CN110943175A - Gold nanoparticle and graphene oxide composite structure modified organic light-emitting diode and preparation method thereof - Google Patents
Gold nanoparticle and graphene oxide composite structure modified organic light-emitting diode and preparation method thereof Download PDFInfo
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
- H10K50/15—Hole transporting layers
- H10K50/155—Hole transporting layers comprising dopants
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Abstract
The invention provides an organic light-emitting diode modified by a gold nanoparticle and graphene oxide composite structure and a preparation method thereof. The organic light-emitting diode modified based on the gold nanoparticles and the novel two-dimensional material composite structure has the advantages of simple preparation method, good repeatability, low cost and wide application prospect.
Description
Technical Field
The invention relates to an organic light-emitting diode modified by a gold nanoparticle and graphene oxide composite structure and a preparation method thereof, belonging to the field of organic light-emitting diodes.
Background
As a new generation of display technology, OLEDs have advantages over liquid crystal flat panel displays: self-luminescence, wide visual angle, flexible display, short reaction time, ultra-thin design (the thickness can be less than 1mm), low working voltage (2-10V) and the like, so the status in the display field is increasingly important. With the further development of the technical level, the application range of the OLED is wider and wider, and the product is more and more favored by consumers. However, as a new technology, OLED has not been developed, and there are many places to be improved in terms of device performance, manufacturing process, lifetime, production cost, and the like. In particular, further improvements in the luminous efficiency of OLED devices are needed to achieve wider commercial applications of OLEDs.
The gold nanoparticles have primary application in OLED devices due to the surface plasmon resonance, and can improve the device performance to a certain extent. The type, shape, size, etc. of the metal nanoparticles play a very important role in the optics, electricity and efficiency of the OLED device. The surface of the metal nano particle can excite plasma resonance, and the electromagnetic field intensity of a luminescence center is greatly enhanced, so that the spontaneous radiation rate of excitons is accelerated. Meanwhile, because the light confined in the device due to total reflection can excite surface plasmon, and the energy of the surface plasmon can be radiated out in the form of light by introducing a proper nano structure. The gold nanoparticles with different shapes and sizes have different surface plasmon resonance peaks, so that the gold nanoparticles with proper shapes and sizes need to be selected according to the PL spectrum of the organic light-emitting material, and the performance of the OLED device is improved to the maximum extent. The resonance peak of the spherical gold nano-particles with the diameter of about 20nm can be well matched with Alq3The emitted green light. The metal nanoparticles are in direct contact with the light emitting layer and can produce detrimental carrier recombination. In order to avoid such contact, an insulating medium is usually coated on the surface of the metal nanoparticles, or a barrier layer is added between the metal nanoparticles and the light-emitting layer to eliminate such harmful carrier recombination.
Graphene Oxide (GO) is used as an important precursor for preparing graphene, has a two-dimensional structure similar to graphene, has a large specific surface area, excellent mechanical strength and flexibility, good electric and thermal conductivity, high migration efficiency and high adsorption capacity, and has functional groups such as hydroxyl, carboxyl, epoxy and the like on the surface and the periphery to endow the graphene oxide with good water solubility, so that the graphene oxide has potential application value in the aspects of surfactants, chemical sensors, photovoltaic cells, organic optoelectronic devices such as OLED and the like.
Disclosure of Invention
The invention aims to solve the technical problem of providing an organic light-emitting diode modified by a gold nanoparticle and graphene oxide composite structure and a preparation method thereof. The gold nanoparticles with surface plasmon resonance are introduced into a hole transport layer of a traditional OLED device for modification, so that the luminous efficiency of the organic light-emitting diode device can be improved. And the method is simple, has low requirement on equipment, high controllability, high efficiency and good repeatability.
The technical scheme adopted by the invention for solving the technical problems is as follows:
an organic light emitting diode modified by gold nanoparticles and graphene oxide comprises an ITO anode, a hole transport layer, a barrier layer, a light emitting layer, an electron transport layer, an electron injection layer and a metal cathode from bottom to top, wherein the hole transport layer is modified by a gold nanoparticle and graphene oxide composite structure.
Preferably, the diameter of the gold nanoparticles is 20-30nm, the gold nanoparticles with smaller size and lower distribution density are adopted, the trapping effect of the metal nanoparticles is effectively reduced, the coupling degree of the PL spectrum of the green light organic light emitting diode device and the plasma resonance peak of the gold nanoparticles in the particle size range is larger, and therefore the brightness and the efficiency of the organic light emitting diode are effectively improved.
Preferably, the gold nanoparticles and graphene oxide modify the hole transport layer in a separated layered structure or modify the hole transport layer in a uniform composite state.
Preferably, the hole transport layer materialAlso includes NPB, PEDOT PSS, TCTA, TAPC, P3HT-Th/MoO3And a spiro-OMeTAD, wherein the thickness of the hole transport layer is 40-50 nm. The NPB material has strong hydrophobicity, and gold nanoparticles are difficult to deposit on the surface of the NPB material in a spin coating or evaporation mode.
Preferably, the barrier layer material comprises NPB, TCTA, PEDOT PSS, TAPC, P3HT-Th/MoO3And the thickness of the barrier layer is 5-10 nm.
Preferably, the material of the luminescent layer is tris (8-hydroxyquinoline) aluminum (Alq)3) The thickness is 30-40 nm, Alq3The organic material with high electron mobility can effectively help electron transmission, improve hole/electron balance in a device, improve device performance, simultaneously has the functions of a light-emitting layer and an electron transmission layer, can simplify the process, reduce the cost, effectively improve the film forming quality of the light-emitting layer, reduce the existence of traps, and further improve the brightness and the efficiency of the organic light-emitting diode.
Preferably, the electron transport layer material comprises PC60BM、Bphen、BCP、Alq3The thickness is 30-50 nm, and the electron transport layer material can also be WS2(ii) a The electron injection layer material comprises lithium fluoride (LiF) and has the thickness of 0.5-1 nm. LiF is used as an electron injection material and can effectively assist electrons to be injected into the electron transport layer from the cathode.
Preferably, the metal cathode material comprises any one of Al, Au and Ag, the thickness of the metal cathode material is 100-120 nm, the metal cathode material has high conductivity, is beneficial to electron injection, has high light reflectivity, and can promote forward light emission of the device.
Preferably, the graphene oxide may be black scaled or MoS2And so on two-dimensional material.
The invention also provides a preparation method of the organic light emitting diode, which comprises the following steps:
(1) depositing a hole transport layer on the ITO anode;
(2) depositing a modified gold nanoparticle and graphene oxide composite material in the hole transport layer in the step (1);
(3) depositing a barrier layer on the gold nanoparticle and graphene oxide composite material in the step (2);
(4) depositing a light-emitting layer on the surface of the barrier layer in the step (3);
(5) and (4) depositing an electron transport layer, an electron injection layer and a surface metal cathode on the surface of the luminescent layer in sequence.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the invention, gold nanoparticles are arranged in the hole transport layer, and a local electric field nearby is enhanced by utilizing a plasma resonance effect, so that the spontaneous radiation rate of excitons is increased, and the brightness and the efficiency of the organic light-emitting diode are improved; the gold nanoparticles can effectively trap holes, so that the number of the holes and the electron pairs is more balanced.
2. According to the invention, while gold nanoparticles are introduced, a two-dimensional GO material is introduced, GO can be used as a supporting material combined with a noble metal nano material to form a composite structure, and the agglomeration of the metal nano structure can be avoided, so that the large surface area and the good physicochemical property are kept, and the good conductivity of graphene oxide is also beneficial to the conduction of hot electrons on the surface of the gold nanoparticles. Therefore, the effect of surface plasmon resonance of the gold nanoparticles can be better enhanced by utilizing the compounding of the graphene oxide and the gold nanoparticles, so that the electroluminescent performance of the OLED device is improved.
3. The preparation process of the invention is relatively simple, and the diode has relatively good stability and repeatability.
Description of the drawings:
fig. 1 is a schematic structural diagram of an organic light emitting diode modified by a gold nanoparticle and graphene oxide composite structure obtained in embodiment 1 of the present invention, wherein:
1, an ITO glass substrate; 2, a graphene oxide layer; 3, NPB hole transport layer; 4, a gold nanoparticle layer; 5, an NPB barrier layer; 6, Alq3A light emitting layer; 7, Alq3An electron transport layer; 8, LiF electricityA sub-injection layer; 9, a metal cathode;
FIG. 2 is a scanning electron microscope image of gold nanoparticles obtained in example 1 of the present invention;
FIG. 3 is a graph of luminance versus current density for a plasmon resonance enhanced green OLED obtained in example 1 of the present invention;
FIG. 4 is a graph of current efficiency versus current density for a plasmon resonance enhanced green OLED obtained in example 1 of the present invention;
fig. 5 is an external quantum efficiency-current density curve of the plasmon resonance enhanced green organic light emitting diode obtained in example 1 of the present invention.
Detailed Description
The invention is described in further detail below with reference to the accompanying drawings.
Example one
The invention provides a gold nanoparticle modified Organic Light Emitting Diode (OLED) based on graphene oxide as a hole injection layer and a preparation method thereof, as shown in figure 1, the organic light emitting diode sequentially comprises an ITO glass substrate 1, a graphene oxide layer 2, an NPB hole transmission layer 3, a gold nanoparticle layer 4, an NPB barrier layer 5 and Alq according to the sequence from bottom to top3Light-emitting layer 6, Alq3Electron transport layer 7, LiF electron injection layer 8, metal cathode 9. The preparation process comprises the following steps:
(1) and respectively ultrasonically cleaning the ITO glass substrate for 5min by using acetone, absolute ethyl alcohol and deionized water in sequence, then blowing and drying by using pure nitrogen gas, and finally treating for 5min by using oxygen plasma.
(2) Spin-coating GO solution with concentration of 0.25mg/ml on the cleaned glass substrate at 6000-8000r/min for 40-60S, and annealing at 70-130 deg.C for 5-10 min.
(3) Putting the glass substrate obtained in the step (2) into a thermal evaporation system, vacuumizing, and keeping the pressure below 10-7After Torr, 30nm of NPB as a hole transport layer was deposited on the substrate by thermal evaporation at a deposition rate of 0.05 nm/s.
(4) And (3) adding 1.8ml of 0.0025mol/l chloroauric acid solution into 1.8ml of trisodium citrate under the condition of boiling water, reacting for 10min to obtain a mixed solution, diluting the mixed solution to 10% of the original concentration by using water, performing ultrasonic homogenization, standing the glass substrate obtained in the step (3) in the mixed solution, and depositing gold nanoparticles on NPB for 20 min.
(5) Putting the glass substrate deposited with the gold nanoparticles in the step (4) into a thermal evaporation system again, vacuumizing the thermal evaporation system, and when the pressure is lower than 10 DEG-7After Torr, NPB was deposited as a barrier layer at a deposition rate of 0.05nm/s by thermal evaporation at 10 nm.
(6) Continuing to deposit luminescent layer Alq by thermal evaporation3(30nm) and an electron transport layer Alq3(30nm), an electron injection layer LiF (0.5nm), and a metal cathode Al (120 nm). The deposition rate of the evaporated opaque metal cathode was 0.1nm/S and the deposition rate of the evaporated organic layer was 0.05 nm/S.
And (5) depositing the diluted gold nanoparticle solution obtained in the step (4) on a silicon chip by adopting the same method as that in the step (4), wherein a scanning electron microscope image of the obtained gold nanoparticles is shown in fig. 2.
Example two
The invention also provides an Organic Light Emitting Diode (OLED) based on the gold nanoparticle graphene oxide composite structure modified hole transport layer and a preparation method thereof, wherein the method comprises the following steps:
(1) and respectively ultrasonically cleaning the ITO glass substrate for 5min by using acetone, absolute ethyl alcohol and deionized water in sequence, then blowing and drying by using pure nitrogen gas, and finally treating for 5min by using oxygen plasma.
(2) Putting the glass substrate in the step (1) into a thermal evaporation system, vacuumizing, and when the pressure is lower than 10 DEG C-7After Torr, 30nm of NPB as a hole transport layer was deposited on the substrate by thermal evaporation at a deposition rate of 0.05 nm/s.
(3) Adding 1.8ml of trisodium citrate with the concentration of 0.05g/ml into 20ml of chloroauric acid solution with the concentration of 0.0025mol/l under the condition of boiling water, reacting for 10min to obtain gold nanoparticle solution, mixing the gold nanoparticle solution and n-butylamine modified 1mg/ml GO solution according to the volume ratio of 1:1, and reacting for 12h at the temperature of 80 ℃. Diluting the obtained mixed solution to 10% and spin-coating on the glass substrate in (2), wherein the rotation speed is 8000-10000r/min, the time is 40-60S, and annealing is carried out at 70-130 ℃ for 5-10 min.
(4) Putting the glass substrate in the step (3) into a thermal evaporation system, vacuumizing, and when the pressure is lower than 10 DEG C-7After Torr, NPB was deposited on the substrate at a deposition rate of 0.05nm/s by thermal evaporation at 10nm as a hole injection layer.
(5) Continuing to deposit luminescent layer Alq by thermal evaporation3(30nm) and an electron transport layer Alq3(30nm), an electron injection layer LiF (0.5nm), and a metal cathode Al (120 nm). The deposition rate of the evaporated opaque metal cathode was 0.1nm/S and the deposition rate of the evaporated organic layer was 0.05 nm/S.
EXAMPLE III
The invention also provides an Organic Light Emitting Diode (OLED) based on the gold nanoparticle graphene oxide composite structure as a hole injection layer and a preparation method thereof, wherein the method comprises the following steps:
(1) and respectively ultrasonically cleaning the ITO glass substrate for 5min by using acetone, absolute ethyl alcohol and deionized water in sequence, then blowing and drying by using pure nitrogen gas, and finally treating for 5min by using oxygen plasma.
(2) Adding 1.8ml of trisodium citrate with the concentration of 0.05g/ml into 20ml of chloroauric acid solution with the concentration of 0.0025mol/l under the condition of boiling water, reacting for 10min to obtain gold nanoparticle solution, mixing the gold nanoparticle solution and n-butylamine modified 1mg/ml GO solution according to the volume ratio of 1:1, and reacting for 12h at the temperature of 80 ℃. Diluting the obtained mixed solution to 10%, spin-coating on the cleaned glass substrate at 8000-10000r/min for 40-60S, and annealing at 70-130 deg.C for 5-10 min.
(3) Putting the glass substrate in the step (2) into a thermal evaporation system, vacuumizing, and when the pressure is lower than 10 DEG C-7After Torr, 40nm of NPB as a hole transport layer was deposited on the substrate by thermal evaporation at a deposition rate of 0.05 nm/s.
(4) Continuing to deposit luminescent layer Alq by thermal evaporation3(30nm) and an electron transport layer Alq3(30nm), an electron injection layer LiF (0.5nm), and a metal cathode Al (120 nm). The deposition rate of the evaporated opaque metal cathode was 0.1nm/S and the deposition rate of the evaporated organic layer was 0.05 nm/S.
Comparative example 1
The comparative example is used for preparing a device which is compared with the performance of the example and does not contain graphene oxide and gold nanoparticles, and comprises the following steps:
(1) and respectively ultrasonically cleaning the ITO glass substrate for 5min by using acetone, absolute ethyl alcohol and deionized water in sequence, then blowing and drying by using pure nitrogen gas, and finally treating for 5min by using oxygen plasma.
(2) Putting the glass substrate obtained in the step (1) into a thermal evaporation system, vacuumizing, and keeping the pressure below 10-7After Torr, 30nm of NPB as a hole transport layer was deposited on the substrate by thermal evaporation at a deposition rate of 0.05 nm/s.
(3) Putting the glass substrate in the step (2) into a thermal evaporation system, vacuumizing, and when the pressure is lower than 10 DEG C-7After Torr, NPB was deposited on the substrate at a deposition rate of 0.05nm/s by thermal evaporation at 10nm as a hole injection layer.
(4) Continuing to deposit luminescent layer Alq by thermal evaporation3(30nm) and an electron transport layer Alq3(30nm), an electron injection layer LiF (0.5nm), and a metal cathode Al (120 nm). The deposition rate of the evaporated opaque metal cathode was 0.1nm/S and the deposition rate of the evaporated organic layer was 0.05 nm/S.
The performance of the devices obtained in the examples and the comparative examples is tested, and the performance of the devices obtained in the examples is greatly improved compared with that of the comparative examples. Wherein the maximum brightness, the maximum current efficiency, and the maximum External Quantum Efficiency (EQE) of the device obtained in comparative example 1 are increased by about 47.0%, 53.4%, and 51.9%, respectively, compared to those of comparative example 1. The reason is that after the gold nanoparticles and the graphene oxide compound are added, the gold nanoparticles generate plasma resonance to enhance an electromagnetic field near a luminescence center, so that the spontaneous radiation rate of excitons is accelerated, and the performance of the device is improved.
The invention is not limited to the specific technical solutions described in the above embodiments, and all technical solutions formed by equivalent substitutions are within the scope of the invention as claimed.
Claims (10)
1. An organic light emitting diode modified by gold nanoparticles and graphene oxide is characterized by comprising an ITO (indium tin oxide) anode, a hole transport layer, a barrier layer, a light emitting layer, an electron transport layer, an electron injection layer and a metal cathode from bottom to top, wherein the hole transport layer is modified by a gold nanoparticle and graphene oxide composite structure.
2. The organic light-emitting diode of claim 1, wherein the gold nanoparticles have a diameter of 20-30 nm.
3. The organic light-emitting diode of claim 1, wherein the gold nanoparticles and graphene oxide modify the hole transport layer in a separated layered structure or in a uniform recombination state.
4. The OLED of claim 2 or 3, wherein the hole transport layer material further comprises NPB, PEDOT PSS, TCTA, TAPC, P3HT-Th/MoO3And a spiro-OMeTAD, wherein the thickness of the hole transport layer is 40-50 nm.
5. The OLED of claim 1, wherein the barrier layer material comprises NPB, TCTA, PEDOT PSS, TAPC, P3HT-Th/MoO3And the thickness of the barrier layer is 5-10 nm.
6. The organic light-emitting diode of claim 1, wherein the light-emitting layer material is tris (8-hydroxyquinoline) aluminum (Alq)3) The thickness is 30 to 40 nm.
7. The organic light emitting diode of claim 1, wherein the electron transport layer material comprises PC60BM、Bphen、BCP、Alq3The thickness is 30-50 nm; the electron injection layer material comprises lithium fluoride and has the thickness of 0.5-1 nm.
8. The method of claim 1An organic light emitting diode, wherein the electron transport layer material comprises WS2。
9. The organic light-emitting diode of claim 1, wherein the graphene oxide is black-scaled or MoS2And (4) replacing.
10. The method for producing an organic light emitting diode according to any one of claims 1 to 9, comprising the steps of:
(1) depositing a hole transport layer on the ITO anode;
(2) depositing a gold nanoparticle and graphene oxide composite material on the hole transport layer in the step (1);
(3) depositing a barrier layer on the gold nanoparticle and graphene oxide composite material in the step (2);
(4) depositing a light-emitting layer on the surface of the barrier layer in the step (3);
(5) and (4) depositing an electron transport layer, an electron injection layer and a surface metal cathode on the surface of the light-emitting layer in sequence to obtain the organic light-emitting diode modified by the gold nanoparticle and graphene oxide composite structure.
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