Molecular mechanism of monodisperse colloidal tin-doped indium oxide nanocrystals by a hot-injection approach
© Jin et al.; licensee Springer. 2013
Received: 21 February 2013
Accepted: 11 March 2013
Published: 2 April 2013
Molecular mechanisms and precursor conversion pathways associated with the reactions that generate colloidal nanocrystals are crucial for the development of rational synthetic protocols. In this study, Fourier transform infrared spectroscopy technique was employed to explore the molecular mechanism associated with the formation of tin-doped indium oxide (ITO) nanocrystals. We found that the reaction pathways of the indium precursor were not consistent with simple ligand replacements proposed in the literature. The resulting understanding inspired us to design a hot-injection approach to separate the ligand replacements of indium acetate and the aminolysis processes, generating quality ITO nanocrystals with decent size distributions. The hot-injection approach was readily applied to the synthesis of ITO nanocrystals with a broad range of tin doping. Structural, chemical, and optical analyses revealed effective doping of Sn4+ ions into the host lattices, leading to characteristic and tunable near-infrared surface plasmon resonance peaks. The size control of ITO nanocrystals by multiple hot-injections of metal precursors was also demonstrated.
Colloidal nanocrystals are an important class of functional materials for both fundamental studies and practical applications due to their remarkable properties and excellent solution processability [1–3]. Research on synthetic chemistry of colloidal nanocrystals paves the way to the development of a wide range of potential applications. In the past 2 decades, enormous efforts have been devoted to explore the crystallization kinetics and mechanisms of high-quality colloidal nanocrystals, focusing on the size and shape evolution [4–12]. However, knowledge on the chemical reactions, especially the molecular mechanisms of precursors associated with the formation of colloidal nanocrystals is still limited. For example, the Alivisatos group suggested that for CdSe nanocrystals, precursor conversion limited the rate of nanocrystal nucleation and growth. Size control of the CdSe nanocrystals could be achieved by tuning the reactivity of precursor molecules . Ozin et al. found that the sulfur-alkylamine solution, a widely used ‘black box’ precursor for sulfur, in-situ generated H2S upon heating, which reacted with metal salts to form metal sulfide nanocrystals . Peng and co-workers demonstrated that the rate-limiting step for synthesis of CdS nanocrystals was the reduction of elemental sulfur by 1-octadecene (ODE), which possessed a critical temperature of ca. 180°C . These reports demonstrate that understanding on molecular mechanisms of the chemical reactions is crucial for the development of rational synthetic protocols for colloidal nanocrystals.
Transparent conducting oxides (TCOs) are degenerately doped semiconductor oxides that possess attractive combination of electrical conductivity and transparency to visible light. ITO is the most widely used TCO because of its superior performance in terms of optical transparency and electrical conductivity as well as its excellent chemical and environmental stability. Nowadays, ITO is applied for many applications, such as transparent electrodes for displays, light-emitting diodes or solar cells, and infrared reflector for energy-saving windows [16–20].
The synthesis of colloidal ITO nanoparticles has attracted considerable research interest. This is largely motivated by the goal of employing low-temperature and cost-effective solution processable techniques to deposit ITO thin films on flexible substrates . Early attempts to obtain ITO nanoparticles by the co-precipitation approach in aqueous media generally led to nanoparticles with broad size distribution and poor colloidal stability [22, 23]. Niederberger and co-workers suggested that the nonaqueous route involving solvothermal treatments of metal precursors in benzyl alcohol may result in relatively uniform crystalline ITO nanoparticles . A few recent studies demonstrated that quality colloidal ITO nanocrystals could be obtained by nonaqueous approaches [25–30]. It is noteworthy that in 2009, Masayuki and co-workers reported the synthesis of ITO nanocrystals with tunable surface plasmon resonance (SPR) peaks by controlling the concentrations of tin doping . This finding is the first example of tunable SPR in the near-infrared (NIR) region for oxide nanoparticles. The strong SPR in the NIR region of ITO nanocrystals arising from the presence of high concentrations of free carriers was confirmed by Radovanic and co-workers . In a recent publication, the Milliron group further suggested that the localized surface plasmons of ITO nanocrystal films could be dynamically controlled by electrochemical modulation of the electron concentrations, which is promising for future development of energy-saving coating on smart windows .
Here we provide a detailed study on the synthesis and characterization of quality monodisperse colloidal ITO nanocrystals with characteristic and tunable SPR peaks in the NIR region. The molecular mechanism of the synthetic method developed by Masayuki et al., which will be called as the Masayuki method in the following text for the sake of presentation, was probed using the Fourier transform infrared spectroscopy (FTIR) technique. The resulting understanding inspired us to modify the synthetic procedures and design a hot-injection approach to synthesize ITO nanoparticles. The key features of the ITO nanocrystals from the hot-injection approach including valance states of tin dopants and molar extinction coefficient were identified. We further applied the hot-injection approach to the synthesis of ITO nanocrystals with a broad range of tin dopants and developed multiple injection procedures, aiming to achieve size control of the products.
Indium acetate and tin(II) 2-ethylhexanoate were purchased from Sigma-Adrich (St. Louis, MO, USA). ODE, n-octylether, and oleylamine were purchased from Acros Organics (Fair Lawn, NJ, USA). Tetrachloroethylene (C2Cl4) and 2-ethylhexanoic acid were purchased from Alfa Aesar (Ward Hill, MA, USA). Hydrochloric acid (HCl), ethyl acetate, and n-hexane were analytical grade reagents from Sinopharm Chemical Reagent Co., Ltd. (Shanghai, China). All chemicals were used without further purification.
The Masayuki method
We repeated the synthesis of ITO nanocrystals using the Masayuki method according to the previous report . Note that the carboxylic acid in the starting materials was changed from n-octanoic acid, which was used in the literature , to 2-ethylhexanoic acid according to Dr. Masayuki Kanehara's kind suggestions because the use of n-octanoic acid led to the formation of ITO nanoflowers, instead of nanoparticles, with significantly broadened SPR peaks (Additional file 1: Figure S1). The proportion of the tin precursor in the reagents, i.e., [tin(II) 2-ethylhexanoate] / ([tin(II) 2-ethylhexanoate] + [indium acetate]), was set to be 10 mol.% because this dopant ratio generated ITO nanocrystals with relatively high free electron density and strong SPR in the NIR region . In a typical reaction, indium acetate (1.08 mmol), tin(II) 2-ethylhexanoate (0.12 mmol), 2-ethylhexanoic acid (3.6 mmol), oleylamine (10 mmol), and ODE (10 ml) were loaded in a three-neck flask and stirred at 80°C under vacuum for 30 min to obtain a clear solution. The solution was heated at 150°C for 60 min under an argon atmosphere. The reaction temperature was further raised to 280°C and stabilized for 2 h to generate ITO nanocrystals. The ITO nanocrystals were precipitated out by adding ethyl acetate, purified, and redispersed in C2Cl4.
The hot-injection approach
In a typical reaction, indium acetate (1.08 mmol), tin(II) 2-ethylhexanoate (0.12 mmol), 2-ethylhexanoic acid (3.6 mmol), and ODE (10 ml) were loaded in a three-neck flask and stirred at 80°C under vacuum for 30 min. The solution was heated at 150°C under an argon atmosphere for 60 min before raising the temperature to 290°C. A separate solution of ODE (5 ml) containing oleylamine (10 mmol) at 220°C was rapidly injected into the reaction flask. The reaction mixture was then kept at 290°C for 2 h to obtain ITO nanocrystals.
Fourier transform infrared spectroscopy analysis
FTIR spectra were recorded on a Bruker Tensor 27 FTIR spectrophotometer at room temperature (Bruker AXS, Inc., Winooski, VT, USA). The samples were prepared by directly spotting hot aliquots onto CaF2 plates. Note that in many spectra shown in the paper, we used very thick films to maximize the absorption signals, which may cause saturation of intensities of some relatively strong peaks.
Powder X-ray diffraction analysis
X-ray diffraction (XRD) measurements were performed on an X'Pert PRO system (PANalytical, Almelo, The Netherlands) operated at 40 keV and 40 mA with Cu KR radiation (λ = 1.5406 Å).
Transmission electron microscopy analysis
Transmission electron microscopy (TEM) images were recorded using a JEOL JEM 1230 microscope (JEOL Ltd., Akishima-shi, Japan) operated at 80 keV. High-resolution TEM (HRTEM) was performed on a Tecnai G2 F20 S-TWIN microscope (FEI, Hillsboro, OR, USA) operated at 200 keV.
X-ray photoelectron spectroscopy analysis
X-ray photoelectron spectroscopy (XPS) were recorded on a Thermo ESCALAB-250 spectrometer (Thermo Fisher Scientific, Waltham, MA, USA) using a monochromatic Al Kα radiation source (1,486.6 eV).
Ultraviolet-visible near-infrared absorption spectra analysis
Ultraviolet-visible near-infrared absorption (UV-vis-NIR) spectra of the samples were recorded on a UV 3600 UV-vis-NIR spectrophotometer (Shimadzu, Kyoto, Japan).
Inductively coupled plasma atomic emission spectroscopy analysis
The purified ITO nanocrystal samples were dissolved in concentrated HCl solutions (36% to 38%). The metal ions were transferred to aqueous phase by extraction twice with distilled water. Elemental analyses were carried out using an IRIS Intrepid II XSP inductively coupled plasma atomic emission spectroscopy (ICP-AES) equipment (Thermo Fisher Scientific, Waltham, MA, USA).
Results and discussion
FTIR is a powerful tool for the identification of the molecular mechanism associated with the formation of the oxide nanocrystals [7, 11, 32–34]. For instance, Peng and co-workers found that in the reaction system, to obtain In2O3 nanocrystals, hydrolysis and alcoholysis were the major reaction pathways for the indium precursors . In a recent study, we showed that the aminolysis approach accounted for the formation of tin-doped ZnO nanocrystals .
Rational choice and design of the metal precursors is one of the most critical issues that control the chemical kinetics of the amide elimination reactions. In the Masayuki method, indium acetate and tin(II) 2-ethylhexanate were used as the initial metal precursors. It was proposed that the acetate groups of indium precursor may be replaced by the long-chain carboxyl groups by introducing free carboxylic acid, i.e., 2-ethylhexanate acid and stirring the reaction mixture of the metal precursors, 2-ethylhexanate acid, oleylamine, and the solvent, at 80°C under vacuum . Nevertheless, we found that the reaction pathways of indium acetate, the initial indium precursor, were debatable because this hypothesis was not consistent with the following facts. As shown in Figure 1, no characteristic peaks of carboxyl acid were observed in the FTIR spectrum of the reaction mixtures at room temperature (top curve). The FTIR spectra of the reaction mixtures exhibited no significant changes after stirring the reaction mixtures at 80°C under vacuum. In addition, the origin of the peak at 1,573 cm−1 in the room temperature FTIR spectra of the reaction mixtures is worthy of further discussion since this peak is not consistent with any characteristic peaks of the reagents, i.e., oleylamine, indium acetate, tin(II) 2-ethylhexanate, 2-ethylhexanatic acid, and ODE (Additional file 1: Figure S2).
Based on the above facts, we suggest that the reaction pathways of the indium acetate in the Masayuki method is more complicated than simple ligand replacement by 2-ethylhexanate. The peaks at 1,573 cm−1 that were observed in FTIR spectra of the reaction mixtures at room temperature, 80°C or 150°C (Figure 1) were due to the formation of ammonium carboxylate salts which consumed free 2-ethylhexanatic acid. The dissolution of indium acetate at 80°C was because of the formation of oleylamine-indium acetate complex, instead of ligand replacement by free carboxylic acid. Given the condition that oleylamine was excessive in the reaction systems, a plausible deduction was that the oleylamine-indium acetate complex was responsible for the formation of ITO nanocrystals. We tested this hypothesis by conducting controlled experiments in which 2-ethylhexanate acid was absent in the reagents. No nanocrystals but agglomerations with poor colloidal stability were formed, implying an exorbitantly fast reaction kinetics of the oleylamine-indium acetate complex. Therefore, the presence of 2-ethylhexanate acid in the starting materials was critical to obtain high-quality ITO nanocrystals for the Masayuki method. This was also reflected by the fact that ITO flowers, instead of nanoparticles, formed when n-octanoic acid, instead of 2-ethylhexanate acid, was used in the starting materials (Additional file 1: Figure S1). We suspect that although majority of the 2-ethylhexanate acid reacted with oleylamine to form ammonium carboxylate salts, considering the reversible nature of the acid-base reaction, 2-ethylhexanate acid may impact in the formation of the oleylamine-indium carboxylate complex with adequate reaction kinetics. Nevertheless, such a process is complicated. Modifications on the Masayuki method that induce evident evolutions of the metal precursors are desirable.
The valence state of tin dopants is critical in terms of modifying the electronic properties of the ITO nanocrystals. Note that aminolysis of pure tin(II) 2-ethylhexanoate, the tin precursor used in our experiments, by oleylamine may lead to tin(II) oxide or tin(IV) oxide depending on specific reaction conditions, as demonstrated by our controlled experiments (Additional file 1: Figure S7). XPS was employed to identify the chemical states of the tin dopants. As shown in Figure 4e and Additional file 1: Figure S8, the binding energy of Sn 3d5/2 peak locates at 487.1 eV, which corresponds to the Sn4+ bonding state [40, 41]. The incorporation of Sn4+ ions into the lattice of the nanocrystals led to high free electron concentrations, as confirmed by the characteristic near-infrared SPR peak (Figure 4f). We determined the extinction coefficient per molar of ITO nanocrystals at the SPR peak of 1,680 nm to be 4.5 × 107 M−1 cm−1, by assuming that the nanocrystals are spherical and 11.4 nm in diameter.
In conclusion, we provide a detailed study on the synthesis and characterization of monodisperse colloidal ITO nanocrystals. The molecular mechanism associated with the formation of the ITO nanocrystals was identified as amide elimination through aminolysis of metal carboxylate salts. We found that the reaction pathways of the indium precursor, which were critical in terms of controlling the chemical kinetics, in the Masayuki method were more complicated than simple ligand replacement proposed in the literature. We designed a hot-injection approach which separated the ligand replacements of the indium acetate and the aminolysis reactions of the metal precursors. The hot-injection approach was readily applied to the synthesis of ITO nanocrystals with a broad range of tin dopants, leading to products with decent size distributions. Further multiple injections of reagents allowed effective size tuning of the colloidal ITO nanocrystals. We revealed the effective doping of different concentrations of Sn4+ ions into the corundum-type lattices of the nanocrystals, resulting in characteristic and tunable near-infrared SPR peaks.
Our study demonstrates that FTIR is a powerful technique for the investigation of the molecular mechanism and precursor conversion pathways associated with the reactions to generate oxide nanocrystals, which may shed light on future rational design of synthetic strategies of oxide nanocrystals.
YZJ is an associate professor at the Materials Science and Engineering Department of Zhejiang University. ZZY is a full professor at the Materials Science and Engineering Department of Zhejiang University. QY and YPR are master students under the supervision of Dr. Jin. XW is a Ph.D. student co-supervised by Dr. Jin and Prof. Ye.
This work is financially supported by the National Natural Science Foundation of China (51172203), National High Technology Research and Development Program of China (2011AA050520), Natural Science Funds for Distinguished Young Scholar of Zhejiang Province (R4110189), and Opening Foundation of Zhejiang Provincial Top Key Discipline. We would like to thank Dr. Masayuki Kanehara (Japan) and Prof. Xiaogang Peng (Zhejiang University, China) for the valuable discussions.
- Yin M, Wu CK, Lou Y, Burda C, Koberstein JT, Zhu Y, O'Brien S: Copper oxide nanocrystals. J Am Chem Soc 2005, 127: 9506–9511. 10.1021/ja050006uView ArticleGoogle Scholar
- Talapin D, Lee J, Kovalenko M, Shevchenko E: Prospects of colloidal nanocrystals for electronic and optoelectronic applications. Chem Rev 2010, 110: 389–458. 10.1021/cr900137kView ArticleGoogle Scholar
- Mcdonald SA, Konstantatos G, Zhang S, Cyr PW, Klem EJ, Levina L, Sargent EH: Solution-processed PbS quantum dot infrared photodetectors and photovoltaics. Nat Mater 2005, 4: 138–142. 10.1038/nmat1299View ArticleGoogle Scholar
- Peng XG, Manna L, Yang WD, Wickham J, Scher E, Kadavanich A, Alivisatos AP: Shape control of CdSe nanocrystals. Nature 2000, 404: 59–61. 10.1038/35003535View ArticleGoogle Scholar
- Peng ZA, Peng X: Nearly monodisperse and shape-controlled CdSe nanocrystals via alternative routes: nucleation and growth. J Am Chem Soc 2002, 124: 3343–3353. 10.1021/ja0173167View ArticleGoogle Scholar
- Peng X: An essay on synthetic chemistry of colloidal nanocrystals. Nano Res 2009, 2: 425–447. 10.1007/s12274-009-9047-2View ArticleGoogle Scholar
- Yang Y, Jin Y, He H, Wang Q, Tu Y, Lu H, Ye Z: Dopant-induced shape evolution of colloidal nanocrystals: the case of zinc oxide. J Am Chem Soc 2010, 132: 13381. 10.1021/ja103956pView ArticleGoogle Scholar
- Yw J, Js C, Cheon J: Shape control of semiconductor and metal oxide nanocrystals through nonhydrolytic colloidal routes. Angew Chem Int Ed 2006, 45: 3414–3439. 10.1002/anie.200503821View ArticleGoogle Scholar
- Murray C, Norris D, Bawendi MG: Synthesis and characterization of nearly monodisperse CdE (E = sulfur, selenium, tellurium) semiconductor nanocrystallites. J Am Chem Soc 1993, 115: 8706–8715. 10.1021/ja00072a025View ArticleGoogle Scholar
- Murray C, Kagan C, Bawendi M: Synthesis and characterization of monodisperse nanocrystals and close-packed nanocrystal assemblies. Annu Rev Mater Sci 2000, 30: 545–610. 10.1146/annurev.matsci.30.1.545View ArticleGoogle Scholar
- Jin Y, Yi Q, Zhou L, Chen D, He H, Ye Z, Hong J, Jin C: Synthesis and characterization of ultrathin tin-doped zinc oxide nanowires. Eur J Inorg Chem 2012, 2012: 4268–4272. 10.1002/ejic.201200659View ArticleGoogle Scholar
- Yang Y, Jin Y, He H, Ye Z: Facile synthesis and characterization of ultrathin cerium oxide nanorods. CrystEngComm 2010, 12: 2663–2665. 10.1039/c004270fView ArticleGoogle Scholar
- Owen JS, Chan EM, Liu H, Alivisatos AP: Precursor conversion kinetics and the nucleation of cadmium selenide nanocrystals. J Am Chem Soc 2010, 132: 18206–18213. 10.1021/ja106777jView ArticleGoogle Scholar
- Thomson JW, Nagashima K, Macdonald PM, Ozin GA: From sulfur−amine solutions to metal sulfide nanocrystals: peering into the oleylamine−sulfur black box. J Am Chem Soc 2011, 133: 5036–5041. 10.1021/ja1109997View ArticleGoogle Scholar
- Li Z, Ji Y, Xie R, Grisham SY, Peng X: Correlation of CdS nanocrystal formation with elemental sulfur activation and its implication in synthetic development. J Am Chem Soc 2011, 133: 17248–17256. 10.1021/ja204538fView ArticleGoogle Scholar
- Granqvist CG, Hultåker A: Transparent and conducting ITO films: new developments and applications. Thin Solid Films 2002, 411: 1–5. 10.1016/S0040-6090(02)00163-3View ArticleGoogle Scholar
- Tadatsugu M: Transparent conducting oxide semiconductors for transparent electrodes. Semicon Sci Tec 2005, 20: S35-S44. 10.1088/0268-1242/20/4/004View ArticleGoogle Scholar
- Chang SJ, Chang CS, Su YK, Lee CT, Chen WS, Shen CF, Hsu YP, Shei SC, Lo HM: Nitride-based flip-chip ITO LEDs. IEEE T Adv Packaging 2005, 28: 273–277.View ArticleGoogle Scholar
- Hamberg I, Granqvist CG: Evaporated Sn-doped In2O3 films: basic optical properties and applications to energy-efficient windows. J Appl Phys 1986, 60: R123-R160. 10.1063/1.337534View ArticleGoogle Scholar
- Granqvist CG: Transparent conductors as solar energy materials: a panoramic review. Sol Energy Mater Sol Cells 2007, 91: 1529–1598. 10.1016/j.solmat.2007.04.031View ArticleGoogle Scholar
- Lee J, Lee S, Li G, Petruska MA, Paine DC, Sun S: A facile solution-phase approach to transparent and conducting ITO nanocrystal assemblies. J Am Chem Soc 2012, 134: 13410–13414. 10.1021/ja3044807View ArticleGoogle Scholar
- Kim KY, Park SB: Preparation and property control of nano-sized indium tin oxide particle. Mater Chem Phys 2004, 86: 210–221. 10.1016/j.matchemphys.2004.03.012View ArticleGoogle Scholar
- Goebbert C, Nonninger R, Aegerter MA, Schmidt H: Wet chemical deposition of ATO and ITO coatings using crystalline nanoparticles redispersable in solutions. Thin Solid Films 1999, 351: 79–84. 10.1016/S0040-6090(99)00209-6View ArticleGoogle Scholar
- Ba J, Fattakhova Rohlfing D, Feldhoff A, Brezesinski T, Djerdj I, Wark M, Niederberger M: Nonaqueous synthesis of uniform indium tin oxide nanocrystals and their electrical conductivity in dependence of the tin oxide concentration. Chem Mate 2006, 18: 2848–2854. 10.1021/cm060548qView ArticleGoogle Scholar
- Buhler G, Tholmann D, Feldmann C: One-pot synthesis of highly conductive indium tin oxide nanocrystals. Adv Mater 2007, 19: 2224–2227. 10.1002/adma.200602102View ArticleGoogle Scholar
- Choi SI, Nam KM, Park BK, Seo WS, Park JT: Preparation and optical properties of colloidal, monodisperse, and highly crystalline ITO nanoparticles. Chem Mater 2008, 20: 2609–2611. 10.1021/cm703706mView ArticleGoogle Scholar
- Gilstrap RA, Capozzi CJ, Carson CG, Gerhardt RA, Summers CJ: Synthesis of a nonagglomerated indium tin oxide nanoparticle dispersion. Adv Mater 2008, 20: 4163–4166.Google Scholar
- Kanehara M, Koike H, Yoshinaga T, Teranishi T: Indium tin oxide nanoparticles with compositionally tunable surface plasmon resonance frequencies in the near-IR region. J Am Chem Soc 2009, 131: 17736–17737. 10.1021/ja9064415View ArticleGoogle Scholar
- Sun Z, He J, Kumbhar A, Fang J: Nonaqueous synthesis and photoluminescence of ITO nanoparticles. Langmuir 2010, 26: 4246–4250. 10.1021/la903316bView ArticleGoogle Scholar
- Wang T, Radovanovic PV: Free electron concentration in colloidal indium tin oxide nanocrystals determined by their size and structure. J Phys Chem C 2010, 115: 406–413.View ArticleGoogle Scholar
- Garcia G, Buonsanti R, Runnerstrom EL, Mendelsberg RJ, Llordes A, Anders A, Richardson TJ, Milliron DJ: Dynamically modulating the surface plasmon resonance of doped semiconductor nanocrystals. Nano Lett 2011, 11: 4415–4420. 10.1021/nl202597nView ArticleGoogle Scholar
- Chen Y, Kim M, Lian G, Johnson MB, Peng X: Side reactions in controlling the quality, yield, and stability of high quality colloidal nanocrystals. J Am Chem Soc 2005, 127: 13331–13337. 10.1021/ja053151gView ArticleGoogle Scholar
- Narayanaswamy A, Xu H, Pradhan N, Kim M, Peng X: Formation of nearly monodisperse In2O3 nanodots and oriented-attached nanoflowers: hydrolysis and alcoholysis vs pyrolysis. J Am Chem Soc 2006, 128: 10310–10319. 10.1021/ja0627601View ArticleGoogle Scholar
- Chen Y, Johnson E, Peng X: Formation of monodisperse and shape-controlled MnO nanocrystals in non-injection synthesis: self-focusing via ripening. J Am Chem Soc 2007, 129: 10937–10947. 10.1021/ja073023nView ArticleGoogle Scholar
- Stuart BH: Infrared Spectroscopy: Fundamentals and Applications. Hoboken: Wiley; 2004.View ArticleGoogle Scholar
- Carey FA: Organic Chemistry. New York: McGraw-Hill; 2000.Google Scholar
- Xie R, Li Z, Peng X: Nucleation kinetics vs chemical kinetics in the initial formation of semiconductor nanocrystals. J Am Chem Soc 2009, 131: 15457–15466. 10.1021/ja9063102View ArticleGoogle Scholar
- Ludi B, Süess MJ, Werner IA, Niederberger M: Mechanistic aspects of molecular formation and crystallization of zinc oxide nanoparticles in benzyl alcohol. Nanoscale 2012, 4: 1982–1995. 10.1039/c1nr11557jView ArticleGoogle Scholar
- Koziej D, Rossell MD, Ludi B, Hintennach A, Novak P, Grunwaldt JD, Niederberger M: Interplay between size and crystal structure of molybdenum dioxide nanoparticles–synthesis, growth mechanism, and electrochemical performance. Small 2011, 7: 377–387. 10.1002/smll.201001606View ArticleGoogle Scholar
- Alam MJ, Cameron DC: Optical and electrical properties of transparent conductive ITO thin films deposited by sol–gel process. Thin Solid Films 2000, 377–378: 455–459.View ArticleGoogle Scholar
- Teixeira V, Cui HN, Meng LJ, Fortunato E, Martins R: Amorphous ITO thin films prepared by DC sputtering for electrochromic applications. Thin Solid Films 2002, 420–421: 70–75.View ArticleGoogle Scholar
This article is published under license to BioMed Central Ltd. This is an Open Access article distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/2.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.