CN113540388A - Flexible transparent ultraviolet organic light-emitting diode and preparation method thereof - Google Patents
Flexible transparent ultraviolet organic light-emitting diode and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000002347 injection Methods 0.000 claims abstract description 40
- 239000007924 injection Substances 0.000 claims abstract description 40
- 239000000758 substrate Substances 0.000 claims abstract description 40
- 239000002131 composite material Substances 0.000 claims abstract description 39
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052709 silver Inorganic materials 0.000 claims abstract description 32
- 239000004332 silver Substances 0.000 claims abstract description 32
- 229910000449 hafnium oxide Inorganic materials 0.000 claims abstract description 31
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 claims abstract description 31
- 230000005525 hole transport Effects 0.000 claims abstract description 20
- 239000010408 film Substances 0.000 claims description 45
- 229910052782 aluminium Inorganic materials 0.000 claims description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 15
- AWXGSYPUMWKTBR-UHFFFAOYSA-N 4-carbazol-9-yl-n,n-bis(4-carbazol-9-ylphenyl)aniline Chemical compound C12=CC=CC=C2C2=CC=CC=C2N1C1=CC=C(N(C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=C1 AWXGSYPUMWKTBR-UHFFFAOYSA-N 0.000 claims description 12
- 101000837344 Homo sapiens T-cell leukemia translocation-altered gene protein Proteins 0.000 claims description 12
- 102100028692 T-cell leukemia translocation-altered gene protein Human genes 0.000 claims description 12
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 12
- 239000010409 thin film Substances 0.000 claims description 10
- 239000010453 quartz Substances 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 7
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 6
- ASQSPTVWFNZGIA-UHFFFAOYSA-N [O-2].[Hf+4].[Ag+] Chemical compound [O-2].[Hf+4].[Ag+] ASQSPTVWFNZGIA-UHFFFAOYSA-N 0.000 claims description 5
- 238000000034 method Methods 0.000 claims 1
- 239000010410 layer Substances 0.000 abstract description 146
- 238000002834 transmittance Methods 0.000 abstract description 14
- 238000004659 sterilization and disinfection Methods 0.000 abstract description 10
- 230000001954 sterilising effect Effects 0.000 abstract description 9
- 238000005452 bending Methods 0.000 abstract description 7
- 239000002346 layers by function Substances 0.000 abstract description 2
- 239000011368 organic material Substances 0.000 abstract description 2
- 238000001704 evaporation Methods 0.000 description 25
- 230000008020 evaporation Effects 0.000 description 14
- 238000002207 thermal evaporation Methods 0.000 description 13
- 238000010894 electron beam technology Methods 0.000 description 11
- 238000001771 vacuum deposition Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000243 solution Substances 0.000 description 5
- ICXAPFWGVRTEKV-UHFFFAOYSA-N 2-[4-(1,3-benzoxazol-2-yl)phenyl]-1,3-benzoxazole Chemical compound C1=CC=C2OC(C3=CC=C(C=C3)C=3OC4=CC=CC=C4N=3)=NC2=C1 ICXAPFWGVRTEKV-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000000411 transmission spectrum Methods 0.000 description 1
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- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/805—Electrodes
- H10K50/81—Anodes
- H10K50/816—Multilayers, e.g. transparent multilayers
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/805—Electrodes
- H10K50/81—Anodes
- H10K50/813—Anodes characterised by their shape
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/805—Electrodes
- H10K50/82—Cathodes
- H10K50/822—Cathodes characterised by their shape
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/805—Electrodes
- H10K50/82—Cathodes
- H10K50/828—Transparent cathodes, e.g. comprising thin metal layers
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
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Abstract
The invention relates to a flexible transparent ultraviolet organic light emitting diode and a preparation method thereof, wherein the preparation method comprises the following steps: preparing a bottom ultraviolet transparent conductive layer on a planar substrate; sequentially preparing an anode interface layer, a hole injection layer, a hole transport layer, a luminescent layer, an electron injection layer and a cathode interface layer on the bottom ultraviolet transparent conductive layer; and preparing a top ultraviolet transparent conductive layer on the cathode interface layer. The flexible transparent ultraviolet organic light emitting diode utilizes HfO with high transmittance in an ultraviolet region2/Ag/HfO2The transparent conductive film is used as a transparent conductive layer, and an organic material is used as a light-emitting functional layer, so that the ultraviolet transparent light-emitting device is realized. The hafnium oxide and silver composite transparent conductive film is utilized to effectively improve the luminous intensity, luminous efficiency and bending stability of the organic ultraviolet light-emitting diodeMeanwhile, the effective working area of the ultraviolet light-emitting diode is effectively increased by using the double ultraviolet transparent electrodes, the sterilization efficiency is greatly increased, and the ultraviolet sterilization device has potential application prospects in the field of ultraviolet sterilization.
Description
Technical Field
The invention relates to the technical field of light emitting diodes, in particular to a flexible transparent ultraviolet organic light emitting diode and a preparation method thereof.
Background
The ultraviolet organic light emitting diode has the advantages of large-area preparation on a flexible substrate, low cost and the like, is a novel green environment-friendly ultraviolet light source, can be applied to a plurality of fields such as excitation light sources, high-density optical storage, biochemical sensors, disinfection, sterilization and the like, and is one of new key application directions in the field of organic electroluminescence. Most of the traditional organic electroluminescent devices adopt Indium Tin Oxide (ITO) as a transparent conductive substrate, mainly because the ITO has higher visible light transmittance and lower resistivity. However, the transmittance of the ITO in the ultraviolet region is reduced sharply, and especially the ITO is almost opaque in the range of 200-300nm of the ultraviolet sterilization waveband, so that the emission operating wavelength of the ultraviolet organic light emitting diode is severely limited. In addition, the ITO transparent electrode film is brittle and cannot resist bending, and the performance of the flexible light-emitting diode is severely limited. Therefore, the development of the flexible transparent conductive film which has high transmittance in an ultraviolet region and can be matched with the active layer energy level has important significance for the development of the flexible ultraviolet organic light-emitting diode, so that the luminous intensity, the luminous efficiency and the bending stability of the organic ultraviolet light-emitting diode can be effectively improved, and the sterilization effect of the ultraviolet organic light-emitting diode is further improved. In addition, if the ultraviolet light emitting diode is prepared into a transparent device capable of emitting light in two directions, the effective working area of the ultraviolet light emitting diode can be effectively increased, and the sterilization efficiency is greatly improved.
Disclosure of Invention
The invention provides a flexible transparent ultraviolet organic light-emitting diode and a preparation method thereof, and aims to solve the technical problems that the ultraviolet region of an ITO electrode used by the traditional ultraviolet organic light-emitting diode in the prior art has low transmittance and is not resistant to bending, and the performance of a flexible ultraviolet light-emitting device is seriously restricted, and the technical problems that the conventional single-side emitting ultraviolet light-emitting device has a single emitting direction and a limited working area are solved.
The invention provides a preparation method of a flexible transparent ultraviolet organic light-emitting diode, which comprises the following steps:
i, preparing a bottom ultraviolet transparent conducting layer on a planar substrate;
step ii, preparing an anode interface layer, a hole injection layer, a hole transport layer, a luminescent layer, an electron injection layer and a cathode interface layer on the bottom ultraviolet transparent conducting layer in sequence;
step iii, preparing a top ultraviolet transparent conducting layer on the cathode interface layer;
the bottom ultraviolet transparent conductive layer is made of a hafnium oxide and silver composite transparent conductive film;
the top ultraviolet transparent conductive layer is made of a composite transparent conductive film of aluminum, hafnium oxide and silver.
In the above technical solution, the hafnium oxide and silver composite transparent conductive thin film structure is HfO2/Ag /HfO2。
In the technical scheme, the thickness of the hafnium oxide and silver composite transparent conductive film is 30-80 nanometers.
In the above technical scheme, the aluminum, hafnium oxide and silver composite transparent conductive thin film structure is Al/HfO2/Ag/HfO2。
In the technical scheme, the thickness of the aluminum, hafnium oxide and silver composite transparent conductive film is 30-80 nanometers.
In the above-mentioned technical solution,
the planar substrate is quartz or CaF2A PET or PEN substrate with a thickness of 1 mm;
the anode interface layer is made of MoO3The thickness is 1-10 nanometers;
the hole injection layer is made of TCTA and has the thickness of 10-50 nanometers;
the hole transport layer is made of CBP with the thickness of 10-50 nanometers;
the light-emitting layer is made of PBD (Poly-p-phenylene benzobisoxazole) and has the thickness of 20-80 nanometers;
the electron injection layer is made of TPBi and has the thickness of 10-50 nanometers;
the cathode interface layer material is LiF, and the thickness is 0.5-2 nanometers.
The invention also provides a flexible transparent ultraviolet organic light-emitting diode, which sequentially comprises the following components from bottom to top:
the solar cell comprises a planar substrate, a bottom ultraviolet transparent conducting layer, an anode interface layer, a hole injection layer, a hole transport layer, a light emitting layer, an electron injection layer, a cathode interface layer and a top ultraviolet transparent conducting layer; wherein:
the bottom ultraviolet transparent conductive layer is made of a hafnium oxide and silver composite transparent conductive film;
the top ultraviolet transparent conductive layer is made of a composite transparent conductive film of aluminum, hafnium oxide and silver.
In the above technical solution, the hafnium oxide and silver composite transparent conductive thin film structure is HfO2/Ag /HfO2。
In the above technical scheme, the aluminum, hafnium oxide and silver composite transparent conductive thin film structure is Al/HfO2/Ag/HfO2。
In the above-mentioned technical solution,
the thickness of the hafnium oxide and silver composite transparent conductive film is 30-80 nanometers;
the thickness of the aluminum, hafnium oxide and silver composite transparent conductive film is 30-80 nanometers;
the planar substrate is quartz or CaF2A PET or PEN substrate with a thickness of 1 mm;
the anode interface layer is made of MoO3The thickness is 1-10 nanometers;
the hole injection layer is made of TCTA and has the thickness of 10-50 nanometers;
the hole transport layer is made of CBP with the thickness of 10-50 nanometers;
the light-emitting layer is made of PBD (Poly-p-phenylene benzobisoxazole) and has the thickness of 20-80 nanometers;
the electron injection layer is made of TPBi and has the thickness of 10-50 nanometers;
the cathode interface layer material is LiF, and the thickness is 0.5-2 nanometers.
The invention has the beneficial effects that:
the flexible transparent ultraviolet organic light emitting diode utilizes HfO with high transmittance in an ultraviolet region2/Ag/HfO2The transparent conductive film is used as a transparent conductive layer, and an organic material is used as a light-emitting functional layer, so that the ultraviolet transparent light-emitting device is realized. The invention not only solves the problems that the ultraviolet region of the ITO electrode used by the traditional ultraviolet organic light-emitting diode has low transmittance and is not resistant to bending and seriously restricts the performance of the flexible ultraviolet light-emitting device, but also solves the problems that the single-side emitting ultraviolet light-emitting device has single emitting direction and limited working area. The hafnium dioxide and silver composite transparent conductive film is utilized to effectively improve the luminous intensity, luminous efficiency and bending stability of the organic ultraviolet light-emitting diode, and meanwhile, the double ultraviolet transparent electrodes are utilized to effectively increase the effective working area of the ultraviolet light-emitting diode, so that the sterilization efficiency is greatly increased, and the organic ultraviolet light-emitting diode has potential application prospects in the field of ultraviolet sterilization.
Drawings
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
Fig. 1 is a schematic structural diagram of a flexible transparent ultraviolet organic light emitting diode of the present invention.
FIG. 2 is a graph showing transmission spectra of ITO and hafnium oxide, silver composite transparent conductive films used in comparative example I and example 1, respectively. Curve 1 represents the ITO transparent electrode, and curve 2 represents the hafnium oxide, silver composite transparent conductive film.
The reference numerals in the figures denote:
1-a planar substrate, 2-a bottom ultraviolet transparent conducting layer, 3-an anode interface layer, 4-a hole injection layer, 5-a hole transport layer, 6-a luminescent layer material, 7-an electron injection layer, 8-a cathode interface layer and 9-a top ultraviolet transparent conducting layer.
Detailed Description
The invention provides a flexible transparent ultraviolet organic light-emitting diode, the structure of which is shown in figure 1: from bottom to top include in proper order:
the solar cell comprises a planar substrate 1, a bottom ultraviolet transparent conducting layer 2, an anode interface layer 3, a hole injection layer 4, a hole transport layer 5, a luminescent layer 6, an electron injection layer 7, a cathode interface layer 8 and a top ultraviolet transparent conducting layer 9; wherein:
the bottom ultraviolet transparent conductive layer 2 is made of a hafnium oxide and silver composite transparent conductive film;
the top ultraviolet transparent conductive layer 9 is made of a composite transparent conductive film of aluminum, hafnium oxide and silver.
Preferably, in the above organic light emitting diode, the hafnium oxide-silver composite transparent conductive thin film structure is HfO2/Ag/HfO2The thickness is 30-80 nanometers.
Preferably, in the organic light emitting diode, the aluminum, hafnium oxide and silver composite transparent conductive thin film structure is Al/HfO2/Ag/HfO2The thickness is 30-80 nanometers.
In the organic light emitting diode, the planar substrate 1 is preferably quartz or CaF2A PET or PEN substrate with a thickness of 1 mm; the anode interface layer 3 is made of MoO3The thickness is 1-10 nanometers; the hole injection layer 4 is made of TCTA and has the thickness of 10-50 nanometers; the hole transport layer 5 is made of CBP and has the thickness of 10-50 nanometers; the material of the light-emitting layer 6 is PBD, and the thickness is 20-80 nanometers; the electron injection layer 7 is made of TPBi and has the thickness of 10-50 nanometers; the cathode interface layer 8 is made of LiF, and the thickness is 0.5-2 nanometers.
The invention also provides a preparation method of the flexible transparent ultraviolet organic light-emitting diode, which comprises the following steps:
i, preparing a bottom ultraviolet transparent conducting layer 2 on a planar substrate 1;
step ii, preparing an anode interface layer 3, a hole injection layer 4, a hole transport layer 5, a luminescent layer 6, an electron injection layer 7 and a cathode interface layer 8 on the bottom ultraviolet transparent conductive layer 2 in sequence;
step iii, preparing a top ultraviolet transparent conducting layer 9 on the cathode interface layer 8;
the bottom ultraviolet transparent conductive layer 2 is made of a hafnium oxide and silver composite transparent conductive film;
the top ultraviolet transparent conductive layer 9 is made of a composite transparent conductive film of aluminum, hafnium oxide and silver.
Specifically, the preparation method of the flexible transparent ultraviolet organic light-emitting diode specifically comprises the following steps:
1) putting the cleaned planar substrate 1 with the thickness of 1 mm and the strip-shaped mask plate into an electron beam vacuum coating device, vacuumizing until the vacuum degree is 2 multiplied by 10-3～8×10-4And when the film is Pascal, evaporating the bottom ultraviolet transparent conducting layer 2 with the thickness of 30-80 nanometers.
2) Taking out the film after the evaporation is finished, transferring the film to a vacuum thermal evaporation device, vacuumizing the vacuum thermal evaporation device when the vacuum degree is 6 multiplied by 10-4～8×10-5And when the cathode is Pascal, sequentially evaporating a 1-10 nanometer anode interface layer 3, a 10-50 nanometer hole injection layer 4, a 10-50 nanometer hole transport layer 5, a 20-80 nanometer light emitting layer 6, a 10-50 nanometer electron injection layer 7 and a 0.5-2 nanometer cathode interface layer 8.
3) Taking out the substrate after the evaporation, putting the substrate into electron beam vacuum coating equipment, vacuumizing until the vacuum degree is 2 multiplied by 10-3～8×10-4And when the film is Pascal, evaporating the top ultraviolet transparent conducting layer 9 with the total thickness of 30-80 nanometers.
Preferably, in the above preparation method, the structure of the hafnium oxide-silver composite transparent conductive thin film is Hf O2/Ag/HfO2The thickness is 30-80 nanometers.
Preferably, in the preparation method, the aluminum, hafnium oxide and silver composite transparent conductive film has an Al/HfO structure2/Ag/HfO2The thickness is 30-80 nanometers.
In the above preparation method, the planar substrate 1 is preferably quartz or CaF2A PET or PEN substrate with a thickness of 1 mm; the anode interface layer 3 is made of MoO3The thickness is 1-10 nanometers; the hole injection layer 4 is made of TCTA and has the thickness of 10-50 nanometers; what is needed isThe hole transport layer 5 is made of CBP and has the thickness of 10-50 nanometers; the material of the light-emitting layer 6 is PBD, and the thickness is 20-80 nanometers; the electron injection layer 7 is made of TPBi and has the thickness of 10-50 nanometers; the cathode interface layer 8 is made of LiF, and the thickness is 0.5-2 nanometers.
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Comparative example i:
putting a cleaned quartz substrate with the thickness of 1 mm and an ITO transparent electrode with the thickness of 150 nanometers and a strip-shaped mask plate into a vacuum thermal evaporation device, vacuumizing, and when the vacuum degree is 4 multiplied by 10-4Pascal, sequentially evaporating to deposit 1 nanometer MoO325 nanometer TCTA, 25 nanometer CBP, 30 nanometer PBD, 25 nanometer TPBi, 1 nanometer LiF and 80 nanometer Al.
Example 1:
1) putting the cleaned quartz substrate 1 with the thickness of 1 mm and the strip-shaped mask plate into an electron beam vacuum coating device, vacuumizing until the vacuum degree is 2 multiplied by 10-3At pascal, the bottom uv transparent conductive layer 2 is evaporated to a thickness of 51 nm.
The structure of the bottom ultraviolet transparent conducting layer 2 is 21 nanometer HfO212 nm Ag and 18 nm HfO2。
2) Taking out the film after the evaporation is finished, transferring the film to a vacuum thermal evaporation device, vacuumizing the vacuum thermal evaporation device, and when the vacuum degree is 4 multiplied by 10-4Pascal, sequentially evaporating to deposit 1 nanometer MoO3 Anode interface layer 3, 25 nm TCTA hole injection layer 4, 25 nm CBP hole transport layer 5, 30 nm PBD light emitting layer 6, 25 nm TPBi electron injection layer 7, 1 nm LiF cathode interface layer 8 and 80 nm Al top uv transparent conducting layer 9.
Example 2:
1) putting the cleaned quartz substrate 1 with the thickness of 1 mm and the strip-shaped mask plate into an electron beam vacuum coating device, vacuumizing until the vacuum degree is 2 multiplied by 10-3Pascal, evaporation thickness of 5A bottom ultraviolet transparent conductive layer 2 of 1 nanometer.
The structure of the bottom ultraviolet transparent conducting layer 2 is 21 nanometer HfO212 nm Ag and 18 nm HfO2。
2) Taking out the film after the evaporation is finished, transferring the film to a vacuum thermal evaporation device, vacuumizing the vacuum thermal evaporation device, and when the vacuum degree is 4 multiplied by 10-4Pascal, sequentially evaporating to deposit 1 nanometer MoO3An anode interface layer 3, a 25 nm TCTA hole injection layer 4, a 25 nm CBP hole transport layer 5, a 30 nm PBD light-emitting layer 6, a 25 nm TPBi electron injection layer 7 and a 1 nm LiF cathode interface layer 8.
3) Taking out the substrate after the evaporation, putting the substrate into electron beam vacuum coating equipment, vacuumizing until the vacuum degree is 2 multiplied by 10-3At pascal, the top uv transparent conductive layer 9 with an evaporation rate of 1 nm/second and an evaporation thickness of 51 nm is set.
The structure of the top ultraviolet transparent conductive layer 9 is 2 nanometer Al and 19 nanometer HfO212 nm Ag and 18 nm HfO2。
Example 3:
1) clean CaF with thickness of 1 mm2Putting the substrate 1 and the strip-shaped mask plate into an electron beam vacuum coating device, vacuumizing until the vacuum degree is 1 multiplied by 10-3At pascal, the bottom uv transparent conductive layer 2 with a thickness of 30 nm is evaporated.
The structure of the bottom ultraviolet transparent conducting layer 2 is 10 nanometer HfO212 nm Ag and 8 nm HfO2。
2) Taking out the film after the evaporation is finished, transferring the film to a vacuum thermal evaporation device, vacuumizing the vacuum thermal evaporation device when the vacuum degree is 6 multiplied by 10-4Pascal, sequentially evaporating 3 nanometer MoO3An anode interface layer 3, a 10 nm TCTA hole injection layer 4, a 50 nm CBP hole transport layer 5, an 80 nm PBD light-emitting layer 6, a 10 nm TPBi electron injection layer 7 and a 0.5 nm LiF cathode interface layer 8.
3) Taking out the substrate after the evaporation, putting the substrate into electron beam vacuum coating equipment, vacuumizing until the vacuum degree is 1 multiplied by 10-3At pascal, the top uv transparent conductive layer 9 is evaporated to a thickness of 30 nanometers.
The structure of the top ultraviolet transparent conductive layer 9 is 2 nanometer Al and 8 nanometer HfO212 nm Ag and 8 nm HfO2。
Example 4:
1) putting the cleaned PET substrate 1 with the thickness of 1 mm and a strip-shaped mask plate into an electron beam vacuum coating device, vacuumizing until the vacuum degree is 8 multiplied by 10-4And when the pressure is pascal, evaporating the bottom ultraviolet transparent conductive layer 2 with the thickness of 80 nanometers.
The structure of the bottom ultraviolet transparent conducting layer 2 is 35 nanometer HfO212 nm Ag and 33 nm HfO2。
2) Taking out the film after the evaporation is finished, transferring the film to a vacuum thermal evaporation device, vacuumizing the vacuum thermal evaporation device when the vacuum degree is 8 multiplied by 10-5Pascal, sequentially evaporating to deposit 10 nanometer MoO3An anode interface layer 3, a 50 nm TCTA hole injection layer 4, a 10 nm CBP hole transport layer 5, a 20 nm PBD light-emitting layer 6, a 50 nm TPBi electron injection layer 7 and a 2 nm LiF cathode interface layer 8.
3) Taking out the substrate after the evaporation, putting the substrate into electron beam vacuum coating equipment, vacuumizing until the vacuum degree is 8 multiplied by 10-4At pascal, the top uv transparent conductive layer 9 is evaporated to a thickness of 80 nanometers.
The structure of the top ultraviolet transparent conductive layer 9 is 2 nanometer Al and 33 nanometer HfO212 nm Ag and 33 nm HfO2。
Example 5:
1) putting the cleaned PEN substrate with the thickness of 1 mm and the strip-shaped mask plate into an electron beam vacuum coating device, vacuumizing until the vacuum degree is 8 multiplied by 10-4And when the pressure is pascal, evaporating the bottom ultraviolet transparent conductive layer 2 with the thickness of 80 nanometers.
The structure of the bottom ultraviolet transparent conducting layer 2 is 35 nanometer HfO212 nm Ag and 33 nm HfO2。
2) Taking out the film after the evaporation is finished, transferring the film to a vacuum thermal evaporation device, vacuumizing the vacuum thermal evaporation device when the vacuum degree is 8 multiplied by 10-5Pascal, sequentially evaporating to deposit 10 nanometer MoO3An anode interface layer 3, a 50 nm TCTA hole injection layer 4, a 10 nm CBP hole transport layer 5, a 20 nm PBD light-emitting layer 6,A 50 nm TPBi electron injection layer 7 and a 2 nm LiF cathode interface layer 8.
3) Taking out the substrate after the evaporation, putting the substrate into electron beam vacuum coating equipment, vacuumizing until the vacuum degree is 8 multiplied by 10-4At pascal, the top uv transparent conductive layer 9 is evaporated to a thickness of 80 nanometers.
The structure of the top ultraviolet transparent conductive layer 9 is 2 nanometer Al and 33 nanometer HfO212 nm Ag and 33 nm HfO2。
As can be understood from the various examples and comparative examples above:
fig. 2 is a graph showing transmittance spectra of the transparent electrodes used in comparative example i and example 1. From the figure, it can be seen that the transmittance of the ITO (curve 1) and the hafnium oxide and silver composite ultraviolet transparent conductive film (curve 2) is obviously different in the ultraviolet wavelength range (200-400 nm). The ITO (curve 1) is almost opaque below 300nm, the transmittance gradually increases at 300-400 nm, the average transmittance is 54%, while the transmittance of the hafnium oxide-silver composite ultraviolet transparent conductive film (curve 2) gradually increases at 200-300nm, and the average transmittance at 300-400 nm is more up to 83%, which is far higher than that of the ITO in the same wavelength range. Therefore, compared with the traditional ITO, the hafnium oxide and silver composite ultraviolet transparent conductive film has higher transmittance in an ultraviolet region, is more beneficial to ultraviolet light emission of an ultraviolet light-emitting diode, and simultaneously has the same surface resistance (12 ohm/square) as that of the traditional ITO transparent electrode when being tested.
Table 1 comparison of performance parameters of light emitting devices
Table 1 shows a comparison of the luminescence properties of examples 1, 2, 3, 4, 5 and comparative example I. Comparative example i, among other things, as a reference opaque device using ITO as a transparent electrode, achieved a maximum power density of 2.13 milliwatts per square centimeter and a maximum external quantum efficiency of 1.25%. In example 1, the ultraviolet transparent bottom electrode is used to replace ITO, so that the maximum power density of 4.56 mw/cm and the maximum external quantum efficiency of 3.68% are achieved, and the maximum external quantum efficiency is increased by more than 1 time compared with that of comparative example i, thereby indicating that the ultraviolet transparent electrode has obvious advantages in improving the performance of the ultraviolet light emitting device. Examples 2, 3, 4, 5, prepared with both a uv transparent top electrode and a uv transparent bottom electrode, had device performance comparable to or superior to that of comparative example i, while the device had higher light transmission in the visible region, 57%, 52%, 43%, 45%, respectively. In addition, examples 4 and 5 based on flexible substrates also exhibit better bending performance.
It is obvious that the above examples are only examples for clearly illustrating the present patent, and are not to be construed as limiting the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (10)
1. A preparation method of a flexible transparent ultraviolet organic light emitting diode is characterized by comprising the following steps:
i, preparing a bottom ultraviolet transparent conductive layer (2) on a planar substrate (1);
step ii, preparing an anode interface layer (3), a hole injection layer (4), a hole transport layer (5), a luminescent layer (6), an electron injection layer (7) and a cathode interface layer (8) on the bottom ultraviolet transparent conductive layer (2) in sequence;
step iii, preparing a top ultraviolet transparent conducting layer (9) on the cathode interface layer (8);
the bottom ultraviolet transparent conductive layer (2) is made of a hafnium oxide and silver composite transparent conductive film;
the top ultraviolet transparent conductive layer (9) is made of a composite transparent conductive film of aluminum, hafnium oxide and silver.
2. The preparation method of claim 1, wherein the hafnium oxide-silver composite transparent conductive thin film structure is HfO2/Ag/HfO2。
3. The preparation method of claim 2, wherein the thickness of the hafnium oxide-silver composite transparent conductive film is 30-80 nm.
4. The preparation method of claim 1, wherein the aluminum, hafnium oxide, silver composite transparent conductive thin film structure is Al/HfO2/Ag/HfO2。
5. The preparation method of claim 4, wherein the thickness of the aluminum, hafnium oxide and silver composite transparent conductive film is 30-80 nm.
6. The method according to any one of claims 1 to 5, wherein the planar substrate (1) is quartz, CaF2A PET or PEN substrate with a thickness of 1 mm;
the anode interface layer (3) is made of MoO3The thickness is 1-10 nanometers;
the hole injection layer (4) is made of TCTA and has the thickness of 10-50 nanometers;
the hole transport layer (5) is made of CBP and has the thickness of 10-50 nanometers;
the material of the light emitting layer (6) is PBD, and the thickness is 20-80 nanometers;
the electron injection layer (7) is made of TPBi and has the thickness of 10-50 nanometers;
the cathode interface layer (8) is made of LiF, and the thickness of the cathode interface layer is 0.5-2 nanometers.
7. The flexible transparent ultraviolet organic light-emitting diode is characterized by comprising the following components in sequence from bottom to top:
the solar cell comprises a planar substrate (1), a bottom ultraviolet transparent conducting layer (2), an anode interface layer (3), a hole injection layer (4), a hole transport layer (5), a luminescent layer (6), an electron injection layer (7), a cathode interface layer (8) and a top ultraviolet transparent conducting layer (9); wherein:
the bottom ultraviolet transparent conductive layer (2) is made of a hafnium oxide and silver composite transparent conductive film;
the top ultraviolet transparent conductive layer (9) is made of a composite transparent conductive film of aluminum, hafnium oxide and silver.
8. The flexible transparent UV OLED as claimed in claim 7, wherein the transparent conductive film structure of hafnia-Ag composite is HfO2/Ag/HfO2。
9. The flexible transparent UV OLED as claimed in claim 7, wherein the Al/Hf/Ag composite transparent conductive thin film structure is Al/HfO2/Ag/HfO2。
10. The flexible transparent UV OLED according to any one of claims 7-9,
the thickness of the hafnium oxide and silver composite transparent conductive film is 30-80 nanometers;
the thickness of the aluminum, hafnium oxide and silver composite transparent conductive film is 30-80 nanometers;
the planar substrate (1) is quartz or CaF2A PET or PEN substrate with a thickness of 1 mm;
the anode interface layer (3) is made of MoO3The thickness is 1-10 nanometers;
the hole injection layer (4) is made of TCTA and has the thickness of 10-50 nanometers;
the hole transport layer (5) is made of CBP and has the thickness of 10-50 nanometers;
the material of the light emitting layer (6) is PBD, and the thickness is 20-80 nanometers;
the electron injection layer (7) is made of TPBi and has the thickness of 10-50 nanometers;
the cathode interface layer (8) is made of LiF, and the thickness of the cathode interface layer is 0.5-2 nanometers.
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