MOCVD法生长Ga、P掺杂的ZnO薄膜

采用金属有机化学气相沉积法在蓝宝石衬底上制备Ga、P掺杂的ZnO薄膜,分别采用X射线衍射、扫描电子显微镜、霍尔效应测试、光致发光谱对样品进行表征。通过Ga、P掺杂分别得到n、p型ZnO薄膜,n型ZnO薄膜的载流子浓度可以达到1×1019cm-3,p型ZnO薄膜的载流子浓度达到1.66×1016cm-3。所制备的ZnO薄膜具有c轴择优生长取向,并且p型ZnO薄膜具有较好的光致发光特性。     

Effect of substrates on the properties of p-type ZnO films

Influence of substrates on the properties of p-type ZnO films, which were fabricated by N–Al co-doping technique, was studied. Hall measurement results indicated that ZnO films deposited on common glass substrate were p-type conductivity when Zn:N:Al atomic ratio amounts to 1:3:0.1. However, ZnO films deposited on corning 7059 glass substrate showed n-type conductivity. Secondary ion mass spectroscopy demonstrated that Na content incorporated into ZnO films deposited on common glass substrate was more evident than that of corning 7059 glass. In addition, Hall mobility and conductivity of p-type ZnO thin films deposited on silicon substrate were improved largely.     

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.     

硼对氮掺杂的p型ZnO薄膜的影响

利用分子束外延设备在蓝宝石衬底上生长了B/N共掺的p型ZnO薄膜,对比了B/N共掺和N单掺杂样品的物理学性能。通过X射线光电子能谱测试证明了在薄膜中存在有B和B-N键。B/N共掺样品的空穴浓度比单一N掺杂样品高近两个量级。且ZnO：（B,N）薄膜在两年多的时间内一直显示稳定的p型电导。这是由于B-N键的存在提高了N在ZnO薄膜中的固溶度,且B-N键之间强的键能和B占据Zn位所表现的弱施主特性不会带来强的施主补偿效应,说明B是N掺杂ZnO薄膜的一种良好的共掺元素。     

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.     

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.     

Shape alterations of ZnO nanocrystal arrays fabricated from NH3·H2O solutions

Well-aligned crystalline ZnO nanorod arrays were synthesized via an aqueous solution route with ammonia and zinc nitrate as inorganic precursors. ZnO crystalline seed films were firstly coated on ITO substrates for epitaxial growth of rods through sol-gel processing and heat treatment. SEM, TEM, SAED and XRD were utilized to characterize morphologies and structures of ZnO crystals. Heterogeneous nucleation is crucial for rod growth. A broad scope of pH favorable for heterogeneous nucleation was disclosed at zinc concentration from 0.04 to 0.1 M in the inorganic system due to the complex reaction of ammonia with Zn²⁺. Elevation of initial zinc concentration or pH promoted growth rate of rods and enlarged rod size. ZnO nanorods were transformed to nanotubes, nanosheets and rods with blanket-like shaped surface mainly by secondary pH adjustment. All ZnO nanocrystals are wurtzite structure preferentially oriented in c-axis direction.     

The microstructures and the electrical and optical properties of ZnO:N films prepared by thermal oxidation of Zn3N2 precursor

Samples of p-type ZnO:N films were prepared on glass substrates by thermal oxidation of Zn₃N₂ precursor, which was produced by reactive magnetron sputtering with a metallic zinc target in Ar/N₂ working gas. The microstructures and the electrical and optical properties of the samples were systematically investigated as a function of the annealing temperature. The results indicate that the annealing temperature has strong effects on the conductivity and photoluminescence (PL) properties of the obtained ZnO:N films. With an annealing temperature of 500 ^°C in oxygen flux, ZnO:N samples show the best p-type characteristics. The doping mechanism and the doping efficiency are briefly discussed based on the experimental results.     

Characterization and ammonia sensing properties of pure and?modified ZnO films

Zinc oxide (ZnO) films have been prepared by thermal oxidation of pre-deposited zinc films on the glass substrate kept at room temperature. These films were surface modified by dipping them into an aqueous solution (0.1 M) of lithium chloride (LiCl) and aluminium chloride (AlCl₃) followed by firing at 500°C. Based on X-ray diffraction results it is observed that modification of pure ZnO by lithium and aluminium precursor results a change in the lattice parameters. Li and Al ions appear to enhance the a-axis orientation and c-axis orientation of pure ZnO films, respectively. Field emission scanning electron micrographs of lithium-modified ZnO film indicate the presence of nanoneedles, while nanorods are observed in case of aluminium-modified ZnO film. The electrical resistance measurements of modified ZnO films also show variation in resistance as compared to pure ZnO film. Pure and Al-modified films of ZnO are sensitive to ammonia at room temperature, while Al-modified ZnO film is found to be more sensitive with 99% of response at 250 ppm.     

通过交替生长气氛调控N掺杂ZnO薄膜电学特性

使用分子束外延方法在c面蓝宝石衬底上生长了系列氮掺杂ZnO薄膜样品。在连续的富锌气氛环境中生长的样品,由于存在大量的施主缺陷,呈现n型电导。为了抑制施主缺陷带来的补偿效应,在生长过程中,通过周期性补充氧气,形成周期性的富氧气氛,缓解了氮掺杂浓度和施主缺陷浓度之间的矛盾。光致发光测量表明,通过交替生长气氛,氧空位和锌间隙等缺陷在薄膜中得到了显著抑制。通过交替生长气氛生长的外延薄膜的结晶质量也有所提高。样品显示出重复性较高的p型电导,载流子浓度可达到10¹⁶ cm^-3。周期性补氧调节生长气氛的生长方式是一种有效实现p型掺杂ZnO的方法。     

Identification of Acceptor States in Li-N Dual-Doped p-Type ZnO Thin Films

Li-N dual-doped p-type ZnO （ZnO：（Li, N）） thin films are prepared by pulsed laser deposition. The optical properties are studied using temperature-dependent photoluminescence. The Lizn-No complex acceptor with an energy 1evel of 138 me V is identified from the free-to-neutral-acceptor （e, A0 ） emission. The Haynes factor is about 0.087 for the Lizn-No complex acceptor, with the acceptor bound-exciton binding energy of 12meV. Another deeper acceptor state located at 248 meV, also identified from the （e, A0） emission, is attributed to zinc vacancy acceptor. The two acceptor states might both contribute to the observed p-type conductivity in ZnO：（Li,N）.     

p型ZnO薄膜的制备及特性

采用射频磁控溅射在Si片上制备ZnO薄膜，通过离子注入对样品进行N掺杂，在不同温度下进行退火并实现了p型转变.用扫描电子显微镜、X射线衍射和Hall测量对薄膜进行了表征，结果表明薄膜具有良好的表面形貌和高度c轴择优取向，退火后p型ZnO薄膜的最高载流子浓度和最低电阻率分别为1.68×10¹⁶cm^-3和41.5Ω·cm.讨论并分析了退火温度和时间对ZnO薄膜p型转变的影响.     

Growth of Al–N codoped p-type ZnMgO thin films on different substrates

Al–N codoped p-type ZnMgO thin films were prepared on three different substrates, namely glass, quartz, and silicon. Significant differences in the crystallinity, surface morphology, and electrical properties on these substrates were investigated by means of x-ray diffraction, field-emission scanning electron microscopy, and Hall-effect measurements. It is demonstrated that the Al donor enhances the incorporation of the N acceptor, resulting in better p-type conductivity. The incorporation of the N acceptor, as well as the Al and Mg, was confirmed x-ray photoelectron spectroscopy. Transmittance and photoluminescence spectra suggested a wider bandgap for the ZnMgO thin films in comparison with ZnO, which is believed to be the result of the incorporation of Mg.     

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.     

Conversion of p-type to n-type conductivity in undoped ZnO films by increasing operating temperature

ZnO thin films with the thickness of about 15 nm on (0 0 0 1) sapphire substrates were prepared by pulsed laser deposition. X-ray photoelectron spectroscopy indicated that both as-grown and post-annealed ZnO thin films were oxygen-rich. H₂ sensing measurements of the films indicated that the conductivity type of both the unannealed and annealed ZnO films converted from p-type to n-type in process of increasing the operating temperature. However, the two films showed different conversion temperatures. The origin of the p-type conductivity in the unannealed and annealed ZnO films should be attributed to oxygen related defects and zinc vacancies related defects, respectively. The conversion of the conductivity type was due to the annealing out of the correlated defects. Moreover, p-type ZnO films can work at lower temperature than n-type ZnO films without obvious sensitivity loss.     

Zn空位对Al-P共掺杂ZnO电子结构影响的第一性原理计算

采用第一性原理平面波赝势法计算ZnO（Al,P）体系的晶格参数和电子结构,重点分析Zn空位对体系晶体结构、形成能、态密度的影响.计算结果表明：Al和P共掺杂过程中,Al_Zn-P_Zn有更低的形成能,能带分析呈现n型.并随着Zn空位浓度的增大使得掺杂后的晶胞体积减小,晶格常数c先增大后减小.存在Zn空位的掺杂体系形成能比Al_Zn-P_O掺杂体系低,体系较稳定.能带分析呈现p型趋势.Al和P以1∶2的比例掺杂时,体系的形成能降低,体系更稳定;同时,比较1个V_Zn和2个V_Zn的Al_Zn-P_Zn共掺杂体系的能带结构发现,随着Zn空位浓度增大,带隙增大,体系p型化特征增强.Al_Zn-2P_Zn共掺杂体系带隙减小为0.56 eV,更有利于提高其导电性质.然而出现2V_Zn后,带隙增大为0.73 eV,小于本征ZnO带隙,p型化程度更强烈;此外态密度分析表明2V_Zn的Al_Zn-2P_Zn共掺杂使得态密度更加分散,更多的电子穿过费米能级使得p型化更明显.因此,将Al/P按1∶2的比例共掺且Zn空位增至2个时,可以获得导电性能更好的p型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.     

籽晶层对喷雾热分解法生长ZnO薄膜结晶质量和光电性能的影响

通过脉冲激光沉积(PLD)方法在Si(100)衬底上沉积一层高质量的ZnO籽晶层,在籽晶层上进一步采用超声喷雾热分解(USP)法生长ZnO薄膜,研究了籽晶层对ZnO薄膜结晶质量和ZnO/Si异质结光电特性的影响。研究结果表明,在籽晶层的诱导作用下,USP法生长ZnO薄膜由多取向结构变为(002)单一取向,结晶性能得到了显著改善;籽晶层上生长的薄膜呈现出垂直于衬底生长的柱状晶结构,微观结构更加致密。通过研究紫外光照前后ZnO/Si异质结的整流特性,发现引入籽晶层后,反向偏压下异质结的光电响应显著增加,并且在开路状态下出现明显的光伏效应。     

Al纳米颗粒表面等离激元对ZnO光致发光增强的研究

基于聚苯乙烯球自组装法,在P型氮化镓(P-GaN)衬底上制备了有序致密的掩模板;采用热蒸发法在该模板上沉积金属Al薄膜,通过甲苯溶液去除聚苯乙烯球,得到了金属Al纳米颗粒阵列;采用原子层沉积法,在Al纳米颗粒阵列表面依次沉积氧化铝(Al_2O_3)和氧化锌(ZnO).通过测试Al纳米颗粒阵列的消光谱以及ZnO薄膜的光致发光谱,研究了Al纳米颗粒表面等离激元与ZnO薄膜激子之间的耦合效应.实验结果表明:引入Al纳米颗粒后,在约380 nm位置附近的ZnO近带边发光峰积分强度增强了1.91倍.对Al纳米颗粒表面等离激元增强ZnO光致发光的机理进行探讨.     

氮等离子体辅助脉冲激光沉积生长p型ZnO:N薄膜的光学和电学性质

通过氮气等离子体辅助脉冲激光沉积(PLD)技术制备了氮掺杂氧化锌(ZnO:N)薄膜.经过低温快速热退火(RTA)处理后,ZnO:N薄膜呈现p型导电特性.利用X射线光电子能谱(XPS)、光致发光(PL)和霍尔测量对ZnO:N薄膜中N的化学状态及其光学和电学性质进行了系列的研究.结果表明:所制得的p型ZnO:N薄膜为高度补...