CN108987590B - Organic light emitting diode and preparation method of hole transport layer thereof - Google Patents
Organic light emitting diode and preparation method of hole transport layer thereof Download PDFInfo
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- CN108987590B CN108987590B CN201711368283.5A CN201711368283A CN108987590B CN 108987590 B CN108987590 B CN 108987590B CN 201711368283 A CN201711368283 A CN 201711368283A CN 108987590 B CN108987590 B CN 108987590B
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- 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
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- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
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Abstract
The invention relates to an organic light-emitting diode and a preparation method of a hole transport layer thereof. The material of the hole transport layer comprises an organic polar material; the preparation method comprises the steps of obtaining a prefabricated part, and depositing the organic polar material on the surface of the prefabricated part in an evaporation mode to form the hole transport layer; during the evaporation, an electric field perpendicular to the surface of the preform is applied simultaneously. The preparation method can reduce the carrier mobility of the hole injection layer material to a certain extent, thereby promoting the balance of carriers in the device and improving the efficiency of the device.
Description
Technical Field
The invention relates to the technical field of light-emitting devices, in particular to an organic light-emitting diode and a preparation method of a hole transport layer of the organic light-emitting diode.
Background
Organic Light Emitting Diodes (OLEDs) have received a great deal of attention because of their broad application prospects in display, lighting, and the like. In organic light emitting diode devices, the carrier mobility of electrons or holes is a very important parameter. From space-charge-limited current theory, it can be seen that current is proportional to carrier mobility, and thus generally the larger the carrier mobility, the smaller the driving voltage.
Generally, the mobility of electron transport materials is 10-6～10-4cm2between/Vs, the hole transport material is 10-5～10- 3cm2between/Vs, only a few electron transport materials can have a mobility of up to 10-3cm2Vs. It can be seen that the carrier mobility of current hole transport materials is faster than that of electron transport materials.
And promoting carrier balance is an effective means for improving the efficiency of the organic light emitting diode. Currently, methods for improving the OLED carrier balance can be mainly divided into three directions: first, using appropriate electron and hole injection materials to balance injected carriers (material selection direction); secondly, balance (structural direction of the device) is achieved by improving the structure of the device; modifying the electron and hole transport material, such as adding or deleting some functional groups in the molecular structure, and further changing the mobility of carriers in the organic transport material to achieve balance (the design and synthesis direction of the material).
Disclosure of Invention
In view of the above, there is a need for a method for preparing a hole transport layer of an organic light emitting diode. The preparation method can reduce the carrier mobility of the hole transport layer material to a certain extent, thereby promoting the balance of carriers in the device and improving the efficiency of the device.
A preparation method of a hole transport layer of an organic light-emitting diode is disclosed, wherein the material of the hole transport layer comprises an organic polar material;
the preparation method comprises the steps of obtaining a prefabricated part, and depositing the organic polar material on the surface of the prefabricated part in an evaporation mode to form the hole transport layer;
during the evaporation, an electric field perpendicular to the surface of the preform is applied simultaneously.
In one embodiment, the electric field is a pulsed signal controlled electric field or an alternating signal controlled electric field;
the strength of an electric field controlled by the pulse signal is 10-50 kv/cm, and the pulse period T1Is 0 < T1≤100μs；
The strength of an electric field controlled by the alternating signal is 10-50 kv/cm, and the alternating period T2Is 0 < T2≤100μs。
In one embodiment, the strength of the electric field controlled by the pulse signal is 20-30 kv/cm, and the pulse period T1Is T is more than or equal to 41≤20μs；
The strength of an electric field controlled by the alternating signal is 10-30 kv/cm, and the alternating period T2Is 10 or less than T2≤50μs。
In one embodiment, the organic polar material is selected from at least one of Spiro-NPB, TAPC, TCTA.
In one embodiment, the organic polar material is selected from at least one of Spiro-NPB and TAPC.
In one embodiment, the thickness of the hole transport layer is 1 to 150 nm.
The invention also provides a hole transport layer of the organic light-emitting diode prepared by the preparation method.
The invention also provides an organic light-emitting diode which comprises a substrate, and a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer and an electron injection layer which are sequentially stacked on the substrate. And stacking the hole injection layer on a substrate to obtain an intermediate structure of the device, namely one structural form of the prefabricated member.
In one embodiment, the material of the electron transport layer is at least one selected from TPBi and Bpy-OXD, and the thickness is 30-80 nm.
In one embodiment, the material of the hole injection layer is selected from at least one of HAT-CN and m-MTDATA, and the thickness is 1-100 nm;
the material of the light-emitting layer is a host material and a guest material doping system, the host material is CDBP, and the guest material is selected from Ir (ppy)2(acac)、Ir(dmppy-pro)2tmd, the guest material accounts for 3-11 wt% of the material of the light-emitting layer, and the thickness of the light-emitting layer is 20-50 nm;
the electron injection layer is made of LiF, and the thickness of the electron injection layer is 0.8-1.2 nm.
In one embodiment, the material of the hole injection layer is HAT-CN, and the thickness is 5-15 nm;
the material of the light-emitting layer is a host material and guest material doping system, the host material is CDBP, and the guest material is Ir (ppy)2(acac), the guest material accounts for 8-10 wt% of the material of the luminescent layer, and the thickness of the luminescent layer is 25-35 nm;
the material of the electron transmission layer is Bpy-OXD, and the thickness is 35-45 nm;
the electron injection layer is made of LiF, and the thickness of the electron injection layer is 1-1.2 nm.
The invention also provides the application of the organic light-emitting diode in a display or lighting device.
Compared with the prior art, the invention has the following beneficial effects:
the method for preparing the hole transport layer of the organic light emitting diode firstly tries to research the carrier balance in the aspect of the preparation process of the organic light emitting diode. The preparation method takes an organic polar material as a material of the hole transport layer and carries out deposition of the material of the hole transport layer by combining an evaporation method. Particularly, an external electric field perpendicular to the prefabricated member is applied during evaporation, and under the action of the external electric field, organic polar materials in the hole transport material are laminated on the prefabricated member in a certain orientation and are regularly arranged.
Furthermore, compared with a direct current electric field, the electric field controlled by a pulse signal or an alternating signal can more effectively control the formation of dimer and condensed state of the organic polar material, and the purpose of effectively regulating and controlling the hole transmission capability is achieved. Therefore, the electric field is set to be an alternating electric field or a pulse electric field, the regularly arranged hole transport material parts form a regular dimer or a condensation state, the hole transport material can be more effectively matched with the electron transport capacity of the electron transport layer in the device, and the efficiency of the device is improved.
Drawings
Fig. 1 is a schematic structural diagram of an organic light emitting diode according to an embodiment of the invention.
Detailed Description
The following will explain the organic light emitting diode and the method for fabricating the hole transport layer thereof in detail with reference to the specific embodiments.
Example 1
An organic light emitting diode of this embodiment, as shown in fig. 1, includes a substrate 100 including an anode, and a hole injection layer 200, a hole transport layer 300, a light emitting layer 400, an electron transport layer 500, an electron injection layer 600, and a cathode 700 sequentially stacked on the substrate 100.
The preparation method of the organic light-emitting diode comprises the following steps:
1) cleaning a glass substrate containing an ITO (120nm) transparent anode by using deionized water and isopropanol, carrying out continuous ultrasonic treatment for 25 minutes, then blowing dry liquid by using a nitrogen gun, putting the glass substrate into an oven for drying, and carrying out treatment for 20 minutes under UV-O (ultraviolet-oxygen) to clean the surface of the ITO and improve the work function of the ITO; the substrate 100 is obtained.
2) Evaporating a hole injection layer 200 on the substrate, wherein the material of the hole injection layer 200 is HAT-CN, and the thickness is 10 nm; obtaining a prefabricated member.
3) And (2) evaporating a hole transport layer 300 on the hole injection layer of the prefabricated member, wherein the material of the hole transport layer 300 is Spiro-NPB, the thickness of the hole transport layer is 40nm, and when the hole transport layer 300 is evaporated, an electric field which is perpendicular to the surface of the hole injection layer of the prefabricated member and is controlled by an alternating signal is applied in an evaporation cavity, the electric field intensity is 16kv/cm, and the period of the alternating signal is 20 mu s.
4) A layer of luminescent layer material with the thickness of 30nm is evaporated on the hole transport layer 300 to form a luminescent layer 400; the light-emitting layer 400 is a host-guest doped system, in which the host material is CDBP and the guest material is Ir (ppy)2(acac), the guest material comprising 9 wt% of the material of the light emitting layer.
5) An electron transport layer 500 was vapor-deposited on the light emitting layer 400, and the material of the electron transport layer 500 was Bpy-OXD and had a thickness of 40 nm.
6) The electron injection layer 600 is vapor-deposited on the electron transport layer 500, and the material of the electron injection layer 600 is LiF and has a thickness of 1.2 nm.
7) A cathode 700 is vapor-deposited on the electron injection layer 600, and the material of the cathode 700 is Al with a thickness of 120 nm.
Example 2
This example is an organic light emitting diode, which has a structure similar to that of example 1 and is prepared by the following method:
1) cleaning a glass substrate containing an ITO (120nm) transparent anode by using deionized water and isopropanol, carrying out continuous ultrasonic treatment for 25 minutes, then blowing dry liquid by using a nitrogen gun, putting the glass substrate into an oven for drying, and carrying out treatment for 20 minutes under UV-O (ultraviolet-oxygen) to clean the surface of the ITO and improve the work function of the ITO; and (5) obtaining the substrate.
2) A hole injection layer is evaporated on the substrate, the material of the hole injection layer is HAT-CN, and the thickness is 10 nm; obtaining a prefabricated member.
3) And (2) evaporating a hole transport layer on the hole injection layer of the prefabricated member, wherein the material of the hole transport layer is Spiro-NPB, the thickness of the hole transport layer is 40nm, and when the hole transport layer is evaporated, an electric field which is perpendicular to the surface of the hole injection layer of the prefabricated member and is controlled by a pulse signal is applied in an evaporation cavity, the electric field intensity is 20kv/cm, and the period of the pulse signal is 10 mu s.
4) A layer of luminescent layer material with the thickness of 30nm is evaporated on the hole transport layer to form a luminescent layer; the light emitting layer is a host-guest doped system, wherein the host material is CDBP and the guest material is Ir (ppy)2(acac), the guest material accounting for 9 wt% of the material of the light emitting layer.
5) And an electron transport layer is evaporated on the light-emitting layer, wherein the material of the electron transport layer is Bpy-OXD, and the thickness of the electron transport layer is 40 nm.
6) And an electron injection layer is evaporated on the electron transport layer, and the material of the electron injection layer is LiF and the thickness of the electron injection layer is 1.2 nm.
7) And evaporating a cathode on the electron injection layer, wherein the cathode material is Al and the thickness of the cathode material is 120 nm.
Example 3
This example is an organic light emitting diode, which has a structure similar to that of example 1 and is prepared by the following method:
1) cleaning a glass substrate containing an ITO (120nm) transparent anode by using deionized water and isopropanol, carrying out continuous ultrasonic treatment for 25 minutes, then blowing dry liquid by using a nitrogen gun, putting the glass substrate into an oven for drying, and carrying out treatment for 20 minutes under UV-O (ultraviolet-oxygen) to clean the surface of the ITO and improve the work function of the ITO; and (5) obtaining the substrate.
2) A hole injection layer is evaporated on the substrate, the material of the hole injection layer is HAT-CN, and the thickness is 10 nm; obtaining a prefabricated member.
3) And (2) evaporating and plating a hole transport layer on the hole injection layer of the prefabricated member, wherein the material of the hole transport layer is TAPC, the thickness of the hole transport layer is 60nm, and when the hole transport layer is evaporated, an electric field which is perpendicular to the surface of the hole injection layer of the prefabricated member and is controlled by an alternating signal is applied in an evaporation cavity, the electric field intensity is 23kv/cm, and the period of the alternating signal is 40 mu s.
4) A layer of luminescent layer material with the thickness of 30nm is evaporated on the hole transport layer to form a luminescent layer; the light emitting layer is a host-guest doped system, wherein the host material is CDBP and the guest material is Ir (ppy)2(acac), the guest material accounting for 9 wt% of the material of the light emitting layer.
5) And an electron transport layer is evaporated on the light-emitting layer, wherein the material of the electron transport layer is Bpy-OXD, and the thickness of the electron transport layer is 40 nm.
6) And an electron injection layer is evaporated on the electron transport layer, and the material of the electron injection layer is LiF and the thickness of the electron injection layer is 1.2 nm.
7) And evaporating a cathode on the electron injection layer, wherein the cathode material is Al and the thickness of the cathode material is 120 nm.
Example 4
This example is an organic light emitting diode, which has a structure similar to that of example 1 and is prepared by the following method:
1) cleaning a glass substrate containing an ITO (120nm) transparent anode by using deionized water and isopropanol, carrying out continuous ultrasonic treatment for 25 minutes, then blowing dry liquid by using a nitrogen gun, putting the glass substrate into an oven for drying, and carrying out treatment for 20 minutes under UV-O (ultraviolet-oxygen) to clean the surface of the ITO and improve the work function of the ITO; and (5) obtaining the substrate.
2) A hole injection layer is evaporated on the substrate, the material of the hole injection layer is HAT-CN, and the thickness is 10 nm; obtaining a prefabricated member.
3) And (2) evaporating and plating a hole transport layer on the hole injection layer of the prefabricated member, wherein the material of the hole transport layer is TAPC, the thickness of the hole transport layer is 60nm, when the hole transport layer is evaporated, an electric field which is perpendicular to the surface of the hole injection layer of the prefabricated member and is controlled by a pulse signal is applied in an evaporation cavity, the electric field strength is 25kv/cm, and the period of the pulse signal is 8 mu s.
4) A layer of luminescent layer material with the thickness of 30nm is evaporated on the hole transport layer to form a luminescent layer; the light emitting layer is a host-guest doped system, wherein the host material is CDBP and the guest material is Ir (ppy)2(acac), the guest material accounting for 9 wt% of the material of the light emitting layer.
5) And an electron transport layer is evaporated on the light-emitting layer, wherein the material of the electron transport layer is Bpy-OXD, and the thickness of the electron transport layer is 40 nm.
6) And an electron injection layer is evaporated on the electron transport layer, and the material of the electron injection layer is LiF and the thickness of the electron injection layer is 1.2 nm.
7) And evaporating a cathode on the electron injection layer, wherein the cathode material is Al and the thickness of the cathode material is 120 nm.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The preparation method of the hole transport layer of the organic light-emitting diode is characterized in that the material of the hole transport layer comprises an organic polar material;
the preparation method comprises the steps of obtaining a prefabricated part, and depositing the organic polar material on the surface of the prefabricated part in an evaporation mode to form the hole transport layer;
simultaneously applying an electric field perpendicular to the surface of the prefabricated member in the evaporation process; the electric field is controlled by a pulse signal or an alternating signal; the strength of an electric field controlled by the pulse signal is 10-50 kv/cm, and the pulse period T1 is more than 0 and less than or equal to T1 and less than or equal to 100 microseconds.
2. The method for preparing a hole transport layer of an organic light emitting diode according to claim 1,
the strength of an electric field controlled by the alternating signal is 10-50 kv/cm, and the alternating period T2Is 0 < T2≤100μs。
3. The method according to claim 2, wherein the intensity of the electric field controlled by the pulse signal is 20-30 kv/cm, and the pulse period T is1Is T is more than or equal to 41≤20μs；
The strength of an electric field controlled by the alternating signal is 10-30 kv/cm, and the alternating period T2Is 10 or less than T2≤50μs。
4. The method of claim 1, wherein the organic polar material is at least one selected from the group consisting of Spiro-NPB, TAPC, and TCTA.
5. The method for preparing a hole transport layer of an organic light emitting diode according to any one of claims 1 to 4, wherein the thickness of the hole transport layer is 1 to 150 nm.
6. The hole transport layer of the organic light emitting diode produced by the production method according to any one of claims 1 to 5.
7. An organic light-emitting diode comprising a substrate, and a hole injection layer, the hole transport layer according to claim 6, a light-emitting layer, an electron transport layer, and an electron injection layer, which are sequentially stacked over the substrate.
8. The organic light-emitting diode of claim 7, wherein the electron transport layer is made of at least one material selected from TPBi and Bpy-OXD and has a thickness of 30-80 nm.
9. The OLED of claim 7 or 8, wherein the hole injection layer is made of at least one material selected from HAT-CN and m-MTDATA and has a thickness of 1-100 nm;
the material of the light-emitting layer is a host material and a guest material doping system, the host material is CDBP, and the guest material is selected from Ir (ppy)2(acac)、Ir(dmppy-pro)2tmd, the guest material accounts for 3-11 wt% of the material of the light-emitting layer, and the thickness of the light-emitting layer is 20-50 nm;
the electron injection layer is made of LiF, and the thickness of the electron injection layer is 0.8-1.2 nm.
10. Use of an organic light emitting diode according to any one of claims 7 to 9 in a display or lighting device.
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| CN102760845A (en) * | 2012-07-27 | 2012-10-31 | 深圳市华星光电技术有限公司 | Film forming method and equipment for organic light-emitting diode |
| CN103579525A (en) * | 2012-07-23 | 2014-02-12 | 海洋王照明科技股份有限公司 | Organic electroluminescence device and preparation method thereof |
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| CN103579525A (en) * | 2012-07-23 | 2014-02-12 | 海洋王照明科技股份有限公司 | Organic electroluminescence device and preparation method thereof |
| CN102760845A (en) * | 2012-07-27 | 2012-10-31 | 深圳市华星光电技术有限公司 | Film forming method and equipment for organic light-emitting diode |
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