Well-aligned Vertically Oriented ZnO Nanorod Arrays and their Application in Inverted Small Molecule Solar Cells

Summary

This manuscript describes how to design and fabricate efficient inverted SMPV1:PC₇₁BM solar cells with ZnO nanorods (NRs) grown on a high quality Al-doped ZnO (AZO) seed layer. The well-aligned vertically oriented ZnO NRs exhibit high crystalline properties. The power conversion efficiency of solar cells can reach 6.01%.

Abstract

This manuscript describes how to design and fabricate efficient inverted solar cells, which are based on a two-dimensional conjugated small molecule (SMPV1) and [6,6]-phenyl-C71-butyric acid methyl ester (PC₇₁BM), by utilizing ZnO nanorods (NRs) grown on a high quality Al-doped ZnO (AZO) seed layer. The inverted SMPV1:PC₇₁BM solar cells with ZnO NRs that grew on both a sputtered and sol-gel processed AZO seed layer are fabricated. Compared with the AZO thin film prepared by the sol-gel method, the sputtered AZO thin film exhibits better crystallization and lower surface roughness, according to X-ray diffraction (XRD) and atomic force microscope (AFM) measurements. The orientation of the ZnO NRs grown on a sputtered AZO seed layer shows better vertical alignment, which is beneficial for the deposition of the subsequent active layer, forming better surface morphologies. Generally, the surface morphology of the active layer mainly dominates the fill factor (FF) of the devices. Consequently, the well-aligned ZnO NRs can be used to improve the carrier collection of the active layer and to increase the FF of the solar cells. Moreover, as an anti-reflection structure, it can also be utilized to enhance the light harvesting of the absorption layer, with the power conversion efficiency (PCE) of solar cells reaching 6.01%, higher than the sol-gel based solar cells with an efficiency of 4.74%.

Introduction

Organic photovoltaic (OPV) devices have recently undergone remarkable developments in the application of renewable energy sources. Such organic devices have many advantages, including solution-process compatibility, low cost, light weight, flexibility, etc.^1,2,3,4,5 Up until now, polymer solar cells (PSCs) with a PCE of more than 10% have been developed by utilizing the conjugated polymers blended with PC₇₁BM⁶. Compared to polymer-based PSCs, small molecule-based OPVs (SM-OPVs) have attracted more attention when it comes to fabricating OPVs due to their several distinct advantages, including well-defined chemical structures, facile synthesis and purification, and generally higher open-circuit voltages (V_oc)^7,8,9. At present, a 2-D structure conjugated small molecule SMPV1 (2,6-Bis[2,5-bis(3-octylrhodanine)-(3,3-dioctyl-2,2':5,2''-terthiophene)]-4,8-bis((5-ethylhexyl)thiophen-2-yl)benzo[1,2-b:4,5-b']dithiophene) with BDT-T (benzo[1,2-b:4,5-b']dithiophene) as the core unit and 3-octylrodanine as the electron-withdrawing end-group¹⁰ has been designed and used to blend with PC₇₁BM for promising sustainable OPVs application. The PCE of conventional small molecule solar cells (SM-OPVs) based on SMPV1 blended with PC₇₁BM has reached more than 8.0%^10,11.

In the past, PSCs could be enhanced and optimized simply by adjusting the thickness of the active layer. However, unlike PSCs, SM-OPVs in general have a shorter diffusion length, which greatly limits the thickness of the active layer. Hence, to further increase the short current density (J_sc) of SM-OPVs, utilizing the nano-structure¹² or NRs⁹ to improve optical absorption of SM-OPVs became necessary.

Among these methods, the anti-reflection NRs structure is generally effective for light harvesting of the active layer over a broad range of wavelengths; therefore, knowing how to grow well-aligned vertically oriented zinc oxide (ZnO) NRs is very critical. The surface roughness of the seed layer below the ZnO NRs layer has a great influence on the orientation of the NR arrays; therefore, in order to deposit well-oriented NRs, the crystallization of the seed layer needs to be precisely controlled⁹.

In this work, the AZO films are prepared by theRadio-Frequency (RF) sputtering technique. Compared with other techniques, RF sputtering is known to be an efficient technology that is transferable to industry for it is a reliable deposition technique, which allows the synthesis of high purity, uniform, smooth, and self-sustainable AZO thin films to grow over large area substrates. Utilizing the RF sputtering deposition enables the forming of high quality AZO films that exhibit high crystallization with reduced roughness of surface. Therefore, in the subsequent growth layer, the orientations of the NRs are highly aligned, even more so when compared to ZnO films prepared by the sol-gel method. Using this technique, the PCE of the inverted small molecule solar cells based on well-aligned vertically oriented ZnO NR arrays can reach 6.01%.

Protocol

1. Growth of AZO Sputtered Seed Layer on ITO Substrate

1. Stick 4 anti-corrosion tape pieces (0.3 x 1.5 cm) on one side of the indium tin oxide (ITO) substrate to form a square (1.5 x 1.5 cm). Put the ITO into hydrochloric acid for 15 min to etch the exposed area of ITO.
2. Remove the tape and clean the sample using a sonicator; sonicate with deionized (DI) water, acetone, ethanol, and isopropanol in turn for 30 min each. Blow-dry the patterned ITO with a compressed nitrogen gun.
3. Attach the cleaned patterned ITO substrates onto the substrate holder by tape, and load the holder into the main chamber of RF sputtering system. Pump the chamber pressure to below 4 x 10^-6 torr via the mechanical and diffusion pump to ensure environmental purity.
4. Insert pure argon gas (flow rate: 30 sccm) into the main chamber and control the pump to maintain the pressure of chamber at 1 mtorr.
5. Prepare the AZO seed layers using the RF (13.56 MHz) sputtering method, based on the reported method¹³. Use a circular 2 in dimension AZO (2 wt% Al₂O₃ in ZnO) ceramic target to deposit them onto pre-cleaned ITO glass substrates. Keep the target-to-substrate distance at 10 cm.
6. Maintain working pressure at 1 mtorr and RF power at 40 W during the deposition. Control the substrate temperature at room temperature. Set the applied DC bias and deposition rate to 187 V and 4 nm/min, respectively to deposit the AZO thin film. The thickness of the AZO seed layer should be controlled at 40 nm based on the quartz crystal thickness monitor.
7. After the sample cools down to 30 °C in the chamber, turn off the pump and insert nitrogen gas into the main chamber until the chamber can be opened. Remove the sample from the substrate holder.

2. Growth of the Sol-gel Processed ZnO Seed Layer on ITO Substrate

1. Deposit the ZnO seed layer on the patterned ITO substrate by the sol-gel spin coating method¹⁴. The zinc acetate dihydrate, 2-methoxethanol, and monoethanolamine (MEA) are used as the starting materials, solvent, and stabilizer, respectively.
   1. Dissolve the zinc acetate dihydrate (4.39 g) in a mixture of 2-methoxethanol (40 mL) and MEA (1.22 g) to obtain the zinc acetate concentration of 0.5 M.
   2. Stir the resulting mixture at 60 °C for 2 h. Let the sol sit for 12 h to form a clear and transparent homogeneous solution.
   3. Deposit the ZnO seed layer onto cleaned ITO patterned glass substrates using the spin coating method. Add 0.1 mL sol-gel solution onto the substrate and rotate at 3,000 rpm for 30 s using a spin coater.
   4. After spin coating, dry the film at 200 °C for 30 min on a hot plate to allow the solvent to evaporate and remove the organic residues. The thickness of the ZnO seed layer should be around 40 nm¹⁴.

3. Growth of ZnO NR Array on a Seed Layer

1. Grow the ZnO NR array using the hydrothermal method.
   1. Mix 1.49 g zinc nitrate hexahydrate (Zn(NO₃)₂·6H₂O) and 0.7 g hexamethylenetetramine (HMT) (C₆H₁₂N₄) in 100 mL DI water. Stir the resulting mixture at room temperature for 30 min.
   2. Attach the ITO side of the AZO sputtered seed layer with the ZnO sol-gel samples to the cover glass using tape. Put the samples in a 50 mL polypropylene conical tube filled with the 50 mL solution of Zn(NO₃)₂·6H₂O and HMT.
   3. During the growth, heat the polypropylene conical tube by laying it horizontally in a laboratory oven with the spin coated samples facing downward, and maintain the temperature at 90 °C for 90 min.
   4. At the end of the growth period, remove the substrates from the solution and immediately rinse the sample surface with DI water and ethanol (inside two wash bottles) in turn for 1 min each to remove residual salt from the surface. Blow-dry the sample using a compressed nitrogen gun and bake it on a hot plate at 250 °C for 10 min.

4. Fabrication and Measurement of Inverted Small Molecule Solar Cells

1. Load the ITO substrate with the ZnO NR array onto a spin coater in the glovebox. Mix 1 mL of toluene containing 15 mg of SMPV1 and 11.25 mg of PC₇₁BM. Add 0.1 mL solution, spin the sample at 2,000 rpm for 40 s using a spin coater, and anneal it at 60 °C for 2 min.
2. After the annealing process, place the substrate in a thermal evaporation system. Pump the vacuum chamber initially using a mechanical pump until the pressure reaches 4 x 10^-2 torr, then switch to a turbo pump to make the ambient pressure < 4 x 10^-6 torr.
3. Deposit the MoO₃ layer at a deposition rate of 0.1 nm/s by heating MoO₃ powder in a resistive molybdenum boat with a Z-ratio of 1.0 and an input current of 105 A. Deposit the Ag layer at a deposition rate of 0.5 nm/s by heating silver ingot in a resistive tungsten boat with a Z-ratio of 0.529 and an input current of 190 A. The system should include a quartz crystal evaporation rate monitor for controlling the evaporation process. The thickness of the MoO₃ and Ag layers should be controlled to be 5 and 150 nm, respectively based on the quartz crystal thickness monitor.
4. After the sample cools down to 30 °C in the chamber, turn off the pump, and insert nitrogen gas into the chamber until the chamber can be opened. Remove the sample from the substrate holder and load the sample into the glovebox.
5. Open the solar simulator system and wait 20 min until the light source of the system is stable. Illuminate the sample at 100 mW/cm² from a solar simulator using an air mass 1.5 global (AM 1.5G) filter. Simultaneously, use the analyzer to sweep the device from -1 V to +1 V to obtain the current density-voltage (J-V) curve^14,15.

5. Characterization Techniques

1. Perform the X-ray diffraction measurment¹⁶ with a Cu Kα source to study the structures of the ZnO NRs, on the AZO sputtered seed layer and the ZnO sol-gel processed seed layer. The scan speed should be 1 °/min, and the scan range should be 10-90 ° (2θ).
2. Characterize the surface morphology and cross-sectional image of the samples by field emission scanning electron microscopy¹⁷ by setting the operating voltage at 10 kV.
3. Obtain the micro photoluminescence (PL) spectra of all of the samples using a 325 nm He-Cd CW laser (20 mW) as the excitation source with a 2,400 grooves/mm grating in the backscattering geometry. AllPL measurements¹⁸ should be performed at room temperature.

Results

The layered structure of the devices consisted of an ITO substrate/AZO (40 nm)/ZnO NRs layer, SMPV1:PC₇₁BM (80 nm)/MoO₃ (5 nm)/Ag (150 nm) as shown in Figure 1. In general, the AZO or ZnO seed layer is widely used to function as the electron transport layer (ETL) in PSCs devices. Apart from PSCs, SM-OPVs usually have a shorter active layer, limited by the shorter diffusion length⁸. Hence, to further improve the li...

Discussion

By utilizing the NRs interlayer, both the J_sc and the FF of the devices can be improved. However, the surface roughness of NRs will also influence the subsequent processes. Thus, the orientation and the surface morphology of the NRs should be carefully manipulated. For a long time, the sol-gel processed ETL such as TiO₂ and ZnO were commonly used in PSCs due to their simple procedures. However, the crystallization of sol-gel processed layers is generally of the amorphous type, and the surface morpho...

Materials

List of materials used in this article

Name	Company	Catalog Number	Comments
AZO target	Ultimate Materials Technology Co., Ltd.	none	AZO (2 wt% Al2O3 in ZnO) , 3”ψx 3mmt + 3mmt Cu B/P + Bonding
SMPV1	Luminescence Technology Corp.	1651168-29-4	2,6-Bis[2,5-bis(3-octylrhodanine)-(3,3-dioctyl-2,2':5,2''-terthiophene)]-4,8-bis((5-ethylhexyl)thiophen-2-yl)benzo[1,2-b:4,5-b']dithiophene
RF sputtering system	Kao Duen Technology Co., Ltd	none	http://www.kaoduen.com.tw/index.php?action=product
Zinc Acetate Dihydrate	J. T. Baker	5970456	4.39 g
Monoethanolamine	J. T. Baker	141435	1.22 g
2-methoxyethanol	Sigma-Aldrich	109864	40 mL
Zinc Nitrate Hexahydrate	J. T. Baker	10196186	1.49 g
Hexamethylenetetramine	Sigma-Aldrich	100-97-0	0.7 g
Indium tin oxide (ITO)	RiTdisplay	none	coated glass substrates (<10 Ω sq–1)
AFM	Veeco	Innova SPM
SEM	FEI	Nova 200 NanoSEM	operation voltage: 10 kV
XRD	Bruker	D8 X-ray diffractometer	2θ range: 10–90 °; step size: 0.008 °
PL	Horiba	Jobin-Yvon HR800	excitation source: 325 nm UV Laser 20 mW
solar simulator	Newport	91192A	AM 1.5G
Precision Semiconductor Parameter Analyzer	Keysight Technologies	Agilent 4156C	sweep from -1 to +1 V
toluene	Sigma-Aldrich	108-88-3	1 mL
PC71BM	Sigma-Aldrich	609771-63-3	11.25 mg
Thermal evaporation system	Kao Duen Technology Co., Ltd	Kao Duen PVD System	http://www.kaoduen.com.tw/index.php?action=product
HCl	Sigma-Aldrich	7647-01-0
MoO3	Alfa Aesar	1313-27-5	99.50%
silver ingot	ADMAT Inc.	none	100.00%
Thin Film Deposition Controller	INFICON	XTC
anti-corrosion tape (Polyimide Film)	3M Taiwan Corporation	none	http://solutions.3m.com.tw/wps/portal/3M/zh_TW/InsulatingTape/home/product/Polyimide/
spin-coater	Chemat Technology, Inc	KW-4A	http://www.chemat.com/chematscientific/KW-4A.aspx