CuCrO2 nanoparticle decorated SnO2 nanofiber composites have been prepared as novel p–n heterostructured semiconductor photocatalysts for the degradation of organic pollutants in wastewater. The composite structure was achieved via drop casting of various amounts of hydrothermally derived CuCrO2 nanoparticles on electrospun SnO2 nanofibers. The microstructural and morphological features of each semiconductor and the formation of p–n heterojunctions between them were characterized. In addition, the photo-response and electrochemical properties of the samples were determined. The photocatalytic activity of the heterostructured photocatalysts was investigated systematically as a function of the amount of CuCrO2 nanoparticles in the samples. Experimental results showed that the optimal decoration amount was 0.6 wt% CuCrO2 on SnO2. This composite photocatalyst displayed a 41% higher rate constant value compared to pure SnO2 nanofibers in the degradation of methylene blue dye molecules and reached 83% degradation under UV/visible light irradiation after 1 h. The increase in the photocatalytic activity was ascribed to the incorporation of Cr3+ and Cu+ cations into the SnO2 host lattice and the more effective electron–hole pair separation in the heterostructured sample. The presented data here are highly convincing in comparison to those of UV active p–n heterostructured photocatalysts reported previously in the literature. Therefore, this work opens the way to develop visible light active p–n heterostructured semiconductor photocatalysts using p-type delafossites with n-type oxides.

UV/visible light active CuCrO2 nanoparticle–SnO2 nanofiber p–n heterostructured photocatalysts for photocatalytic applications

CuFeO2, the structure prototype of the delafossite family, has received renewed interest in recent years. Thermodynamic modeling and several experimental Cu-Fe-O system investigations did not focus specifically on the possible nonstoichiometry of this compound, which is, nevertheless, a very important optimization factor for its physicochemical properties. In this work, through a complete set of analytical and thermostructural techniques from 50 to 1100 °C, a fine reinvestigation of some specific regions of the Cu-Fe-O phase diagram under air was carried out to clarify discrepancies concerning the delafossite CuFeO2 stability region as well as the eutectic composition and temperature for the reaction L = CuFeO2 + Cu2O. Differential thermal analysis and Tammann's triangle method were used to measure the liquidus temperature at 1050 ± 2 °C with a eutectic composition at Fe/(Cu + Fe) = 0.105 mol %. The quantification of all of the present phases during heating and cooling using Rietveld refinement of the high-temperature X-ray diffraction patterns coupled with thermogravimetric and differential thermal analyses revealed the mechanism of formation of delafossite CuFeO2 from stable CuO and spinel phases at 1022 ± 2 °C and its incongruent decomposition into liquid and spinel phases at 1070 ± 2 °C. For the first time, a cationic off-stoichiometry of cuprous ferrite CuFe1- yO2-δ was unambiguous, as evidenced by two independent sets of experiments: (1) Electron probe microanalysis evidenced homogeneous micronic CuFe1- yO2-δ areas with a maximum y value of 0.12 [i.e., Fe/(Cu + Fe) = 0.47] on Cu/Fe gradient generated by diffusion from a perfect spark plasma sintering pristine interface. Micro-Raman provided structural proof of the existence of the delafossite structure in these areas. (2) Standard Cu additions from the stoichiometric compound CuFeO2 coupled with high-temperature X-ray diffraction corroborated the possibility of obtaining a pure Cu-excess delafossite phase with y = 0.12. No evidence of an Fe-rich delafossite was found, and complementary analysis under a neutral atmosphere shows narrow lattice parameter variation with an increase of Cu in the delafossite structure. The consistent new data set is summarized in an updated experimental Cu-Fe-O phase diagram. These results provide an improved understanding of the stability region and possible nonstoichiometry value of the CuFe1- yO2-δ delafossite in the Cu-Fe-O phase diagram, enabling its optimization for specific applications.

https://hal.archives-ouvertes.fr/hal-02121917/document

Insights on the Stability and Cationic Nonstoichiometry of CuFeO2 Delafossite.

The correlation between the dielectric and magnetic properties is investigated on the triangular-lattice antiferromagnets ACrO2 (A=Cu, Ag, Li, or Na) with a 120-degree spiral structure. For the A=Cu and Ag compounds with a delafossite structure, the ferroelectric polarization emerges with a spiral-spin order, implying strong coupling between ferroelectricity and the spiral-spin structure. For the A=Li and Na compounds with an ordered rock salt structure, on the other hand, no spontaneous polarization is discerned, while the clear anomaly in the dielectric constant can be observed upon the transition to the spiral-spin ordered state. This feature can be ascribed to the possible antiferroelectric state induced by the alternate stacking of the Cr-spin sheet with opposite vector spin chirality.

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Spin-driven ferroelectricity in triangular lattice antiferromagnets $A$CrO$_2$ ($A$ = Cu, Ag, Li, or Na)

In this work, we report the enhancement of the functional properties of CuCrO2, a promising p-type transparent conductive oxide, achieved in out of stoichiometry CuCrO2 thin films synthesized by aerosol-assisted chemical vapor deposition. Out of stoichiometry films consisting of Cr-deficient CuCrO2, i.e. Cu-rich CuCrO2 phase, have a resistivity value of 0.05 Ω cm and an average transmittance of 58% in the visible range, resulting in a Gordon's figure of merit of 2200 μS. This is the highest ever published figure of merit among Cu-rich CuCrO2 films synthesized by chemical methods. A remarkable result is that when further increasing the Cu/(Cu + Cr) ratio, the formation of CuO was not detected, allowing the synthesis of composite films formed by Cu2O and CuCrO2 p-type oxides, which are more conductive than the Cu-rich CuCrO2 phase. These nanocomposite films present an improved carrier mobility, with a resistivity value of around 0.02 Ω cm, and a reduced energy gap, with a transmittance of 52%, resulting in a figure of merit of 1400 μS. Both these thin films can find applications as a hole transport layer in various transparent optoelectronic devices where p-type TCOs are required, especially when synthesized by a solution-based process at a low temperature and ambient pressure over large surface areas.

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Out of stoichiometry CuCrO2 films as a promising p-type TCO for transparent electronics

Abstract Transparent conductive oxides (TCOs) constitute a class of materials that combine high electrical conductivity and optical transparency. These features led to the development of the transparent electronics applications, such as flat panel displays, “smart” windows or functional glasses. N -type TCOs dominate the applications market, and the lack of a suitable p-type counterpart limits the fabrication of a completely transparent active device, which might be considered as a technological breakthrough. Among the wide range of p-type candidates, delafossite CuCrO 2 (and its out-of-stoichiometry derivatives) is a promising material to achieve the desired p-type TCO properties as, up to date, it is presenting the foremost trade-off between optical and electrical properties. The present paper covers the research work and the major achievements related to copper chromium delafossite. A comprehensive overview of fabrication methods and opto-electronic properties is presented. The source of doping and the charge carriers transport mechanism are also thoroughly discussed. Graphical abstract 

/pdf/a-review-on-the-p-type-transparent-cu-cr-o-delafossite-2gaxovau.pdf

A review on the p-type transparent Cu–Cr–O delafossite materials

Structural, transport, and magnetoelectric (ME) properties of delafossite oxides CuCr1−xO2 with 0 ≦ x ≦ 0.10 were extensively investigated. The Rietveld refinement shows that the Cu-O bond length decreases with increasing Cr deficiency, indicative of the presence of a mixed valence state of Cu+/Cu2+ and an enhancement of the hybridization between Cu 3d and O 2p orbitals. As a result, it leads to a decrease of room-temperature resistivity by two orders of magnitude. The deduced effective moment for the Cr-deficient samples is larger than the one only taking into account the contribution from Cr3+ with S = 3/2. This demonstrates that Cu2+ is present in the Cr-deficient samples, giving rise to excess holes at the Cu site. Below TN(Cr) ∼ 24 K, the magnetocapacitance [e(H)−e(0)]/e(0) exhibits a distinct field dependence and deviates from the square of magnetization M2. These findings suggest that the ME coupling in CuCr1−xO2 with higher x is modulated by an increase of the spin fluctuations in the CrO2 triangu...

P. H. Yeh

Papers

Effect of Cr deficiency on physical properties of triangular-lattice antiferromagnets CuCr1―xO2 (0 ≦ x ≦ 0.10)