Advance in Metal-based Nanoparticles for the Enhanced Performance of Organic Optoelectronics Devices†

doi:10.7503/cjcu20150916

Abstract

Abstract:

Metal nanoparticles(NPs) have made great contributions to the optical and electrical properties in the field of materials science, primary to the interest in their unique small size effect, quantum effect, surface effect and macro quantum tunnel effect. Recently, utilizing the unique optical and electrical properties of metal NPs enable them to be extensive applied in organic optoelectronic devices for further enhancing device performances, has becoming the research focus area. Until now, the best enhancement ratio of efficiency in organic light-emitting diodes and organic photovoltaics are 150% and 70%, respectively, especially the successful applications in the high-performance optoelectronic devices. The enhancement mechanism could be concluded to metal enhanced fluorescence, plasma enhanced absorption, energy transfer, electrical effect, scattering effect and so on. Here we review the different enhancement mechanisms introduced by surface plasma resonance and electrical effect of metal NPs, present the different strategies of incorporating different NPs and summarize the research works of metal NPs-based enhancing the performance of organic optoelectronic devices. The local surface plasma resonance of NPs also exist some problems when applied in devices, such as the limitation of action range, the enhanced wavelength region should matching with plasma resonance and so on. The researchers proposed some new design views such as “far-field” effect, the adjusting between NPs and excitons profile, scattering effect. With the comprehensive understanding of the mechanisms, further improvement in device performance and emerging applications can be expected for the new class of NPs-incorporated organic optoelectronic devices.

Key words: Metal nanoparticles, Organic light-emitting diode, Organic photovoltaics, Optical effect, Electrical effect

CLC Number:

O621

TrendMD:

WU Xiaoyan, LIU Linlin, XIE Zengqi, MA Yuguang. Advance in Metal-based Nanoparticles for the Enhanced Performance of Organic Optoelectronics Devices^†[J]. Chem. J. Chinese Universities, 2016, 37(3): 409.

Figures/Tables 17

Fig.1 Classical Jablonski diagram for the free-space condition(A) and the modified form in the presence of metal particles(B) E: Excitation; Em: metal enhanced excitation rate; Γm: radiative rate in the presence of metal.

Fig.2 Structure designs of plasmonic-enhanced OPVs[27](A) Nanostructure behaving as scattering centers; incident photons are scattered mostly into the material having a higher dielectric constant at the thin film surface; (B) embedded NPs positioned in organic semiconductors to enhance the near-field in the cell; scattering events also possibly occur in such solar cells; (C) a periodical structure induces SPPs, which can turn the incident solar flux by 90°. Copyright from the Royal Society of Chemistry.

Fig.3 Schematic device structure of OLEDs incorporating Au NPs, TEM and high-resolution TEM images of the synthesized Au NPs(A), time-resolved PL spectra detected at the wavelength of 530 nm via a 370 nm laser source(B), current density-voltage(C), luminous efficiency characteristics of Alq3 OLEDs with and without Au NPs(D) and current efficiency of red emission OLEDs with and without Au NPs(E)[54] Inset of (B) shows the absorption spectra of the PEDOT∶PSS mixed and without Au NPs and the PL spectrum of an Alq3 layer. Insets of (C, E) are the corresponding EL spectra at the current density of 40 and 20 mA/cm2, respectively. Copyright from the AIP Publishing LLC.

Fig.4 TEM image of the Au NPs@SiO2 core-shell NPs(A), normalized EL spectra of the PLEDs and the normalized UV-Vis absorption spectra of 8 nm Au NPs and Au NPs@SiO2 dispersed in water(B), schematic of the device structure of the PLEDs(C), the current density-luminance-voltage characteristics(D) and luminous efficiency characteristics of devices with and without Au NPs@SiO2(E) and luminance-voltage and luminous efficiency-current density characteristics of a device with Au NPs(without the shell)(F)[82] Copyright from the AIP Publishing LLC.

Fig.5 Experimental(A) and theoretical(B) absorbance enhancement factor of the active layer with different amounts of Au NPs and theoretical near field distribution around an Au NP in the active layer(C)[49]Copyright from the Royal Society of Chemistry.

Fig.6 Device structure and the energy level of iPLEDs/Au NPs(A), characteristics of current density vs. applied voltage(B), luminous efficiency vs. current density curves as a function of different electrostatic adsorption time of Au NPs(C) and time-resolved PL spectra detected at the wavelength of 518 nm excited by a 405 nm laser source(D)[45] Inset is PL spectra of P-PPV layer with and without Au NPs(D). The w/o Au NPs represent without Au NPs. Copyright from the American Chemical Society.

Fig.7 Device structures of the OPVs(A), SEM image of the Au NPs(B), current density vs. voltage characteristics(C), recorded under illumination at 100 mW/cm2(AM 1.5 G) of the OPVs prepared with Cs2CO3 layers incorporating various amounts of Au NPs[93]Copyright from the AIP Publishing LLC.

Fig.8 Device structure and schematic of near effect and far-effect working distance(A), PL spectra of MEH-PPV, P-PPV, PFO film(B) and the relationship between Ztheory-PL and ZB or ZLE as a function of distance between Au NPs and fluorescent moleculars(C)[44]In (C), dash line stands for Ztheory-PL, filled rectangle represents for ZLE, empty rectangle stands for ZB. Red, green, blue colors represent MEH-PPV, P-PPV, PFO, respectively. Copyright from the John Wiley and Sons.

Fig.9 Theoretical electric field profile in the PEDOT∶PSS∶Au NPs/P3HT∶PC61BM OPVs(A) and optical density of the PEDOT∶PSS/P3HT∶PC61BM film with or without Au NPs incorporation(B)[53] Copyright from the Royal Society of Chemistry.

Fig.10 Current vs. voltage characteristics of the PDOF/gold NPs nanocomposite devices with different nanoparticle volume fractions(A), schematically illustrated mechanism of the formation of roughened surface(B)[28]Copyright from the American Chemical Society.

Fig.11 Chemical structures of PCDTBT and PC70BM, a schematic of the device structure and SEM images of synthesized Ag NPs of several diameters using polyol process(A) and UPS spectra of the plain OPVs(a) and the OPVs with Ag clusters(b)(B)[34] Copyright from the John Wiley and Sons.

Fig.12 Architechture and energy levels of the PLEDs(A) and luminous efficiency vs. current density curves as a function of Au NPs thickness(B)[46]The w/o Au NPs represent without Au NPs. Copyright from the Royal Society of Chemistry.

Fig.13 Current density vs. voltage curves of OPVs with various ZnO overlayer on top of Au NPs under simulated 1 sun AM1.5 illumination[103]Control(no Au NPs, black circle), Au NPs without ZnO overlayer(red square), 4 nm ZnO overlayer(orange cross), 8 nm ZnO overlayer(green triangle), 16 nm ZnO overlayer(blue inverse triangle), 24 nm ZnO overlayer(magenta diamond). Inset: schematic representation of the device structures. Copyright from the American Chemical Society.

Fig.14 Schematics of ITO-free PLEDs based on super yellow with an Ag NPs containing PEDOT∶PSS electrode(A), photoluminescence spectra of super yellow films on NMP∶PH500 and Ag@NMP∶PH500 electrodes(B), light-emitting characteristics of current density vs. applied voltage(C) and power efficiency vs. voltage curves(D)[39]Copyright from the Royal Society of Chemistry.

Fig.15 Chemical structures of PBDTTT-C-T and PC71BM(left), schematic of the device structure: NP device(top), grating device(bottom), and dual metallic structural device(right)(A), current density vs. voltage characteristics of devices with different structures measured under AM 1.5 illumination at 100 mW/cm2(B), the extracted absorption of the control flat OPVs and NPs+G750 OPVs, and the absorption enhancement of NPs50+G750, G750, and NPs 50 compared to the control flat OPVs(C) and the current density vs. voltage characteristics of hole-only device of ITO/PEDOT∶PSS/active layer/Au(D) and electron-only device with structure of ITO/TiO2/active layer/Ca/Al(E)[51]The 1-R-T resprents the 1-differse reflection(R)-diffuse transmission(T). Copyright from the John Wiley and Sons.

Table 1 Summary of device characteristics of OLEDs employing NPs with different nanostructures and locations

Geometry	OLEDs emissive layer	Luminous efficiency/ (cd·A^-1)		Enhancement ratio (%)	Mechanism	Ref.
Geometry	OLEDs emissive layer	Initial		Enhancement ratio (%)	Mechanism	Final
NPs dispersed into the anode
CD-Ag NPs	Super yellow	11.65	27.16	133	LSPR, “hot spot”	[37]
Au NPs	MEH-PPV	1.40	1.61	15	LSPR	[38]
Cu NPs			1.74	24
Au-Cu NPs			1.57	12
Au NPs	Alq₃	1.04	1.28	25	LSPR	[54]
Au NPs@PS	PVK∶PBD∶Ir(ppy)₃	20.3	28.9	42	LSPR	[63]
Au NPs	CBP∶Ir(ppy)₃	11.0	27.7	150	LSPR	[75]
Pt₃Co NPs	CBP∶Ir(ppy)₃	44.2	76.4	73	Electrical	[95]
Au NPs	Alq₃	3.4	5.7	68	LSPR, electrical	[55]
Pt₃Co NPs	Alq₃	13.0	29.3	125	LSPR, scattering	[56]
Au NPs	MEH-PPV	0.51	0.68	33	Far-field	[43]
	P-PPV	11.3	14.9	32		[44]
	PFO	1.89	2.58	37
NPs dispersed into the emissive layer
Au NPs	PVK∶PBD∶Ir(mppy)₃	27	36	33	LSPR	[30]
Au NPs@SiO₂	Green-B	6.3	10.0	60	LSPR	[82]
NPs dispersed into the cathode
Au NPs	P-PPV	4.4	10.5	140	LSPR	[45]
Au NPs	P-PPV	15.4	18.3	19	Electrical	[46]
Au NPs	CBP∶Ir(ppy)₃	17.6	18.0	2	Electrical	[90]

Table 2 Summary of device characteristics of OPVs employing NPs with different nanostructures and locations

Geometry	OPVs active layer	PCE(%)		Enhancement ratio (%)	Mechanism	Ref.
Geometry	OPVs active layer	Initial		Enhancement ratio (%)	Mechanism	Final
NPs dispersed into the anode
Au NPs	P3HT∶PCBM	3.48	4.19	20	LSPR	[33]
Au NPs	P3HT∶PCBM	2.37	2.91	23	LSPR	[40]
Au NPs	MEH-PPV∶PCBM	1.99	2.36	19	LSPR	[41]
CD-Ag NPs	PTB7∶PC₇₁BM	7.53	8.31	10	LSPR, “hot spot”	[37]
Au NPs	Tandem P3HT∶IPCA, PSBTBT∶PC₇₀BM	5.22	6.24	20	Strong local near-field	[78]
Au NPs	P3HT∶PCBM	3.61	4.32	20	LSPR	[57]
Au NPs	P3HT∶PCBM	3.10	3.51	13	Hole collection	[53]
Ag NPs	PTBT∶PC₆₁BM	3.27	4.31	32	LSPR, Electrical	[39]
NPs dispersed into the active layer
Ag NWs	P3HT∶PCBM	3.16	3.72	18	LSPR	[47]
Au NPs	PFSDCN∶PCBM	1.64	2.17	32	LSPR	[49]
Ag NPs+Ag nanoparims	P3HT∶PCBM	3.60	4.30	19	LSPR	[50]
Ag NPs	PCBTBT∶PC₇₀BM	6.30	7.10	13	Electrical	[34]
Au NPs	P3OT-C₆₀	1.27	1.90	50	Electrical	[102]
Ag NPs+Ag Grating	PBDTTT-C-T∶PC₇₁BM	7.59	8.79	16	LSPR, Electrical	[51]
NPs dispersed into the cathode
Au NPs	PIDT-PhanQ∶PC₇₁BM	6.65	7.50	13	LSPR	[36]
Au NPs	P3HT∶PCBM	3.12	3.54	13	LSPR	[93]
Au NPs	P3HT∶PCBM	2.25	2.35	5	Electrical	[103]

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