PECVD法制备高结晶GaN薄膜及其光电响应性能

采用一种简单、绿色、低成本的等离子增强化学气相沉积(PECVD)法,在950℃下成功制备了高结晶质量的GaN薄膜.为了提高GaN薄膜结晶质量和弄清GaN薄膜光响应机制,研究了GaN缓冲层制备温度对GaN薄膜结晶质量和光电性能的影响.研究表明,随着GaN缓冲层制备温度的增加,GaN薄膜的结晶质量先提高后降低,在缓冲层温度为875℃时,结晶质量最高,此时计算得出的总位错密度为9.74×10~9 cm^-2,载流子迁移率为0.713 cm~2/(V·s).经过退火后,GaN薄膜的总位错密度降低到7.38×10~9 cm^-2,载流子迁移率增大到43.5 cm~2(V·s),此时GaN薄膜光响应度为0.20 A/W,光响应时间为15.4 s,恢复时间为24 s,可应用于紫外光探测器.通过Hall测试和X射线光电子能谱仪分析得出,GaN薄膜内部存在着N空位、Ga空位或O掺杂,它们作为深阱能级束缚和复合光生电子和空穴,使得光响应度与偏压呈抛物线关系;另外,空位和O掺杂形成的深阱能级也是导致GaN薄膜的光电流响应和恢复缓慢的根本原因.     

反向外延生长3C-SiC薄膜中残余应力的工艺优化

本文为改善反向外延生长3C-SiC薄膜中残余应力的工艺优化方法,采用LPCVD技术,将甲烷和氢气按1∶10比例混合后与n-Si(111)衬底反应,制备3C-SiC薄膜。通过X射线衍射分析仪、激光拉曼光谱仪和场发射扫描电子显微镜进行测试和分析。在该方法中,反应恒温1200℃为最优温度,反应温度过高或过低都不利于3C-SiC薄膜生长;在反应温度为1200℃时,为增加薄膜厚度而单纯增加反应时长,缺陷浓度也会相应地增加,从而薄膜结晶质量相应降低;但在1250℃反应温度时,增加反应时长不仅会增加薄膜的厚度,而且也会缓减薄膜中残余应力,同时改善薄膜的结晶质量。另外研究结果还表明:1250℃时经过一个恒温的等时退火工艺后,再降温的方式可进一步降低薄膜中本征残余应力,从而改善薄膜的结晶质量和晶格失配。     

ZnO纳米线的合成与生长机理

采用化学气相沉积系统制备ZnO纳米线,以覆盖一层约5nm厚的Ag薄膜的单晶Si(001)为衬底,纳米线的生长遵循气-液-固(VLS)机理。对得到的样品采用X射线衍射(XRD)和扫描电镜(SEM)进行晶体结构和形貌的表征。XRD结果表明衬底温度在600~700℃时生长的ZnO纳米线具有六方结构和统一的取向。通过扫描电子显微镜分析,比较了生长温度对纳米线直径和长度的影响。实验表明我们可以通过催化剂和温度来实现ZnO纳米线生长的可控。与传统的VLS生长方式不同的是在我们制备的ZnO纳米线顶端并没有看到催化剂颗粒,表明纳米线的生长方式是底部生长,我们对其生长机理进行了研究。     

碳泡沫衬底上氮化铝纳米线的生长及其光致发光特性研究

为了简化了AlN/C复合泡沫材料的制备流程, 本文采用复分解反应法制备AlN纳米材料, 并通过800℃退火处理使其在碳泡沫衬底上重结晶为六方相AlN纳米线. 通过形貌表征测试, 纳米线为表面光滑的长直形圆柱体, 直径约50 nm, 长度10 μm以上, 在碳微球表面沿[001]方向生长. 同时, 采用VLS生长机理对纳米线的生长进行了解释. 对样品光致发光谱的研究表明, 中心波长423 nm处存在一尖锐发光峰且随温度升高发生明显的红移现象, 系C替N杂质能级跃迁发光所致. 样品在紫光波段具有良好的光致发光特性, 有望应用于光探测器领域.     

低温CVD法在玻璃衬底上制备ZnO纳米线阵列

采用化学气相沉积(CVD)法在镀Cr(20nm)的玻璃衬底上,低温制备了ZnO纳米线阵列。利用扫描电子显微镜(SEM)和X射线衍射(XRD)对样品的表面形貌和微结构进行了分析表征。结果表明:源分解温度1350℃,衬底温度450～500℃,氩气流量为35sccm时,ZnO纳米线在玻璃衬底上呈现有序生长;XRD谱图中只观测到ZnO(002)衍射峰。表明制备的纳米线阵列具有高度c轴择优取向生长特性和较高的结晶质量。     

基于氧化锌纳米线的紫外发光二极管

构建了基于n-ZnO纳米线/p-Si异质结的紫外发光二极管.ZnO纳米线准阵列采用水热法生长于重掺p型Si片上.此法简易，反应温度低，易于大规模生产；其产物ZnO纳米线结晶良好，以c轴为优势取向，光激发下的紫外荧光发射很强.二极管的电学接触采用聚合物填充的In阴极或以氧化铟锡(ITO)玻璃紧压形成阴极.它们的I-V特性体现出良好的二极管性质.在正向偏置电压驱动下，构建的发光二极管可稳定发射波长在387nm的较强的近紫外光和较弱的绿光. 关键词： ZnO纳米线 异质结 电致发光 水热法     

化学气相沉积法制备GaN纳米结构设计性实验

在无催化剂辅助条件下,采用化学气相沉积法生长了GaN纳米线.通过调整衬底、NH3气流、生长时间等,实现了半导体GaN纳米线的生长以及形貌调控.用X射线衍射仪和扫描电子显微镜对产物的物相及形貌进行了表征.获得了合成GaN纳米线的优化条件.     

Si纳米线的固-液-固可控生长及其形成机理分析

以Au膜作为金属催化剂,直接从n-(111)Si单晶衬底上制备了直径为30—60nm和长度从几微米到几十微米的高质量Si纳米线.实验研究了Au膜层厚、退火温度、N2气流量和生长时间对Si纳米线形成的影响.结果表明,通过合理选择和优化组合上述各种工艺条件,可以实现直径、长度、形状和取向可控的纳米线生长.基于固-液-固生长机理,定性阐述了Si纳米线的形成过程.     

在6H-SiC衬底上用低压MOVPE法生长AlN和GaN的过程中用(AlN/GaN)多层缓冲层来控制残余应力

人们已提出用BAlGaN四元系材料制备紫外光谱区的光发射器件.GaN和AlN二元系是这种四元材料在器件应用中的基础材料.6H-SiC衬底在氮化物生长中因其晶格失配小是一大优势,而且SiC衬底的热膨胀系数也和AlN的很接近.然而,对于AlN外延层来说,需要控制其中的残余应力,因为在SiC衬底上直接生长的AlN外延层中存在着因晶格失配所产生的压缩应力.另一方面,在SiC衬底上直接生长的GaN外延层中存在着拉伸应力.这种拉伸应力起源于GaN比衬底有着更大的热膨胀系数.本文讨论了在6H-SiC衬底上生长的氮化物外延层中残余应力的类型、数量及控制.为此目的,提出了在6H-SiC衬底上,无论是生长AlN,还是生长GaN,都可以采用(GaN/AlN)多层缓冲层的办法,作为控制残余应力的有效方法.我们还讨论了AlN和GaN外延层的结晶质量和残余应力间的关系.     

衬底位置对化学气相沉积法制备的磷掺杂p型ZnO纳米材料形貌和特性的影响

采用化学气相沉积方法,在无催化剂的条件下,通过改变衬底位置在Si(100)衬底上制备出了高取向的磷掺杂ZnO纳米线和纳米钉.测试结果表明,当衬底位于反应源上方1.5 cm处时,所制备的样品为钉状结构,而当衬底位于反应源下方1 cm处时样品为线状结构.对不同形貌磷掺杂ZnO纳米结构的生长机理进行了研究.此外,在ZnO纳米结构的低温光致发光谱中观测到了一系列与磷掺杂相关的受主发光峰.还对磷掺杂ZnO纳米结构/n-Si异质结I-V曲线进行了测试,结果表明,该器件具有良好的整流特性,纳米线和纳米钉异质结器件的开启电压分别为4.8和3.2 V.     

Nucleation of III nitride semiconductors in heteroepitaxy

The nucleation of III nitride semiconductors in heteroepitaxy is theoretically investigated using GaN nucleation on the AlN surface as an example. It is inferred that the mechanism of this process is determined by the temperature at the initial stage of the layer formation (T). At low temperatures (T<500°C), liquid gallium droplets appear and the chemical reaction between the Ga and N atoms results in the formation of GaN nuclei. At substrate temperatures T>650°C, there arise only GaN nuclei. It is revealed that the GaN nucleation is governed by the generalized diffusion coefficient of GaN, which is a combination of the diffusion coefficients for gallium and nitrogen atoms. It is shown that the generalized diffusion coefficient of GaN on the crystal surface increases by seven orders of magnitude as the growth temperature increases from 600 to 800°C. This is accompanied by a change in the growth mechanism of the III nitride semiconductor epitaxial layers.     

Large-scale crystalline GaN nanowires synthesized through a chemical vapor deposition method

Large-scale, high-density gallium nitride nanowires were successfully synthesized by the direct reaction of gallium and ammonia using gold as initiator. The as-synthesized product was characterized by XRD, SEM, TEM, SAED, and EDS. The results showed that the product is hexagonal wurtzite GaN with high purity. The nanowires have diameters in the range of 60–100 nm and are a few tens of micrometers in length. A remarkable feature is that catalyst particles were observed at the ends of the nanowires, indicating that the growth process can be controlled by the vapor–liquid–solid mechanism. The present results revealed that gold is an effective and advantageous catalyst for the growth of GaN nanowires. PACS 81.05.Ea; 81.10.Bk; 68.65.-k     

Mechanism and kinetics of early growth stages of a GaN film

The growth of GaN islands on the substrate surface covered with an AlN buffer layer is theoretically investigated at the stages of nucleation and Ostwald ripening in the temperature range 480–1000°C. The following inferences are made from analyzing the results obtained. (1) At temperatures T>650°C, the growth of islands is controlled by the chemical reaction of formation of GaN molecules around the periphery of the island surface. Islands nucleated at these temperatures are characterized by a large spread in their sizes. (2) At temperatures T<600°C, the island growth is governed by the surface diffusion of nitrogen atoms. Islands nucleated at these temperatures are virtually identical in size. (3) In the temperature range 600–650°C, the mechanism of island growth gradually changes over from the mechanism associated with the surface diffusion of nitrogen atoms with a large mean free path to the mechanism determined by the diffusion of gallium atoms with a smaller mean free path. The supersaturation, flux, and size distribution functions of GaN nuclei are calculated at different substrate temperatures. The phase diagrams describing the evolution in the phase composition of GaN islands with variations in temperature are constructed.     

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.     

High-quality GaN nanowires synthesized using a CVD approach

High-quality GaN nanowires were synthesized on a large-area Si substrate by direct reaction of gallium with ammonia using InCl₃ as a catalyst. The morphology and microstructure of the resulting products were characterized using a field-emission scanning electron microscope (SEM), a high-resolution transmission electron microscope, and X-ray diffraction (XRD). XRD and electron diffraction revealed that the nanowires are of a hexagonal GaN phase with the wurtzite structure. The SEM study showed that the nanowires are straight and have a smooth morphology with lengths up to 500 μm. The present results reveal that InCl₃ is an optimal catalyst in GaN nanowire production. Received: 2 April 2002 / Accepted: 12 April 2002 / Published online: 19 July 2002     

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。     

One-dimensional gallium nitride micro/nanostructures synthesized by a space-confined growth technique

Hexagonal GaN prismatic sub-micro rods and cone nanowires have been synthesized in a large scale by a novel and controllable space-confined growth method. The as-synthesized GaN products are highly crystalline with a wurtzite structure. The prismatic rods have lengths of 15∼20 μm and diameters of 400∼500 nm enclosed by hexagonal smooth side surfaces and a pyramidal end. And the cone nanowires have average diameters of 150∼200 nm and lengths up to several tens of μm with a cone tip. The photoluminescence (PL) studies reveal prominent band-gap UV emission properties of GaN products and narrow FWHM, indicating the excellent luminescent performance and high crystal quality. For field emission characteristic of GaN nanowires, the turn-on field is about 9.5 V/μm and the current density reaches 1.0 mA/cm² at an electric field of 18 V/ μm. The contrast experiments indicate a novel growth control can be achieved by using a graphite tube as reaction vessel. The sealed graphite tube combined with metallic initiator is greatly responsible for large-scale and uniform preparation of GaN prismatic rods and cone nanowires. Highly symmetric GaN hexagonal micropyramids are grown on a bare Si substrate. The growth mechanism and the control function of the graphite tube are demonstrated. These low-dimensional structures not only enrich semiconducting GaN family, but also are good building blocks for optoelectronic devices. PACS 81.10.Bk; 81.07.-b; 81.05.Ea     

未钝化和H钝化GaN纳米线的电子结构

用密度泛函理论研究直径为9.5Å,15.9Å和22.5Å,未钝化和H钝化GaN纳米线的能带和态密度.结果表明:未钝化和H钝化GaN纳米线的能隙都是直接带隙,未钝化GaN纳米线的禁带宽度随着直径的增加减小,但是变化不明显,H钝化GaN纳米线的禁带宽度随着直径增大也是减小的,但是减小的幅度比未钝化的大.未钝化GaN纳米线表面N原子的2p电子主要聚集在价带顶,表面Ga原子的4p电子主要聚集在导带底,这两种电子都具有很强的局域性,而且决定着能隙值;加H钝化可以消除表面原子产生的表面效应.     

Preparation and characterization of carbon nanotubes encapsulated GaN nanowires

A novel two-step catalytic reaction is developed to synthesize gallium nitride nanowires encapsulated inside carbon nanotubes (GaN@CNT). The nanowires are prepared from the reaction of gallium metal and ammonium using metals or metal alloys as a catalyst. After the formation of the nanowires, carbon nanotubes are subsequently grown along the nanowires by chemical vapor deposition of methane. The structural and optical properties of pure GaN nanowires and GaN@CNT are characterized using scanning electron microscopy, transmission electron microscopy, X-ray diffraction, energy dispersive X-ray spectroscopy and Raman spectroscopy. The results show that GaN nanowires are indeed encapsulated inside carbon nanotubes. The field emission studies show that the turn-on field of GaN@CNT is higher than that of carbon nanotubes, but substantially lower than that of pure GaN nanowires. This work provides a wide route toward the preparation and applications of new one-dimensional semiconductor nanostructures.     

Spontaneous Ga incorporation in ZnO nanowires epitaxially grown on GaN substrate

Surface‐diffusion‐induced spontaneous Ga incorporation process is demonstrated in ZnO nanowires grown on GaN substrate. Crucially, contrasting distributions of Ga atoms in axial and radial directions are experimentally observed. Ga atoms uniformly distribute along the ～10 μm long ZnO nanowire and show a rapidly gradient distribution in the radial direction, which is attributed substantially to the difference between surface and volume diffusion. The understanding on the incorporation process can potentially modulate doping and properties in semiconductor nanomaterials.