CN105720206A - QLED device and preparation method thereof - Google Patents
QLED device and preparation method thereof Download PDFInfo
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- CN105720206A CN105720206A CN201610298352.9A CN201610298352A CN105720206A CN 105720206 A CN105720206 A CN 105720206A CN 201610298352 A CN201610298352 A CN 201610298352A CN 105720206 A CN105720206 A CN 105720206A
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/324—Thermal treatment for modifying the properties of semiconductor bodies, e.g. annealing, sintering
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- 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
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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Abstract
The invention provides a QLED device and a preparation method thereof. The preparation method of the QLED device comprises the following steps: providing a substrate, and forming a bottom electrode on the substrate; depositing an electron transmission material on the bottom electrode, and carrying out the RTP treatment on the electron transmission material to obtain an electron transmission layer; depositing an interface decorative material on the electron transmission layer to form an interface decorative layer, wherein the interface decorative material is a material with a permanent dipole moment; and successively depositing a quantum dot luminescent layer and a top electrode on the interface decorative layer.
Description
Technical field
The invention belongs to Display Technique field, particularly relate to a kind of QLED device and preparation method thereof.
Background technology
Quantum dot has that glow peak is narrow, quantum yield advantages of higher, prepare plus available typography, so be recently subject to the common concern of people based on the light emitting diode (i.e. light emitting diode with quantum dots: QLED) of quantum dot, its device performance index also quickly grows.
In order to improve the injection efficiency of electronics, generally electron transfer layer is set between the negative electrode of QLED device and quantum dot light emitting layer.Existing electron transport material, all can improve the injection efficiency of electronics, to a certain extent thus improving electron mobility.Particularly nano zine oxide, as electron transport material commonly used in QLED device, its conduction level is conducive to electronics injection from negative electrode to quantum dot, and its deeper valence-band level can play the effect effectively stopping hole.But, how the photoelectric characteristic relative deficiency of existing electron transport material such as nano zine oxide, therefore, improve the photoelectric characteristic of electron transport material such as nano zine oxide further thus the luminous efficiency improving QLED device is an emphasis of research at present.
At present, when electron transfer layer is prepared in solution processing, the preparation of electron transport material such as nano zine oxide is generally adopted the sol-gel process of low temperature, the nano material thus obtained such as nano zine oxide, its degree of crystallinity is relatively low, there is substantial amounts of fault of construction such as room, dislocation etc., and these faults of construction become the radiationless complex centre of exciton, thus reducing transporting and the light transmission of device, affect the luminous efficiency of QLED.It addition, the conduction level of existing electron transport material such as nano zine oxide is low not enough, so its injection efficiency particularly injection efficiency in blue-light device is not highly effective.
Summary of the invention
The preparation method that it is an object of the invention to provide a kind of QLED device, it is intended to solve the electron transport material particularly nano zine oxide of preparation of existing low-temperature sol-gel method owing to degree of crystallinity is relatively low, fault of construction is more, cause the transporting of electron transfer layer and the problem that light transmission is limited.
Another object of the present invention is to provide a kind of QLED device prepared by said method.
The preparation method that the present invention is achieved in that a kind of QLED device, comprises the following steps:
One substrate is provided, forms hearth electrode over the substrate；
Described hearth electrode deposits electron transport material, described electron transport material is carried out RTP process, obtains electron transfer layer；
Deposition interface decorative material forms interface-modifying layer on the electron transport layer, and described modifying interface material is the material with permanent dipole moment；
Described interface-modifying layer is sequentially depositing quantum dot light emitting layer and top electrode.
And, a kind of QLED device, described QLED device prepares according to the method described above, including the substrate set gradually, hearth electrode, electron transfer layer, interface-modifying layer, quantum dot light emitting layer and top electrode.
The preparation method of QLED device provided by the invention, by electron transport material such as nano zine oxide in described QLED device is carried out RTP process thus improving its degree of crystallinity, reduce the fault of construction of described electric transmission material, and then improve transporting and the light transmission of described electron transfer layer.And the present invention adopts the electric transmission layer film that the preparation of RTP method is fine and close, compare that traditional heat treatment method energy consumption is low, the time is short, be also more suited for the large-scale typographical display technology of low cost.Additionally, by introducing the interface-modifying layer with permanent dipole moment at the interface of described electron transfer layer and described quantum dot light emitting layer, on the one hand, the setting of described interface-modifying layer, the surface potential of described electron transfer layer can be improved, thus improving the Injection Level of electronics；On the other hand, owing to the surface defect of traditional electron transport material is more, and it is limited after all to adopt RTP process to carry out the ability of surface defect improvement, therefore, finishing is carried out by introducing described interface-modifying layer on the electron transport layer, the effect being passivated described electron transport material surface defect can being played, thus reducing the surface defect compound to the cancellation of exciton and carrier herein, and then being effectively improved the luminous efficiency of described QLED device.The present invention, adopting RTP to process on the basis preparing described electron transfer layer, introduces interface-modifying layer, it is possible to be effectively improved the overall performance of described QLED device time on the electron transport layer.
Described QLED device provided by the invention, its electron transfer layer processes technique by RTP and is prepared from, and the interface of described electron transfer layer and described quantum dot light emitting layer is provided with the interface-modifying layer with permanent dipole moment simultaneously.On the one hand, the degree of crystallinity of electron transport layer materials of the present invention improves, by increasing capacitance it is possible to increase carrier mobility, improves transmission performance and the light transmission of QLED device；On the other hand, the double-decker of electron transfer layer/interface-modifying layer, it is possible to improve the electron transport ability of electron transport material, light transmittance and interface energy level structure further, and then improve the luminescent properties of QLED device, the especially luminescent properties of blue-light device.
Accompanying drawing explanation
Fig. 1 is the QLED device architecture schematic diagram that the embodiment of the present invention provides；
Fig. 2 is the QLED device architecture schematic diagram with hole transmission layer that the embodiment of the present invention provides；
Fig. 3 is the surface potential figure of the electron transfer layer after the introducing interface-modifying layer that the embodiment of the present invention 3 provides；
Fig. 4 is the surface potential figure of the electron transfer layer being not introduced into interface-modifying layer that comparative example 2 of the present invention provides.
Detailed description of the invention
In order to make the technical problem to be solved in the present invention, technical scheme and beneficial effect clearly understand, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein is only in order to explain the present invention, is not intended to limit the present invention.
The preparation method embodiments providing a kind of QLED device, comprises the following steps:
S01., one substrate is provided, forms hearth electrode over the substrate；
S02. on described hearth electrode, deposit electron transport material, described electron transport material is carried out RTP process, obtains electron transfer layer；
S03. deposition interface decorative material forms interface-modifying layer on the electron transport layer, and described modifying interface material is the material with permanent dipole moment；
S04. on described interface-modifying layer, it is sequentially depositing quantum dot light emitting layer and top electrode.
Concrete, in above-mentioned steps S01, the selection of described substrate is unrestricted, it is possible to select flexible substrate, it is also possible to select hard substrates, such as glass substrate.The method forming hearth electrode over the substrate can adopt this area conventional method to realize, such as vacuum evaporation.
In above-mentioned steps S02, be different from the preparation of electron transfer layer of routine, the embodiment of the present invention described state hearth electrode deposits electron transport material after, described electron transport material is carried out RTP process (rapid thermal treatment).Concrete, described RTP processes the heat treatment mode very fast for a kind of programming rate, annealing temperature is higher and temperature retention time is very short, prepares described electron transfer layer by the method, not only deposited other good Rotating fields will not be made and performance becomes to destroy；And by described RTP process, it is possible to improving the degree of crystallinity of described electron transport material, reduce the surface texture defect of described electric transmission material, thus obtaining the fine and close electron transfer layer of high mobility, high light transmittance, improving the light output efficiency of described QLED device.As the presently preferred embodiments, the method that described RTP processes is: in 5-10s, temperature being risen to annealing temperature, then carry out isothermal holding and temperature retention time≤3min, concrete, described temperature retention time can be 20s, 30s, 40s, 50s etc.；It is furthermore preferred that the time of described isothermal holding is 20-30s.Herein, it is to be understood that, described annealing temperature be different from prior heat treatment heating-up temperature (same material be heated process temperature relatively low, and annealing temperature is higher), it can be set according to the character of each electron transport material, can up to 300-500 DEG C, such as, when described electron transport material selects nano zine oxide, described annealing temperature is chosen as 300 DEG C (in order to avoid heating-up temperature when causing damage, prior heat treatment to prepare nano zine oxide electron transfer layer other Rotating fields is generally 150 DEG C).Further, the heating rate that described RTP processes is advisable with the speed lower than 100 DEG C/s.Additionally, in the embodiment of the present invention, the atmosphere that described RTP processes includes vacuum, nitrogen atmosphere, air atmosphere, oxygen atmosphere and atmosphere of hydrogen etc., more preferably air atmosphere.
In the embodiment of the present invention, adopt described RTP to process the electron transport material preparing described electron transfer layer and include the one in metal-oxide, blended metal oxide, 2-6 race semi-conducting material, 3-5 race semi-conducting material, 1-3-6 race semi-conducting material.Concrete, described metal-oxide includes but not limited to zinc oxide, titanium oxide；Metal-oxide in described blended metal oxide includes but not limited to zinc oxide, titanium oxide, and doped chemical includes but not limited at least one in aluminum, magnesium, indium, gallium；Described 2-6 semiconductor family material includes but not limited to ZnS, ZnSe, CdS；Described 3-5 semiconductor family material includes but not limited to InP, GaP；Described 1-3-6 race semi-conducting material includes but not limited to CuInS, CuGaS.As most preferred embodiment, described electron transport material is nano zine oxide.Post-depositional nano zine oxide is carried out described RTP process, can more effectively improve its degree of crystallinity, reduce the impact that transporting and the light transmission of described electron transfer layer are brought by surface texture defect, so that the nano zine oxide electron transfer layer obtained has better performance.
In above-mentioned steps S03, after described electron transport material is carried out described RTP process, it is additionally included on described electron transfer layer and deposits the modifying interface material with permanent dipole moment forms interface-modifying layer.On the one hand, described modifying interface material is owing to having permanent dipole moment, it is possible to improve the surface potential of described electron transfer layer.And surface potential is as the built in field of described QLED, the surface potential increased can improve electronics active force in built in field, thus accelerating transmission, and hole is here subject to electric field action and is prevented from, and thus reaches the purpose improved electronics Injection Level, stop hole transport simultaneously.On the other hand, introduce described interface-modifying layer on the electron transport layer and carry out finishing, the effect being passivated described electron transport material surface defect can be played, thus reducing the surface defect compound to the cancellation of exciton and carrier herein, and then it is effectively improved the luminous efficiency of described QLED device.As the presently preferred embodiments, described modifying interface material is PFN (poly-[9,9-bis-(3 '-(N, N-dimethylamino) propyl group)-2,7-fluorenes]-2,7-(9,9-dioctyl fluorene))]), PEG (Polyethylene Glycol), PEIE (polyethoxy aziridine), at least one in CPE (conjugated polymers electrolyte), PEO (polyethylene glycol oxide).
In above-mentioned steps S04, the mode being sequentially depositing quantum dot light emitting layer on described interface-modifying layer does not have considered critical, it is possible to adopt solution processing mode to realize, such as ink jet printing.The material of described quantum dot light emitting layer also can be selected for the quanta point material that this area is conventional.Described quantum dot light emitting layer deposits the mode step restriction of described top electrode, it is possible to adopt this area conventional method to realize, such as vacuum evaporation.
As the presently preferred embodiments, before depositing described top electrode, at least one of which of deposition of hole transport layer, hole injection layer is also included.
The preparation method of the QLED device that the embodiment of the present invention provides, by electron transport material such as nano zine oxide in described QLED device is carried out RTP process thus improving its degree of crystallinity, reduce the fault of construction of described electric transmission material, and then improve transporting and the light transmission of described electron transfer layer.And the embodiment of the present invention adopts the electric transmission layer film that the preparation of RTP method is fine and close, compare that traditional heat treatment method energy consumption is low, the time is short, be also more suited for the large-scale typographical display technology of low cost.Additionally, by introducing the modifying interface material with permanent dipole moment at the interface of described electron transfer layer and described quantum dot light emitting layer, on the one hand, the setting of described interface-modifying layer, the surface potential of described electron transfer layer can be improved, thus improving the Injection Level of electronics；On the other hand, owing to the surface defect of traditional electron transport material is more, and it is limited after all to adopt RTP process to carry out the ability of surface defect improvement, therefore, finishing is carried out by introducing described interface-modifying layer on the electron transport layer, the effect being passivated described electron transport material surface defect can being played, thus reducing the surface defect compound to the cancellation of exciton and carrier herein, and then being effectively improved the luminous efficiency of described QLED device.The embodiment of the present invention, adopting RTP to process on the basis preparing described electron transfer layer, introduces interface-modifying layer, it is possible to be effectively improved the overall performance of described QLED device time on the electron transport layer.
And, in conjunction with Fig. 1,2, the embodiment of the present invention additionally provides a kind of QLED device, and described QLED device prepares according to the method described above, including the substrate 1 set gradually, hearth electrode 2, electron transfer layer 3, interface-modifying layer 4, quantum dot light emitting layer 5 and top electrode 7, as shown in Figure 1.
Concrete, electron transfer layer 3 described in the embodiment of the present invention is the described RTP electron transfer layer processed, and therefore, it has high mobility and high light transmittance.The material of described electron transfer layer 3 as described above, in order to save length, repeats no more herein.
Described interface-modifying layer 4 is made up of the modifying interface material with permanent dipole moment.The introducing of described interface-modifying layer 4, can not only improve the surface potential of described electron transfer layer, improves the Injection Level of electronics；And the surface defect of described electron transport material can be passivated, reduce the surface defect compound to the cancellation of exciton and carrier herein, and then be effectively improved the luminous efficiency of described QLED device.
As it is preferred that embodiment, described QLED device also includes at least one of which in hole injection layer (not marking in figure), hole transmission layer 6.Of course it is to be understood that when described hole transmission layer 6 has the function of hole injection and transmission simultaneously, described hole transmission layer 6 can be only set and realize the function of electronics injection and electric transmission simultaneously.
As a particular preferred embodiment, as in figure 2 it is shown, described QLED device prepares according to the method described above, including the substrate 1 set gradually, hearth electrode 2, electron transfer layer 3, interface-modifying layer 4, quantum dot light emitting layer 5, electron transfer layer 6 and top electrode 7.
The described QLED device that the embodiment of the present invention provides, its electron transfer layer processes technique by RTP and is prepared from, and the interface of described electron transfer layer and described quantum dot light emitting layer is provided with the interface-modifying layer with permanent dipole moment simultaneously.On the one hand, the degree of crystallinity of described electron transport layer materials improves, by increasing capacitance it is possible to increase carrier mobility, improves transmission performance and the light transmission of QLED device；On the other hand, the double-decker of described electron transfer layer/interface-modifying layer, the electron transport ability of electron transport material, light transmittance and interface energy level structure be can improve further, and then the luminescent properties of QLED device, the especially luminescent properties of blue-light device improved.
Below, it is illustrated in connection with specific embodiments.
Embodiment 1
The preparation method of a kind of QLED device, comprises the following steps:
S11., one substrate is provided, forms hearth electrode over the substrate；
S12. depositing nano zine oxide on described hearth electrode, described nano zine oxide is carried out RTP process, obtains electron transfer layer, wherein, the mode that described RTP processes is 300 DEG C of isothermal holding 30s in air；
S13. deposition interface decorative material forms interface-modifying layer on the electron transport layer, and described modifying interface material is the material with permanent dipole moment；
S14. on described interface-modifying layer, it is sequentially depositing quantum dot light emitting layer, hole transmission layer and top electrode.
Embodiment 2
The preparation method of a kind of QLED device, its method and embodiment 1 are different in that, prepare in the step of electron transfer layer, and the mode that described RTP processes is 300 DEG C of isothermal holding 30s in vacuum.
Comparative example 1
The preparation method of a kind of QLED device, comprises the following steps:
D11., one substrate is provided, forms hearth electrode over the substrate；
D12. depositing nano zine oxide on described hearth electrode, be heated described nano zine oxide processing, obtain electron transfer layer, wherein, the heating-up temperature of described heat treated is 150 DEG C, and heat time heating time is 15min；
D13. on described interface-modifying layer, it is sequentially depositing quantum dot light emitting layer, hole transmission layer and top electrode.
Electron transfer layer called after 1,2,3 successively of QLED device comparative example 1, embodiment 1-2 second step prepared, measure the electron mobility of each electron transfer layer, and result is as shown in table 1 below:
Table 1
As seen from the above table, compared with traditional heat treatment method, electron transfer layer after RTP described in the embodiment of the present invention processes, its mobility is improved, particularly in carrying out the electron transfer layer after RTP process in air atmosphere, its mobility is nearly 5 times of the electron transfer layer that prior heat treatment obtains.
Embodiment 3
The preparation method of a kind of QLED device, comprises the following steps:
S31., one substrate is provided, forms hearth electrode over the substrate；
S32. after depositing electron transport material on described hearth electrode, described electron transport material being carried out RTP process, obtains electron transfer layer, wherein, described electron transport material is nano zine oxide；
S33. deposition interface decorative material forms interface-modifying layer on the electron transport layer, and described modifying interface material is the PFN with permanent dipole moment；
S34. on described interface-modifying layer, it is sequentially depositing quantum dot light emitting layer, hole transmission layer and top electrode.
Comparative example 2
The preparation method of a kind of QLED device, its method and embodiment 3 are different in that, Direct precipitation quantum dot light emitting layer on the electron transport layer.
The surface potential of the electron transfer layer of QLED device prepared by test above-described embodiment 3, comparative example 2, result is respectively as shown in Figure 3, Figure 4.As seen from the figure, after introducing modifying interface material PFN on the electron transport layer, the surface potential of described electron transfer layer improves 130mV, thus being conducive to the injection of electronics and the stop in hole.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all any amendment, equivalent replacement and improvement etc. made within the spirit and principles in the present invention, should be included within protection scope of the present invention.
Claims (10)
1. a preparation method for QLED device, comprises the following steps:
One substrate is provided, forms hearth electrode over the substrate；
Described hearth electrode deposits electron transport material, described electron transport material is carried out RTP process, obtains electron transfer layer；
Deposition interface decorative material forms interface-modifying layer on the electron transport layer, and described modifying interface material is the material with permanent dipole moment；
Described interface-modifying layer is sequentially depositing quantum dot light emitting layer and top electrode.
2. the preparation method of QLED device as claimed in claim 1, it is characterised in that the method that described RTP processes is: in 5-10s, temperature is risen to annealing temperature, then carries out isothermal holding and temperature retention time≤3min.
3. the preparation method of QLED device as claimed in claim 2, it is characterised in that the time of described isothermal holding is 20-30s.
4. the preparation method of QLED device as claimed in claim 1, it is characterised in that described electron transport material is the one in metal-oxide, blended metal oxide, 2-6 race semi-conducting material, 3-5 race semi-conducting material, 1-3-6 race semi-conducting material.
5. the preparation method of QLED device as claimed in claim 4, it is characterised in that described metal-oxide is zinc oxide or titanium oxide；And/or
Metal-oxide in described blended metal oxide is zinc oxide or titanium oxide, and doped chemical is at least one in aluminum, magnesium, indium, gallium；And/or
Described 2-6 semiconductor family material is ZnS, ZnSe or CdS；And/or
Described 3-5 semiconductor family material is InP or GaP；And/or
Described 1-3-6 race semi-conducting material is CuInS or CuGaS.
6. the preparation method of QLED device as claimed in claim 5, it is characterised in that described electron transport material is nano zine oxide.
7. the preparation method of the QLED device as described in as arbitrary in claim 1-6, it is characterised in that described modifying interface material is at least one in PFN, PEG, PEIE, CPE, PEO.
8. the preparation method of the QLED device as described in as arbitrary in claim 1-6, it is characterised in that before depositing described top electrode, also include at least one of which of deposition of hole transport layer, hole injection layer.
9. a QLED device, it is characterised in that described QLED device prepares according to the arbitrary described method of claim 1-7, including the substrate set gradually, hearth electrode, electron transfer layer, interface-modifying layer, quantum dot light emitting layer and top electrode.
10. QLED device as claimed in claim 9, it is characterised in that also include at least one of which in hole injection layer, hole transmission layer.
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