CN114613927B - Charge generation layer, electroluminescent device and preparation method thereof - Google Patents
Charge generation layer, electroluminescent device and preparation method thereof Download PDFInfo
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Abstract
The invention provides a charge generation layer, an electroluminescent device and a preparation method thereof. The charge generation layer is formed by combining an n-type semiconductor doping layer and a p-type semiconductor doping layer, wherein the main material of the n-type semiconductor doping layer is selected from any one of 4, 7-diphenyl-1, 10-phenanthroline, 4, 7-diphenyl-1, 10-phenanthroline derivatives, 9, 10-di (6-phenylpyridine-3-yl) anthracene, 8-hydroxyquinoline-lithium and 1,3, 5-tri (1-phenyl-1H-benzimidazole-2-yl) benzene, and the doping material is selected from any one of Ag, Zn and Cr; the host material of the P-type semiconductor doping layer is any one selected from TAPC, m-MTDATA, TCTA, NPB, 4P-NPB, MCP, CBP and pentacene. The charge generation layer provided by the invention has excellent capacity of generating and transferring charges.
Description
Technical Field
The invention relates to a charge generation layer, an electroluminescent device and a preparation method thereof, belonging to the technical field of electroluminescence, in particular to the technical field of inverted lamination organic electroluminescence.
Background
Since the discovery of Organic Light Emitting Diodes (OLEDs), they have shown great potential in the display and solid state lighting areas due to their light weight, flexibility, and excellent optoelectronic properties. The brightness of an OLED as a current-driven device is often dependent on the magnitude of the current density. However, the high temperature and coulomb force degradation caused by the high current density will greatly reduce the service life of the OLED device, resulting in inevitable loss. In fact, high brightness and long lifetime are important conditions for successful commercial application of OLEDs, and it is often difficult for conventional single-layer OLED devices to satisfy both conditions.
Light-emitting devices may be classified into a single-type (or unitary-type) light-emitting device including a single organic light-emitting layer and a tandem-type (or tandem-type) light-emitting device including two or more organic light-emitting layers arranged in a tandem configuration, according to a method of configuring an organic light-emitting layer. Among them, the tandem-type (or tandem-type) organic light emitting diode device has features in terms of improved efficiency, high stability, long life, and the like, relative to the single-type (or unitary-type) organic light emitting diode device, and thus can be used for a display device or an illumination device requiring high luminance and long life. In order to implement the tandem type (or tandem type) organic light emitting diode device, there is a Charge Generation Layer (CGL) in the device that couples (or connects) two or more organic light emitting layers.
However, the conventional charge generation layer has a problem in that it increases the driving voltage of a tandem-type (or tandem-type) light emitting device by about 1.3 to 2 times or more than that of a conventional single-type (or unitary-type) organic light emitting diode device due to its poor ability to generate and transfer charges, thereby reducing the power efficiency and lifespan of the organic light emitting diode device. To address this problem, various structures of charge generation layers have been prepared in the industry.
1. Chinese patent CN107123742A provides an inverted bottom emission organic light emitting diode and a method for manufacturing the same. The inverted organic light-emitting diode is prepared by a charge generation layer structure, wherein m-MTDATA, TAPC or NPB is selected as a p-type semiconductor, HAT-CN is selected as an n-type semiconductor to prepare a charge generation layer, metal oxide doped Bphen is selected as an electron transport layer, and MoO3 doped NPB is selected as a hole transport layer; although the scheme of the inverted device solves the problem of the service life of the device to a certain extent and improves the power efficiency of the device, the scheme also has the following problems: a. the charge generation layer needs to be manufactured independently, so that the thickness of the device is increased, two evaporation processes are additionally added, and the difficulty is increased for the implementation of a mass production technology; b. the maximum power efficiency of the blue light device is only about 9 lm/W.
2. Chinese patent CN102185112A provides a laminated organic light emitting diode and a method for manufacturing the same. The organic light emitting diode comprises a laminated organic light emitting diode prepared by another charge generation layer structure, wherein n-type semiconductors are selected from fullerene and derivatives thereof or perylene derivatives; the p-type semiconductor is selected from metal phthalocyanine compounds, thiophene compounds or polycyclic aromatic hydrocarbons; the charge generation layer in the invention can release carriers, thereby offsetting high voltage generated by coexistence of a plurality of light emitting units, remarkably reducing the working voltage of the laminated organic light emitting diode and improving the power efficiency of the laminated organic light emitting diode. However, this prior art also has some problems: a. the thermal stability of the device is poor, and the performance is poor at 80 ℃; b. the maximum power efficiency of the blue light device is only about 10 lm/W.
Disclosure of Invention
It is an object of the present invention to overcome the disadvantages of the prior art and to provide a charge generation layer, an electroluminescent device and a method for manufacturing the same, the charge generation layer being capable of providing excellent capability of generating and transferring charges.
It is a first object of the present invention to provide a novel charge generation layer.
It is a second object of the present invention to provide an electroluminescent device comprising the above novel charge generation layer.
The third purpose of the invention is to provide a preparation method of the electroluminescent device.
The technical scheme of the invention is as follows:
a charge generation layer is composed of a combination of an n-type semiconductor doped layer made of a host material and a dopant material and a p-type semiconductor doped layer also made of a host material and a dopant material,
wherein:
the main material of the n-type semiconductor doping layer is selected from any one of 4, 7-diphenyl-1, 10-phenanthroline, 4, 7-diphenyl-1, 10-phenanthroline derivatives, 9, 10-di (6-phenylpyridine-3-yl) anthracene, 8-hydroxyquinoline-lithium, 1,3, 5-tri (1-phenyl-1H-benzimidazole-2-yl) benzene, and the doping material is selected from any one of Ag, Zn and Cr.
In a preferred embodiment of the present invention, the main material of the n-type semiconductor doped layer is 4, 7-diphenyl-1, 10-phenanthroline, and the doped material is Ag, that is, the n-type semiconductor doped layer is Ag-doped Bphen.
The host material of the P-type semiconductor doped layer is selected from TAPC (4, 4 '-cyclohexylbis [ N, N-bis (4-methylphenyl) aniline ]), m-MTDATA (4, 4',4 '-tris (N-3-methylphenyl-N-phenylamino) triphenylamine), TCTA (4, 4',4'' -tris (carbazol-9-yl) triphenylamine), NPB (N, N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine), 4P-NPB (N, N '-bis (1-naphthalene) -N, N' -diphenyl- [1,1':4'14, 1QUATERPHENYL ] -4, 4-diamine), MCP (9, any one of 9'- (1, 3-phenyl) di-9H-carbazole), CBP (4, 4' -di (9-carbazole) biphenyl) and pentacene; the doping material is selected from any one of MoO3, WO3, V2O5 or copper phthalocyanine.
In a preferred embodiment of the present invention, the host material of the p-type semiconductor doped layer is NPB, and the doped material is MoO 3 That is, the p-type semiconductor doped layer is MoO 3 Doping NPB.
Further, the thickness of the n-type semiconductor doping layer is 1-100nm, preferably 5-30nm, and more preferably 10-15 nm.
Further, the thickness of the p-type semiconductor doping layer is 1-100nm, preferably 5-30nm, and more preferably 10-15 nm.
In the charge generation layer, the combination mode of the n-type semiconductor doping layer and the p-type semiconductor doping layer is any one of p-n, n-p, p-n-p and n-p-n.
The invention also provides an electroluminescent device comprising the charge generation layer, which comprises a substrate, a first electrode layer, a second electrode layer, an organic functional layer and a packaging layer which are arranged according to a certain rule, wherein a light emitting layer, a charge generation layer, an electron transport layer and a hole transport layer which are arranged according to a certain rule are arranged in the organic functional layer.
Further, in the organic functional layer, the number of the light emitting layers is one or more, the number of the charge generation layers is one or more, the number of the electron transport layers is one or more, and the number of the hole transport layers is one or more.
The invention also provides a preparation method of the electroluminescent device, which comprises the following steps:
s1, plating an ITO film on the glass substrate through a magnetron sputtering process, then obtaining a first electrode layer through an etching process, and obtaining a clean patterned ITO substrate through cleaning, drying and ultraviolet irradiation;
s2, sequentially depositing organic functional layers including but not limited to a light-emitting layer, a charge generation layer, an electron transport layer and a hole transport layer by an evaporation process, wherein each film layer is sequentially evaporated according to a specific structure;
s3, switching the evaporation mask plate, and continuing to evaporate the second electrode layer material;
and S4, packaging the evaporated device through the processes of dispensing, pressing, UV curing and baking to prepare the sealed OLED device.
The working principle of the invention is as follows:
on the one hand, Ag doped Bphen as an n-type semiconductor doping layer has good electron transport performance and can block the transport of holes to a certain extent, and MoO is the same 3 NPB is doped as a p-type semiconductor doping layer, has good hole transport performance and blocks the transport of electrons to a certain extent; between adjacent organic functional layers, an n-type semiconductor doping layer formed by Ag doping Bphen and MoO 3 The p-type semiconductor doping layers formed by doping NPB are connected to form a p-n junction interface, an external electric field induces dipole separation of the p-n junction interface, electrons on the HOMO energy level of the p-type material tunnel to the LUMO energy level of the n-type material, an organic p-n heterojunction is formed, and a charge generation layer is formed.
In another aspect, the Bphen: Ag and NPB: MoO of the invention 3 The charge generation layer is formed, on the basis of energy band bending caused by p-type doping and n-type doping, an electric field generated by strong external reverse bias can induce dipole separation of a p-n junction interface, electrons on the LUMO energy level of the p-type doped semiconductor are injected to the LUMO energy level of the n-type doped semiconductor through a depletion layer of the p-n junction by a tunneling effect, and therefore the electrons on the LUMO energy level of the p-type doped semiconductor are injected to the LUMO energy level of the n-type doped semiconductor through the depletion layer of the p-n junctionThe charge generation phenomenon is generated, so that the device of the charge generation layer has good electrical performance under the condition of forward bias or reverse bias.
Meanwhile, Bphen is Ag, NPB is MoO 3 The charge generation layer thus constituted also exhibits excellent thermal stability.
The charge generation layer and the electroluminescent device have the following beneficial effects:
1) the charge generation layer of the present invention can provide excellent ability to generate and transfer charges; as can be seen from FIG. 2 of example 1, the current density of the device A can reach 6000 mA/cm under the working voltage of 8V 2 The current density of the device B can reach 4000 mA/cm under the working voltage of 8V 2 The difference between the two is caused by the difference of work functions of the ITO and Al electrodes;
2) the charge generation layer has excellent electrical properties under forward and reverse bias electric fields; as can be seen from FIG. 4 of example 2, the current density of the device C can reach 6000 mA/cm under both forward and reverse bias 2 The electric properties of the charge generation layer of the device C under positive and negative bias are excellent;
3) in the charge generation layer, the Bphen is doped with Ag to form a silver complex, so that the thermal stability of the device can be improved.
4) The electroluminescent device has excellent photoelectric performance in a laminated device and an inverted laminated device.
5) The charge generation layer and the electroluminescent device have simple structures, are formed in the evaporation process, do not need additional processes and are convenient for mass production.
Drawings
For a better understanding of the nature and technical aspects of the present invention, reference should be made to the following detailed description of the invention, which is to be read in connection with the accompanying drawings, wherein the following drawings are provided for illustrative purposes only and are not intended to limit the invention.
FIG. 1 is a schematic view of the structure of a device A/B in embodiment 1 of the present invention. Wherein a is a structural diagram of the device A, and B is a structural diagram of the device B.
FIG. 2 is a J-V plot of the device A/B in example 1 of the present invention. Wherein a is a J-V curve chart of the device A under forward and reverse bias, and B is a J-V curve chart of the device B under forward and reverse bias.
FIG. 3 is a schematic structural view of a device C/D in embodiment 2 of the present invention. Where a is the structural diagram of device C and b is the structural diagram of device D.
FIG. 4 is a J-V plot of a device C/D in example 2 of the present invention. Wherein a is a J-V curve chart of the device C under forward and reverse bias, and b is a J-V curve chart of the device D under forward and reverse bias.
FIG. 5 is a schematic structural view of a device E-0/E-1/E-2/E-3 in example 3 of the present invention.
FIG. 6 is a schematic structural view of a device E-0/E-1/E-2/E-3 in embodiment 4 of the present invention.
FIG. 7 is a J-V plot of the device E-0/F in example 5 of the present invention.
FIG. 8 is a schematic view showing the structure of a device F-1 in comparative example 1 of the present invention.
In fig. 6: reference numeral 10 denotes a substrate, 20 denotes a first electrode layer, 31 denotes a charge generation layer, 32 denotes an n-type semiconductor doping layer, 33 denotes a p-type semiconductor doping layer, 34 denotes a light-emitting layer, 35 denotes an electron transport layer, 36 denotes a hole transport layer, 40 denotes a second electrode layer, and 50 denotes an encapsulation layer.
Detailed Description
The invention provides a charge generation layer, which is formed by combining an n-type semiconductor doping layer and a p-type semiconductor doping layer; the invention also provides an electroluminescent device containing the charge generation layer, and the electroluminescent device comprises a substrate, a first electrode layer, an organic functional layer, a second electrode layer and an encapsulation layer.
Wherein:
the first electrode layer and the second electrode layer respectively correspond to an anode and a cathode of the device. In the inverted device, the first electrode layer is a cathode and the second electrode layer is an anode; on the contrary, the first electrode layer is an anode, and the second electrode layer is a cathode.
The organic functional layer comprises a plurality of charge generation layers, a light emitting layer, an electron transport layer and a hole transport layer;
the combination mode of each functional layer in the organic functional layer is different according to the implementation mode, and the effect is also different.
In the present invention, the substrate may be made of rigid glass or flexible polymer film.
In the invention, the first electrode layer can be a transparent metal oxide film, such as ITO, IZO, FTO, TCO and the like, the thickness is 50-300nm, the square resistance is 5-30 omega/□, the film layer is prepared by a magnetron sputtering process, and the pattern is prepared by an etching process; the first electrode layer can also be made of transparent metal films, such as Ag, Al, Mg and other materials, the thickness of the first electrode layer is 5-100nm, the sheet resistance is 5-30 omega/□, the film layer is prepared by a magnetron sputtering process, and the pattern is prepared by an etching process;
in the inverted OLED device, the first electrode layer can be a film formed by Ag/Al/Mg and other metals, has the thickness of 100-500 nm, preferably 150nm, and is prepared by an evaporation process;
in the invention, the n-type semiconductor doping layer is made of a main material and a doping material, the main material is an electron transport material with coordination capacity, such as any one of 4, 7-diphenyl-1, 10-phenanthroline (Bphen) and derivatives thereof, 9, 10-di (6-phenylpyridine-3-yl) anthracene, 8-hydroxyquinoline-lithium, 1,3, 5-tri (1-phenyl-1H-benzimidazole-2-yl) benzene; the doping material is selected from a metal simple substance with coordination capability or a mixture main body material, such as any one of Ag, Zn and Cr. In the invention, the main material of the n-type semiconductor doping layer is preferably Bphen; the doping material is preferably Ag, namely the n-type semiconductor doping layer is Ag doped with Bphen; the doping ratio is 5-30% w/w, preferably 15% w/w. And doping the doping material into the main body material by adopting a mixed evaporation method. A mixed evaporation method belongs to the prior art.
In the invention, the P-type semiconductor doping layer is made of a main material and a doping material, the main material is selected from any one of TAPC, m-MTDATA, TCTA, NPB, 4P-NPB, MCP, CBP and pentacene, and the doping material is selected from MoO 3 、WO 3 、V 2 O 5 Or copper phthalocyanine. In the invention, the main material of the p-type semiconductor doping layer is preferably NPB, the doping material is preferably MoO 3 That is, the p-type semiconductor doped layer is MoO 3 Doping NPB; the doping ratio is 5-40% w/w, preferably 20% w/w. And doping the doping material into the main body material by adopting a mixed evaporation method. A mixed evaporation method belongs to the prior art.
In the invention, the thickness of the n-type semiconductor doped layer is 1-100nm, preferably 5-30nm, and more preferably 10-15 nm.
In the invention, the thickness of the p-type semiconductor doping layer is 1-100nm, preferably 5-30nm, and more preferably 10-15 nm.
In the present invention, the charge generation layer may be formed by combining an n-type semiconductor doping layer and a p-type semiconductor doping layer, and may be any one of p-n, n-p, p-n-p, and n-p-n.
In the invention, the light-emitting layer is divided into a host material AND a guest material, wherein the host material is any one or more of Alq3, CBP, TCP AND AND; the guest material is selected from one or more of DCJTB, C545T, DPAVBi and DSA-ph.; the weight percentage of guest material is preferably 5%.
In the invention, the material of the electron transport layer is selected from one or more of materials such as B3PYMPM, TmPyPB, TpPyPB, PBN and the like.
In the invention, the hole transport layer material is selected from any one or more of TPD, TAPC, TCTA and the like.
In the invention, the second electrode layer is a film formed by Ag/Al/Mg and other metals, has the thickness of 100-500 nm, preferably 150nm, and is prepared by an evaporation process;
in the invention, the packaging layer can be packaged by a glass cover plate of UV glue and a drying agent or a film prepared from silicon nitride/silicon oxide; the packaged device has better water and oxygen resistance.
In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention will be described in detail with reference to the accompanying drawings
This invention may 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 and will fully convey the concept of the invention to those skilled in the art, and the present invention will only be defined by the appended claims. In the drawings, the size and relative sizes of layers and regions may be exaggerated for clarity. It will be understood that when an element such as a layer, region or substrate is referred to as being "formed on" or "disposed on" another element, it can be directly on the other element or intervening elements may also be present. In contrast, when an element is referred to as being "directly formed on" or "directly disposed on" another element, there are no intervening elements present.
Example 1
Example 1 provides two structures (an n-p structure and a p-n structure) of the charge generation layer of the present invention, as shown in fig. 1.
And (3) preparing the electrical devices with the two structures, and testing the electrical properties of the electrical devices under forward and reverse bias voltages.
1. The implementation mode is as follows:
the substrate material is glass;
the first electrode layer is an ITO film;
the material of the n-type semiconductor doped layer is selected from Bphen, 15 wt.% Ag (30 nm);
material selection of p-type semiconductor doped layer NPB (N, P-type boron nitride) of 20 wt.% MoO 3 (40 nm) ；
The material of the second electrode layer is Al;
the device structure of example 1 a is indium tin oxide ITO/Bphen: 15 wt.% Ag (30 nm)/NPB: 20 wt.% MoO 3 (40 nm)/ Al (150 nm)；
The B device structure of example 1 is indium tin oxide ITO/NPB: 20 wt.% MoO 3 (40 nm) /Bphen： 15 wt.%Ag (30 nm)/ Al (150 nm)。
2. The preparation method of the device comprises the following steps:
s1, at a temperature of less than 2.0X 10 -5 Plating an ITO film (150nm) on a glass substrate by magnetron sputtering under the base pressure of mbar, and then etching to obtain a patterned ITO glass substrate;
s2, pouring detergent, cleaning powder and deionized water on the ITO glass substrate, performing ultrasonic treatment in an ultrasonic machine for 3 times, each time for 90 minutes, with the power of 900W, replacing the ultrasonic treatment with new deionized water, acetone and isopropanol each time, repeating the steps, drying, and irradiating for 20 minutes at the ultraviolet wavelength of 185nm to obtain a clean ITO glass substrate;
s3, putting materials to be subjected to evaporation into each boat source or crucible source of an evaporation chamber, putting a clean ITO substrate into the evaporation chamber for evaporation, sequentially depositing an n-type semiconductor doping layer and a p-type semiconductor doping layer to obtain a device A, and sequentially depositing the p-type semiconductor doping layer and the n-type semiconductor doping layer to obtain a device B;
s4, switching the evaporation mask, and continuing to evaporate the second electrode layer material Al (150 nm);
and S5, packaging the evaporated device through the processes of dispensing, pressing, UV curing and baking to prepare the sealed inverted laminated OLED device.
3. And (3) performance testing:
1) the test method comprises the following steps:
the J-V test mainly focuses on the magnitude and variation trend of the current density of the measured sample at different voltages so as to determine the electrical properties of the sample, and the J-V test is performed by using a current Source of a Keithley 2400 Source Meter (Keithley Instruments, inc., Cleveland), and the relevant test method is to measure the corresponding current magnitude every 0.2 mV and calculate the current density.
2) Test results
The test results of example 1 are shown in fig. 2, in which the current densities of the device a and the device B are slightly different under the same voltage condition (the device a is about 6000 mA/cm) due to the difference in carrier injection barrier caused by the difference in work function between the ITO electrode and the Al electrode 2 And device B is about 4000 mA/cm 2 And 8V).
However, due to the presence of the charge generation layer, the electrical properties of the device a and the device B are good under forward and reverse bias.
Example 2
Example 2 provides two other structures (an n-p-n structure and a p-n-p structure) of the charge generation layer of the present invention, as shown in fig. 3.
And (3) preparing the electrical devices with the two structures, and testing the electrical properties of the electrical devices under forward and reverse bias voltages.
1. The implementation mode is as follows:
the substrate material is glass;
the first electrode layer is an ITO film;
the material of the n-type semiconductor doped layer is selected from Bphen, 15 wt.% Ag (30 nm);
material selection of p-type semiconductor doped layer NPB (N, P-type boron nitride) of 20 wt.% MoO 3 (40 nm) ；
The material of the second electrode layer 40 is Al;
the C device structure of example 2 was indium tin oxide ITO/Bphen: 15 wt.% Ag (20 nm)/NPB: 20 wt.% MoO 3 (40 nm)/ Bphen: 15 wt.% Ag (20 nm)/ Al (150 nm)
The D device structure of example 2 was indium tin oxide ITO/NPB 20 wt.% MoO 3 (20 nm)/ Bphen: 15 wt.% Ag (30 nm)/ NPB: 20 wt.% MoO 3 (20 nm)/ Al (150 nm);
2. The preparation method of the device comprises the following steps:
the preparation of example 2 was carried out in the same manner as in example 1 except for the step of S3.
S3, putting materials to be evaporated on each boat source or crucible source of an evaporation chamber, putting a clean ITO substrate in the evaporation chamber for evaporation, and sequentially depositing an n-type semiconductor doping layer, a p-type semiconductor doping layer and an n-type semiconductor doping layer to obtain a C device; and sequentially depositing a p-type semiconductor doping layer, an n-type semiconductor doping layer and a p-type semiconductor doping layer to obtain the D device.
3. Performance testing
1) The test method comprises the following steps:
the test method of the J-V test in example 2 is the same as that of example 1.
2) Test results
The test results of example 2 are shown in fig. 4;
the device C is under forward bias condition due toUnder the influence of the external electric field E1, a charge generation layer is formed at the y-position, as shown by a in fig. 3. Here with a p-type semiconductor doped layer (MoO) 3 NPB) electrons dissociated on the HOMO level reach the LUMO level of the n-type semiconductor doping layer (Bphen: Ag) through a tunneling effect, are continuously transmitted to the ITO electrode, and are recombined with anode holes. In addition, holes on the HOMO energy level of the p-type semiconductor doping layer are transmitted to the direction of the Al cathode and are combined with electrons transmitted through the Ag-doped Bphen electron transport layer at the x position, and therefore a complete current loop is formed.
Under reverse bias conditions, due to the influence of an external electric field E2, the device C has a charge generation layer at the x position, and the generated holes recombine with ITO cathode electrons at the y position, while the electrons are in hole recombination at the Al anode, as shown in fig. 3 a.
Similarly, the J-V relationship of the device D under forward and reverse bias is basically the same as that of the device C. Under the condition of forward bias voltage, under the influence of an external bias electric field E1, the charge generation layer is located at the x position (shown in b in FIG. 3), the generated electrons are recombined with anode holes at the y position, and the holes pass through the p-type semiconductor doping layer (MoO) 3 NPB) is transferred to the cathode for recombination. Similarly, under reverse bias, the charge generation layer is located at the y-position (shown as b in fig. 3), and the generated electrons recombine with Al anode holes at the x-position, and the holes are transported to the ITO cathode interface for recombination.
In summary, due to the existence of the charge generation layer, the electrical properties of the device C and the device D are good under forward and reverse bias.
Example 3
Embodiment 3 provides a structure of an electroluminescent device including a charge generation layer of the present invention and a method for manufacturing the same, the device is an inverted structure, and optimal parameters are searched by comparing different thicknesses of n-type semiconductor doping layers; the specific structure is shown in fig. 5.
1. The implementation mode is as follows:
the substrate material is glass;
the first electrode layer is an ITO film;
the material of the n-type semiconductor doped layer is selected from Bphen, 15 wt.% Ag (30 nm);
material selection of p-type semiconductor doped layer NPB (N, P-type boron nitride) of 20 wt.% MoO 3 (40 nm) ；
The material selection for the light-emitting layer was ADN 5 wt.% DSA-ph. (20 nm);
the material of the electron transport layer is B3PYMPM (30 nm);
the material of the hole transport layer is TCTA (10 nm);
selecting AL as the material of the second electrode layer;
the structures of devices E-0, E-1, E-2 and E-3 of example 3 are: ITO/Bphen 15 wt.% Ag (15 nm)/B3 PYMPM (30 nm)/ADN 5 wt.% DSA-ph. (20 nm)/TCTA (10 nm)/NPB 20 wt.% MoO 3 (40 nm)/ Bphen: 15 wt.% Ag (λnm) / Al (150 nm), λ= 0, 10, 20, 40。
λ = 0 in device E-0; λ = 10 in device E-1; λ = 20 in device E-2; λ =40 in device E-3.
2. The preparation method of the device comprises the following steps:
example 3 the same preparation as in example 1 except for the steps S3 and S4
S3, putting materials to be subjected to evaporation into each boat source or crucible source of an evaporation chamber, putting a clean ITO substrate into the evaporation chamber for evaporation, and sequentially depositing an n-type semiconductor doping layer, an electron transport layer, a light emitting layer, a hole transport layer, a p-type semiconductor doping layer and an n-type semiconductor doping layer to obtain the device;
s4, switching the evaporation mask, and continuing to evaporate the second electrode layer material Al (150 nm).
3. Performance testing
1) The test method comprises the following steps:
and testing the electrical performance parameters by using a Keithley 2400 Source Meter, testing the wide performance parameters by using a PR670, and calculating to obtain the related photoelectric performance parameters.
2) Test results
The test results are shown in the following table:
the test result shows that the Bphen/Ag functional layer with the thickness of 10 nm in the p-n junction has good device performance.
Example 4
Example 4 provides a structure of another electroluminescent device comprising a charge generation layer according to the present invention, which is a dual-cell inverted stack structure, and a method for preparing the same, as shown in fig. 6.
1. The implementation mode is as follows:
the substrate 10 is made of glass;
the first electrode layer 20 is an ITO thin film;
the material of the n-type semiconductor doping layer 32 is selected from Bphen, 15 wt.% Ag (10, 15 nm);
p-type semiconductor doped layer 33 material selection NPB 20 wt.% MoO 3 (40 nm) ；
The material for the light-emitting layer 34 was selected from ADN: 5 wt.% DSA-ph. (20 nm);
the electron transport layer 35 is made of B3PYMPM (30 nm);
the hole transport layer 36 is made of TCTA (10 nm);
the material of the second electrode layer 40 is Al;
the structure of device F in example 4 is: ITO/Bphen 15 wt.% Ag (15 nm)/B3 PYMPM (30 nm)/ADN 5 wt.% DSA-ph. (20 nm)/TCTA (10 nm)/NPB 20 wt.% MoO 3 (40 nm)/ Bphen: 15 wt.% Ag (10 nm) / B3PYMPM (30 nm)/ ADN: 5 wt.% DSA-ph. (20 nm)/ TCTA (10 nm)/ NPB: 20 wt.% MoO 3 (40 nm)/ Al (150 nm) 。
2. The preparation method of the device comprises the following steps:
example 4 the same preparation as in example 1 except for the steps S3 and S4
S3, putting materials to be subjected to vapor deposition on each boat source or crucible source of a vapor deposition chamber, putting a clean ITO substrate into the vapor deposition chamber for vapor deposition, and sequentially depositing an n-type semiconductor doping layer 32, an electron transport layer 35, a light emitting layer 34, a hole transport layer 36, a p-type semiconductor doping layer 33, the n-type semiconductor doping layer 32, the electron transport layer 35, the light emitting layer 34, the hole transport layer 36 and the p-type semiconductor doping layer 33 to obtain the device;
s4, switching the evaporation mask, and continuing to evaporate the second electrode layer material Al (150 nm).
3. Performance testing
1) The test method comprises the following steps:
and testing the electrical performance parameters by using a Keithley 2400 Source Meter, testing the wide performance parameters by using a PR670, and calculating to obtain the related photoelectric performance parameters and a J-V curve.
2) Test results
Through tests, relevant photoelectric parameters and J-V curves of the device F are obtained, and in order to further explain the effect of a charge generation layer (x position) in the laminated device, the photoelectric parameters and the J-V curves of the device F in the embodiment 4 are compared with those of an E-0 device (a single-layer inverted device and no charge generation layer) in the embodiment 3; the J-V curve pair is shown in FIG. 7; the photoelectric parameters are compared as shown in the following table:
as can be seen from the above table and the data shown in fig. 7, example 4 prepared an inverted stacked OLED device F exhibiting good photoelectric properties;
on the other hand, compared with the inverted single-layer device E-0, the current efficiency of the inverted laminated device F is improved by about two times; meanwhile, the driving current density of the device is 0-25 mA/cm 2 Within the range, the brightness enhancement is kept about twice; the maximum power efficiency of the S-S of the laminated device also realizes the transformation from 9.25 lm/W to 11.05 lm/W, the promotion amplitude is about 19.4 percent, which shows that NPB is MoO 3 Ag intermediate connection layer plays a good role in charge generation, separation and injection.
Comparative example 1
To further illustrate the advantages of the present invention, comparative example 1 provides an electroluminescent device similar to that of example 4 of the present invention, but not within the scope of the present invention, and the optoelectronic properties of the electroluminescent device are tested, and compared with example 4, the specific structure is shown in fig. 8.
1. The implementation mode is as follows:
the substrate material is glass;
the first electrode layer is an ITO film;
the material selection of the n-type semiconductor doped layer is Bphen, 15 wt.% Cs 2 CO 3 (30 nm) ；
Material selection of p-type semiconductor doped layer NPB (N, P-type boron nitride) of 20 wt.% MoO 3 (40 nm) ；
The material selection for the light-emitting layer was ADN 5 wt.% DSA-ph. (20 nm);
the material of the electron transport layer is B3PYMPM (30 nm);
the material of the hole transport layer is TCTA (10 nm);
the material of the second electrode layer is Al;
the structure of device F-1 in comparative example 1 is: ITO/Bphen 15 wt.% Cs 2 CO 3 (15 nm)/ B3PYMPM (30 nm)/ ADN: 5 wt.% DSA-ph. (20 nm)/ TCTA (10 nm)/ NPB: 20 wt.% MoO 3 (40 nm)/ Bphen: 15 wt.% Cs 2 CO 3 (10 nm) / B3PYMPM (30 nm)/ ADN: 5 wt.% DSA-ph. (20 nm)/ TCTA (10 nm)/ NPB: 20 wt.% MoO 3 (40 nm)/ Al (150 nm) ；
2. The preparation method of the device comprises the following steps:
comparative example 1 was prepared in the same manner as in example 1 except for the steps S3 and S4
S3, putting materials to be subjected to evaporation into each boat source or crucible source of an evaporation chamber, putting a clean ITO substrate into the evaporation chamber for evaporation, and sequentially depositing an n-type semiconductor doping layer, an electron transport layer, a light emitting layer, a hole transport layer, a p-type semiconductor doping layer, an n-type semiconductor doping layer, an electron transport layer, a light emitting layer, a hole transport layer and a p-type semiconductor doping layer to obtain the device;
s4, switching the evaporation mask, and continuing to evaporate the second electrode layer material Al (150 nm);
3. performance testing
1) The test method comprises the following steps:
and testing the electrical performance parameters by using a Keithley 2400 Source Meter, testing the wide performance parameters by using a PR670, and calculating to obtain the related photoelectric performance parameters and a J-V curve.
2) Test results
Through tests, relevant photoelectric parameters and J-V curves of the device F-1 are obtained, and in order to further explain the effect of a charge generation layer (x position) in the laminated device, the photoelectric parameters and the J-V curves of the device F-1 in comparative example 1 are compared with those of the device F in example 4; the J-V curve pair is shown in FIG. 7; the photoelectric parameters are compared as shown in the following table:
the data of comparative example 1 and example 4 show that the charge generation layer made of Ag, which is the n-type semiconductor structure, has better charge generation effect under the condition that other structures are the same.
Therefore, the above experimental results show that the NPB: MoO of the present invention 3 The Ag structure is used as a charge generation layer of the laminated OLED device, and the more efficient photoelectric performance of the OLED can be realized.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner. It should be noted that, for those skilled in the art, without departing from the principle of the present invention, several improvements and modifications can be made, and these improvements and modifications should also be construed as the protection scope of the present invention.
Claims (8)
1. A charge generation layer is characterized by being formed by combining an n-type semiconductor doping layer and a p-type semiconductor doping layer, wherein the n-type semiconductor doping layer is made of a main material and a doping material, and the p-type semiconductor doping layer is also made of a main material and a doping material;
the main material of the n-type semiconductor doping layer is 4, 7-diphenyl-1, 10-phenanthroline, the doping material is Ag, namely the n-type semiconductor doping layer is Ag-doped Bphen;
the main material of the p-type semiconductor doping layer is NPB, and the doping material is MoO 3 I.e. the p-type semiconductor dopingThe impurity layer is MoO 3 Doping NPB.
2. The charge generation layer according to claim 1, wherein the n-type semiconductor doped layer has a thickness of 1 to 100 nm; the thickness of the p-type semiconductor doping layer is 1-100 nm.
3. The charge generation layer according to claim 2, wherein the n-type semiconductor doped layer has a thickness of 5 to 30 nm; the thickness of the p-type semiconductor doping layer is 5-30 nm.
4. The charge generation layer according to claim 3, wherein the n-type semiconductor doped layer has a thickness of 10-15 nm; the thickness of the p-type semiconductor doping layer is 10-15 nm.
5. The charge generation layer according to claim 1, wherein the n-type semiconductor doping layer and the p-type semiconductor doping layer are combined in any one of p-n, n-p, p-n-p, and n-p-n in the charge generation layer.
6. An electroluminescent device comprising the charge generation layer according to any of claims 1 to 5, wherein the electroluminescent device comprises a substrate, a first electrode layer, a second electrode layer, an organic functional layer and an encapsulation layer arranged in a regular pattern, wherein the organic functional layer is provided with a light emitting layer, a charge generation layer, an electron transport layer and a hole transport layer arranged in a regular pattern.
7. The electroluminescent device according to claim 6, wherein the number of the light-emitting layers is one or more, the number of the charge generation layers is one or more, the number of the electron transport layers is one or more, and the number of the hole transport layers is one or more, in the organic functional layer.
8. The method of manufacturing an electroluminescent device according to claim 6, comprising the steps of:
s1, plating an ITO film on the glass substrate through a magnetron sputtering process, then obtaining a first electrode layer through an etching process, and obtaining a clean patterned ITO substrate through cleaning, drying and ultraviolet irradiation;
s2, sequentially depositing organic functional layers including a light-emitting layer, a charge generation layer, an electron transport layer and a hole transport layer by an evaporation process, wherein each film layer is sequentially evaporated according to a specific structure;
s3, switching the evaporation mask plate, and continuing to evaporate the second electrode layer material;
and S4, packaging the evaporated device through the processes of dispensing, pressing, UV curing and baking to prepare the sealed OLED device.
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| CN109065746A (en) * | 2018-07-17 | 2018-12-21 | 华南理工大学 | A kind of forward and reverse luminous Organic Light Emitting Diode |
| CN114420878A (en) * | 2022-01-17 | 2022-04-29 | 南京迪视泰光电科技有限公司 | Inverted OLED device with high thermal stability and preparation method thereof |
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