Fabrication of p-type ZnO thin films via magnetron sputtering and phosphorus diffusion

ZnO thin films were deposited on heavily phosphorus-doped (n⁺-Si) substrates by radio frequency magnetron sputtering. The films were changed from n-type to p-type by phosphorus diffusion from the n⁺-Si substrates to the ZnO films and being activated thermally during deposition. n-Type ZnO (n-ZnO) films were also deposited onto the p-type ZnO (p-ZnO) films to form n-ZnO/p-ZnO/n⁺-Si multilayer structures. The cross section of the multilayer structure was examined by scanning electron microscopy. Crystal structures of the p-ZnO films were studied by X-ray diffraction and were confirmed to be highly c-axis oriented primarily perpendicular to the substrate. Photoluminescence spectra of the p-ZnO films showed that band-edge UV emission predominated. The hole concentration of the p-ZnO films was between +1.78×10¹⁸ cm⁻³ and +1.34×10¹⁹ cm⁻³, and the hole mobility was 13.1-6.08 cm²/V s measured by Hall effect experiment. The formation of p-ZnO films was confirmed by the rectifying characteristics of the p-ZnO/n⁺-Si heterojunctions and the n-ZnO/p-ZnO homojunction on the multilayer structure as well as by the experimental results of Hall effect.     

Stable p-type conductivity and enhanced photoconductivity from nitrogen-doped annealed ZnO thin film

We report on the growth of p-type ZnO thin films with improved stability on various substrates and study the photoconductive property of the p-type ZnO films. The nitrogen doped ZnO (N:ZnO) thin films were grown on Si, quartz and alumina substrates by radio frequency magnetron sputtering followed by thermal annealing. Structural studies show that the N:ZnO films possess high crystallinity with c-axis orientation. The as-grown films possess higher lattice constants compared to the undoped films. Besides the high crystallinity, the Raman spectra show clear evidence of nitrogen incorporation in the doped ZnO lattice. A strong UV photoluminescence emission at ~ 380 nm is observed from all the N:ZnO thin films. Prior to post-deposition annealing, p-type conductivity was found to be unstable at room temperature. Post-growth annealing of N:ZnO film on Si substrate shows a relatively stable p-type ZnO with room temperature resistivity of 0.2 Ω cm, Hall mobility of 58 cm²/V s and hole concentration of 1.95 × 10¹⁷ cm^− 3. A homo-junction p-n diode fabricated on the annealed p-type ZnO layer showed rectification behavior in the current-voltage characteristics demonstrating the p-type conduction of the doped layer. Doped ZnO films (annealed) show more than two orders of magnitude enhancement in the photoconductivity as compared to that of the undoped film. The transient photoconductivity measurement with UV light illumination on the doped ZnO film shows a slow photoresponse with bi-exponential growth and bi-exponential decay behaviors. Mechanism of improved photoconductivity and slow photoresponse is discussed based on high mobility of carriers and photodesorption of oxygen molecules in the N:ZnO film, respectively.     

Highly luminescent columnar ZnO films grown directly on n-Si and p-Si substrates by low-temperature electrochemical deposition

In this study, nanocolumnar zinc oxide thin films were catalyst-free electrodeposited directly on n-Si and p-Si substrates, what makes an important junction for optoelectronic devices. We demonstrate that ZnO thin films can be grown on Si at low cathodic potential by electrochemical synthesis. The scanning electron microscopy SEM showed that the ZnO thin films consist of nanocolumns with radius of about 150 nm on n-Si and 200 nm on p-Si substrates, possess uniform size distribution and fully covers surfaces. X-ray diffraction (XRD) measurements show that the films are crystalline material and are preferably grown along (0 0 2) direction. The impact of thermal annealing in the temperature range of 150-800 °C on ZnO film properties has been carried out. Low-temperature photoluminescence (PL) spectra of the as-prepared ZnO/Si samples show the extremely high intensity of the near bandgap luminescence along with the absence of visible emission. The optical quality of ZnO thin films was improved after post-deposition thermal treatment at 150 °C and 400 °C in our experiments, however, the luminescence intensity was found to decrease at higher annealing temperatures (800 °C). The obtained results indicate that electrodeposition is an efficient low-temperature technique for the growth of high-quality and crystallographically oriented ZnO thin films on n-Si and p-Si substrates for device applications.     

AlN codoping and fabrication of ZnO homojunction by RF sputtering

The ZnO homojunction fabricated from undoped and 1 mol% AlN doped (codoped) ZnO targets by RF magnetron sputtering has been reported. The grown films on Si (100) substrate have been characterized by X-ray diffraction (XRD), Energy dispersive spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS), Photoluminescence (PL) and Hall measurements. The increase of d-space value (compared with unstressed bulk) found from XRD for AlN codoped ZnO film supports the formation of p-ZnO due to the N incorporation. The presence of N in the film has been confirmed by EDS and XPS analysis. Further, the p-conductivity in AlN codoped ZnO has been evidenced by low temperature PL (donor-acceptor-pair emission) and room temperature PL (red shift in near-band-edge emission). Hall measurement shows that 1 mol% AlN codoped ZnO has the hole concentration of 3.772 × 10¹⁹ cm⁻³. The fabricated homojunction with 1% AlN doped ZnO (p-type) and undoped ZnO (n-type) exhibits a typical rectification behavior with high breakdown voltage, and rectification ratio, 13.4. The junction parameters such as ideality factor, barrier height and series resistance have also been calculated for the fabricated p-n junction. The energy band diagram has been proposed for the fabricated homojunction.     

Study of n-ZnO/p-Si (100) thin film heterojunctions by pulsed laser deposition without buffer layer

ZnO/Si heterojunctions were fabricated by growing ZnO thin films on p-type Si (100) substrate by pulsed laser deposition without buffer layers. The crystallinity of the heterojunction was analyzed by high resolution X-ray diffraction and atomic force microscopy. The optical quality of the film was analyzed by room temperature (RT) photoluminescence measurements. The high intense band to band emission confirmed the high quality of the ZnO thin films on Si. The electrical properties of the junction were studied by temperature dependent current-voltage measurements and RT capacitance-voltage (C-V) analysis. The charge carrier concentration and the barrier height (BH) were calculated, to be 5.6 × 10¹⁹ cm^− 3 and 0.6 eV respectively from the C-V plot. The BH and ideality factor, calculated using the thermionic emission (TE) model, were found to be highly temperature dependent. We observed a much lower value in Richardson constant, 5.19 × 10^− 7 A/cm² K² than the theoretical value (32 A/cm² K²) for ZnO. This analysis revealed the existence of a Gaussian distribution (GD) with a standard deviation of σ² = 0.035 V. By implementing the GD to the TE, the values of BH and Richardson constant were obtained as 1.3 eV and 39.97 A/cm² K² respectively from the modified Richardson plot. The obtained Richardson constant value is close to the theoretical value for n-ZnO. These high quality heterojunctions can be used for solar cell applications.     

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 phosphorus doping source temperatures on fabrication and properties of p-type ZnO thin films

Phosphorus-doped p-type ZnO thin films have been deposited by metalorganic chemical vapor deposition using P₂O₅ as the dopant source. The conductivity types of the as-grown thin films were strongly temperature-dependent. When the substrate temperature maintains at the optimal one of 420 °C, the evaporating temperature of the phosphorus source plays significant roles in controlling the phosphorus content doping into films, then influences the films' performance. Optimizing the growth parameters, the optimal results were obtained with a resistivity of 6.49 Ω cm, a Hall mobility of 0.40 cm²/V s and a hole concentration of 2.42 × 10¹⁸ cm^− 3. The optical property of the optimal film was characterized by PL measurements, which indicated the film is of high optical quality.     

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.     

Structural properties of low-temperature grown ZnO thin films determined by X-ray diffraction and X-ray absorption spectroscopy

The epitaxial growth of ZnO thin films on Al₂O₃ (0001) substrates have been achieved at a low-substrate temperature of 150 °C using a dc reactive sputtering technique. The structures and crystallographic orientations of ZnO films varying thicknesses on sapphire (0001) were investigated using X-ray diffraction (XRD). We used angle-dependent X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectroscopy to examine the variation of local structure. The XRD data showed that the crystallinity of the film is improved as the film thickness increases and the strain is fully released as the film thickness reached about 800 Å. The Zn K-edge XANES spectra of the ZnO films have a strong angle-dependent spectral feature resulting from the preferred c-axis orientation. The wurtzite structure of the ZnO films was explicitly shown by the XRD and EXAFS analysis. The carrier concentration, Hall mobility and resistivity of the 800 Å-thick ZnO film were 1.84 × 10¹⁹ cm^− 3, 24.62 cm²V^− 1s^− 1, and 1.38 × 10^− 2 Ω cm, respectively.     

Nitrogen-doped p-type ZnO thin films and ZnO/ZnSe p-n heterojunctions grown on ZnSe substrate by radical beam gettering epitaxy

We investigate the p-type doping in ZnO prepared by the method of radical beam gettering epitaxy using NO gas as the oxygen source and nitrogen dopant. Secondary ion mass spectroscopy measurements demonstrate that N is incorporated into ZnO film in concentration of about 8 × 10¹⁸ cm^− 3. The hole concentration of the N-doped p-type ZnO films was between 1.4 × 10¹⁷ and 7.2 × 10¹⁷ cm^− 3, and the hole mobility was 0.9-1.2 cm²/Vs as demonstrated by Hall effect measurements. The emission peak of 3.312 eV is observed in the photoluminescence spectra at 4.2  of N-doped p-type ZnO films, probably neutral acceptor bound. The activation energy of the nitrogen acceptor was obtained by temperature-dependent Hall-effect measurement and equals about 145 meV. The p-n heterojunctions ZnO/ZnSe were grown on n-type ZnSe substrate and have a turn-on voltage of about 3.5 V.     

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.     

Deposition and characterization of c-axis oriented aluminum nitride films by radio frequency magnetron sputtering without external substrate heating

Aluminum nitride (AlN) films were deposited on a variety of substrates (glass, Si, oxidized Si, Al-SiO₂-Si, Cr-SiO₂-Si, and Au-Cr-SiO₂-Si) by radio frequency (RF) magnetron sputtering using an AlN target. The films were deposited without external substrate heating. The effect of RF power, ambient gas (Ar and Ar-N₂) and sputtering pressure on deposition rate and crystallinity were investigated. The structure and morphology of the films were studied by X-ray diffraction, scanning electron microscopy and atomic force microscopy techniques. These investigations revealed that the AlN films prepared in mixed gas ambient (Ar-N₂) were highly c-axis oriented with moderate surface roughness on all the substrate. A strong IR absorption band was observed around 670 cm^− 1 which confirms the presence of Al-N bond in the film. The dc resistivity of the films was measured to be in the range of 10¹¹ to 10¹² Ω-cm at moderate electric fields. The application of these films in piezoelectric based micro-electro-mechanical systems is discussed.     

Large-sized-mismatched group-V element doped ZnO films fabricated on silicon substrates by pulsed laser deposition

Pulsed laser deposition has been utilized to synthesize impurity-doped ZnO thin films on silicon substrate. Large-sized-mismatched group-V elements (A^V) including P, As, Sb and Bi were used as dopants. Hall effect measurements show that hole concentration in the order of 10¹⁶-10¹⁸ cm⁻³, resistivity in the range of 10-100 Ω cm, Hall mobility in the range of 10-100 cm²/Vs were obtained only for ZnO:As and ZnO:Bi thin films. X-ray diffraction measurements reveal that the films possess polycrystallinity or nanocrystallinity with ZnO (002) preferred orientation. Guided by X-ray photoemission spectroscopy analyses and theoretical calculations for large-sized-mismatched group-V dopant in ZnO, the A_Zn^V-2V_Zn complexes are believed to be the most possible acceptors in the p-type A^V-doped ZnO thin films.     

Synthesis of boron-doped diamond films by DC plasma CVD using a CH4+CO2+H2 gas mixture at lower substrate temperature and formation of an n-Si/p-diamond heterojunction

Diamond films were synthesized by direct current plasma chemical vapour deposition using a CH₄+CO₂+H₂ gas mixture on Si substrates. The optimum deposition conditions were determined. It was found that 0.4 A/cm² current density, at applied voltage of 1 kV, resulted in good-quality diamond films. The substrate temperature was 750 K which is considerably lower than the conventional requirement of ∼1100 K. Boron doping was achieved by passing a portion of the gas mixture through boric acid dissolved in methanol. The boron-doped p-type diamond films were deposited on an n-type single crystalline Si substrate and an n-Si/p-diamond heterojunction was fabricated. The p-n junction was characterized in terms of current-voltage (I-V) and capacitance-voltage (C-V) measurements.     

Effect of annealing temperature on structural, electrical and optical properties of B-N codoped ZnO thin films

The B-N codoped p-type ZnO thin films have been prepared by radio frequency magnetron sputtering using a mixture of nitrogen and oxygen as sputtering gas. The effect of annealing temperature on the structural, electrical and optical properties of B-N codoped films was investigated by using X-ray diffraction, Hall-effect, photoluminescence and optical transmission measurements. Results indicated that the electrical properties of the films were extremely sensitive to the annealing temperature and the conduction type could be changed dramatically from n-type to p-type, and finally changed to weak p-type in a range from 600 °C to 800 °C. The B-N codoped p-type ZnO film with good structural, electrical and optical properties can be obtained at an intermediate annealing temperature region (e.g., 650 °C). The codoped p-type ZnO had the lowest resistivity of 2.3 Ω cm, Hall mobility of 11 cm²/Vs and carrier concentration of 1.2 × 10¹⁷ cm^− 3.     

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 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.     

Study on Raman line at 1080.2 cm in ZnO thin films prepared under high RF power

ZnO thin films were prepared on glass or on homo-buffer/glass by a RF magnetron sputtering method at RF power of 100-550 W. The structural and Raman characteristics of the films were analyzed by X-ray diffraction and Raman scattering. There appeared a sharp peak of 1080.2 cm⁻¹ near the A₁(2LO) mode (1156 cm⁻¹) of ZnO in the Raman spectra when the RF power was higher than 300 W. In this case, the (100) peak of ZnO film appeared obviously. It was speculated that the Raman mode at 1080.2 cm⁻¹ was induced by the ordered distribution of Zn_i defects in ZnO lattice.     

Oxidation of nanostructured Ti films produced by low energy cluster beam deposition: An X-ray Photoelectron Spectroscopy characterization

We used in-situ X-ray Photoelectron Spectroscopy (XPS) to study the oxidation process of a cluster-assembled metallic titanium film exposed to molecular oxygen at room temperature. The nanostructured film has been grown on a Si(111) substrate, in ultra high vacuum conditions, by coupling a supersonic cluster beam deposition system with an XPS experimental chamber. Our results show that upon in-situ oxygen exposure Ti^3 + is the first oxidation state observed, followed by Ti^4 +, whereas Ti^2 + is practically absent during the whole process. Our results compare well with the existing literature on Ti films produced using other techniques.     

Reactive magnetron sputtering from a composite target for large area BaPbO3 thin film electrode

Radio frequency reactive magnetron sputtering from a composite target made of PbO pellets uniformly positioned on a metallic Ba disc has been utilized for BaPbO₃ electrode deposition on 150 mm Si wafers. The reactive sputtering process has been analyzed in relation to sputtering parameters for composite targets with different percentage of PbO coverage. The process optimization method for in situ crystallized BaPbO₃ thin film fabrication has been emphasized. The growth of BaPbO₃ films has been discussed from the viewpoint of the BaO-PbO phase diagram and thermodynamics of Ba_n + 1Pb_nO_3n + 1 (n = 1, 2, ∞) phase formation. The microstructure analysis of the deposited films has been performed with atomic force microscopy and wide-angle X-ray diffraction (XRD) techniques. The grazing angle XRD measurements reveal the formation of a Ba₂PbO₄ phase in the film fabricated at 450 °C. The Ba₂PbO₄ phase content decreases with decreasing substrate temperature. The BaPbO₃ film deposited at a substrate temperature of 430 °C on naturally oxidized (001) Si wafers shows an electrical resistivity of 1.13 mΩ·cm. The BaPbO₃ films deposited on SiO₂ (native oxide)/Si wafer do not exhibit a preferred orientation whereas use of (111) Pt/SiO₂/Si substrate results in highly (111)-oriented films.