Nanostructure of photocatalytic TiO2 films sputtered at temperatures below 200 °C

The article reports on correlations between the process parameters of reactive pulsed dc magnetron sputtering, physical properties and the photocatalytic activity (PCA) of TiO₂ films sputtered at substrate surface temperature T_surf ≤ 180 °C. Films were deposited using a dual magnetron system equipped with Ti (Ø50 mm) targets in Ar + O₂ atmosphere in oxide mode of sputtering. The TiO₂ films with highly photoactive anatase phase were prepared without a post-deposition thermal annealing. The decomposition rate of the acid orange 7 (AO7) solution during the photoactivation of the TiO₂ film with UV light was used for characterization of the film PCA. It was found that (i) the partial pressure of oxygen pO₂ and the total sputtering gas pressure p_T are the key deposition parameters influencing the TiO₂ film phase composition that directly affects its PCA, (ii) the structure of sputtered TiO₂ films varies along the growth direction from the film/substrate interface to the film surface, (iii) ∼500 nm thick anatase TiO₂ films with high PCA were prepared and (iv) the structure of sputtered TiO₂ films is not affected by the substrate surface temperature T_surf when T_surf < 180 °C. The interruption of the sputtering process and deposition in long (tens of minutes) pulses alternating with cooling pauses has no effect on the structure and the PCA of TiO₂ films and results in a decrease of maximum value of T_surf necessary for the creation of nanocrystalline nc-TiO₂ film. It was demonstrated that crystalline TiO₂ films with high PCA can be sputtered at T_surf ≤ 130 °C. Based on obtained results a phase zone model of TiO₂ films was developed.     

Characterization of single-crystalline In2O3 films deposited on Y-stabilized ZrO2 (1 0 0) substrates by MOCVD

Epitaxial In₂O₃ films have been deposited on Y-stabilized ZrO₂ (YSZ) (1 0 0) substrates by metalorganic chemical vapor deposition (MOCVD). The films were deposited at different substrate temperatures (450-750 °C). The film deposited at 650 °C has the best crystalline quality, and observation of the interface area shows a clear cube-on-cube epitaxial relationship of In₂O₃(1 0 0)||YSZ(1 0 0) with In₂O₃[0 0 1]||YSZ[0 0 1]. The Hall mobility of the single-crystalline In₂O₃ film deposited at 650 °C is as high as 66.5 cm² V⁻¹ s⁻¹ with carrier concentration of 1.5 × 10¹⁹ cm⁻³ and resistivity of 6.3 × 10⁻³ Ω cm. The absolute average transmittance of the obtained films in the visible range exceeds 95%.     

High-throughput characterization of BixY3−xFe5O12 combinatorial thin films by magneto-optical imaging technique

Bi_xY_3−xFe₅O₁₂ thin films have been grown on GGG (Gd₃Ga₅O₁₂) (1 1 1) substrates by the combinatorial composition-spread techniques under substrate temperature (T_sub) ranging from 410 to 700 °C and O₂ pressure of 200 mTorr. In order to study the effect of substrates on the deposition of Bi_xY_3−xFe₅O₁₂ thin films, garnet substrates annealed at 1300 °C for 3 h were also used. Magneto-optical properties were characterized by our home-designed magneto-optical imaging system. From the maps of Faraday rotation angle θ_F, it was evident that the Faraday effect appears only when T_sub = 430-630 °C. θ_F reaches to the maximum value (∼6°/μm, λ = 632 nm) at 500 °C, and is proportional to the Bi contents. XRD and EPMA analyses showed that Bi ions are easier to substitute for Y sites and better crystallinity is obtained for annealed substrates than for commercial ones.     

The investigation of room temperature ferromagnetism in (1 0 0) oriented BaNb2O6 PLD films on LaAlO3 (1 0 0) substrate

(1 0 0) oriented BaNb₂O₆ films have been successfully grown on LaAlO₃ (1 0 0) substrate at 750 °C or 450 °C in vacuum by pulsed laser deposition. The deposited BaNb₂O₆ PLD films exhibit room-temperature ferromagnetism. Ab initio calculations demonstrate that stoichiometric BaNb₂O₆ and that with barium vacancy are nonmagnetic, while oxygen and niobium vacancy can induce magnetism due to the spin-polarization of Nb s electrons and O p electrons respectively. Moreover, ferromagnetic coupling is energetically more favorable when two Nb/O vacancies are located third-nearest-neighbored. The observed room temperature ferromagnetism in BaNb₂O₆ films should be mainly induced by oxygen vacancies introduced during vacuum deposition, with certain contribution by Nb vacancies.     

Epitaxial MoOx nanostructures on TiO2(1 1 0) obtained using thermal decomposition of Mo(CO)6

Stoichiometric and highly-defective TiO₂(1 1 0) surfaces (called as yellow and blue, respectively) were exposed to Mo(CO)₆ vapours in UHV and in a reactive O₂ atmosphere. In the case of yellow-TiO₂, an O₂ reactive atmosphere was necessary to obtain the Mo(CO)₆ decomposition at 450 °C with deposition of MoO_x nanostructures where, according to core level photoemission data, the Mo⁺⁴ state is predominant. In the case of blue-TiO₂ it was possible to obtain Mo deposition both in UHV and in an O₂ atmosphere. A high dose of Mo(CO)₆ in UHV on blue-TiO₂ allowed the deposition of a thick metallic Mo layer. An air treatment of this sample at 580 °C led to the elimination of Mo as MoO₃ and to the formation of a transformed layer of stoichiometry of Ti_(1−x)Mo_xO₂ (where x is close to 0.1) which, according to photoelectron diffraction data, can be described as a substitutional near-surface alloy, where Mo⁺⁴ ions are embedded into the titania lattice. This embedding procedure results in a stabilization of the Mo⁺⁴ ions, which are capable to survive to air exposure for a rather long period of time. After exposure of the blue-TiO₂(1 1 0) substrate to Mo(CO)₆ vapours at 450 °C in an O₂ atmosphere it was possible to obtain a MoO₂ epitaxial ultrathin layer, whose photoelectron diffraction data demonstrate that is pseudomorphic to the substrate.     

CO2 adsorption on Cr(1 1 0) and Cr2O3(0 0 0 1)/Cr(1 1 0)

We attempt to correlate qualitatively the surface structure with the chemical activity for a metal surface, Cr(1 1 0), and one of its surface oxides, Cr₂O₃(0 0 0 1)/Cr(1 1 0). The kinetics and dynamics of CO₂ adsorption have been studied by low energy electron diffraction (LEED), Aug er electron spectroscopy (AES), and thermal desorption spectroscopy (TDS), as well as adsorption probability measurements conducted for impact energies of E_i = 0.1-1.1 eV and adsorption temperatures of T_s = 92-135 K. The Cr(1 1 0) surface is characterized by a square shaped LEED pattern, contamination free Cr AES, and a single dominant TDS peak (binding energy E_d = 33.3 kJ/mol, first order pre-exponential 1 × 10¹³ s⁻¹). The oxide exhibits a hexagonal shaped LEED pattern, Cr AES with an additional O-line, and two TDS peaks (E_d = 39.5 and 30.5 kJ/mol). The initial adsorption probability, S₀, is independent of T_s for both systems and decreases exponentially from 0.69 to 0.22 for Cr(1 1 0) with increasing E_i, with S₀ smaller by ∼0.15 for the surface oxide. The coverage dependence of the adsorption probability, S(Θ), at low E_i is approx. independent of coverage (Kisliuk-shape) and increases initially at large E_i with coverage (adsorbate-assisted adsorption). CO₂ physisorbs on both systems and the adsorption is non-activated and precursor mediated. Monte Carlo simulations (MCS) have been used to parameterize the beam scattering data. The coverage dependence of E_d has been obtained by means of a Redhead analysis of the TDS curves.     

L10 FePt thin films with [0 0 1] crystalline growth fabricated by SiO2 addition—rapid thermal annealing and dot patterning of the films

FePt films that have a high degree of order S in their L1₀ structure (S>0.90) and well-defined [0 0 1] crystalline growth perpendicular to the film plane were fabricated on thermally oxidized Si substrates by the addition of an oxide and successive rapid thermal annealing (RTA). The mechanism of L1₀ ordering and [0 0 1] crystalline growth perpendicular to the film plane arising through the oxide addition and RTA process is also discussed. The L1₀ ordering (S>0.90) and the [0 0 1] crystalline growth were achieved by (1) lowering the activation energy due to in-plane tensile stress and the initiation of L1₀ ordering at a low temperature, (2) [0 0 1] crystalline growth through in-plane tensile stress, and (3) enhancement of atomic diffusion via the addition of an oxide and the resultant lowering of the ordering temperature. Effect (1) was observed in the case of SiO₂ addition, effect (2) was generally observed in the case of oxide addition and the RTA process, and effect (3) was prominent in the case of ZnO addition. With the addition of ZnO, the L1₀ ordering started at below 400 °C and was completed at 500 °C. Finally, dot patterns were successfully fabricated down to a diameter of 15 nm using electron beam lithography, and the magnetic state of the dot pattern was observed by magnetic force microscopy.     

Molecular dynamics simulation of the (0 0 0 1) α-Al2O3 and α-Cr2O3 surfaces

A simple, rigid pair-potential model is applied to investigate the dynamics of the (0 0 0 1) α-Al₂O₃ and α-Cr₂O₃ surfaces using the molecular dynamics technique. The simulations employ a two-stage equilibration process: in the first stage the simulation-cell size is determined via the constant-stress ensemble, and in the second stage the equilibration of the size-corrected simulation cell is continued in the canonical ensemble. The thermal expansion coefficients of bulk alumina and chromia are evaluated as a function of temperature. Furthermore, the surface relaxation and mean-square displacement of the atoms versus depth into the slab are calculated, and their behaviour in the surface region analysed in detail. The calculations show that even moderate temperatures (∼400 °C) give rise to displacements of the atoms at the surface which are similar to the lattice mismatch between α-alumina and chromia. This will help in the initial nucleation stage during thin film growth, and thus facilitate the deposition of α-Al₂O₃ on (0 0 0 1) α-Cr₂O₃ templates.     

Mn:BiFeO3/Zn:BiFeO3 bilayered thin films of (1 1 1) orientation

Ferroelectric and fatigue behavior of bilayered thin films consisting of Mn⁴⁺-modified BiFeO₃ and Zn²⁺-modified BiFeO₃, which were deposited on SrRuO₃-buffered Pt coated silicon substrates, were systematically investigated. The (1 1 1) orientation is induced for the BiFe_0.95Mn_0.05O₃/BiFe_0.95Zn_0.05O₃ bilayer, due to the introduction of the bottom BiFe_0.95Zn_0.05O₃ layer. With increasing the thickness ratio of the BiFe_0.95Mn_0.05O₃ layer, their leakage current decreases, and the fatigue endurance is greatly improved owing to the introduction of the BiFe_0.95Mn_0.05O₃ layer with a lower fatigue rate. The BiFe_0.95Mn_0.05O₃/BiFe_0.95Zn_0.05O₃ bilayer with the thickness ratio of 3:1 exhibits a larger remanent polarization of 2P_r ∼ 161.0 μC/cm² than those of bilayers with different thickness ratios, while their coercive field slightly increases with increasing the thickness ratio of the BiFe_0.95Mn_0.05O₃ layer.     

The interaction of ultrathin Cr layers with SrTiO3(1 0 0)

The growth of ultrathin Cr overlayers on SrTiO₃(1 0 0) was studied by X-ray photoelectron spectroscopy, scanning tunneling microscopy, and transmission electron microscopy. It is found that the metal-oxide interaction strongly depends on the deposition temperature. At T < 600 °C, the interfaces are atomically sharp. Local charge transfer happens between the interfacial Cr adatoms and the topmost substrate atoms. The binding energy shift of Cr 2p is dominated by the final state effects. In case of T > 600 °C, bulk diffusion of oxygen in the oxide substrate may occur, which results in a redox reaction and the formation of new reaction phases at the interfaces. In this temperature regime, the binding energy shift of Cr 2p is mainly controlled by the initial state effects.     

Conductivity and sintering property of LaNi1 − xFexO3 ceramics prepared by Pechini method

Preparation of LaNi_1 − xFe_xO₃, which is one of the candidate materials of solid oxide fuel cell cathode, current collecting layer and interconnect coating was examined with Pechini method and solid state reaction method. Single phase LaNi_1 − xFe_xO₃ with large Ni content has successfully been prepared by low temperature sintering as 750 °C with Pechini method, whereas large amount of raw materials has remained with solid state reaction method by sintering at the same temperature. It can be ascribed to more homogenous cation distribution in raw powder material prior to sintering with Pechini method. It has also been revealed that LaNi_1 − xFe_xO₃ with x lower than 0.3 is thermodynamically unstable in air above 1000 °C. LaNi_0.6Fe_0.4O₃ showed superior property as cathode material with high electrical conductivity, thermodynamic stability and appropriate sintering property.     

CoPt alloy grown on the WSe2(0 0 0 1) van der Waals surface

The structural and magnetic properties of 3-nm-thick CoPt alloys grown on WSe₂(0 0 0 1) at various temperature are investigated. Deposition at room temperature leads to the formation of a chemically disordered fcc CoPt alloy with [1 1 1] orientation. Growth at elevated temperatures induces L1₀ chemical order starting at 470 K accompanied with an increase in grain size and a change in grain morphology. As a consequence of the [1 1 1] growth direction, the CoPt grains can adopt one of the three possible variants of the L1₀ phase with tetragonal c-axis tilted from the normal to the film plane direction at 54°. The average long-range order parameter is found to be 0.35(±0.05) and does not change with the increase in the deposition temperature from 570 to 730 K. This behavior might be related to Se segregation towards the growing facets and surface disorder effects promoted by a high surface-to-volume ratio. Magnetic studies reveal a superparamagnetic behavior for the films grown at 570 and 730 K in agreement with the film morphology and degree of chemical order. The measurements at 10 K reveal the orientation of the easy axis of the magnetization lying basically in the film plane.     

Ultrathin ZrO2 films on Si-rich SiC(0 0 0 1)-(3 × 3): Growth and thermal stability

The growth and thermal stability of ultrathin ZrO₂ films on the Si-rich SiC(0 0 0 1)-(3 × 3) surface have been explored using photoelectron spectroscopy (PES) and X-ray absorption spectroscopy (XAS). The films were grown in situ by chemical vapor deposition using the zirconium tetra tert-butoxide (ZTB) precursor. The O 1s XAS results show that growth at 400 °C yields tetragonal ZrO₂. An interface is formed between the ZrO₂ film and the SiC substrate. The interface contains Si in several chemically different states. This gives evidence for an interface that is much more complex than that formed upon oxidation with O₂. Si in a 4+ oxidation state is detected in the near surface region. This shows that intermixing of SiO₂ and ZrO₂ occurs, possibly under the formation of silicate. The alignment of the ZrO₂ and SiC band edges is discussed based on core level and valence PES spectra. Subsequent annealing of a deposited film was performed in order to study the thermal stability of the system. Annealing to 800 °C does not lead to decomposition of the tetragonal ZrO₂ (t-ZrO₂) but changes are observed within the interface region. After annealing to 1000 °C a laterally heterogeneous layer has formed. The decomposition of the film leads to regions with t-ZrO₂ remnants, metallic Zr silicide and Si aggregates.     

Adsorption dynamics of CO2 on Cu(1 1 0): A molecular beam study

Molecular beam scattering measurements have been conducted to examine the adsorption dynamics of CO₂ on Cu(1 1 0). The initial adsorption probability, S₀, decreases exponentially from 0.43 ± 0.03 to a value close to the detection limit (∼0.03) within the impact energy range of E_i = (0.12-1.30) eV. S₀ is independent of the adsorption temperature, T_s, and the impact angle, α_i, i.e., the adsorption is non-activated and total energy scaling is obeyed. The coverage, Θ, dependent adsorption probability, S(Θ), agrees with precursor-assisted adsorption dynamics (Kisliuk type) above T_s ∼ 91 K. However, below that temperature adsorbate-assisted adsorption (S increases with Θ) has been observed. That effect is most distinct at large E_i and low T_s. The S(Θ) data have been modeled by Monte Carlo simulations. No indications of CO₂ dissociation were obtained from Auger Electron Spectroscopy or the molecular beam scattering data.     

Effect of crystallinity of Co layer on perpendicular exchange bias in Au-capped ultrathin Co film on Cr2O3(0 0 0 1) thin film

The effect of the crystalline quality of ultrathin Co films on perpendicular exchange bias (PEB) has been investigated using a Au/Co/Au/α-Cr₂O₃ thin film grown on a Ag-buffered Si(1 1 1) substrate. Our investigation is based on the effect of the Au spacer layer on the crystalline quality of the Co layer and the resultant changes in PEB. An α-Cr₂O₃(0 0 0 1)layer is fabricated by the thermal oxidization of a Cr(1 1 0) thin film. The structural properties of the α-Cr₂O₃(0 0 0 1) layer including the cross-sectional structure, lattice parameters, and valence state have been investigated. The fabricated α-Cr₂O₃(0 0 0 1) layer contains twin domains and has slightly smaller lattice parametersthan those of bulk-Cr₂O₃. The valence state of the Cr₂O₃(0 0 0 1) layer is similar to that of bulk Cr₂O₃. The ultrathin Co film directly grown on the α-Cr₂O₃(0 0 0 1) deposited by an e-beam evaporator is polycrystalline. The insertion of a Au spacer layer with a thickness below 0.5 nm improves the crystalline quality of Co, probably resulting in hcp-Co(0 0 0 1). Perpendicular magnetic anisotropy (PMA) appears below the Néel temperature of Cr₂O₃ for all the investigated films. Although the PMA appears independently of the crystallinequality of Co, PEB is affected by the crystalline quality of Co. For the polycrystalline Co film, PEB is low, however, a high PEB is observed for the Co films whose in-plane atom arrangement is identical to that of Cr³⁺ in Cr₂O₃(0 0 0 1). The results are qualitatively discussed on the basis of the direct exchange coupling between Cr and Co at the interface as the dominant coupling mechanism.     

Structural evolution and epitaxial stabilisation of pulsed laser deposited Sm0.55Nd0.45NiO3 solid solution nanostructured films on undoped Si (1 0 0) and NdGaO3 substrates

We report on the effects of substrate, ambient oxygen pressure and deposition time on the crystal structure, and morphology of Sm_0.55Nd_0.45NiO₃ solid solution nanostructured films synthesized by pulsed-laser deposition. In each film the structure was found to be consistent with a perovskite structure with preferential planes growth and reveals a strong orientation along the orthorhombic (2 1 0) plane of the perovskite subcell for the film deposited on NdGaO₃ where highly crystalline films were obtained within 15 min deposition time with a low surface roughness of 8.79 nm. Similar structure is observed on Si (1 0 0) substrate only at O₂ pressure of 0.4 mbar. The surface morphology of the different samples shows a net dense film structure with several droplets population. The nano-scaled droplets are in general spherical in shape; a detailed analysis indicates that the laser ablation of this nickelate family is governed to a certain extent by a heat transfer phenomenon.     

Scanning tunneling microscopy study of growth of Pt nanoclusters on thin film Al2O3/NiAl(1 0 0)

The growth of Pt nanoclusters on thin film Al₂O₃ grown on NiAl(1 0 0) was studied by using scanning tunneling microscopy (STM). The samples were prepared by vapor depositing various amounts of Pt onto the Al₂O₃/NiAl(1 0 0) at different substrate temperatures in ultra high vacuum (UHV). The STM images show that sizeable Pt nanoclusters grow solely on crystalline Al₂O₃ surface. These Pt clusters appear to be randomly distributed and only a few form evident alignment patterns, contrasting with Co clusters that are highly aligned on the crystalline Al₂O₃. The size distributions of these Pt clusters are rather broader than those of the Co clusters on the same surface and the sizes are evidently smaller. With increasing coverage or deposition temperature, the number of larger clusters is enhanced, while the size of the majority number of the clusters remains around the same (0.4 nm as height and 2.25 nm as diameter), which differs drastically from the Pt clusters on γ-Al₂O₃/NiAl(1 1 0) observed earlier. These Pt cluster growth features are mostly attributed to smaller diffusion length and ease to form stable nucleus, arising from strong Pt-Pt and Pt-oxide interactions and the peculiar protrusion structures on the ordered Al₂O₃/NiAl(1 0 0). The thermal stability of Pt nanoclusters was also examined. The cluster density decreased monotonically with annealing temperature up to 1000 K at the expense of smaller clusters but coalescence is not observed.     

Valence band and band gap photoemission study of (1 1 1) In2O3 epitaxial films under interactions with oxygen, water and carbon monoxide

Synchrotron radiation ultraviolet photoemission experiments at photon energies of 150 and 49 eV were performed on an epitaxial layer of (1 1 1) In₂O₃ with good crystallinity as established by a standard scanning probe and diffraction methods. Valence band (VB) and band gap photoemission spectra were monitored under separate oxygen, water and carbon monoxide exposures (100 L) at different activation temperatures within the range utilized for chemiresistive gas sensors (160-450 °C). Large changes in photoemission response within the whole VB were observed for all gases. Regular shifts of the valence band edge relative to the Fermi energy were found under gas exposures on two kinds of surface (partially reduced or partially oxidized), and are interpreted as changes of surface potential. Treatments in oxygen resulted in upward band bending (∼0.5 eV at T = 320 °C). Regardless of activation temperature, treatments in water resulted in downward band bending, but with small changes (<0.1 eV). Reduction properties of carbon monoxide were observed only at high temperatures of T ? 370 °C. At temperatures of 160 and 250 °C unusual “oxidizing” behavior of CO was observed with upward band bending of ∼0.7 eV (160 °C). Oxidizing and reducing effects of the gas interactions with the (1 1 1) In₂O₃ surface in all cases were accompanied by a corresponding behavior, i.e., a decrease or increase in photoemission response from so-called defect states in the band gap near the top of the valence band. The increases of photoemission within a band gap with maxima at binding energies (BE) of 0.4 (O₂-induced peak) and 1.0 eV (CO-induced peak) were, respectively, found for interactions with O₂ and CO for low temperatures (T = 160 and 250 °C). These responses were ascribed to acceptor-like electronic levels of O₂ and CO chemisorption states, respectively. A definite split of the top VB peak (BE ∼ 4.0 eV) was found under CO dosing at 160 °C. Established knowledge of the CO interaction with the (1 1 1) In₂O₃ surface explains earlier revealed acceptor-like behavior of In₂O₃ film conductivity during CO detection at operational temperatures lower than 250 °C through the formation of acceptor-like electronic levels of adsorbed CO molecules.     

Characterization of bicrystalline epitaxial LaNiO3 films fabricated on MgO (1 0 0) substrates by pulsed laser deposition

A series of metallic LaNiO₃ (LNO) thin films were deposited on MgO (1 0 0) substrates by pulsed laser deposition (PLD) under the oxygen pressure of 20 Pa at different substrate temperatures from 450 to 750 °C. X-ray diffraction (XRD) was used to characterize the crystal structure of LNO films. θ-2θ scans of XRD indicate that LNO film deposited at a substrate temperature of 700 °C has a high orientation of (l l 0). At other substrate temperatures, the LNO films have mixed phases of (l l 0) and (l 0 0). Furthermore, pole figure measurements show that LNO thin films, with the bicrystalline structure, were epitaxially deposited on MgO (1 0 0) substrates in the mode of LNO (1 1 0)//MgO (1 0 0) at 700 °C. Reflection high-energy electric diffraction (RHEED) and atomic force microscopy (AFM) were also performed to investigate the microstructure of LNO films with the high (l l 0) orientation. RHEED patterns clearly confirm this epitaxial relationship. An atomically smooth surface of LNO films at 700 °C was obtained. In addition, bicrystalline epitaxial LNO films, fabricated at 700 °C, present a excellent conductivity with a lower electrical resistivity of 300 μ Ω cm. Thus, the obtained results indicate that bicystalline epitaxial LNO films could serve as a promising candidate of electrode materials for the fabrication of ferroelectric or dielectric films.     

Structural and electrical transport properties of ZnxFe3−xO4 thin film deposited on Si (1 1 1) by pulsed-laser deposition

Polycrystalline thin films of Fe_3−xZn_xO₄ (x = 0.0, 0.01 and 0.02) were prepared by pulsed-laser deposition technique on Si (1 1 1) substrate. X-ray diffraction studies of parent as well as Zn doped magnetite show the spinel cubic structure of film with (1 1 1) orientation. The order–disorder transition temperature for Fe₃O₄ thin film with thickness of 150 nm are at 123 K (Si). Zn doping leads to enhancement of resistivity by Zn²⁺ substitution originates from a decrease of the carrier concentration, which do not show the Verwey transition. The Raman spectra for parent Fe₃O₄ on Si (1 1 1) substrate shows all Raman active modes for thin films at energies of T_2g¹, T_2g³, T_2g², and A_1g at 193, 304, 531 and 668 cm⁻¹. It is noticed that the frequency positions of the strongest A_1g mode are at 668.3 cm⁻¹, for all parent Fe₃O₄ thin film shifted at lower wave number as 663.7 for Fe_2.98Zn_0.02O₄ thin film on Si (1 1 1) substrate. The integral intensity at 668 cm⁻¹ increased significantly with decreasing doping concentration and highest for the parent sample, which is due to residual stress stored in the surface.