SiC/AlN上外延GaN薄膜的黄带发光与晶体缺陷的关系

利用室温光致发光(PL)技术研究了在6HSiC(0001)上用金属有机物化学汽相沉积(MOCVD)外延生长的GaN薄膜“黄带”发光(YL)特点,与扫描电子显微镜(SEM)、X射线衍射(XRD)技术得到的GaN薄膜的表面形貌质量和内部结晶质量的结果相对照,表明“YL”发光强度与GaN薄膜的扩展缺陷多少直接相对应通过二次离子质谱(SIMS)技术获取的GaN薄膜中Ga元素深度分布揭示出镓空位(V_Ga)最可能是“YL”发光的微观来源分析认为,虽然宏观扩展缺陷(丝状缺陷、螺形位错等)和微观点缺陷V_Ga及其与杂质的络合物(complexes)都表现出与“YL”发射密切相关,但V_Ga及其与杂质的络合物更可能是“YL”发射的根本微观来源室温下获得的样品“YL”发射强度和光谱精细结构可用于分析GaN薄膜缺陷和晶体质量.     

First principle study of the influence of vacancy defects on optical properties of GaN

We employ plane-wave with ultrasoft pseudopotential method to calculate and compare the total density of states and partial density of states of bulk-phase GaN,Ga0.9375 N,and GaN0.9375 systems based on the first-principle density-functional theory(DFT).For Ga and N vacancies,the electronic structures of their neighbor and next-neighbor atoms change partially.The Ga0.9375 N system has n-type semiconductor conductive properties,whereas the GaN0.9375 system has p-type semiconductor conductive properties.By studying the optical properties,the influence of Ga and N vacancy defects on the optical properties of GaN has been shown as mainly in the low-energy area and very weak in high-energy area.The dielectric peak influenced by vacancy defects expands to the visible light area,which greatly increases the electronic transition in visible light area.     

Atomic structure of defects in GaN:Mg grown with Ga polarity

The atomic structure of characteristic defects (Mg-rich hexagonal pyramids and truncated pyramids) in GaN:Mg thin films grown with Ga polarity was determined at atomic resolution by reconstruction of the scattered electron wave in a transmission electron microscope. Small cavities within the defects have inside walls covered by GaN of reverse polarity. We propose that lateral overgrowth of the cavities restores matrix polarity on the defect base. From matrix to defect, exchange of Ga and N sublattices leads to a 0.6+/-0.2 A displacement of Ga sublattices. We observe a [1100]/3 shift from matrix AB stacking to BC stacking for the entire pyramid. Electron energy loss spectroscopy detected changes in N edge and presence of oxygen on the defect walls. Our results explain commonly observed decrease of acceptor concentration in heavily doped GaN:Mg.     

GaN中与C和O有关的杂质能级第一性原理计算

用局域密度泛函线性丸盒轨道大型超原胞方法(32个原子),对纯纤锌矿结构的GaN用调节计算参数(如原子球与“空球”的占空比)在自洽条件下使Eg的计算值(323eV)接近实验值(35eV).然后以原子替代方式自洽计算杂质能级在Eg中的相对位置.模拟计算了六角结构GaN中自然缺陷以及与C和O有关的杂质能级位置,包括其复合物.计算结果表明,单个缺陷如镓空位VGa、氮空位VN、氧代替氮ON、炭代替氮CN、炭代替镓CGa等与已有的计算结果基本一致.计算结果表明杂质复合物会导致单个杂质能级位置的相对变化.计算了CNON,CGaCN,CNOV和CGaVGa,其中CNON分别具有深受主与浅施主的特征,是导致GaN黄光的一种可能的结构. 关键词： GaN 杂质能级 电子结构     

Ga vacancy induced ferromagnetism enhancement and electronic structures of RE-doped GaN

Because of their possible applications in spintronic and optoelectronic devices, GaN dilute magnetic semiconductors (DMSs) doped by rare-earth (RE) elements have attracted much attention since the high Curie temperature was obtained in RE-doped GaN DMSs and a colossal magnetic moment was observed in the Gd-doped GaN thin film. We have systemically studied the GaN DMSs doped by RE elements (La, Ce–Yb) using the full-potential linearized augmented plane wave method within the framework of density functional theory and adding the considerations of the electronic correlation and the spin-orbital coupling effects. We have studied the electronic structures of DMSs, especially for the contribution from f electrons. The origin of magnetism, magnetic interaction and the possible mechanism of the colossal magnetic moment were explored. We found that, for materials containing f electrons, electronic correlation was usually strong and the spin–orbital coupling was sometimes crucial in determining the magnetic ground state. It was found that GaN doped by La was non-magnetic. GaN doped by Ce, Nd, Pm, Eu, Gd, Tb and Tm are stabilized at antiferromagnetic phase, while GaN doped by other RE elements show strong ferromagnetism which is suitable materials for spintronic devices. Moreover, we have identified that the observed large enhancement of magnetic moment in GaN is mainly caused by Ga vacancies (3.0μB per Ga vacancy), instead of the spin polarization by magnetic ions or originating from N vacancies. Various defects, such as substitutional Mg for Ga, O for N under the RE doping were found to bring a reduction of ferromagnetism. In addition, intermediate bands were observed in some systems of GaN:RE and GaN with intrinsic defects, which possibly opens the potential application of RE-doped semiconductors in the third generation high efficiency photovoltaic devices.     

Role of defect sites and Ga polarization in the magnetism of Mn-doped GaN

We report a study of the Mn local structure, magnetism, and Ga moments in molecular beam epitaxy grown Mn-doped GaN films. Using x-ray absorption spectroscopy and magnetic circular dichroism, we find two distinct Mn sites and a Ga moment antiparallel to Mn. First-principles calculations reproduce this phenomenology and indicate that Mn preferentially populates Ga sites neighboring N split interstitial defects. These results show that defects may strongly affect the Mn ordering and magnetism, and that the GaN valence band is polarized, providing a long-range ferromagnetic ordering mechanism for Ga1-xMnxN.     

GaAs(111)衬底上生长的GaN的极性与生长方法和生长条件的关系

研究了在GaAs(111)衬底上生长的六角相GaN的极性的相关关系.在高Ⅴ/Ⅲ比的条件下用MOVPE和MOMBE方法生长的GaN的极性和GaAs衬底的极性一致;在(111)A-Ga表面上的生长层呈现Ga的极性,而在(111)B-As表面上的生长层呈现N的极性.然而,在低的Ⅴ/Ⅲ比,或采用一个AIN中间层的条件下,用HVPE和MOMBE方法在GaAs(111)B表面上生长的GaN呈现出Ga的极性.目前,其原因尚不清楚,但是这些结果表明采用HVPE生长方法或用一高温AlN阻挡层可以得到高质量的GaN.     

Growth behavior of GaN film along non-polar [1 1 -2 0] directions

We studied the atomic assembly mechanisms of non-polar GaN films by the molecular dynamics method as a function of the N:Ga flux ratio at a fixed adatom energy on non-polar planes. Our study revealed that high quality crystal growth occurred only when off-lattice atoms (which are usually associated with amorphous embryos or defect complexes) formed during deposition were able to move to unoccupied lattice sites by thermally activated diffusion processes, which attests to the experimental difficulties in obtaining smooth surfaces due to dense stacking faults lying in non-polar GaN. Furthermore, surface structures on different planes played an important role. We further suggested favorable conditions for growing high quality GaN films and nano-structures along non-polar directions.     

Electronic Structures of Wurtzite GaN with Ga and N Vacancies

The electronic band structures of wurtzite GaN with Ga and N vacancy defects are investigated by means of the first-principles total energy calculations in the neutral charge state. Our results show that the band structures can be significantly modified by the Ga and N vacancies in the GaN samples. Generally, the width of the valence band is reduced and the band gap is enlarged. The defect-induced bands can be introduced in the band gap of GMV due to the Ga and N vacancies. Moreover, the GaN with high density of N vacancies becomes an indirect gap semiconductor. Three defect bands due to Ga vacancy defects are created within the band gap and near the top of the valence band. In contrast, the N vacancies introduce four defect bands within the band gap. One is in the vicinity of the top of the valence band, and the others are near the bottom of the conduction band. The physical origin of the defect bands and modification of the band structures due to the Ga and N vacancies are analysed in depth.     

Performance improvement of InGaN/GaN multiple quantum well visible-light photodiodes by optimizing TEGa flow

The performance of an InGaN/GaN multiple quantum well(MQW) based visible-light Schottky photodiode(PD)is improved by optimizing the source flow of TEGa during In Ga N QW growth. The samples with five-pair InGaN/GaN MQWs are grown on sapphire substrates by metal organic chemical vapor deposition. From the fabricated Schottky-barrier PDs, it is found that the smaller the TEGa flow, the lower the reverse-bias leakage is. The photocurrent can also be enhanced by depositing the In GaN QWs with using lower TEGa flow. A high responsivity of 1.94 A/W is obtained at 470 nm and -3-V bias in the PD grown with optimized TEGa flow. Analysis results show that the lower TEGa flow used for depositing In Ga N may lead to superior crystalline quality with improved InGaN/GaN interface, and less structural defects related non-radiative recombination centers formed in the MQWs.     

Ga空位对GaN:Gd体系磁性影响的第一性原理研究

采用基于密度泛函理论的第一性原理结合投影缀加平面波的方法,研究了GaN中Ga被稀土元素Gd替代以及与邻近N或Ga空位组成的缺陷复合体的晶格常数、磁矩、形成能以及电子结构等性质.结果发现,Gd掺杂GaN后禁带宽度变窄,由直接带隙半导体转为间接带隙半导体;单个Gd原子掺杂给体系引入大约7μB的磁矩;在Gd与Ga或N空位形成的缺陷复合体系中,N空位对引入磁矩贡献很小,大约0.1μB,Ga空位能引入约2μB的磁矩.随着Ga空位的增多,体系总磁矩增加,但增加量与Ga空位的位置分布密切相关.当Ga空位分布较为稀疏时,Gd单原子磁矩受影响较小,但当Ga空位距离较近且倾向于形成团簇时,Gd单原子磁矩明显增加,而且这种情况下空位形成能也最小.     

Effect of Ⅲ/Ⅴ Ratio of HT-AIN Buffer Layer on Polarity Selection and Electrical Quality of GaN Films Grown by Radio Frequency Molecular Beam Epitaxy

We investigate the effect of A/N ratio of the high temperature （HT） AIN buffer layer on polarity selection and electrical quality of GaN films grown by radio frequency molecular beam epitaxy. The results show that low Al/N ratio results in N-polarity GaN films and intermediate Al/N ratio leads to mixed-polarity GaN films with poor electrical quality. GaN films tend to grow with Ga polarity on Al-rich AIN buffer layers. GaN films with different polarities are confirmed by in-situ reflection high-energy electron diffraction during the growth process. Wet chemical etching, together with atomic force microscopy, also proves the polarity assignments. The optimum value for room-temperature Hall mobility of the Ga-polarity GaN film is 703cm^2/V.s, which is superior to the N-polarity and mixed-polarity GaN films.     

MFM and Raman studies in PEMBE-grown (Ga,Mn)N thin films showing room-temperature ferromagnetism

We present the room-temperature ferromagnetism in the (Ga,Mn)N films grown on n-type GaN templates by plasma-enhanced molecular beam epitaxy for semiconductor spintronic device applications. Despite of the possible interface effects between the (Ga,Mn)N layers and n-type GaN templates, the (Ga,Mn)N films were found to exhibit the ferromagnetic ordering above room temperature. The magnetic force microscopy identified the magnetic domains with the different magnetic orientations at room temperature, indicating the existence of the ferromagnetic long-range ordering. In Raman spectra, an additional peak at 578 cm⁻¹ was observed, which is attributed to the local vibration of substitutional Mn in the (Ga,Mn)N lattice. Therefore, it is believed that the ferromagnetic ordering in (Ga,Mn)N is due to the carrier-mediated Ruderman-Kittle-Kasuya-Yosida interaction.     

Hybrid density functional study of optically active Er3+ centers in GaN

Understanding the luminescence of GaN doped with erbium (Er) requires a detailed knowledge of the interaction between the rare‐earth dopant and the nitride host, including intrinsic defects and other impurities that may be present in the host material. We address this problem through a first‐principles hybrid density functional study of the structure, energetics, and transition levels of the Er impurity and its complexes with N and Ga vacancies, substitutional C and O impurities, and H interstitials in wurtzite GaN. We find that, in the interior of the material, Er_Ga is the dominant Er³⁺ center with a formation energy of 1.55 eV, Er_Ga–V_N possesses a deep donor level at 0.61 eV which can assist in the transfer of energy to the 4f ‐electron core. Multiple optically active Er³⁺ centers are possible in Er‐doped GaN. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Shallow versus deep nature of Mg acceptors in nitride semiconductors

We investigate the properties of Mg acceptors in nitride semiconductors with hybrid functional calculations. We find that although the thermodynamic transition level is relatively close to the valence band in GaN (260 meV), Mg(Ga) exhibits key features of a deep acceptor: the hole is localized on a N atom neighboring the Mg impurity, inducing a large local lattice distortion and giving rise to broad blue luminescence. We show that the ultraviolet photoluminescence peak attributed to Mg acceptors in GaN is likely related to Mg-H complexes, explaining the results of photoluminescence and electron paramagnetic resonance experiments. Predictions for Mg acceptors in AlN and InN are also presented.     

Effect of N isotopic mass on the photoluminescence and cathodoluminescence spectra of gallium nitride

GaN is a wurtzite-type semiconductor at ambient conditions whose natural composition consists of almost pure ¹⁴N (99.63% ¹⁴N and 0.37% ¹⁵N) and a mixture of 60.1% ⁶⁹Ga, and 39.9% ⁷¹Ga. We report a low-temperature photoluminescence and cathodoluminescence study of GaN thin films made from natural Ga and N, and from natural Ga and isotopically pure ¹⁵N. The contribution of the nitrogen vibrations to the bandgap renormalization by electron-phonon interaction has been estimated from the nitrogen isotopic mass coefficient of the bound exciton energy. The temperature dependence of the bandgap of GaN can be explained with the measured isotopic mass coefficients of Ga and N. We have estimated the aluminum and indium contribution to the bandgap renormalization in AlN and InN from the temperature dependence of the AlN and InN bandgap up to 300 K, assuming that the N contribution is similar to that found in GaN. The similar bandgap isotopic mass coefficients of C, N, and O, of Al, Si and P, of Zn, Ga and Ge, and of Cd and In suggests that elements of the same row of the periodic table have similar bandgap isotopic mass coefficients.Received: 5 December 2004, Published online: 20 July 2004PACS: 71.20.Nr Semiconductor compounds     

等离子增强原子层沉积低温生长GaN薄膜

采用等离子增强原子层沉积技术在低温下于单晶硅衬底上成功生长了Ga N多晶薄膜,利用椭圆偏振仪、低角度掠入射X射线衍射仪、X射线光电子能谱仪对薄膜样品的生长速率、晶体结构及薄膜成分进行了表征和分析.结果表明,等离子增强原子层沉积技术生长Ga N的温度窗口为210—270?C,薄膜在较高生长温度下呈多晶态,在较低温度下呈非晶态;薄膜中N元素与大部分Ga元素结合成N—Ga键生成Ga N,有少量的Ga元素以Ga—O键存在,多晶Ga N薄膜含有少量非晶态Ga_2O_3.     

CVD法制备硅基氮化镓薄膜

利用化学气相沉积法(CVD),分别以三氧化二镓(Ga₂O₃)和氨气(NH₃)为镓源和氮源在硅衬底合成了一种由片状微晶构成的氮化镓(GaN)薄膜,实验中没有使用缓冲层。通过场发射扫描电子显微镜(FESEM)、电子能量散射谱(EDS)、X射线衍射(XRD)、高分辨电镜(HRTEM)和光致发光谱(PL)对样品进行分析,生成物为质量较好的富镓的纯氮化镓薄膜。片状氮化镓微晶表面大小约数百纳米,厚度数十纳米,薄膜表面平整、致密,没有裂纹或龟裂现象,与Si衬底结合紧密。氮化镓薄膜的带边峰位于367nm处,同时出现了黄光发射峰。并对此种氮化镓薄膜的生长机理进行了探讨。     

Intrinsic magnetism induced by vacancy in GaN

We performed total energy electronic-structure calculations based on DFT that clarify the intrinsic magnetism of undoped GaN. The magnetism is due to Ga, instead of N, vacancies. The origin of magnetism arises from the unpaired 2p electrons of N surrounding Ga vacancy. At a vacancy concentration of 5.6%, the ferromagnetic state is 181 meV lower than the antiferromagnetic state. Our findings are helpful to gain a more novel understanding of structural and spin properties of Ga vacancy in wurtzite GaN and also provide a possible way to generate magnetic GaN by introducing Ga vacancies instead of doping with transition-metal atoms.     

Bulk GaN single crystals: a reinvestigation of growth mechanism using Li3N flux

The GaN growth mechanism using Li₃N flux was reinvestigated by designing a new experiment that allowed us to grow GaN simultaneously under varying Ga/Li₃N molar ratios. The results confirm the two-step reactions involved in the Ga–Li₃N system: Li₃N+Ga→Li₃GaN₂+Li (1) and Li₃GaN₂+Ga→GaN+Li (2). It is found that reaction (2) is the main cause leading to small GaN crystals in the products. Larger GaN crystals, however, can grow by a different pathway. The growing process is concerned with the formation of Li–Ga–N melt by dissolving Li₃GaN₂ in Li–Ga melt after reaction (1). GaN crystals up to 3 mm grow from the Li–Ga–N melt upon cooling on the GaN particles by reaction (2). Our results suggest that it is necessary to restrain reaction (2) by choosing proper Ga/Li₃N molar ratios so as to obtain GaN crystals in larger size. PACS 81.05.Ea; 81.10.Dn