Thin Solid Films 519 (2011) 18451850

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Thin Solid Films

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Electrodeposition of black chromium spectrally selective coatings from a Cr(III)ionic liquid solution
Snia Eugnio a,, Carmen Mireya Rangel a,b, Rui Vilar a, Ana Maria Botelho do Rego c
a b c

Departamento de Engenharia de Materiais, Instituto Superior Tcnico, Universidade Tcnica de Lisboa, Av. Rovisco Pais, 1049-001 Lisboa, Portugal Laboratrio Nacional de Energia e Geologia, Pao do Lumiar 22, 1649-038 Lisboa, Portugal Centro de Qumica-Fsica Molecular and IN, DEQB, Instituto Superior Tcnico, Universidade Tcnica de Lisboa, Av. Rovisco Pais, 1049-001 Lisboa, Portugal

a r t i c l e

i n f o

a b s t r a c t
In the present study, black chromium coatings were electrodeposited from a 1-butyl-3-methylimidazolium tetrauoroborate ([BMIm][BF4]) solution containing Cr(III) under potentiostatic control on copper substrates. The electrochemical behavior of the electrolyte was studied by cyclic voltammetry. The reduction of Cr(III) species in the solution is a two-step process, from Cr(III) to Cr(II) and from Cr(II) to Cr(0). The potential of each reaction shifts positively with the increase of the electrolyte temperature. The parameters for the electrodeposition of black chromium lms were optimized. Homogeneous black chromium lms with spectrally selective optical properties were produced by applying a potential of 1.5 V for 1800 s, at an electrolyte temperature of 85 C. The coatings consist of a mixture of chromium oxide/hydroxide and metallic chromium. They are amorphous and present a sub-micrometric granular structure. 2010 Elsevier B.V. All rights reserved.

Article history: Received 20 January 2010 Received in revised form 1 October 2010 Accepted 7 October 2010 Available online 21 October 2010 Keywords: Ionic liquids Electrodeposition Black chromium

1. Introduction Black chromium is widely used as a spectrally selective coating material in thermal energy conversion applications [1,2], due to its optical properties, high corrosion resistance and good thermal stability [3]. These coatings are usually obtained by electrodeposition from water-based hexavalent chromium (Cr(VI)) solutions [3], but these electrolytes raise serious health and environmental concerns, so it is of the utmost importance to replace them as soon as possible. Ionic liquids have a number of unique properties that make them extremely interesting solvents for electrodeposition. They can dissolve many organic and inorganic compounds, present a wider electrochemical window and better chemical stability than water, negligible vapour pressure and high thermal and chemical stability. A wide range of metals, metal alloys and semiconductors has been electrodeposited from ionic liquid solutions [4,5], including reactive materials such as aluminium, silicon, germanium and titanium [48], impossible to obtain by electrodeposition from aqueous solutions. Aluminium electrodeposition has been the object of particular attention and pure aluminium and several aluminium alloys have been electrodeposited from chloroaluminate-based ionic liquids [9 17] and from water and air-stable ionic liquid solutions [18]. Metals, such as silver [19], copper [20], nickel [2123], zinc [21] and manganese [21,24], which can also be obtained from aqueous solutions, have frequently been electrodeposited from ionic liquid
Corresponding author. E-mail addresses: s.eugenio@ist.utl.pt (S. Eugnio), carmen.rangel@ineti.pt (C.M. Rangel), rui.vilar@ist.utl.pt (R. Vilar), amrego@ist.utl.pt (A.M. Botelho do Rego). 0040-6090/$ see front matter 2010 Elsevier B.V. All rights reserved. doi:10.1016/j.tsf.2010.10.029

electrolytes with better properties, due to the absence of hydrogen evolution. The electrodeposition of chromium from ionic liquid-based electrolytes has been the object of only very few publications up to this moment. Ali et al. [9] studied the electrodeposition of aluminium chromium alloys from CrCl2 solutions in AlCl3-N-(n-butylpyridinium chloride). Depending on the applied current density, potential, and concentration of the Cr(II) ion in the electrolyte, aluminium chromium alloys with chromium concentrations between 0 and to 94 at.% were obtained. Abbott et al. [2527] reported the electrodeposition of chromium from an ionic liquid consisting of choline chloride and hexahydrated chromium salt, producing a pale blue/grey amorphous lm [25] or, if LiCl is added to the solution, a nanocrystalline black chromium lm [27]. In a more recent paper [26], the same authors describe the electrodeposition of hard and bright chromium lms from the same ionic liquid. In the present paper, we report the electrodeposition of black chromium thin lms from an ionic liquid solution of Cr(III) ions. The ionic liquid used as solvent is 1-butyl-3-methylimidazolium tetrauoroborate ([BMIm][BF4]). 2. Experimental details The preparation of the electrolyte and the electrochemical experiments were performed under an argon atmosphere in a glove box with a gas purication system capable of ensuring that the H2O and O2 contents in the atmosphere remained below 2 ppm. Solutions of 1-butyl-3-methylimidazolium tetrauoroborate ([BMIm][BF4]) containing 0.4 M Cr(III) were prepared by adding CrCl3.6H2O to the

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ionic liquid and mixing both components for several hours under vacuum. The electrochemical experiments were performed using an Autolab PGSTAT100 potentiostat controlled by the NOVA software and a conventional 3-electrode cell. Cyclic voltammograms were obtained by sweeping the potential at a scan rate of 50 mVs 1 in the cathodic direction from the open-circuit potential up to the cathodic limit, then reversing the scan until the anodic limit was reached. At this point, the scan direction was reversed again and the scan stopped at the starting potential. A glassy carbon (GC) disc (A = 0.071 cm2) was used as the working electrode. The counter-electrode was a platinum plate (A = 1 cm2) and the quasi-reference electrode (QRE) a wire of the same material. All potentials are referred to the QRE. The temperature of the electrolyte was kept constant using a thermostated bath and varied between 30 and 85 C. Electrodeposition was carried out on Cu plates, under potentiostatic control. Prior to the experiments, the substrates were polished with 1000 grit SiC abrasive paper, cleaned in an alkaline solution ultrasonic bath for 15 min, immersed in a 1:1 HNO3:H2O solution for 15 s, thoroughly rinsed with distilled water and dried with hot air. During the electrodeposition experiments, the electrolyte was agitated using a magnetic stirrer to ensure a uniform supply of metal ions to the cathodeelectrolyte interface and the temperature was kept constant by a thermostated bath. After deposition, the samples were rinsed with deionized water and acetone and dried with hot air. The coatings were characterized by scanning electron microscopy (SEM) and energy dispersive X-ray spectrometry (EDS) using a JEOL model 7001F eld-emission gun, a scanning electron microscope with an Oxford X-ray EDS spectrometer, with an acceleration voltage of 15 kV. The chemical composition of the lms was studied by X-ray photoelectron spectroscopy (XPS) using a XSAM800 (KRATOS) spectrometer equipped with an AlK source (photon energy equal to 1486.6 eV). The XPS spectra were submitted to a Shirley-type background subtraction and tted with GaussianLorentzian product functions using the XPSPeak 4.1 software. The crystallographic structure was assessed by glancing-incidence X-ray diffraction (GIXRD) analysis performed using a Siemens D5000 diffractometer, with Cu K radiation and an incidence angle of 1. The peaks observed in the diffractograms were indexed by comparison with JCPDS database les. Transmission electron microscopy (TEM) was performed using a Hitachi 8100 microscope, at an operation voltage of 200 kV. The samples for TEM were obtained by scratching the coatings from the substrate and collecting the coating fragments on a 200 mesh copper grid coated with a formvar lm. The optical properties of the black chromium coatings were evaluated by spectral reectance measurements in the near and medium infrared range. The spectra were obtained with a Nicolet Fourier-transform IR spectrometer, equipped with a reection accessory. 3. Results The cyclic voltammograms of pure [BMIm][BF4] and of a solution of this ionic liquid containing 0.4 M Cr(III), on a GC electrode are presented in Fig. 1. Pure [BMIm][BF4] is electrochemically stable in the range 2.5 to + 1 V, in agreement with published studies on the electrochemical behavior of this liquid [28]. The presence of Cr(III) ions in the solution changes signicantly the voltammogram, which shows new cathodic and anodic peaks related to the reduction and oxidation of the Cr species in the solution. In the forward scan, a rst cathodic peak is detected at 0.9 V (IC), corresponding to the reduction of Cr(III) to Cr(II) in the solution. A second cathodic peak, appearing at 1.6 V (IIC), corresponds to the reduction of Cr(II) to Cr (0). The ratio between the integrated charges of peaks IC and IIC is larger than 1, suggesting that only part of the Cr(II) is reduced to Cr (0). In the reverse scan, a rst anodic peak occurs at 1 V (IA), which

Fig. 1. Cyclic voltammogram of pure [BMIm][BF4] (dashed line) and [BMIm][BF4]Cr (III) solution (solid line) at room temperature on a GC electrode. Scan rate: 50 mVs 1.

can be attributed to the oxidation/stripping of Cr(0) formed during the forward scan. Again, the ratio between the integrated charges of the cathodic (IIC) and of anodic peaks (IIA) of the reaction is higher than 1, indicating that this oxidation is only partial. A second peak is observed at 0.2 V (IIA), which corresponds to the oxidation of the Cr (II) formed in the forward scan that was not reduced to Cr(0). The peak may also include a contribution from the oxidation of the species formed in the reaction corresponding to peak IIA, as conrmed by the relation between the peak integrated charges. The effect of the temperature on the electrochemical behavior of the 0.4 M Cr(III)[BMIm][BF4] solution is illustrated in Fig. 2. Increasing the electrolyte temperature leads to an increase in the current density and to a shift of the reduction peaks to less negative potentials, especially for temperatures in the range 50 to 85 C. This evolution can be attributed to the decrease of the solution viscosity, which enhances the mass transport of the active species in the solution and, hence, the current density. This effect is frequently observed in ionic liquid-based electrolytes [19]. The electrodeposition experiments were carried at 30, 50 or 85 C with applied potentials varying between 1.5 and 2 V and deposition times of 900 and 1800 s. Several combinations of these parameters were tested in order to uncover a set of experimental conditions allowing the deposition of homogeneous and adherent lms. Fig. 3 illustrates the inuence of the electrolyte temperature and deposition time on the surface topography of the coatings obtained at a potential of 1.5 V. For an electrolyte temperature of 30 C the lms present a brownish color and are iridescent, while for 50 and 85 C they are uniformly black. The coatings are formed of globular aggregates of nanometric particles (Fig. 4). The size of these aggregates increases with increasing electrolyte temperature and deposition time.

Fig. 2. Cyclic voltammograms obtained in the [BMIm][BF4]Cr(III) solution at (a) 30 C, (b) 50 C and (c) 85 C, on a GC electrode. Scan rate: 50 mVs 1.

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Fig. 3. SEM images of the (a) copper substrate surface, and black chromium lms produced by potentiostatic deposition at 1.5 V for 900 s at (b) 30, (c) 50 and (d) 85 C and for 1800 s at (e) 30, (f) 50 and (g) 85 C.

The surface topography of the coatings is strongly related to the initial surface topography of the substrate, and reveals the microstructure of the substrate material. Prior to the electrodeposition experiments, the copper substrates were etched in diluted nitric acid and present a surface relief revealing grain boundaries and other microstructural features (Fig. 3a). This topographic relief leads to local current density maxima where the nucleation and growth of the coating material are faster, resulting in an accentuation of the initial surface relief. The small thickness of the coating also contributes to this effect because it is not sufcient for a complete leveling of the lm surface. A similar effect of the electrolyte temperature and deposition time is observed when the deposition is carried out at 1.6 V, except for lms deposited during 1800 s at 85 C, which show a cauliower-like morphology, typical of an excessive cathode polarization. For more cathodic potentials (1.8 and 2.0 V), the lms became discontinuous independently of the electrolyte temperature and deposition time. Some lms formed at these potentials and at 85 C show evidence of gas evolution during the electrodeposition process. Cross-sections of a black chromium lm electrodeposited at 1.5 V, for 1800 s at a temperature of 85 C are presented in Fig. 5. The lm thickness is approximately 2 m and the cross-section microstructure structure appears to be quite featureless.

Chemical analysis of the deposited lms, performed by EDS, identied chromium and oxygen as the main elements constituting all the lms. The chemical composition does not depend on the electrodeposition parameters. The penetration of the electron probe in the material being larger than the thickness of the lms, peaks related to the copper substrate are observed in the EDS spectra. The lms shown in Fig. 3c, d, f and g present only very small copper peaks in the EDS spectra conrming a larger lm thickness. Small quantities of Cl and F are also detected, suggesting that some electrolyte is trapped in the lm during its formation. XPS was performed on the lms without any preliminary sputtering cleaning. The XPS spectrum (Fig. 6) presents peaks corresponding to Cr, O and F, in agreement with the EDS results, as well as the peaks of C and N. The Cr 2p3/2 peak (Fig. 6) can be peak tted with three peaks. The peak centered at 574.2 0.2 eV is assigned to metallic Cr (Cr(0)) [29,30]. The peak at 576.7 0.2 eV can be attributed to Cr(III) in Cr2O3 [29], Finally, a peak centered at 577.8 0.2 eV is assignable to Cr(OH)3 since the values found in the literature for the hydroxide, when presented together with the oxide, are systematically higher than the ones for the oxide by around 1 eV [31,32]. The O1s spectrum (Fig. 6) has been peak tted with three peaks. The low energy peak at 530.1 eV is attributed to O2 in Cr2O3

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Fig. 4. Detailed morphology of the black chromium lm produced by potentiostatic deposition at 1.5 V for 1800 s at 85 C.

Fig. 5. Cross-sections of the black chromium lm obtained from potentiostatic deposition at 1.5 V for 1800 s, at 85 C on the copper substrate.

[30] while the high energy peak at 533.2 eV is attributed to adsorbed water [29]. The intense peak at 531.5 eV can be attributed to hydroxide/oxyhydroxide species and adsorbed oxygen [30,33]. These results indicate the presence of both Cr2O3 and Cr(OH)3 in the most external layers of the lm. The peak of carbon C1s can be peak tted with 3 peaks (Fig. 6). The peak of carbon C1s can be deconvoluted in 3 peaks (Fig. 6). The peaks at 286.9 and 288.6 eV can be attributed to the carbon of the imidazolium ring of the [BMIm][BF4] ionic liquid [34], while the peak at 285 eV is typical of contamination of the surface by hydrocarbons. Fluorine and nitrogen peaks may originate from the traces of the [BMIm][BF4] electrolyte [34] adsorbed at the surface of the coatings. Diffractograms of the coatings are presented in Fig. 7. All peaks in the diffractograms can be ascribed to the copper substrate. The difference in the relative intensity of diffraction peaks in the diffractograms is due to the crystallographic texture of the polycrystalline copper substrates that were obtained from rolled copper plates. No peaks related to metallic chromium or chromium oxides are detected. Fig. 8a shows a TEM image of a thin lm produced by electrodeposition at 85 C, with an applied potential of 1.5 V for 1800 s. The thin lm presents the typical mottled contrast of an amorphous structure. The amorphous nature of the lm is conrmed by the selected area electron diffraction pattern (Fig. 8b), which shows only diffuse halo-like rings. A similar behavior is observed in all lms, independent of the deposition parameters. The spectral reectance of a coating obtained by potentiostatic deposition at 1.5 V during 900 s is presented in Fig. 9. The values of and were calculated using the method described by Dufe and Beckman [2]. The coating presents a high absorbance ( = 0.97) for radiation with wavelengths between 0.8 and 4 m (near-IR region) and a low emittance ( = 0.19) for higher wavelengths (mid-IR

region).These values conrm the potential applications of these coatings for solar energy applications. 4. Discussion The present results show that a 0.4 M Cr(III)[BMIm][BF4] solution can be used as an electrolyte for the electrodeposition of black chromium coatings on copper substrates. The reduction of Cr(III) in the Cr(III)[BMIm][BF4] ionic liquid solution is a two-step process involving two consecutive reduction reactions, the rst one from Cr (III) to Cr(II) and from Cr(II) to Cr(0) (Fig. 1). These results are similar to those obtained with aqueous [35,36] and choline chloride electrolytes [25,27] containing Cr(III). However, contrary to what was observed for the choline chloride-based electrolytes [25,27], in the present system the electrode surface is not passivated after the reduction of Cr(III) to Cr(II), suggesting that the Cr(II) exists in the solution. Homogenous and adherent black chromium lms have been electrodeposited on copper substrates at a constant potential of 1.5 V. The thickness of the lms (0.52 m) is in the optimum range for solar energy applications [37,38] and they present good optical properties, similar to black chromium coatings electrodeposited from Cr(VI) aqueous solutions [38]. The lms are formed of globular clusters of nanometric particles (Fig. 3) similar to those observed in black chromium lms deposited from Cr(VI) [3742] aqueous solutions. Frequently the chromium concentration in such lms varies as a function of the distance to the substrate, the region near the substrate being richer in metallic chromium and the surface of the lm richer in Cr2O3 and Cr hydroxides [40,43]. In the present study, the small amount of metallic chromium detected by XPS (Fig. 5) at the surface of the lms can also

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Fig. 6. XPS spectra of black Cr lm obtained from potentiostatic deposition at 1.5 V for 1800 s.

indicate the presence of a Cr concentration gradient throughout the thickness of the lm. Chromium lms obtained from choline chloridebased solutions containing LiCl [27] are also black in color but they seem to consist only of metallic chromium. The structure of the lms could not be fully characterized. Neither SEM (Fig. 3) nor TEM (Fig. 7) analysis allowed observing metallic chromium and chromium oxide/hydroxide particles. The microstructure of black chromium coatings electrodeposited from aqueous Cr (VI) solutions is quite complex and has been the subject of several studies. Inal et al. [40] observed that the lms consisted of crystals of Cr and Cr2O3 and of Cr aggregates engulfed in Cr2O3 while Mabon et al. [41] studied the black chromium lms by TEM concluding that Cr is

Fig. 7. Diffractograms of black Cr lms deposited on copper substrates by potentiostatic deposition at 1.5 V for 900 s (a) and 1800 s (b).

Fig. 8. (a) TEM image of a coating electrodeposited at 85 C, with an applied potential of 1.5 V for 1800 s. (b) Selected area electron diffraction pattern.

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Fig. 9. Optical properties of the black Cr lm deposited on copper substrates by potentiostatic deposition at 1.5 V for 1800 s.

encapsulated in an amorphous Cr2O3 matrix. Sweet et al. [38] used effective medium theory models for the dielectric function of a composite system of Cr metal, Cr2O3 and void volume and concluded that the best overall agreement between theory and experiments was the MaxwellGarnett dielectric function for Cr spheres surrounded by Cr2O3 distributed in an air matrix. In black chromium lms obtained from [BMIm][BF4]Cr(III) solutions no crystalline chromium phases were detected by XRD, which indicates that the microstructure of the lms can be different. 5. Conclusions Black chromium electrodeposition from a [BMIm][BF4]Cr(III) solution is reported. The electrodeposition of black chromium occurs in two steps involving Cr(III) and Cr(II) electroactive species. The lms are amorphous, present a nodular nanostructured morphology and are formed of chromium oxide, chromium hydroxide and metallic chromium. The black chromium lms are also found to be spectrally selective. Acknowledgements This work was nancially supported by the European Community under the project IOLISURF (STRP-517002) and Fundao para a Cincia e Tecnologia (FCT) under the project PTDC/CTM/68847/2006. Snia Eugnio acknowledges a PhD grant from FCT.