Hydrogen and nitrogen codoping of anatase TiO2 for efficiency enhancement in organic solar cells.
ABSTRACT: TiO2 has high chemical stability, strong catalytic activity and is an electron transport material in organic solar cells. However, the presence of trap states near the band edges of TiO2 arising from defects at grain boundaries significantly affects the efficiency of organic solar cells. To become an efficient electron transport material for organic photovoltaics and related devices, such as perovskite solar cells and photocatalytic devices, it is important to tailor its band edges via doping. Nitrogen p-type doping has attracted considerable attention in enhancing the photocatalytic efficiency of TiO2 under visible light irradiation while hydrogen n-type doping increases its electron conductivity. DFT calculations in TiO2 provide evidence that nitrogen and hydrogen can be incorporated in interstitial sites and possibly form NiHi, NiHO and NTiHi defects. The experimental results indicate that NiHi defects are most likely formed and these defects do not introduce deep level states. Furthermore, we show that the efficiency of P3HT:IC60BA-based organic photovoltaic devices is enhanced when using hydrogen-doping and nitrogen/hydrogen codoping of TiO2, both boosting the material n-type conductivity, with maximum power conversion efficiency reaching values of 6.51% and 6.58%, respectively, which are much higher than those of the cells with the as-deposited (4.87%) and nitrogen-doped TiO2 (4.46%).
Project description:The two important factors that affect sunlight assisted water splitting ability of TiO2 are its charge recombination and large band gap. We report the first demonstration of nitrogen doped triphase (anatase-rutile-brookite) TiO2 nanotubes as sun light active photocatalyst for water splitting with high quantum efficiency. Nitrogen doped triphase TiO2 nanotubes, corresponding to different nitrogen concentrations, are synthesized electrochemically. Increase in nitrogen concentration in triphase TiO2 nanotubes is found to induce brookite to anatase phase transformation. The variation in density of intra-band states (Ti3+ and N 2p states) with increase in nitrogen doping are found to be critical in tuning the photocatalytic activity of TiO2 nanotubes. The presence of bulk heterojunctions in single nanotube of different nitrogen doped TiO2 samples is confirmed from HRTEM analysis. The most active nitrogen doped triphase TiO2 nanotubes are found to be 12 times efficient compared to pristine triphase TiO2, for solar hydrogen generation. The band alignment and charge transfer pathways in nitrogen doped TiO2 with triphase heterojunctions are delineated. Bulk heterojunctions among the three phases present in the nanotubes with intra-band defect states is shown to enhance the photocatalytic activity tremendously. Our study also confirms the theory that three phase system is efficient in photocatalysis compared to two phase system.
Project description:BACKGROUND PURPOSE: Photocatalytic water splitting for hydrogen evolution is a potential way to solve many energy and environmental issues. Developing visible-light-active photocatalysts to efficiently utilize sunlight and finding proper ways to improve photocatalytic activity for H2 evolution have always been hot topics for research. This study attempts to expand the use of sunlight and to enhance the photocatalytic activity of TiO2 by N doping and Au loading. METHODS: Au/N-doped TiO2 photocatalysts were synthesized and successfully used for photocatalytic water splitting for H2 evolution under irradiation of UV and UV-vis light, respectively. The samples were characterized using X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), UV-vis diffuse reflectance spectroscopy (DRS), photoluminescence spectroscopy (PL), and photoelectrochemical characterizations. RESULTS: DRS displayed an extension of light absorption into the visible region by doping of N and depositing with Au, respectively. PL analysis indicated electron-hole recombination due to N doping and an efficient inhibition of electron-hole recombination due to the loaded Au particles. Under the irradiation of UV light, the photocatalytic hydrogen production rate of the as-synthesized samples followed the order Au/TiO2 > Au/N-doped TiO2 > TiO2 > N-doped TiO2. While under irradiation of UV-vis light, the N-TiO2 and Au/N-TiO2 samples show higher H2 evolution than their corresponding nitrogen-free samples (TiO2 and Au/TiO2). This inconsistent result could be attributed to the doping of N and the surface plasmonic resonance (SPR) effect of Au particles extending the visible light absorption. The photoelectrochemical characterizations further indicated the enhancement of the visible light response of Au/N-doped TiO2. CONCLUSION: Comparative studies have shown that a combination of nitrogen doping and Au loading enhanced the visible light response of TiO2 and increased the utilization of solar energy, greatly boosting the photocatalytic activity for hydrogen production under UV-vis light.
Project description:Formation of planar heterojunction perovskite solar cells exhibiting both high efficiency and stability under continuous operation remains a challenge. Here, we show this can be achieved by using a defective TiO2 thin film as the electron transport layer. TiO2 layers with native defects are deposited by electron beam evaporation in an oxygen-deficient environment. Deep-level hole traps are introduced in the TiO2 layers and contribute to a high photoconductive gain and reduced photocatalytic activity. The high photoconductivity of the TiO2 electron transport layer leads to improved efficiency for the fabricated planar devices. A maximum power conversion efficiency of 19.0% and an average PCE of 17.5% are achieved. In addition, the reduced photocatalytic activity of the TiO2 layer leads to enhanced long-term stability for the planar devices. Under continuous operation near the maximum power point, an efficiency of over 15.4% is demonstrated for 100?h.
Project description:In this work, C-doped TiO2 nanorods were synthesized through doping carbon black into hydrothermally synthesized solid-state TiO2 nanowires (NWs) via calcination. The effects of carbon content on the morphology, phase structure, crystal structure, and photocatalytic property under both UV and solar light by the degradation of methylene blue (MB) were explored. Besides, the photoelectrochemical property of C-TiO2 was systematically studied to illustrate the solar light degradation mechanism. After doping with C, TiO2 NWs were reduced into nanorods and the surface became rough with dispersed particles. Results showed that C has successfully entered the TiO2 lattice, resulting in the lattice distortion, reduction of band gap, and the formation of C-Ti-O, which expands TiO2 to solar light activation. Comparing with P25 and anatase TiO2 NWs, doping with carbon black showed much higher UV light and solar light photocatalytic activity. The photocatalytic activity was characterized via the degradation of MB, showing that K ap was 0.0328 min-1 under solar light, while 0.1634 min-1 under UV irradiation. The main free radicals involved in methylene blue degradation are H+ and OH•-. Doping with carbon black led to the reduction of photocurrent in a long-term operation, while C-doping reduced the electron-hole recombination and enhanced the carrier migration.
Project description:Herein, we report the cooperative effect of Zr doping and vacuum annealing on the carrier dynamics and interfacial kinetics of anodized TiO2 nanotubes for light-driven water oxidation. After evaluation of different Zr loads and different annealing conditions, it was found that both Zr doping and vacuum annealing lead to a significantly enhanced light harvesting efficiency and photoelectrochemical performance. The substitution of Zr4+ by Ti4+ species leads to a higher density of surface defects such as oxygen vacancies, facilitating electron trapping on Zr4+, which reduced the charge recombination and hence boosted the charge transfer kinetics. More importantly, vacuum annealing promoted the presence of surface defects. Furthermore, the mechanistic study through impedance spectroscopy revealed that both charge transfer and surface conductivity are significantly enhanced due the presence of an oxygen-deficient TiO2 surface. These results represent an important step forward in the optimization of nanostructured TiO2-based photoelectrodes, with high potential in photocatalytic applications, including solar fuel production.
Project description:Ti(3+) species are highly unstable in air owing to their facile oxidation into Ti(4+) species, and thus they cannot concentrate in the surface layer of TiO2 but are mainly present in its bulk. We report generation of abundant and stable Ti(3+) species in the surface layer of TiO2 by boron doping for efficient utilization of solar irradiation. The resultant photocatalysts (denoted as B-TiO2-x) exhibit extremely high and stable solar-driven photocatalytic activity toward hydrogen production. The origin of the solar-light activity enhancement in the B-TiO2-x photocatalysts has been thoroughly investigated by various experimental techniques and density functional theory (DFT) calculations. The unique structure invoked by presence of sufficient interstitial boron atoms can lead to substantial variations in density of states of B-TiO2-x, which not only significantly narrow the band gap of TiO2 to improve its visible-light absorption, but also promote the photogenerated electron mobility to enhance its solar-light photocatalytic activity.
Project description:Nitrogen doped TiO2 (N-TiO2) nanoparticles were synthesized via a novel plasma enhanced electrolysis method using bulk titanium (Ti) as a source material and nitric acid as the nitrogen dopant. This method possesses remarkable merits with regard to the direct-metal synthesis of nanoparticles with its one-step process, eco-friendliness, and its ability to be mass produced. The nanoparticles were synthesized from bulk Ti metal and dipped in 5-15 mmol of a nitric acid electrolyte under the application of AC 500 V, the minimum range of voltage to generate plasma. By controlling the electrolyte concentration, the nanoparticle size distribution could be tuned between 12.1 and 24.7 nm using repulsion forces via variations in pH. The prepared N-TiO2 nanoparticles were calcined at between 100 and 300°C to determine their photocatalytic efficiency within the visible-light region, which depended on their crystal structure and N doping content. Analysis showed that the temperature treatment yielded an anatase TiO2 crystalline structure when the N doping content was varied from 0.4 to 0.54 at.%. In particular, the 0.4 at.% N doped TiO2 catalyst exhibited the highest catalytic performance with quadruple efficiency compared to the P-25 standard TiO2 nanoparticles, which featured a 91% degradation of methyl orange organic dye within 300 min. This solid-liquid reaction based on plasma enhanced electrolysis could open new pathways with regard to high purity mass producible ceramic nanoparticles with advanced properties.
Project description:Intensive studies on low-temperature deposited electron transport materials have been performed to improve the efficiency of n-i-p type planar perovskite solar cells to extend their application on plastic and multijunction device architectures. Here, a TiO2 film with enhanced conductivity and tailored band edge is prepared by magnetron sputtering at room temperature by hydrogen doping (HTO), which accelerates the electron extraction from perovskite photoabsorber and reduces charge transfer resistance, resulting in an improved short circuit current density and fill factor. The HTO film with upward shifted Fermi level guarantees a smaller loss on VOC and facilitates the growth of high-quality absorber with much larger grains and more uniform size, leading to devices with negligible hysteresis. In comparison with the pristine TiO2 prepared without hydrogen doping, the HTO-based device exhibits a substantial performance enhancement leading to an efficiency of 19.30% and more stabilized photovoltaic performance maintaining 93% of its initial value after 300 min continuous illumination in the glove box. These properties permit the room-temperature magnetron sputtered HTO film as a promising electron transport material for flexible and tandem perovskite solar cell in the future.
Project description:The photocatalytic activities of reduced titanium dioxide (TiO2) materials have been investigated by measuring their ability to produce hydroxyl radicals under UV and visible light irradiation. Degussa P25 TiO2 was doped with nitrogen (N), fluorine (F), and/or phosphorus (P) and then subjected to surface modification employing a thermo-physicochemical process in the presence of reducing agent sodium borohydride (NaBH4). The reduced TiO2 materials were characterized by a number of X-ray, spectroscopic and imaging methods. Surface doping of TiO2 was employed to modulate the band gap energies into the visible wavelength region for better overlap with the solar spectrum. Hydroxyl radical generation, central to TiO2 photocatalytic water purification applications, was quantitated using coumarin as a trap under UV and visible light irradiation of the reduced TiO2 materials. At 350 nm irradiation, the yield of hydroxyl radicals generated by the reduced forms of TiO2 was nearly 90% of hydroxyl radicals generated by the Degussa P25 TiO2. Hydroxyl radical generation by these reduced forms of TiO2 was also observed under visible light irradiation (419 and 450 nm). These results demonstrated that simple surface modification of doped TiO2 can lead to visible light activity, which is important for more economical solar-driven applications of TiO2 photocatalysis.
Project description:Donor-? bridge-acceptor (D-?-A) organic dyes, well studied in dye-sensitized solar cells (DSSCs), are found to possess great potential in light-inducing hydrogen evolution due to their distinguished light-harvesting ability and suitable electron energy level. In this work, multicarbazole-based organic dyes (2C, 3C, 4C) were used as photosensitizers of Pt/TiO2 for photocatalytic hydrogen evolution (PHE) from water under visible light irradiation. 3C-Pt/TiO2 shows the best photocatalytic activity among the three dye-sensitized photocatalysts, with a hydrogen evolution rate of 24.7 ?mol h-1 and a turnover number of 247 h-1. The activity of 3C-Pt/TiO2 declines significantly after 3 h irradiation. The deactivation was caused by the partial degradation of the electron acceptor, cyanoacrylate moiety, during the photocatalytic process, which was evidenced by UV-vis, Fourier transform infrared spectra (FT-IR), NMR, and mass spectra. This work is expected to contribute toward the understanding of stability issues of organic dyes and the development of more efficient and steady dyes for hydrogen evolution from water splitting.