CN109560211A - Gold nanorods are in the application being inverted in OLED device - Google Patents
Gold nanorods are in the application being inverted in OLED device Download PDFInfo
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Abstract
The invention discloses gold nanorods to improve the application being inverted in OLED device luminescent properties.The invention also discloses the inversion OLED device of gold nanorods hydridization and the preparation methods of the device.This method passes through the surface plasmon resonance effect using gold nanorods, greatly accelerate being excited and radiation transistion process for electronics, by the aspect ratio for adjusting gold nanorods, keep its surface plasmon resonance absorption band and the Absorption and emission spectra of luminescent material be overlapped respectively, achieve the purpose that farthest to enhance OLED device performance, compared with initial devices, the device brightness and luminous efficiency of gold nanorods hydridization are 2.07 times and 1.86 times of initial devices brightness and luminous efficiency, effectively increase the performance for being inverted OLED device.
Description
Technical field
The present invention relates to Organic Light Emitting Diode technical fields, specifically, being related to gold nanorods is being inverted OLED device
In application.
Background technique
Organic Light Emitting Diode (OLED) is a kind of active luminescent device for being hopeful to replace liquid crystal screen displays at present, tool
Having advantages, the common structures such as low-work voltage, high brightness, flexible, visual angle be wide is by positive/negative electrode, hole/electricity
Sub- transport layer and organic luminous layer composition, device working principle are that hole and electronics are injected by anode and cathode respectively, are passed through respectively
Hole and electron transfer layer are crossed, the recombination luminescence in luminescent layer.Metal nanoparticle has surface phasmon under light excitation
The brightness and efficiency of luminescent material can be improved in resonance effects, and metal nanoparticle is applied in OLED device, can be improved
Its performance.
The OLED device of inverted structure usually has the advantages that stability is good, this is because electronics is from electro-conductive glass
(ITO) one end is injected, and does not use the metal electrode of environmental stability difference in the devices, and gold nanorods are applied to be inverted OLED
Device simultaneously enhances its performance, there is no report at present.
Summary of the invention
The present invention provides gold nanorods (AuNRs) in the application being inverted in OLED device, by utilizing gold nanorods
Surface plasmon resonance effect effectively improves the performance for being inverted OLED device, by adjusting the aspect ratio of gold nanorods, makes it
Surface plasmon resonance absorption band and the Absorption and emission spectra of luminescent material are be overlapped respectively, and reaching farthest enhances
The purpose of OLED device performance.
The present invention is realized by following scheme:
One, gold nanorods are improving the application being inverted in OLED device luminescent properties.
Specifically, the position of the gold nanorods transverse direction absorption band, in 525nm, the position of longitudinal absorption band is greater than 600nm.
Specifically, the aspect ratio of the gold nanorods is 80nm:40nm.
Further, the luminescent properties that improve are the aspect ratios by adjusting gold nanorods, make its surface phasmon
RESONANCE ABSORPTION band and the Absorption and emission spectra of luminescent material are Chong Die respectively to be realized.
Further, the luminescent material is red emissive material, dark red light-emitting material and near infrared light emissive material
In any one.
Two, a kind of inversion OLED device of gold nanorods hydridization, including electro-conductive glass ITO layer, gold nanorods layer, electronics pass
Defeated layer, luminescent layer, hole transmission layer and metal silver electrode.
Specifically, the electron transport layer materials are zinc oxide.
Specifically, the material of the luminescent layer is MEH-PPV.
Specifically, the material of the hole transmission layer is molybdenum oxide.
Three, a kind of preparation method of the inversion OLED device according to above-mentioned gold nanorods hydridization, comprising the following steps:
(1) one layer of gold nanorods are deposited by the method for Electrostatic Absorption self assembly first on electro-conductive glass ITO;
(2) a thin layer zinc oxide is prepared as electron transfer layer by the method for spin coating again;
(3) subsequent one layer of luminescent material of spin coating again;
(4) molybdenum oxide and metal silver electrode are prepared finally by the method for vapor deposition.
Further, between the gold nanorods and luminescent material between be divided into 6 ~ 12nm.
Further, the light emitting layer thickness is 70 ~ 100nm.
The present invention compared with the existing technology, the advantage is that: this method pass through utilize gold nanorods surface phasmon
Resonance effects, greatly accelerate electronics be excited with radiation transistion process, gold nanorods tool is there are two surface plasmon resonance
Absorption band, wherein the position of longitudinal absorption band is adjustable, therefore can by adjusting the aspect ratios of gold nanorods, make its surface etc. from
Plasmon resonance absorption band and the Absorption and emission spectra of luminescent material are be overlapped respectively, reach farthest enhancing OLED device
The purpose of energy, compared with initial devices, the device brightness and luminous efficiency of gold nanorods hydridization are initial devices brightness and lumen
2.07 times of efficiency and 1.86 times, effectively increase the performance for being inverted OLED device.
Detailed description of the invention:
Fig. 1 is the OLED device structure of gold nanorods hydridization of the present invention, 1, metal silver electrode, 2, molybdenum oxide, 3, luminescent layer, 4, electricity
Sub- transport layer, 5, gold nanorods, 6, electro-conductive glass (ITO);
Fig. 2 is absorption and the emission spectrum of red light material MEH-PPV film, and aspect ratio is the gold nanorods solution of 80nm:40nm
With the absorption spectrum of film;
Fig. 3 is electron microscope of the gold nanorods in ITO substrate that aspect ratio is 80nm:40nm, length of the scale 100nm;
Fig. 4 is under the excitation of 500nm light, the luminous intensity of the MEH-PPV film of gold nanorods hydridization and pure MEH-PPV film with
The comparison of fluorescence lifetime, Fig. 4 (a) be pure MEH-PPV film, gold nanorods hydridization MEH-PPV film emission spectrum;Fig. 4
It (b) is pure MEH-PPV film, the time resolution fluorescence spectral of the MEH-PPV film of gold nanorods hydridization;
Fig. 5 compares for the device performance of initial devices and gold nanorods hydridization, and Fig. 5 (a) is voltage-current density-brightness curve,
Fig. 5 (b) is current density-luminous efficiency curve.
Fig. 6 is absorption and the emission spectrum of red light material MEH-PPV film, and diameter is the AuNPs solution and film of 20nm
Absorption spectrum;
Fig. 7 is electron microscope of the AuNPs in ITO substrate that diameter is 20nm, length of the scale 100nm;
Fig. 8 is under the excitation of 500nm light, the luminous intensity of the MEH-PPV film of AuNPs hydridization and pure MEH-PPV film with it is glimmering
The comparison in light service life, Fig. 8 (a) be pure MEH-PPV film, AuNPs hydridization MEH-PPV film emission spectrum;Fig. 8 (b) is
Pure MEH-PPV film, AuNPs hydridization MEH-PPV film time resolution fluorescence spectral;
Fig. 9 compares for the device performance of initial devices and AuNPs hydridization, and Fig. 9 (a) is voltage-current density-brightness curve, Fig. 9
It (b) is current density-luminous efficiency curve.
Specific embodiment
With reference to embodiment, the present invention is furture elucidated, as described below, is only to preferable implementation of the invention
Example, not limits the present invention, any person skilled in the art is possibly also with the disclosure above
Technology contents changed or be modified as the equivalent embodiment changed on an equal basis, without departing from the concept of the present invention, foundation
Technical spirit any simple modification, equivalent change and modification made to the above embodiment of the invention, all fall within of the invention
In protection scope.
Embodiment 1
A kind of inversion OLED device of gold nanorods hydridization, including electro-conductive glass ITO, gold nanorods, zinc oxide, red light material
MEH-PPV, molybdenum oxide layer and metal silver electrode, preparation flow are as follows:
(1) firstly, depositing one layer of gold nanorods by the method for Electrostatic Absorption self assembly on electro-conductive glass (ITO);
(2) a thin layer zinc oxide is prepared as electron transfer layer, between gold nanorods and luminescent material by the method for spin coating again
Between be divided into 6nm;
(3) subsequent one layer of luminescent material of spin coating again, thickness control 70nm;
(4) molybdenum oxide and metal silver electrode are prepared finally by the method for vapor deposition, obtains product.
Embodiment 2
A kind of inversion OLED device of gold nanorods hydridization, including electro-conductive glass ITO, gold nanorods, zinc oxide, red light material
MEH-PPV, molybdenum oxide layer and metal silver electrode, preparation flow are as follows:
(1) firstly, depositing one layer of gold nanorods by the method for Electrostatic Absorption self assembly on electro-conductive glass (ITO);
(2) a thin layer zinc oxide is prepared as electron transfer layer, between gold nanorods and luminescent material by the method for spin coating again
Between be divided into 9nm;
(3) subsequent one layer of luminescent material of spin coating again, thickness control 85nm;
(4) molybdenum oxide and metal silver electrode are prepared finally by the method for vapor deposition, obtains product.
Embodiment 3
A kind of inversion OLED device of gold nanorods hydridization, including electro-conductive glass ITO, gold nanorods, zinc oxide, red light material
MEH-PPV, molybdenum oxide layer and metal silver electrode, preparation flow are as follows:
(1) firstly, depositing one layer of gold nanorods by the method for Electrostatic Absorption self assembly on electro-conductive glass (ITO);
(2) a thin layer zinc oxide is prepared as electron transfer layer, between gold nanorods and luminescent material by the method for spin coating again
Between be divided into 12nm;
(3) subsequent one layer of luminescent material of spin coating again, thickness control 100nm;
(4) molybdenum oxide and metal silver electrode are prepared finally by the method for vapor deposition, obtains product.
Test example 1
Gold nanorods usually have two surface plasmon resonance absorption bands of vertical and horizontal, wherein lateral absorption band exists
525nm or so, and the position of longitudinal absorption band can be adjustable with the aspect ratio of gold nanorods, when the absorption of metal nanoparticle
When band is with the absorption of luminescent material or Chong Die emission spectrum, surface plasmon resonance effect can just be fully utilized, therefore, gold
Longitudinal absorption band of nanometer rods is can be regulated and controled according to the absorption of luminescent material and transmitting feature, is effective enhancing
The performance of OLED, in general, the position of longitudinal absorption band of gold nanorods are greater than 600nm, therefore, gold nanorods for
Feux rouges, dark red light and the photoemissive material of near-infrared have apparent advantage in application aspect.
Classical red light material MEH-PPV is chosen as the luminescent layer for being inverted OLED device, the absorption and transmitting of film
Spectrum is as shown in Fig. 2, the substantial scope absorbed is in 430 ~ 560nm, and in 580 ~ 660nm, aspect ratio is the substantial scope of transmitting
Although the longitudinal main peak position that absorbs of the gold nanorods of 80nm:40nm in the solution is in 680nm or so, it has blue shift in the film
To 625nm or so, just there is greater overlap with the emission spectrum of MEH-PPV, can effectively enhance the performance for being inverted OLED device;
And the lateral absorption peak (525nm) and the absorption spectrum of MEH-PPV of gold nanorods are also substantially overlapping, to the performance of enhancing OLED
Also there is positive contribution.
Fig. 3 is electron microscope of the gold nanorods in ITO substrate, it was confirmed that the method by Electrostatic Absorption self assembly is can be with
So that gold nanorods is deposited on the surface ITO, is used to prepare the inversion OLED device of gold nanorods hydridization.
Test example 2
Under the excitation of 500nm light, the luminous intensity and fluorescence of the MEH-PPV film of gold nanorods hydridization and pure MEH-PPV film
The comparison in service life, test result such as Fig. 4.
Under the excitation of 500nm light, as shown in Figure 4 (a), the luminescence generated by light of the MEH-PPV film of gold nanorods hydridization is strong
Degree is about 2 times (Fig. 4 a) of pure MEH-PPV film, and this is mainly due to the quickenings of the surface plasmon resonance effect of gold nanorods
Being excited and radiation transistion process of electronics;By the time resolution fluorescence spectral of Fig. 4 (b) it is found that the fluorescence of pure MEH-PPV film
Service life is then 0.64ns, and the fluorescence lifetime of the MEH-PPV film of gold nanorods hydridization is only 0.09ns, and the decline in service life is also demonstrate,proved
The real quickening of radiation transistion process.
Test example 3
The brightness of the device and initial devices of gold nanorods hydridization and the comparison of luminous efficiency, test result such as Fig. 5.
As shown in Fig. 5 (a) and Fig. 5 (b), the device brightness and luminous efficiency of gold nanorods hydridization are respectively up to 4111cd/
m2And 0.41cd/A, it is initial devices brightness (1988cd/m2) and 2.07 times and 1.86 times of luminous efficiency (0.22cd/A).
Comparative example 1
Diameter is the luminescent properties of the OLED device of gold nanoparticle (AuNPs) hydridization of 20nm.
1, the absorption of red light material MEH-PPV film and emission spectrum, diameter are the suction of the AuNPs solution and film of 20nm
Receive spectrum
The same luminescent layer for choosing classical red light material MEH-PPV as OLED device, the Absorption and emission spectra of film
As shown in fig. 6, the substantial scope absorbed is in 430 ~ 560nm, the substantial scope of transmitting is in 580 ~ 660nm.Diameter is 20nm's
Absorption main peak position of the AuNPs in solution and film is just also substantially heavy with the absorption spectrum of MEH-PPV all in 525nm or so
It is folded, also there is positive contribution to the performance of enhancing OLED.
Fig. 7 is electron microscope of the AuNPs in ITO substrate, it was confirmed that the method by Electrostatic Absorption self assembly is can to make
AuNPs is deposited on the surface ITO, is used to prepare the OLED device of AuNPs hydridization.
2, under the excitation of 500nm light, the luminous intensity of the MEH-PPV film of AuNPs hydridization and pure MEH-PPV film with it is glimmering
The comparison in light service life, test result such as Fig. 8 (a) and Fig. 8 (b).
Under the excitation of 500nm light, the photoluminescence intensity of the MEH-PPV film of AuNPs hydridization is pure MEH-PPV film
About 1.6 times, this is mainly due to the surface plasmon resonance effects of AuNPs to accelerate being excited and radiation transistion mistake for electronics
Journey;By the time resolution fluorescence spectral of Fig. 8 (b) it is found that the fluorescence lifetime of pure MEH-PPV film is then 0.64ns, and AuNPs is miscellaneous
The fluorescence lifetime of the MEH-PPV film of change is only 0.31ns, and the decline in service life also demonstrates the quickening of radiation transistion process.
3, the comparison of the brightness of the device and initial devices of AuNPs hydridization and luminous efficiency, test result such as Fig. 9 (a) and
Fig. 9 (b).
As shown in Fig. 9 (a) and Fig. 9 (b), the device brightness and luminous efficiency of AuNPs hydridization are respectively up to 2946cd/m2With
0.31cd/A is initial devices brightness (1988cd/m2) and 1.48 times and 1.41 times of luminous efficiency (0.22cd/A).
By being tested above it is found that can be mentioned using the surface plasmon resonance effect of gold nanorods and gold nanoparticle
High OLED device performance, however, there are two surface plasmon resonance absorption bands for gold nanorods tool, wherein the position of longitudinal absorption band
Set it is adjustable, therefore can by adjust gold nanorods aspect ratio, make its surface plasmon resonance absorption band and luminescent material
Absorption and emission spectra be overlapped respectively, achieve the purpose that farthest enhance OLED device performance, compared with initial devices,
The device brightness and luminous efficiency of gold nanoparticle hydridization are 1.48 times and 1.41 times of initial devices brightness and luminous efficiency, and
The device brightness of gold nanorods hydridization and luminous efficiency up to 2.07 times and 1.86 times of initial devices brightness and luminous efficiency, by
This is as it can be seen that the device of gold nanorods hydridization can be improved preferably compared with initial devices and the device of gold nanoparticle hydridization
Luminescent properties.
Claims (12)
1. gold nanorods are improving the application being inverted in OLED device luminescent properties.
2. application according to claim 1, which is characterized in that the position of the gold nanorods transverse direction absorption band in 525nm,
The position of longitudinal absorption band is greater than 600nm.
3. application according to claim 2, which is characterized in that the aspect ratio of the gold nanorods is 80nm:40nm.
4. application according to claim 1, which is characterized in that the raising luminescent properties are by adjusting gold nanorods
Aspect ratio makes its surface plasmon resonance absorption band and the Absorption and emission spectra of luminescent material are Chong Die respectively to realize.
5. application according to claim 4, which is characterized in that the luminescent material is red emissive material, dark red light hair
Penetrate any one in material and near infrared light emissive material.
6. a kind of inversion OLED device of gold nanorods hydridization, which is characterized in that the OLED device includes electro-conductive glass ITO
Layer, gold nanorods layer, electron transfer layer, luminescent layer, hole transmission layer and metal silver electrode.
7. the inversion OLED device of gold nanorods hydridization according to claim 6, which is characterized in that the electron transfer layer
Material is zinc oxide.
8. the inversion OLED device of gold nanorods hydridization according to claim 6, which is characterized in that the material of the luminescent layer
Material is MEH-PPV.
9. the inversion OLED device of gold nanorods hydridization according to claim 6, which is characterized in that the hole transmission layer
Material be molybdenum oxide.
10. a kind of preparation method of the inversion OLED device of gold nanorods hydridization according to claim 6, feature exist
In, comprising the following steps:
(1) one layer of gold nanorods are deposited by the method for Electrostatic Absorption self assembly first on electro-conductive glass ITO;
(2) a thin layer zinc oxide is prepared as electron transfer layer by the method for spin coating again;
(3) subsequent one layer of luminescent material of spin coating again;
(4) molybdenum oxide and metal silver electrode are prepared finally by the method for vapor deposition.
11. the preparation method of the inversion OLED device of gold nanorods hydridization according to claim 10, which is characterized in that institute
6 ~ 12nm is divided between stating between gold nanorods and luminescent material.
12. the preparation method of the inversion OLED device of gold nanorods hydridization according to claim 10, which is characterized in that institute
Stating light emitting layer thickness is 70 ~ 100nm.
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