带有A1N插入层的GaN薄膜的结构及应变研究

利用金属有机化学汽相沉积(MOCVD)法在硅衬底上生长具有AIN插入层的GaN外延膜，采用高分辨X射线衍射(HRXRD)和卢瑟福背散射/沟道(RBS/Channeling)技术研究分析其结构和应变性质。从RBS＜0001＞沟道谱可知，该外延膜具有良好的结晶品质，χ_(min)＝2.5％。利用不同方位角上XRD摇摆曲线测量，可得出GaN(0001)面与Si(111)面之间的夹角β＝1.379°。通过对GaN(0002)和GaN(10(1-bar)5)衍射面的θ-2θ扫描，可以得出GaN外延膜在垂直方向和水平方向的平均弹性应变分别为-0.10%±0.02％和0.69％±0.09％。通过对{10(1-bar)0}面内非对称<1(2-bar)13>轴RBS角扫描可得出由弹性应变引起的四方畸变e_T在近表面处为0.35％±0.02％。外延膜弹性性质表明GaN膜在水平方向具有张应力(e~〃＞0)、在垂直方向具有压应力(e~⊥＜0)，印证了XRD的结果。四方畸变是深度敏感的，通过对不同深度的四方畸变计算可知，A1N插入层下面的GaN外延膜弹性应变释放速度比A1N层上面的GaN层弹性应变释放快，说明A1N层的插入缓解了应变释放速度。

掺铒GaN薄膜的背散射/沟道分析和光致发光研究

采用背散射(RBS)/沟道(channeling)分析和傅里叶变换红外光谱(FT-IR)研究了掺铒GaN薄膜的晶体结构和光致发光(PL)特性.背散射/沟道分析结果表明:随退火温度的升高,薄膜中辐照损伤减少;但当退火温度达到1000℃,薄膜中的缺陷又明显增加.Er浓度随注入深度呈现高斯分布.通过沿GaN的<0001>轴方向的沟道分析,对于900℃,30min退火的GaN:Er样品,Er在晶格中的替位率约76%.光谱研究表明:随退火温度的升高,室温下样品的红外PL峰强度增加;但是当退火温度达到1000℃,样品的PL峰强度明显下降;测量温度从15K变化到300K时,样品(900℃,30min退火的GaN:Er)的1540nm处PL温度猝灭为30%.

横向外延GaN结晶质量的同步辐射研究

采用同步辐射X光衍射技术研究了α-Al_2O_3(0001)衬底上横向外延GaN的结构特征。发现横向生长区的GaN（0001）晶面与窗口区的GaN(0001)晶面在垂直掩模方向上存在取向差。ω/2θ联动扫描发现横向生长区的GaN的衍射峰半高宽约为窗口区GaN的一半，这表明横向外延生长技术在降低GaN穿透位错密度的同时，还能大幅度提高GaN的晶粒尺寸。

(111)Si上外延生长六方GaN的TEM观察

利用衍衬、SAED、HRTEM对在（111）Si上外延生长的六方GaN进行了观察分析。GaN外延层与缓冲层和基底的取向关系为(0001)_(GaN)∥(0001)_(AlN)∥(111)_(Si)，[11(2-bar)0]_(GaN)∥[11(2-bar)0]_(AlN)∥[110]_(Si)。GaN外延层中存在倒反畴。GaN中位错以刃型位错为主。In_(0.1) Ga_(0.9) N/GaN的多重量子阱结构（MQW）具有阻挡穿透位错，降低位错密度的作用。

First-principles study of oxygenates on Co surfaces in Fischer-Tropsch synthesis

Extensive density function theory calculations are performed to study the mechanism of the formation of aldehyde and alcohol on Co surfaces in Fischer-Tropsch synthesis, a challenging issue in heterogeneous catalysis. Three possible pathways for the production of formaldehyde and methanol on flat and stepped Co(0001) surfaces are investigated: (i) CO + 4H -> CHO + 3H -> CH2O + 2H -> CH3O + H -> CH3OH; (ii) CO + 4H -> COH + 3H -> CHOH + 2H -> CH2OH + H -> CH3OH; and (iii) the coupling reactions of CH2 + O -> CH2O and CH3 + OH -> CH3OH. It is found that these pathways are generally favored at step sites, and the preferred mechanism is pathway (i) via CHO. Furthermore, the three traditional chain growth mechanisms in Fischer-Tropsch synthesis are semi quantitatively compared and discussed. Our results suggest that the two mechanisms involving oxygenate intermediates (the CO-insertion and hydroxycarbene mechanisms) are less important than the carbene mechanism in the production of long chain hydrocarbons. However, the CO-insertion mechanism may be responsible for the production of long-chain oxygenates.

Crecimiento, fabricación y caracterización de heteroestructuras y nanocolumnas ordenadas basadas en nitruros del grupo III para aplicaciones sensoras

Esta memoria está basada en el crecimiento y caracterización de heteroestructuras Al(Ga)N/GaN y nanocolumnas ordenadas de GaN, y su aplicación en sensores químicos. El método de crecimiento ha sido la epitaxia de haces moleculares asistida por plasma (PAMBE). En el caso de las heteroestructuras Al(Ga)N/GaN, se han crecido barreras de distinto espesor y composición, desde AlN de 5 nm, hasta AlGaN de 35 nm. Además de una caracterización morfológica, estructural y eléctrica básica de las capas, también se han fabricado a partir de ellas dispositivos tipo HEMTs. La caracterización eléctrica de dichos dispositivos (carga y movilidad de en el canal bidimensional) indica que las mejores heteroestructuras son aquellas con un espesor de barrera intermedio (alrededor de 20 nm). Sin embargo, un objetivo importante de esta Tesis ha sido verificar las ventajas que podían tener los sensores basados en heteroestructuras AlN/GaN (frente a los típicos basados en AlGaN/GaN), con espesores de barrera muy finos (alrededor de 5 nm), ya que el canal de conducción que se modula por efecto de cambios químicos está más cerca de la superficie en donde ocurren dichos cambios químicos. De esta manera, se han utilizado los dispositivos tipo HEMTs como sensores químicos de pH (ISFETs), y se ha comprobado la mayor sensibilidad (variación de corriente frente a cambios de pH, Ids/pH) en los sensores basados en AlN/GaN frente a los basados en AlGaN/GaN. La mayor sensibilidad es incluso más patente en aplicaciones en las que no se utiliza un electrodo de referencia. Se han fabricado y caracterizado dispositivos ISFET similares utilizando capas compactas de InN. Estos sensores presentan peor estabilidad que los basados en Al(Ga)N/GaN, aunque la sensibilidad superficial al pH era la misma (Vgs/pH), y su sensibilidad en terminos de corriente de canal (Ids/pH) arroja valores intermedios entre los ISFET basados en AlN/GaN y los valores de los basados en AlGaN/GaN. Para continuar con la comparación entre dispositivos basados en Al(Ga)N/GaN, se fabricaron ISFETs con el área sensible más pequeña (35 x 35 m2), de tamaño similar a los dispositivos destinados a las medidas de actividad celular. Sometiendo los dispositivos a pulsos de voltaje en su área sensible, la respuesta de los dispositivos de AlN presentaron menor ruido que los basados en AlGaN. El ruido en la corriente para dispositivos de AlN, donde el encapsulado no ha sido optimizado, fue tan bajo como 8.9 nA (valor rms), y el ruido equivalente en el potencial superficial 38.7 V. Estos valores son más bajos que los encontrados en los dispositivos típicos para la detección de actividad celular (basados en Si), y del orden de los mejores resultados encontrados en la literatura sobre AlGaN/GaN. Desde el punto de vista de la caracterización electro-química de las superficies de GaN e InN, se ha determinado su punto isoeléctrico. Dicho valor no había sido reportado en la literatura hasta el momento. El valor, determinado por medidas de “streaming potential”, es de 4.4 y 4 respectivamente. Este valor es una importante característica a tener en cuenta en sensores, en inmovilización electrostática o en la litografía coloidal. Esta última técnica se discute en esta memoria, y se aplica en el último bloque de investigación de esta Tesis (i.e. crecimiento ordenado). El último apartado de resultados experimentales de esta Tesis analiza el crecimiento selectivo de nanocolumnas ordenadas de GaN por MBE, utilizando mascaras de Ti con nanoagujeros. Se ha estudiado como los distintos parámetros de crecimiento (i.e. flujos de los elementos Ga y N, temperatura de crecimiento y diseño de la máscara) afectan a la selectividad y a la morfología de las nanocolumnas. Se ha conseguido con éxito el crecimiento selectivo sobre pseudosustratos de GaN con distinta orientación cristalina o polaridad; templates de GaN(0001)/zafiro, GaN(0001)/AlN/Si, GaN(000-1)/Si y GaN(11-20)/zafiro. Se ha verificado experimentalmente la alta calidad cristalina de las nanocolumnas ordenadas, y su mayor estabilidad térmica comparada con las capas compactas del mismo material. Las nanocolumnas ordenadas de nitruros del grupo III tienen una clara aplicación en el campo de la optoelectrónica, principalmente para nanoemisores de luz blanca. Sin embargo, en esta Tesis se proponen como alternativa a la utilización de capas compactas o nanocolumnas auto-ensambladas en sensores. Las nanocolumnas auto-ensambladas de GaN, debido a su alta razón superficie/volumen, son muy prometedoras en el campo de los sensores, pero su amplia dispersión en dimensiones (altura y diámetro) supone un problema para el procesado y funcionamiento de dispositivos reales. En ese aspecto, las nanocolumnas ordenadas son más robustas y homogéneas, manteniendo una alta relación superficie/volumen. Como primer experimento en el ámbito de los sensores, se ha estudiado como se ve afectada la emisión de fotoluminiscencia de las NCs ordenadas al estar expuestas al aire o al vacio. Se observa una fuerte caída en la intensidad de la fotoluminiscencia cuando las nanocolumnas están expuestas al aire (probablemente por la foto-adsorción de oxigeno en la superficie), como ya había sido documentado anteriormente en nanocolumnas auto-ensambladas. Este experimento abre el camino para futuros sensores basados en nanocolumnas ordenadas. Abstract This manuscript deals with the growth and characterization of Al(Ga)N/GaN heterostructures and GaN ordered nanocolumns, and their application in chemical sensors. The growth technique has been the plasma-assisted molecular beam epitaxy (PAMBE). In the case of Al(Ga)N/GaN heterostructures, barriers of different thickness and composition, from AlN (5 nm) to AlGaN (35 nm) have been grown. Besides the basic morphological, structural and electrical characterization of the layers, HEMT devices have been fabricated based on these layers. The best electrical characteristics (larger carriers concentration and mobility in the two dimensional electron gas) are those in AlGaN/GaN heterostructures with a medium thickness (around 20 nm). However, one of the goals of this Thesis has been to verify the advantages that sensors based on AlN/GaN (thickness around 7 nm) have compared to standard AlGaN/GaN, because the conduction channel to be modulated by chemical changes is closer to the sensitive area. In this way, HEMT devices have been used as chemical pH sensors (ISFETs), and the higher sensitivity (conductance change related to pH changes, Ids/pH) of AlN/GaN based sensors has been proved. The higher sensibility is even more obvious in application without reference electrode. Similar ISFETs devices have been fabricated based on InN compact layers. These devices show a poor stability, but its surface sensitivity to pH (Vgs/pH) and its sensibility (Ids/pH) yield values between the corresponding ones of AlN/GaN and AlGaN/GaN heterostructures. In order to a further comparison between Al(Ga)N/GaN based devices, ISFETs with smaller sensitive area (35 x 35 m2), similar to the ones used in cellular activity record, were fabricated and characterized. When the devices are subjected to a voltage pulse through the sensitive area, the response of AlN based devices shows lower noise than the ones based on AlGaN. The noise in the current of such a AlN based device, where the encapsulation has not been optimized, is as low as 8.9 nA (rms value), and the equivalent noise to the surface potential is 38.7 V. These values are lower than the found in typical devices used for cellular activity recording (based on Si), and in the range of the best published results on AlGaN/GaN. From the point of view of the electrochemical characterization of GaN and InN surfaces, their isoelectric point has been experimentally determined. Such a value is the first time reported for GaN and InN surfaces. These values are determined by “streaming potential”, being pH 4.4 and 4, respectively. Isoelectric point value is an important characteristic in sensors, electrostatic immobilization or in colloidal lithography. In particular, colloidal lithography has been optimized in this Thesis for GaN surfaces, and applied in the last part of experimental results (i.e. ordered growth). The last block of this Thesis is focused on the selective area growth of GaN nanocolumns by MBE, using Ti masks decorated with nanoholes. The effect of the different growth parameters (Ga and N fluxes, growth temperature and mask design) is studied, in particular their impact in the selectivity and in the morphology of the nanocolumns. Selective area growth has been successful performed on GaN templates with different orientation or polarity; GaN(0001)/sapphire, GaN(0001)/AlN/Si, GaN(000- 1)/Si and GaN(11-20)/sapphire. Ordered nanocolumns exhibit a high crystal quality, and a higher thermal stability (lower thermal decomposition) than the compact layers of the same material. Ordered nanocolumns based on III nitrides have a clear application in optoelectronics, mainly for white light nanoemitters. However, this Thesis proposes them as an alternative to compact layers and self-assembled nanocolumns in sensor applications. Self-assembled GaN nanocolumns are very appealing for sensor applications, due to their large surface/volume ratio. However, their large dispersion in heights and diameters are a problem in terms of processing and operation of real devices. In this aspect, ordered nanocolumns are more robust and homogeneous, keeping the large surface/volume ratio. As first experimental evidence of their sensor capabilities, ordered nanocolumns have been studied regarding their photoluminiscence on air and vacuum ambient. A big drop in the intensity is observed when the nanocolumns are exposed to air (probably because of the oxygen photo-adsortion), as was already reported in the case of self-assembled nanocolumns. This opens the way to future sensors based on ordered III nitrides nanocolumns.

Integrated luminescent chemical microsensors based on GaN LEDs for security applications using smartphones

Development of PCB-integrateable microsensors for monitoring chemical species is a goal in areas such as lab-on-a-chip analytical devices, diagnostics medicine and electronics for hand-held instruments where the device size is a major issue. Cellular phones have pervaded the world inhabitants and their usefulness has dramatically increased with the introduction of smartphones due to a combination of amazing processing power in a confined space, geolocalization and manifold telecommunication features. Therefore, a number of physical and chemical sensors that add value to the terminal for health monitoring, personal safety (at home, at work) and, eventually, national security have started to be developed, capitalizing also on the huge number of circulating cell phones. The chemical sensor-enabled “super” smartphone provides a unique (bio)sensing platform for monitoring airborne or waterborne hazardous chemicals or microorganisms for both single user and crowdsourcing security applications. Some of the latest ones are illustrated by a few examples. Moreover, we have recently achieved for the first time (covalent) functionalization of p- and n-GaN semiconductor surfaces with tuneable luminescent indicator dyes of the Ru-polypyridyl family, as a key step in the development of innovative microsensors for smartphone applications. Chemical “sensoring” of GaN-based blue LED chips with those indicators has also been achieved by plasma treatment of their surface, and the micrometer-sized devices have been tested to monitor O2 in the gas phase to show their full functionality. Novel strategies to enhance the sensor sensitivity such as changing the length and nature of the siloxane buffer layer are discussed in this paper.

The role of Ti as a catalyst for the dissociation of hydrogen on a Mg(0001) surface

In this paper, the dissociative chemisorption of hydrogen on both pure and Ti-incorporated Mg(0001) surfaces are studied by ab initio density functional theory (DFT) calculations. The calculated dissociation barrier of hydrogen molecule on a pure Mg(0001) surface (1.05 eV) is in good agreement with comparable theoretical studies. For the Ti-incorporated Mg(0001) surface, the activated barrier decreases to 0.103 eV due to the strong interaction between the molecular orbital of hydrogen and the d metal state of Ti. This could explain the experimentally observed improvement in absorption kinetics of hydrogen when transition metals have been introduced into the magnesium materials.

Direct chemical vapor deposition of large-area carbon thin films on gallium nitride for transparent electrodes: A first attempt

Direct formation of large-area carbon thin films on gallium nitride by chemical vapor deposition without metallic catalysts is demonstrated. A high flow of ammonia is used to stabilize the surface of the GaN (0001)/sapphire substrate during the deposition at 950°C. Various characterization methods verify that the synthesized thin films are largely sp 2 bonded, macroscopically uniform, and electrically conducting. The carbon thin films possess optical transparencies comparable to that of exfoliated graphene. This paper offers a viable route toward the use of carbon-based materials for future transparent electrodes in III-nitride optoelectronics, such as GaN-based light emitting diodes and laser diodes. © 1988-2012 IEEE.

CdS/CdSe lateral heterostructure nanobelts by a two-step physical vapor transport method.

The two-dimensional heterostructure nanobelts with a central CdSe region and lateral CdS structures are synthesized by a two-step physical vapor transport method. The large growth rate difference between lateral CdS structures on both +/- (0001) sides of the CdSe region is found. The growth anisotropy is discussed in terms of the polar nature of the side +/- (0001) surfaces of CdSe. High-resolution transmission electron microscopy reveals the CdSe central region covered with non-uniform CdS layer/islands. From micro-photoluminescence measurements, a systematic blueshift of emission energy from the central CdSe region in accordance with the increase of lateral CdS growth temperature is observed. This result indicates that the intermixing rate in the CdSe region with CdS increases with the increase of lateral CdS growth temperature. In conventional CdSSe ternary nanostructures, morphology and emission wavelength were correlated parameters. However, the morphology and emission wavelength are independently controllable in the CdS/CdSe lateral heterostructure nanobelts. This structure is attractive for applications in visible optoelectronic devices.

R面、C面蓝宝石上生长的InGaN多层量子点的发光性质研究

采用表面钝化和MOCVD低温生长在蓝宝石（0001）面（即C面）和蓝宝石(1(1-bar)02)面（即R面）上形成了InGaN量子点，并构成了该量子点的多层结构。原子力显微镜测试的结果表明单层InGaN量子点平均宽约40nm，高约15nm；而多层量子点上层的量子点则比单层的InGaN量子点大。R面蓝宝石衬底上生长的InGaN量子点和C面蓝宝石衬底上生长的InGaN量子点相比，其PL谱不仅强度高，而且没有多峰结构。这是由于在C面蓝宝石衬底上生长的InGaN/GaN多层量子点沿生长方向[0001]存在较强的内建电场，而在R面蓝宝石衬底上得到的多层量子点沿着生长方向[11(2-bar)0]没有内建电场。InGaN量子点变温光致发光（PL）谱研究发现量子点相关的峰有快速红移现象，这是量子点系统所特有的PL谱特征。用在R面蓝宝石上生长的InGaN量子点作有源层有望避免内建电场的影响，得到高量子效率且发光波长稳定的发光器件。

Direct measurement of surface forces between sapphire crystals in aqueous solutions

Measurements are presented of the electrical double layer and van der Waals forces between the (0001) surfaces of two single-crystal sapphire platelets immersed in an aqueous solution of NaCl at pH values from 6.7 to 11. The results fit the standard Deryaguin-Landau-Verwey-Overbeek (DLVO) theory, with a Hamaker constant of 6.7 × 10−20 J. These are the first measurements made using the Israelachvili surface forces apparatus without mica as a substrate material, and they demonstrate the possibility of using this technique to explore the surface chemistry of a wider range of materials.

Growth and structural properties of GaN films on flat and vicinal SiC(0001) substrates

Initial stage GaN growth by molecular-beam epitaxy (MBE) on SiC(0001) substrate is followed by in situ scanning tunneling microscopy. Comparison is made between growth on nominally flat and vicinal substrate surfaces and the results reveal characteristic differences between the two. Ex situ transmission electron microscopy (TEM) and X-ray diffraction (XRD) rocking curve measurements of the films show lower density of defects and better structural quality of the vicinal film. We suggest the improved structural quality of the vicinal film is related to the characteristic difference in its initial stage nucleation and coalescence proccsses than that of the flat film.

Growth and structural properties of GaN films on flat and vicinal SiC(0001) substrates

Initial stage GaN growth by molecular-beam epitaxy (MBE) on SiC(0001) substrate is followed by in situ scanning tunneling microscopy. Comparison is made between growth on nominally flat and vicinal substrate surfaces and the results reveal characteristic differences between the two. Ex situ transmission electron microscopy (TEM) and X-ray diffraction (XRD) rocking curve measurements of the films show lower density of defects and better structural quality of the vicinal film. We suggest the improved structural quality of the vicinal film is related to the characteristic difference in its initial stage nucleation and coalescence proccsses than that of the flat film.