CN106531895B - Light emitting diode with quantum dots and preparation method thereof and illuminating module, display device - Google Patents
Light emitting diode with quantum dots and preparation method thereof and illuminating module, display device Download PDFInfo
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- 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
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Abstract
The present invention discloses light emitting diode with quantum dots and preparation method thereof and illuminating module, display device, and the light emitting diode with quantum dots successively includes anode, hole injection layer, hole transmission layer, quantum dot light emitting layer, electron transfer layer and cathode；Wherein, the hole injection layer is doping copper sulfide film.The present invention prepares hole injection layer to adulterate copper sulfide film, this is because not only material is cheap for doping copper sulfide used, but also non-toxic stable.In addition, replace traditional PEDOT:PSS as hole injection layer by using doping copper sulfide, ITO surface work function, the band structure of CuS and carrier transmission performance can be adjusted well, hole injection efficiency and translucency are effectively improved, to improve the luminous efficiency of QLED device, stability and service life.
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 systems
Preparation Method and illuminating module, display device.
Background technique
Quantum dot (Quantum dots, QDs) is a kind of nanocrystalline material that particle size is 1 ~ 10 nm, has hair
Penetrate that spectrum is narrow, luminous efficiency is high, stability of photoluminescence is good, luminescent spectrum is with special advantages such as size adjustables, potential substitution tradition
Organic or inorganic illuminator become the core of next-generation luminescent device.Light emitting diode (Quantum based on quantum dot
Dot light-emitting diodes, QLED) and traditional LED and Organic Light Emitting Diode (Organic light-
Emitting diode, OLED) compared to apparent advantage is shown on color saturation, stability and preparation cost, it is expected into
For the contenders of next-generation display and lighting engineering.
It is most of to use poly- (3,4-ethylene dioxythiophene)-polystyrolsulfon acid in the QLED device studied at present
(PEDOT:PSS) it is used as hole injection layer, main function is that hole is made smoothly to 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 corrodes ITO, seriously affects QLED device
The stability of part.In addition, the work function (about 5.2 eV) of PEDOT:PSS is more shallow than the valence band of quantum dot, and cannot guarantee simultaneously
Ohmic contact is formed between PEDOT:PSS layers and different quantum dots, to injecting there are certain influence for electronics, is eventually resulted in
Device light emitting efficiency reduces.For this reason, it is necessary to find more hole injection layer of the suitable material as QLED device.
Currently, existing many reports use hole injection/transport layer material of the inorganic p-type metal oxide as QLED device
Material, such as NiOx、MoOx、WOx、VOx, NiLiMgO etc..Nevertheless, prepared by these metal oxide hole injection/transport layers
Journey is complex, and the surface roughness and light transmittance to ITO bring certain influence, and generally has lower hole note
Enter/efficiency of transmission, it is difficult to meet the needs of industrialized production.
Therefore, the existing technology needs to be improved and developed.
Summary of the invention
In view of above-mentioned deficiencies of the prior art, the purpose of the present invention is to provide a kind of light emitting diode with quantum dots and its systems
Preparation Method and illuminating module, display device, it is intended to solve existing hole injection layer material hole injection efficiency and translucency 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 successively includes anode, hole injection
Layer, hole transmission layer, quantum dot light emitting layer, electron transfer layer and cathode；
Wherein, the hole injection layer is doping copper sulfide film.
The light emitting diode with quantum dots, wherein doping copper sulfide is that Cu adulterates copper sulfide, Co adulterates copper sulfide, Zn
Doping copper sulfide, Mg adulterate copper sulfide, Ni adulterates copper sulfide, Mn doping copper sulfide, Ho doping copper sulfide, In adulterate copper sulfide,
Sb adulterates one of copper sulfide or a variety of.
The light emitting diode with quantum dots, wherein it is described doping copper sulfide film with a thickness of 1 ~ 50 nm.
The light emitting diode with quantum dots, wherein adulterate copper sulfide film shape be spheric granules, sheet, it is rodlike,
One of nano wire, reticular structure are a variety of.
The light emitting diode with quantum dots, wherein the structure of the doping copper sulfide film is compact texture or porous
Structure.
The preparation method of a kind of as above any light emitting diode with quantum dots, wherein include:
Step A, hole injection layer is prepared on anode；Wherein, the hole injection layer is doping copper sulfide film；
Step B, hole transmission layer is then prepared on hole injection layer；
Step C, quantum dot light emitting layer is then prepared on the hole transport layer；
Step D, electron transfer layer is finally prepared on quantum dot light emitting layer, and evaporation cathode is on electron transfer layer, shape
At light emitting diode with quantum dots.
The preparation method of the light emitting diode with quantum dots, wherein the doping copper sulfide film is using doping vulcanization
Copper solution is prepared, and the preparation method of the doping vulcanization copper solution includes: that sodium sulfide solution is added to copper chloride, lemon
Sour sodium, doped metal salt mixed solution in, after mixing evenly, mixed solution is heated to 60 ~ 100 °C, reaction 10 ~ 120
Min obtains doping vulcanization copper solution.
The preparation method of the 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 described in any item light emitting diode with quantum dots as above.
A kind of display device, wherein the display device includes illuminating module as described above.
The utility model has the advantages that the present invention uses doping copper sulfide film as hole injection layer, to adjust ITO surface work well
Function, the band structure of CuS and carrier transmission performance, effectively improve hole injection efficiency and translucency, to improve
Luminous efficiency, stability and the service life of QLED device.
Detailed description of the invention
Fig. 1 is a kind of structural schematic diagram of light emitting diode with quantum dots preferred embodiment of the invention.
Fig. 2 is a kind of flow chart of the preparation method preferred embodiment of light emitting diode with quantum dots of the 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 solution and effect are clearer, define, and the present invention is described in more detail below.It should be appreciated that this
Locate described specific embodiment to be only used to explain the present invention, be not intended to limit the present invention.
Referring to Fig. 1, Fig. 1 is a kind of structural schematic diagram of light emitting diode with quantum dots preferred embodiment of the invention, such as
Shown in figure, the light emitting diode with quantum dots successively includes anode 1, hole injection layer 2, hole transmission layer 3, quantum dot light emitting layer
4, electron transfer layer 5 and cathode 6；Wherein, the hole injection layer 2 is doping copper sulfide film.
The present invention prepares hole injection layer to adulterate copper sulfide film, this is because doping copper sulfide used not only material
Material is cheap, and non-toxic stable.In addition, replace traditional PEDOT:PSS as hole injection layer by using doping copper sulfide,
ITO surface work function, the band structure of CuS and carrier transmission performance can be adjusted well, effectively improve hole injection
Efficiency and translucency, to improve the luminous efficiency of QLED device, stability and service life.
The chemical general formula that the present invention adulterates copper sulfide is Cu1-xMxS, wherein CuS is matrix, Mn+For Doped ions, x's is taken
Being worth range is 0 ~ 0.5, it is preferable that the value range 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+One of or it is a variety of.Adulterate sulphur
Changing copper can be for Cu doping copper sulfide, Co adulterate copper sulfide, Zn adulterates copper sulfide, Mg adulterates copper sulfide, Ni adulterates copper sulfide, Mn
Adulterate one of copper sulfide, Ho doping copper sulfide, In doping copper sulfide, Sb doping copper sulfide or a variety of.
Specifically, it is of the present invention doping copper sulfide film with a thickness of 1 ~ 50 nm, for example, thickness can be 1 nm, 25
Nm or 50 nm.
Specifically, it is of the present invention doping copper sulfide film shape can for spheric granules, sheet, rodlike, nano wire,
One of reticular structure is a variety of.The structure of the doping copper sulfide film can be compact texture or porous structure.
Doping copper sulfide of the present invention can be as obtained by chemical method or physical method preparation, and wherein chemical method includes but not
Be limited to sol-gel method (Sol-gel method), chemical bath deposition method (Chemical bath deposition, CBD),
Chemical vapour deposition technique (Chemical vapor deposition, CVD), is total to hydro-thermal method (Hydrothermal method)
The precipitation method, electrochemical deposition method；Physical method 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 method.
Copper sulfide (CuS) of the present invention has important research in fields such as photocatalysis as a kind of excellent p-type semiconductor,
And by being doped to CuS, it can further adjust its band structure and change its material property.The present invention is based on CuS
Material properties, to adulterate quantum dot light emitting device of the copper sulfide as hole injection layer, the introducing of the hole injection layer can not only
Enough overcome the shortcomings of traditional PEDOT:PSS hole injection layer material, and ITO and hole injection layer and hole can be made to inject
Layer is more matched from the energy band between different quantum dots, and the hole injection gesture from ITO substrate to quantum dot light emitting layer is effectively reduced
It builds, the more conducively injection in hole, to improve the luminous efficiency and stability of QLED device.
Specifically, anode of the present invention can be but be not limited to indium doping tin oxide (ITO), fluorine-doped tin oxide
(FTO), one of antimony-doped tin oxide (ATO), aluminium-doped zinc oxide (AZO) or a variety of.
Specifically, hole transmission layer of the present invention can 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 phenyl) diphenylamines) (TFB), polyvinylcarbazole (PVK), poly- (N, N'
Bis- bis- (phenyl) benzidine of (4- butyl phenyl)-N, N'-) (poly-TPD), poly- (double-N of 9,9- dioctyl fluorene -co-, N- phenyl-
1,4- phenylenediamine) (PFB), 4,4 ', 4 ' '-three (carbazole -9- base) triphenylamine (TCTA), 4,4'- bis- (9- carbazole) biphenyl (CBP),
N, N '-diphenyl-N, N '-two (3- aminomethyl phenyl) -1,1 '-biphenyl -4,4 '-diamines (TPD), N, N '-diphenyl-N, N '-(1-
Naphthalene) -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 race
One of compound semiconductor, Group III-V compound semiconductor, IV-VI compound semiconductor and its core-shell structure are more
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、CsCO3One of or it is a variety of.Preferably, the electron transfer layer is N-shaped ZnO.
Specifically, the material of cathode of the present invention can be various conductive carbon materials, conductive metal oxide material, gold
Belong to one of material or a variety of；Wherein conductive carbon material includes but is not limited to doped or non-doped carbon nanotube, doping or non-
Doped graphene, doped or non-doped graphene oxide, C60, graphite, carbon fiber, more empty carbon or their mixture；Conductive gold
Belonging to oxide material includes but is not limited to ITO, FTO, ATO, AZO or their mixture；Metal material include but is not limited to Al,
Ag, Cu, Mo, Au or their alloy；Wherein in the metal material, 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 cathode be Ag or
Al。
The above-mentioned autologous light emitting diode with quantum dots of the present invention is not limited to above-mentioned functional layer, can also further comprise 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 of layer, electrode modification layer, isolated protective layer are a variety of.
It is not limited to prepare autologous light emitting diode with quantum dots it should be noted that the present invention adulterates copper sulfide film,
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 function
Layer, equally can further comprise interfactial work ergosphere or interface-modifying layer, and the interfactial work ergosphere or interface-modifying layer include but unlimited
In one of electronic barrier layer, hole blocking layer, electrode modification layer, isolated protective layer or a variety of.
The present invention also provides a kind of illuminating modules comprising light emitting diode with quantum dots as described above.
The present invention also provides a kind of display devices comprising light emitting diode with quantum dots as described above, or including as above
The illuminating module.
Based on above-mentioned light emitting diode with quantum dots, the present invention also provides a kind of as above any two poles of quantum dot light emitting
The flow chart of the preparation method preferred embodiment of pipe, as shown in Figure 2, comprising:
Step S100, hole injection layer is prepared on anode；Wherein, the hole injection layer is doping copper sulfide film；
Step S200, hole transmission layer is then prepared on hole injection layer；
Step S300, quantum dot light emitting layer is then prepared on the hole transport layer；
Step S400, electron transfer layer is finally prepared on quantum dot light emitting layer, and evaporation cathode is on electron transfer layer,
Form light emitting diode with quantum dots.
Specifically, by taking prepared by solwution method as an example, doping copper sulfide film of the present invention can vulcanize copper solution system by doping
Standby to form, the preparation method of the doping vulcanization copper solution includes: that 1 ~ 5 mL concentration is slow for the sodium sulfide solution of 0.1 ~ 1 M
Be added to 100 mL copper chlorides, sodium citrate, doped metal salt (such as zinc chloride) mixed solution in, wherein copper chloride is dense
Degree is 0.5 ~ 10 mM, and 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 mixing evenly, mixed solution is heated to 60 ~ 100 °C, reacts 10 ~ 120 min, obtain doping vulcanization copper solution.
Present invention doping well prepared in advance vulcanizes copper solution, then passes through solution film forming mode such as spin coating, ink-jet, blade coating etc.
Doping copper sulfide film is made as hole injection layer in technique on anode.
The preparation method of the above-mentioned each functional layer of the present invention can be chemical method or physical method, and wherein physical method includes but unlimited
It is steamed in spin-coating method, spray coating method, 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 method of the present invention preparation is simple, efficiently solves in the prior art that structure is complicated, material cost is high and is difficult to industry
The problems such as change.In addition, prepared device performance is excellent, stability is good, long service life.
Here is described in detail by taking the preparation process that the material of hole injection layer is prepared with QLED device as an example.
Embodiment 1
1), Zn adulterates the preparation of CuS: the sodium sulfide solution that 1 mL concentration is 0.1 M is slowly added into 100 mL chlorinations
Copper, sodium citrate, zinc chloride mixed solution in, wherein the concentration of copper chloride is 1 mM, and the concentration of sodium citrate is 0.06
MM, chlorination zinc concentration are 0.01 mM.After mixing evenly, mixed solution is heated to 100 DEG C, reacts 20 min, obtains Zn
Adulterate CuS nanoparticles solution.
2), the preparation step of QLED device is as follows:
The Zn that spin coating a layer thickness is 10 nm on ITO substrate adulterates CuS film as hole injection layer；
One layer of PVK hole transmission layer of spin coating on Zn doping CuS film；
Then, one layer of CdSe quantum dot luminescent layer of spin coating on PVK hole transmission layer；
Then, the spin coating layer of ZnO electron transfer layer on CdSe quantum dot luminescent layer；
Finally, one layer of Al cathode is deposited on ZnO electron transfer layer, light emitting diode with quantum dots is obtained.
Embodiment 2
1), Co adulterates the preparation of CuS: the sodium sulfide solution that 1 mL concentration is 0.1 M is slowly added into 100 mL chlorinations
Copper, sodium citrate, cobalt chloride mixed solution in, wherein the concentration of copper chloride is 1 mM, and the concentration of sodium citrate is 0.06
MM, the concentration of cobalt chloride are 0.01 mM.After mixing evenly, mixed solution is heated to 100 °C, reacts 20 min, obtains Co
Adulterate CuS nanoparticles solution.
2), the preparation step of QLED device is as follows:
The Co that spin coating a layer thickness is 10 nm on ITO substrate adulterates CuS film as hole injection layer；
One layer of PVK hole transmission layer of spin coating on Co doping CuS film；
Then, one layer of CdSe quantum dot luminescent layer of spin coating on PVK hole transmission layer；
Then, the spin coating layer of ZnO electron transfer layer on CdSe quantum dot luminescent layer；
Finally, one layer of Al cathode is deposited on ZnO electron transfer layer, light emitting diode with quantum dots is obtained.
Embodiment 3
1), Ni adulterates the preparation of CuS: the sodium sulfide solution that 1 mL concentration is 0.1 M is slowly added into 100 mL chlorinations
Copper, sodium citrate, nickel chloride mixed solution in, wherein the concentration of copper chloride is 1 mM, and the concentration of sodium citrate is 0.06
MM, the concentration of nickel chloride are 0.01 mM.After mixing evenly, mixed solution is heated to 100 °C, reacts 20 min, obtains Ni
Adulterate CuS nanoparticles solution.
2), the preparation step of QLED device is as follows:
The Ni that spin coating a layer thickness is 10 nm on ITO substrate adulterates CuS film as hole injection layer；
One layer of PVK hole transmission layer of spin coating on Ni doping CuS film；
Then, one layer of CdSe quantum dot luminescent layer of spin coating on PVK hole transmission layer；
Then, the spin coating layer of ZnO electron transfer layer on CdSe quantum dot luminescent layer；
Finally, one layer of Al cathode is deposited on ZnO electron transfer layer, light emitting diode with quantum dots is obtained.
Embodiment 4
1), Sb adulterates the preparation of CuS: the sodium sulfide solution that 1 mL concentration is 0.1 M is slowly added into 100 mL chlorinations
Copper, sodium citrate, antimony trichloride mixed solution in, wherein the concentration of copper chloride is 1 mM, and the concentration of sodium citrate is 0.06
MM, the concentration of antimony trichloride are 0.01 mM.After mixing evenly, mixed solution is heated to 100 °C, reacts 20 min, obtains
Sb adulterates CuS nanoparticles solution.
2), the preparation step of QLED device is as follows:
The Sb that spin coating a layer thickness is 10 nm on ITO substrate adulterates CuS film as hole injection layer；
One layer of PVK hole transmission layer of spin coating on Sb doping CuS film；
Then, one layer of CdSe quantum dot luminescent layer of spin coating on PVK hole transmission layer；
Then, the spin coating layer of ZnO electron transfer layer on CdSe quantum dot luminescent layer；
Finally, one layer of Al cathode is deposited on ZnO electron transfer layer, light emitting diode with quantum dots is obtained.
Embodiment 5
1) sodium sulfide solution that 1 mL concentration is 0.1 M, the preparation of Zn and Co codope CuS: is slowly added into 100
The copper chloride of mL, sodium citrate, zinc chloride, cobalt chloride mixed solution in, wherein the concentration of copper chloride is 1 mM, citric acid
The concentration of sodium is 0.06 mM, and chlorination zinc concentration is 0.01 mM, and the concentration of cobalt chloride is 0.01 mM.After mixing evenly, it will mix
It closes solution and is heated to 100 °C, react 20 min, obtain Zn and Co codope CuS nanoparticles solution.
2), the preparation step of QLED device is as follows:
Spin coating a layer thickness is Zn the and Co codope CuS film of 10 nm as hole injection layer on ITO substrate；
One layer of PVK hole transmission layer of spin coating on Zn and Co codope CuS film；
Then, one layer of CdSe quantum dot luminescent layer of spin coating on PVK hole transmission layer；
Then, the spin coating layer of ZnO electron transfer layer on CdSe quantum dot luminescent layer；
Finally, one layer of Al cathode is deposited on ZnO electron transfer layer, light emitting diode with quantum dots is obtained.
Embodiment 6
1), Zn adulterates the preparation of CuS: the sodium sulfide solution that 1 mL concentration is 0.1 M is slowly added into 100 mL chlorinations
Copper, sodium citrate, zinc chloride mixed solution in, wherein the concentration of copper chloride is 1 mM, and the concentration of sodium citrate is 0.06
MM, chlorination zinc concentration are 0.05 mM.After mixing evenly, mixed solution is heated to 100 °C, reacts 20 min, obtains Zn
Adulterate CuS nanoparticles solution.
2), the preparation step of QLED device is as follows:
The Zn that spin coating a layer thickness is 10 nm on ITO substrate adulterates CuS film as hole injection layer；
One layer of PVK hole transmission layer of spin coating on Zn doping CuS film；
Then, one layer of CdSe quantum dot luminescent layer of spin coating on PVK hole transmission layer；
Then, the spin coating layer of ZnO electron transfer layer on CdSe quantum dot luminescent layer；
Finally, one layer of Al cathode is deposited on ZnO electron transfer layer, light emitting diode with quantum dots is obtained.
Embodiment 7
1), Zn adulterates the preparation of CuS: the sodium sulfide solution that 1 mL concentration is 0.1 M is slowly added into 100 mL chlorinations
Copper, sodium citrate, zinc chloride mixed solution in, wherein the concentration of copper chloride is 1 mM, and the concentration of sodium citrate is 0.06
MM, chlorination zinc concentration are 0.1 mM.After mixing evenly, mixed solution is heated to 100 °C, reacts 20 min, obtains Zn and mix
Miscellaneous CuS nanoparticles solution.
2), the preparation step of QLED device is as follows:
The Zn that spin coating a layer thickness is 10 nm on ITO substrate adulterates CuS film as hole injection layer；
One layer of PVK hole transmission layer of spin coating on Zn doping CuS film；
Then, one layer of CdSe quantum dot luminescent layer of spin coating on PVK hole transmission layer；
Then, the spin coating layer of ZnO electron transfer layer on CdSe quantum dot luminescent layer；
Finally, one layer of Al cathode is deposited on ZnO electron transfer layer, light emitting diode with quantum dots is obtained.
Embodiment 8
1), Zn adulterates the preparation of CuS: the sodium sulfide solution that 1 mL concentration is 0.1 M is slowly added into 100 mL chlorinations
Copper, sodium citrate, zinc chloride mixed solution in, wherein the concentration of copper chloride is 1 mM, and the concentration of sodium citrate is 0.06
MM, chlorination zinc concentration are 0.25 mM.After mixing evenly, mixed solution is heated to 100 °C, reacts 20 min, obtains Zn
Adulterate CuS nanoparticles solution.
2), the preparation step of QLED device is as follows:
The Zn that spin coating a layer thickness is 10 nm on ITO substrate adulterates CuS film as hole injection layer；
One layer of PVK hole transmission layer of spin coating on Zn doping CuS film；
Then, one layer of CdSe quantum dot luminescent layer of spin coating on PVK hole transmission layer；
Then, the spin coating layer of ZnO electron transfer layer on CdSe quantum dot luminescent layer；
Finally, one layer of Al cathode is deposited on ZnO electron transfer layer, light emitting diode with quantum dots is obtained.
Embodiment 9
1), Zn adulterates the preparation of CuS: the sodium sulfide solution that 1 mL concentration is 0.1 M is slowly added into 100 mL chlorinations
Copper, sodium citrate, zinc chloride mixed solution in, wherein the concentration of copper chloride is 1 mM, and the concentration of sodium citrate is 0.06
MM, chlorination zinc concentration are 0.05 mM.After mixing evenly, mixed solution is heated to 100 °C, reacts 20 min, obtains Zn
Adulterate CuS nanoparticles solution.
2), the preparation step of QLED device is as follows:
The Zn that spin coating a layer thickness is 20 nm on ITO substrate adulterates CuS film as hole injection layer；
One layer of PVK hole transmission layer of spin coating on Zn doping CuS film；
Then, one layer of CdSe quantum dot luminescent layer of spin coating on PVK hole transmission layer；
Then, the spin coating layer of ZnO electron transfer layer on CdSe quantum dot luminescent layer；
Finally, one layer of Al cathode is deposited on ZnO electron transfer layer, light emitting diode with quantum dots is obtained.
In conclusion a kind of light emitting diode with quantum dots provided by the invention and preparation method thereof and illuminating module, display
Device, the present invention prepare hole injection layer to adulterate copper sulfide film, preferably adjust in a big way with this method
The band structure and carrier transmission performance for saving ITO surface work function, CuS, to improve the luminous efficiency of QLED device.Together
When, attachment of the doping metals sulfide on ITO can't change the surface roughness and translucency of ITO, and will not produce to ITO
Raw corrosion, effectively improves the stability and service life of QLED device.
It should be understood that the application of the present invention is not limited to the above for those of ordinary skills can
With improvement or transformation based on the above description, all these modifications and variations all should belong to the guarantor of appended claims of the present invention
Protect range.
Claims (8)
1. a kind of light emitting diode with quantum dots, which is characterized in that the light emitting diode with quantum dots successively includes anode, hole note
Enter layer, hole transmission layer, quantum dot light emitting layer, electron transfer layer and cathode；
Wherein, the hole injection layer is doping copper sulfide film；
The doping copper sulfide is that Cu adulterates copper sulfide, Co adulterates copper sulfide, Zn adulterates copper sulfide, Mg adulterates copper sulfide, Ni mixes
One of miscellaneous copper sulfide, Mn doping copper sulfide, Ho doping copper sulfide, In doping copper sulfide, Sb doping copper sulfide are a variety of.
2. light emitting diode with quantum dots according to claim 1, which is characterized in that the thickness of the doping copper sulfide film
For 1 ~ 50 nm.
3. light emitting diode with quantum dots according to claim 1, which is characterized in that the shape for adulterating copper sulfide film is ball
One of shape particle, sheet, rodlike, nano wire, reticular structure are a variety of.
4. light emitting diode with quantum dots according to claim 1, which is characterized in that the structure of the doping copper sulfide film
For compact texture or porous structure.
5. a kind of preparation method of the light emitting diode with quantum dots as described in claim 1 ~ 4 is any characterized by comprising
Step A, hole injection layer is prepared on anode；Wherein, the hole injection layer is doping copper sulfide film；
Step B, hole transmission layer is then prepared on hole injection layer；
Step C, quantum dot light emitting layer is then prepared on the hole transport layer；
Step D, electron transfer layer is finally prepared on quantum dot light emitting layer, and evaporation cathode is on electron transfer layer, forming amount
Sub- point luminescent diode；
The doping copper sulfide film is prepared using doping vulcanization copper solution, the preparation method of the doping vulcanization copper solution
Include: by sodium sulfide solution be added to copper chloride, sodium citrate, doped metal salt mixed solution in, after mixing evenly, will mix
It closes solution and is heated to 60 ~ 100 °C, react 10 ~ 120 min, obtain doping vulcanization copper solution.
6. the preparation method of light emitting diode with quantum dots according to claim 5, which is characterized in that the vulcanized sodium it is dense
Degree is 0.1 ~ 1 M, and 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.
7. a kind of illuminating module, which is characterized in that the illuminating module includes such as the described in any item quantum dots of claim 1 ~ 4
Light emitting diode.
8. a kind of display device, which is characterized in that the display device includes illuminating module as claimed in claim 7.
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 |
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| 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 |
| CN109390476B (en) * | 2017-08-02 | 2020-11-17 | Tcl科技集团股份有限公司 | QLED device with graphene oxide interface layer and preparation method thereof |
| CN110660926B (en) * | 2018-06-28 | 2021-06-04 | Tcl科技集团股份有限公司 | Transparent conductive film and preparation method and application thereof |
| CN108922984B (en) * | 2018-07-26 | 2021-04-16 | 京东方科技集团股份有限公司 | Display panel, preparation method thereof and display device |
| 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 |
| 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 |
| CN113258009B (en) * | 2020-04-17 | 2022-08-05 | 广东聚华印刷显示技术有限公司 | Composite material and preparation method thereof, and quantum dot light-emitting diode |
| 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 |
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