CN103333355A - Method for increasing stability of film electroluminescent device - Google Patents
Method for increasing stability of film electroluminescent device Download PDFInfo
- Publication number
- CN103333355A CN103333355A CN2013101261019A CN201310126101A CN103333355A CN 103333355 A CN103333355 A CN 103333355A CN 2013101261019 A CN2013101261019 A CN 2013101261019A CN 201310126101 A CN201310126101 A CN 201310126101A CN 103333355 A CN103333355 A CN 103333355A
- Authority
- CN
- China
- Prior art keywords
- film
- pedot
- acid
- luminescent device
- pss
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Abstract
The invention belongs to the field of electroluminescent devices, and relates to a new method for improving luminescence property and luminescence stability of a film electroluminescent device by using a simple low-cost acid treatment process. According to the method, an inorganic acid is adopted to treat a PEDOT:PSS film adopted as a charge transfer layer in a film electroluminescent device so as to reduce affinity on water and oxygen in air, such that improvement of luminescence property of the film electroluminescent device based on application of an inorganic fluorescent nanometer crystal as a luminescence layer, especially improvement of air stability, is achieved.
Description
Technical field
The invention belongs to the electroluminescent device field, relate to a kind of use cheaply simple and easy acid treatment process improve the novel method of luminescent properties and the stability of photoluminescence of membrane electro luminescent device.
Background technology
Inorganic quantum dot claim again semiconductor nano (quantum dot, QD).Its unique luminous spectrum is narrow, color is with size adjustable, stable advantages of higher, can remedy the various defectives on photochromic of luminous organic material in the Organic Light Emitting Diode (OLED), therefore being used in the photodiode field serves as luminescent layer, thereby has derived quantum dot light emitting diode (QD-LED).Quantum dot light emitting diode (QD-LED) is the thin-film light emitting device of future generation that development potentiality is arranged after Organic Light Emitting Diode (OLED) very much.In its evolution, parameters such as cut-in voltage, brightness, efficient, life-span are the emphasis that the researchist pays close attention to and puts forth effort to improve always.Because the organic film of introducing as charge transport layer in the device is very responsive to water, oxygen etc., thereby cause the aerial less stable of device integral body (under the non-encapsulation situation), it is very fast to cause not the luminescent properties of packaging to be decayed in air, has improved manufacturing cost so to a certain extent and has limited its application in practice.For the quantum dot light emitting diode, adopt multiple material to form multi-layer film structure at present and improve luminous efficiency, but mostly adopt conductive polymer poly 3,4-ethene dioxythiophene/polystyrolsulfon acid (PEDOT:PSS) as basic buffer layer and hole moving layer to improve device performance.But PEDOT:PSS is originally as the aqueous solution, though the subsequent annealing treating processes is arranged, it just shows that as medium itself it has higher affinity to water molecules with water, so must cause the aerial stability of corresponding device to have a strong impact on.Because the major portion that transmission is worked to electric charge in the PEDOT:PSS rete is to have 3 of high conductivity, 4-ethene dioxythiophene (PEDOT) part, and the polystyrolsulfon acid of insulativity (PSS) thus be that PEDOT is water-soluble to simplify the preparation process of film to form solution in order to impel.Therefore, the existence of PSS is the major cause that causes the easy adsorbed water molecule of PEDOT:PSS rete.Principal feature of the present invention is the shortcoming at the easy adsorbed water molecule of PEDOT:PSS rete, and this layer is taked treatment process targetedly, thereby effectively improves the stability of photoluminescence of quantum dot light emitting diode.
Summary of the invention
The object of the present invention is to provide a kind of simple efficient, low cost, environmental protection, PEDOT:PSS thin film passivation method repeatably, thus reduce the PEDOT:PSS rete to the affinity of water molecules, and then effectively improve the aerial stability of QD-LED device.
The technical solution used in the present invention is as follows:
The present invention uses certain density acid to being coated on ito glass and handling through the PEDOT:PSS of anneal film, handles about 5 ~ 10 minutes through 120 ~ 160 ℃ vacuum drying oven then.Use deionized water that film is carried out rinsing (1 ~ 3 time) after drying finishes, handled again about 5 ~ 10 minutes finally by vacuum drying oven.Obtain the PEDOT:PSS film of vitriolization, be substrate with this PEDOT:PSS film, apply again that (or vacuum evaporation) corresponding hole transmission layer (electronic barrier layer), semiconductor fluorescence are nanocrystalline, electron transfer layer (hole blocking layer) and back electrode just obtained air stability QD-LED luminescent device preferably.
Acid wherein can be mineral acids such as sulfuric acid, nitric acid, hydrochloric acid, and employed semiconductor nano is II-VI family, III-V family and I-III-VI
2Semiconductor nano or nucleocapsid structure semiconductor nanos such as family, employed hole and electron transfer layer can be organic materials, also can be inorganic materials.
The present invention has following advantage with respect to prior art:
The inventive method operation is simple, and good reproducibility, the solvent of use are easy to obtain and are with low cost; Need not that the structure of luminescent device and composition material are carried out any change and can effectively reduce the cut-in voltage of device and significantly improve the aerial stability of QD-LED luminescent device, have higher using value.
Description of drawings
Fig. 1. the structure iron of the basic device of embodiment 1 and embodiment 2 contain the device architecture figure (being called for short ZnO-LED) of the nanocrystalline electron transfer layer of inorganic oxide zinc (ZnO)
Fig. 2 .(a) all fluorescence spectrum contrasts that relate to the electroluminescent spectrum of device and be used for the semiconductor-quantum-point of luminescent layer among embodiment 1 and the embodiment 2.(b) no acid treatment and the acid-treated PEDOT:PSS film cut-in voltage contrast in basic device and ZnO-LED device.
Fig. 3. by in the test implementation example 1 repeatedly through the device of acid treatment PEDOT:PSS film with without the current density-voltage (J-V) of the device of acid treatment PEDOT:PSS film and result's contrast of brightness-voltage (B-V) curve.(a) air stability of the current density of the device of no acid treatment; (b) air stability of the current density of acid-treated device; (c) device of no acid treatment is placed 1 day brightness constancy in air; (d) acid-treated device is placed the brightness constancy in 18 days in air.
Fig. 4. the quantum dot light emitting layer among the embodiment 1 in no acid treatment and the best acid-treated device and the surface topography scanning electron microscope result of PEDOT:PSS film.(a) sem photograph of the quantum dot light emitting layer in the device of no acid treatment; (b) sem photograph of the quantum dot light emitting layer in the acid-treated device; (c) sem photograph of original PEDOT:PSS film; (d) sem photograph of acid-treated PEDOT:PSS film; (e) the acid-treated PEDOT:PSS film of no washing process; (f) original PEDOT:PSS film air is placed the sem photograph after several days.
Fig. 5. the ZnO-LED device performance comparison diagram of embodiment 2.(a) nanocrystalline during as the inorganic electronic transport layer with ZnO, the device current density of no acid treatment and acid treatment PEDOT:PSS rete and brightness results contrast; (b) the ZnO-LED device after the acid treatment is placed the luminance test contrast behind the different time in air.
Embodiment
Below with specific embodiment technical scheme of the present invention is described, but protection scope of the present invention is not limited thereto:
Acid treatment PEDOT:PSS film improves the stability of quantum dot membrane electro luminescent device: with the patterning ito glass substrate ultraviolet-ozonize machine (UV/O that cleans
3) handled 15 minutes, utilize the method for spin-coating to prepare the PEDOT:PSS film then.With the ITO substrate of the good PEDOT:PSS film of spin coating in 160 ℃ vacuum drying oven after the drying treatment, take out immediately and place on the sol evenning machine, rapidly the dropping sulphuric acid soln that can cover the PEDOT:PSS film was with the rotating speed rotation of 3000 rpm 1 minute, and in 160 ℃ baking oven dry 5 ~ 10 minutes, then use deionized water rinse three times in the same way, to remove the impurity of absorption, dry 5 ~ 10 minutes then.Mode spin coating poly-triphenylamine (Poly-TPD) with spin-coating is hole transmission layer equally, and CdSe/ZnS nuclear shell structured nano-crystalline substance is as luminescent layer, and last vacuum evaporation Al prepares the quantum dot membrane electro luminescent device as back electrode.
The structure of basic device shown in Fig. 1 (a), with spline structure but the PEDOT:PSS rete without the object of reference of acid-treated device as performance comparison.The contrast of the electroluminescent spectrum of corresponding device and the fluorescence spectrum of quantum dot and the cut-in voltage of device (1 cd/m
2) contrast as shown in Figure 2, the performance comparison of respective devices as shown in Figure 3, without the PEDOT:PSS rete after acid-treated PEDOT:PSS film and the acid treatment and accordingly quantum dot layer scanning electron microscope pattern result as shown in Figure 4.
Introduce inorganic ZnO nanometer crystal layer among the embodiment 1 in the device architecture as electron transfer layer, the corresponding device structure is shown in Fig. 1 (b).This layer is to containing acid treatment PEDOT:PSS film and containing without the performance comparison of acid treatment PEDOT:PSS membrane module as shown in Figure 5.
Claims (6)
1. one kind is utilized poly-3 in the simple sour Passivation Treatment quantum dot membrane electro luminescent device, 4-ethene dioxythiophene/polystyrolsulfon acid (PEDOT:PSS) organic polymer film improves the method for membrane electro luminescent device stability, and its characteristics are may further comprise the steps:
At first go up to drip certain density mineral acid to the PEDOT:PSS film (through 160 ℃ of vacuum drying treatment) that is coated on the ito glass, then immediately with the rotating speed spin coating of 3000 rpm 1 minute, then in 160 ℃ vacuum drying oven dry 5 ~ 10 minutes; After this still adopt the mode be coated with deionized water film to be carried out three rinses, the amount of the deionized water that each rinse drips can be paved with 2/3rds of whole film approximately and get final product, at last drying 5 ~ 10 minutes again in baking oven; After obtaining acid-treated PEDOT:PSS film, be coated with poly-triphenylamine (Poly-TPD), luminescent quantum dot (QDs) more in the above, last vacuum evaporation one deck Al just obtained having the quantum dot light emitting diode (QD-LED) of certain air stability or between quantum dot and Al electrode spin coating one deck zinc oxide (ZnO), obtaining with ZnO is the QD-LED device of electron transfer layer.
2. the method for raising membrane electro luminescent device stability according to claim 1, its characteristics are to comprise sulfuric acid, hydrochloric acid, nitric acid etc. for the treatment of the mineral acid of PEDOT:PSS film.
3. the method for raising membrane electro luminescent device stability according to claim 1, its characteristics are that the material of luminescent layer comprises II-VI family, III-V family and I-III-VI
2Semiconductor nano or nucleocapsid structure semiconductor nanos such as family.
4. the method for raising membrane electro luminescent device stability according to claim 1, its characteristics are that charge transfer material can be organic materials, comprise Poly-TPD, TFB, PVK etc. can be inorganic nano materials also, comprise ZnO, TiO
2, MoO
3Deng.
5. the method for raising membrane electro luminescent device stability according to claim 1, its characteristics are the membrane electro luminescent device that is applicable to that multiple rete preparation methods such as spin coating, printing, heat transhipment, vacuum evaporation make.
6. the method for raising membrane electro luminescent device stability according to claim 1, the thin-film light emitting device that its characteristics are to prepare are placed luminous efficiency after 18 days and still can be kept former efficient more than 75% under no encapsulation situation in air.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013101261019A CN103333355A (en) | 2013-04-11 | 2013-04-11 | Method for increasing stability of film electroluminescent device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013101261019A CN103333355A (en) | 2013-04-11 | 2013-04-11 | Method for increasing stability of film electroluminescent device |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103333355A true CN103333355A (en) | 2013-10-02 |
Family
ID=49241569
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2013101261019A Pending CN103333355A (en) | 2013-04-11 | 2013-04-11 | Method for increasing stability of film electroluminescent device |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103333355A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103824877A (en) * | 2014-02-28 | 2014-05-28 | 上海和辉光电有限公司 | QD-LED pixel display device, manufacturing method and display panel |
| CN106098967A (en) * | 2016-07-05 | 2016-11-09 | 南昌航空大学 | The electric charge of a kind of light emitting diode with quantum dots injects, transmits and complex method |
| CN106654026A (en) * | 2016-11-22 | 2017-05-10 | 纳晶科技股份有限公司 | Quantum dot light-emitting device and display device and lighting device with same |
| CN106784406A (en) * | 2016-12-28 | 2017-05-31 | 深圳市华星光电技术有限公司 | A kind of preparation method of OLED |
| CN110911570A (en) * | 2018-09-18 | 2020-03-24 | 浙江大学 | Quantum dot light-emitting device and preparation method thereof |
| CN111384271A (en) * | 2018-12-29 | 2020-07-07 | Tcl集团股份有限公司 | Quantum dot light-emitting diode and preparation method thereof |
| CN112382732A (en) * | 2020-11-25 | 2021-02-19 | 合肥福纳科技有限公司 | Method for producing an electronic conductor with low electron transport properties |
| WO2021084599A1 (en) * | 2019-10-29 | 2021-05-06 | シャープ株式会社 | Light emitting element, light emitting device and display device |
-
2013
- 2013-04-11 CN CN2013101261019A patent/CN103333355A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| 陶景: "量子点发光二极管的制备与稳定性研究", 《中国优秀硕士学位论文全文数据库 基础科学辑》 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103824877A (en) * | 2014-02-28 | 2014-05-28 | 上海和辉光电有限公司 | QD-LED pixel display device, manufacturing method and display panel |
| CN106098967A (en) * | 2016-07-05 | 2016-11-09 | 南昌航空大学 | The electric charge of a kind of light emitting diode with quantum dots injects, transmits and complex method |
| CN106654026A (en) * | 2016-11-22 | 2017-05-10 | 纳晶科技股份有限公司 | Quantum dot light-emitting device and display device and lighting device with same |
| CN106784406A (en) * | 2016-12-28 | 2017-05-31 | 深圳市华星光电技术有限公司 | A kind of preparation method of OLED |
| CN106784406B (en) * | 2016-12-28 | 2018-09-25 | 深圳市华星光电技术有限公司 | A kind of preparation method of OLED device |
| US10193106B2 (en) | 2016-12-28 | 2019-01-29 | Shenzhen China Star Optoelectronics Technology Co., Ltd. | Method for manufacturing OLED device |
| CN110911570A (en) * | 2018-09-18 | 2020-03-24 | 浙江大学 | Quantum dot light-emitting device and preparation method thereof |
| CN110911570B (en) * | 2018-09-18 | 2021-11-19 | 浙江大学 | Quantum dot light-emitting device and preparation method thereof |
| CN111384271A (en) * | 2018-12-29 | 2020-07-07 | Tcl集团股份有限公司 | Quantum dot light-emitting diode and preparation method thereof |
| WO2021084599A1 (en) * | 2019-10-29 | 2021-05-06 | シャープ株式会社 | Light emitting element, light emitting device and display device |
| CN112382732A (en) * | 2020-11-25 | 2021-02-19 | 合肥福纳科技有限公司 | Method for producing an electronic conductor with low electron transport properties |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103333355A (en) | Method for increasing stability of film electroluminescent device | |
| CN105161629B (en) | Exchange driving QLED and preparation method thereof | |
| CN107507918B (en) | A kind of perovskite light emitting diode and preparation method thereof | |
| CN109473559B (en) | Electroluminescent device, manufacturing method thereof and display device | |
| CN105206718B (en) | The inorganic perovskite light emitting diode with quantum dots of CsPbX3 prepared by a kind of solwution method | |
| Chen et al. | Effect and mechanism of encapsulation on aging characteristics of quantum-dot light-emitting diodes | |
| CN105789467B (en) | A kind of In doping MoO3The preparation method of film and its application in QLED | |
| CN106410051B (en) | A kind of application of metallic element doping zinc oxide nanometer material in the light emitting diode | |
| CN105161635B (en) | A kind of QLED devices with self assembly electron transfer layer and preparation method thereof | |
| CN107369774B (en) | A kind of compound multiple quantum wells LED of perovskite and preparation method thereof | |
| WO2018192334A1 (en) | Acrylate copolymer modified metal oxide, preparation method and quantum dot light emitting diode | |
| CN108511616B (en) | Preparation method of perovskite film layer and perovskite light-emitting diode device | |
| CN104701430B (en) | A kind of method for improving the light emitting diode with quantum dots life-span | |
| CN103972416A (en) | Semiconductor quantum dot LED based on reverse structure and preparation method thereof | |
| CN108417739B (en) | A kind of perovskite light emitting diode and preparation method thereof based on spraying process | |
| CN108336244A (en) | A kind of perovskite light emitting diode and preparation method thereof based on modifying interface | |
| CN108735905A (en) | A kind of QLED devices and preparation method | |
| CN108039416A (en) | Lamination white light emitting diode based on quanta point electroluminescent and preparation method thereof | |
| CN109256475A (en) | A kind of perovskite light emitting diode and preparation method based on ultraviolet thermal anneal process | |
| CN105826483A (en) | Quantum dot light-emitting diode and preparation method thereof | |
| WO2022134993A1 (en) | Composite carrier transport layer and preparation method therefor, solar cell, and light emitting device | |
| CN107068884B (en) | A kind of ultraviolet organic electroluminescence device of high efficiency and preparation method thereof | |
| CN105895829B (en) | A kind of Cu：NiO nano-particles, light emitting diode and preparation method thereof | |
| CN108807724A (en) | Preparation method, application and perovskite luminescent device of perovskite luminescent layer and preparation method thereof | |
| CN107046101A (en) | Enhanced blue light organic emissive diode of plasma resonance and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C05 | Deemed withdrawal (patent law before 1993) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20131002 |