CN106374054A - ZrO2 thin film and post-processing method thereof, QLED and preparation method of QLED - Google Patents

ZrO2 thin film and post-processing method thereof, QLED and preparation method of QLED Download PDF

Info

Publication number
CN106374054A
CN106374054A CN201610863077.0A CN201610863077A CN106374054A CN 106374054 A CN106374054 A CN 106374054A CN 201610863077 A CN201610863077 A CN 201610863077A CN 106374054 A CN106374054 A CN 106374054A
Authority
CN
China
Prior art keywords
thin film
zro
light emitting
solution
emitting diode
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.)
Granted
Application number
CN201610863077.0A
Other languages
Chinese (zh)
Other versions
CN106374054B (en
Inventor
王宇
曹蔚然
杨行
杨一行
钱磊
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
TCL Corp
Original Assignee
TCL Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by TCL Corp filed Critical TCL Corp
Priority to CN201610863077.0A priority Critical patent/CN106374054B/en
Publication of CN106374054A publication Critical patent/CN106374054A/en
Application granted granted Critical
Publication of CN106374054B publication Critical patent/CN106374054B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • 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]
    • H10K50/14—Carrier transporting layers
    • H10K50/16—Electron transporting layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass

Landscapes

  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

The invention discloses a ZrO2 thin film and a post-processing method thereof, a QLED and a preparation method of the QLED. The post-processing method comprises the steps of firstly depositing the ZrO2 thin film on a substrate and then soaking the ZrO2 thin film into 0.1-0.5mol/L of TiCl4 solution or SnCl2 solution or a mixed solution of the TiCl4 solution and the SnCl2 solution for 5-30 minutes; cleaning the ZrO2 thin film by using a solvent; and carrying out annealing treatment after the surface of the ZrO2 thin film is dried and finishing post-processing of the ZrO2 thin film. Through modification on the surface of the ZrO2 thin film, electrons are easier to transmit, so that the transmission capability of the electrons is improved. The ZrO2 thin film can be dispersed into an alcoholic solution, so that the ZrO2 thin film and an oil-soluble QD layer can form an orthogonal solvent. The ZrO2 thin film can be used for positive and negative OLEDs.

Description

zro2Thin film and its post-processing approach, qled and preparation method thereof
Technical field
The present invention relates to LED technology field, more particularly, to a kind of zro2Thin film and its post-processing approach, qled And preparation method thereof.
Background technology
At present in qled and oled device, zno, tio2And zro2As inorganic electron injecting layer, and it is widely used；And And the performance of device is improved.In the oxide of these N-shapeds, its preparation method is also varied, wherein main May be summarized to be two big class, mainly prepared by the method for collosol and gel and the method for nano-particle.Current thin In membrane module, the impact to device of the pattern of every layer film and the mobility of carrier is all very big.Then just there are a lot of researchs Report the performance to improve device by using the surface of monolayer or acid treatment or polymer treatment oxide.
Yang yang in 2016 teaches seminar just by carrying out a post processing to the surface of titanium dioxide, then makes The efficiency obtaining perovskite solaode is improved.Wherein post processing mainly improves the quality of titanium deoxid film, And then improve the efficiency of device.
But also rarely found to the report of zirconic surface post processing at present, the carrier mobility of simultaneous oxidation zirconium is relatively Low, energy level is unsuitable for the qd in addition to inp.
Therefore, prior art has yet to be improved and developed.
Content of the invention
A kind of in view of above-mentioned the deficiencies in the prior art, it is an object of the invention to provide zro2Thin film and its post processing side Method, qled and preparation method thereof are it is intended to solve prior art to zro2The report of the surface post processing of thin film is also rarely found, simultaneously Zirconic carrier mobility is relatively low, and energy level is unsuitable for the problem of the qd in addition to inp.
Technical scheme is as follows:
A kind of zro2The method of thin film post processing, wherein, including step:
One layer of zro is deposited first on substrate2Thin film, then by zro2Thin film immerses the ticl containing 0.1-0.5mol/l4Solution Or sncl2Solution or in the mixed liquor of the two, soak time is 5-30min, then using solvent clean zro2Thin film, Treat zro2After film surface is dried, is made annealing treatment, completed zro2Thin film post processing.
Described zro2The method of thin film post processing, wherein, ticl4Solution or sncl2Solution is all using ethanol as molten Agent.
Described zro2The method of thin film post processing, wherein, the condition of annealing: temperature is 100 DEG C -300 DEG C, the time For 15-30min.
A kind of zro2Thin film, wherein, using as above arbitrary described zro2The method of thin film post processing is prepared from, and is ti And/or the zro of sn doping2Thin film.
A kind of preparation method of light emitting diode with quantum dots, wherein, including step:
A, hearth electrode and zro are sequentially prepared on substrate2Thin film, then by zro2Thin film immerses containing 0.1-0.5mol/l's ticl4Or sncl2Or for, in the mixed liquor of the two, soak time is 5-30min, then using solvent clean zro2Thin film, Treat zro2After film surface is dried, made annealing treatment；
B, the zro after processing through step a2Quantum dot light emitting layer is prepared on thin film, then prepares empty on quantum dot light emitting layer Cave transport layer；
C, top electrode is prepared on hole transmission layer, be then packaged, obtain qled.
A kind of light emitting diode with quantum dots, wherein, described light emitting diode with quantum dots includes substrate, bottom from bottom to top successively Electrode, zro2Thin film, quantum dot light emitting layer, hole transmission layer and top electrode；Described zro2Thin film is zro as above2Thin Film.
Described light emitting diode with quantum dots, wherein, the material of described quantum dot light emitting layer is red light quantum point, green glow amount At least one in sub- point, blue light quantum point and gold-tinted quantum dot and infrared light quantum dot and ultraviolet light quantum dot.
Described light emitting diode with quantum dots, wherein, the material of described hole transmission layer is tfb, pvk, poly-tpd, Any one or more in tcta, cbp.
Described light emitting diode with quantum dots, wherein, the material of described top electrode is ag, in al, cu, au, alloy electrode One kind.
Described light emitting diode with quantum dots, wherein, described substrate is rigidity substrate or flexible substrate.
Beneficial effect: the present invention is by zro2Thin film carries out post processing so that zro2Thin film is finer and close, is conducive to carrying The transmission of stream.It is easier to allow zro simultaneously after processing2Middle incorporation ti element or sn element or by zro2Middle generation is at a low price Zirconium, and then improve zro2Electron transport ability.
Brief description
Fig. 1 is a kind of flow chart of the preparation method preferred embodiment of light emitting diode with quantum dots of the present invention.
Fig. 2 is a kind of structural representation of present invention light emitting diode with quantum dots preferred embodiment.
Specific embodiment
The present invention provides a kind of zro2Thin film and its post-processing approach, qled and preparation method thereof, for making the mesh of the present invention , technical scheme and effect clearer, clear and definite, the present invention is described in more detail below.It should be appreciated that it is described herein Specific embodiment only in order to explain the present invention, be not intended to limit the present invention.
A kind of zro of the present invention2The method preferred embodiment of thin film post processing, it includes step:
One layer of zro is deposited first on substrate2Thin film, then by zro2Thin film immerses the ticl containing 0.1-0.5mol/l4Solution Or sncl2Solution or in the mixed liquor of the two, soak time is 5-30min, then using solvent clean zro2Thin film, Treat zro2After film surface is dried, is made annealing treatment, completed zro2Thin film post processing.
Above-mentioned steps are specifically, deposit one layer of zro first on the substrate containing hearth electrode2Thin film, then by zro2Thin film The ticl containing 0.1-0.5mol/l for the immersion4Solution or sncl2In the hermetic container of solution, or by zro2Thin film immersion contains There is the ticl of 0.1-0.5mol/l4And sncl2The hermetic container of mixed liquor in, above-mentioned ticl4Solution or sncl2Solution is equal It is using ethanol as solvent.The time soaked is 5-30min(such as 20min), then using water or ethanol purge zro2Thin film, treats zro2After film surface is dried, anneal under 100 DEG C -300 DEG C (as 150 DEG C) 15-30min(such as 20min), complete zro2Thin Film post processing.
The present invention is by zro2Thin film carries out post processing so that zro2Thin film is finer and close, is conducive to the biography of carrier Defeated.Simultaneously it is easier to allow zro after post processing2Middle incorporation ti element or sn element or zro2The middle zirconium producing low price, enters And improve zro2Electron transport ability.zro2The reason zirconium of middle generation lower valency, is: the decomposition of titanium tetrachloride easily produces ti3+And sn2+There is very strong reproducibility, so easily making zro2Produce the zirconium of low price and then produce in more donors The heart, and then promote the transmission of electronics.
zro2The specific embodiment of thin film post processing is as follows:
Embodiment 1
Deposition there is zro2The substrate of thin film, immerses the ticl containing 0.2mol/l4Solution (ticl4Solution is using ethanol as molten Agent) sealing container in, then container is carried out with one 60 DEG C heating, soak time is 20min, soak after terminating using water and Ethanol is by zro2Film surface cleans up, then using 150 DEG C of annealing 20min.
Embodiment 2
Deposition there is zro2The substrate of thin film, immerses the ticl containing 0.5mol/l4Solution (ticl4Solution is using ethanol as molten Agent) sealing container in, then container is carried out with one 60 DEG C heating, soak time is 5min, soak after terminating using water and Ethanol is by zro2Film surface cleans up, then using 300 DEG C of annealing 15min.
Embodiment 3
Deposition there is zro2The substrate of thin film, immerses the sncl containing 0.1mol/l2Solution (sncl2Solution is using ethanol as molten Agent) sealing container in, soak time is 5min, soaks zro after terminating using water and ethanol2Film surface cleans up, Then using 300 DEG C of nitrogen atmospheres annealing 30min.
Embodiment 4
Deposition there is zro2The substrate of thin film, immerses the sncl containing 0.1mol/l2Solution (sncl2Solution is using ethanol as molten Agent) sealing container in, soak time is 5min, soaks zro after terminating using water and ethanol2Film surface cleans up, Then using 150 DEG C of nitrogen atmospheres annealing 15min.
Embodiment 5
Deposition there is zro2The substrate of thin film, immerses the sncl containing 0.4mol/l2Solution (sncl2Solution is using ethanol as molten Agent) sealing container in, soak time is 30min, soaks zro after terminating using water and ethanol2Film surface cleans up, Then using 150 DEG C of in the airs annealing 20min.
Embodiment 6
Deposition there is zro2The substrate of thin film, immerses the sncl containing 0.4mol/l2Solution (sncl2Solution is using ethanol as molten Agent) sealing container in, soak time is 30min, soaks zro after terminating using water and ethanol2Film surface cleans up, Then using 150 DEG C of in the airs annealing 30min.
Embodiment 7
Deposition there is zro2The substrate of thin film, immerses the ticl containing 0.2mol/l4Solution and the sncl of 0.02mol/l2Solution (ticl4Solution and sncl2Solution is all using ethanol as solvent) the sealing container of mixed solvent in, soak time is 30min, soaks zro after terminating using water and ethanol2Film surface cleans up, and is then annealed using 150 DEG C of in the airs 30min.
Embodiment 8
Deposition there is zro2The substrate of thin film, immerses the ticl containing 0.2mol/l4Solution and the sncl of 0.02mol/l2Solution (ticl4Solution and sncl2Solution is all using ethanol as solvent) the sealing container of mixed solvent in, soak time is 30min, soaks zro after terminating using water and ethanol2Film surface cleans up, then using 300 DEG C of ANs 30min.
The present invention provides a kind of zro2Thin film, wherein, using as above arbitrary described zro2The method preparation of thin film post processing Form, be the zro of ti and/or sn doping2Thin film.
Fig. 1 is a kind of flow chart of the preparation method preferred embodiment of light emitting diode with quantum dots of the present invention, as schemed institute Show, it includes step:
S100, hearth electrode and zro are sequentially prepared on substrate2Thin film, then by zro2Thin film immersion contains 0.1-0.5mol/l Ticl4Solution or sncl2Solution or in the mixed liquor of the two, soak time is 5-30min, then clear using solvent Wash zro2Thin film, treats zro2After film surface is dried, made annealing treatment；
In step s100, substrate prepares hearth electrode, this hearth electrode is as negative electrode.Then using spin coating method in hearth electrode Upper spin coating zro2Solution, between 1000rpm-6000rpm, then 50 ~ 70 DEG C (as 60 DEG C) anneal its rotating speed, obtain zro2Thin Film.Then by zro2Thin film immerses the ticl containing 0.1-0.5mol/l4Solution or sncl2Solution or be the mixing of the two In liquid, soak time is 5-30min, then using solvent clean zro2Thin film, treats zro2After film surface is dried, 100 Anneal at DEG C -300 DEG C 15-30min.The zro being obtained using the above-mentioned post-processing approach of the present invention2Thin film is finer and close, is conducive to The transmission of carrier, so that qled obtains higher efficiency.
Prepare quantum dot light emitting layer on s200, the zirconia film after processing through step s100, then send out in quantum dot Hole transmission layer is prepared on photosphere；
The material of quantum dot light emitting layer of the present invention can be common red light quantum point, green light quantum point, blue light quantum point With at least one in gold-tinted quantum dot and infrared light quantum dot and ultraviolet light quantum dot.Described hole transmission layer can be One or more of tfb, pvk, poly-tpd, tcta, cbp, can also be peodt:pss, moo3、woo3、nio、cuo、 v2o5, one or more of cus etc..
S300, top electrode is prepared on hole transmission layer, be then packaged, obtain qled.
The top electrode of one layer of 100nm, in step s300, is prepared by way of evaporation on hole transmission layer, to be deposited complete Cheng Hou, is packaged to it, obtains the qled of reciprocal form structure.The present invention can also use letter using conventional machine encapsulation Single manual encapsulation.Wherein, as anode, its material can be in ag, al, cu, au, alloy electrode to described top electrode Kind.
The present invention also provides a kind of light emitting diode with quantum dots, wherein, described light emitting diode with quantum dots from bottom to top according to Secondary inclusion substrate, hearth electrode, zro2Thin film, quantum dot light emitting layer, hole transmission layer and top electrode；Described zro2Thin film is as above Described zro2Thin film, by said method, the light emitting diode with quantum dots luminous efficiency of the present invention made is high and electricity is transmitted Excellent performance.
A kind of qled of the reciprocal form structure of the present invention, as shown in Fig. 2 including successively from bottom to top: substrate 1, hearth electrode 2, zro2Thin film 3, quantum dot light emitting layer 4, hole transmission layer 5 and top electrode 6.
In sum, a kind of zro that the present invention provides2Thin film and its post-processing approach, qled and preparation method thereof.This Bright by zro2Thin film carries out post processing so that zro2Thin film is finer and close, is conducive to the transmission of carrier.Post processing simultaneously Later it is easier to allow zro2Middle incorporation ti element or sn element or zro2The middle zirconium producing low price, and then improve zro2's Electron transport ability.The zro of the present invention2Thin film is applied in the qled of transoid, improves the luminous effect of light emitting diode with quantum dots Rate and electricity transmission performance.
It should be appreciated that the application of the present invention is not limited to above-mentioned citing, for those of ordinary skills, can To be improved according to the above description or to convert, all these modifications and variations all should belong to the guarantor of claims of the present invention Shield scope.

Claims (10)

1. a kind of zro2The method of thin film post processing is it is characterised in that include step:
One layer of zro is deposited first on substrate2Thin film, then by zro2Thin film immerses the ticl containing 0.1-0.5mol/l4Solution Or sncl2Solution or in the mixed liquor of the two, soak time is 5-30min, then using solvent clean zro2Thin film, Treat zro2After film surface is dried, is made annealing treatment, completed zro2Thin film post processing.
2. zro according to claim 12The method of thin film post processing is it is characterised in that ticl4Solution or sncl2Molten Liquid is all using ethanol as solvent.
3. zro according to claim 12The method of thin film post processing is it is characterised in that the condition of annealing: temperature is 100 DEG C -300 DEG C, the time is 15-30min.
4. a kind of zro2Thin film is it is characterised in that adopt described zro as arbitrary in claim 1 ~ 32The method of thin film post processing Process forms, and is the zro of ti and/or sn doping2Thin film.
5. a kind of preparation method of light emitting diode with quantum dots is it is characterised in that include step:
A, hearth electrode and zro are sequentially prepared on substrate2Thin film, then by zro2Thin film immerses containing 0.1-0.5mol/l's ticl4Solution or sncl2Solution or in the mixed liquor of the two, soak time is 5-30min, then using solvent clean zro2Thin film, treats zro2After film surface is dried, made annealing treatment；
B, the zro after processing through step a2Quantum dot light emitting layer is prepared on thin film, then hole is prepared on quantum dot light emitting layer Transport layer；
C, top electrode is prepared on hole transmission layer, be then packaged, obtain qled.
6. a kind of light emitting diode with quantum dots is it is characterised in that described light emitting diode with quantum dots includes serving as a contrast from bottom to top successively Bottom, hearth electrode, zro2Thin film, quantum dot light emitting layer, hole transmission layer and top electrode；Described zro2Thin film is described in claim 4 Zro2Thin film.
7. light emitting diode with quantum dots according to claim 6 is it is characterised in that the material of described quantum dot light emitting layer is In red light quantum point, green light quantum point, blue light quantum point and gold-tinted quantum dot and infrared light quantum dot and ultraviolet light quantum dot At least one.
8. light emitting diode with quantum dots according to claim 6 is it is characterised in that the material of described hole transmission layer is Any one or more in tfb, pvk, poly-tpd, tcta, cbp.
9. according to the light emitting diode with quantum dots described in claim 6 it is characterised in that the material of described top electrode be ag, al, One of cu, au, alloy electrode.
10. light emitting diode with quantum dots according to claim 6 is it is characterised in that described substrate is rigidity substrate or soft Property substrate.
CN201610863077.0A 2016-09-29 2016-09-29 ZrO2Film and its post-processing approach, QLED and preparation method thereof Active CN106374054B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610863077.0A CN106374054B (en) 2016-09-29 2016-09-29 ZrO2Film and its post-processing approach, QLED and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610863077.0A CN106374054B (en) 2016-09-29 2016-09-29 ZrO2Film and its post-processing approach, QLED and preparation method thereof

Publications (2)

Publication Number Publication Date
CN106374054A true CN106374054A (en) 2017-02-01
CN106374054B CN106374054B (en) 2019-06-04

Family

ID=57897257

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610863077.0A Active CN106374054B (en) 2016-09-29 2016-09-29 ZrO2Film and its post-processing approach, QLED and preparation method thereof

Country Status (1)

Country Link
CN (1) CN106374054B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023125074A1 (en) * 2021-12-27 2023-07-06 Tcl科技集团股份有限公司 Thin film and preparation method therefor, and photoelectric device

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103035410A (en) * 2011-10-08 2013-04-10 索尼公司 Dye-sensitized photoelectric conversion device and manufacturing method thereof and metal oxide slurry
US20150014627A1 (en) * 2006-11-07 2015-01-15 Cbrite Inc. Two-terminal electronic devices and their methods of fabrication
CN105655490A (en) * 2016-04-15 2016-06-08 厦门大学 Preparation method of perovskite solar cell

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150014627A1 (en) * 2006-11-07 2015-01-15 Cbrite Inc. Two-terminal electronic devices and their methods of fabrication
CN103035410A (en) * 2011-10-08 2013-04-10 索尼公司 Dye-sensitized photoelectric conversion device and manufacturing method thereof and metal oxide slurry
CN105655490A (en) * 2016-04-15 2016-06-08 厦门大学 Preparation method of perovskite solar cell

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
《APPLIED SURFACE SCIENCE》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023125074A1 (en) * 2021-12-27 2023-07-06 Tcl科技集团股份有限公司 Thin film and preparation method therefor, and photoelectric device

Also Published As

Publication number Publication date
CN106374054B (en) 2019-06-04

Similar Documents

Publication Publication Date Title
CN105374953B (en) A kind of light emitting diode with quantum dots and preparation method, illuminating module and display device
CN105336862B (en) A kind of integral stacked binode perovskite solar cell and preparation method thereof
CN104124291B (en) A kind of perovskite solar cell and preparation method thereof
CN106098949B (en) A kind of preparation method of perovskite thin film solar cell
WO2018192334A1 (en) Acrylate copolymer modified metal oxide, preparation method and quantum dot light emitting diode
CN103794729B (en) The preparation method of large area polymer solar battery and its active layer
CN105789467B (en) A kind of In doping MoO3The preparation method of film and its application in QLED
CN104916782A (en) Inverted solar cell structure adopting surface plasmon effect and manufacturing method thereof
CN104953030B (en) A kind of Ca-Ti ore type solar cell of modifying interface and preparation method thereof
CN105895829B (en) A kind of Cu：NiO nano-particles, light emitting diode and preparation method thereof
CN108735905A (en) A kind of QLED devices and preparation method
CN106887482A (en) A kind of mechanical lamination solar cell and preparation method thereof
CN109545972A (en) A kind of high stability perovskite solar battery and preparation method
CN109888104A (en) A kind of perovskite solar battery and preparation method thereof based on the anti-reflection structure sheaf of staggeredly flannelette
CN111987220A (en) Perovskite solar cell based on down-conversion layer and preparation method
CN110350087A (en) Perovskite/silicon heterogenous solar battery preparation method and lamination solar cell
CN114914363A (en) Efficient and stable perovskite solar cell and preparation method thereof
CN111435706B (en) Composite hole transport layer, solar cell with composite hole transport layer and preparation method of composite hole transport layer
CN108899433A (en) Hole transmission layer, preparation method and semiconductor photoelectric device
CN106374054A (en) ZrO2 thin film and post-processing method thereof, QLED and preparation method of QLED
CN114914362A (en) Preparation method of efficient and stable titanium ore solar cell
CN106299063B (en) A kind of zirconia film of doping, QLED and preparation method
CN106159108A (en) A kind of QLED and preparation method thereof
CN106252516A (en) A kind of planar inverted translucent hybrid perovskite solar cell device and preparation method
CN109427978A (en) A kind of QLED device and preparation method thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant