CN106356466A - White-light QLED (Quantum Dot Light Emitting Diode) device based on quantum dots with pre-set size and preparation method - Google Patents
White-light QLED (Quantum Dot Light Emitting Diode) device based on quantum dots with pre-set size and preparation method Download PDFInfo
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Abstract
The invention discloses a white-light QLED (Quantum Dot Light Emitting Diode) device based on quantum dots with a pre-set size and a preparation method. The white-light QLED device comprises a substrate, a bottom electrode, a hole injection layer, a hole transmission layer, a quantum dot light emitting layer, an electron transmission layer and a top electrode, which are stacked in sequence from bottom to top, wherein the quantum dot light emitting layer is composed of the quantum dots with the pre-set size. The quantum dots with single size and single component are used as white-light light emitting materials. Based on the white-light QLED device prepared by the technology, a color drifting phenomenon of different devices along with utilization time, caused by different three-primary-color light emitting materials, in stacking and mixing structures of a previous three-primary-color white-light technology, is avoided, the structure of the device is simplified and the production cost is reduced; and meanwhile, energy transferring between the different light emitting materials is not caused, so that the light emitting efficiency is improved.
Description
Technical field
The present invention relates to qled white light parts technical field, more particularly, to a kind of white light based on preliminary dimension quantum dot
Qled device and preparation method.
Background technology
It is high that light emitting diode with quantum dots has an excitation, frivolous can the characteristic such as flexibility, and be suitable for large area coating process
Preparation, not only has good application prospect in terms of display, and because its preparation cost is low, so also have latent in lighting field
Advantage.
The usual method preparing white light-emitting diodess has two kinds, and one is stacking using rgb three primary colours that is to say, that same
There is the luminescent layer of three colors of RGB, two is same by the difference of redgreenblue luminescent material doping ratio in device
White light is obtained in luminescent layer.But both aspects have the shortcomings that oneself, its device architecture of method of such as three primary colours stacking
Complexity, and the method for three primary colours doping, due to there is energy transfer process, reduces luminous efficiency, additionally for both approaches
Due to the difference of three-color light-emitting material stability, all deposit the problem of chromaticity coordinates drift in use.
In order to solve the above problems, obtaining white light using single luminous body just becomes optimized selection.It is primarily based on list
The white light parts structure of luminiferous material preparation is simple, when secondly there is not red-green-blue luminescent material doping acquisition white light
It is possible to obtain efficient device, finally single luminescent material ensure that device was using to energy transfer each other
In journey, the drifting problem of chromaticity coordinates can be alleviated significantly.
For luminescent quantum dot, its glow color can be with change in particle size.When quantum dot size is gradually increased, send out
Light color starts slowly red shift from blue, therefore can obtain the luminous of red-green-blue by adjusting particle size.But
When the size of quantum dot is in a particular value, quantum dot can send efficient white light, and this size is then referred to as making a reservation for
Size.The white light of preliminary dimension quantum dot is intrinsic luminous luminous with defect state two parts including quantum dot in fact, wherein
Intrinsic lighting is high energy, blue-light-emitting, and it is then mental retardation that defect state lights, Yellow luminous.Generally defect state is for luminous
It is quenched, be the radiationless complex centre of exciton, even the defect state of radiation center one is too low to be limited by the density of states, two
Come wayward, so luminous intensity is not high also less using as luminous body.But be in order at preliminary dimension quantum dot its lack
Lighting of sunken state, only just has very high intensity under preliminary dimension, is therefore strong luminous body, and controllability compares
Good, it is preferable white light emitting material.
Therefore, prior art has yet to be improved and developed.
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 white based on preliminary dimension quantum dot
Light qled device and preparation method adopt three primary colours stacked structure or mixed structure it is intended to solve existing quantum dot light emitting layer,
Lead to the energy transfer between different luminescent materials, the chromaticity coordinates that different luminescent materials produce with use time decay difference
The problem of drift.
Technical scheme is as follows:
A kind of white light qled device based on preliminary dimension quantum dot, wherein, described white light qled device wraps from bottom to top successively
Include substrate, hearth electrode, hole injection layer, hole transmission layer, quantum dot light emitting layer, electron transfer layer and top electrode, wherein, institute
The material stating quantum dot light emitting layer is the quantum dot of preliminary dimension.
The described white light qled device based on preliminary dimension quantum dot, wherein, the quantum dot of described preliminary dimension is 2 ~
The quantum dot of 10nm.
The described white light qled device based on preliminary dimension quantum dot, wherein, the quantum dot of described preliminary dimension is pre-
The ii-vi race quantum dot of sizing.
The described white light qled device based on preliminary dimension quantum dot, wherein, the ii-vi race quantum of described preliminary dimension
Point is cdse, cds, cdses, cdxzn1-xseys1-yOne of, cdxzn1-xseys1-yIn, 0≤x≤1,0≤y≤1, and x
It is 0 when different with y.
The described white light qled device based on preliminary dimension quantum dot, wherein, described hole injection layer is pedot:
One of pss, molybdenum oxide, nickel oxide, hatcn.
The described white light qled device based on preliminary dimension quantum dot, wherein, described hole transmission layer be pvk, tfb,
polytpb、npb、tapc、nio、v2o5、moo3、wo3One of.
The described white light qled device based on preliminary dimension quantum dot, wherein, described electron transfer layer is alq, oxd-
7、zno、tio2One of.
The described white light qled device based on preliminary dimension quantum dot, wherein, the thickness of described quantum dot light emitting layer is
20 ~ 50 nanometers, the thickness of described hole injection layer is 10 ~ 30 nanometers.
The described white light qled device based on preliminary dimension quantum dot, wherein, the thickness of described hole transmission layer is 40 ~
60 nanometers.
A kind of preparation method of as above arbitrary described white light qled device based on preliminary dimension quantum dot, wherein, bag
Include step:
A, hole injection layer, hole transmission layer and quantum dot light emitting layer are sequentially prepared on the hearth electrode containing substrate, wherein, institute
The material stating quantum dot light emitting layer is the quantum dot of preliminary dimension；
B and then electron transfer layer is prepared on quantum dot light emitting layer；
D, it is deposited with a top electrode on the electron transport layer, form white light qled device.
Beneficial effect: the present invention by the use of preliminary dimension single quantum dot material as luminous body, it is possible to obtain efficiently white
Light qled device, one side device architecture is simple it is not necessary to using stacking technique, another aspect does not have different colours luminous body
Between energy transmission, reduce loss.In addition, white light qled device of the present invention can obviously improve device in use due to
The problem of the white light chromaticity coordinates drift that different luminous body stability differences cause.
Brief description
Fig. 1 is a kind of structural representation of white light qled device preferred embodiment based on preliminary dimension quantum dot of the present invention
Figure.
Fig. 2 is cdse the absorbing and luminous schematic diagram at different wavelengths of preliminary dimension of the present invention.
Fig. 3 is a kind of preparation method preferred embodiment of white light qled device based on preliminary dimension quantum dot of the present invention
Flow chart.
Specific embodiment
The present invention provides a kind of white light qled device based on preliminary dimension quantum dot and preparation method, for making the present invention's
Purpose, 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 place is retouched
The specific embodiment stated only in order to explain the present invention, is not intended to limit the present invention.
Refer to Fig. 1, Fig. 1 is a kind of white light qled device preferred embodiment based on preliminary dimension quantum dot of the present invention
Structural representation, as illustrated, described white light qled device include successively from bottom to top substrate 1, hearth electrode 2, hole injection
Layer 3, hole transmission layer 4, quantum dot light emitting layer 5, electron transfer layer 6 and top electrode 7, wherein, described quantum dot light emitting layer 5
Material is the quantum dot of preliminary dimension.The present invention is by the use of single white light emitting material as quantum dot light emitting layer, not only device architecture letter
Single, and there is not energy transmission, improve luminous efficiency, there is no different colours service life in three primary colours white light parts simultaneously
Different problems.
For white light emitting diode device at present mainly adopt two ways, one be three primary colours stacking knot
, that is to say, that comprising three kinds of different luminescent layers of RGB in device respectively, this device architecture is extremely complex, leads to non-defective unit for structure
Rate is low, and preparation cost is high；Another is the structure of three primary colours mixing, mixes respectively according to the ratio optimizing in same luminescent layer
Appropriate red-green-blue luminescent material, due to there is the energy transmission between different colours luminous body in this device, because
This reduces the overall luminous efficiency of device.And realize the method for white light it is impossible to avoid three kinds of materials by three kinds of luminescent materials
The luminous chromaticity coordinates that material differential declines characteristic is brought is with using the drift producing.
Quantum dot light emitting layer of the present invention adopt preliminary dimension quantum dot, luminous inclusion two parts of this quantum dot, one
It is derived from the blue-light-emitting with transition for the intrinsic band, another is derived from the long wave of defect state, luminous, the therefore table of broad band
Reveal very strong white light emission.The quantum dot of preliminary dimension have simultaneously to carry the intrinsic blue with transition light and come
Light from the long wave in defect state, therefore show very strong white light that is to say, that single size, single component can be passed through
Quantum dot obtain white luminous.In quantum dot building-up process, mainly include three parts: (1) nucleation and growth, (2) tie
Crystalline substance, (3) surface reconstruction.The luminous peak position of wherein quantum dot can be with growth course, that is, the mistake that particle size is constantly grown up
, gradually there is red shift in journey.Crystallization is constantly to complete quantum point lattice structure, reduces the process of internal flaw.Growth and crystallization two
Individual process all can reduce defect concentration, and defect is typically considered radiationless complex centre.But when the growth of quantum dot is entered
When entering certain size, defect shows strong hole acceptor properties, and because the size of preliminary dimension quantum dot is very little, leads to
There is strong overlapping in electron wave function and surface anion position, then the hole captured by surface defect state occurs radiation recombination
Probability just considerably increase, here it is preliminary dimension quantum dot has very strong defect state the reason light.Once quantum dot
Continue to grow up, exceeded preliminary dimension, then defect state reduces, and radiation recombination probability reduces.Fig. 2 is the pre- scale of the present invention
The very little cdse schematic diagram absorbing and lighting at different wavelengths.
The quantum dot of preliminary dimension of the present invention is about the quantum dot of 2 ~ 10nm, that is, when the size of single quantum dot exists
When in the range of 2 ~ 10nm, quantum dot can send efficient white light.Preferably, the quantum dot of described preliminary dimension can be predetermined
The ii-vi race quantum dot of size, the preliminary dimension of described ii-vi race quantum dot is about 2 ~ 4nm, for example, described preliminary dimension
Ii-vi race quantum dot can for but be not limited to cdse, cds, cdses, cd of preliminary dimensionxzn1-xseys1-y(wherein 0≤x≤
One of 1,0≤y≤1, and be 0 when x with y is different) etc., specifically, the preliminary dimension of described cdse is about 3nm, cds
Preliminary dimension be about 3nm, the preliminary dimension of cdses is about 2.5nm, described cdxzn1-xseys1-yPreliminary dimension about
For 4nm.The present invention adopts the quantum dot of above-mentioned preliminary dimension as the material of quantum dot light emitting layer, is applied to white light-emitting diodess device
During part makes, on the one hand due to using single size, the white-light emitting body of single component, so not needing using stacking knot
Structure, process is simple, it is possible to decrease production cost, do not exist between different luminescent materials in another aspect single white luminescent material
Energy transfer, can improve the luminous efficiency of device.Last do not exist using luminescent materials different in three primary colours white light technology yet
The chromaticity coordinates drifting problem producing with use time decay difference.
Fig. 3 is the preparation of a kind of as above arbitrary described white light qled device based on preliminary dimension quantum dot of the present invention
The flow chart of method preferred embodiment, as illustrated, it includes step:
S100, hole injection layer, hole transmission layer and quantum dot light emitting layer are sequentially prepared on the hearth electrode containing substrate, its
In, the material of described quantum dot light emitting layer is the quantum dot of preliminary dimension；
Step s100 is specifically, the present invention is before preparing above-mentioned hole injection layer, hole transmission layer and quantum dot light emitting layer, right
Substrate carries out pretreatment.Pretreatment specifically includes step: clean substrate (as glass substrate) is processed with oxygen gas plasma
(plasma treatment), with the Organic substance of substrate of going out further (as glass substrate) surface attachment and improve the work(of substrate
Function, this process may also be employed UV-ozone and processes (uv-ozone treatment) to complete.
Then one hearth electrode is deposited with the substrate processing, prepares one layer of hole injection layer, this layer on hearth electrode surface
Thickness can be 10 ~ 30 nanometers, the material of hole injection layer can for but be not limited to pedot:pss, molybdenum oxide, nickel oxide,
One of hatcn etc. or other have the material of good hole injection efficiency, herein preferably pedot:pss conduct
Hole injection layer.
Then it is placed in nitrogen atmosphere, prepare one layer of hole transmission layer on hole injection layer surface, this hole transmission layer
Material can be conventional conducting polymer pvk, tfb, polytpb, npb, tapc etc. and inorganic oxide nio, v2o5、
moo3、wo3Deng, can also be other high performance hole mobile materials, the thickness of prepared hole transmission layer can for 40 ~
60 nanometers.
Quantum dot light emitting layer is prepared on hole transmission layer.The material of described quantum dot light emitting layer is the quantum of preliminary dimension
Point, the quantum dot of described preliminary dimension is preferably the ii-vi race quantum dot of preliminary dimension, for example, it is possible to for but be not limited to cdse,
cds、cdxzn1-xseys1-yDeng one of quantum dot.
S200 and then electron transfer layer is prepared on quantum dot light emitting layer；
Step s200 is specifically, prepare one layer of electron transfer layer in quantum dot light emitting layer surface.Wherein, described electron transfer layer can
Think but be not limited to alq, oxd-7, inorganic oxide zno, tio2One of, described electron transfer layer preferably has high electricity
The zinc oxide of sub- transmission performance, its preferably thickness is 10-30nm.
S300, it is deposited with a top electrode on the electron transport layer, form white light qled device；
Step s300 passes through mask plate hot evaporation one top electrode specifically, being placed in the substrate after above-mentioned process in evaporation storehouse,
Obtain white light qled device.
The above-mentioned each functional layer of the present invention all can pass through the solwution method such as spin coating, printing and spraying or vacuum evaporation, sputtering
Deng vacuum method preparation.
The present invention utilizes single size, and the quantum dot of single component is as white light emitting material.Based on the preparation of this technology
White light qled device, before not only avoiding, three primary colours white light technology is included in stacking and mixed structure due to three-color light-emitting material
The color drift phenomenon that the device that material difference causes occurs with use time, and simplify device architecture, reduce life
Producing cost, there is not the energy transmission between different luminescent materials, so improving luminous efficiency simultaneously.
It should be noted that, preliminary dimension quantum dot of the present invention is not limited to use in prepares top emitting or bottom emitting；It is also not necessarily limited to
For preparing eurymeric device or transoid device.
Below by embodiment, the present invention is described in detail.
Embodiment 1
In one white light qled device, substrate is glass, and hearth electrode is 120nmito, and hole injection layer is pedot:pss
(20nm).Hole transmission layer is tfb, and thickness of hole transport layer is 45nm.Quantum dot light emitting layer is the cdse quantum dot of 3nm, thick
Degree is 30 nanometers.Electron transfer layer is nano zine oxide, and electron transfer layer thickness is 20nm.Top electrode is al.
Embodiment 2
In one white light qled device, substrate is glass, and hearth electrode is 120nmito, and hole injection layer is pedot:pss
(20nm).Hole transmission layer is tfb, and thickness of hole transport layer is 50nm.Quantum dot light emitting layer is the cdses quantum dot of 2.5nm,
Thickness is 25 nanometers.Electron transfer layer is nano zine oxide, and electron transfer layer thickness is 25nm.Top electrode is al.
Embodiment 3
In one white light qled device, substrate is glass, and hearth electrode is 120nmito, and hole injection layer is pedot:pss
(20nm).Hole transmission layer is poly-tpd, and thickness of hole transport layer is 45nm.Quantum dot light emitting layer is the cbs quantum of 3nm
Point, thickness is 30 nanometers.Etl is nano zine oxide, and electron transfer layer thickness is 20nm.Top electrode is al.
In sum, the present invention provides a kind of white light qled device based on preliminary dimension quantum dot and preparation method,
The present invention utilizes single size, and the preliminary dimension quantum dot of single component is as white light emitting material.Based on the preparation of this technology
White light qled device, before not only avoiding, three primary colours white light technology is included in stacking and mixed structure due to three-color light-emitting material
The color drift phenomenon that the device that material difference causes occurs with use time, and simplify device architecture, reduce life
Producing cost, there is not the energy transmission between different luminescent materials, so improving luminous efficiency simultaneously.
It should be appreciated that the application of the present invention is not limited to above-mentioned citing, for those of ordinary skills, can
To be improved according to the above description or to convert, all these modifications and variations all should belong to the guarantor of claims of the present invention
Shield scope.
Claims (10)
1. a kind of white light qled device based on preliminary dimension quantum dot it is characterised in that described white light qled device from lower and
On include successively substrate, hearth electrode, hole injection layer, hole transmission layer, quantum dot light emitting layer, electron transfer layer and top electricity
Pole, wherein, the material of described quantum dot light emitting layer is the quantum dot of preliminary dimension.
2. the white light qled device based on preliminary dimension quantum dot according to claim 1 is it is characterised in that described make a reservation for
The quantum dot of size is the quantum dot of 2 ~ 10nm.
3. the white light qled device based on preliminary dimension quantum dot according to claim 1 is it is characterised in that described make a reservation for
The quantum dot of size is the ii-vi race quantum dot of preliminary dimension.
4. the white light qled device based on preliminary dimension quantum dot according to claim 3 is it is characterised in that described make a reservation for
The ii-vi race quantum dot of size is cdse, cds, cdses, cdxzn1-xseys1-yOne of, cdxzn1-xseys1-yIn, 0≤x
≤ 1,0≤y≤1, and be 0 when x with y is different.
5. the white light qled device based on preliminary dimension quantum dot according to claim 1 is it is characterised in that described hole
Implanted layer is one of pedot:pss, molybdenum oxide, nickel oxide, hatcn.
6. the white light qled device based on preliminary dimension quantum dot according to claim 1 is it is characterised in that described hole
Transport layer is pvk, tfb, polytpb, npb, tapc, nio, v2o5、moo3、wo3One of.
7. the white light qled device based on preliminary dimension quantum dot according to claim 1 is it is characterised in that described electronics
Transport layer is alq, oxd-7, zno, tio2One of.
8. the white light qled device based on preliminary dimension quantum dot according to claim 1 is it is characterised in that described quantum
The thickness of point luminescent layer is 20 ~ 50 nanometers, and the thickness of described hole injection layer is 10 ~ 30 nanometers.
9. the white light qled device based on preliminary dimension quantum dot according to claim 1 is it is characterised in that described hole
The thickness of transport layer is 40 ~ 60 nanometers.
10. a kind of preparation method of the described white light qled device based on preliminary dimension quantum dot as arbitrary in claim 1 ~ 9,
It is characterized in that, including step:
A, hole injection layer, hole transmission layer and quantum dot light emitting layer are sequentially prepared on the hearth electrode containing substrate, wherein, institute
The material stating quantum dot light emitting layer is the quantum dot of preliminary dimension；
B and then electron transfer layer is prepared on quantum dot light emitting layer；
D, it is deposited with a top electrode on the electron transport layer, form white light qled device.
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| CN110165066A (en) * | 2019-06-10 | 2019-08-23 | 南昌航空大学 | A kind of light emitting diode with quantum dots and preparation method thereof |
| CN110614863A (en) * | 2019-09-06 | 2019-12-27 | 华南理工大学 | Method for realizing uniform pattern array of ink-jet printing |
| CN112687821A (en) * | 2021-01-20 | 2021-04-20 | 福州大学 | Quantum dot intelligent lighting QLED device and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107093673A (en) * | 2017-05-17 | 2017-08-25 | 南昌航空大学 | Multi-layer quantum white point luminescent device |
| CN110165066A (en) * | 2019-06-10 | 2019-08-23 | 南昌航空大学 | A kind of light emitting diode with quantum dots and preparation method thereof |
| CN110614863A (en) * | 2019-09-06 | 2019-12-27 | 华南理工大学 | Method for realizing uniform pattern array of ink-jet printing |
| CN110614863B (en) * | 2019-09-06 | 2022-05-24 | 华南理工大学 | Method for realizing uniform pattern array of ink-jet printing |
| CN112687821A (en) * | 2021-01-20 | 2021-04-20 | 福州大学 | Quantum dot intelligent lighting QLED device and preparation method thereof |
| CN112687821B (en) * | 2021-01-20 | 2022-03-25 | 福州大学 | Quantum dot intelligent lighting QLED device and preparation method thereof |
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