Structural and electrical properties of nitrogen and aluminum codoped p-type ZnO films

To resolve the problem of p-type doping in ZnO, nitrogen and aluminum (N-Al) codoped ZnO films were prepared by the ultrasonic spray pyrolysis (USP) technique. The structural and electrical properties of N-Al codoped ZnO films were investigated. The results demonstrate that the undoped ZnO films exhibit the preferential orientation of (002) plane, while ZnO films show high orientation of (101) plane after codoping with N and Al. The N-Al codoped ZnO films under optimum conditions show p-type conduction, with a low resistivity of 1.7×10⁻²Ω cm, carrier concentration of 5.09×10¹⁸ cm⁻³ and high Hall mobility of 73.6 cm² V⁻¹ s⁻¹. A conversion from p-type conduction to n-type was observed during the increase of measurement temperature.     

Fabrication of high hole-carrier density p-type ZnO thin films by N-Al co-doping

In order to obtain p-type ZnO thin films, effect of atomic ratio of Zn:N:Al on the electronic and structural characteristic of ZnO thin films was investigated. Hall measurement indicated that with the increase of Al doping, conductive type of as-grown ZnO thin films changed from n-type to p-type and then to n-type again, reasons are discussed in details. Results of X-ray diffraction revealed that co-doped ZnO thin films have similar crystallization characteristic (0 0 2 preferential orientation) like that of un-doping. However, SEM measurement indicated that co-doped ZnO thin films have different surface morphology compared with un-doped ZnO thin films. p-type ZnO thin films with high hole concentration were obtained on glass (4.6 × 10¹⁸ cm⁻³) and n-type silicon (7.51 × 10¹⁹ cm⁻³), respectively.     

Fabrication and characterization of magnetron sputtered arsenic doped p-type ZnO epitaxial thin films

Arsenic doped p-type ZnO thin films were grown on sapphire substrate by magnetron sputtering. As grown films reveal p-type conduction confirmed by Hall-effect and photoluminescence measurements. The p-type film with a hole concentration of 2.16× 10¹⁷ cm⁻³, mobility of 1.30 cm²/V.s and resistivity of 22.29 Ω-m were obtained at substrate temperature of 700 °C. ZnO homojunction synthesized by in-situ deposition of As doped p-ZnO layer on Al doped n-ZnO layer showed p-n diode like characteristics. X-ray pole figure and Transmission Electron Microscope studies confirm epitaxial nature of the films. Photoluminescence results exhibit the peaks associated with donor acceptor pair emission.     

Investigation of p-type behavior in Ag-doped ZnO thin films by E-beam evaporation

Ag-doped ZnO (ZnO:Ag) thin films were grown on glass substrates by E-beam evaporation technique. The structural, electrical and optical properties of the films were investigated as a function of annealing temperature. The films were subjected to post annealing at different temperatures in the range of 350-650 °C in an air ambient. All the as grown and annealed films at temperature of 350 °C showed p-type conduction. The films lost p-type conduction after post annealing treatment temperature of above 350 °C, suggesting a narrow post annealing temperature window for the fabrication of p-type ZnO:Ag films. ZnO:Ag film annealed at 350 °C revealed lowest resistivity of 7.25 × 10⁻² Ω cm with hole concentration and mobility of 5.09 × 10¹⁹ cm⁻³ and 1.69 cm²/V s, respectively. Observation of a free-to-neutral-acceptor (e,A^o) and donor-acceptor-pair (DAP) emissions in the low temperature photoluminescence measurement confirms p-type conduction in the ZnO:Ag films.     

p-Type conduction in phosphorus-doped ZnO thin films by MOCVD and thermal activation of the dopant

Phosphorus-doped p-type ZnO thin films have been realized by metalorganic chemical vapor deposition (MOCVD). The conduction type of ZnO films is greatly dependent on the growth temperature. ZnO films have the lowest resistivity of 11.3 Ωcm and the highest hole concentration of 8.84 × 10¹⁸ cm⁻³ at 420 °C. When the growth temperature is higher than 440 °C, p-type ZnO films cannot be achieved. All the films exhibited p-type conduction after annealing, and the electrical properties were improved comparing with the as-grown samples. Secondary ion mass spectroscopy (SIMS) test proved that phosphorus (P) has been incorporated into ZnO.     

Synthesis and characterization of Al-N codoped p-type ZnO epitaxial films using high-temperature homo-buffer layer

Al-N codoped p-type ZnO thin films have been prepared by DC magnetron reactive sputtering reproducibly using a high-temperature (HT) homo-buffer layer. The influence of HT buffer layer deposition time (T_ht) on film properties was investigated by X-ray diffraction (XRD), scanning electron micro-spectra (SEM) and Hall measurement. The Al-N codoped ZnO film was improved evidently in its crystal quality by varying the value of T_ht. Results of Hall effect showed that all of the Al-N codoped ZnO thin films were p-type conduction and had resistivity mainly below 50 Ω cm. The optimum deposition time of HT buffer layer is around 3 min from the comprehensive consideration of structural, electrical, and optical properties. The obtained ZnO thin film can meet the need of application in optoelectronic devices based on ZnO.     

Effects of annealing ambience on ZnO:N films grown by MOCVD and the p-type doping mechanism of ZnO:N films investigated by XANES

ZnO:N thin films were deposited on sapphire substrate by metal organic chemical vapor deposition with NH₃ as N-doping sources. The reproducible p-type ZnO:N film with hole concentration of ∼10¹⁷ cm⁻³ was successfully achieved by subsequent in situ thermal annealing in N₂O plasma protective ambient, while only weak p-type ZnO:N film with remarkably lower hole concentration of ∼10¹⁵ cm⁻³ was obtained by annealing in O₂ ambient. To understand the mechanism of the p-type doping behavior of ZnO:N film, X-ray photoelectron spectroscopy (XPS) and soft X-ray absorption near-edge spectroscopy (XANES) measurements have been applied to investigate the local electronic structure and chemical states of nitrogen atoms in ZnO:N films.     

Influence of Al concentration on electrical, structural and optical properties of Al-As codoped p-ZnO thin films

We report the influence of Al concentration on electrical, structural, optical and morphological properties of Al-As codoped p-ZnO thin films using RF magnetron sputtering. Al-As codoped p-ZnO films with different Al concentrations were fabricated using As back diffusion from the GaAs substrate and sputtering Al₂O₃ mixed ZnO targets (1, 2 and 4 at%). The grown films were investigated by Hall effect measurement, X-ray diffraction (XRD), electron probe microanalysis (EPMA), energy dispersive spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS), photoluminescence (PL) and atomic force microscopy (AFM) to study the electrical, structural, optical and morphological properties of the films. From the XRD, it was observed that both full-width at half-maximum (FWHM) and c-axis lattice constant have similar trends with respect to Al concentration. Hall measurements showed that the hole concentration increases as the Al concentration increases from 10¹⁵ to 10²⁰ cm⁻³. The increase in hole concentration upon codoping was supported by the red shift in the near-band-edge (NBE) emission observed from room temperature PL spectra. The proposed p-type mechanism due to As_Zn-2V_Zn complex was confirmed by low temperature PL and XPS analysis. The low FWHM, resistivity and peak-to-valley roughness observed by XRD, Hall measurement and AFM, respectively, suggest that 1 at% Al-doped ZnO:As film is the best codoped film.     

Realization of p-ZnO thin films by GaP codoping

An attempt has been made to realize p-ZnO by directly doping (codoping) GaP into ZnO thin films. GaP codoped ZnO thin films of different concentrations (1, 2 and 4 mol%) have been grown by RF magnetron sputtering. The grown films on sapphire substrate have been characterized by X-ray diffraction (XRD), Hall measurement, Photoluminescence (PL) and Energy dispersive spectroscopy (EDS) to validate the p-type conduction. XRD result shows that all the films have been preferentially oriented along (0 0 2) orientation. The decrease of full-width at half maximum (FWHM) with increase in GaP doping depicts the decrease in native donor defects. Hall measurement shows that among the three films, 2 and 4 mol% GaP doped ZnO shows p-conductivity due to the sufficient amount of phosphorous incorporation. It has been found that low resistivity (2.17 Ωcm) and high hole concentration (1.8×10¹⁸ cm⁻³) for 2% GaP codoped ZnO films due to best codoping. The red shift in near-band-edge (NBE) emission and donar-acceptor-pair (DAP) and neutral acceptor bound recombination (A°X) observed by room temperature and low temperature (10 K) PL, respectively, well acknowledged the formation of p-ZnO. The incorporated phosphorous in the film has been also confirmed by EDS analysis.     

Effects of growth temperature on Li-N dual-doped p-type ZnO thin films prepared by pulsed laser deposition

Li-N dual-doped p-type ZnO (ZnO:(Li,N)) thin films have been prepared by pulsed laser deposition. The introduction of Li and N was confirmed by secondary ion mass spectrometry measurements. The structural, electrical, and optical properties as a function of growth temperature were investigated in detail. The lowest room-temperature resistivity of 3.99 Ω cm was achieved at the optimal temperature of 450 °C, with a Hall mobility of 0.17 cm²/V s and hole concentration of 9.12 × 10¹⁸ cm⁻³. The ZnO:(Li,N) films exhibited good crystal quality with a complete c-axis orientation, a high transmittance (about 90%) in the visible region, and a predominant UV emission at room temperature. The two-layer-structure p-ZnO:(Li,N)/n-ZnO homojunctions were fabricated on a sapphire substrate. The current-voltage characteristics exhibited the rectifying behavior of a typical p-n junction.     

Formation of Al-N co-doped p-ZnO/n-Si (1 0 0) heterojunction structure by RF co-sputtering technique

Al-N co-doped ZnO (ZnO:Al-N) thin films were grown on n-Si (1 0 0) substrate by RF co-sputtering technique. As-grown ZnO:Al-N film exhibited n-type conductivity whereas on annealing in Ar ambient the conduction of ZnO:Al-N film changes to p-type, typically at 600 °C the high hole concentration of ZnO:Al-N co-doped film was found to be 2.86 × 10¹⁹ cm⁻³ and a low resistivity of 1.85 × 10⁻² Ω-cm. The current-voltage characteristics of the obtained p-ZnO:Al-N/n-Si heterojunction showed good diode like rectifying behavior. Room temperature photoluminescence spectra of annealed co-doped films revealed a dominant peak at 3.24 eV.     

Structural, optical and electrical properties of Al-N codoped ZnO films by RF-assisted MOCVD method

N-doped ZnO films were produced using N₂ as N source by metal-organic chemical vapor deposition (MOCVD) system which has been improved with radio-frequency (RF)-assisted equipments. The data of secondary ion mass spectroscopy (SIMS) indicate that the concentration of N in N-doped ZnO films is around 5 × 10²⁰ cm⁻³, implying that sufficient incorporation of N into ZnO can be obtained by RF-assisted equipment. On this basis, the structural, optical and electrical properties of Al-N codoped ZnO films were studied. Then, the effect of RF power on crystal quality, surface morphologies, optical properties was analyzed using X-ray diffraction, atomic force microscopy and photo-luminescence methods. The results illustrate that the RF plasma is the key factor for the improvement of crystal quality. Then the observation of A⁰X recombination associated with N_O acceptor in low-temperature PL spectrum proved that some N atoms have occupied the positions of O atoms in ZnO films. Hall measurements shown that p-type ZnO film deposited on quartz glasses was obtained when RF power was 150 W for the Al-N codoped ZnO films, while the resistivity of N-doped ZnO films was rather high. Compared with the Al-doped ZnO film, the obviously increased resistivity of codoped films indicates that the formation of N_O acceptors compensate some donors in ZnO films effectively.     

Post-annealing influence on properties of N-In codoped ZnO thin films prepared by ion beam enhanced deposition method

N-In codoped ZnO thin films were prepared by ion beam enhanced deposition method (IBED) and were annealed in nitrogen and oxygen ambient after deposition. The influence of post-annealing on structure, electrical and optical properties of thin films were investigated. As-deposited and all post-annealed samples showed preferential orientation along (0 0 2) plane. Electrical property studies indicated that the as-deposited ZnO film showed p-type with a sheet resistance of 67.5 kΩ. For ZnO films annealed in nitrogen with the annealing temperature increasing from 400 to 800 °C, the conduction type of the ZnO film changed from p-type to n-type. However, for samples annealed in oxygen the resistance increased sharply even at a low annealing temperature of 400 °C and the conduction type did not change. Room temperature PL spectra of samples annealed in N₂ and in O₂ showed UV peak located at 381 and 356 nm, respectively.     

Preparation of p-type ZnO:(Al, N) by a combination of sol--gel and ion-implantation techniques

We report the preparation of p-type ZnO thin films on (0001) sapphire substrates by a combination of sol--gel and ion-implantation techniques. The results of the Hall-effect measurements carried out at room temperature indicate that the N-implanted ZnO:Al films annealed at 600\du\ have converted to p-type conduction with a hole concentration of $1.6\times10¹⁸cm^-3, a hole mobility of 3.67cm²/V.s and a minimum resistivity of 4.80cm.\Omega$. Ion-beam induced damage recovery has been investigated by x-ray diffraction (XRD), photoluminescence (PL) and optical transmittance measurements. Results show that diffraction peaks and PL intensities are decreased by N ion implantation, but they nearly recover after annealing at 600\du. Our results demonstrate a promising approach to fabricate p-type ZnO at a low cost.     

Effect of growth time on the structure, Raman shift and photoluminescence of Al and Sb codoped ZnO nanorod ordered array thin films

Al and Sb codoped ZnO nanorod ordered array thin films have been deposited on glass substrate with a ZnO seed layer by hydrothermal method at different growth time. The effect of growth time on structure, Raman shift, and photoluminescence (PL) was studied. The thin films at growth time of 5 h consist of nanorods growth vertically oriented with ZnO seed layer, and the nanorods with an average diameter of 27.8 nm and a length of 1.02 μm consist of single crystalline wurtzite ZnO crystal and grow along [0 0 1] direction. Raman scattering analysis demonstrates that the thin films at the growth time of 5 h have great Raman shift of 15 cm⁻¹ to lower wavenumber and have low asymmetrical factor Г_a/Г_b of 1.17. Room temperature photoluminescence reveals that there is more donor-related PL in films with growth time of 5 h.     

Deposition and properties of B-N codoped p-type ZnO thin films by RF magnetron sputtering

B-N codoped p-type ZnO thin films have been realized by radio frequency (rf) magnetron sputtering using a mixture of argon and oxygen as sputtering gas. Types of conduction and electrical properties in codoped ZnO films were found to be dependent on oxygen partial pressure ratios in the sputtering gas mixture. When oxygen partial pressure ratio was 70%, the codoped ZnO film showed p-type conduction and had the best electrical properties. Additionally, the p-ZnO/n-Si heterojunction showed a clear p-n diode characteristic. XRD results indicate that the B-N codoped ZnO film prepared in 70% oxygen partial pressure ratio has high crystal quality with (0 0 2) preferential orientation. Meanwhile, the B-N codoped ZnO film has high optical quality and displays the stronger near band edge (NBE) emission in the temperature-dependent photoluminescence spectrum, the acceptor energy level was estimated to be located at 125 meV above the valence band.     

Fabrication of Sb-doped p-type ZnO thin films by pulsed laser deposition

p-Type ZnO thin films have been realized via monodoping antimony (Sb) acceptor by using pulsed laser deposition. The obtained films with the best electrical properties show a hole concentration in the order of 10¹⁸ cm⁻³ and resistivity in the range of 2-4 Ω cm. X-ray diffraction measurements revealed that all the films possessed a good crystallinity with (0 0 2)-preferred orientation. Guided by X-ray photoemission spectroscopy analysis and a model for large-sized-mismatched group-V dopant in ZnO, an Sb_Zn-2V_Zn complex is believed to be the most possible acceptor in the Sb-doped p-type ZnO thin films.     

Formation of p-type ZnMgO thin films by In-N codoping method

In-N codoped ZnMgO films have been prepared on glass substrates by direct current reactive magnetron sputtering. The p-type conduction could be obtained in ZnMgO films by adjusting the N₂O partial pressures. The lowest resistivity was found to be 4.6 Ω cm for the p-type ZnMgO film deposited under an optimized N₂O partial pressure of 2.3 mTorr, with a Hall mobility of 1.4 cm²/V s and a hole concentration of 9.6 × 10¹⁷ cm⁻³ at room temperature. The films were of good crystal quality with a high c-axis orientation of wurtzite ZnO structure. The presence of In-N bonds was identified by X-ray photoelectron spectroscopy, which may enhance the nitrogen incorporation and respond for the realization of good p-type behavior in In-N codoped ZnMgO films. Furthermore, the ZnMgO-based p-n homojunction was fabricated by deposition of an In-doped n-type ZnMgO layer on an In-N codoped p-type ZnMgO layer. The p-n homostructural diode exhibits electrical rectification behavior of a typical p-n junction.     

Rapid thermal annealing effects on the structural and optical properties of Na–N codoped ZnO films

Polycrystalline ZnO thin films codoped with Na and N were obtained by chemical bath deposition. The structural characteristic and the optical properties of the rapid thermal annealed ZnO:(Na,N) films were investigated by X-ray diffraction, scanning electron microscopy, energy dispersive spectrometer (EDS), Raman spectrum and room-temperature photoluminescence. After RTA treatment, the XRD spectra showed a continuous decrease of the full- width at half-maximum (FWHM) of the (0 0 2) diffraction peak of the ZnO:(Na,N) film. The Raman spectra revealed that the intensity of the mode around 582 cm⁻¹ increased with the increase of the RTA temperature. The PL spectra showed different trends in the UV luminescence of ZnO:(Na,N) films after RTA treatments.     

Determination of electrical types in the P-doped ZnO thin films by the control of ambient gas flow

Phosphorus (P)-doped ZnO thin films with amphoteric doping behavior were grown on c-sapphire substrates by radio frequency magnetron sputtering with various argon/oxygen gas ratios. Control of the electrical types in the P-doped ZnO films was achieved by varying the gas ratio without post-annealing. The P-doped ZnO films grown at a argon/oxygen ratio of 3/1 showed p-type conductivity with a hole concentration and hole mobility of 1.5 × 10¹⁷ cm⁻³ and 2.5 cm²/V s, respectively. X-ray diffraction showed that the ZnO (0 0 0 2) peak shifted to lower angle due to the positioning of P³⁻ ions with a larger ionic radius in the O²⁻ sites. This indicates that a p-type mechanism was due to the substitutional P_O. The low-temperature photoluminescence of the p-type ZnO films showed p-type related neutral acceptor-bound exciton emission. The p-ZnO/n-Si heterojunction light emitting diode showed typical rectification behavior, which confirmed the p-type characteristics of the ZnO films in the as-deposited status, despite the deep-level related electroluminescence emission.