Growth of p-type ZnO thin films by using an atomic layer epitaxy technique and NH3 as a doping source

Nitrogen-doped, p-type ZnO thin films have been grown successfully on sapphire (0001) substrates by atomic layer epitaxy (ALE) using Zn(C₂H₅)₂ [Diethylzinc, DEZn], H₂O and NH₃ as a zinc precursor, an oxidant and a doping source gas, respectively. The lowest electrical resistivity of the p-type ZnO films grown by ALE was 210 Ω cm with a hole concentration of 3.41 × 10¹⁶ cm^− 3. Low temperature-photoluminescence analysis results support that the nitrogen ZnO after annealing is a p-type semiconductor. Also a model for change from n-type ZnO to p-type ZnO by annealing is proposed.     

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.     

Electrical and optical properties of P-doped ZnO thin films by annealing temperatures in Nitrogen ambient

The effects of post-annealing temperature on the optical and electrical properties of P-doped ZnO thin films, grown on sapphire substrate, have been investigated when the annealing is performed under nitrogen ambient. Analysis of the XRD shows that regardless of the post-annealing temperature, the P-doped ZnO thin films have grown the (002) peak. The full width of half maximum decreases from 0.194 to 0.181° as the annealing temperature increases from 700 to 900 °C. This phenomenon means that the increase of annealing temperature causes enhancement of the thin film’s crystalline properties. The results of Hall effect measurements indicate that the P-doped ZnO thin films, annealed at 750 and 800 °C exhibit p-type behavior, with hole concentrations of 5.71 × 10¹⁷ cm⁻³ and 1.20 × 10¹⁸ cm⁻³, and hole mobilities of 0.12 cm²/Vs and 0.08 cm²/Vs, respectively. The low-temperature (10 K) photoluminescence results reveal that the peaks related to the neutral-acceptor exciton (A⁰X) at 3.355 eV, free electrons to neutral acceptor (FA) at 3.305 eV and donor acceptor pair (DAP) at 3.260 and 3.170 eV are observed in the films showing p-type behavior with the acceptors. Because P atoms replace O atoms to produce acceptors from P-doped ZnO thin films by the thermal activation process at the appropriate annealing temperature with nitrogen ambient, the p-type ZnO thin films can be fabricated in this way.     

Deposition of Na–N dual acceptor doped p-type ZnO thin films and fabrication of p-ZnO:(Na,N)/n-ZnO:Eu homojunction

Sodium and nitrogen dual acceptor doped p-type ZnO (ZnO:(Na, N)) films have been prepared by spray pyrolysis technique at a substrate temperature of 623 K. The ZnO:(Na, N) films are grown at a fixed N doping concentration of 2 at.% and varying the nominal Na doping concentration from 0 to 8 at.%. The XRD results show that all the ZnO:(Na, N) films exhibited (0 0 2) preferential orientation. The EDX and elemental mapping analysis shows the presence and distribution of Zn, O, Na and N in the deposited films. The Hall measurement results demonstrate that the Na–N dual acceptor doped ZnO films show excellent p-type conduction. The p-type ZnO:(Na, N) films with comparatively low resistivity of 5.60 × 10⁻² Ω cm and relatively high carrier concentration of 3.15 × 10¹⁸ cm⁻³ are obtained at 6 at.%. ZnO based homojunction is fabricated by depositing n-type layer (Eu doped ZnO) grown over the p-type layer ZnO:(Na, N). The current–voltage (I–V) characteristics measured from the two-layer structure show typical rectifying characteristics of p-n junction with a low turn on voltage of about 1.69 V. The ZnO:(Na, N) films exhibit a high transmittance (about >90%) and the average reflectance is 8.9% in the visible region. PL measurement shows near-band-edge (NBE) emission and deep-level (DL) emission in the ZnO:(Na, N) thin films.     

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.     

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.     

Study on the Hall-effect and photoluminescence of N-doped p-type ZnO thin films

N-doped, p-type ZnO thin films have been grown by plasma-assisted metal-organic chemical vapor deposition method. The results under optimized growth conditions included a resistivity of 1.72 Ω cm, a Hall mobility of 1.59 cm²/V s, and a hole concentration of 2.29 × 10¹⁸ cm^− 3, and were consistently reproducible. A N-related free-to-neutral-acceptor emission and an associated phonon replica were evident in room temperature photoluminescence spectra, from which the N acceptor energy level in ZnO was estimated to be 180 meV above the valence band maximum.     

Dependence of photoluminescence and electrical properties with rapid thermal annealing in nitrogen-implanted ZnO films

Undoped (as-grown) ZnO films grown by pulsed laser deposition on Al₂O₃ (0001) substrates were doped with nitrogen by means of an ion implantation process. Post-implantation annealing behavior in the temperature range between 500 and 700 °C has been studied by photoluminescence and Hall effect measurements. The implanted films show no peak other than the excitonic recombination emission in the as-implanted state, however, after rapid thermal annealing at 700 °C they reveal a nitrogen acceptor related emission at 3.273 eV. The as-implanted ZnO films show more electron concentrations than the as-grown, unimplanted ZnO film. In contrast, after annealing, the electron concentration in the implanted films is significantly reduced, indicating that the incorporated nitrogen becomes activated after the thermal annealing, then produces holes and eventually compensates for certain amount of electrons. The results imply that a proper nitrogen implantation and subsequent annealing may be a way to produce p-type ZnO films.     

Realization of phosphorus-doped p-type ZnO thin films via diffusion and thermal activation

ZnO thin films were initially deposited on a heavily phosphorus-doped Si (n⁺-Si) substrate by radio frequency magnetron sputtering. The transition from n-type ZnO to p-type one was realized by phosphorus diffusing from Si substrate to ZnO film and being thermally activated during post annealing. Crystal structures of the ZnO films were confirmed to be highly c-axis oriented wurtzite structure by X-ray diffraction experiment. Photoluminescence spectra of the ZnO films showed strong ultraviolet emissions originated from the recombination of the band-edge excitons. The composition of the films was measured by X-ray photoelectron spectroscopy, and a typical concentration of phosphorus was about 0.48% corresponding to the order of atomic density of 10¹⁹/cm³. The hole concentration of the film was + 1.28 × 10¹⁹/cm³ measured by Hall effect apparatus. Formation of the p-type ZnO films can be further confirmed by the rectifying I-V curves of p-ZnO/n⁺-Si heterojunctions.     

P-type conductivity in doped and codoped ZnO thin films synthesized by RF magnetron sputtering

N-doped and Al–N codoped ZnO thin films with different volume ratios of N₂ reactive gas were deposited on plane glass substrates using the radio frequency magnetron sputtering method. The phase transition temperature and absorption edge of the ZnO powder were studied by differential scanning calorimetry at different heating rates and with Fourier transform infrared spectroscopy, respectively. The target used for the sputtering was synthesized using a palletize machine. It was sintered at 450 °C for 5 h. The X-ray diffraction results confirm that the thin films have wurtzite hexagonal structures with a very small distortion. The results indicate that the ZnO thin films have obviously enhanced transmittance of up to 80% on an average in the visible region. The Al–N codoped ZnO thin films exhibited the best p-type conductivity with a resistivity of 0.825 Ω-cm, a hole concentration of 6.55 × 10¹⁹ cm^?3, and a Hall mobility of 1.25 cm²/Vs. The p-type conductivity was observed after doping and codoping of the ZnO thin film.     

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.     

Investigation of thin solid ZnO films prepared by sputtering

Zinc oxide (ZnO) thin films have attracted great attention in recent years due to their unique piezoelectric and piezooptic properties, making them suitable for various microelectronics and optoelectronics applications, such as surface acoustic wave devices, optical fibers, solar cells etc. ZnO is a semiconductor with a band gap of 3.3 eV and a large exciton binding energy of 60 meV. Undoped ZnO exhibits intrinsic n-type conductivity and it enables achieving high electron concentration. However, it may be doped to obtain low resistivity p-type thin films. Among group V of the periodic table, nitrogen is used as a popular p-type dopant due to its small atomic size. However, it is difficult to achieve p-type conduction in ZnO films due to the low solubility of nitrogen and its high intensity in self compensating process upon doping.Sputtering techniques enable us to form dense and homogeneous films due to the relatively high energy of the sputtered atoms. Thus we can grow high quality ZnO films with c-axis orientation, low growth temperature, high deposition rate, large area deposition, and availability in various growths ambient. In this work, the zinc oxide films were prepared using various DC sputtering methods in an atmosphere of pure argon and an atmosphere of mixed argon with nitrogen. Optical and electrical properties of the films were investigated.     

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.     

P-type ZnO thin film deposited by spray pyrolysis technique: The effect of solution concentration

The aim of this research is to study the role of concentration variations on precursor solution of nitrogen doped ZnO (ZnO:N) thin films which has been prepared by spray pyrolysis technique. SEM micrographs show that ZnO:N films in 0.1 ML concentration have a mono-disperse surface with nano-spheres of 50 nm in diameter. In higher molarities the nano-spheres agglomerate leading to particle formation. For 0.4 ML concentrations this change is observed, where plume like particles are seen over the surface of ZnO:N thin film. This change corresponds also to changes observed in the XRD spectra, where crystal orientation of ZnO:N thin films changes from (002) to (100). All of the ZnO:N thin films have kept their sharp ultra violet absorption edge, but the transparency in visible spectra region decreases as the molarities in precursor solution increase. Photoluminescence spectra at room temperature revealed emissions at 2.33 eV, 2.54 eV and 3.16 eV that can be attributed to the presence of nitrogen in ZnO structure. We also observe that all samples analyzed show a p-type Hall effect behavior, and that as the molarities in the precursor solution increase, the electrical resistivity of the films decreases, due to an enhancement of free carriers, while the mobility decreases. These data prove the capability of spray pyrolysis as a viable technique in preparing p-type TCO materials and so, fully transparent CMOS-like devices.     

Metal organic chemical vapor deposition and investigation of ZnO thin films grown on sapphire

A new type of large area metal organic chemical vapor deposition (MOCVD) system for the growth of high quality and large size ZnO materials is introduced. Materials properties of the un-doped, n- and p-doped ZnO epi-films grown on sapphire substrates by this MOCVD system are studied by various techniques, including high resolution X-ray diffraction (XRD), UV-Visible optical transmission (OT), photoluminescence (PL) and photoluminescence excitation (PLE), synchrotron radiation X-ray photoelectron spectroscopy (SR-XPS). The wurtzite (w) ZnO crystal structures grown with primary (0002) orientation were identified. Results have shown the high crystalline quality of MOCVD-grown ZnO films, indicated by the narrow XRD, PL and Raman line widths, strong PL signals, sharp OT edge and smooth surface. In particular, high p-type carrier concentration of > 10¹⁷ cm^− 3 have been achieved besides the good n-type doping in ZnO.     

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.     

Effect of Ga Doping Concentration on Electrical and Optical Properties of Nano-ZnO:Ga Transparent Conductive Films

Transparent conductive nano ZnO thin films with different Ga doping concentrations (1, 3, 5, 7 at.%) were prepared on glass substrate by RF magnetron sputtering. The influence of Ga doping concentration on the structural, electrical and optical properties of ZnO:Ga films was investigated by XRD, SEM, Hall measurement and optical-transmission spectroscopy. It shows that the nano ZnO:Ga films are dense and flat, and have polycrystalline structure with preferential (002) and weak (101) orientation. The grain sizes, carrier concentration and Hall mobility changes non-linearly with the increase of Ga-content. The lowest resistivity of 1.44×10⁻³ Ωcm appears at 3 at.% Ga doping concentration. The average transmittance of the films is about 80∼90% in the visible range. The optical band gap obtained for these films is larger than for pure ZnO (∼3.37 eV).     

Structure and optical properties of ZnO:V thin films with different doping concentrations

A series of ZnO thin films doped with various vanadium concentrations were prepared on glass substrates by direct current reactive magnetron sputtering. The results of the X-ray diffraction (XRD) show that the films with doping concentration less than 10 at.% have a wurtzite structure and grow mainly along the c-axis orientation. The residual stress, estimated by fitting the XRD diffraction peaks, increases with the doping concentration and the grain size also has been calculated from the XRD results, decreases with increasing the doping concentration. The surface morphology of the ZnO:V thin films was examined by SEM. The optical constants (refractive index and extinction coefficient) and the film thickness have been obtained by fitting the transmittance. The optical band gap changed from 3.12 eV to 3.60 eV as doping concentration increased from 1.8 at.% to 13 at.% mol. All the results have been discussed in relation with doping concentration.     

Properties of epitaxial ZnO:P films

Epitaxial ZnO:P films have been produced by annealing ZnP₂ substrates in atomic oxygen and characterized by X-ray diffraction, atomic force microscopy, Hall effect measurements, X-ray photoelectron spectroscopy, and photoluminescence measurements. The X-ray diffraction patterns of the films showed the 002 peak, indicating that their c axis was normal to the substrate surface. According to the Hall effect data, the layers were p-type, with a resistivity of ～20 Ω cm, hole mobility of ～9 cm²/(V s), and hole concentration of ～7.8 × 10¹⁷ cm^?3. The photoluminescence spectra of the ZnO:P films showed a peak at 3.356 eV (neutral acceptor bound exciton). Our results indicate that the ZnO:P films contain the P_Zn-2V_Zn defect complex as a shallow acceptor responsible for their p-type conductivity.     

Evidence of p-doping in ZnO films deposited on GaAs

Successful p-type ZnO thin films have been reported by depositing it on semi insulating GaAs substrates by Pulsed Laser Deposition (PLD) technique. The PLD samples were subsequently subjected to Rapid Thermal Annealing to achieve the required doped ZnO. X-ray Diffraction, Atomic Force Microscopy and Van der Pauw Hall measurements were performed on the annealed samples and compared with as-deposited ones. The XRD results confirm growth of <002> ZnO along with better crystallinity for the annealed sample. The AFM results reveal that the thin films deposited were highly uniform having very low roughness values. Van der Pauw Hall measurements show a transition from n-type conductivity for as-deposited sample to p-type for annealed samples. The hole concentration and Hall mobility measured were reported to be as high as 4.475 × 10²⁰ cm^− 3 and 39.73 cm²/V-sec respectively. These are probably the highest reported values to date and are encouraging from the point of successful fabrication of efficient ZnO-based optoelectronics devices like LED, laser, photodiodes, etc. in the near future.