Journal of Materials Chemistry

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Synthesis and photoresponse of novel Cu2CdSnS4 semiconductor nanorods

Yong Cui, Gang Wang* and Daocheng Pan*
Received 1st April 2012, Accepted 18th May 2012 DOI: 10.1039/c2jm32034g
Downloaded by Shivaji University on 26 February 2013 Published on 21 May 2012 on http://pubs.rsc.org | doi:10.1039/C2JM32034G

Novel semiconductor Cu2CdSnS4 nanorods with a wurtzite structure have been successfully synthesized and characterized in detail. The suitable band gap of 1.4 eV and photoresponse property of Cu2CdSnS4 nanorods indicate that they have a high potential application in low-cost thin lm solar cells. Recently, stoichiometric Cu2(MII)(MIV)(S,Se)4 (MII Mn, Fe, Co, Ni, Zn, Cd, Hg; MIV Si, Ge, Sn) chalcogenide semiconductor nanocrystals have obtained great interest because of their potential application in thin lm solar cells for structure analogues to CuIn(Ga)Se2.1 These multiple component semiconductors possess suitable band gap (1.11.5 eV) and high absorption coefcient (104 to 105 cm1) and do not contain low abundance elements, such as indium and gallium. Recently, the high power conversion efciencies of solar cells using Cu2ZnSnS(Se)4 and Cu2ZnSn(Ge)S(Se)4 nanocrystals as high as 7.2% and 6.8% have been reported by Agrawals group,2,3 but the synthesis of other similar multiple component nanocrystals is still a challenging task. To our best knowledge, only chalcogenide Cu2CoSnS4, Cu2FeSnS4, and Cu2CdSnSe4 nanocrystals have been synthesized46 and there are no reports of these nanocrystals with a one-dimensional (1D) structure but Cu2ZnSnS4 nanorods.7 It should be noted that the nanocrystal shape can strongly inuence their optical and electrical properties, and one-dimensional nanorods have been observed to exhibit unusual optical properties and excellent charge transport performance, for instance CdSe nanorods showed higher efciency than CdSe nanoparticles in CdSe P3HT hybrid solar cells, because the nanorods provide a directed path for electrical transport.8 Therefore, the synthesis of 1D semiconductor nanorods is critically important to develop next-generation, low-cost, and high-performance solar cells. Here, we adopted a solvent thermal approach to prepare wurtzite Cu2CdSnS4 nanorods with a suitable band gap of 1.4 eV, which indicates that they have a high potential application in the eld of low-cost thin lm solar cells. It is well known that Cu2CdSnS4 (CCTS) compound usually crystallizes in a stannite (space group: I 42m) or kesterite (space
State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, 5625 Renmin Street, Changchun 130022, China. E-mail: wsu@ciac.jl.cn; pan@ ciac.jl.cn Electronic supplementary information (ESI) available: Detailed synthesis of nanocrystals; unit cells, crystal data, EDS spectra, chemical compositions and size distribution. See DOI: 10.1039/c2jm32034g

group: I 4) structure in the literature, and all of the metal ions have ~ez and coworkers a xed position in the unit cells.9 Recently, Iba an have synthesized the sphere-like Cu2CdSnSe4 nanocrystals with a tetragonal chalcopyrite structure.10 However, the surface energy difference between various facets of chalcopyrite structure is insignicant. Thus it is difcult to synthesize 1D chalcopyrite structure nanorods. For wurtzite semiconductor nanocrystals, the difference of surface energies is large, therefore it is quite possible to synthesize 1D nanorods with a wurtzite structrue.11 More recently, wurtzite CuIn(Ga)S2 and Cu2ZnSnS4 nanorods have been successfully synthesized through controlling the release speed of sulfur source under relatively high reaction temperature (240290  C).7,12 Here, a solvothermal approach was utilized to synthesize wutzite Cu2CdSnS4 nanorods under mild experimental conditions.13 We choose hexylamine as solvent, carbon disulde as sulfur source, and 3-mercaptopopionic acid (MPA) as a capping agent. The stoichiometric wurtzite Cu2CdSnS4 nanorods were nucleated at low temperature (140  C) and then grown at high temperature (180  C). The detailed experimental procedure and synthetic conditions are provided in the ESI. X-ray diffraction (XRD) was utilized to analyze the crystal structure of Cu2CdSnS4 nanocrystals. Fig. 1 shows the XRD pattern of assynthesized Cu2CdSnS4 nanocrystals with a wurtzite structure. It is found that our diffraction pattern does not match those reported for bulk Cu2CdSnS4 in the literature9 and those standard patterns in JCPDS card database (stannite phase, PDF no. 29-0537). Therefore,

Fig. 1 The experimental and simulated powder XRD patterns of wurtzite Cu2CdSnS4 nanorods.

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Downloaded by Shivaji University on 26 February 2013 Published on 21 May 2012 on http://pubs.rsc.org | doi:10.1039/C2JM32034G

we simulated an XRD pattern for wurtzite Cu2CdSnS4. As can be seen in Fig. 1, the experimental pattern matches well with the simulated one by comparison between the experimental and simulated XRD peak positions in Table S1, indicating that CCTS nanocrystals possess a wurtzite structure. The major diffraction peaks centered at 2q 26.47, 27.89, 29.98, 38.90, 46.73, 50.59, 55.29 can be indexed to the (100), (002), (101), (102), (110), (103), and (112) crystal planes of the wurtzite crystal structure, respectively. Fig. S1 shows the unit cell of wurtzite Cu2CdSnS4. While wurtzite CCTS nanocrystals can be viewed as the deviation of wurtzite ZnS. In this structure, sulfur anions are hexagonally close packed, and Cu+, Cd2+, and Sn4+ ions randomly occupy Zn2+ position, and their occupancy possibilities are 1/2, 1/4 and 1/4, respectively. Additionally, no other impure phases, such as stannite or kesterite structure, could be observed in our XRD pattern, signifying that a pure wurtzite structure is obtained. During the synthesis process, 3-mercaptopopionic acid plays a key role in the formation of wurtzite CCTS nanorods since MPA has a strong bonding strength with precursors, which leaves the majority of precursors for the growth of nanorods. Transmission electron microscopy (TEM) was used to characterize the morphologies of the Cu2CdSnS4 nanorods. As shown in Fig. 2a, the TEM image reveals that CCTS nanocrystals have a rod-like structure. The average diameter and length of CCTS nanorods are about 5.7 nm and 26 nm, respectively, and the aspect ratio (length/ diameter) of CCTS nanorods was about 4.7. In addition, the high resolution TEM image in Fig. 2b conrms the high crystallinity of CCTS nanorods. Selected area electron diffraction (SAED) can further conrm the crystal structure of these Cu2CdSnS4 nanorods. The SAED image in Fig. 2c clearly reveals that the as-synthesized CCTS nanorods possess a wurtzite structure instead of traditional

stannite, chalcopyrite, or kesterite structure. Note that a low nucleation temperature is very important for the formation of CCTS nanorods, because a low nucleation temperature results in less critical nuclei and leaves the majority of precursors for the growth of longer nanorods. In the initial period of reaction, the nuclei were formed and then extended anisotropically in the (002) facet direction in the following reaction time. Due to sufciently different binding afnity of the capping ligand on different crystal facets and difference of the surface energy, unequal growth rates in different directions result in different morphologies, such as semiconductor nanorods and nanowires which were grown along the c-axis via preferential passivation of facets perpendicular to the growth axis. This mechanism is similar to the formation mechanism of wurtzite ZnSe,14 CdS,15 and CdSe16 nanorods or nanowires. To conrm the chemical composition of Cu2CdSnS4 nanorods, energy dispersive X-ray spectroscopy was applied to analyze the elemental composition. Approximately 10 different points on the nanocrystal lm were detected. As shown in Fig. S2, the molar ratio of Cu/Cd/Sn/S is close to 2 : 1 : 1 : 4, which is consistent with the stoichiometric composition of Cu2CdSnS4. The valence states of Cu, Cd, Sn, S in CCTS nanocrystals were determined by X-ray photoelectron spectroscopy (XPS). Two peaks of Cu2p, Cd3d, and Sn3d, located at 931.2 eV and 951.1 eV, 404.8 eV and 411.4 eV, 485.9 eV and 494.2 eV, suggest that the valence states of Cu, Cd, and Sn ions in the nanocrystals are +1, +2, and +4, respectively (Fig. 3). The two peaks of sulfur located at 161.3 eV and 162.5 eV are assigned to S2p with a valence of 2. Fig. 4 shows the UV-vis-NIR absorption spectrum of CCTS nanorods. Note that CuxS nanocrystals do not exist in our sample because of the absence of the absorption in the range of 10001400 nm resulting from CuxS nanocrystals.17,18 Inset of Fig. 4 displays the abs2 vs. eV curve for the nanocrystals; the band gap is approximately 1.4 eV, which is in good agreement with the literature value of 1.37 eV.19 This band gap value of CCTS nanorods indicates that CCTS nanocrystals have a high potential application in thin lm solar cells. To evaluate the potential applicability of wurtzite CCTS nanorods as a photovoltaic material, the IV curves of CCTS thin lm have

Fig. 2 Low resolution (a) and high resolution (b) TEM as well as SAED (c) images of wurtzite Cu2CdSnS4 nanorods.

Fig. 3 The X-ray photoelectron spectroscopy (XPS) spectra of assynthesized Cu2CdSnS4 nanorods; (a) Cu2p; (b) Cd3d; (c) Sn3d; (d) S2p.

12472 | J. Mater. Chem., 2012, 22, 1247112473

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In conclusion, a solvothermal approach has been successfully utilized to synthesize wurtzite Cu2CdSnS4 nanorods for the rst time. The absorption spectrum demonstrates that Cu2CdSnS4 nanorods have an optical band gap of 1.4 eV. The observed photoresponse from the spin casted lm of the nanorods indicated that the earthabundant Cu2CdSnS4 nanorods are promising semiconductor material for low-cost thin lm solar cells. This work was supported by the National Natural Science Foundation of China (Grant no. 21071142; 51172229), the Fund for Creative Research Groups (Grant no. 20921002), the Natural Science Foundation for Young Scientists of Jilin Province (20100105).

Downloaded by Shivaji University on 26 February 2013 Published on 21 May 2012 on http://pubs.rsc.org | doi:10.1039/C2JM32034G

Notes and references

1 D. B. Mitzi, O. Gunawan, T. K. Todorov, K. Wang and S. Guha, Sol. Energy Mater. Sol. Cells, 2011, 6, 1421. 2 Q. J. Guo, G. M. Ford, W. C. Yang, B. C. Walker, E. A. Stach, H. W. Hillhouse and R. Agrawal, J. Am. Chem. Soc., 2010, 132, 17384. 3 G. M. Ford, Q. J. Guo, R. Agrawal and H. W. Willhouse, Chem. Mater., 2011, 23, 2626. 4 (a) J. Y. Chane-Ching, A. Gillorin, O. Zaberca, A. Balocchi and X. Marie, Chem. Commun., 2011, 47, 5229; (b) A. Gillorin, A. Balocchi, X. Marie, P. Dufour and J. Y. Chane-Ching, J. Mater. Chem., 2011, 21, 5615. 5 C. Yan, C. Huang, J. Yang, F. Y. Liu, J. Liu, Y. Q. Lai, J. Li and Y. X. Liu, Chem. Commun., 2012, 48, 2603. 6 F. J. Fan, B. Yu, Y. X. Wang, Y. L. Zhu, X. J. Liu, S. H. Yu and Z. F. Ren, J. Am. Chem. Soc., 2011, 133, 15910. 7 A. Singh, H. Geaney, F. Lafr and K. M. Ryan, J. Am. Chem. Soc., 2012, 134, 2910. 8 W. U. Huynh, J. J. Dittmer and A. P. Alivisatos, Science, 2002, 295, 2425. 9 (a) W. Sch afer and R. Nitsche, Mater. Res. Bull., 1974, 9, 645; (b) M. Himmrich and H. Haeuseler, Spectrochim. Acta, Part A, 1991, 47, 933; (c) K. Ito and T. Nawazawa, Jpn. J. Appl. Phys., 1988, 27, 2094; (d) S. Wagner and P. M. Bridebaugh, J. Cryst. Growth, 1977, 39, 151; (e) H. Matsushita, T. Maeda, A. Katsui and T. Takizawa, J. Cryst. Growth, 2000, 208, 416. ~ez, D. Cadavid, R. Zamani, N. Garc a, 10 M. Iba an a-Castello V. Izquierdo-Roca, W. H. Li, A. Fairbrother, J. D. Prades, A. Shavel, J. Arbiol, A. Pe arez-Rodr guez, J. R. Morante and A. Cabot, Chem. Mater., 2012, 24, 562. 11 (a) P. D. Cozzoli, T. Pellegrino and L. Manna, Chem. Soc. Rev., 2006, 35, 1195; (b) L. Manna, D. J. Milliron, A. Meisel, E. C. Scher and A. P. Alivisatos, Nat. Mater., 2003, 2, 382; (c) S. Kudela, L. Carbone, M. F. Casula, R. Cingolani, A. Falqui, E. Snoeck, W. J. Parak and L. Manna, Nano Lett., 2005, 5, 45; (d) X. T. Lu, Z. B. Zhuang, Q. Peng and Y. D. Li, CrystEngComm, 2011, 13, 4039. 12 Y. H. Wang, X. Y. Zhang, N. Z. Bao, B. P. Lin and A. Gupta, J. Am. Chem. Soc., 2011, 133, 11072. 13 (a) L. J. Chen, J. D. Liao, Y. J. Chuang and Y. S. Fu, J. Am. Chem. Soc., 2011, 133, 3704; (b) J. Yang, C. Xue, S. H. Yu, J. H. Zeng and Y. T. Qian., Angew. Chem., Int. Ed., 2002, 41, 4697; (c) H. C. Jiang, P. C. Dai, Z. Y. Feng, W. L. Fan and J. H. Zhan, J. Mater. Chem., 2012, 22, 7502. 14 A. B. Panda, S. Acharya and S. Efrima, Adv. Mater., 2005, 17, 2471. 15 D. V. Talapin, J. H. Nelson, E. V. Shevchenko, S. Aloni, B. Sadtler and A. P. Alivisatos, Nano Lett., 2007, 7, 2951. 16 L. Manna, E. C. Scher and A. P. Alivisatos, J. Am. Chem. Soc., 2000, 122, 12700. 17 X. T. Lu, Z. B. Zhuang, Q. Peng and Y. D. Li, Chem. Commun., 2011, 47, 3141. 18 R. G. Xie, M. Rutherford and X. G. Peng, J. Am. Chem. Soc., 2009, 131, 5691. 19 H. Matsushita, T. Ichikawa and A. Katsui, J. Mater. Sci., 2005, 40, 2003.

Fig. 4 UV-vis-NIR absorption spectrum of wurtzite Cu2CdSnS4 nanorods. The inset displays a plot of (abs2) vs. hv for the Cu2CdSnS4 nanorods with the band gap estimated at 1.4 eV.

Fig. 5 The currentvoltage (IV) curves of the Cu2CdSnS4 lm: in the dark (black) and under simulated solar light illumination (red).

been measured in the dark and under illumination of the solar simulator. A smooth CCTS lm was obtained by spin casting concentrated nanocrystal solution and then post-annealed at 400  C on a ceramic hot plate for a few minutes in the glove-box. After the removal of ligands, electrical conductivity of CCTS lm was signicantly improved. The sheet resistance of CCTS lm with a thickness of 730 nm after post-treatment is approximately 16 000 U ,1, which is close to the sheet resistance of a semiconductor material, conrming that the CCTS nanorod thin lm possesses semiconductor property. The IV curves, shown in Fig. 5, for the CCTS nanorod thin lm, exhibit photoresponse property. The current of the CCTS nanorods at 5 V changes from 28 mA in the dark to 62 mA under AM 1.5 G irradiation (100 mW cm2), two times higher, and the Ilight/Idark ratio of the Cu2CdSnS4 nanorod lm is close to those of Cu2ZnSnS4 nanocrystal lm.17 This result demonstrates that CCTS nanorods can be potentially applied as an absorbing layer material in thin lm solar cells.

This journal is The Royal Society of Chemistry 2012

J. Mater. Chem., 2012, 22, 1247112473 | 12473