CN106505158B - A kind of light emitting diode with quantum dots device and preparation method thereof - Google Patents
A kind of light emitting diode with quantum dots device and preparation method thereof Download PDFInfo
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- CN106505158B CN106505158B CN201611091220.5A CN201611091220A CN106505158B CN 106505158 B CN106505158 B CN 106505158B CN 201611091220 A CN201611091220 A CN 201611091220A CN 106505158 B CN106505158 B CN 106505158B
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- H10K50/00—Organic light-emitting devices
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- 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 light emitting diode with quantum dots device and preparation method thereof, the device successively includes substrate, hearth electrode, hole injection layer, hole transmission layer, quantum dot light emitting layer, electron transfer layer, electron injecting layer and top electrode, it is characterized in that, the substrate surface is deposited with an anti-reflection layer, the laminated construction that the anti-reflection layer is made of TaON or its dopant and TaOx or its dopant.The present invention is by depositing an anti-reflection layer being made of TaON or its dopant and TaOx or its dopant in substrate surface；According to the principle of interference of light, the anti-reflection layer can effectively reduce the reflection of the light of quantum dot light emitting layer sending, increase the transmission of light, give out light the light extraction efficiency of diode component to achieve the purpose that enhance quantum dot；And the present invention is by carrying out microcosmic texturing processing to anti-reflection layer surface, can further enhance quantum dot and give out light the light extraction efficiency of diode component.
Description
Technical field
The present invention relates to technology of quantum dots field more particularly to a kind of light emitting diode with quantum dots device and its preparation sides
Method.
Background technique
Quantum dot light emitting material based on inorganic nano-crystal is saturated with emergent light color, Wavelength tunable, photic, electroluminescent hair
The advantages of suitable Performance Monitor part such as quantum yield height；From the point of view of preparation process angle, quantum dot light emitting material is applicable in
Spin coating, printing under non-vacuum condition, printing device；Therefore, the light emitting diode with quantum dots prepared with quantum dot film
(QLED) become the contenders of next-generation display technology.
QLED device generally includes electrode 1, hole injection, hole transmission layer, luminescent layer, electron-transport, electron injecting layer
With electrode 2.However, in light emitting diode with quantum dots device, due to the loss of waveguiding effect, from the wide portion that luminescent layer issues
Dividing can only be in the internal communication of device, and is predominantly absorbed, and causes the light extraction efficiency of light emitting diode with quantum dots device low.
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 light emitting diode with quantum dots device and
Preparation method, it is intended to solve to pass in the inside of device in existing quantum dot device from the wide part that luminescent layer issues
It broadcasts, and is predominantly absorbed, the problem for causing the light extraction efficiency of light emitting diode with quantum dots device low.
Technical scheme is as follows:
A kind of light emitting diode with quantum dots device successively includes substrate, hearth electrode, hole injection layer, hole transmission layer, amount
Son point luminescent layer, electron transfer layer, electron injecting layer and top electrode, wherein the substrate surface is deposited with an anti-reflection layer, institute
State the laminated construction that anti-reflection layer is made of TaON or its dopant and TaOx or its dopant.
Preferably, the light emitting diode with quantum dots device, wherein the anti-reflection layer surface is microcosmic texturing table
Face.
Preferably, the light emitting diode with quantum dots device, wherein the anti-reflection layer with a thickness of 20-400nm.
Preferably, the light emitting diode with quantum dots device, wherein the TaON or its dopant and TaOx or its mix
The ranges of indices of refraction of sundries is 1-4.
Preferably, the light emitting diode with quantum dots device, wherein in the anti-reflection layer, close to the folding of substrate surface
It penetrates rate and is greater than the refractive index far from substrate surface.
Preferably, the light emitting diode with quantum dots device, wherein the material of the quantum dot light emitting layer is II-VI
Compounds of group, III-V compound, II-V compounds of group, III-VI compound, group IV-VI compound, I-III-VI race chemical combination
One of object, II-IV-VI compounds of group or IV race simple substance are a variety of.
Preferably, the light emitting diode with quantum dots device, wherein the quantum dot light emitting layer with a thickness of 10-
100nm。
Preferably, the light emitting diode with quantum dots device, wherein the thickness of the hole transmission layer and electron transfer layer
Degree is 5-100nm.
A kind of preparation method of light emitting diode with quantum dots device, wherein comprising steps of
A, TaON or its dopant and TaOx or its dopant are first deposited on the substrate for contain hearth electrode as anti-reflection layer；
B, hole injection layer and hole transmission layer are sequentially depositing in anti-reflection layer surface；
C, in hole transport layer surface deposition point luminescent layer;
D, electron transfer layer is deposited in quantum dot light emitting layer surface;
E, electron injecting layer is deposited in electron-transport layer surface;
F, top electrode is made in electron injection layer surface.
Preferably, the preparation method of the light emitting diode with quantum dots device, wherein after the step A, step B
Before further include:
S, using one of ibl, chemical solution etching, physics sand-blast or plasma etching method side
Method carries out microcosmic texturing processing to anti-reflection layer surface.
The utility model has the advantages that the present invention provides a kind of light emitting diode with quantum dots device and preparation method thereof, wherein by serving as a contrast
Bottom surface deposits an anti-reflection layer, the lamination knot that the anti-reflection layer is made of TaON or its dopant and TaOx or its dopant
Structure；According to the principle of interference of light, the anti-reflection layer can effectively reduce the reflection of the light of quantum dot light emitting layer sending, increase the saturating of light
It penetrates, gives out light the light extraction efficiency of diode component to achieve the purpose that enhance quantum dot；And the present invention passes through to anti-reflection layer table
Face carries out microcosmic texturing processing, can further enhance quantum dot and give out light the light extraction efficiency of diode component.
Detailed description of the invention
Fig. 1 is a kind of first structure diagram of light emitting diode with quantum dots device preferred embodiment of the present invention.
Specific embodiment
The present invention provides a kind of light emitting diode with quantum dots device and preparation method thereof, to make the purpose of the present invention, technology
Scheme and effect are clearer, clear, and the present invention is described in more detail below.It should be appreciated that described herein specific
Embodiment 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 structural schematic diagram of light emitting diode with quantum dots device preferred embodiment of the present invention,
As shown, the embodiment of the present invention, by taking eurymeric light emitting diode with quantum dots device as an example, the device successively includes from bottom to up
Substrate 10, hearth electrode 30, hole injection layer 40, hole transmission layer 50, quantum dot light emitting layer 60, electron transfer layer 70, electronics note
Enter layer 80 and top electrode 90, wherein 10 surface of substrate is deposited with an anti-reflection layer 20, the anti-reflection layer be by TaON or its
The laminated construction of dopant and TaOx or its dopant composition.
Specifically, in the present invention, the substrate 10 is ito glass, before depositing ITO, is first plated in glass substrate 10
One layer of anti-reflection layer 20, the laminated construction that the anti-reflection layer 20 is made of TaON or its dopant and TaOx or its dopant, institute
Stating the element adulterated in TaON and TaOx can be any one or more in Si, Al, W, Cu, Au, Ag.
The TaON and TaOx is a kind of electric material with high dielectric property and high refractive index, when using TaON/TaOx's
When laminated construction is as anti-reflection layer, the reflection of light can be effectively reduced, enhances the transmission of light, to improve light emitting diode with quantum dots
Light extraction efficiency.
It is explained below by further to the present invention program by taking the anti-reflection layer that TaON/TaOx is formed as an example:
In the present invention, right as shown in Figure 1, in order to further enhance the light extraction efficiency of light emitting diode with quantum dots device
Anti-reflection layer surface carries out microcosmic texturing processing, and anti-reflection layer surface is made to form microcosmic textured surfaces；Preferably, for example pass through
Ion etching process carries out microcosmic texturing processing, i.e., is bombarded using Ar ion in anti-reflection layer surface, make anti-reflection layer surface
Nanoscale or micron-sized hole are left, its surface roughness is increased, forms microcosmic textured surfaces.
Relative to smooth surface, microcosmic textured surfaces can effectively reduce the reflection of light, increase the transmission of light, to improve
The light extraction efficiency of light emitting diode with quantum dots.
Further, the present invention is using Ecr plasma method deposition TaON/TaOx laminated construction as anti-reflection
Layer, the anti-reflection layer stacked structure sequence can be, but not limited to TaON/TaOx, that is to say, that can first deposit on substrate
TaON film layer, redeposited TaOx film layer；TaOx film layer, redeposited TaON film layer can also be first deposited on substrate；
Further, in the present invention, the ranges of indices of refraction of the TaON or its dopant and TaOx or its dopant is
1-4, and in anti-reflection layer, it is greater than the film refractive index far from substrate surface, folding close to the film refractive index of substrate surface
The control of rate difference is penetrated within 0.5；For example, the laminated construction sequence when anti-reflection layer is TaON/TaOx, then NTaON>NTaOx；It is preferred that
Ground, when the refractive index of TaON is 2.5, the refractive index of TaOx is 2.2.Refractive index by controlling TaON and TaOx can be effective
The transmission for enhancing light, to improve the light extraction efficiency of light emitting diode with quantum dots device.
Further, in the present invention, the anti-reflection layer with a thickness of 20-400nm；It preferably, will be in the anti-reflection layer
The thickness of TaON film layer and TaOx film layer is disposed as 1/4 times of lambda1-wavelength, such as when incident light is blue light,
Wavelength is 440nm, then can deposit TaON/TaOx with a thickness of 100nm/100nm.The present invention can be reached by controlling anti-reflection layer thickness
To making two beams reflection optical path difference be that the n π times (n radix) of lambda1-wavelength enhances the transmission of light to reduce reflection, to reach
Go out the purpose of light to enhancing device.
Further, in the present invention, the material of the quantum dot light emitting layer is II-VI group compound, iii-v chemical combination
Object, II-V compounds of group, III-VI compound, group IV-VI compound, I-III-VI group compound, II-IV-VI compounds of group
Or one of IV race simple substance or a variety of；The compound includes binary compound, ternary compound and quaternary compound.
Specifically, the semiconductor material that the quantum dot light emitting layer uses includes but is not limited to the nanometer of II-VI semiconductor
Crystalline substance, such as CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, HgS, HgSe, HgTe, PbS, PbSe, PbTe and other binary, three
The II-VI compound of member, quaternary；Nanocrystalline, such as GaP, GaAs, InP, InAs and other binary, three of Group III-V semiconductor
Member, the III-V compound of quaternary；Described is also not limited to II-V compounds of group, III- for electroluminescent semiconductor material
VI compound, group IV-VI compound, I-III-VI group compound, II-IV-VI compounds of group, IV race simple substance etc..
Further, in the present invention, the thickness of the hole transmission layer and electron transfer layer is 5-100nm；The amount
Son point luminescent layer with a thickness of 10-100nm；Preferably, in light emitting diode with quantum dots device provided by the invention, the sky
The thickness of cave transport layer is set as 30nm, and the thickness of the electron transfer layer is set as 30nm, the thickness of the quantum dot light emitting layer
Degree is 50nm；In the thickness value, the electric conductivity of the hole transmission layer and electron transfer layer is best, required driving voltage compared with
It is low, so that the light emission luminance of device and luminous efficiency all have a distinct increment.
Based on a kind of above-mentioned light emitting diode with quantum dots device, the present invention also provides a kind of light emitting diode with quantum dots devices
Preparation method, including step:
A kind of preparation method of light emitting diode with quantum dots device, wherein comprising steps of
S100, TaON or its dopant and TaOx or its dopant are first deposited on the substrate for contain hearth electrode as anti-reflection
Layer；
S200, hole injection layer and hole transmission layer are sequentially depositing in anti-reflection layer surface；
S300, in hole transport layer surface deposition point luminescent layer;
S400, electron transfer layer is deposited in quantum dot light emitting layer surface;
S500, electron injecting layer is deposited in electron-transport layer surface;
S600, top electrode is made in electron injection layer surface.
Preferably, after the step S100, before step S200 further include:
S, using one of ibl, chemical solution etching, physics sand-blast or plasma etching method pair
Anti-reflection layer surface carries out microcosmic texturing processing.
Preferably, in the present invention, it, should using Ecr plasma method deposited oxide tantalum/nitrogen tantalum oxide
The film compactness of method deposition is good, and refractive index is high, and deposition rate is fast, is suitable as anti-reflection layer；Preferably, using ion beam
Etching carries out processing to anti-reflection layer surface and forms microcosmic textured surfaces, further promotes device light emission rate；
Further, hole injection layer, hole transmission layer and electron transfer layer can pass through the solution such as printing, spin coating and spraying
The preparation of the vacuum methods such as method or vacuum evaporation, sputtering and chemical vapor deposition；Quantum dot light emitting layer can by spin coating, printing and
The methods of spraying is realized；Top electrode then can be used chemical vapor deposition (CVD), magnetron sputtering, sol-gel method etc. to realize.
Below by specific embodiment, further explanation is made to the present invention program:
Embodiment 1
Glass substrate is scrubbed clean, is cleaned 3 times in aqueous isopropanol sonic oscillation, finally rinses after-blow with deionized water
It is dry, it is put into ECR equipment vacuum feeding room, ECR reaction chamber is sent into, vacuumizes, until vacuum degree reaches 3 × 10-4Pa can be opened
Beginning is deposited.Technological parameter: the first step is set, TaON film 30nm is deposited, microwave power Coil power is 400W, and electric current is
2.7A；Substrate bias power is set as 300W, and gas flow is set as Ar:O2: N2=20:0.5:1.5, unit: sccm, substrate inclination
Angle is set as 30 °, time 240s.Baffle is shut, and pre-deposition is first carried out, and is deposited 60s using identical technological parameter, is beaten after complete
Baffle deposition 240s is opened, the TaON thin layer of a layer thickness about 30nm is plated in glass surface, 300s is vacuumized after complete and carries out lower step；
Second step, deposits TaOx film 20nm, and microwave power Coil power is 500W, electric current 2.7A；Substrate bias power is set as
300W, gas flow are set as Ar:O2: N2=20sccm:2sccm:0sccm, substrate tilt angle are set as 30 °, time 160s,
It shuts baffle and carries out pre-deposition 60s, then open baffle deposition 160s, the TaOx with a thickness of 20nm is plated on TaON film, is formed
TaON/TaOx lamination antireflective film.
Anti-reflection layer has been plated, by manipulator in transfer chamber, sample has been sent to IBE vacuum chamber, reach 3 to vacuum ×
10-4Parameter is arranged in pa, and radio-frequency power is set as 180W, and Grid61 voltage is -525V, and Grid62 voltage is 100V, gas flow
Ar:O2=18:0, unit sccm, substrate tilt angle are 65 °, time 15s, check that errorless rear click starts, just complete and subtract
The anti-microcosmic texturing of layer surface.
Embodiment 2
Glass substrate is scrubbed clean, aqueous isopropanol sonic oscillation is put and cleans 3 times, finally rinse after-blow with deionized water
It is dry, it is put into ECR equipment vacuum feeding room, ECR reaction chamber is sent into, vacuumizes, until vacuum degree reaches 3 × 10-4Pa can be opened
Beginning is deposited.Technological parameter: the first step is set, TaON film 30nm is deposited, microwave power Coil power is 400W, and electric current is
2.7A；Substrate bias power is set as 300W, and gas flow is set as Ar:O2: N2=20:0.5:1.5, unit: sccm, substrate inclination
Angle is set as 30 °, time 240s.Baffle is shut, and pre-deposition is first carried out, and is deposited 60s using identical technological parameter, is beaten after complete
Baffle deposition 240s is opened, the TaON thin layer of a layer thickness about 30nm is plated in glass surface, 300s is vacuumized after complete and carries out lower step；
Second step, deposits TaOx film 50nm, and microwave power Coil power is 500W, electric current 2.7A；Substrate bias power is set as
300W, gas flow are set as Ar:O2: N2=20sccm:2sccm:0sccm, substrate tilt angle are set as 30 °, time 400s,
It shuts baffle and carries out pre-deposition 60s, then open baffle deposition 160s, the TaOx with a thickness of 50nm is plated on TaON film, is formed
TaON/TaOx lamination antireflective film.
Anti-reflection layer has been plated, by manipulator in transfer chamber, sample has been sent to IBE vacuum chamber, reach 3 to vacuum ×
10-4Parameter is arranged in pa, and radio-frequency power is set as 180W, and Grid61 voltage is -525V, and Grid62 voltage is 100V, gas flow
Ar:O2=18:0, unit sccm, substrate tilt angle are 65 °, time 15s, check that errorless rear click starts, just complete and subtract
The anti-microcosmic texturing of layer surface.
Embodiment 3
Glass substrate is scrubbed clean, aqueous isopropanol sonic oscillation is put and cleans 3 times, finally rinse after-blow with deionized water
It is dry, it is put into ECR equipment vacuum feeding room, ECR reaction chamber is sent into, vacuumizes, until vacuum degree reaches 3 × 10-4Pa can be opened
Beginning is deposited.Technological parameter: the first step is set, TaON film 30nm is deposited, microwave power Coil power is 400W, and electric current is
2.7A；Substrate bias power is set as 300W, and gas flow is set as Ar:O2: N2=20:0.5:1.5, unit: sccm, substrate inclination
Angle is set as 30 °, time 240s.Baffle is shut, and pre-deposition is first carried out, and is deposited 60s using identical technological parameter, is beaten after complete
Baffle deposition 240s is opened, the TaON thin layer of a layer thickness about 30nm is plated in glass surface, 300s is vacuumized after complete and carries out lower step；
Second step, deposits TaOx film 70nm, and microwave power Coil power is 500W, electric current 2.7A；Substrate bias power is set as
300W, gas flow are set as Ar:O2: N2=20sccm:2sccm:0sccm, substrate tilt angle are set as 30 °, time 560s,
It shuts baffle and carries out pre-deposition 60s, then open baffle deposition 160s, the TaOx with a thickness of 70nm is plated on TaON film, is formed
TaON/TaOx lamination antireflective film.
Anti-reflection layer has been plated, by manipulator in transfer chamber, sample has been sent to IBE vacuum chamber, reach 3 to vacuum ×
10-4Parameter is arranged in pa, and radio-frequency power is set as 180W, and Grid61 voltage is -525V, and Grid62 voltage is 100V, gas flow
Ar:O2=18:0, unit sccm, substrate tilt angle are 65 °, time 15s, check that errorless rear click starts, just complete and subtract
The anti-microcosmic texturing of layer surface.
In conclusion the present invention provides a kind of light emitting diode with quantum dots device and preparation method thereof, wherein by serving as a contrast
Bottom surface deposits an anti-reflection layer, the lamination knot that the anti-reflection layer is made of TaON or its dopant and TaOx or its dopant
Structure；According to the principle of interference of light, the anti-reflection layer can effectively reduce the reflection of the light of quantum dot light emitting layer sending, increase the saturating of light
It penetrates, gives out light the light extraction efficiency of diode component to achieve the purpose that enhance quantum dot；And the present invention passes through to anti-reflection layer table
Face carries out microcosmic texturing processing, can further enhance quantum dot and give out light the light extraction efficiency of diode component.
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 light emitting diode with quantum dots device successively includes substrate, hearth electrode, hole injection layer, hole transmission layer, quantum
Point luminescent layer, electron transfer layer, electron injecting layer and top electrode, which is characterized in that between the substrate and the hearth electrode
Equipped with an anti-reflection layer, laminated construction that the anti-reflection layer is made of TaON or its dopant and TaOx or its dopant；
In the laminated construction, the layer structure formed by TaON or its dopant is close to the one side of substrate.
2. light emitting diode with quantum dots device according to claim 1, which is characterized in that the anti-reflection layer surface is microcosmic
Textured surfaces.
3. light emitting diode with quantum dots device according to claim 1, which is characterized in that the anti-reflection layer with a thickness of
20-400nm。
4. light emitting diode with quantum dots device according to claim 1, which is characterized in that the TaON or its dopant and
The ranges of indices of refraction of TaOx or its dopant is 1-4.
5. light emitting diode with quantum dots device according to claim 1, which is characterized in that in the anti-reflection layer, close to lining
The refractive index of bottom surface is greater than the refractive index far from substrate surface.
6. light emitting diode with quantum dots device according to claim 1, which is characterized in that the material of the quantum dot light emitting layer
Material is II-VI group compound, III-V compound, II-V compounds of group, III-VI compound, group IV-VI compound, I-
One of III-VI compounds of group, II-IV-VI compounds of group or IV race simple substance are a variety of.
7. light emitting diode with quantum dots device according to claim 1, which is characterized in that the thickness of the quantum dot light emitting layer
Degree is 10-100nm.
8. light emitting diode with quantum dots device according to claim 1, which is characterized in that the hole transmission layer and electronics
The thickness of transport layer is 5-100nm.
9. a kind of preparation method of light emitting diode with quantum dots device, which is characterized in that comprising steps of
Substrate is provided, TaON or its dopant and TaOx or its dopant are deposited on substrate as anti-reflection layer, the anti-reflection layer is
The laminated construction being made of TaON or its dopant and TaOx or its dopant, in the laminated construction, by TaON or its doping
The layer structure that object is formed is close to the one side of substrate；
Hearth electrode is formed in anti-reflection layer surface；
In hearth electrode surface deposition of hole implanted layer；
In hole injection layer surface deposition of hole transport layer；
In hole transport layer surface deposition point luminescent layer；
Electron transfer layer is deposited in quantum dot light emitting layer surface；
Electron injecting layer is deposited in electron-transport layer surface；
Top electrode is made in electron injection layer surface.
10. the preparation method of light emitting diode with quantum dots device according to claim 9, which is characterized in that described to serve as a contrast
It deposits TaON or its dopant and TaOx on bottom or its dopant is used as after anti-reflection layer, described in anti-reflection layer surface to form bottom electric
Before pole further include:
Using one of ibl, chemical solution etching, physics sand-blast or plasma etching method method to subtracting
Anti- layer surface carries out microcosmic texturing processing.
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