CN106856228A - A kind of QLED devices and preparation method thereof - Google Patents
A kind of QLED devices and preparation method thereof Download PDFInfo
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- CN106856228A CN106856228A CN201611225783.9A CN201611225783A CN106856228A CN 106856228 A CN106856228 A CN 106856228A CN 201611225783 A CN201611225783 A CN 201611225783A CN 106856228 A CN106856228 A CN 106856228A
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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- 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
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Abstract
The present invention discloses a kind of QLED devices and preparation method thereof, and the QLED devices are column structure, and the QLED devices include internal layer electrode, functional layer and outer electrode successively from inside to outside.The present invention carries out structure improvement and optimization to traditional stratiform QLED device architectures, forms the QLED devices of column structure, by column structure come equilbrium carrier charge velocity, so that device light emitting efficiency is improved, while column structure can also improve out device light emission rate.
Description
Technical field
The present invention relates to display technology field, more particularly to a kind of QLED devices and preparation method thereof.
Background technology
It is the main of current New LED research using quanta point material as the light emitting diode with quantum dots (QLED) of luminescent layer
One of direction, has the advantages that light excitation is high, luminous quantum efficiency is high, glow color is adjustable, long service life, and in illumination
And flat display field has broad application prospects.It is external quantum efficiency to characterize one of main parameter of QLED devices, its
Influence factor mainly has following：(1) injection balance in electronics, hole；(2) recombination velocity in electronics, hole；(3) amount in
Sub- efficiency；(4) light extraction efficiency.Wherein, electronics, the injection balance in hole use the longevity for improving external quantum efficiency and extending it
Life is more crucial, but existing QLED devices, and its electronics, the injection balance in hole still have much room for improvement, i.e., existing QLED devices
The performance of carrier charge velocity is simultaneously uneven.
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 QLED devices and preparation method thereof,
Aim to solve the problem that the problem that the electronics of existing QLED devices, the injection balance in hole still have much room for improvement.
Technical scheme is as follows：
A kind of QLED devices, wherein, the QLED devices are column structure, and the QLED devices include internal layer successively from inside to outside
Electrode, functional layer and outer electrode.
Described QLED devices, wherein, the functional layer includes successively from inside to outside：Electron transfer layer, quantum dot light emitting
Layer, hole transmission layer, hole injection layer.
Described QLED devices, wherein, the functional layer includes successively from inside to outside：Hole injection layer, hole transmission layer,
Quantum dot light emitting layer, electron transfer layer.
Described QLED devices, wherein, the material of the electron transfer layer is ZnO, TiO2, SnO, AlZnO, ZnSnO and
One or more in InSnO.
Described QLED devices, wherein, the material of the hole injection layer is PEDOT:PSS, molybdenum oxide, vanadium oxide, oxygen
Change one or more in tungsten and chromium oxide.
Described QLED devices, wherein, the material of the hole transmission layer is Poly-THX, TFB, PVK, CBP and TCTA
In one or more.
Described QLED devices, wherein, the quantum dot in described quantum dot light emitting layer is Binary-phase quantum dot, ternary phase
Quantum dot or quaternary phase quantum dot；The Binary-phase quantum dot is in CdS, CdSe, CdTe, InP, AgS, PbS, PbSe, HgS
One or more, the ternary phase quantum dot is ZnxCd1-xS、CuxIn1-xS、ZnxCd1-xSe、ZnxSe1-xS、ZnxCd1-xTe、
PbSexS1-xIn one or more, the quaternary phase quantum dot be ZnxCd1-xS/ZnSe、CuxIn1-xS/ZnS、ZnxCd1-xSe/
ZnS、CuInSeS、ZnxCd1-xTe/ZnS、 PbSexS1-xOne or more in/ZnS.
A kind of preparation method of QLED devices as described above, wherein, including step：
A, the internal layer electrode that column is first deposited on substrate；
B and then in internal layer electrode surface deposit functional layers；
C, it is last deposit outer electrode in function layer surface, be then packaged and obtain QLED devices.
The preparation method of described QLED devices, wherein, the step A is specifically included：
A1, perforated membrane is transplanted on substrate；
The internal layer electrode of column is deposited in A2, the duct on the perforated membrane；
A3, the duct to the perforated membrane carry out expanding treatment, the duct aperture of the perforated membrane is become big.
The preparation method of described QLED devices, wherein, the perforated membrane is porous anodic alumina films.
Beneficial effect：The present invention carries out structure improvement and optimization to traditional stratiform QLED device architectures, forms column structure
QLED devices, by column structure come equilbrium carrier charge velocity, so as to improve device light emitting efficiency, while column structure
Also device light emission rate can be improved out.
Brief description of the drawings
Fig. 1 is a kind of the first viewing angle constructions schematic diagram of QLED devices preferred embodiment of the invention.
Fig. 2 is a kind of the second viewing angle constructions schematic diagram of QLED devices preferred embodiment of the invention.
Fig. 3 is a kind of flow chart of the preparation method preferred embodiment of QLED devices of the invention.
Fig. 4 is a kind of structural representation of QLED devices specific embodiment one of the invention.
Fig. 5 is a kind of structural representation of QLED devices specific embodiment two of the invention.
Specific embodiment
The present invention provides a kind of QLED devices and preparation method thereof, to make the purpose of the present invention, technical scheme and effect more
Plus it is clear, clear and definite, the present invention is described in more detail below.It should be appreciated that specific embodiment described herein is only used
To explain the present invention, it is not intended to limit the present invention.
A kind of QLED devices preferred embodiment of the present invention, as depicted in figs. 1 and 2, the QLED devices are column structure, institute
State QLED devices includes internal layer electrode 10, functional layer 11 and outer electrode 12 successively from inside to outside.
The present invention is a kind of QLED devices of new structure, and it is theed improvement is that, by traditional stratiform QLED device architectures
Column structure is improved to, by column structure come equilbrium carrier charge velocity, to improve device light emitting efficiency, column knot in addition
The QLED devices of structure can also improve out device light emission rate, and on the whole, its external quantum efficiency of QLED devices of the invention is relative to layer
Shape QLED devices, improve a lot, while device service life can also be extended.
In the present invention, because QLED devices are column structure, so QLED device layers are column structure, and each layer from
It is interior to surrounding successively outward.
According to the difference of QLED device architectures, the structure of the functional layer 11 is also different.
Specifically, the functional layer 11 includes successively from inside to outside：Electron transfer layer, quantum dot light emitting layer, hole transport
Layer, hole injection layer, the QLED devices with above-mentioned functions layer 11 are eurymeric QLED devices.Can also as needed increase electricity in addition
Sub- implanted layer, i.e., the functional layer 11 includes successively from inside to outside on the whole：Electron injecting layer, electron transfer layer, quantum dot hair
Photosphere, hole transmission layer, hole injection layer.
In addition, the functional layer 11 can also be following structure：Include hole injection layer, hole transport successively from inside to outside
Layer, quantum dot light emitting layer, electron transfer layer, the QLED devices with above-mentioned functions layer 11 are transoid QLED devices.May be used also in addition
Increase electron injecting layer as needed, i.e., the functional layer 11 includes successively from inside to outside on the whole：Hole injection layer, hole pass
Defeated layer, quantum dot light emitting layer, electron transfer layer, electron injecting layer.
Specifically, the material of the electron transfer layer is preferably ZnO, TiO2, in SnO, AlZnO, ZnSnO and InSnO
One or more.The ZnO is preferably N-shaped ZnO, and it has electronic transmission performance high.The thickness of the electron transfer layer is excellent
Elect 10-100nm as, its preferably thickness is 30-60nm, such as 40nm.
Specifically, the material of the hole injection layer is preferably PEDOT:PSS, molybdenum oxide, vanadium oxide, tungsten oxide and oxygen
Change one or more in chromium.The thickness of the hole injection layer is preferably 10-150nm, such as 75nm.
Specifically, the material of the hole transmission layer is preferably the one kind in Poly-THX, TFB, PVK, CBP and TCTA
Or it is various.The thickness of the hole transmission layer is 1-150nm, such as preferably 40-50nm, 45nm.
Specifically, the quantum dot in described quantum dot light emitting layer is Binary-phase quantum dot, ternary phase quantum dot or quaternary
Phase quantum dot；The Binary-phase quantum dot is one or more in CdS, CdSe, CdTe, InP, AgS, PbS, PbSe, HgS,
The ternary phase quantum dot is ZnxCd1-xS、CuxIn1-xS、ZnxCd1-xSe、ZnxSe1-xS、ZnxCd1-xTe、PbSexS1-xIn one
Plant or several, the quaternary phase quantum dot is ZnxCd1-xS/ZnSe、CuxIn1-xS/ZnS、ZnxCd1-xSe/ZnS、CuInSeS、
ZnxCd1-xTe/ZnS、 PbSexS1-xOne or more in/ZnS.The thickness of the quantum dot light emitting layer is preferably 10-
100nm, such as 50nm.
Specifically, the material of the electron injecting layer is CsF, LiF or CsCO3Deng compound.The electron injecting layer
Thickness is preferably 10-150nm, such as such as 50-80nm, 65nm.
The internal layer electrode 10 is preferably metal electrode, such as described internal layer electrode is Al, Ag, Au or its alloy.
The outer electrode 12 is preferably ITO or IZO electrodes, or other transparency electrodes.
The present invention also provides a kind of preparation method of QLED devices as described above, as shown in figure 3, it includes step：
S1, the internal layer electrode that column is first deposited on substrate；
S2 and then in internal layer electrode surface deposit functional layers；
S3, it is last deposit outer electrode in function layer surface, be then packaged and obtain QLED devices.
In the step S1, the internal layer electrode of column is first deposited on substrate；The substrate is glass substrate, flexibility
Substrate or metal substrate.Using before substrate, first substrate is cleaned, ultra-pure water, acetone and different are such as placed in order
It is cleaned by ultrasonic in propyl alcohol.Treat after the completion of ultrasound to dry up substrate nitrogen gun standby.
The step S1 is specifically included：
S11, perforated membrane is transplanted on substrate；
The internal layer electrode of column is deposited in S12, the duct on the perforated membrane；
S13, the duct to the perforated membrane carry out expanding treatment, the duct aperture of the perforated membrane is become big.
I.e. the present invention is the internal layer electrode that column is first deposited using the duct of perforated membrane；After the pillared internal layer electrode of shape,
Expanding treatment is carried out to corresponding duct, so that duct becomes big, such duct is relative to the internal layer electrode for depositing before, aperture
Become big, there is certain space, follow-up functional layer and outer electrode between the inner side in duct and the outside of internal layer electrode
Deposition space is there has been, the deposition of each layer is smoothly completed.In addition, the present invention is preferably has deposited one layer afterwards every, just carry out
Expanding treatment, the aperture of reaming（Refer both to diameter）Be 2 times of next layer of thickness, such as after having deposited internal layer electrode,
Assuming that to deposit electron transfer layer, then deposition internal layer electrode just carries out expanding treatment, and the aperture of reaming is electric transmission thickness
2 times of degree, so just can just deposit the electron transfer layer of required thickness, and expanding treatment, such as next step are then carried out again
Deposition quantum dot light emitting layer, then the aperture of reaming is 2 times of quantum dot light emitting layer thickness, so just can just be deposited required
The quantum dot light emitting layer of thickness, the like, current layer has often been deposited, expanding treatment is just carried out, the aperture of reaming is next layer
2 times of thickness.
Perforated membrane therein is preferably porous anodic alumina films, has multiple on the porous anodic alumina films surface
Duct, duct is preferably shaped to column, to deposit the internal layer electrode of column.The aperture in duct be preferably 50 ~ 500nm,
The spacing in duct is preferably 500 ~ 1500nm, the hole depth in duct is preferably 50 ~ 400nm.In addition, the perforated membrane can pass through
PMMA film is transplanted, i.e., first substrate is cleaned, then the deionized water in drop on substrate, then by with perforated membrane
PMMA film is adsorbed in substrate surface, then removes PMMA film with acetone solvent, and such perforated membrane has just been transplanted on substrate.Heavy
Accumulate after internal layer electrode, weak acid treatment porous film surface can have been used, unnecessary electrode material outside removal duct.
Internal layer electrode therein is metal electrode, and such as internal layer electrode is Al, Ag, Au or its alloy.
In the step S2, produce functional layer, according to the difference of QLED structures, can internal layer electrode surface from it is interior to
It is sequentially depositing electron transfer layer, quantum dot light emitting layer, hole transmission layer, hole injection layer outward；Also can internal layer electrode surface from
It is interior to hole injection layer, hole transmission layer, quantum dot light emitting layer, electron transfer layer is sequentially depositing outward, electronics can be also increased in addition
Implanted layer, then internal layer electrode surface be sequentially depositing from inside to outside electron injecting layer, electron transfer layer, quantum dot light emitting layer,
Hole transmission layer, hole injection layer, or include successively from inside to outside on internal layer electrode surface：Hole injection layer, hole transport
Layer, quantum dot light emitting layer, electron transfer layer, electron injecting layer.
In the step S3, outer electrode is deposited in the function layer surface for having deposited, outer electrode therein is ITO
Or IZO electrodes, or other transparency electrodes.
Embodiment one：The preparation of eurymeric QLED devices
(1) glass substrate is cleaned, is placed in order in ultra-pure water, acetone and isopropanol and is cleaned by ultrasonic.Wait to surpass
It is after the completion of sound that glass substrate is standby with nitrogen gun drying.
(2) porous anodic aluminium oxide (AAO) film is transplanted in glass substrate by PMMA film, the aperture in AAO fenestras road
（Diameter）For 200nm, duct spacing for 1000nm, duct hole depth be 200nm.
(3) glass substrate is transferred to settling chamber, vacuum suction in settling chamber's is dropped to 10-6After holding in the palm or being lower,
The metal Al internal layer electrodes 20 of column are deposited in AAO fenestras road, as shown in Figure 4.
(4) AAO films surface is processed with weak acid, unnecessary metal Al internal layer electrodes 20 outside removal duct, and AAO
Film makes AAO fenestras road borehole enlargement to 300nm to row expanding treatment.Specifically, CuCl can be used2Or FeCl3Immersion 10
Minute, to remove unnecessary metal Al internal layer electrodes 20, reuse the dilute phosphoric acid solution immersion 2 that mass percent is 4% small
When, to row expanding treatment, to make the borehole enlargement in AAO fenestras road to 300nm, i.e. borehole enlargement 100nm to AAO films, expand
Space be to deposit the thick functional layer of next layer of 50nm.
(5) and then drying and processing is carried out（Drying temperature is preferably 80 DEG C, and drying time is preferably 1 hour）, after treatment again
It is secondary to be transferred into settling chamber, and vacuum suction in settling chamber's is dropped to 10-6After holding in the palm or being lower, one is deposited in the duct for expanding
Layer 50nm thick ZnO electron transfer layers 21, the ZnO electron transfer layers 21 can be deposited on the surface of metal Al internal layer electrodes 20.Due to
The borehole enlargement in duct 100nm before, so the thickness of the ZnO electron transfer layers 21 of this step deposition is just 50nm.
After having deposited ZnO electron transfer layers 21, then expanding treatment is carried out, so that the borehole enlargement in duct, to deposit next layer
Functional layer, such as next layer be CdSe/ZnS quantum dot light emitting layers 22, its thickness be 40nm, then need to arrive borehole enlargement
380nm, that is, expand 80nm, is 2 times of the thickness of CdSe/ZnS quantum dot light emitting layers 22.
(6) repeat step (4) and (5), be sequentially depositing one layer of CdSe/ZnS quantum dot light emitting layer 22 of 40nm, one
The TFB hole transmission layers 23 of layer 50nm, one layer of PEDOT hole injection layers 24 and one layer of ITO outer electrode of 80nm of 50nm
25.In addition it should be noted that, deposited every time after an one functional layer, it is necessary to carry out expanding treatment, so as to depositing subsequent function
Layer, the aperture of expansion is 2 times of next functional layer thickness.
(7) finally device is packaged.
Embodiment two：The preparation of eurymeric QLED devices
(1) glass substrate is cleaned, is placed in order in ultra-pure water, acetone and isopropanol and is cleaned by ultrasonic.Wait to surpass
It is after the completion of sound that glass substrate is standby with nitrogen gun drying.
(2) porous anodic aluminium oxide (AAO) film is transplanted in glass substrate by PMMA film, the aperture in AAO fenestras road
（Diameter）For 200nm, duct spacing for 1000nm, duct hole depth be 200nm.
(3) substrate is transferred to settling chamber, vacuum suction in settling chamber's is dropped to 10-6After holding in the palm or being lower, in AAO
The ITO internal layer electrodes 30 of column are deposited in fenestra road, as shown in Figure 5.
(4) to AAO films surface with processing, ITO internal layer electrodes 30 unnecessary outside duct are removed, and AAO films expand row
Hole is processed, and uses AAO fenestras road borehole enlargement to 300nm.Specifically, CuCl can be used2Or FeCl3Immersion 10 minutes, with
Just unnecessary ITO internal layer electrodes 30 are removed, the dilute phosphoric acid solution that mass percent is 4% is reused and is soaked 2 hours, with to AAO films
To row expanding treatment, make the borehole enlargement in AAO fenestras road to 300nm, i.e. borehole enlargement 100nm, the space of expansion is deposition
Next layer of 50nm thick functional layer.
(5) and then drying and processing is carried out（Drying temperature is preferably 80 DEG C, and drying time is preferably 1 hour）, after treatment
Settling chamber is transferred into again, and vacuum suction in settling chamber's is dropped to 10-6After holding in the palm or being lower, deposited in the duct for expanding
One layer of PEDOT hole injection layer 31 of 50nm, the PEDOT hole injection layers 31 can be deposited on the surface of TO internal layer electrodes 30, due to
The borehole enlargement in duct 100nm before, so the thickness of the PEDOT hole injection layers 31 of this step deposition is just 50nm.
After PEDOT hole injection layers 31 have been deposited, then expanding treatment is carried out, so that the borehole enlargement in duct, to deposit down
One layer of functional layer, such as next layer is TFB hole transmission layers 32, and its thickness is 50nm, then need to arrive borehole enlargement
400nm, that is, expand 100nm, is 2 times of the thickness of TFB hole transmission layers 32.
(6) repeat step (4) and (5), be sequentially depositing one layer of TFB hole transmission layer 32 of 50nm, one layer of 40nm's
CdSe/ZnS quantum dot light emitting layers 33, one layer of ZnO electron transfer layers 34 and one layer of Al outer electrode 35 of 80nm of 50nm.Separately
It is outer it should be noted that, deposited every time after an one functional layer, it is necessary to carry out expanding treatment, so as to depositing subsequent functional layer, expand
Big aperture is 2 times of next functional layer thickness.
(7) finally device is packaged.
In sum, the present invention carries out structure improvement and optimization to traditional stratiform QLED device architectures, forms column structure
QLED devices, by column structure come equilbrium carrier charge velocity, so as to improve device light emitting efficiency, while column structure
Also device light emission rate can be improved out.
It should be appreciated that application of the invention is not limited to above-mentioned citing, and for those of ordinary skills, can
To be improved according to the above description or converted, all these modifications and variations should all belong to the guarantor of appended claims of the present invention
Shield scope.
Claims (10)
1. a kind of QLED devices, it is characterised in that the QLED devices are column structure, the QLED devices are from inside to outside successively
Including internal layer electrode, functional layer and outer electrode.
2. QLED devices according to claim 1, it is characterised in that the functional layer includes successively from inside to outside：Electronics
Transport layer, quantum dot light emitting layer, hole transmission layer, hole injection layer.
3. QLED devices according to claim 1, it is characterised in that the functional layer includes successively from inside to outside：Hole
Implanted layer, hole transmission layer, quantum dot light emitting layer, electron transfer layer.
4. QLED devices according to Claims 2 or 3, it is characterised in that the material of the electron transfer layer be ZnO,
TiO2, one or more in SnO, AlZnO, ZnSnO and InSnO.
5. QLED devices according to Claims 2 or 3, it is characterised in that the material of the hole injection layer is PEDOT:
One or more in PSS, molybdenum oxide, vanadium oxide, tungsten oxide and chromium oxide.
6. QLED devices according to Claims 2 or 3, it is characterised in that the material of the hole transmission layer is Poly-
One or more in THX, TFB, PVK, CBP and TCTA.
7. QLED devices according to Claims 2 or 3, it is characterised in that the quantum dot in described quantum dot light emitting layer
It is Binary-phase quantum dot, ternary phase quantum dot or quaternary phase quantum dot；The Binary-phase quantum dot be CdS, CdSe, CdTe,
One or more in InP, AgS, PbS, PbSe, HgS, the ternary phase quantum dot is ZnxCd1-xS、CuxIn1-xS、ZnxCd1- xSe、ZnxSe1-xS、ZnxCd1-xTe、PbSexS1-xIn one or more, the quaternary phase quantum dot be ZnxCd1-xS/ZnSe、
CuxIn1-xS/ZnS、ZnxCd1-xSe/ZnS、CuInSeS、ZnxCd1-xTe/ZnS、 PbSexS1-xOne or more in/ZnS.
8. a kind of preparation method of QLED devices as claimed in claim 1, it is characterised in that including step：
A, the internal layer electrode that column is first deposited on substrate；
B and then in internal layer electrode surface deposit functional layers；
C, it is last deposit outer electrode in function layer surface, be then packaged and obtain QLED devices.
9. the preparation method of QLED devices according to claim 8, it is characterised in that the step A is specifically included：
A1, perforated membrane is transplanted on substrate；
The internal layer electrode of column is deposited in A2, the duct on the perforated membrane；
A3, the duct to the perforated membrane carry out expanding treatment, the duct aperture of the perforated membrane is become big.
10. the preparation method of the QLED devices according to right wants 9, it is characterised in that the perforated membrane is porous anode oxygen
Change aluminium film.
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