Raman scattering studies of Mn-doped ZnO thin films deposited under pure Ar or Ar + N2 sputtering atmosphere

This paper investigates the anomalous and specific Raman modes present in Mn-doped ZnO thin films deposited using the magnetron co-sputtering method. To trace these peaks, we prepared Mn-doped ZnO films with different Mn concentrations by altering the sputtering power of the Mn target in a pure Ar or Ar + N₂ sputtering atmosphere. A broad band observed in the Raman spectra of heavily Mn-doped ZnO films ranges from 500 to 590 cm^− 1. This band involves the enhanced A₁ longitudinal mode and activated silent modes of ZnO, as well as a characteristic mode of Mn₂O₃. Four anomalous Raman peaks at approximately 276, 510, 645 and 585 cm^− 1 are present in pure and Mn-doped ZnO films deposited under the Ar + N₂ sputtering atmosphere. The peaks at 276 cm^− 1 and 510 cm^− 1 may originate from the complex defects of Zn_i-N_O and Zn_i-O_i, respectively, while the peak at approximately 645 cm^− 1 could be due to a complex defect of Zn_i coupled with both the N and Mn dopants. The results of this study suggest classifying the origins of anomalous and specific Raman peaks in Mn-doped ZnO films into three major types: structural disorder and morphological changes caused by the Mn dopant, Mn-related oxides and intrinsic host-lattice defects coupled with/without the N dopant.     

RF diode reactive sputtering of n- and p-type zinc oxide thin films

We present the relationship between parameters of reactive RF diode sputtering from a zinc oxide (ZnO) target and the crystalline, electrical and optical properties of n-/p-type ZnO thin films. The properties of the ZnO thin films depended on RF power, substrate temperature and, particularly, on working gas mixtures of Ar/O₂ and of Ar/N₂. Sputtering in Ar+O₂ working gas (up to 75% of O₂) improved the structure of an n-type ZnO thin film, from fibrous ZnO grains to columnar crystallites, both preferentially oriented along the c-axis normally to the substrate (〈0 0 2〉 direction). These films had good piezoelectric properties but also high resistivity (ρ≈10³ Ω cm). ZnO:N p-type films exhibited nanograin structure with preferential 〈0 0 2〉 orientation at 25% N₂ and 〈1 0 0〉 orientation for higher N₂ content. The presence of nitrogen N_O at O-sites forming N_O-O acceptor complexes in ZnO was proven by SIMS and Raman spectroscopy. A minimum value of resistivity of 790 Ω cm, a p-type carrier concentration of 3.6×10¹⁴ cm⁻³ and a Hall mobility of 22 cm² V⁻¹ s⁻¹ were obtained at 75% N₂.     

Effect of microwave power and C2 emission intensity on structural and surface properties of nanocrystalline diamond films

Nanocrystalline diamond (NCD) films are synthesized using microwave plasma enhanced chemical vapour deposition technique at 2 × 10⁴ Pa and 600 °C with microwave power of 600-1600 W. Deposition is carried out on n-type (100) silicon wafer with Ar/H₂/CH₄ gas mixtures. The film properties are analyzed using micro Raman spectroscopy, Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), scanning electron microscopy and atomic force microscopy. Raman spectra show two predominant peaks centered around 1335 cm⁻¹ and 1560 cm^− 1 and two humps around 1160 cm^− 1 and 1450 cm^− 1, respectively. FTIR spectra show C:H stretching modes around 3000 cm^− 1. XRD patterns show a peak at 44° (2θ). In situ diagnostic of plasma is carried out using Optical Emission Spectroscopy. It has been observed that C₂ dimer plays an important role in the nucleation of diamond crystals during NCD film deposition and the emission intensity of C₂ can be adjusted by varying the microwave power. It has also been observed that the structural properties like growth rate, surface morphology and grain size of the growing film are dependent on the C₂ intensity during deposition.     

Power and pressure effects upon magnetron sputtered aluminum doped ZnO films properties

In this work, polycrystalline aluminum doped zinc oxide (ZnO:Al) films with c-axis (002) orientation have been grown on glass and silicon substrates by RF (radio frequency) magnetron sputtering technique, at room temperature. A systematic study of the effect of sputtering deposition parameters (i.e. RF power and argon gas pressure) on the structural, optical and electrical properties of the films was carried out. We observed that, with increasing RF power the growth rate increased, while it decreased with increasing gas pressure. As mentioned above, the films were polycrystalline in nature with a strong preferred (002) orientation. The intrinsic compressive stress was found to decrease with both increasing RF power and gas pressure, and near stress-free film was obtained at 200 W RF power and 2 × 10^− 1 Pa gas pressure. The obtained ZnO:Al films, not only have an average transmittance greater than 90% in the visible region, but also have an optical band gap between 3.33 and 3.47 eV depending on the sputtering parameters. Moreover, a low value of the electrical resistivity (~ 1.25 × 10^− 3 Ω cm) was obtained for the film deposited at 200 W and 2 × 10^− 3 mbar.     

Radio frequency sputter deposition of high-quality conductive and transparent ZnO:Al films on polymer substrates for thin film solar cells applications

Thick aluminum-doped zinc oxide films were deposited at substrate temperatures from 100 °C to room temperature on polyethylene terephthalate by radio frequency magnetron sputtering, varying the deposition parameters such as radio frequency power and working pressure.Structural, optical and electrical properties were analyzed using an x-ray diffractometer, a spectrophotometer and a four-point probe, respectively. Films were polycrystalline showing a strong preferred c-axis orientation (002). The best optical and electrical results were achieved using a substrate temperature of 100 °C. Furthermore, high transmittances close to 80% in the visible wavelength range were obtained for those films deposited at the lowest Argon pressure used of 0.2 Pa. In addition, resistivities as low as 1.1 × 10^− 3 Ω cm were reached deposited at a RF power of 75 W. Finally, a comparison of the properties of the films deposited on polymer and glass substrates was performed, obtaining values of the figure of merit for the films on polymer comparable to those obtained on glass substrates, 17,700 Ω^− 1 cm^− 1 vs 14,900 Ω^− 1 cm^− 1, respectively.     

Ni-doped vertically aligned zinc oxide nanorods prepared by hybrid wet chemical route

Ni-doped zinc oxide (Ni:ZnO) nanorods were synthesized by incorporating nickel in vertically aligned ZnO nanorods. Ni was evaporated onto ZnO nanorods and the composite structure was subjected to rapid thermal annealing for dispersing Ni in ZnO nanorods. The optical band gap decreased with increasing amount of Ni incorporation. The origin of the photoluminescence peak at ∼ 400 nm was related to the defect levels introduced due to substitution of Ni²⁺ in the Zn²⁺ site with annealing. The Raman spectra indicated the presence of the characteristic peak at ∼ 436 cm^− 1 which was identified as high frequency branch of E₂ mode of ZnO. The Fourier Transformed Infrared spectra indicated the existence of the distinct characteristic absorption peak at 481 cm^− 1 for ZnO stretching modes. Current-voltage characteristics indicated that the current changed linearly with voltage for both the doped and undoped samples.     

Tungsten-doped ZnO transparent conducting films deposited by direct current magnetron sputtering

Highly conducting and transparent thin films of tungsten-doped ZnO (ZnO:W) were prepared on glass substrates by direct current (DC) magnetron sputtering at low temperature. The effect of film thickness on the structural, electrical and optical properties of ZnO:W films was investigated. All the deposited films are polycrystalline with a hexagonal structure and have a preferred orientation along the c-axis perpendicular to the substrate. The electrical resistivity first decreases with film thickness, and then increases with further increase in film thickness. The lowest resistivity achieved was 6.97 × 10⁻⁴ Ω cm for a thickness of 332 nm with a Hall mobility of 6.7 cm² V⁻¹ s⁻¹ and a carrier concentration of 1.35 × 10²¹ cm⁻³. However, the average transmittance of the films does not change much with an increase in film thickness, and all the deposited films show a high transmittance of approximately 90% in the visible range.     

Fabrication of p-type ZnO nanowires based heterojunction diode

Vertically aligned p-type ZnO (Li–N co-doped) nanowires have been synthesized by hydrothermal method on n-type Si substrate. X-ray diffraction pattern indicated a strong peak from (0 0 0 2) planes of ZnO. The appearance of a strong peak at 437 cm⁻¹ in Raman spectra was attributed to E₂ mode of ZnO. Fourier transformed infrared studies indicated the presence of a distinct characteristic absorption peaks at 490 cm⁻¹ for ZnO stretching mode. Compositional studies revealed the formation of Li–N co-doped ZnO, where Li was bonded with both O and N. The junction properties of p-type ZnO nanowires/n-Si heterojunction diodes were evaluated by measuring I–V and C–V characteristics. I–V characteristics exhibited the rectifying behavior of a typical p–n junction diode.     

Effects of sputtering power and pressure on properties of ZnO:Ga thin films prepared by oblique-angle deposition

The effects of power and pressure on radiofrequency (RF) diode sputtering in oblique-angle (80°) deposition arrangement are presented. Oblique-angle sputtering of ZnO:Ga (GZO) thin films resulted in a tilted columnar crystalline structure and inclination of the c-axis by an angle of approximately 9° with respect to the substrate. This improved their structural, electrical and optical properties in comparison with films deposited perpendicularly to the substrate. GZO films sputtered by an RF power of 600 W at room temperature of the substrate in Ar pressure 1.3 Pa showed strong crystalline (002) texture, lowest electrical resistivity 3.4 × 10^− 3 Ωcm, highest electron mobility 10 cm² V^− 1 s^− 1, high electron concentration 1.8 × 10²⁰ cm^− 3 and good optical transparency up to 88%. The small inclination angle of the film structure is caused by the high kinetic energy of sputtered species and additional energetic particle bombardment causes random surface diffusion, which is suppressing the shadow effect produced by oblique-angle sputtering.     

Transparent conducting Al and Y codoped ZnO thin film deposited by DC sputtering

Transparent conducting Al and Y codoped zinc oxide (AZOY) thin films with high transparency and low resistivity were deposited by DC magnetron sputtering. The effects of substrate temperature on the structural, electrical and optical properties of AZOY thin films deposited on glass substrates have been investigated. X-ray diffraction spectra indicate that no diffraction peak of Al₂O₃ or Y₂O₃ except that of ZnO (0 0 2) is observed. The AZOY thin film prepared at substrate temperature of 250 °C has the optimal crystal quality inferring from FWHM of ZnO (0 0 2) diffraction peak, but the AZOY thin film deposited at 300 °C has the lowest resistivity of 3.6 × 10⁻⁴ Ω-cm, the highest mobility of 30.7 cm² V⁻¹ s⁻¹ and the highest carrier concentration of 5.6 × 10²⁰ cm⁻³. The films obtained have disorderly polyhedral surface morphology indicating possible application in thin film solar cell with good quality and high haze factor without the need of post-deposition etching.     

Changes in the structural and electrical properties of vacuum post-annealed tungsten- and titanium-doped indium oxide films deposited by radio frequency magnetron sputtering

Tungsten- and titanium-doped indium oxide (IWO and ITiO) films were deposited at room temperature by radio frequency (RF) magnetron sputtering, and vacuum post-annealing was used to improve the electron mobility. With increasing deposition power, the as deposited films showed an increasingly crystalline nature. Compared with ITiO films, IWO films showed crystallinity at lower RF power. IWO films are partially crystallized at 10 W deposition power and become nearly fully crystalline at 20 W. ITiO films are fully crystalline only at 75 W. For this reason, film thickness has a greater impact on the electrical properties of IWO films than ITiO films. Vacuum post-annealing is more effective in improving electron mobility for amorphous than for (partially) crystalline IWO and ITiO films. Changes in the electrical properties of ITiO films can be better controlled as a function of annealing temperature than those of IWO films. Finally, post annealed 308 nm-thick IWO and 325 nm-thick ITiO films have approximately 80% transmittance in visible and near infrared wavelengths (up to 1100 nm), while their sheet resistances decrease to 9.3 and 10 Ω/□, and their electron mobilities are 51 cm²V^− 1 s^− 1 and 50 cm²V^− 1 s^− 1, respectively, making them suitable for use as Transparent Conductive Oxide layers of low bandgap solar cells.     

Effect of rf power on the growth of silicon nanowires by hot-wire assisted plasma enhanced chemical vapor deposition (HW-PECVD) technique

Silicon nanowires (SiNWs) were synthesized by simultaneous evaporation of Au and Si deposition using H₂ diluted SiH₄. The deposition techniques combined hot-wire (HW) and plasma enhanced chemical vapor deposition (PECVD). Au wires were placed on the filament and heated simultaneously with the activation of the rf plasma for the dissociation of SiH₄ and H₂ gases. Five set of samples were deposited on ITO-coated glass substrate at different rf power varied from 20 to 100 W in an interval of 20 W, keeping other deposition parameters constant. High yield of SiNWs with diameter ranging from 60 to 400 nm and length about 10 μm were grown at rf power of 80 W (power density ~ 1018 mW cm⁻²). Rf power of 100 W (power density ~ 1273 mW cm⁻²) suppressed the growth of these SiNWs. The growth mechanisms of SiNWs are tentatively proposed. The nanocrystalline structure of SiNWs is confirmed by Raman spectra and HRTEM measurement.     

Chemical states of carbon in amorphous boron carbide thin films deposited by radio frequency magnetron sputtering

Boron carbide thin films were deposited by radio frequency (RF) magnetron sputtering and characterized by X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and high resolution transmission electron microscopy. The results reveal that the structure of thin films deposited at substrate temperatures lower than 350 °C is amorphous. We found that there are four chemical states for carbon in amorphous boron carbide thin films deposited by RF magnetron sputtering. One is the segregated carbon in form of the graphitic inclusions in the thin film identified by Raman spectroscopy and Raman mapping using two strong peaks at ~ 1360 cm^− 1 and ~ 1590 cm^− 1, but the XPS results show that the graphitic inclusions do not connect to the substrate directly. On the surface the carbon forms C=O bonds characterized by the peak of C1s core level at 285.0 eV besides B-C bonds in the boron carbide with the peak of C1s being at 282.8 eV. The detailed analysis of B-C bonds in the boron carbide shows that there are two states for carbon atoms in B-C bonds: in the C-B-C models with C1s peak at 282.3 eV and in the icosahedra with C1s peak at 283.3 eV.     

Low-temperature deposition of ZnO thin films on PET and glass substrates by DC-sputtering technique

The structural, optical and electrical properties of ZnO thin films (260 - 490 nm thick) deposited by direct-current sputtering technique, at a relatively low-substrate temperature (363 K), onto polyethylene terephthalate and glass substrates have been investigated. X-ray diffraction patterns confirm the proper phase formation of the material. Optical transmittance data show high transparency (80% to more than 98%) of the films in the visible portion of solar radiation. Slight variation in the transparency of the films is observed with a variation in the deposition time. Electrical characterizations show the room-temperature conductivity of the films deposited onto polyethylene terephthalate substrates for 4 and 5 h around 0.05 and 0.25 S cm^− 1, respectively. On the other hand, for the films deposited on glass substrates, these values are 8.5 and 9.6 S cm^− 1 for similar variation in the deposition time. Room-temperature conductivity of the ZnO films deposited on glass substrates is at least two orders of magnitude higher than that of ZnO films deposited onto polyethylene terephthalate substrates under identical conditions. Hall-measurements show the maximum carrier concentration of the films on PET and glass substrate around 2.8 × 10¹⁶ and 3.1 × 10²⁰ cm^− 3, respectively. This report will provide newer applications of ZnO thin films in flexible display technology.     

Fabrication of high frequency ZnO thin film SAW devices on silicon substrate with a diamond-like carbon buffer layer using RF magnetron sputtering

Diamond-like carbon (DLC) film is a promising candidate for surface acoustic wave (SAW) device applications because of its higher acoustic velocity. A zinc oxide (ZnO) thin film has been deposited on DLC film/Si substrate by RF magnetron sputtering; the optimized parameters for the ZnO sputtering are RF power density of 0.55 W/cm², substrate temperature of 380 °C, gas flow ratio (Ar/O₂) of 5/1 and total sputter pressure of 1.33 Pa. The results showed that when the thickness of the ZnO thin films was decreased, the phase velocity of the SAW devices increased significantly.     

Raman analysis of nitrogen doped ZnO

The mechanism of nitrogen doping is essential for making p-type ZnO. This paper demonstrates that Raman characterization is a potentially powerful tool to study the mechanism of nitrogen doping. We have observed new Raman features near 280, 510, 570, 642, 773, 1360 and 1565 cm^− 1 shift in nitrogen doped ZnO (ZnO:N) thin films compared with undoped ZnO films. Peaks at 280, 510, 570, 642, and 773 cm^− 1 are attributed to the nitrogen related defect complex. The Raman peaks at 1360 cm^− 1 and 1565 cm^− 1 shift are assigned to D—(disordered) and G—(Graphitic) bands associated with the carbon-related defect complex, respectively. The intensity and the intensity ratio of peaks at 1360 cm^− 1 and 1565 cm^− 1 have been found to be sensitive parameters that reflect the conductivity type of ZnO:N. Explanations are presented which correlate the Raman features to the electric conductivity of the films. From this analysis, we found that at temperature lower than or at 400 °C, nitrogen incorporation will form the nitrogen or possible nitrogen carbon related defect complex. As the growth temperature increases to 500 °C, the features associated with nitrogen are difficult to distinguish and the features associated to carbon begin to emerge. This observation possibly indicates the decrease of the nitrogen content and the increase of the carbon content in the ZnO:N film. The increase of carbon content may affect the donor behavior of the film. This observation suggests that growth conditions should be controlled to avoid carbon into the film.     

Low temperature (< 100 °C) fabrication of thin film silicon solar cells by HWCVD

Amorphous silicon films have been made by HWCVD at a very low substrate temperature of ≤ 100 °C (in a dynamic substrate heating mode) without artificial substrate cooling, through a substantial increase of the filament-substrate distance (∼ 80 mm) and using one straight tantalum filament. The material is made at a reasonable deposition rate of 0.11 nm/s. Optimized films made this way have device quality, as confirmed by the photosensitivity of > 10⁵. Furthermore, they possess a low structural disorder, manifested by the small Γ/2 value (half width at half maximum) of the transverse optic (TO) Si-Si vibration peak (at 480 cm^− 1) in the Raman spectrum of ∼ 30.4 cm^− 1, which translates into a bond angle variation of only ∼ 6.4°. The evidence gathered from the studies on the structure of the HWCVD grown film by three different techniques, Raman spectroscopy, spectroscopic ellipsometry and transmission electron microscopy, indicate that we have been able to make a photosensitive material with a structural disorder that is smaller than that expected at such a low deposition temperature.Tested in a p-i-n solar cell on Asahi SnO₂:F coated glass (without ZnO at the back reflector), this i-layer gave an efficiency of 3.4%. To our knowledge, this is the first report of a HWCVD thin film silicon solar cell made at such a low temperature.     

Structural and optical properties of Ti-doped ZnO thin films prepared by the cathodic vacuum arc technique with different annealing processes

Highly transparent Ti-doped ZnO thin films were prepared on glass substrates at a deposition rate of approximately 33 nm/min using the cathodic vacuum arc technique with a Zn target power of 550 W and a Ti target power of 750 W, respectively. X-ray diffraction measurements have shown that the Ti-doped ZnO thin film with a vacuum post-annealing condition is c-axis oriented but an amorphous phase at the other post-annealing atmosphere and as-deposited condition. Transmittance measurements show that the best optical quality of the Ti-doped ZnO thin films occurred at a post-annealing atmosphere of N₂/H₂ mixed gases. Additionally, the optical transmittance of all films has been found more than 85% in a range of 500-700 nm. The lowest electrical resistivity was 3.48 × 10⁻³ Ω cm, obtained on as-deposited films. However, the post-annealing condition greatly increased the resistivity.     

p-type doping of ZnO by means of high-density inductively coupled plasmas

A custom-designed inductively coupled plasma assisted radio-frequency magnetron sputtering deposition system has been used to fabricate N-doped p-type ZnO (ZnO:N) thin films on glass substrates from a sintered ZnO target in a reactive Ar + N₂ gas mixture. X-ray diffraction and scanning electron microscopy analyses show that the ZnO:N films feature a hexagonal crystal structure with a preferential (002) crystallographic orientation and grow as vertical columnar structures. Hall effect and X-ray photoelectron spectroscopy analyses show that N-doped ZnO thin films are p-type with a hole concentration of 3.32 × 10¹⁸ cm^− 3 and mobility of 1.31 cm² V^− 1 s^− 1. The current-voltage measurement of the two-layer structured ZnO p-n homojunction clearly reveals the rectifying ability of the p-n junction. The achievement of p-type ZnO:N thin films is attributed to the high dissociation ability of the high-density inductively coupled plasma source and effective plasma-surface interactions during the growth process.     

Characteristics of sputtered Al-doped ZnO films for transparent electrodes of organic thin-film transistor

Aluminum-doped ZnO (AZO) thin-films were deposited with various RF powers at room temperature by radio frequency (RF) magnetron sputtering method. The electrical properties of the AZO film were improved with the increasing RF power. These results can be explained by the improvement of the crystallinity in the AZO film. We fabricated the organic thin-film transistor (OTFT) of the bottom gate structure using pentacene active and poly-4-vinyl phenol gate dielectric layers on the indium tin oxide gate electrode, and estimated the device properties of the OTFTs including drain current-drain voltage (I_D-V_D), drain current-gate voltage (I_D-V_G), threshold voltage (V_T), on/off ratio and field effect mobility. The AZO film that grown at 160 W RF power exhibited low resistivity (1.54 × 10^− 3 Ω·cm), high crystallinity and uniform surface morphology. The pentacene thin-film transistor using the AZO film that's fabricated at 160 W RF power exhibited good device performance such as the mobility of 0.94 cm²/V s and the on/off ratio of ~ 10⁵. Consequently, the performance of the OTFT such as larger field-effect carrier mobility was determined the conductivity of the AZO source/drain (S/D) electrode. AZO films prepared at room temperature by the sputtering method are suitable for the S/D electrodes in the OTFTs.