CN106356466B - A kind of white light QLED device and preparation method based on predetermined size quantum dot - Google Patents
A kind of white light QLED device and preparation method based on predetermined size quantum dot Download PDFInfo
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Abstract
The present invention discloses a kind of white light QLED device and preparation method based on predetermined size quantum dot, the white light QLED device successively includes substrate, hearth electrode, hole injection layer, hole transmission layer, quantum dot light emitting layer, electron transfer layer and top electrode from bottom to top, wherein, the material of the quantum dot light emitting layer is the quantum dot of predetermined size.The present invention utilizes single size, and the quantum dot of single component is as white light emitting material.White light QLED device based on the preparation of this technology, before not only avoiding three primary colours white light technology include stack in mixed structure due to three-color light-emitting material it is different caused by device with the color drift phenomenon for using the time and occurring, and simplify device architecture, reduce production cost, there is no the energy transmissions between different luminescent materials simultaneously, so improving luminous efficiency.
Description
Technical field
The present invention relates to QLED white light parts technical field more particularly to a kind of white lights based on predetermined size quantum dot
QLED device and preparation method.
Background technique
Light emitting diode with quantum dots has excitation purity high, it is frivolous can the characteristics such as flexibility, and be suitble to large area coating process
Preparation, not only has good application prospect, and since its preparation cost is low, so also having in lighting area latent in terms of display
Advantage.
There are two types of the usual methods for preparing white light-emitting diodes, first is that using the stacking of RGB three primary colours, that is to say, that same
There is the luminescent layer of three colors of RGB in device, second is that by the difference of redgreenblue luminescent material doping ratio same
White light is obtained in luminescent layer.However both aspects the shortcomings that having oneself, such as method its device architecture that three primary colours stack
Complexity, and the method for three primary colours doping reduces luminous efficiency, in addition for both methods since there are energy transfer processes
Due to the difference of three-color light-emitting material stability, the problem of chromaticity coordinates drifts about in use is all deposited.
To solve the above-mentioned problems, obtaining white light using single illuminator just becomes the selection of optimization.It is primarily based on list
The white light parts structure of luminiferous material preparation is simple, when secondly obtaining white light there is no the doping of red-green-blue luminescent material
Mutual energy transfer, it is possible to obtain efficient device, last single luminescent material ensure that device was using
The drifting problem of chromaticity coordinates can be alleviated significantly in journey.
For luminescent quantum dot, luminescent color can be with change in particle size.When quantum dot size is gradually increased, hair
Light color slowly red shift since blue, therefore shining for red-green-blue can be obtained by adjusting particle size.However
When the size of quantum dot is in a particular value, quantum dot can issue efficient white light, and this size is then referred to as predetermined
Size.The white light of predetermined size quantum dot is luminous two parts of intrinsic luminous and defect state for including quantum dot in fact, wherein
Intrinsic shine is high energy, blue-light-emitting, and it is then low energy that defect state, which shines, Yellow luminous.Usual defect state is for shining
It is quenched, is the radiationless complex centre of exciton, even the defect state one of radiation center is too low to be limited by the density of states, two
It is difficult to control, is also less used as illuminator so luminous intensity is high.But it is lacked for the quantum dot of predetermined size
Shining for state is fallen into, just there is very high intensity only under predetermined size, therefore be both strong illuminator, and controllability compares
It is good, it is ideal white light emitting material.
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 based on the white of predetermined size quantum dot
Light QLED device and preparation method, it is intended to it solves existing quantum dot light emitting layer and uses three primary colours stacked structure or mixed structure,
Lead to the energy transfer between different luminescent materials, different luminescent materials are with the chromaticity coordinates for using time decaying different and generating
The problem of drift.
Technical scheme is as follows:
A kind of white light QLED device based on predetermined size quantum dot, wherein the white light QLED device from bottom to top according to
It is secondary include substrate, hearth electrode, hole injection layer, hole transmission layer, quantum dot light emitting layer, electron transfer layer and top electrode,
In, the material of the quantum dot light emitting layer is the quantum dot of predetermined size.
The white light QLED device based on predetermined size quantum dot, wherein the quantum dot of the predetermined size be 2 ~
The quantum dot of 10nm.
The white light QLED device based on predetermined size quantum dot, wherein the quantum dot of the predetermined size is pre-
The II-VI group quantum dot of scale cun.
The white light QLED device based on predetermined size quantum dot, wherein the II-VI group quantum of the predetermined size
Point is CdSe, CdS, CdSeS, CdxZn1-xSeyS1-yOne of, CdxZn1-xSeyS1-yIn, 0≤x≤1,0≤y≤1, and x
It is not simultaneously 0 with y.
The white light QLED device based on predetermined size quantum dot, wherein the hole injection layer is PEDOT:
One of PSS, molybdenum oxide, nickel oxide, HATCN.
The white light QLED device based on predetermined size quantum dot, wherein the hole transmission layer be PVK, TFB,
polyTPB、NPB、TAPC、NiO、V2O5、MoO3、WO3One of.
The white light QLED device based on predetermined size quantum dot, wherein the electron transfer layer is Alq, OXD-
7、ZnO、TiO2One of.
The white light QLED device based on predetermined size quantum dot, wherein the quantum dot light emitting layer with a thickness of
20 ~ 50 nanometers, the hole injection layer with a thickness of 10 ~ 30 nanometers.
The white light QLED device based on predetermined size quantum dot, wherein the hole transmission layer with a thickness of 40 ~
60 nanometers.
The preparation method of a kind of as above any white light QLED device based on predetermined size quantum dot, wherein packet
Include step:
A, hole injection layer, hole transmission layer and quantum dot light emitting layer are sequentially prepared on the hearth electrode containing substrate,
In, the material of the quantum dot light emitting layer is the quantum dot of predetermined size；
B, electron transfer layer is then prepared on quantum dot light emitting layer；
D, a top electrode is deposited on the electron transport layer, forms white light QLED device.
The utility model has the advantages that the present invention using the single quantum dot material of predetermined size as illuminator, can obtain it is efficient white
Light QLED device, one side device architecture is simple, does not need that different colours illuminator is on the other hand not present using technique is stacked
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 white light chromaticity coordinates caused by different illuminator stability are different drifts about.
Detailed description of the invention
Fig. 1 is a kind of structural representation of white light QLED device preferred embodiment based on predetermined size quantum dot of the invention
Figure.
Fig. 2 is the absorption of the CdSe of predetermined size of the present invention at different wavelengths and luminous schematic diagram.
Fig. 3 is a kind of preparation method preferred embodiment of white light QLED device based on predetermined size quantum dot of the invention
Flow chart.
Specific embodiment
The present invention provides a kind of white light QLED device and preparation method based on predetermined size quantum dot, of the invention to make
Purpose, technical solution and effect are clearer, clear, and the present invention is described in more detail below.It should be appreciated that this place is retouched
The specific embodiment stated is only used to explain the present invention, is not intended to limit the present invention.
Referring to Fig. 1, Fig. 1 is a kind of white light QLED device preferred embodiment based on predetermined size quantum dot of the invention
Structural schematic diagram, as shown, the white light QLED device from bottom to top successively include 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 the quantum dot light emitting layer 5
Material is the quantum dot of predetermined size.The present invention is using single white light emitting material as quantum dot light emitting layer, not only device architecture letter
It is single, and energy transmission is not present, luminous efficiency is improved, while without different colours service life in three primary colours white light parts
Different problems.
For white light emitting diode device at present mainly use two ways, one be three primary colours stacking knot
Structure, that is to say, that three kinds of different luminescent layers of RGB are separately included in device, this device architecture is extremely complex, leads to non-defective unit
Rate is low, and preparation cost is high；The other is the structure of three primary colours mixing, mixes in same luminescent layer according to the ratio of optimization respectively
Suitable red-green-blue luminescent material, due to there are the energy transmission between different colours illuminator in this device, because
This reduces the luminous efficiency of device entirety.And by the method for three kinds of luminescent materials realization white lights, three kinds of materials are not can avoid
Expect that differential declines characteristic bring shines chromaticity coordinates with the drift for using generation.
Quantum dot light emitting layer of the present invention use predetermined size quantum dot, the quantum dot shine include two parts, one
It is derived from blue-light-emitting of the intrinsic band with transition, the other is deriving from the long wave of defect state, broad band shines, therefore table
Reveal very strong white light emission.The quantum dot of predetermined size has luminous and next to carry the intrinsic blue with transition simultaneously
It shines from the long wave in defect state, therefore shows very strong white light, that is to say, that single size, single component can be passed through
Quantum dot obtain it is white luminous.Mainly include three parts in quantum dot synthesis process: (1) being nucleated and grow, (2) knot
Crystalline substance, (3) surface reconstruction.Wherein the luminous peak position of quantum dot can be with growth course, that is, the mistake that particle size is constantly grown up
Red shift gradually occurs for journey.Crystallization is continuous completion quantum point lattice structure, reduces the process of internal flaw.Growth and crystallization two
A process can all reduce defect concentration, and defect is typically considered radiationless complex centre.However when quantum dot growth into
When entering certain size, defect shows strong hole acceptor properties, and since the size of predetermined size quantum dot is very small, cause
Electron wave function and surface anion position occur it is strong overlapping, then radiation recombination occurs for the hole captured by surface defect state
Probability just considerably increase, here it is predetermined size quantum dot have very strong defect state shine reason.Once quantum dot
Continue to grow up, be more than predetermined size, then defect state is reduced, and radiation recombination probability reduces.Fig. 2 is the pre- scale of the present invention
The absorption of very little CdSe at different wavelengths and luminous schematic diagram.
The quantum dot of predetermined size of the present invention is about the quantum dot of 2 ~ 10nm, i.e., when the size of single quantum dot exists
When within the scope of 2 ~ 10nm, quantum dot can issue efficient white light.Preferably, the quantum dot of the predetermined size can be predetermined
The predetermined size of the II-VI group quantum dot of size, the II-VI group quantum dot is about 2 ~ 4nm, for example, the predetermined size
II-VI group quantum dot can be but be not limited to CdSe, CdS, CdSeS, Cd of predetermined sizexZn1-xSeyS1-y(wherein 0≤x≤
1,0≤y≤1, and one of 0) etc. x and y are simultaneously for, specifically, the predetermined size of the CdSe is about 3nm, CdS
Predetermined size be about 3nm, the predetermined size of CdSeS is about 2.5nm, the CdxZn1-xSeyS1-yPredetermined size about
For 4nm.Material of the present invention using the quantum dot of above-mentioned predetermined size as quantum dot light emitting layer, is applied to white light-emitting diodes device
In part production, on the one hand due to stacking knot so not needing to use using single size, the white-light emitting body of single component
Structure, simple process can reduce production cost, be not present between different luminescent materials in another aspect single white luminescent material
Energy transfer can improve the luminous efficiency of device.Finally also there is no using luminescent materials different in three primary colours white light technology
With the chromaticity coordinates drifting problem for using time decaying different and generating.
Fig. 3 is the preparation of a kind of as above any white light QLED device based on predetermined size quantum dot of the invention
The flow chart of method preferred embodiment, as shown, itself comprising steps of
S100, hole injection layer, hole transmission layer and quantum dot light emitting layer are sequentially prepared on the hearth electrode containing substrate,
Wherein, the material of the quantum dot light emitting layer is the quantum dot of predetermined size；
Step S100 specifically, the present invention prepare above-mentioned hole injection layer, hole transmission layer and quantum dot light emitting layer it
Before, substrate is pre-processed.Pretreatment specifically includes step: clean substrate (such as glass substrate) is used oxygen gas plasma
It handles (Plasma treatment), with the organic matter of substrate of further going out (such as glass substrate) surface attachment and improves substrate
Work function, this process can also be used UV-ozone processing (UV-Ozone treatment) and completes.
Then a hearth electrode is deposited on processed substrate, 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 be but be not limited to PEDOT:PSS, molybdenum oxide, nickel oxide,
One of HATCN etc. is also possible to other materials with good hole injection efficiency, herein preferred PEDOT:PSS conduct
Hole injection layer.
Then it is placed in nitrogen atmosphere, prepares one layer of hole transmission layer on hole injection layer surface, this hole transmission layer
Material can be common 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 the hole transport layer.The material of the quantum dot light emitting layer is the quantum of predetermined size
Point, the quantum dot of the predetermined size are preferably the II-VI group quantum dot of predetermined size, for example, can be but be not limited to CdSe,
CdS、CdxZn1-xSeyS1-yOne of equal quantum dots.
S200, electron transfer layer is then 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, the electron-transport
Layer can be but be not limited to Alq, OXD-7, inorganic oxide ZnO, TiO2One of, the electron transfer layer preferably has height
Electronic transmission performance zinc oxide, preferably with a thickness of 10-30nm.
S300, a top electrode is deposited on the electron transport layer, forms white light QLED device；
Step S300 pushes up electricity by mask plate hot evaporation one specifically, will be placed in through treated substrate in vapor deposition storehouse
Pole obtains white light QLED device.
The above-mentioned each functional layer of the present invention can pass through the solwution methods such as spin coating, printing and spraying or vacuum evaporation, sputtering
Equal vacuum methods 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, three primary colours white light technology includes in stacking and mixed structure due to three-color light-emitting material before not only avoiding
Device caused by material is different simplifies device architecture with the color drift phenomenon for using the time and occurring, and reduces life
Cost is produced, while there is no the energy transmissions between different luminescent materials, so improving luminous efficiency.
It should be noted that predetermined size quantum dot of the present invention is not limited to use in and prepares top emitting or bottom emitting；It is also not necessarily limited to
It is used to prepare 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 transport 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 transport 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 are 30 nanometers.ETL is nano zine oxide, and electron transport layer thickness is 20nm.Top electrode is Al.
In conclusion a kind of white light QLED device and preparation method based on predetermined size quantum dot provided by the invention,
The present invention utilizes single size, and the predetermined size quantum dot of single component is as white light emitting material.Based on the preparation of this technology
White light QLED device, three primary colours white light technology includes in stacking and mixed structure due to three-color light-emitting material before not only avoiding
Device caused by material is different simplifies device architecture with the color drift phenomenon for using the time and occurring, and reduces life
Cost is produced, while there is no the energy transmissions between different luminescent materials, so improving luminous efficiency.
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 (9)
1. a kind of white light QLED device based on predetermined size quantum dot, which is characterized in that the white light QLED device from lower and
On successively include 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 the quantum dot light emitting layer is the quantum dot of predetermined size；
The quantum dot emission white light of the predetermined size, including it is intrinsic shine and defect state shines two parts, intrinsic shine be
Blue-light-emitting, it is Yellow luminous that defect state, which shines,；
The size of the quantum dot of the predetermined size is 2 ~ 10nm.
2. the white light QLED device according to claim 1 based on predetermined size quantum dot, which is characterized in that the quantum
Point is II-VI group quantum dot.
3. the white light QLED device according to claim 2 based on predetermined size quantum dot, which is characterized in that the II-
VI race quantum dot is CdSeS, CdxZn1-xSeyS1-yOne of, CdxZn1-xSeyS1-yIn, 0≤x≤1,0≤y≤1, and x
It is not simultaneously 0 with y.
4. the white light QLED device according to claim 1 based on predetermined size quantum dot, which is characterized in that the hole
Implanted layer is one of PEDOT:PSS, molybdenum oxide, nickel oxide, HATCN.
5. the white light QLED device according to claim 1 based on predetermined size quantum dot, which is characterized in that the hole
Transport layer is PVK, TFB, polyTPB, NPB, TAPC, NiO, V2O5、MoO3、WO3One of.
6. the white light QLED device according to claim 1 based on predetermined size quantum dot, which is characterized in that the electronics
Transport layer is Alq, OXD-7, ZnO, TiO2One of.
7. the white light QLED device according to claim 1 based on predetermined size quantum dot, which is characterized in that the quantum
Point luminescent layer with a thickness of 20 ~ 50 nanometers, the hole injection layer with a thickness of 10 ~ 30 nanometers.
8. the white light QLED device according to claim 1 based on predetermined size quantum dot, which is characterized in that the hole
Transport layer with a thickness of 40 ~ 60 nanometers.
9. a kind of preparation method of the white light QLED device based on predetermined size quantum dot as described in claim 1 ~ 8 is any,
Characterized in that it comprises the following steps:
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 for stating quantum dot light emitting layer is the quantum dot of predetermined size；The quantum dot emission white light of the predetermined size, including it is intrinsic
It shines and defect state shines two parts, intrinsic to shine as blue-light-emitting, it is Yellow luminous that defect state, which shines,；The predetermined size
Quantum dot size be 2 ~ 10nm；
B, electron transfer layer is then prepared on quantum dot light emitting layer；
D, a top electrode is deposited on the electron transport layer, forms white light QLED device.
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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 |
| CN110614863B (en) * | 2019-09-06 | 2022-05-24 | 华南理工大学 | Method for realizing uniform pattern array of ink-jet printing |
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