CN109935706A - A kind of QLED device and preparation method thereof - Google Patents
A kind of QLED device and preparation method thereof Download PDFInfo
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- CN109935706A CN109935706A CN201711349852.1A CN201711349852A CN109935706A CN 109935706 A CN109935706 A CN 109935706A CN 201711349852 A CN201711349852 A CN 201711349852A CN 109935706 A CN109935706 A CN 109935706A
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Abstract
The present invention discloses a kind of QLED device and preparation method thereof, the QLED device includes the cathode, quantum dot light emitting layer and anode being stacked, it wherein, further include the boundary layer being set between quantum dot light emitting layer and anode, the material of the boundary layer is carbon quantum dot.Transoid QLED device prepared by the present invention, by the way that a boundary layer is arranged between htl layer and QD layers, the boundary layer can prevent whole soln method prepare transoid QLED device HTL or HIL during on QD layer caused by dissolve wash away influence, to improve the efficiency of device.
Description
Technical field
The present invention relates to QLED devices fields more particularly to a kind of QLED device and preparation method thereof.
Background technique
Light emitting diode with quantum dots (QLED) has that peak width at half height is narrow, Color tunable and can the excellent spy such as solution method preparation
Point has become the contenders of next-generation display science and technology.Researcher studies QLED from different angles, including
Research to QDs, HTL, ETL and electrode；There are also to the properity of device and the research of stability.What researcher was studied
QLED device is all the eurymeric QLED device architecture of bottom emitting mostly, and the QLED structure for really screen application being suitble to need is anti-
Type QLED device architecture.Because transoid QLED structure has the advantage being directly connected to the TFT transistor backboard of n- channel-type.
In research in recent years, researcher, which also obtains, has high brightness, high efficiency and low cut-in voltage device performance
Transoid QLED device.Currently, transoid device architecture is mainly the structure of ITO/ETL/QDs/HTL/HIL/Al, wherein HTL is normal
Deposition materials are the materials such as TFB, PVK, TCTA, poly-TPD, CBP and mCP, can dissolve the solvent of HTL deposition materials
It is all mostly chlorobenzene, toluene or dichloro-benzenes etc., and these solvents can similarly dissolve QDs.So using whole soln
It is unavoidable when depositing HTL QDs layers to be impacted, it might even be possible to by QDs layers when method prepares transoid QLED structure
It all washes away, thereby reduces the efficiency of device.
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 QLED device and preparation method thereof,
Aim to solve the problem that the prior art when using HTL or HIL of whole soln method preparation transoid QLED device, impacts QDs layers
Problem.
Technical scheme is as follows: a kind of QLED device, including the cathode, quantum dot light emitting layer and sun being stacked
Pole, wherein further include the boundary layer being set between quantum dot light emitting layer and anode, the material of the boundary layer is carbon quantum
Point.The QLED device, wherein further include the hole functional layer being set between boundary layer and anode.The QLED device
Part, wherein the hole functional layer is at least one of hole transmission layer, hole injection layer.The QLED device,
In, it further include the electronic work ergosphere being set between quantum dot light emitting layer and cathode.The QLED device, wherein the boundary
Surface layer with a thickness of 2-20nm.A kind of preparation method of QLED device, wherein the following steps are included:
Cathode is provided；
Quantum dot light emitting layer is prepared on cathode；
Carbon quantum dot solution is deposited on quantum dot light emitting layer, obtains boundary layer；
Anode is prepared on boundary layer, obtains QLED device.
The preparation method of the QLED device, wherein it is described before the step of preparing anode on boundary layer, also wrap
It includes: preparing hole functional layer on boundary layer.
The preparation method of the QLED device, wherein it is described before the step of preparing quantum dot light emitting layer on cathode,
Further include: electronic work ergosphere is prepared on cathode.
The preparation method of the QLED device, wherein the carbon quantum dot solution is scattered in solvent by carbon quantum dot
It is formulated, the preparation method of the carbon quantum dot makes hydramine and oxidant reaction comprising steps of hydramine is mixed with oxidant
Obtain carbon quantum dot.
The preparation method of the QLED device, wherein the hydramine is ethanol amine；And/or the oxidant is dioxygen
Water.
The utility model has the advantages that the present invention between anode by being arranged a boundary layer at QDs layers, the boundary layer is by carbon quantum dot
It is prepared.The boundary layer has similar hole transmission layer effect, can realize that the orientation of carrier has under electric field action
The controllable migration of sequence；The solvent that the present invention dissolves boundary layer deposition materials is a kind of solvent for not readily dissolving QDs, so as to keep away
Exempt from solvent influence caused by QDs in deposited interfacial layer.
Detailed description of the invention
Fig. 1 is transoid QLED device architecture schematic diagram prepared by the embodiment of the present invention 1.
Fig. 2 is transoid QLED device architecture schematic diagram prepared by the embodiment of the present invention 2.
Specific embodiment
The present invention provides a kind of QLED device and preparation method thereof, to make the purpose of the present invention, technical solution and effect more
Add clear, clear, 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.
The present invention provides a kind of preparation method of carbon quantum dot, wherein comprising steps of hydramine is mixed with oxidant, makes
Hydramine and oxidant reaction obtain carbon quantum dot.
The preparation method of the carbon quantum dot, specifically includes step: hydramine being uniformly mixed with oxidant, then in temperature
For hydramine in 150-300 DEG C of reacting furnace and oxidant reaction 5-200min, solution from it is initial it is colourless become last black,
Wherein hydramine all participates in reacting and generating water with oxidant, finally moisture is made to volatilize in the state of heating completely, obtains carbon
Quantum dot (C-QD).The C-QD is washed, is finally distributed it in methoxyethanol solution or in alcoholic solution.This
It invents obtained its HOMO energy level of C-QD and is more advantageous to the note in hole closer to the HOMO energy level of current quantum dot in 6 eV
Enter.
Preferably, the hydramine is that ethanol amine etc. is without being limited thereto.
Preferably, the oxidant is that hydrogen peroxide etc. is without being limited thereto.
It preferably, is 1:5-5:5 by the volume ratio of hydramine and oxidant in the step of hydramine being mixed with oxidant, it will
The hydramine is mixed with the oxidant.Under the volume ratio, it is ensured that ethanol amine can react completely, while hydrogen peroxide is also complete
Portion participates in reacting and ultimately produces water.
Preferably, in the step of making hydramine and oxidant reaction obtain carbon quantum dot, reaction temperature is 150-300 DEG C, instead
It is 5-200min between seasonable.
The present invention provides a kind of transoid QLED device, including the cathode, quantum dot light emitting layer and anode being stacked,
In, it further include the boundary layer being set between quantum dot light emitting layer and anode, the material of the boundary layer is carbon quantum dot (C-
QD).
The present invention is directed to the prior art when using HTL or HIL of whole soln method preparation transoid QLED device, to QDs layers
The problem of impacting replaces existing HTL or HIL as hole transmission layer using the boundary layer made of C-QD, to avoid
The problem of QDs layers are impacted when HTL or HIL of existing solwution method preparation transoid QLED device.This is because C-QD's is molten
The solvent of agent and QD are orthogonal solvents, and C-QD is mainly dissolved in 2-methyl cellosolve (MEA) or alcoholic solution, and QD is substantially
It is dissolved in toluene, in chlorobenzene equal solvent, insoluble in alcohols solvent, avoids to impact QD in this way.The boundary layer tool
There is hole transmission layer, the oriented and ordered controllable migration of carrier can be realized under electric field action.In addition, due to C-
The valence-band level of QD relatively with the valence-band level of current QD, is more advantageous to the injection in hole, to improve about in 6eV
The efficiency of device.
Preferably, the transoid QLED device can also include the hole functional layer being set between boundary layer and anode.
Wherein the hole functional layer includes at least one of hole injection layer and hole transmission layer.In other words, the hole function
Ergosphere can be hole transmission layer；It may be hole injection layer；It can also simultaneously include hole transmission layer and hole injection layer,
Wherein the hole injection layer and the top electrode overlap.
The present invention is directed to the prior art when using HTL or HIL of whole soln method preparation transoid QLED device, to QDs layers
The problem of impacting, by the way that an interfacial layer is arranged between quantum dot light emitting layer and hole functional layer, the boundary layer
Material is C-QD, can effectively prevent solwution method when preparing HTL or HIL of transoid QLED device on influence caused by QDs layers.This
It is because the solvent of C-QD and the solvent of QD are orthogonal solvents, C-QD is mainly dissolved in 2-methyl cellosolve (MEA) or alcoholic solution
In, and QD is substantially dissolved in toluene, in chlorobenzene equal solvent, insoluble in alcohols solvent, avoids to cause shadow to QD in this way
It rings.In addition, since the valence-band level of C-QD is about in 6eV, relatively with the valence-band level of current QD, it is more advantageous to hole
Injection, to improve the efficiency of device.
Preferably, the transoid QLED device can also include the electronics being set between quantum dot light emitting layer and hearth electrode
Functional layer, the electronic work ergosphere includes at least one of electron transfer layer and electron injecting layer.In other words, the electronics
Functional layer can be electron transfer layer；It may be electron injecting layer；It can also simultaneously include electron transfer layer and electron injection
Layer, wherein the electron injecting layer and the hearth electrode overlap.
Preferably, the boundary layer with a thickness of 2-20nm.
Preferably, the material of the cathode can be selected from one of ITO, FTO, ATO, AZO or a variety of.
Preferably, the material of the electron injecting layer can be selected from the metals such as Ca, Ba of low work function, can also be selected from
CsF、LiF、CsCO3Equal compounds, can also be other Electrolyte type electron injecting layer materials.
Preferably, the material of the electron transfer layer can be selected from the material with good electronic transmission performance, such as can
Think but be not limited to ZnO, TiO of N-shaped2、Fe2O3、SnO2、Ta2O3, one of AlZnO, ZnSnO, InSnO etc. or a variety of.Into
One step is preferred, and the material of the electron transfer layer is the ZnO of N-shaped.It is further preferred that the electron transfer layer with a thickness of
10-60nm。
Preferably, the material of the quantum dot light emitting layer (QDs) can be selected from common red light quantum point, green quantum
One of point, blue light quantum point, gold-tinted quantum dot, infrared light quantum dot and ultraviolet light quantum dot are a variety of.Further preferably
, the quantum dot light emitting layer with a thickness of 5-50nm.
Preferably, the material of the hole transmission layer can be selected from NiO, CuO, CuS, VOx、WOx、MoOxOne of or
It is a variety of；It can also be one or more selected from PEDOT:PSS, TFB, PVK, Poly-TPD, TCTA, CBP, mCP, HAT-CN, NPB.
It is further preferred that the hole transmission layer with a thickness of 0-100nm.When the hole transmission layer is with a thickness of 0nm, at this time
QLED structure in boundary layer also assume responsibility for the effect of hole transmission layer.
Preferably, the material of the hole injection layer can be selected from NiO, CuO, CuS, VOx、WOx、MoOxOne of or
It is a variety of；It can also be one or more selected from PEDOT:PSS, TFB, PVK, Poly-TPD, TCTA, CBP, mCP, HAT-CN, NPB.
It is further preferred that the hole injection layer with a thickness of 20-100nm.
Preferably, the material of the anode can be selected from one of Ag, Al, Cu, Au or a variety of.It is further preferred that
The anode with a thickness of 50-200nm.
The present invention also provides a kind of preparation methods of transoid QLED device, wherein the following steps are included:
Cathode is provided；
Quantum dot light emitting layer is prepared on cathode；
Carbon quantum dot solution is deposited on quantum dot light emitting layer, obtains boundary layer；
Anode is prepared on boundary layer, obtains transoid QLED device.
The preparation method of the transoid QLED device, wherein the solvent in the carbon quantum dot solution is alcohols solvent.
Transoid QLED device of the present invention by being arranged a boundary layer between anode at QDs layers, the boundary layer by
Carbon quantum dot is prepared.The boundary layer has similar hole transmission layer effect, can realize carrier under electric field action
Oriented and ordered controllable migration；QDs layers are impacted when can also avoid existing deposition HTL or HIL layers simultaneously.The present invention
Whole soln method uses the solvent for dissolving boundary layer deposition materials when preparing transoid QLED device be a kind of to not readily dissolve the molten of QDs
Agent, so as to avoid solvent influence caused by QDs in deposited interfacial layer.Preferably, the solvent of interlayer materials is dissolved
For alcohols solvent, such as: 2-methyl cellosolve (MEA), ethyl alcohol alcohols solvent.Most preferably, it uses by volume ratio as 80:1's
The C-QD stability of solution highest of the mixed liquor of dimethoxy-ethanol and ethyl alcohol preparation, on QDs without influence.
Preferably, described before the step of preparing anode on boundary layer, further includes: hole function is prepared on boundary layer
Layer.Transoid QLED device of the present invention is prepared using whole soln method.Using in whole soln preparation process, need
HTL or HIL deposition materials are first dissolved in the solution that HTL or HIL deposition materials are prepared in solvent, then by HTL or HIL
Deposition materials solution is deposited by way of spin coating.Solvent for dissolving HTL or HIL deposition materials be mostly chlorobenzene,
Toluene or dichloro-benzenes equal solvent, and quantum dot light emitting layer QDs can be also dissolved in above-mentioned solvent, therefore, conventional method is direct
When depositing HTL or HIL on quantum dot light emitting layer, inevitably QDs layers are impacted, it might even be possible to all by QDs layers
It washes away, thereby reduces the efficiency of device.Transoid QLED device of the present invention at QDs layers between htl layer by being arranged
One boundary layer, the boundary layer are prepared by carbon quantum dot.The boundary layer not only has similar hole transmission layer effect, energy
Enough oriented and ordered controllable migrations that carrier is realized under electric field action；Simultaneously can also avoid deposition HTL or HIL layers when pair
QDs layers impact.The solvent of dissolution boundary layer deposition materials is used when whole soln method preparation transoid QLED device of the present invention
It is a kind of solvent for not readily dissolving QDs, so as to avoid solvent influence caused by QDs in deposited interfacial layer.Preferably,
The solvent for dissolving interlayer materials is alcohols solvent, such as: 2-methyl cellosolve (MEA), ethyl alcohol alcohols solvent.Most preferably,
The C-QD stability of solution highest prepared by volume ratio for the mixed liquor of the dimethoxy-ethanol of 80:1 and ethyl alcohol is used, to QDs
Without influence.
Preferably, the preparation method of the QLED device, wherein the step that quantum dot light emitting layer is prepared on cathode
Before rapid, further include: electronic work ergosphere is prepared on cathode.
Technical solution of the present invention is described in detail below by specific embodiment.
Embodiment 1
1, the preparation method of C-QD, comprising the following steps:
3mL ethanolamine solutions and 4.5mL hydrogen peroxide solution are uniformly mixed, then react 120min in 250 DEG C of reacting furnace,
Reaction solution from it is initial it is colourless become last black, wherein ethanol amine reacts completely, and it is last that hydrogen peroxide also all participates in reaction
Water is generated, finally moisture volatilizees completely in the state of heating, obtains C-QD.Then the mixed of dimethoxy-ethanol and ethyl alcohol is added
Liquid (its volume ratio is 80:1) is closed, the C-QD solution that C-QD concentration is 5mg/mL is finally configured to.
2, the preparation method of transoid QLED device, comprising the following steps:
Using spin-coating method first by ZnO concentration is the ZnO liquid deposition of 30mg/mL on ITO, and wherein revolving speed is 3Krpm, and
Temperature makes annealing treatment 15min under conditions of being 80 DEG C, obtains ETL layers；
Then using spin-coating method by luminescent quantum dot concentration is the luminescent quantum dot liquid deposition of 30mg/mL on ETL layer, wherein
Revolving speed 3Krpm, and 15min is made annealing treatment under conditions of temperature is 80 DEG C, obtain QDs layers；
Then using spin-coating method by C-QD concentration is the C-QD liquid deposition of 5mg/mL on QDs layer, and wherein revolving speed is 5Krpm,
And 15min is made annealing treatment under conditions of temperature is 80 DEG C, obtain C-QD layers；
Then using spin-coating method by TFB concentration is the TFB liquid deposition of 8g/mL on C-QD layer, and wherein revolving speed is 3Krpm, and
15min is made annealing treatment under conditions of temperature is 120 DEG C, obtains htl layer；
Then use spin-coating method by PEDOT:PSS liquid deposition on htl layer, wherein revolving speed is 5Krpm, and is 120 in temperature
15min is made annealing treatment under conditions of DEG C, obtains HIL layers；
Then use Al that the Al metal electrode that a layer thickness is 100nm is deposited on HIL layer for raw material；
It is finally packaged, obtains transoid QLED device architecture as shown in Figure 1.
Embodiment 2
1, the preparation method of C-QD, comprising the following steps:
The hydrogen peroxide solution of 3mL ethanolamine solutions and 4mL is uniformly mixed, then reacts 120min in 250 DEG C of reacting furnace,
Reaction solution from it is initial it is colourless become last black, wherein ethanol amine reacts completely, and it is last that hydrogen peroxide also all participates in reaction
Water is generated, finally moisture volatilizees completely in the state of heating, obtains C-QD.Then dimethoxy-ethanol is added, finally prepares
The C-QD solution for being 3mg/mL at C-QD concentration.
2, the preparation method of transoid QLED device, comprising the following steps:
Using spin-coating method first by ZnO concentration is the ZnO liquid deposition of 30mg/mL on ITO, and wherein revolving speed is 3Krpm, and
Temperature makes annealing treatment 15min under conditions of being 80 DEG C, obtains ETL layers；
Then using spin-coating method by luminescent quantum dot concentration is the luminescent quantum dot liquid deposition of 30mg/mL on ETL layer, wherein
Revolving speed is 3Krpm, and makes annealing treatment 15min under conditions of temperature is 80 DEG C, obtains QDs layers；
Then using spin-coating method by C-QD concentration is the C-QD liquid deposition of 3mg/mL on QDs layer, and wherein revolving speed is 5Krpm,
And 15min is made annealing treatment under conditions of temperature is 80 DEG C, obtain C-QD layers；
Then using spin-coating method by TFB concentration is the TFB liquid deposition of 8g/mL on C-QD layer, and wherein revolving speed is 3Krpm, and
15min is made annealing treatment under conditions of temperature is 120 DEG C, obtains HIL layers；
Then use Al that the Al metal electrode that a layer thickness is 100nm is deposited on C-QD layer for raw material；
It is finally packaged, obtains transoid QLED device architecture as shown in Figure 2.
In conclusion a kind of preparation method of carbon quantum dot provided by the invention, transoid QLED device and preparation method thereof.
C- QD layers is provided in the structure of transoid QLED device of the present invention between QD layers and HTL or HIL layers, to avoid
HTL or HIL layers of influence to QD layers, and then improve the efficiency of device.
It should be understood that the application of the present invention is not limited to the above for those of ordinary skills can
With improvement or transformation based on the above description, all these modifications and variations all should belong to the guarantor of appended claims of the present invention
Protect range.
Claims (10)
1. a kind of QLED device, including the cathode, quantum dot light emitting layer and anode being stacked, which is characterized in that further include setting
The boundary layer being placed between quantum dot light emitting layer and anode, the material of the boundary layer are carbon quantum dot.
2. QLED device according to claim 1, which is characterized in that further include the sky being set between boundary layer and anode
Acupoints layer.
3. QLED device according to claim 2, which is characterized in that the hole functional layer is hole transmission layer, hole
At least one of implanted layer.
4. QLED device according to claim 1, which is characterized in that further include be set to quantum dot light emitting layer and cathode it
Between electronic work ergosphere.
5. QLED device according to claim 1 to 4, which is characterized in that the boundary layer with a thickness of 2-20nm.
6. a kind of preparation method of QLED device, which comprises the following steps:
Cathode is provided；
Quantum dot light emitting layer is prepared on cathode；
Carbon quantum dot solution is deposited on quantum dot light emitting layer, obtains boundary layer；
Anode is prepared on boundary layer, obtains QLED device.
7. the preparation method of QLED device according to claim 6, which is characterized in that described to prepare anode on boundary layer
The step of before, further include: on boundary layer prepare hole functional layer.
8. the preparation method of QLED device according to claim 6, which is characterized in that described to prepare quantum dot on cathode
Before the step of luminescent layer, further include: electronic work ergosphere is prepared on cathode.
9. the preparation method of QLED device according to claim 6, which is characterized in that the carbon quantum dot solution is by carbon amounts
Son point is scattered in solvent and is formulated, and the preparation method of the carbon quantum dot makes comprising steps of hydramine is mixed with oxidant
Hydramine and oxidant reaction obtain carbon quantum dot.
10. the preparation method of QLED device according to claim 9, which is characterized in that the hydramine is ethanol amine；With/
Or the oxidant is hydrogen peroxide.
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| CN114039004A (en) * | 2020-12-31 | 2022-02-11 | 广东聚华印刷显示技术有限公司 | Light emitting device and method of manufacturing the same |
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| CN113122260A (en) * | 2019-12-30 | 2021-07-16 | Tcl集团股份有限公司 | Quantum dot material, preparation method thereof and quantum dot light-emitting diode |
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