One-Step Synthesis of Monodisperse In-Doped ZnO Nanocrystals
© The Author(s) 2010
Received: 23 November 2009
Accepted: 15 March 2010
Published: 31 March 2010
A method for the synthesis of high quality indium-doped zinc oxide (In-doped ZnO) nanocrystals was developed using a one-step ester elimination reaction based on alcoholysis of metal carboxylate salts. The resulting nearly monodisperse nanocrystals are well-crystallized with typically crystal structure identical to that of wurtzite type of ZnO. Structural, optical, and elemental analyses on the products indicate the incorporation of indium into the host ZnO lattices. The individual nanocrystals with cubic structures were observed in the 5% In–ZnO reaction, due to the relatively high reactivity of indium precursors. Our study would provide further insights for the growth of doped oxide nanocrystals, and deepen the understanding of doping process in colloidal nanocrystal syntheses.
Transparent conductive oxides (TCOs) are impurity doped metal oxides, such as indium oxide (In2O3), zinc oxide (ZnO), and tin oxide (SnO2), which exhibit excellent properties of controllable low resistivity and high transparency in the visible region . TCOs, generally fabricated as polycrystalline or amorphous thin films, are employed as transparent electrodes in a wide variety of optoelectronic devices, e.g., flat panel displays, light emitting diodes, and photovoltaics [2–4]. Currently, the TCO thin films are deposited by sputtering, thermal deposition, chemical vapor deposition, or other gas phase deposition approaches, which generally require high temperature processing [5, 6]. Nevertheless, high temperature treatments are disadvantageous to be applied on flexible or heat-sensitive substrates . The development of TCO nanocrystals, together with printing techniques, may address the problem and lead to low cost printable transparent electrodes.
Recently, research into the production of TCO nanocrystals, particularly indium-doped tin oxide (ITO) nanocrystals, has steadily increased over the last few years [7–10]. For example, ITO nanoparticles were achieved by an approach comprising microwave-assisted synthesis in ionic liquids . Park et al. prepared colloidal ITO nanoparticles by thermal decomposition of tin and indium precursors in oleylamine . In another study, non-agglomerated ITO nanoparticles were obtained via a combination of nucleophilic attack and condensation–hydrolysis cascade reactions . However, the synthesis of TCO nanocrystals, which corresponds to the growth of doped oxide nanocrystals, still faces significant challenges. A successful synthetic strategy to generate TCO nanocrystals with high crystallinity, narrow size distribution, and homogeneous composition is yet to be achieved. This is due to lack of detailed understanding on the formation of doped nanocrystals, although attempts have been reported in literature. For instance, “self purification”, a thermodynamical concept, was invoked to explain the low doping concentration in the case of Mn-doped CdSe nanocrystals . In contrast, Erwin et al. show that for the Mn-doped II–VI nanocrystals doping is controlled by impurity adsorption on the nanocrystal surfaces and the doping efficiency is mainly determined by three factors: surface morphology, nanocrystal shapes, and surfactants in the growth solution . In a recent publication, Chen et al. suggest that the nanocrystal doping processes are strongly temperature-dependent . Further research is essential to uncover the critical factors that govern the growth of doped nanocrystals.
In this article, we describe a simple and facile approach to the generation of In-doped ZnO nanocrystals. We choose to study the In-doped ZnO nanocrystal system because In-doped ZnO thin films have been well-studied, demonstrating superior optoelectronic properties as TCO thin films. In addition, both zinc oxide and indium oxide nanocrystals are readily synthesized by a one-step ester elimination reaction based on alcoholysis of metal carboxylate salts [14, 15]. The reactions can be monitored by Fourier transform infrared spectroscopy (FTIR) and UV–Visible absorption spectra (UV–Vis), making them ideal for investigating the processes. The resulting nanocrystals from the reactions have been characterized by transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), energy-dispersive spectroscopy (EDS), inductively coupled plasma atomic emission spectrometer (ICP-AES), X-ray diffraction (XRD), and UV–Vis.
Indium acetate (In(Ac)3) and stearic acid (SA) was purchased from Aldrich. Zinc stearate (Zn(St)2) and 1-Octadecanol (ODA) was purchased from Alfa Aesar. 1-Octadecene (ODE, tech 90%) was purchased from Acros. All chemicals were used without further purification.
Indium stearate, which was used as indium precursor in the ester elimination reactions, was prepared as follows . In(Ac)3 (20 mmol) was mixed with SA (80 mmol) and heated to 140 °C under an argon atmosphere. The mixture was heated for 5 h, and then the product was isolated by addition of acetone. The resulting precipitate was filtered, vacuum-dried, and again treated with SA (80 mmol) to ensure complete conversion of acetate to stearate. The final product (In(St)3) was washed several times with acetone to remove excess SA.
Four typical reactions, namely pure ZnO reaction (starting with 1 mmol of Zn(St)2), 2% In–ZnO reaction (starting with 0.02 mmol of In(St)3 and 0.98 mmol of Zn(St)2), 5% In–ZnO reaction (starting with 0.05 mmol of In(St)3 and 0.95 mmol of Zn(St)2), and In2O3 reaction (starting with 1 mmol of In(St)3), were studied in this work. In a typical procedure, the metal carboxylate salts and 20 g of 1-octadecene (ODE) were loaded into a three-necked flask. The flask was purged with argon several times, and degassed under vacuum at 120 °C for 20 min with vigorous magnetic stirring. The entire reaction system became a clear solution. Then the solution was heated to 290 °C. 1-Octadecanol (5 mmol) dissolved in 5 g of ODE at 150 °C was quickly injected into the reaction solution. The reaction temperature was set at 290 °C throughout the entire synthesis. After 20 min, the flask was cooled to 50 °C. 50 mL of ethyl acetate were used to precipitate nanocrystals, and the nanocrystals were collected by centrifugation. The nanocrystals were then dispersed in toluene, and any insoluble residue was removed by centrifugation. In-doped ZnO nanocrystals were precipitated by isopropyl alcohol and collected by centrifugation.
Transmission electron microscopy (TEM) and high-resolution TEM images were taken on a JEOL JEM 1230 microscope operated at 80 kV and TECNAI G2 F20 transmission electron microscope at 200 kV equipped with an X-ray energy-dispersive spectroscopy (EDS) system. Specimens were prepared by depositing a drop of CHCl3 solution containing the purified nanocrystals or the aliquots taken during the course of the reaction onto holey carbon-coated Cu grids. X-ray diffraction patterns were obtained on a Bede D1 system operating at 20 kV and 30 mA, using a Cu Kα line (λ = 1.5418 Å). FTIR spectra were obtained on a Bruker Vector 22 spectrophotometer. The samples were prepared by directly spotting hot aliquots of a reaction mixture onto a KBr crystal. The C=C group peak at 1,641 cm−1 was chosen as the reference. IRIS Intrepid II XSP inductively coupled plasma atomic emission spectrometer (ICP-AES) were used for elemental analysis of doped nanocrystals. The optical properties of the colloidal In-doped ZnO nanocrystal solution were analyzed using UNICO UV 2102 ultraviolet–visible spectrophotometer.
Results and Discussion
The UV–Vis absorption spectra provide more information related to the doping of the nanocrystals. Fitting the data to the sigmoidal formula gives an effective band gap of 3.35, 3.43, and 3.46 eV for the nanocrystals from the pure ZnO reaction, the 2% In–ZnO reaction and the 5% In–ZnO reaction, respectively . The average diameter of the undoped ZnO nanoparticles is ca. 16 nm. Thus, the obtained band gap agrees well with the reported bulk value (3.37 eV) at room temperature. While the average diameter of the In-doped nanoparticles is ca. 10 nm, about 5–6 times of the exciton Bohr radius of ZnO (1.8 nm), suggesting a likely presence of moderate quantum confinement effect (QCE) . Theoretical calculations predict a blueshift of ~45 meV for ZnO nanoparticles with diameters of ca. 10 nm . Therefore, the observed blue-shift shall be due to both QCE and the Burstein–Moss effect associated with heavy doping. Accordingly, the contribution of indium doping to the blueshift of the optical band gap is deduced as ~35 and ~65 meV for the nanocrystals from the 2% In–ZnO reaction and the 5% In–ZnO reaction, respectively. Such a value is smaller than that expected if we assume all the indium ions are on the substitutional sites. In other words, part of the dopant atoms may resident on the surface of nanocrystals, or congregate as nanocrystals with cubic crystal structures which are found in the products from the 5% In–ZnO reactions.
In-doped ZnO nanocrystals with high crystallinity and relatively narrow size distribution have been synthesized through a one-step reaction based on alcoholysis of metal carboxylate salts. TEM analyses reveal a significant reduction in the sizes of the In-doped ZnO nanocrystals compared with that of the undoped ZnO nanocrystals. HRTEM, EDS, ICP-AES, XRD investigations, together with UV–Vis analyses indicate the incorporation of indium into the host ZnO lattices, leading to a blue-shift of the absorption peak. Individual nanocrystals with cubic structures are observed in the products from the 5% In–ZnO reactions, due to the relatively high reactivity of the indium precursor. Our results may provide insights for the growth of doped oxide nanocrystals.
The study was financially supported by the Zi Jin program of Zhejiang University, Qian Jiang Foundation of Zhejiang Province under Grant No. QJD0702004, and National Natural Science Foundation of China under Grant No. 50802085.
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- Ellmer K: J. Phys. D. 2000, 33: R17. COI number [1:CAS:528:DC%2BD3cXhs1Sisr8%3D]; Bibcode number [2000JPhD...33R..17E] COI number [1:CAS:528:DC%2BD3cXhs1Sisr8%3D]; Bibcode number [2000JPhD...33R..17E] 10.1088/0022-3727/33/4/201View ArticleGoogle Scholar
- Shen Z, Burrows PE, Bulovi V, Forrest SR, Thompson ME: Science. 1997, 276: 2009. COI number [1:CAS:528:DyaK2sXkt1Wms7w%3D] COI number [1:CAS:528:DyaK2sXkt1Wms7w%3D] 10.1126/science.276.5321.2009View ArticleGoogle Scholar
- Klimov VI, Ivanov SA, Nanda J, Achermann M, Bezel I, McGuire JA, Piryatinski A: Nature. 2007, 447: 441. COI number [1:CAS:528:DC%2BD2sXlsFOgsrs%3D]; Bibcode number [2007Natur.447..441K] COI number [1:CAS:528:DC%2BD2sXlsFOgsrs%3D]; Bibcode number [2007Natur.447..441K] 10.1038/nature05839View ArticleGoogle Scholar
- Herrero J, Guillen C: Thin Solid Films. 2004, 451–452: 630. 10.1016/j.tsf.2003.11.050View ArticleGoogle Scholar
- Ni J, Yan H, Wang A, Yang Y, Stern CL, Metz AW, Jin S, Wang L, Marks TJ, Ireland JR, Kannewurf CR: J. Am. Chem. Soc.. 2005, 127: 5613. COI number [1:CAS:528:DC%2BD2MXisVynsrs%3D] COI number [1:CAS:528:DC%2BD2MXisVynsrs%3D] 10.1021/ja044643gView ArticleGoogle Scholar
- Canhola P, Martins N, Raniero L, Pereira S, Fortunato E, Ferreira I, Martins R: Thin Solid Films. 2005, 487: 271. COI number [1:CAS:528:DC%2BD2MXms1Ontr8%3D]; Bibcode number [2005TSF...487..271C] COI number [1:CAS:528:DC%2BD2MXms1Ontr8%3D]; Bibcode number [2005TSF...487..271C] 10.1016/j.tsf.2005.01.078View ArticleGoogle Scholar
- Richard AG, Charles JC, Cantwell GC, Rosario AG, Christopher JS: Adv. Mater.. 2008, 20: 4163.Google Scholar
- Bühler G, Thölmann D, Feldmann C: Adv. Mater.. 2007, 19: 2224. 10.1002/adma.200602102View ArticleGoogle Scholar
- Choi S, Nam KM, Park BK, Seo WS, Park JT: Chem. Mater.. 2008, 20: 2609. COI number [1:CAS:528:DC%2BD1cXjs1Gjurk%3D] COI number [1:CAS:528:DC%2BD1cXjs1Gjurk%3D] 10.1021/cm703706mView ArticleGoogle Scholar
- Ba J, Fattakhova Rohlfing D, Feldhoff A, Brezesinski T, Djerdj I, Wark M, Niederberger M: Chem. Mater.. 2006, 18: 2848. COI number [1:CAS:528:DC%2BD28XksFKkurw%3D] COI number [1:CAS:528:DC%2BD28XksFKkurw%3D] 10.1021/cm060548qView ArticleGoogle Scholar
- Mikulec FV, Kuno M, Bennati M, Hall DA, Griffin RG, Bawendi MG: J. Am. Chem. Soc.. 2000, 122: 2532. COI number [1:CAS:528:DC%2BD3cXhsVGhsrw%3D] COI number [1:CAS:528:DC%2BD3cXhsVGhsrw%3D] 10.1021/ja991249nView ArticleGoogle Scholar
- Erwin SC, Zu L, Haftel MI, Efros AL, Kennedy TA, Norris DJ: Nature. 2005, 436: 91. COI number [1:CAS:528:DC%2BD2MXlvVGhs74%3D]; Bibcode number [2005Natur.436...91E] COI number [1:CAS:528:DC%2BD2MXlvVGhs74%3D]; Bibcode number [2005Natur.436...91E] 10.1038/nature03832View ArticleGoogle Scholar
- Chen D, Viswanatha R, Ong GL, Xie R, Balasubramaninan M, Peng X: J. Am. Chem. Soc.. 2009, 131: 9333. COI number [1:CAS:528:DC%2BD1MXntVSkt70%3D] COI number [1:CAS:528:DC%2BD1MXntVSkt70%3D] 10.1021/ja9018644View ArticleGoogle Scholar
- Chen Y, Kim M, Lian G, Johnson MB, Peng X: J. Am. Chem. Soc.. 2005, 127: 13331. COI number [1:CAS:528:DC%2BD2MXpt1Cnt7s%3D] COI number [1:CAS:528:DC%2BD2MXpt1Cnt7s%3D] 10.1021/ja053151gView ArticleGoogle Scholar
- Narayanaswamy A, Xu H, Pradhan N, Kim M, Peng X: J. Am. Chem. Soc.. 2006, 128: 10310. COI number [1:CAS:528:DC%2BD28XmvFCqu70%3D] COI number [1:CAS:528:DC%2BD28XmvFCqu70%3D] 10.1021/ja0627601View ArticleGoogle Scholar
- Du YP, Zhang YW, Sun LD, Yan CH: J. Phys. Chem. C. 2008, 112: 12234. COI number [1:CAS:528:DC%2BD1cXoslamsrw%3D] COI number [1:CAS:528:DC%2BD1cXoslamsrw%3D] 10.1021/jp802958xView ArticleGoogle Scholar
- Farvid SS, Dave N, Wang T, Radovanovic PV: J. Phys. Chem. C. 2009, 113: 15928. COI number [1:CAS:528:DC%2BD1MXhtVSgtb7E] COI number [1:CAS:528:DC%2BD1MXhtVSgtb7E] 10.1021/jp905281kView ArticleGoogle Scholar
- Martin RW, Middleton PG, O’Donnell KP, Van der Stricht W: Appl. Phys. Lett.. 1999, 74: 263. COI number [1:CAS:528:DyaK1MXit1Wntw%3D%3D]; Bibcode number [1999ApPhL..74..263M] COI number [1:CAS:528:DyaK1MXit1Wntw%3D%3D]; Bibcode number [1999ApPhL..74..263M] 10.1063/1.123275View ArticleGoogle Scholar
- Fonoberov VA, Balandin AA: Phys. Rev. B. 2004, 70: 195410. Bibcode number [2004PhRvB..70s5410F] Bibcode number [2004PhRvB..70s5410F] 10.1103/PhysRevB.70.195410View ArticleGoogle Scholar
- Viswanatha R, Sapra S, Satpati B, Satyam PV, Dev BN, Sarma DD: J. Mater. Chem.. 2004, 14: 661. COI number [1:CAS:528:DC%2BD2cXhtlWms74%3D] COI number [1:CAS:528:DC%2BD2cXhtlWms74%3D] 10.1039/b310404dView ArticleGoogle Scholar
- Xie R, Rutherford M, Peng X: J. Am. Chem. Soc.. 2009, 131: 5691. COI number [1:CAS:528:DC%2BD1MXktVKlsL4%3D] COI number [1:CAS:528:DC%2BD1MXktVKlsL4%3D] 10.1021/ja9005767View ArticleGoogle Scholar