Rutile Thin Films Research Articles

Growth of water-insoluble rutile GeO2 thin films on (001) TiO2 substrates with graded Ge x Sn1−x O2 buffer layers

Rutile GeO2 (r-GeO2) is an ultrawide bandgap semiconductor with the potential for ambipolar doping and bulk single-crystal growth. In this study, we investigated r-GeO2 thin films grown on (001) TiO2 substrates with graded Ge x Sn1−x O2 buffer layers. GeO2 grown on bare TiO2 substrates via mist chemical vapor deposition exhibited water-soluble amorphous and/or α-quartz phases alongside the rutile phase. In contrast, the insertion of graded Ge x Sn1−x O2 buffer layers on the TiO2 substrate allowed the growth of single-phase water-insoluble r-GeO2 thin films. This study contributes to the development of water-insoluble r-GeO2 thin films for various applications.

Corrosion mechanisms of TiO2 photoelectrode coatings in alkaline conditions

The crystal structure of TiO2 has a significant impact on the chemical stability of the protective TiO2 thin films used in photoelectrochemical conditions. By altering the deposition temperature of atomic layer deposition method, and by post-deposition annealing treatments, amorphous, microcrystalline anatase, and Ti3+-rich nanocrystalline rutile structures can be achieved. In this paper, the chemical stability in alkaline solution and failure mechanisms of ALD grown TiO2 thin films on Si(100) were studied by SEM, XPS, EIS, and ellipsometry. The results showed that the electrically conductive Ti3+-rich nanocrystalline rutile thin film was chemically stable, whereas other samples failed within the first 10 h of the test in 1.0 M NaOH. More detailed analysis in 0.1 M NaOH revealed that the anatase sample experienced sudden failure after NaOH solution penetrated the TiO2 via grain boundaries, causing the Si substrate to dissolve. In contrast, the amorphous TiO2 films had more gradual failure as the NaOH solution permeated the TiO2 film, causing it to swell up to three times the initial thickness of the film.

Enhancement of electrochromic efficiency of TiO2 nanorods

In this study, the rutile TiO2 nanorods thin films were deposited via hydrothermal method on fluorine-doped tin oxide (FTO) substrate. To form a porous morphology layer, a thin film of amorphous titanium oxide (TiOx) was deposited on the TiO2 nanorods through sputtering at high pressure. The samples were annelid at 450ᵒC to transform the amorphous surface to anatase phase. Structural, optical, morphology and electrochemical properties of the samples were examined via X-ray diffraction (XRD), Raman scattering, UV–Vis NIR and photoluminescence (PL) spectroscopies, field-emission scanning electron microscopy (FE-SEM) and Potentiostat device respectively. The samples exhibited a large optical bandgap of 3.35–3.40 eV and high transparency of over 77 % at a wavelength of 555 nm. Raman analysis confirmed the formation of anatase phase on the rutile nanorods under thermal treatment. PL analysis indicated that the oxygen vacancies reached their maximum after sputtering, while the intensity of PL emission significantly increased after annealing. Investigation of the electrochromic properties revealed an increase in coloration efficiency from 2.6 C−1cm2 for bare nanorods to 10.0 C−1cm2 for nanorods after sputtering deposition, which decreased to 5.4 C−1cm2 after thermal treatment.

Facet-Dependent Selectivity of Rutile IrO2 for Oxygen and Chlorine Evolution Reactions

Water electrolysis is a promising route for sustainable production of hydrogen as an energy storage medium and valuable precursor for industrial chemical syntheses such as ammonia and methanol. Direct electrolysis of seawater circumvents costly desalination and purification steps to reduce the price of renewable hydrogen to achieve cost parity with carbon-intensive steam reforming. However, the significant concentration of chloride salts in seawater poses a challenge to selectivity of seawater electrolysis. In aqueous chloride electrolytes, the chlorine evolution reaction (CER) is kinetically favored over the oxygen evolution reaction (OER). Rutile-type iridium dioxide (IrO2) is a state-of-the-art electrocatalyst for water electrolysis but is also a benchmark chlorine evolution electrocatalyst in the industrial chlor-alkali process. Understanding OER/CER selectivity is needed to make seawater electrolysis a viable energy conversion technology in the future.In this work, we seek to understand the relationship between crystallographic facet and competitive reaction pathway between OER and CER on epitaxial, rutile IrO2 thin films. We investigate facet-dependent OER and CER activity on a series of single-crystalline IrO2 thin films using a rotating disk electrode geometry. The OER/CER selectivity, reaction rate order, and reaction intermediate electroadsorption affinities are explored to add fundamental insight into the reactivity of rutile IrO2 surface. To gain further insight into OER intermediate adsorption affinities, we paired electrochemical measurements with surface-sensitive ambient pressure x-ray photoelectron spectroscopy (AP-XPS). Moving forward, our facet-dependent study of OER/CER selectivity of rutile IrO2 can be used to design selective seawater electrocatalysts for cost-effective and sustainable hydrogen production.

Rutile, anatase, brookite and titania thin film from Hubbard corrected and hybrid DFT

As a benchmark, the structural, electronic and optical properties of the three main phases of TiO2 crystals have been calculated using Hubbard U correction and hybrid functional methods in density-functional theory. These calculations are compared concerning the available experimental observations on pristine TiO2 crystals. Modified hybrid functionals, particularly the PBE0 functional with 11.4% fraction of exact exchange, are shown to provide highly accurate atomic structures and also accurate electronic structure data, including optical excitation energies. With DFT + U, accurate optical spectra are also possible, but only if the Hubbard U is applied on the O 2p electrons exclusively. Furthermore, both methods, the 11.4%-PBE0 hybrid functional and the DFT + U p scheme have been used to study TiO2 amorphous ultra-thin films, confirming the agreement of the two methods even with respect to small details of the optical spectra. Our results show that the proposed DFT + U p methodology is computationally efficient, but still accurate. It can be applied to well-ordered TiO2 polymorphs as well as to amorphous TiO2 and will allow for the calculations of complex titania-based structures.

Orbital polarization change and magnetic enhancement in rutile MnO2-δ epitaxial films

Effectively manipulating the orbital configuration is an emerging method to design quantum functional materials with novel electronic ground states. Here, we report the realization of orbital polarization change in rutile MnO2-δ epitaxial thin films by reductive treatments such as CaH2 coating annealing and hydrogen atmosphere annealing. These treated samples show significant lattice expansion due to the generation of oxygen vacancies and incorporation of H, and the mixed valence states of Mn2+ and Mn3+ are formed with the decrease in the Mn valence state. The X-ray linear dichroism results show that the electron occupied state of Mn in the treated film samples changes from 3d3z2-r2 to 3dx2-y2, which means that the deprivation of oxygen atoms in the oxygen octahedron of MnO6 causes a change of orbital polarization. The resulting high spin state in the treated MnO2-δ films greatly enhances the magnetic properties of the films. This work not only demonstrates how the oxygen atoms in the edge-shared oxygen octahedron of rutile structures are replaced by reduction but also extends the study of orbital polarization and magnetic ground state control in oxide epitaxial films.

Deep Ultraviolet Transparent Electrode: Ta-Doped Rutile Sn1–xGexO2

Transparent conductive oxides (TCOs) are key materials for highly efficient optoelectronic devices such as light-emitting diodes (LEDs) and photovoltaic cells. While high-performance TCOs have been developed for use in the visible light spectrum, few materials are identified as TCOs feasible for deep ultraviolet (DUV) devices, especially at wavelengths shorter than 280 nm (UV-C region). Herein, we demonstrate that an alloy of rutile SnO2 and isostructural GeO2, rutile Sn1–xGexO2 (SGO), is a promising host semiconductor for a DUV-TCO. The optical band gap for (001)-oriented rutile SGO epitaxial thin films grown on Al2O3 (10–10) substrates increases monotonically from 3.79 eV (x = 0) to 4.09 eV (x = ∼0.7) with increasing GeO2 content. The rutile SGO thin films with a low Ge content (x ≤ 0.36) exhibit a low electrical resistivity of 2–3 × 10–4 Ω cm on doping with Ta5+ as a donor impurity. The increase in carrier electrons simultaneously enhances the DUV transparency of the films owing to the Burstein–Moss effect, resulting in an optical band gap of ∼4.2 eV for the film with x = ∼0.30. Notably, Ta-doped rutile SGO thin films can also be grown on AlN substrates, and their performance as DUV-TCOs is superior to that of conventional TCOs and competitive with state-of-the-art DUV-TCOs. These results indicate that Ta-doped rutile SGO thin films are promising candidates for transparent electrodes on III–V nitride semiconductor-based DUV-LEDs.

Radiation effects on He+- and H+-implantation for ion slicing of rutile titanium dioxide thin film

The thin film exfoliation mechanisms of He+- and H+- implanted rutile-phase titanium dioxide (r-TiO2), as well as the surface morphology and lattice damage in the implanted r-TiO2 samples, are investigated and compared. Layer splitting in the He+-implanted r-TiO2 samples after annealing at 350 °C was observed. Due to the formation of He bubbles accumulated by nano-defects during annealing, the peak damage ratio in the damage layer is enhanced. The microcracks induced by He+-implantation found in the damage layer correspond two types of defects, which were analyzed. In contrast, H+-implantation in the r-TiO2 samples induced only little lattice damage, and with low annealing temperature the damage is almost fully removed, suggesting thermal activity of the implanted H+-ions in the r-TiO2.

Germanium dioxide: A new rutile substrate for epitaxial film growth

Rutile compounds have exotic functional properties that can be applied for various electronic applications; however, the limited availability of epitaxial substrates has restricted the study of rutile thin films to a limited range of lattice parameters. Here, rutile GeO2 is demonstrated as a new rutile substrate with lattice parameters of a=4.398Å and c=2.863Å. Rutile GeO2 single crystals up to 4 mm in size are grown by the flux method. X-ray diffraction reveals high crystallinity with a rocking curve having a full width half-maximum of 0.0572°. After mechanical polishing, a surface roughness of less than 0.1 nm was obtained, and reflection high-energy electron diffraction shows a crystalline surface. Finally, epitaxial growth of (110)-oriented TiO2 thin films on GeO2 substrates was demonstrated using molecular beam epitaxy. Templated by rutile GeO2 substrates, our findings open the possibility of stabilizing new rutile thin films and strain states for the tuning of physical properties.

Low-Temperature Route to Direct Amorphous to Rutile Crystallization of TiO2 Thin Films Grown by Atomic Layer Deposition

The physicochemical properties of titanium dioxide (TiO2) depend strongly on the crystal structure. Compared to anatase, rutile TiO2 has a smaller bandgap, a higher dielectric constant, and a higher refractive index, which are desired properties for TiO2 thin films in many photonic applications. Unfortunately, the fabrication of rutile thin films usually requires temperatures that are too high (>400 °C, often even 600–800 °C) for applications involving, e.g., temperature-sensitive substrate materials. Here, we demonstrate atomic layer deposition (ALD)-based fabrication of anatase and rutile TiO2 thin films mediated by precursor traces and oxide defects, which are controlled by the ALD growth temperature when using tetrakis(dimethylamido)titanium(IV) (TDMAT) and water as precursors. Nitrogen traces within amorphous titania grown at 100 °C inhibit the crystal nucleation until 375 °C and stabilize the anatase phase. In contrast, a higher growth temperature (200 °C) leads to a low nitrogen concentration, a high degree of oxide defects, and high mass density facilitating direct amorphous to rutile crystal nucleation at an exceptionally low post deposition annealing (PDA) temperature of 250 °C. The mixed-phase (rutile–brookite) TiO2 thin film with rutile as the primary phase forms upon the PDA at 250–500 °C that allows utilization in broad range of TiO2 thin film applications.

Perturbed Angular Correlation Technique at ISOLDE/CERN Applied for Studies of Hydrogenated Titanium Dioxide (TiO2): Observation of Cd-H Pairs

Profound understanding of the local electronic and defect structure in semiconductors always plays a vital role in the further developing of applications of such materials. In the present work an investigation of the electronic structure in hydrogenated TiO2 (rutile) thin films is conducted by virtue of Time-Differential γ-γ Perturbed Angular Correlation spectroscopy (TDPAC or PAC) with 111mCd/Cd isotope, produced and implanted at ISOLDE/CERN. The measurements were performed at 581 K as a function of the temperature of the samples during hydrogenation. Despite the fact, that rutile single crystals usually show the presence of two local environments, when are studies with Cd/In isotopes, the current pristine thin films sample had a single electric field gradient. Upon various degrees of hydrogenation, Cd probe atoms showed underwent alterations, resulting in up to 3 different local surroundings, generally with high electric field gradients. Broad EFG distributions are likely due to randomly distributed point defects in the neighbourhood of Cd acceptors. Observed results suggest that hydrogenations performed at RT and 423 K are not able to promote unique defect configurations, while in the range of 473-573 K the formation of such configurations is observed. Therefore, one may assume that the formation of Cd-defect complexes (Cd-H pairs) is temperature enhanced. At higher levels of hydrogenation (663 K), the samples become partly amorphous that further hinders any atomistic studies with strong damped PAC spectra. Cd-H complexes seem to be stable up to annealing up to 581 K annealing. The obtained results give a deep insight into complex hydrogen defects, their interactions and bond formations with Cd acceptor.

Comparison of the sputtered TiO2 anatase and rutile thin films as electron transporting layers in perovskite solar cells

AbstractWe examine comparatively the performance of sputtered TiO2 rutile and anatase thin films as an electron transport layer (ETL) in MAPbI3‐based perovskite solar cells. Both anatase and rutile TiO2 ETLs are deposited (on fluorine‐doped tin oxide [FTO] substrates) by magnetron sputtering in the form of nanocrystalline thin films. We systematically investigate the role of crystallographic phase composition of TiO2 ETLs on the photovoltaic performance of perovskite solar cells. The champion power conversion efficiencies (PCEs) of 18.4% and 17.7% under reverse scan mode are obtained for perovskite solar cells based on TiO2 anatase and TiO2 rutile ETL, respectively. The results show that the magnetron sputtering deposited ETLs differ from each other only in their phase composition while the overall performance of the devices is not greatly affected by the crystallographic phase of the TiO2 ETLs. Our results point to an important fact that for a proper and reliable comparison between the performance of TiO2 anatase and rutile ETLs, it is crucial to investigate films of similar morphology and structure that are synthesize under similar conditions.

Establishment of a growth route of crystallized rutile GeO2 thin film (≧1 μm/h) and its structural properties

Recently, rutile germanium dioxide (r-GeO2) has emerged as a novel ultra-wide bandgap semiconductor due to its theoretical excellent properties, that is, high thermal conductivity, ambipolar dopability, and high carrier mobility, in addition to its wide bandgap (4.44–4.68 eV). In this study, r-GeO2 thin films were grown on (001) r-TiO2 substrates by mist chemical vapor deposition. To optimize the growth conditions, we analyzed the decomposition processes of the Ge source (C6H10Ge2O7) by thermogravimetry-differential thermal analysis. It is found that GeO2 was synthesized from C6H10Ge2O7 at 553–783 °C in aqueous vapor. We accomplished fabrication of (001)-oriented r-GeO2 on r-TiO2 with a growth rate of 1.2–1.7 μm/h. On the other hand, under lower growth rate conditions (50 nm/h), the full width at half maximum of the r-GeO2 002 peak remarked a relatively small value of 560 arc sec. In addition, clear diffraction spots of r-GeO2 and r-TiO2 were observed at the r-GeO2/r-TiO2 interface, and the film was found to be significantly strained along the in-plane direction (∼2.3%) by cross-sectional transmission electron microscopy. The growth rate of ≧1 μm/h must contribute to the fabrication of thick r-GeO2 films, which can be utilized as power electronics devices with high breakdown voltage.

Reduced extrinsic recombination process in anatase and rutile TiO2 epitaxial thin films for efficient electron transport layers

TiO2 is the most widely used material for the electron transport layers (ETLs) because it is characterized by proper band alignment with light absorbers, adequate optical transmittance, and high electron mobility. There are two thermodynamically stable crystal phases of TiO2: anatase and rutile. However, understanding which phase is more effective as the ETL is still required. In this paper, we demonstrate the different effects of using epitaxial anatase TiO2 and epitaxial rutile TiO2 (both grown using pulsed laser deposition) as the ETL material on the electrical and optical properties. Epitaxial Nb-doped TiO2 layers were used as the common electrode material for the both epitaxial ETLs for which the crystalline structural analysis revealed high crystalline qualities and good coherency for both phases. By analyzing the recombination kinetics, the anatase phase shows a preferable performance in comparison with the rutile phase, although both epitaxial phases show remarkably reduced extrinsic recombination properties, such as trap-assisted recombination. This study demonstrates not only a better electron transporting performance of anatase phase but also reduced extrinsic recombination through epitaxy growth.

Influence of the Quality of SnO2 Electron Transport Layer on the Stability of FA1-XCsxpb(I1-yBry)3 perovskite Layer

Organic-inorganic lead halide perovskites have attracted great attention as light absorbers of hybrid perovskite solar cells (PSCs). Among the organic-inorganic hybrid perovskites (OIHP), CH3NH3PbI3 (MAPbI3) and CH(NH2)2PbI3 (FAPbI3) have been extensively studied as light absorbers of PSCs. PSCs are expected to be next-generation solar cells due to their high conversion efficiency and low fabrication cost. However, power conversion efficiency of PSCs declines shortly after being fabricated, because of degradation of hybrid perovskite layers. OIHP such as FAPbI3 decomposes easily into PbI2 and transforms to d-phase from a-phase, which is suitable for the application to the solar cells, under ambient condition [1]. It was reported that partial substitution of inorganic monovalent ions such as Cs and Rb ions at FA site is effective to improve the phase stability of a-phase [2]. This can be easily explained by the Goldschmidt tolerance factor [3], which is an indicator for the stability of perovskite structure. Ionic radius of FA is too large, but the partial substitution of Cs or Rb can make the average ionic radius smaller than that of FA, which stabilizes the a-phase. For example, d-phase is the stable phase in FAPbI3 at ambient condition, which transforms to a-phase above 165 ℃ [4]. However, the partially substituted FAxCsyPbI3 is stable even at room temperature. The perovskite layers are grown on electron transport layers (ETL) such as TiO2, SnO2, and ZnO by spin-coating method. Although TiO2 has been widely used for ETL of PSCs, SnO2 has been also applied to ETL because of its excellent band energy level alignment with that of the perovskite layers and its higher electron mobility [5]. In addition, devices using SnO2 as ETL decrease their photoconversion efficiency more slowly than using TiO2 under ambient condition, which suggests that decomposition processes of the perovskites on TiO2 and SnO2 is different [6]. In the fabrication process of ETL, SnO2 is annealed after spin-coating. If the annealing temperature is high above 450 degrees Celsius, rutile structured crystalline SnO2 thin film grows, while only amorphous structured SnO2 thin film appear by the low temperature annealing, such as between 150 and 200 degrees Celsius. Some studies have shown that amorphous SnO2 fabricated by low temperature process increases performances of devices compared with crystalline SnO2 [7, 8].In this study, FA1-xCsxPb(I1-yBry)3 was synthesized by spin-coating method on the SnO2 layers and annealed at various temperature to evaluate the dependence of SnO2 substrate structure on the stability of perovskite layers. Stability of all the samples here synthesized were monitored with the X-ray diffraction technique at 0, 1, 2, 3, 4, 24, 96 and 168 hours kept in air after fabrications. Fig.1 shows the intensity of diffraction peaks of d-FAPbI3 (100) as a function of time. Although the intensity of d-FAPbI3 peaks increased in FA0.85Cs0.15PbI3 and FA0.85Cs0.15Pb(I0.85Br0.15)3 formed on SnO2 annealed at 450 ℃ , it unchanged in FA0.85Cs0.15PbI3 and FA0.85Cs0.15Pb(I0.85Br0.15)3 on SnO2 annealed at 180 degree Celsius. These results sugessts that the stability of a-FAPbI3 grown on SnO2 annealed at 180 degree Celsius is better than that annealed at 450 degree Celsius. The crystal structures of SnO2 annealed at 200, 300 and 400 degree Celsius were characterized with the Glazing Incident X-ray diffraction technique. The surface morphology of SnO2 were obsereved with the scannning electron microscope, which suggest SnO2 surface became rougher as annealing temperature increased. The chemical composition of the surface of SnO2 layers were investigated by Auger electron spectroscopy, from which Cl peaks were obsererved in SnO2 annealed at 200 ℃ and 300 ℃, while Cl were not detected in SnO2 annealed at 400 degree Celsius.[1] T. Leijtens et al., J. Mater. Chem. A.5, 11483-11500 (2017)[2] M. Saliba et al., Science 354, 206-209 (2016)[3] C. C. Stoumpos et al., Acc. Chem. Res. 48, 2791-2802 (2015)[4] Z. Li et al., Chem. Mater. 28, 284-292 (2016)[5] L. B. Xiong et al., J. Mater. Chem. A.4, 8374-8383 (2016)[6] Q. Dong et al., Nano Energy 40, 336-344 (2017)[7] W. J. Ke et al., J. Mater. Chem. A.3, 24163-24168 (2015)[8] K.-H Jung et al., J. Mater. Chem. A.5, 24790-24803 (2017) Figure 1

Interfacial Titanium Diffusion Self-Adapting Layer in Ultrathin Epitaxial MnO2/TiO2 Heterostructures

The electrochemical performance of supercapacitors is suppressed by a large number of defects in the interface of heterostructure due to lattice mismatch. In this paper, the (001) oriented rutile MnO2 thin films with different thicknesses were grown on rutile TiO2 substrates. The lattice mismatch between film and substrate was minimized through a Ti diffusion self-adapting layer. The energy-dispersive spectroscopy mappings were used to measure the diffusion range of Ti. The results of high-resolution X-ray diffraction confirmed that the dependence of the out-of-plane lattice parameter on the thickness was consistent with the self-adapting interface model, indicating that Ti diffusion can indeed alleviate the lattice mismatch. In addition, the results of the synchrotron soft X-ray absorption spectrum indicated that the capacitance of the thin films with a large proportion of Ti diffusion increased with electrons involved in the reaction. Although the decrease of carrier density and conductivity of the thinner films depressed the electrochemical activity, it is worth mentioning that the film we designed still has considerable specific capacitance even when it is very thin, which can provide a new idea for the development of thinner and larger capacity potential micro-supercapacitors.

Strain-induced structural transition of rutile type ReO2 epitaxial thin films

Rutile-related (tetragonal rutile and monoclinic distorted rutile) ReO2 epitaxial thin films were grown on rutile TiO2 single crystalline substrates by reactive pulsed laser deposition of the Re metal target under a N2O atmosphere. The ReO2 film underwent structural phase transition from the monoclinic to tetragonal phase with the decreasing film thickness, driven by compressive lattice strain from the substrate. X-ray photoelectron spectroscopy and electrical transport measurements revealed that both phases had metallic properties above 25 K. The distinct difference in valence band spectra between the two phases might be due to reconstruction of the band structure dominated by Re 5d t2g.

Epitaxial stabilization of rutile germanium oxide thin film by molecular beam epitaxy

Ultrawide bandgap (UWBG) semiconductors (Eg >3 eV) have tremendous potential for power-electronic applications. The current state-of-the-art UWBG materials such as β-Ga2O3, diamond, and AlN/AlGaN, however, show fundamental doping and thermal conductivity limitations that complicate technological adaption and motivate the search for alternative materials with superior properties. Rutile GeO2 (r-GeO2) has been theoretically established to have an ultrawide bandgap (4.64 eV), high electron mobility, high thermal conductivity (51 W m−1 K−1), and ambipolar dopability. While single-crystal r-GeO2 has been synthesized in bulk, the synthesis of r-GeO2 thin films has not been previously reported but is critical to enable microelectronics applications. Here, we report the growth of single-crystalline r-GeO2 thin films on commercially available R-plane sapphire substrates using molecular beam epitaxy. Due to a deeply metastable glass phase and high vapor pressure of GeO, the growth reaction involves the competition between absorption and desorption as well as rutile and amorphous formation. We control the competing reactions and stabilize the rutile-phase growth by utilizing (1) a buffer layer with reduced lattice misfit to reduce epitaxial strain and (2) the growth condition that allows the condensation of the preoxidized molecular precursor yet provides sufficient adatom mobility. The findings advance the synthesis of single-crystalline films of materials prone to glass formation and provide opportunities to realize promising ultra-wide-bandgap semiconductors.

Effect of photonic processing of rutile thin films with cadmium sulfide quantum dots on the formation of conditions for the separation of nonequilibrium charge carriers

Effect of photonic processing of rutile thin films with cadmium sulfide quantum dots on the formation of conditions for the separation of nonequilibrium charge carriers

CZTS counter electrode in dye-sensitized solar cell: enhancement in photo conversion efficiency with morphology of TiO2 nanostructured thin films

In the present investigation, kesterite phase Cu2ZnSnS4 (CZTS) nanoparticle, and one-dimensional (1D) nanorods and three-dimensional (3D) flower-like rutile phase TiO2 thin films were obtained by the conventional hydrothermal method. The (112) plane–oriented single-phase CZTS nanoparticles with chemical composition Cu/(Zn + Sn) = 0.84, 0.90, 1.05 were obtained by changing the copper concentration of the precursor solution. The CZTS thin films were prepared on fluorine-doped tin oxide (FTO) substrate by the doctor blade coating method. The effect of reaction time on growth of the hydrothermal deposited rutile phase TiO2 nanorod thin films were investigated. The detailed structural properties, phase identification, and morphological developments were investigated using X-ray diffraction (XRD), Raman spectroscopy, high-resolution transmission electron microscopy (HRTEM), and scanning electron microscopy (SEM) techniques. The dye-sensitized solar cells were fabricated with CZTS counter electrodes (CEs) and hydrothermal deposited nanostructured TiO2 photoanodes. The device formed with three-dimensional TiO2 nanostructured photoanode showed higher efficiency (2.65%) than one-dimensional microstructures (1.74%). The study demonstrates that the nanostructure-based morphologies of TiO2 photoanodes affect the performance of CZTS CEs–based dye-sensitized solar cell.