the steps of,the metal oxide in the doped metal oxide is selected from ZnO, baO, tiO 2 And SnO 2 The doping element is at least one selected from Al, mg and Li.
Preferably, the mass fraction of the electron transport material in the electron transport layer is 90-99%, and the mass fraction of the first additive in the electron transport layer is 1-10%;
More preferably, the mass fraction of the electron transport material in the electron transport layer is 93% to 97%, and the mass fraction of the first additive in the electron transport layer is 3% to 7%.
In one embodiment, the hole injection layer is made of at least one material selected from the group consisting of TFB, cuPc, PVK, poly-TPD, DNTPD, TCATA, TCCA, CBP, TPD, NPB, NPD, PEDOT: PSS, TAPC, MCC, F4-TCNQ, HATCN, 4' -tris (N-3-methylphenyl-N-phenylamino) triphenylamine, polyaniline, transition metal oxide, transition metal sulfide, transition metal stannide, doped graphene, undoped graphene, and C60.
Preferably, the mass fraction of the hole injection material in the hole injection layer is 60% -99%, and the mass fraction of the second additive in the hole injection layer is 1% -40%;
more preferably, the mass fraction of the hole injection material in the hole injection layer is 65% to 90%, and the mass fraction of the second additive in the hole injection layer is 10% to 35%.
In one embodiment, the light emitting device further comprises a hole transport layer disposed between the hole injection layer and the light emitting layer, the hole transport layer having a material selected from one or more of TPD, poly-TPD, PVK, CBP, NPB, TCTA, mCP, TAPC, and TFB.
In one embodiment, the quantum dot luminescent material is at least one of single-structure quantum dots and core-shell structure quantum dots, and the material of the single-structure quantum dots is at least one of II-VI compound, IV-VI compound, III-V compound and I-III-VI compoundWherein the group II-VI compound is selected from at least one of 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, hgZnTe, cdZnSeS, cdZnSeTe, cdZnSTe, cdHgSeS, cdHgSeTe, cdHgSTe, hgZnSeS, hgZnSeTe and HgZnSTe, the group IV-VI compound is selected from at least one of SnS, snSe, snTe, pbS, pbSe, pbTe, snSeS, snSeTe, snSTe, pbSeS, pbSeTe, pbSTe, snPbS, snPbSe, snPbTe, snPbSSe, snPbSeTe and SnPbSTe, the group III-V compound is selected from at least one of GaN, 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 or InAlPSb, and the group I-III-VI compound is selected from CuInS 2 、CuInSe 2 AgInS 2 At least one of (a) and (b); the core of the quantum dot with the core-shell structure comprises any one of the quantum dots with the single structure, and the shell material of the quantum dot with the core-shell structure comprises CdS, cdTe, cdSeTe, cdZnSe, cdZnS, cdSeS, znSe, znSeS, znS and at least one of the quantum dots with the single structure.
Compared with the traditional scheme, the light-emitting device and the manufacturing method thereof have the following beneficial effects:
the light emitting device includes an electron transport layer and/or a hole injection layer. The electron transport layer contains an electron transport material and a first additive having a molecular structure of-NH 2 and-COOH groups, wherein when the electron transport material is mixed with the additive, the-COOH groups in the additive molecule will bond with metal atoms in the metal oxide and/or doped metal oxide, thereby being capable of lowering the LUMO level of the electron transport material and blocking electron injection from the cathode layer to the electron transport layer. At the same time, -NH 2 The existence of the group can establish an interface dipole at the interface of the electron transport layer and the light emitting layer, and the interface dipole can further block electricityThe electrons are injected from the electron transport layer to the light emitting layer, and electron accumulation is formed in the electron transport layer, so that unbalance of the number of holes and electrons in the light emitting layer is relieved, and the efficiency and stability of the device are improved.
The hole injection layer contains a hole injection material and a second additive. The molecular structure of the additive has multiple electrophilic groups (-NH) 2 ) And a plurality of aprotic groups (-c=o), when the hole injection material is mixed with the additive, the HOMO level of the hole injection material can be reduced, and injection of holes is promoted, so that unbalance of the number of holes and electrons in the light emitting layer is reduced, and device efficiency and stability are improved.
Drawings
Fig. 1 is a schematic structural view of a light emitting device according to an embodiment;
FIG. 2 is a diagram showing energy level structure of a light emitting layer and an electron transporting layer, wherein (a) is a diagram showing energy level structure of an electron transporting layer when no additive is added, and (b) is a diagram showing energy level structure of an electron transporting layer when an additive is added;
fig. 3 is an energy level structure diagram of the hole injection layer and the hole transport layer, wherein (a) is an energy level structure diagram when no additive is added to the hole injection layer, and (b) is an energy level structure diagram when an additive is added to the hole injection layer.
Reference numerals illustrate:
100. a light emitting device; 110. an anode layer; 120. a light emitting layer; 130. an electron transport layer; 140. a cathode layer; 150. a hole injection layer; 160. a hole transport layer; 170. a substrate.
Detailed Description
In order that the invention may be readily understood, a more complete description of the invention will be rendered by reference to the appended drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
It will be understood that when an element is referred to as being "disposed on" another element, it can be directly on the other element or intervening elements may also be present. When an element is referred to as being "connected" to another element, it can be directly connected to the other element or intervening elements may also be present.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
The invention provides a light emitting device.
As shown in fig. 1, the light emitting device 100 of an embodiment includes an anode layer 110, a light emitting layer 120, and a cathode layer 140, which are sequentially stacked. The light emitting layer 120 contains a quantum dot light emitting material.
The light emitting device 100 further includes an electron transport layer 130 and/or a hole injection layer 150.
The electron transport layer 130 contains an electron transport material and a first additive.
The hole injection layer 150 contains a hole injection material and a second additive.
The first additive and the second additive are each independently selected from at least one of the following compounds:
wherein R11 is selected from: hydrogen, substituted or unsubstituted C6-C18 aryl, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C1-C18 heteroaryl;
r12 and R13 are each independently selected from: hydrogen, halogen, substituted or unsubstituted C1-C20 alkyl;
r21 is selected from: hydrogen, substituted or unsubstituted C6-C18 aryl, substituted or unsubstituted C1-C20 alkyl;
r22 is selected from: hydrogen, halogen, carboxyl, hydroxyl, substituted or unsubstituted C1-C20 alkyl.
The substituents in R11, R12, R13, R21 and R22 are independently selected from one or more of C1-C10 ester group, C1-C10 amide group, C1-C10 alkoxy group, C1-C10 alkylthio group, C1-C10 alkyl group, C6-C10 aryl group, carboxyl group, mercapto group, phosphine group, phosphonic acid group, amino group, nitro group, cyano group, halogen, hydroxyl group and vinyl group.
The first additive and the second additive may be the same or different.
In one example, the first additive and the second additive each independently select at least one of ampicillin, amoxicillin, cefalexin and cefaclor, and have the following molecular structures.
The light emitting device 100 described above includes an electron transport layer 130 and/or a hole injection layer 150. The electron transport layer 130 contains an electron transport material and a first additive having a molecular structure of-NH 2 and-COOH groups, wherein when the electron transport material is mixed with the additive, the-COOH groups in the additive molecule can bond with metal atoms in the metal oxide and/or doped metal oxide, which can lower the LUMO energy level of the electron transport material, blocking electron injection from the cathode layer 140 to the electron transport layer 130. At the same time, as shown in FIG. 2, -NH 2 The existence of the group can establish an interface dipole at the interface between the electron transport layer 130 and the light emitting layer 120, and the interface dipole can further obstruct the injection of electrons from the electron transport layer 130 to the light emitting layer 120, and form electron accumulation in the electron transport layer 130, so as to reduce the imbalance of the number of holes and electrons in the light emitting layer 120, and improve the efficiency and stability of the device.
The hole injection layer 150 contains a hole injection material and a second additive. The molecular structure of the additive has multiple electrophilic groups (-NH) 2 ) And a plurality of aprotic groups (-c=o), the hole injection material, when mixed with the above additives, can reduce HOMO level of the hole injection material, promote injection of holes, and thereby reduce the number of holes and electrons in the light emitting layer 120And the unbalance of the device improves the efficiency and the stability of the device.
In one example, the mass fraction of the electron transport material in the electron transport layer 130 is 90% to 99%, and the mass fraction of the additive is 1% to 10%. In one example, the electron transport material in the electron transport layer 130 has a mass fraction of 93% to 97% and the additive has a mass fraction of 3% to 7%.
The electron transport material is selected from at least one of a metal oxide or a doped metal oxide. Alternatively, the metal oxide may be, but is not limited to ZnO, baO, tiO 2 And SnO 2 At least one of them. The metal oxide in the doped metal oxide may be, but is not limited to ZnO, baO, tiO 2 And SnO 2 The doping element may be, but is not limited to, at least one of Al, mg, li.
the-COOH groups in the additive molecule may bond with metal atoms in the metal oxide and/or doped metal oxide, which can lower the LUMO level of the electron transporting material, blocking electron injection from the cathode layer to the electron transporting layer.
When the electron transport material and the additive are dissolved together in a solvent such as ethanol, the-COOH is bonded to the metal atoms in the metal oxide and/or the doped metal oxide, and the-NH which is not bonded to the electron transport material 2 The groups may cause the mixed solution to exhibit a weak alkalinity, for example a pH of 7-7.5.
In one example, the electron transport layer 130 has a thickness of 20nm-80nm.
In one example, the hole injection layer is made of a material selected from at least one of TFB, cuPc, PVK, poly-TPD, DNTPD, TCATA, TCCA, CBP, TPD, NPB, NPD, PEDOT: PSS, TAPC, MCC, F4-TCNQ, HATCN, 4' -tris (N-3-methylphenyl-N-phenylamino) triphenylamine, polyaniline, transition metal oxide, transition metal sulfide, transition metal stannate, doped graphene, undoped graphene, and C60.
Taking PEDOT PSS as an example, when the hole injection material is mixed with the second additive, the electrophilic group in the second additive molecule will be the same as the electron-donating group in PEDOT PSS 3 The additive is added into the PEDOT and PSS to reduce the HOMO energy level of the PEDOT and PSS and promote the injection of holes, thereby reducing the unbalance of the number of holes and electrons in the light-emitting layer 120 and improving the efficiency and stability of the device.
When the hole injection material and the above-mentioned additives are dissolved together in a solvent such as water, the hydrophilic group not bonded to the hole injection material may cause the mixed solution to be acidic, for example, to have a pH of 3.5 to 4.5.
In one example, the mass fraction of the hole injection material in the hole injection layer 150 is 60% to 99%, and the mass fraction of the second additive in the hole injection layer is 1% to 40%. More preferably, the mass fraction of the hole injection material in the hole injection layer 150 is 65% to 90%, and the mass fraction of the second additive in the hole injection layer is 10% to 35%.
In one example, the hole injection layer 150 has a thickness of 10nm-100nm.
The material of the anode layer 110 is a conductive material, such as a high work function metal, such as ITO, IZO, au, and a metal oxide.
In one example, the anode layer 110 has a thickness of 10nm-200nm.
The material of the cathode layer 140 is a conductive material, such as Al, ag, mgAg alloy.
In one example, the cathode layer 140 has a thickness of 10nm-200nm.
The quantum dot luminescent material is at least one of single-structure quantum dots and core-shell structure quantum dots, the material of the single-structure quantum dots is at least one of II-VI compound, IV-VI compound, III-V compound and I-III-VI compound, wherein the II-VI compound is 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, hgZnTe, cdZnSeS, cdZnSeTe, cdZnSTe, cdHgSeS, cdHgSeTe, cdHgSTe, hgZnSeS, H At least one of gZnSeTe and HgZnSte, at least one of IV-VI compound selected from SnS, snSe, snTe, pbS, pbSe, pbTe, snSeS, snSeTe, snSTe, pbSeS, pbSeTe, pbSTe, snPbS, snPbSe, snPbTe, snPbSSe, snPbSeTe and SnPbSTe, at least one of GaN, 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 or InAlPSb, and at least one of I-III-VI compound selected from CuInS 2 、CuInSe 2 AgInS 2 At least one of (a) and (b); the core of the quantum dot with the core-shell structure comprises any one of the quantum dots with the single structure, and the shell material of the quantum dot with the core-shell structure comprises CdS, cdTe, cdSeTe, cdZnSe, cdZnS, cdSeS, znSe, znSeS, znS and at least one of the quantum dots with the single structure.
It will be appreciated that organic ligands may also be bound to the quantum dot luminescent material. The organic ligand may be selected from at least one of OA (oleic acid), OAM (oleylamine), TOP (trioctylphosphorus), but not limited thereto.
In one example, the thickness of the light emitting layer 120 is 10nm-50nm.
In one example, the light emitting device 100 further includes a hole transport layer 160, the hole transport layer 160 being disposed between the hole injection layer 150 and the light emitting layer 120.
In the above-mentioned additive molecule, as shown in fig. 3, the presence of the aprotic group may create an interfacial dipole at the interface between the hole injection layer 150 and the hole transport layer 160, which may promote hole injection, and form hole accumulation in the hole injection layer 150, thereby reducing imbalance in the number of holes and electrons in the light emitting layer 120 and improving device efficiency and stability.
Alternatively, the material of the hole transport layer 160 may be selected from, but not limited to, any one or more of TPD, poly-TPD, PVK, CBP, NPB, TCTA, mCP, TAPC, and TFB.
In one example, the hole transport layer 160 has a thickness of 10nm to 100nm.
It will be appreciated that the display device further includes a substrate 170. The light emitting device 100 shown in fig. 1 is a front-end device, and the anode layer 110 is disposed on the substrate 170. Specifically, the light emitting device 100 includes a substrate 170, an anode layer 110, a hole injection layer 150, a hole transport layer 160, a light emitting layer 120, an electron transport layer 130, and a cathode layer 140, which are sequentially stacked. For an inverted device, the cathode layer 140 is disposed on the substrate 170, and the device structure includes, for example, the substrate 170, the cathode layer 140, the electron transport layer 130, the light emitting layer 120, the hole transport layer 160, the hole injection layer 150, and the anode layer 110, which are sequentially stacked.
The substrate 170 includes a substrate and a TFT driving array disposed on the substrate. The substrate may be a rigid substrate, such as a glass substrate, preferably a silicon-based substrate with good thermal conductivity, or may be a flexible substrate, such as a PI (polyimide) substrate.
The present invention provides a method of fabricating the light emitting device 100 of any of the examples described above.
A method for manufacturing a light emitting device 100 according to an embodiment includes the steps of:
manufacturing a cathode layer on a substrate;
manufacturing an electron transport layer on the cathode layer;
manufacturing a light-emitting layer on the electron transport layer;
a hole injection layer is manufactured on the light-emitting layer;
preparing a light emitting layer on the hole injection layer;
and manufacturing an anode layer on the light-emitting layer to obtain the light-emitting device.
Or,
manufacturing an anode layer on a substrate;
manufacturing a hole injection layer on the anode layer;
manufacturing a light-emitting layer on the hole injection layer;
manufacturing an electron transport layer on the light-emitting layer;
manufacturing a cathode layer on the electron transport layer to obtain the light-emitting device;
wherein the light emitting layer contains a quantum dot light emitting material;
preferably, the electron transport layer contains an electron transport material and a first additive,
and/or the hole injection layer contains a hole injection material and a second additive.
In one example, the step of fabricating the electron transport layer includes:
mixing an electron transport material and the additive and dissolving the mixture in a solvent to obtain ink;
and (3) coating the ink on a cathode layer or a light-emitting layer, and drying to form a film.
Wherein the solvent may be, but is not limited to, one or more of ethanol, ethylene glycol, 3-methoxybutanol.
The coating may be, but is not limited to, spray coating, spin coating, knife coating, ink jet printing, and the like.
Similarly, the hole injection layer may be formed by the method for forming the electron transport layer.
The following examples are provided to illustrate the invention, but the invention is not limited to the following examples. It is to be understood that the appended claims outline the scope of the invention, and those skilled in the art, guided by the inventive concepts herein provided, will appreciate that certain modifications to the various embodiments of the invention will be covered by the spirit and scope of the appended claims.
Example 1
The light emitting device of this embodiment includes a substrate, an anode layer, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and a cathode layer, which are sequentially stacked.
The manufacturing method of the light-emitting device comprises the following steps:
Step 1, providing a glass substrate, depositing ITO on the glass substrate, and forming an anode layer.
And 2, manufacturing a hole injection layer on the anode layer. The ink containing PEDOT and PSS is spin-coated on the anode layer, dried to form a film, and then annealed at 150 ℃ for 15min to form a hole injection layer with the thickness of 45 nm.
And step 3, manufacturing a hole transport layer on the hole injection layer. And spin-coating the ink containing the TFB on the hole injection layer, drying to form a film, and annealing at 230 ℃ for 30min to form the hole transport layer with the thickness of 20 nm.
And step 4, manufacturing a light-emitting layer on the hole transport layer. And (3) adopting CdSe/ZnS red quantum dots, wherein an organic ligand is OA (oleic acid), spin-coating red quantum dot ink on the hole transport layer, drying to form a film, and annealing at 100 ℃ for 10min to form a light-emitting layer with the thickness of 15 nm.
And step 5, manufacturing an electron transport layer on the light-emitting layer. ZnO and ampicillin are taken and dissolved in ethanol according to the mass ratio of 95:5 to prepare the ink, and the pH value of the ink is 7.3. The ink was spin-coated on the light-emitting layer, dried to form a film, and then annealed at 100℃for 10 minutes to form an electron transport layer having a thickness of 30 nm.
And 6, evaporating an Ag layer on the electron transport layer to form a cathode layer with the thickness of 150 nm.
And 7, packaging to prepare the light-emitting device.
The whole process is carried out in a glove box under the protection of nitrogen.
Example 2
This example is essentially identical to example 1 with the difference that: in step 5 the additive is amoxicillin instead of ampicillin as in example 1.
Example 3
This example is essentially identical to example 1 with the difference that: in step 5 the additive was cefalexin instead of ampicillin in example 1.
Example 4
This example is essentially identical to example 1 with the difference that: cefaclor was used in step 5 as an additive to replace ampicillin in example 1.
Example 5
This example is essentially identical to example 1 with the difference that: the additive ampicillin was used in step 2 and the mass ratio of PEDOT: PSS to ampicillin was 8:2, no additive being used in step 5.
Example 6
This example is essentially identical to example 1 with the difference that: the additive amoxicillin was used in step 2 and the mass ratio of PEDOT: PSS to amoxicillin was 8:2, no additive was used in step 5.
Example 7
This example is essentially identical to example 1 with the difference that: the additive cefalexin was used in step 2 and the mass ratio PEDOT: PSS to cefalexin was 8:2, no additive was used in step 5.
Example 8
This example is essentially identical to example 1 with the difference that: the additive cefaclor was used in step 2 and the mass ratio of PEDOT: PSS to cefaclor was 8:2, no additive being used in step 5.
Example 9
This example is essentially identical to example 1 with the difference that: in step 2, the additive ampicillin was used, and the mass ratio of PEDOT: PSS to ampicillin was 8:2.
Comparative example 1
This example is essentially identical to example 1 with the difference that: in step 5, no additives are used.
The whole process is carried out in a glove box under the protection of nitrogen.
The light emitting devices fabricated in examples 1 to 4 and comparative example 1 described above were subjected to performance tests including external quantum efficiency, current efficiency, and lifetime (t95@1000nit). The test results are shown in Table 1.
TABLE 1 light emitting device Performance test results
The devices of examples 1 to 4 described above have additives in the electron transport layer, the devices of examples 5 to 8 have additives in the hole injection layer, and the device of example 9 has additives in both the electron transport layer and the hole injection layer. As can be seen from the results of Table 1, the comparative relationship between the external quantum efficiency and the current efficiency was example 9 > examples 1 to 4 > examples 5 to 8 > comparative examples. Since the current efficiency is generally positively correlated with lifetime, the higher the current efficiency, the better the lifetime, and the longer the lifetime, the more the device lifetime comparison is.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. The scope of the invention is, therefore, indicated by the appended claims, and the description may be intended to interpret the contents of the claims.
Claims (12)
1. The light-emitting device is characterized by comprising an anode layer, a light-emitting layer and a cathode layer which are sequentially stacked, wherein the light-emitting layer contains quantum dot light-emitting materials;
the light emitting device further includes an electron transport layer disposed between the light emitting layer and the cathode layer, the electron transport layer containing an electron transport material and a first additive;
And/or the light emitting device further comprises a hole injection layer disposed between the light emitting layer and the anode layer, the hole injection layer containing a hole injection material and a second additive;
the first additive and the second additive are each independently selected from at least one of the following compounds:
wherein R11 is selected from: hydrogen, substituted or unsubstituted C6-C18 aryl, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C1-C18 heteroaryl;
r12 and R13 are each independently selected from: hydrogen, halogen, substituted or unsubstituted C1-C20 alkyl;
r21 is selected from: hydrogen, substituted or unsubstituted C6-C18 aryl, substituted or unsubstituted C1-C20 alkyl;
r22 is selected from: hydrogen, halogen, carboxyl, hydroxyl, substituted or unsubstituted C1-C20 alkyl;
the substituent is independently selected from one or more of C1-C10 ester group, C1-C10 amide group, C1-C10 alkoxy group, C1-C10 alkylthio group, C1-C10 alkyl group, C6-C10 aryl group, carboxyl group, sulfhydryl group, phosphino group, phosphonic acid group, amino group, nitro group, cyano group, halogen, hydroxyl group and vinyl group.
2. The light-emitting device according to claim 1, wherein R11 is selected from: substituted or unsubstituted C6-C18 aryl, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C1-C18 heteroaryl, preferably substituted or unsubstituted C6-C10 aryl;
R12 and R13 are each independently selected from: hydrogen, halogen, substituted or unsubstituted C1-C10 alkyl, preferably C1-C10 alkyl;
r21 is selected from: substituted or unsubstituted C6-C18 aryl, substituted or unsubstituted C1-C10 alkyl, preferably substituted or unsubstituted C6-C10 aryl;
r22 is selected from: hydrogen, halogen, carboxyl, hydroxyl, substituted or unsubstituted C1-C10 alkyl, preferably carboxyl.
3. The light-emitting device according to claim 1, wherein the first additive and the second additive are each independently selected from at least one of the following compounds:
4. a light-emitting device according to any one of claims 1 to 3, wherein the electron transport material is selected from at least one of a metal oxide or a doped metal oxide, preferably the metal oxide is selected from ZnO, baO, tiO 2 And SnO 2 At least one of (a) and (b);
preferably, the metal oxide in the doped metal oxide is selected from ZnO, baO, tiO 2 And SnO 2 The doping element is at least one selected from Al, mg and Li.
5. The light-emitting device according to any one of claims 1 to 4, wherein a mass fraction of the electron transport material in the electron transport layer is 90% to 99%, and a mass fraction of the first additive in the electron transport layer is 1% to 10%;
Preferably, the mass fraction of the electron transport material in the electron transport layer is 93% -97%, and the mass fraction of the first additive in the electron transport layer is 3% -7%.
6. The light-emitting device according to any one of claims 1 to 5, wherein the hole injection layer is made of a material selected from at least one of TFB, cuPc, PVK, poly to TPD, DNTPD, TCATA, TCCA, CBP, TPD, NPB, NPD, PEDOT: PSS, TAPC, MCC, F4-TCNQ, HATCN, 4' -tris (N-3-methylphenyl-N-phenylamino) triphenylamine, polyaniline, a transition metal oxide, a transition metal sulfide, a transition metal stannide, doped graphene, undoped graphene, and C60.
7. The light-emitting device according to any one of claims 1 to 6, wherein a mass fraction of the hole injection material in the hole injection layer is 60% to 99%, and a mass fraction of the second additive in the hole injection layer is 1% to 40%;
preferably, the mass fraction of the hole injection material in the hole injection layer is 65% -90%, and the mass fraction of the second additive in the hole injection layer is 10% -35%.
8. The light-emitting device according to any one of claims 1 to 7, further comprising a hole-transporting layer provided between the hole-injecting layer and the light-emitting layer, wherein a material of the hole-transporting layer is selected from one or more of TPD, poly-TPD, PVK, CBP, NPB, TCTA, mCP, TAPC, and TFB;
the quantum dot luminescent material is selected from at least one of single-structure quantum dots and core-shell structure quantum dots, the material of the single-structure quantum dots is selected from at least one of II-VI compound, IV-VI compound, III-V compound and I-III-VI compound, wherein the II-VI compound is selected from at least one of 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, hgZnTe, cdZnSeS, cdZnSeTe, cdZnSTe, cdHgSeS, cdHgSeTe, cdHgSTe, hgZnSeS, hgZnSeTe and HgZnSTe, the IV-VI compound is selected from at least one of SnS, snSe, snTe, pbS, pbSe, pbTe, snSeS, snSeTe, snSTe, pbSeS, pbSeTe, pbSTe, snPbS, snPbSe, snPbTe, snPbSSe, snPbSeTe and SnPbSTe, the III-V compound is selected from at least one of GaN, 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 or InAlPSb, and the I-III-VI compound The material is selected from CuInS 2 、CuInSe 2 AgInS 2 At least one of (a) and (b); the core of the quantum dot with the core-shell structure comprises any one of the quantum dots with the single structure, and the shell material of the quantum dot with the core-shell structure comprises CdS, cdTe, cdSeTe, cdZnSe, cdZnS, cdSeS, znSe, znSeS, znS and at least one of the quantum dots with the single structure.
9. A method of fabricating a light emitting device, comprising the steps of:
manufacturing a cathode layer on a substrate;
manufacturing an electron transport layer on the cathode layer;
manufacturing a light-emitting layer on the electron transport layer;
a hole injection layer is manufactured on the light-emitting layer;
preparing a light emitting layer on the hole injection layer;
manufacturing an anode layer on the light-emitting layer to obtain the light-emitting device;
or,
manufacturing an anode layer on a substrate;
manufacturing a hole injection layer on the anode layer;
manufacturing a light-emitting layer on the hole injection layer;
manufacturing an electron transport layer on the light-emitting layer;
manufacturing a cathode layer on the electron transport layer to obtain the light-emitting device;
wherein the light emitting layer contains a quantum dot light emitting material; the method comprises the steps of carrying out a first treatment on the surface of the
Preferably, the electron transport layer contains an electron transport material and a first additive,
And/or the hole injection layer contains a hole injection material and a second additive;
the first additive and the second additive are each independently selected from at least one of the following compounds:
wherein R11 is selected from: hydrogen, substituted or unsubstituted C6-C18 aryl, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C1-C18 heteroaryl;
r12 and R13 are each independently selected from: hydrogen, halogen, substituted or unsubstituted C1-C20 alkyl;
r21 is selected from: hydrogen, substituted or unsubstituted C6-C18 aryl, substituted or unsubstituted C1-C20 alkyl;
r22 is selected from: hydrogen, halogen, carboxyl, hydroxyl, substituted or unsubstituted C1-C20 alkyl;
the substituent is independently selected from one or more of C1-C10 ester group, C1-C10 amide group, C1-C10 alkoxy group, C1-C10 alkylthio group, C1-C10 alkyl group, C6-C10 aryl group, carboxyl group, sulfhydryl group, phosphino group, phosphonic acid group, amino group, nitro group, cyano group, halogen, hydroxyl group and vinyl group.
10. The method of manufacturing a light-emitting device according to claim 9, wherein the electron transport material is at least one selected from a metal oxide or a doped metal oxide, preferably the metal oxide is selected from ZnO, baO, tiO 2 And SnO 2 At least one of (a) and (b);
preferably, the metal oxide in the doped metal oxide is selected from ZnO, baO, tiO 2 And SnO 2 At least one doping element selected from at least one of Al, mg and Li;
preferably, the mass fraction of the electron transport material in the electron transport layer is 90-99%, and the mass fraction of the first additive in the electron transport layer is 1-10%;
more preferably, the mass fraction of the electron transport material in the electron transport layer is 93% to 97%, and the mass fraction of the first additive in the electron transport layer is 3% to 7%.
11. The method of manufacturing a light-emitting device according to claim 9 or 10, wherein the hole injection layer is made of a material selected from at least one of TFB, cuPc, PVK, poly to TPD, DNTPD, TCATA, TCCA, CBP, TPD, NPB, NPD, PEDOT of PSS, TAPC, MCC, F4-TCNQ, HATCN, 4' -tris (N-3-methylphenyl-N-phenylamino) triphenylamine, polyaniline, a transition metal oxide, a transition metal sulfide, a transition metal tin compound, doped graphene, undoped graphene, and C60;
preferably, the mass fraction of the hole injection material in the hole injection layer is 60% -99%, and the mass fraction of the second additive in the hole injection layer is 1% -40%;
More preferably, the mass fraction of the hole injection material in the hole injection layer is 65% to 90%, and the mass fraction of the second additive in the hole injection layer is 10% to 35%.
12. The method of manufacturing a light-emitting device according to any one of claims 9 to 11, wherein the light-emitting device further comprises a hole-transporting layer provided between the hole-injecting layer and the light-emitting layer, and wherein a material of the hole-transporting layer is one or more selected from TPD, poly-TPD, PVK, CBP, NPB, TCTA, mCP, TAPC, and TFB;
the quantum dot luminescent material is at least one of single-structure quantum dots and core-shell structure quantum dots, the material of the single-structure quantum dots is at least one of II-VI group compounds, IV-VI group compounds, III-V group compounds and I-III-VI group compounds, wherein the II-VI group compounds are at least one of 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, hgZnTe, cdZnSeS, cdZnSeTe, cdZnSTe, cdHgSeS, cdHgSeTe, cdHgSTe, hgZnSeS, hgZnSeTe and HgZnSTe, the IV-VI group compounds are at least one of SnS, snSe, snTe, pbS, pbSe, pbTe, snSeS, snSeTe, snSTe, pbSeS, pbSeTe, pbSTe, snPbS, snPbSe, snPbTe, snPbSSe, snPbSeTe and SnPbSTe, and the III-V group compounds are at least one of SnS, snSe, snTe, pbS, pbSe, pbTe, snSeS, snSeTe, snSTe, pbSeS, pbSeTe, pbSTe, snPbS, snPbSe, snPbTe, snPbSSe, snPbSeTe and SnPbSTe GaN, 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 or InAlPSb, the group I-III-VI compound being selected from CuInS 2 、CuInSe 2 AgInS 2 At least one of (a) and (b); the core of the quantum dot with the core-shell structure comprises any one of the quantum dots with the single structure, and the shell material of the quantum dot with the core-shell structure comprises CdS, cdTe, cdSeTe, cdZnSe, cdZnS, cdSeS, znSe, znSeS, znS and at least one of the quantum dots with the single structure.
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