CN106531895A - Quantum dot light emitting diode and preparation method therefor, light emitting module and display apparatus - Google Patents
Quantum dot light emitting diode and preparation method therefor, light emitting module and display apparatus Download PDFInfo
- Publication number
- CN106531895A CN106531895A CN201611140900.1A CN201611140900A CN106531895A CN 106531895 A CN106531895 A CN 106531895A CN 201611140900 A CN201611140900 A CN 201611140900A CN 106531895 A CN106531895 A CN 106531895A
- Authority
- CN
- China
- Prior art keywords
- light emitting
- layer
- doping
- emitting diode
- copper
- 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
Links
Classifications
-
- 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]
- H10K50/17—Carrier injection layers
-
- 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
- H10K50/115—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising active inorganic nanostructures, e.g. luminescent quantum dots
Landscapes
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Electroluminescent Light Sources (AREA)
- Luminescent Compositions (AREA)
Abstract
The invention discloses a quantum dot light emitting diode and a preparation method therefor, a light emitting module and a display apparatus. The quantum dot light emitting diode comprises a positive electrode, a hole injection layer, a hole transport layer, a quantum dot light emitting layer, an electron transport layer and a negative electrode in sequence, wherein the hole injection layer is a doped copper sulfide thin film. The doped copper sulfide thin film is adopted to prepare the hole injection layer because that the adopted doped copper sulfide is low in material cost, and non-toxic and stable; and in addition, the doped copper sulfide is adopted to replace a conventional PEDOT: PSS to be used as the hole injection layer, so that an ITO surface work function, a CuS energy band structure and carrier transmission performance can be well adjusted, and the hole injection efficiency and light transmission can be effectively improved, thereby improving the light emitting efficiency and stability and prolonging the service life of a QLED device.
Description
Technical field
The present invention relates to light emitting diode with quantum dots technical field, more particularly to a kind of light emitting diode with quantum dots and its system
Preparation Method and illuminating module, display device.
Background technology
Quantum dot（Quantum dots, QDs）Be a kind of particle size be 1 ~ 10 nm nanocrystalline material, its have send out
Penetrate that spectrum is narrow, luminous efficiency is high, stability of photoluminescence good, luminescent spectrum is with the special benefits such as size adjustable, potential replacement tradition
Organic or inorganic illuminator become the core of luminescent device of future generation.Light emitting diode based on quantum dot（Quantum
dot light-emitting diodes, QLED）With traditional LED and Organic Light Emitting Diode（Organic light-
emitting diode, OLED）Compare and obvious advantage is shown on color saturation, stability and preparation cost, be expected to into
For the contenders shown with lighting engineering of future generation.
In the QLED devices studied at present, great majority are using poly-（3,4- ethylenedioxy thiophenes）- polystyrolsulfon acid
（PEDOT:PSS）Used as hole injection layer, its Main Function is to make hole smoothly be injected into quantum dot light emitting layer from ito anode.
But PEDOT:PSS has very strong water imbibition and extremely strong acidity（pH≈2~3）, easily corrode ITO, have a strong impact on QLED devices
The stability of part.Additionally, PEDOT:The work function of PSS（About 5.2 eV）It is more shallow than the valence band of quantum dot, and can not ensure simultaneously
PEDOT:Ohmic contact is formed between PSS layer and different quantum dots, the injection to electronics has certain impact, eventually results in
Device light emitting efficiency is reduced.For this reason, it is necessary to find more hole injection layer of the suitable material as QLED devices.
At present, existing many reports use inorganic p-type metal oxide as the hole injection/transport layer material of QLED devices
Material, such as NiOx、MoOx、WOx、VOx, NiLiMgO etc..Even so, prepared by these metal oxide hole injection/transport layers
Journey is complex, brings certain impact to the surface roughness and light transmittance of ITO, and typically there is relatively low hole to note
Enter/efficiency of transmission, it is difficult to meet the demand of industrialized production.
Therefore, prior art has yet to be improved and developed.
The content of the invention
In view of above-mentioned the deficiencies in the prior art, it is an object of the invention to provide a kind of light emitting diode with quantum dots and its system
Preparation Method and illuminating module, display device, it is intended to solve the hole injection efficiency and translucency of existing hole injection layer material compared with
Low problem.
Technical scheme is as follows：
A kind of light emitting diode with quantum dots, wherein, the light emitting diode with quantum dots includes anode, hole injection layer, sky successively
Cave transport layer, quantum dot light emitting layer, electron transfer layer and negative electrode；
Wherein, the hole injection layer is doping copper sulfide film.
Described light emitting diode with quantum dots, wherein, doping copper sulfide is Cu doping copper sulfides, Co doping copper sulfides, Zn
Doping copper sulfide, Mg doping copper sulfide, Ni doping copper sulfide, Mn doping copper sulfide, Ho doping copper sulfide, In doping copper sulfide,
One or more in Sb doping copper sulfides.
Described light emitting diode with quantum dots, wherein, the thickness of the doping copper sulfide film is 1 ~ 50 nm.
Described light emitting diode with quantum dots, wherein, adulterate copper sulfide film be shaped as spheric granules, sheet, it is bar-shaped,
One or more in nano wire, network structure.
Described light emitting diode with quantum dots, wherein, the structure of the doping copper sulfide film is compact texture or porous
Structure.
A kind of preparation method of as above arbitrary described light emitting diode with quantum dots, wherein, including：
Step A, hole injection layer is prepared on anode；Wherein, the hole injection layer is doping copper sulfide film；
Step B and then hole transmission layer is prepared on hole injection layer；
Step C, quantum dot light emitting layer is then prepared on hole transmission layer；
Step D, finally electron transfer layer is prepared on quantum dot light emitting layer, and evaporation cathode is on electron transfer layer, forming amount
Sub- point luminescent diode.
The preparation method of described light emitting diode with quantum dots, wherein, the doping copper sulfide film is using doping sulfuration
Copper solution is prepared from, and the preparation method of the doping sulfuration copper solution includes：Sodium sulfide solution is added to into copper chloride, lemon
In sour sodium, the mixed solution of doped metal salt, after stirring, mixed solution is heated to into 60 ~ 100 °C, reaction 10 ~ 120
Min, obtains doping sulfuration copper solution.
The preparation method of described light emitting diode with quantum dots, wherein, the concentration of the vulcanized sodium is 0.1 ~ 1 M, described
The concentration of copper chloride is 0.5 ~ 10 mM, and the concentration of the sodium citrate is 0.01 ~ 0.5 mM, the concentration of the doped metal salt
For 0 ~ 5 mM.
A kind of illuminating module, wherein, the illuminating module includes the light emitting diode with quantum dots described in as above any one.
A kind of display device, wherein, the display device includes illuminating module as above.
Beneficial effect：The present invention adopts doping copper sulfide film as hole injection layer, to adjust ITO surface works well
Function, the band structure of CuS and carrier transmission performance, effectively improve hole injection efficiency and translucency, so as to improve
The luminous efficiency of QLED devices, stability and service life.
Description of the drawings
Fig. 1 is a kind of structural representation of light emitting diode with quantum dots preferred embodiment of the present invention.
Fig. 2 is a kind of flow chart of the preparation method preferred embodiment of light emitting diode with quantum dots of the present invention.
Specific embodiment
The present invention provides a kind of light emitting diode with quantum dots and preparation method thereof and illuminating module, display device, to make this
The purpose of invention, technical scheme and effect are clearer, clear and definite, and the present invention is described in more detail below.It should be appreciated that this
The described specific embodiment in place is not intended to limit the present invention only to explain the present invention.
Fig. 1 is referred to, Fig. 1 is a kind of structural representation of light emitting diode with quantum dots preferred embodiment of the present invention, such as
Shown in figure, the light emitting diode with quantum dots includes anode 1, hole injection layer 2, hole transmission layer 3, quantum dot light emitting layer successively
4th, electron transfer layer 5 and negative electrode 6；Wherein, the hole injection layer 2 is doping copper sulfide film.
The present invention to adulterate copper sulfide film preparing hole injection layer, this is because doping copper sulfide used not only material
Material is cheap, and non-toxic stable.In addition, replacing traditional PEDOT by adopting doping copper sulfide:PSS as hole injection layer,
ITO surface work functions, the band structure of CuS and carrier transmission performance can be adjusted well, effectively improve hole injection
Efficiency and translucency, so as to improve luminous efficiency, stability and the service life of QLED devices.
The chemical general formula of present invention doping copper sulfide is Cu1-xMxS, wherein, CuS is matrix, Mn+For Doped ions, x's takes
Value scope is 0 ~ 0.5, it is preferable that the span of x is 0.01 ~ 0.25；The band gap of the doping copper sulfide is 2.1 ~ 3.6 eV.
Preferably, the Mn+For Cu+、Co2+、Zn2+、Mg2+、Ni2+、Mn2+、Ho3+、In3+、Sb3+In one or more.Adulterate sulphur
It can be Cu doping copper sulfides, Co doping copper sulfides, Zn doping copper sulfides, Mg doping copper sulfides, Ni doping copper sulfides, Mn to change copper
One or more in doping copper sulfide, Ho doping copper sulfides, In doping copper sulfides, Sb doping copper sulfides.
Specifically, it is of the present invention doping copper sulfide film thickness be 1 ~ 50 nm, for example, thickness can for 1 nm, 25
Nm or 50 nm.
Specifically, it is of the present invention doping copper sulfide film shape can for spheric granules, sheet, bar-shaped, nano wire,
One or more in network structure.The structure of the doping copper sulfide film can be compact texture or loose structure.
Doping copper sulfide of the present invention can pass through obtained by chemical method or Physical preparation, and wherein chemical method is included but not
It is limited to sol-gel process（Sol-gel method）, chemical bath deposition method（Chemical bath deposition, CBD）、
Chemical vapour deposition technique（Chemical vapor deposition, CVD）, hydro-thermal method（Hydrothermal method）, altogether
The precipitation method, electrochemical deposition method；Physical includes but is not limited to thermal evaporation coating method, electron beam evaporation deposition method, magnetron sputtering
Method, multi-arc ion coating embrane method, electrolysis.
Copper sulfide of the present invention（CuS）As a kind of excellent p-type semiconductor, there is important research in fields such as photocatalysis,
And by being doped to CuS, can further adjust its band structure and change its material behavior.The present invention is based on CuS
Material character, the quantum dot light emitting device with the copper sulfide that adulterates as hole injection layer, the introducing of the hole injection layer can not only
Enough overcome traditional PEDOT:The deficiency of PSS hole injection layer materials, and ITO can be made to inject with hole injection layer and hole
Layer is more matched from the energy band between different quantum dots, effectively reduces the hole injection gesture from ITO substrate to quantum dot light emitting layer
Build, the more conducively injection in hole, so as to improve the luminous efficiency and stability of QLED devices.
Specifically, anode of the present invention can be but be not limited to indium doping tin oxide（ITO）, fluorine-doped tin oxide
（FTO）, antimony-doped tin oxide（ATO）, aluminium-doped zinc oxide（AZO）In one or more.
Specifically, hole transmission layer of the present invention may be selected from the organic material with cavity transmission ability, can be but
It is not limited to poly- (9,9- dioctyl fluorene-CO-N- (4- butyl phenyls) diphenylamines)（TFB）, polyvinylcarbazole（PVK）, poly- (N, N'
Double (phenyl) benzidine of double (4- butyl phenyls)-N, N'-)（poly-TPD）, it is poly- (double-N of 9,9- dioctyl fluorenes -co-, N- phenyl-
1,4- phenylenediamines)（PFB）, 4,4 ', 4 ' '-three (carbazole -9- bases) triphenylamine（TCTA）, 4,4'- bis- (9- carbazoles) biphenyl（CBP）、
N, N '-diphenyl-N, N '-two (3- aminomethyl phenyls) -1,1 '-biphenyl -4,4 '-diamines（TPD）, N, N '-diphenyl-N, N '-（1-
Naphthyl）- 1,1 '-biphenyl -4,4 '-diamines（NPB）, doped graphene, undoped Graphene, C60Or their mixture.
Specifically, hole transmission layer of the present invention is further selected from the inorganic material with cavity transmission ability, Ke Yiwei
But it is not limited to NiO, WO3、MoO3、CuO、VO2、CrO3、MoS2、MoSe2、WS2、WSe2, CuS or their mixture.
Specifically, the material of quantum dot light emitting layer of the present invention can be but be not limited to doped or non-doped II-V races
One kind or many in compound semiconductor, Group III-V compound semiconductor, IV-VI compound semiconductors and its core shell structure
Kind.Specifically, the material of electron transfer layer of the present invention can be N-shaped ZnO, TiO2、SnO2、Ta2O3、AlZnO、ZnSnO、
InSnO、Alq3、Ca、Ba、CsF、LiF、CsCO3In one or more.Preferably, the electron transfer layer is N-shaped ZnO.
Specifically, the material of negative electrode of the present invention can be various conductive carbon materials, conducting metal oxide material, gold
One or more in category material；Wherein conductive carbon material includes but is not limited to doped or non-doped CNT, doping or non-
Doped graphene, doped or non-doped graphene oxide, C60, graphite, carbon fiber, many sky carbon or their mixture；Conductive gold
Category oxide material includes but is not limited to ITO, FTO, ATO, AZO or their mixture；Metal material including but not limited to Al,
Ag, Cu, Mo, Au or their alloy；In wherein described metal material, its form includes but is not limited to dense film, nanometer
Line, nanosphere, nanometer rods, nanocone, nano-hollow ball or their mixture；Preferably, the material of the negative electrode be Ag or
Al。
The above-mentioned autologous light emitting diode with quantum dots of the present invention is not limited to above-mentioned functions layer, can also further include boundary
Face functional layer or interface-modifying layer, the interfactial work ergosphere or interface-modifying layer include but is not limited to electronic barrier layer, hole barrier
One or more in layer, electrode modification layer, isolated protective layer.
It should be noted that, present invention doping copper sulfide film is not limited to prepare autologous light emitting diode with quantum dots,
The light emitting diode with quantum dots of reciprocal form structure can also be prepared.The light emitting diode with quantum dots of reciprocal form structure is not limited to above-mentioned functions
Layer, can equally further include interfactial work ergosphere or interface-modifying layer, and the interfactial work ergosphere or interface-modifying layer include but do not limit
One or more in electronic barrier layer, hole blocking layer, electrode modification layer, isolated protective layer.
The present invention also provides a kind of illuminating module, and which includes light emitting diode with quantum dots as above.
The present invention also provides a kind of display device, and which includes light emitting diode with quantum dots as above, or including as above
Described illuminating module.
Based on above-mentioned light emitting diode with quantum dots, the present invention also provides a kind of as above arbitrary described two pole of quantum dot light emitting
The flow chart of the preparation method preferred embodiment of pipe, as shown in Fig. 2 including：
Step S100, hole injection layer is prepared on anode；Wherein, the hole injection layer is doping copper sulfide film；
Step S200 and then hole transmission layer is prepared on hole injection layer；
Step S300, quantum dot light emitting layer is then prepared on hole transmission layer；
Step S400, finally electron transfer layer is prepared on quantum dot light emitting layer, and evaporation cathode is on electron transfer layer, formed
Light emitting diode with quantum dots.
Specifically, by taking solwution method preparation as an example, doping copper sulfide film of the present invention can be by doping sulfuration copper solution system
Standby to form, the preparation method of the doping sulfuration copper solution includes：1 ~ 5 mL concentration is slow for the sodium sulfide solution of 0.1 ~ 1 M
It is added to 100 mL copper chlorides, sodium citrate, doped metal salt（Such as zinc chloride etc.）Mixed solution in, wherein copper chloride is dense
Spend for 0.5 ~ 10 mM, the concentration of sodium citrate is 0.01 ~ 0.5 mM, and the concentration of doped metal salt is 0 ~ 5 mM.Preferably, chlorine
The concentration for changing copper is 0.5 ~ 2 mM, and the concentration of citric acid is 0.05 ~ 0.1 mM, and the concentration of doped metal salt is 0.01 ~ 0.25
mM.After stirring, mixed solution is heated to into 60 ~ 100 °C, reacts 10 ~ 120 min, obtain doping sulfuration copper solution.
Present invention doping sulfuration copper solution well prepared in advance, then by solution film forming mode such as spin coating, ink-jet, blade coating etc.
Technique makes doping copper sulfide film on anode as hole injection layer.
The preparation method of the above-mentioned each functional layer of the present invention can be chemical method or Physical, and wherein Physical includes but do not limit
Steam in spin-coating method, spraying process, roll coating process, impact system, print process, ink-jet method, dip-coating method, thermal evaporation coating method, electron beam
Send out coating method, magnetron sputtering method, multi-arc ion coating embrane method；Chemical method includes but is not limited to chemical vapour deposition technique, continuous ionic
Layer absorption and reaction method, anodizing, strike, coprecipitation.
The inventive method prepares simple, efficiently solves complex structure in prior art, material cost is high and is difficult to industry
The problems such as change.In addition, prepared device performance is excellent, good stability, long service life.
It is presented herein below and describes in detail by taking the preparation process that the material of hole injection layer is prepared with QLED devices as an example.
Embodiment 1
1）, Zn adulterate CuS preparation：The sodium sulfide solution that 1 mL concentration is 0.1 M is slowly added into into 100 mL copper chlorides, lemon
Lemon acid sodium, in the mixed solution of zinc chloride, the wherein concentration of copper chloride is 1 mM, and the concentration of sodium citrate is 0.06 mM, chlorination
Zinc concentration is 0.01 mM.After stirring, mixed solution is heated to into 100 DEG C, reacts 20 min, obtain Zn doping CuS
Nanoparticles solution.
2）, QLED devices preparation process it is as follows：
On ITO substrates, spin coating a layer thickness is the Zn doping CuS films of 10 nm as hole injection layer；
One layer of PVK hole transmission layer of spin coating on Zn doping CuS films；
Then, one layer of CdSe quantum dot luminescent layer of spin coating on PVK hole transmission layers；
Then, the spin coating layer of ZnO electron transfer layer on CdSe quantum dot luminescent layer；
Finally, one layer of Al negative electrode is deposited with ZnO electron transfer layers, obtain light emitting diode with quantum dots.
Embodiment 2
1）, Co adulterate CuS preparation：By the sodium sulfide solution that 1 mL concentration is 0.1 M be slowly added into 100 mL copper chlorides,
In sodium citrate, the mixed solution of cobalt chloride, the wherein concentration of copper chloride is 1 mM, and the concentration of sodium citrate is 0.06 mM, chlorine
The concentration for changing cobalt is 0.01 mM.After stirring, mixed solution is heated to into 100 °C, reacts 20 min, obtain Co doping
CuS nanoparticles solutions.
2）, QLED devices preparation process it is as follows：
On ITO substrates, spin coating a layer thickness is the Co doping CuS films of 10 nm as hole injection layer；
One layer of PVK hole transmission layer of spin coating on Co doping CuS films；
Then, one layer of CdSe quantum dot luminescent layer of spin coating on PVK hole transmission layers；
Then, the spin coating layer of ZnO electron transfer layer on CdSe quantum dot luminescent layer；
Finally, one layer of Al negative electrode is deposited with ZnO electron transfer layers, obtain light emitting diode with quantum dots.
Embodiment 3
1）, Ni adulterate CuS preparation：By the sodium sulfide solution that 1 mL concentration is 0.1 M be slowly added into 100 mL copper chlorides,
In sodium citrate, the mixed solution of nickel chloride, the wherein concentration of copper chloride is 1 mM, and the concentration of sodium citrate is 0.06 mM, chlorine
The concentration for changing nickel is 0.01 mM.After stirring, mixed solution is heated to into 100 °C, reacts 20 min, obtain Ni doping
CuS nanoparticles solutions.
2）, QLED devices preparation process it is as follows：
On ITO substrates, spin coating a layer thickness is the Ni doping CuS films of 10 nm as hole injection layer；
One layer of PVK hole transmission layer of spin coating on Ni doping CuS films；
Then, one layer of CdSe quantum dot luminescent layer of spin coating on PVK hole transmission layers；
Then, the spin coating layer of ZnO electron transfer layer on CdSe quantum dot luminescent layer；
Finally, one layer of Al negative electrode is deposited with ZnO electron transfer layers, obtain light emitting diode with quantum dots.
Embodiment 4
1）, Sb adulterate CuS preparation：The sodium sulfide solution that 1 mL concentration is 0.1 M is slowly added into into 100 mL copper chlorides, lemon
Lemon acid sodium, in the mixed solution of trichloride antimony, the wherein concentration of copper chloride is 1 mM, and the concentration of sodium citrate is 0.06 mM, three
The concentration of antimony chloride is 0.01 mM.After stirring, mixed solution is heated to into 100 °C, reacts 20 min, obtain Sb doping
CuS nanoparticles solutions.
2）, QLED devices preparation process it is as follows：
On ITO substrates, spin coating a layer thickness is the Sb doping CuS films of 10 nm as hole injection layer；
One layer of PVK hole transmission layer of spin coating on Sb doping CuS films；
Then, one layer of CdSe quantum dot luminescent layer of spin coating on PVK hole transmission layers；
Then, the spin coating layer of ZnO electron transfer layer on CdSe quantum dot luminescent layer；
Finally, one layer of Al negative electrode is deposited with ZnO electron transfer layers, obtain light emitting diode with quantum dots.
Embodiment 5
1）, Zn and Co codope CuS preparation：The sodium sulfide solution that 1 mL concentration is 0.1 M is slowly added into into 100 mL
In copper chloride, sodium citrate, zinc chloride, the mixed solution of cobalt chloride, wherein the concentration of copper chloride be 1 mM, sodium citrate it is dense
Spend for 0.06 mM, chlorination zinc concentration is 0.01 mM, and the concentration of cobalt chloride is 0.01 mM.After stirring, by mixed solution
100 °C are heated to, 20 min are reacted, is obtained Zn and Co codope CuS nanoparticles solutions.
2）, QLED devices preparation process it is as follows：
On ITO substrates, spin coating a layer thickness is Zn the and Co codope CuS films of 10 nm as hole injection layer；
One layer of PVK hole transmission layer of spin coating on Zn and Co codope CuS films；
Then, one layer of CdSe quantum dot luminescent layer of spin coating on PVK hole transmission layers；
Then, the spin coating layer of ZnO electron transfer layer on CdSe quantum dot luminescent layer；
Finally, one layer of Al negative electrode is deposited with ZnO electron transfer layers, obtain light emitting diode with quantum dots.
Embodiment 6
1）, Zn adulterate CuS preparation：By the sodium sulfide solution that 1 mL concentration is 0.1 M be slowly added into 100 mL copper chlorides,
In sodium citrate, the mixed solution of zinc chloride, the wherein concentration of copper chloride is 1 mM, and the concentration of sodium citrate is 0.06 mM, chlorine
Change zinc concentration is 0.05 mM.After stirring, mixed solution is heated to into 100 °C, reacts 20 min, obtain Zn doping
CuS nanoparticles solutions.
2）, QLED devices preparation process it is as follows：
On ITO substrates, spin coating a layer thickness is the Zn doping CuS films of 10 nm as hole injection layer；
One layer of PVK hole transmission layer of spin coating on Zn doping CuS films；
Then, one layer of CdSe quantum dot luminescent layer of spin coating on PVK hole transmission layers；
Then, the spin coating layer of ZnO electron transfer layer on CdSe quantum dot luminescent layer；
Finally, one layer of Al negative electrode is deposited with ZnO electron transfer layers, obtain light emitting diode with quantum dots.
Embodiment 7
1）, Zn adulterate CuS preparation：By the sodium sulfide solution that 1 mL concentration is 0.1 M be slowly added into 100 mL copper chlorides,
In sodium citrate, the mixed solution of zinc chloride, the wherein concentration of copper chloride is 1 mM, and the concentration of sodium citrate is 0.06 mM, chlorine
Change zinc concentration is 0.1 mM.After stirring, mixed solution is heated to into 100 °C, reacts 20 min, obtain Zn doping CuS
Nanoparticles solution.
2）, QLED devices preparation process it is as follows：
On ITO substrates, spin coating a layer thickness is the Zn doping CuS films of 10 nm as hole injection layer；
One layer of PVK hole transmission layer of spin coating on Zn doping CuS films；
Then, one layer of CdSe quantum dot luminescent layer of spin coating on PVK hole transmission layers；
Then, the spin coating layer of ZnO electron transfer layer on CdSe quantum dot luminescent layer；
Finally, one layer of Al negative electrode is deposited with ZnO electron transfer layers, obtain light emitting diode with quantum dots.
Embodiment 8
1）, Zn adulterate CuS preparation：By the sodium sulfide solution that 1 mL concentration is 0.1 M be slowly added into 100 mL copper chlorides,
In sodium citrate, the mixed solution of zinc chloride, the wherein concentration of copper chloride is 1 mM, and the concentration of sodium citrate is 0.06 mM, chlorine
Change zinc concentration is 0.25 mM.After stirring, mixed solution is heated to into 100 °C, reacts 20 min, obtain Zn doping
CuS nanoparticles solutions.
2）, QLED devices preparation process it is as follows：
On ITO substrates, spin coating a layer thickness is the Zn doping CuS films of 10 nm as hole injection layer；
One layer of PVK hole transmission layer of spin coating on Zn doping CuS films；
Then, one layer of CdSe quantum dot luminescent layer of spin coating on PVK hole transmission layers；
Then, the spin coating layer of ZnO electron transfer layer on CdSe quantum dot luminescent layer；
Finally, one layer of Al negative electrode is deposited with ZnO electron transfer layers, obtain light emitting diode with quantum dots.
Embodiment 9
1）, Zn adulterate CuS preparation：By the sodium sulfide solution that 1 mL concentration is 0.1 M be slowly added into 100 mL copper chlorides,
In sodium citrate, the mixed solution of zinc chloride, the wherein concentration of copper chloride is 1 mM, and the concentration of sodium citrate is 0.06 mM, chlorine
Change zinc concentration is 0.05 mM.After stirring, mixed solution is heated to into 100 °C, reacts 20 min, obtain Zn doping
CuS nanoparticles solutions.
2）, QLED devices preparation process it is as follows：
On ITO substrates, spin coating a layer thickness is the Zn doping CuS films of 20 nm as hole injection layer；
One layer of PVK hole transmission layer of spin coating on Zn doping CuS films；
Then, one layer of CdSe quantum dot luminescent layer of spin coating on PVK hole transmission layers；
Then, the spin coating layer of ZnO electron transfer layer on CdSe quantum dot luminescent layer；
Finally, one layer of Al negative electrode is deposited with ZnO electron transfer layers, obtain light emitting diode with quantum dots.
In sum, a kind of light emitting diode with quantum dots that the present invention is provided and preparation method thereof and illuminating module, display
Device, the present invention prepare hole injection layer to adulterate copper sulfide film, and profit is preferably adjusted interior in a big way in this way
Section ITO surface work functions, the band structure of CuS and carrier transmission performance, so as to improve the luminous efficiency of QLED devices.Together
When, attachment of the doping metals sulfide on ITO can't change the surface roughness and translucency of ITO, and ITO will not be produced
Raw corrosion, effectively improves the stability and service life of QLED devices.
It should be appreciated that the application of the present invention is not limited to above-mentioned citing, and for those of ordinary skills, can
To be improved according to the above description or be converted, all these modifications and variations should all belong to the guarantor of claims of the present invention
Shield scope.
Claims (10)
1. a kind of light emitting diode with quantum dots, it is characterised in that the light emitting diode with quantum dots includes that anode, hole are noted successively
Enter layer, hole transmission layer, quantum dot light emitting layer, electron transfer layer and negative electrode；
Wherein, the hole injection layer is doping copper sulfide film.
2. light emitting diode with quantum dots according to claim 1, it is characterised in that doping copper sulfide is Cu doping sulfurations
Copper, Co doping copper sulfides, Zn doping copper sulfides, Mg doping copper sulfides, Ni doping copper sulfides, Mn doping copper sulfides, Ho doping sulphur
Change one or more in copper, In doping copper sulfides, Sb doping copper sulfides.
3. light emitting diode with quantum dots according to claim 1, it is characterised in that the thickness of the doping copper sulfide film
For 1 ~ 50 nm.
4. light emitting diode with quantum dots according to claim 1, it is characterised in that doping copper sulfide film is shaped as ball
One or more in shape particle, sheet, bar-shaped, nano wire, network structure.
5. light emitting diode with quantum dots according to claim 1, it is characterised in that the structure of the doping copper sulfide film
For compact texture or loose structure.
6. a kind of preparation method of the light emitting diode with quantum dots as described in claim 1 ~ 5 is arbitrary, it is characterised in that include：
Step A, hole injection layer is prepared on anode；Wherein, the hole injection layer is doping copper sulfide film；
Step B and then hole transmission layer is prepared on hole injection layer；
Step C, quantum dot light emitting layer is then prepared on hole transmission layer；
Step D, finally electron transfer layer is prepared on quantum dot light emitting layer, and evaporation cathode is on electron transfer layer, forming amount
Sub- point luminescent diode.
7. the preparation method of light emitting diode with quantum dots according to claim 6, it is characterised in that the doping copper sulfide
Film is prepared from using doping sulfuration copper solution, and the preparation method of the doping sulfuration copper solution includes：By sodium sulfide solution
It is added in the mixed solution of copper chloride, sodium citrate, doped metal salt, after stirring, mixed solution is heated to into 60 ~
100 °C, 10 ~ 120 min are reacted, obtain doping sulfuration copper solution.
8. the preparation method of light emitting diode with quantum dots according to claim 7, it is characterised in that the vulcanized sodium it is dense
Spend for 0.1 ~ 1 M, the concentration of the copper chloride is 0.5 ~ 10 mM, and the concentration of the sodium citrate is 0.01 ~ 0.5 mM, described
The concentration of doped metal salt is 0 ~ 5 mM.
9. a kind of illuminating module, it is characterised in that the illuminating module includes the quantum dot as described in any one of claim 1 ~ 5
Light emitting diode.
10. a kind of display device, it is characterised in that the display device includes illuminating module as claimed in claim 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611140900.1A CN106531895B (en) | 2016-12-12 | 2016-12-12 | Light emitting diode with quantum dots and preparation method thereof and illuminating module, display device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611140900.1A CN106531895B (en) | 2016-12-12 | 2016-12-12 | Light emitting diode with quantum dots and preparation method thereof and illuminating module, display device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106531895A true CN106531895A (en) | 2017-03-22 |
| CN106531895B CN106531895B (en) | 2019-09-10 |
Family
ID=58341964
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611140900.1A Active CN106531895B (en) | 2016-12-12 | 2016-12-12 | Light emitting diode with quantum dots and preparation method thereof and illuminating module, display device |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106531895B (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108922984A (en) * | 2018-07-26 | 2018-11-30 | 京东方科技集团股份有限公司 | Display panel and preparation method thereof, display equipment |
| CN109216568A (en) * | 2017-07-05 | 2019-01-15 | Tcl集团股份有限公司 | A kind of preparation method of QLED device |
| CN109390476A (en) * | 2017-08-02 | 2019-02-26 | Tcl集团股份有限公司 | A kind of QLED device and preparation method thereof with graphene oxide boundary layer |
| CN110660926A (en) * | 2018-06-28 | 2020-01-07 | Tcl集团股份有限公司 | Novel transparent conductive film and preparation method and application thereof |
| CN110931640A (en) * | 2018-09-19 | 2020-03-27 | 君泰创新（北京）科技有限公司 | Perovskite solar cell and preparation method thereof |
| CN111689512A (en) * | 2019-03-13 | 2020-09-22 | 中国科学院上海高等研究院 | In-doped Cu-S-based thermoelectric material and preparation method thereof |
| CN113130774A (en) * | 2019-12-30 | 2021-07-16 | Tcl集团股份有限公司 | Quantum dot light-emitting diode, preparation method thereof and display device |
| CN113258009A (en) * | 2020-04-17 | 2021-08-13 | 广东聚华印刷显示技术有限公司 | Composite material, preparation method thereof and quantum dot light-emitting diode |
| CN114267800A (en) * | 2020-09-16 | 2022-04-01 | Tcl科技集团股份有限公司 | Quantum dot light-emitting diode and preparation method thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080204849A1 (en) * | 2005-05-31 | 2008-08-28 | Konica Minolta Holdings, Inc. | Display Element |
| CN103151463A (en) * | 2013-02-28 | 2013-06-12 | 武汉大学 | Organic solar battery and preparation method thereof |
| CN103915567A (en) * | 2014-03-28 | 2014-07-09 | 中国科学院上海技术物理研究所 | Perovskite solar cell with inorganic compound as hole transfer layer |
| CN104124381A (en) * | 2013-04-24 | 2014-10-29 | 海洋王照明科技股份有限公司 | Organic electroluminescent device and preparation method thereof |
| CN105153807A (en) * | 2015-07-21 | 2015-12-16 | 京东方科技集团股份有限公司 | Quantum dot ink |
| WO2016039585A1 (en) * | 2014-09-11 | 2016-03-17 | 경희대학교 산학협력단 | Organic light emitting diode using p-type oxide semiconductor containing gallium, and preparation method therefor |
| CN105552184A (en) * | 2016-01-20 | 2016-05-04 | Tcl集团股份有限公司 | All-inorganic quantum dot light emitting diode and preparation method therefor |
| CN105720206A (en) * | 2016-05-06 | 2016-06-29 | Tcl集团股份有限公司 | QLED device and preparation method thereof |
-
2016
- 2016-12-12 CN CN201611140900.1A patent/CN106531895B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080204849A1 (en) * | 2005-05-31 | 2008-08-28 | Konica Minolta Holdings, Inc. | Display Element |
| CN103151463A (en) * | 2013-02-28 | 2013-06-12 | 武汉大学 | Organic solar battery and preparation method thereof |
| CN104124381A (en) * | 2013-04-24 | 2014-10-29 | 海洋王照明科技股份有限公司 | Organic electroluminescent device and preparation method thereof |
| CN103915567A (en) * | 2014-03-28 | 2014-07-09 | 中国科学院上海技术物理研究所 | Perovskite solar cell with inorganic compound as hole transfer layer |
| WO2016039585A1 (en) * | 2014-09-11 | 2016-03-17 | 경희대학교 산학협력단 | Organic light emitting diode using p-type oxide semiconductor containing gallium, and preparation method therefor |
| CN105153807A (en) * | 2015-07-21 | 2015-12-16 | 京东方科技集团股份有限公司 | Quantum dot ink |
| CN105552184A (en) * | 2016-01-20 | 2016-05-04 | Tcl集团股份有限公司 | All-inorganic quantum dot light emitting diode and preparation method therefor |
| CN105720206A (en) * | 2016-05-06 | 2016-06-29 | Tcl集团股份有限公司 | QLED device and preparation method thereof |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109216568A (en) * | 2017-07-05 | 2019-01-15 | Tcl集团股份有限公司 | A kind of preparation method of QLED device |
| CN109390476A (en) * | 2017-08-02 | 2019-02-26 | Tcl集团股份有限公司 | A kind of QLED device and preparation method thereof with graphene oxide boundary layer |
| CN110660926A (en) * | 2018-06-28 | 2020-01-07 | Tcl集团股份有限公司 | Novel transparent conductive film and preparation method and application thereof |
| CN108922984A (en) * | 2018-07-26 | 2018-11-30 | 京东方科技集团股份有限公司 | Display panel and preparation method thereof, display equipment |
| CN110931640A (en) * | 2018-09-19 | 2020-03-27 | 君泰创新（北京）科技有限公司 | Perovskite solar cell and preparation method thereof |
| CN111689512A (en) * | 2019-03-13 | 2020-09-22 | 中国科学院上海高等研究院 | In-doped Cu-S-based thermoelectric material and preparation method thereof |
| CN113130774A (en) * | 2019-12-30 | 2021-07-16 | Tcl集团股份有限公司 | Quantum dot light-emitting diode, preparation method thereof and display device |
| CN113130774B (en) * | 2019-12-30 | 2022-06-24 | Tcl科技集团股份有限公司 | Quantum dot light-emitting diode, preparation method thereof and display device |
| CN113258009A (en) * | 2020-04-17 | 2021-08-13 | 广东聚华印刷显示技术有限公司 | Composite material, preparation method thereof and quantum dot light-emitting diode |
| CN114267800A (en) * | 2020-09-16 | 2022-04-01 | Tcl科技集团股份有限公司 | Quantum dot light-emitting diode and preparation method thereof |
| CN114267800B (en) * | 2020-09-16 | 2023-10-10 | Tcl科技集团股份有限公司 | Quantum dot light emitting diode and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106531895B (en) | 2019-09-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106531895B (en) | Light emitting diode with quantum dots and preparation method thereof and illuminating module, display device | |
| US10826009B2 (en) | Quantum dot light-emitting diode and display apparatus thereof | |
| CN109390476B (en) | QLED device with graphene oxide interface layer and preparation method thereof | |
| CN108807720B (en) | Functionalized cathode, QLED, preparation method, light-emitting module and display device | |
| CN106531860B (en) | Quantum dot light emitting layer and device and preparation method, illuminating module and display device | |
| CN107112424B (en) | Use the light-emitting component and its manufacturing method of the charge generating layers formed by solution process | |
| CN109980097B (en) | Preparation method of thin film and QLED device | |
| CN106410051A (en) | Application of metal element-doped ZnO nano material in light-emitting diode | |
| WO2018166428A1 (en) | Quantum dot solid-state film and method for preparing same, and quantum dot light-emitting diode | |
| CN109390475A (en) | A kind of QLED device | |
| US11183657B2 (en) | Quantum dot light emitting diode and preparation method thereof | |
| CN106856227A (en) | A kind of wearable light emitting diode with quantum dots of flexible ventilating and preparation method thereof | |
| CN109935719A (en) | Quantum dot film and preparation method thereof, QLED device and preparation method thereof | |
| CN109390483B (en) | Display device and preparation method thereof | |
| CN109427939B (en) | QLED device and preparation method thereof | |
| CN111129320A (en) | Quantum dot light-emitting diode | |
| CN109285947B (en) | LED thin film LED substrate for printing, LED thin film LED device and preparation method thereof | |
| CN113130631B (en) | Heterojunction nano material, preparation method thereof, thin film and quantum dot light-emitting diode | |
| CN114695695A (en) | Quantum dot light-emitting diode and preparation method thereof | |
| CN109390477B (en) | Multi-channel hole transport layer, electrical device and QLED device | |
| CN109390492B (en) | Display device and preparation method thereof | |
| CN113809245B (en) | Zinc oxide nano material, preparation method thereof and semiconductor device | |
| CN112397661B (en) | Nano material, preparation method thereof and quantum dot light-emitting diode | |
| CN112397658B (en) | Composite material, preparation method thereof and quantum dot light-emitting diode | |
| CN109980107B (en) | CuMO2Preparation method thereof and light-emitting device |
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 |