In situ synthesis of P3HT-capped CdSe superstructures and their application in solar cells
© Peng et al.; licensee Springer. 2013
Received: 7 January 2013
Accepted: 2 February 2013
Published: 26 February 2013
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© Peng et al.; licensee Springer. 2013
Received: 7 January 2013
Accepted: 2 February 2013
Published: 26 February 2013
Organic/inorganic hybrid solar cells have great potentials to revolutionize solar cells, but their use has been limited by inefficient electron/hole transfer due to the presence of long aliphatic ligands and unsatisfying continuous interpenetrating networks. To solve this problem, herein, we have developed a one-pot route for in situ synthesis of poly(3-hexylthiophene) (P3HT)-capped CdSe superstructures, in which P3HT acts directly as the ligands. These CdSe superstructures are in fact constructed from numerous CdSe nanoparticles. The presence of P3HT ligands has no obvious adverse effects on the morphologies and phases of CdSe superstructures. Importantly, higher content of P3HT ligands results in stronger photoabsorption and fluorescent intensity of CdSe superstructure samples. Subsequently, P3HT-capped CdSe superstructures prepared with 50 mg P3HT were used as a model material to fabricate the solar cell with a structure of PEDOT:PSS/P3HT-capped CdSe superstructures: P3HT/Al. This cell gives a power conversion efficiency of 1.32%.
The quest and demand for clean and economical energy sources have increased the interest in the development of solar applications. In particular, direct conversion of solar energy to electrical energy using photovoltaic cells has attracted much attention for several decades[1–4]. Among various photovoltaic cells, organic polymer-based solar cells have received considerable attention as a new alternative photovoltaic technology due to their flexibility, light weight, low-cost fabrication, and easy integration into a wide variety of devices. Importantly, bulk heterojunction (BHJ) solar cells based on intimate blends of organic polymer as the donor and inorganic nanomaterials as the acceptor are currently attracting increasingly widespread scientific and technological interests because of the advantages, resulting from these two types of materials, such as low cost, outstanding chemical and physical properties, easy preparation from organic polymers, high electron mobility, excellent chemical and physical stabilities, size tunability, and complementary light absorption from inorganic semiconductors[6–8]. Various organic–inorganic hybrid solar cells have been reported based on the conjunction of organic polymers, such as poly(3-hexylthiophene) (P3HT)[9–12], poly(3,4-ethylenedioxythio-phene) with poly-(styrene sulfonate) (PEDOT:PSS), poly[2-methoxy-5-(3′,7′-dimethyloctyloxy)-1,4-phenylenevinylene] (MDMO-PPV), and poly(2-methoxy,5-(2-ethyl-hexyloxy)-p-phenyl vinylene) (MEH-PPV)[15, 16], and inorganic nanocrystals, such as CdSe nanorods, hyperbranched CdSe nanocrystals[9, 14, 18], ZnO[19, 20], PbS[10, 21], Sb2S3[11, 12], and Si nanocrystals.
In these organic–inorganic hybrid solar cells, the polymer as the donor can be excited by solar light, resulting in the generation of strong-bound excitons that can be dissociated at the interface between the polymer and inorganic nanocrystals. Thus, the interface between the polymer and inorganic nanocrystals plays a very important role. Unfortunately, inorganic nanocrystals used as the acceptor are typically capped with organic aliphatic ligands, such as trioctylphosphine oxide (TOPO) and oleic acid (OA). The presence of organic aliphatic ligands prevents electron transferring from the photoexcited polymer to the nanoparticles.
To solve this problem, three strategies have been developed. The first strategy is to prepare inorganic nanocrystals capped with thermally cleavable solubilizing ligands and then heat the nanocrystals for shortening the ligands. However, there are very limited kinds of thermally cleavable solubilizing ligands. The second strategy involves replacing the original long organic layer with short ligands. For example, pyridine[16, 24, 27], tert-butylthiol,[28, 29], or acetate acid treatment methods have been used to remove TOPO and OA. However, these processes may be costly and complicated, and precise control of some factors (such as exchange rates) may be difficult. The last strategy is to directly synthesize hybrid inorganic nanocrystals that are capped with donor polymer such as P3HT or PPV. The negative effects of the capping organic aliphatic ligands on charge exchange are eliminated, and the step of transferring inorganic nanocrystals into the polymer solution for exchange can be bypassed, achieving direct synthesis of nanoparticles with photoelectronic polymers as ligands. To this day, several kinds of hybrid inorganic nanocrystals have been well developed for BHJ solar cells, including P3HT-capped CdS single-crystal nanorods, MDMO-PPV-capped PbS quantum dots, MEH-PPV-capped PbS nanorods, and MEH-PPV-capped PbS nanocrystals. It should be noted that these nanoparticles usually have very small diameters (2 to 5 nm), and thus, it is difficult for them to form a well continuous inorganic network, leading to the difficulty of electron transfer and low photoelectric conversion efficiency. Fortunately, it has been found that the shapes of inorganic nanocrystals have a strong effect on the formation of continuous inorganic network in BHJ solar cells. For example, the BHJ solar cells based on CdSe inorganic nanostructures including nanorods[17, 35] or nanobranches[36, 37] have better continuous interpenetrating networks and thus exhibit more superior photoelectric performances compared with the cells based on CdSe nanoparticles. Furthermore, compared with CdSe nanorods and nanobranches, spherical superstructures constructed by nanosubstructures may be more suitable to form well continuous inorganic network.
To the best of our knowledge, there is no report on the synthesis of inorganic superstructures capped with conductive donor polymer for BHJ solar cells. In this report, we employed P3HT as the ligands to synthesize P3HT-capped CdSe superstructures in a mixed solution of 1,2,4-trichlorobenzene (TCB) and dimethyl sulfoxide (DMSO). This synthetic procedure yielded homogeneous CdSe superstructures that were constructed by 5- to 10-nm CdSe nanoparticles. These P3HT-capped CdSe superstructures can be dissolved in many kinds of solvents, such as 1,2-dichlorobenzene and chloroform, from which thin films can be readily cast to fabricate BHJ solar cells.
All of the chemicals were commercially available and were used without further purification. Cadmium acetate dihydrate (Cd(CH3COO)2·2H2O), selenium (Se), DMSO, isopropyl alcohol ((CH3)2CHOH), ethanol, chloroform (CHCl3), TCB, and sodium hydroxide (NaOH) were purchased from Sinopharm Chemical Reagent Co., Ltd. (Shanghai, China). The PEDOT:PSS solution (solvent H2O, weight percentage 1.3%) was obtained from Sigma-Aldrich Corporation (St. Louis, MO, USA). The fluorine tin oxide (FTO)-coated glass (resistivity 14 Ω/sq) was purchased from Georgia & Education Equipment Co., Ltd. (Wuhan, China). P3HT was bought from Guanghe Electronic Materials Co., Ltd. (Luoyang, China).
In a typical synthesis, Cd(CH3COO)2·2H2O (0.133 g) as precursor was dissolved in the mixture of TCB (16 mL) and DMSO (8 mL) in a three-neck round-bottom flask. After magnetically stirring for 30 min, different amounts (0, 10, 50, or 100 mg) of P3HT were added into the mentioned solutions, and the color of the solution became dark red immediately. The solution was held at 100°C for 30 min with stirring magnetically and purging periodically with dry nitrogen to remove residual water and oxygen, and then the color of the solution became red. Subsequently, this solution was heated to 180°C with the protection of dry nitrogen. In addition, another TCB solution (8 mL) containing Se powder (0.019 g) was heated to 180°C until a transparent red solution was obtained and then injected to the mentioned solution in a three-neck round-bottom flask. After a 10-min reaction at 180°C, the mixture was then cooled to room temperature, isolated via centrifugation at 8,000 rpm, and washed in ethanol three times.
A part of the conductive layer of FTO block was removed by 1 mol/L hydrochloric acid solution containing zinc powder. The FTO-coated glass was ultrasonically cleaned by detergent, saturation (CH3)2CHOH solution of NaOH, deionized water, and ethanol. The PEDOT:PSS solution was filtered by a 450-nm membrane and spun at the speed of 4,000 rpm to form the PEDOT:PSS layer with a thickness of 120 nm on FTO glass. The PEDOT:PSS layer (about 120-nm thick), as the anode, was annealed at 120°C for 30 min. Subsequently, P3HT-capped CdSe/CdSe sample (20 mg) and P3HT (5 mg) were dispersed in CHCl3 solution (1 mL). This solution was filtered by a 450-nm membrane and spun to form about 450-nm-thick CdSe film on PEDOT:PSS layer, and then two drops of CHCl3 solution containing 4 mg/mL P3HT were spun on the earlier CdSe layer. Afterwards, this as-fabricated device was annealed at 150°C for 30 min. Finally, an Al layer (about 100-nm thick) was sputtered for 50 min in a metal mask under 4 Pa of argon environment. This Al layer acted as the cathode in the as-fabricated solar cell device. The resulting solar cell device had a structure of FTO/PEDOT:PSS/P3HT-capped CdSe superstructures:P3HT/Al.
The sizes and morphologies of CdSe superstructures and P3HT-capped CdSe superstructures were investigated by scanning electron microscopy (SEM) (Hitachi S-4800, Hitachi High-Tech, Minato-ku, Tokyo, Japan) and transmission electron microscopy (TEM) (JEM-2010F, JEOL Ltd., Akishima, Tokyo, Japan). The X-ray diffraction (XRD) (Rigaku D/max-g B, Rigaku Corporation, Tokyo, Japan) measurement was carried out using a Cu-Kα radiation source (λ = 1.5418 Å). Fourier transform infrared (FTIR) spectra of ligands in CdSe were obtained by measuring pellets of KBr and sample using an FTIR-Raman spectrometer (Thermo Fisher Scientific, Waltham, MA, USA). A UV–vis spectrophotometer and a fluorescence spectrometer (FP-6600, JASCO Inc., Easton, MD, USA) were used for the optical measurements of CHCl3 solution (0.04 mg/mL) containing CdSe superstructures, P3HT-capped CdSe superstructures, and P3HT, respectively. The thermogravimetric analysis (TGA) measurements of the samples were done using the Discovery TGA instrument (TA Instruments, New Castle, DE, USA) under a nitrogen flow rate of 50 mL/min at the heating rate of 10°C/min from 50°C to 600°C.
The photocurrent density-voltage curves of solar cells were measured under illumination (100 mW cm−2) using a computerized Keithley model 2400 source meter unit (Keithley Instruments Inc., Cleveland, OH, USA) and a 300-W xenon lamp (69911, Newport Corporation, Irvine, CA, USA) serving as the light source.
To evaluate the P3HT ligand content in CdSe superstructures prepared with different amounts of P3HT, TGA was performed (Figure 2b). For comparison, the TGA curve of pure P3HT (Figure 2b, black curve) was also recorded, and it shows that an initial decomposition occurs at 450°C and a sharp drop of the pure P3HT in weight percentage takes place at 500°C. Similarly, all these CdSe superstructures show weight loss between 450°C and 500°C, and the weight loss in this stage reflects the content of P3HT ligands. Obviously, with the increase of P3HT amount from 10 to 50 mg and then to 100 mg in the precursor solution, between 450°C and 500°C, the resulting CdSe superstructures exhibit the weight losses which go up from 0.5 to 10 wt.% and then to 12 wt.% of the total weight. These results indicate that the higher content of P3HT in the precursor solution results in more P3HT ligands in CdSe superstructures.
It is well known that traditional P3HT-CdSe hybrid solar cells have been constructed based on CdSe nanomaterials capped with organic aliphatic ligands, such as TOPO and OA, and these aliphatic ligands prevent electron transferring from the photoexcited polymer to nanomaterials. In our case, P3HT was used directly as the ligands of CdSe superstructures, and thus, the adverse effects of the capping ligands on charge exchange can be eliminated. In addition, CdSe superstructures constructed from CdSe nanoparticles with a diameter of 5 to 10 nm may be easy to form a well continuous inorganic network in a bulk heterojunction structure, probably resulting in the efficient electron transfer in inorganic network and the high photoelectric conversion efficiency.
In summary, an in situ growth method has been developed to synthesize P3HT-capped CdSe superstructures for their applications in solar cells. The amount of P3HT in the reaction solution has no obvious effect on the shapes and phases of CdSe superstructure samples, but the P3HT ligands in the CdSe superstructures promote the photoabsorption and PL emission intensities. The solar cell based on the P3HT-capped CdSe superstructures demonstrates an overall energy conversion efficiency (η) of 1.32%.
This work was financially supported by the National Natural Science Foundation of China (grant numbers 21171035, 11204030, 50902021, and 51272299), the Key Grant Project of Chinese Ministry of Education (grant number 313015), the Science and Technology Commission of Shanghai-based ‘Innovation Action Plan’ Project (grant number 10JC1400100), Shanghai Natural Science Foundation (10ZR1400200), Ph.D. Programs Foundation of Ministry of Education of China (grant number 20110075110008), the Fundamental Research Funds for the Central Universities, the Shanghai Leading Academic Discipline Project (grant number B603), and the Program of Introducing Talents of Discipline to Universities (grant number 111-2-04). Shanghai Rising-Star Program (grant number 11QA1400100), Innovation Program of Shanghai Municipal Education Commission (grant number 13ZZ053), and Fundamental Research Funds for the Central Universities.
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