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.     

Improvement of electrical and optical properties of Ga and N co-doped p-type ZnO thin films with thermal treatment

Ga and N co-doped p-type ZnO thin films were epitaxially grown on sapphire substrate using magnetron sputtering technique. The process of synthesized Ga and N co-doped ZnO films was performed in ambient gas of N₂O. Hall measurement shows a significant improvement of p-type characteristics with rapid thermal annealing (RTA) process in N₂ gas flow, where more N acceptors are activated. The film rapid thermal annealed at 900 °C in N₂ ambient revealed the highest carrier concentration of 9.36 × 10¹⁹ cm⁻³ and lowest resistivity of 1.39 × 10⁻¹ Ω cm. In room and low temperature photoluminescence measurements of the as grown and RTA treated film, donor acceptor pair emission and exciton bound to acceptor recombination at 3.25 and 3.357 eV, respectively, were observed.     

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.     

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.     

Nitrogen-doped ZnO prepared by capillaritron reactive ion beam sputtering deposition

Nitrogen-doped ZnO thin films have been prepared by reactive ion beam sputtering deposition utilizing a capillaritron ion source. X-ray diffraction (XRD) analysis of the as-deposited film exhibits a single strong ZnO (002) diffraction peak centred at 34.40°. Post-growth annealing causes increase of grain size and decrease of c-axis lattice constant. Micro-Raman spectroscopy analysis of the as-deposited film shows strong nitrogen-related local vibration mode at 275, 582, 640 and 720 cm⁻¹, whereas the E₂ mode of ZnO at 436 cm⁻¹ can barely be identified. Annealing at 500-800 °C causes decrease of 275, 582, 640 and 720 cm⁻¹ and increase of 436 cm⁻¹ intensity, indicating out-diffusion of nitrogen and improvement of ZnO crystalline quality. Unlike un-doped ZnO, the surface roughness of nitrogen-doped ZnO deteriorates after annealing, which is also attributed to the out-diffusion of nitrogen. A nitrogen concentration of ∼10²¹/cm³ was observed while type conversion from n-type to p-type was not achieved, which is likely due to the formation of Zn_I-N_O or (N₂)_O that act as donor/double donors.     

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.     

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.     

Induction of p-type conduction in sputtered deposited Al-N codoped ZnO thin films

Al and N codoped ZnO thin films were grown on n-Si (100) substrate by sputtering technique. Hall effect measurements of as-grown films exhibited n-type conduction, however 500 °C Ar annealed codoped films showed p-type conductivity with a hole concentration of 9.9 × 10¹⁶ cm^− 3, resistivity of 15.95 Ω-cm and hole mobility of 3.95 cm²/Vs, respectively. Codoped ZnO thin films were found to be highly c-axis oriented with good crystal quality. A neutral acceptor-bound exciton and donor-acceptor-pair emissions that appeared at room temperature photoluminescence measurement verify p-type conduction in Al and N codoped ZnO film. The current-voltage characteristics of p-n heterojunction evidently showed a diode like rectifying behaviour.     

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

p-Type ZnO thin films have been realized via doping Li as acceptor by using pulsed laser deposition. In our experiment, Li₂CO₃ was used as Li precursor, and the growth temperature was varied from 400 to 600 °C in pure O₂ ambient. The Li-doped ZnO film prepared at 450 °C possessed the lowest resistivity of 34 Ω cm with a Hall mobility of 0.134 cm² V⁻¹ s⁻¹ and hole concentration of 1.37 × 10¹⁸ cm⁻³. X-ray diffraction (XRD) measurements showed that the Li-doped ZnO films grown at different substrate temperatures were of completely (0 0 2)-preferred orientation.     

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.     

Optical and electrical properties of p-type ZnO fabricated by NH3 plasma post-treated ZnO thin films

In this paper, a simple method is reported to obtain nitrogen-doped p-ZnO film. In this method NH₃ plasma, generated in a plasma-enhanced chemical vapor deposition system, was employed to treat ZnO thin film. By Hall-effect measurement, a p-type conductivity was observed for the treated film with the hole density of 2.2 × 10¹⁶ cm⁻³. X-ray photoelectron spectroscopy (XPS) results confirmed that nitrogen was incorporated into ZnO film during the treatment process to occupy the oxygen positions. In low temperature photoluminescence spectra, an emission peak corresponding to acceptor-donor pair was observed. From this emission peak we calculated the N-related acceptor binding energy to be 130 meV.     

Room-temperature ferromagnetism in N+-implanted ZnO:Mn thin films

Mn–N co-doped ZnO films with wurtzite structure were fabricated by RF magnetron sputtering together with the ion-implantation technique. Then a post-annealing at 650 °C for 10 min in a N₂ atmosphere was performed to activate the implanted N⁺ ions and recover the crystal quality, and a p-type ZnO:Mn–N film with a hole concentration of about 2.1×10¹⁶ cm^?3 was obtained. It is found that the Mn mono-doped ZnO film only exhibits paramagnetic behavior, while after N⁺-implantation, it shows ferromagnetism at 300 K, and the magnetization of the ZnO:Mn–N films can be further enhanced by thermal annealing due to the activation of the N acceptors. Our experimental results confirm that the codoping N acceptors are favorable for ferromagnetic ordering of Mn²⁺ ions in ZnO, which is consistent with the recent theoretical calculations.     

As-doped p-type ZnO films grown on SiO2/Si by radio frequency magnetron sputtering

p-Type ZnO:As films with a hole concentration of 10¹⁶-10¹⁷ cm⁻³ and a mobility of 1.32-6.08 cm²/V s have been deposited on SiO₂/Si substrates by magnetron sputtering. XRD, SEM, Hall measurements are used to investigate the structural and electrical properties of the films. A p-n homojunction comprising an undoped ZnO layer and a ZnO:As layer exhibits a typical rectifying behavior. Our study demonstrates a simple method to fabricate reproducible p-type ZnO film on the SiO₂/Si substrate for the development of ZnO-based optoelectronic devices on Si-based substrates.     

p-type conduction in ZnO dual-acceptor-doped with nitrogen and phosphorus

A dual-acceptor doping method was proposed to produce p-type conduction in ZnO. Both nitrogen and phosphorus were used as the p-type doping agents. ZnO:(N, P) films were prepared by spray pyrolysis. The p-type conduction was achieved by thermal annealing at appropriate temperatures (500-700 ^°C) for 20 min in O₂ ambient. The lowest resistivity of , with a hole concentration and Hall mobility of 5.3×10¹⁷ cm⁻³ and 0.94 cm² V ⁻¹ s⁻¹, respectively, was obtained at an optimal annealing temperature of 600 ^°C. The p-type behavior was reproducible and stable. The introduction of nitrogen and phosphorus in ZnO were identified by secondary ion mass spectroscopy.     

Preparation and characteristics of transparent p-type ZnO film by Al and N co-doping method

Al-N co-doped ZnO films were fabricated by gaseous ammonia annealing at various temperatures. The structure and the electrical properties of Al-N-doped ZnO films strongly depend on the annealing temperature. XRD and SEM analysis indicate that the ZnO films possess a good crystallinity with c-axis orientation, uniform thickness and dense surface. Optical transmission spectra show a high transmittance (∼85%) in the visible region. Hall measurement demonstrates that ZnO films have p-type conduction with high carrier concentration of 8.3 × 10¹⁸ cm⁻³ and low resistivity of 25.0 Ω cm when the annealing temperature is 700 °C. Also the growth process of Al-N co-doped at various temperatures is discussed in detail.     

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.     

Ag-N doped ZnO film and its p-n junction fabricated by ion beam assisted deposition

Ag-N doped ZnO film was synthesized by ion beam assisted deposition and its electrical properties and annealing property were investigated. The films remained p-type even after annealing at 400 °C in air for 10 min. While the annealing temperature went up to 500 °C, the conduction type of these films shifted from p-type to n-type. The p-type ZnO film revealed low resistivity (0.0016 Ω cm), low Hall mobility (0.65 cm² V⁻¹ s⁻¹) and high carrier concentration (5.8 × 10²⁰ cm⁻³). ZnO p-n homojunction consisting of a p-type layer (Ag-N doped ZnO film) and an n-type layer (In-doped ZnO film) had been fabricated by ion beam assisted deposition. With electrical measurement, its current-voltage curve had a typical rectifying characteristic with current rectification ratio of 25 at bias ±5 V and a reverse current of 0.01 mA at −5 V. The depletion width was estimated 3.8 nm by using p-n junction equation.     

Ultraviolet electroluminescence from ZnO-based light-emitting diode with p-ZnO:N/n-GaN:Si heterojunction structure

A p-ZnO:N/n-GaN:Si structure heterojunction light-emitting diode (LED) is fabricated on c-plane sapphire by full metal organic chemical vapor deposition (MOCVD) technique. The p-type layer with hole concentration of 8.94×10¹⁶ cm⁻³ is composed of nitrogen-doped ZnO using NH₃ as the doping source with subsequent annealing in N₂O plasma ambient. Silicon-doped GaN film with electron concentration of 1.15×10¹⁸ cm⁻³ is used as the n-type layer. Desirable rectifying behavior is observed from the current-voltage (I-V) curve of the device. The forward turn on voltage is about 4 V and the reverse breakdown voltage is more than 7 V. A distinct ultraviolet (UV) electroluminescence (EL) with a dominant emission peak centered at 390 nm is detected at room temperature from the heterojunction structure under forward bias conditions. The origins of the EL emissions are discussed in comparison with the photoluminescence (PL) spectra.     

N离子注入富氧ZnO薄膜的p型导电及拉曼特性研究

采用射频磁控溅射法在富氧环境下制备ZnO薄膜, 继而结合N离子注入及热退火实现薄膜的N掺杂及p 型转变, 借助霍尔测试和拉曼光谱研究了N离子注入富氧ZnO薄膜的p型导电及拉曼特性. 结果表明, 在 600 ℃温度下退火120 min可获得性能较优的p-ZnO: N薄膜, 其空穴浓度约为2.527×10¹⁷ cm^-3. N离子注入ZnO引入了三个附加拉曼振动模, 分别位于274.2, 506.7和640.4 cm^-1. 结合电学及拉曼光谱的分析发现, 退火过程中施主缺陷与N受主之间的相互作用对p-ZnO的形成产生重要影响.     

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.