基于胶体球掩模板法制备图形化蓝宝石衬底

制备并研究了纳米级图形化蓝宝石衬底.采用磁控溅射技术在蓝宝石衬底上沉积 SiO2薄膜,利用自组装方法在SiO2薄膜上制备单层聚苯乙烯(PS)胶体球阵列,利用感应耦合等离子体干法刻蚀将周期性PS胶体球的图形转移到SiO2薄膜上,通过湿法腐蚀制备了纳米级图形化蓝宝石衬底.利用扫描电子显微镜对胶体球掩膜、SiO2纳米柱掩膜和图形化蓝宝石衬底结构进行了观察,研究了湿法腐蚀蓝宝石衬底的中间产物对刻蚀的影响,分析了腐蚀温度和腐蚀时间对蓝宝石衬底的影响.结果表明,湿法腐蚀的中间产物会降低蓝宝石衬底的刻蚀速率.蓝宝石衬底的腐蚀速率随着腐蚀温度的升高而加快;在同一腐蚀温度下,随着腐蚀时间的增加,图形尺寸进一步减小.     

垂直沉积法在GaAs衬底上制备有序SiO2胶体晶体

报道了一种利用直径为286nm的单分散SiO2胶体颗粒制备胶体晶体的方法。乙醇悬浮中的SiO2颗粒通过毛细作用力在垂直插入其中的GaAs衬底表面自组装成胶体晶体。扫描电子显微镜（SEM）和紫外-可见分光光度计对胶体晶体的形貌和光学特性进行了表征。结果显示,所得到的胶体晶体膜具有较好的三维有序结构。分析了退火对样品光子带隙的影响。     

高电荷密度聚苯乙烯微球的制备及胶体晶体组装

以甲基丙烯酸(MAA)为共聚单体,采用无皂乳液聚合法制备了单分散聚(苯乙烯-甲基丙烯酸)共聚微球,再在恒温恒湿条件下采用限制注射法制备出胶体晶体,最后对微球的组成、粒径大小及形态、表面电学性质、胶体晶体的显微形貌进行了测试分析。结果表明:制得的微球粒径均匀,球形度良好且呈单分散性,Zeta电势为–37.2mV;微球组装的胶体晶体排列有序,呈密堆积结构。     

垂直沉积法制备高质量胶体光子晶体

利用乳液聚合方法制备了粒径约为262 nm的单分散聚苯乙烯(PS)微球。通过控制溶剂蒸发温度和液体表面下降的速度,用垂直沉积法较快速地制备出了在较大范围呈现很好有序性的密排结构聚苯乙烯胶体光子晶体,其在626 nm波长处存在光子带隙。在扫描电子显微镜(SEM)下,观察到该胶体光子晶体是面心立方(fcc)密排结构。实验结果表明,对于粒径为262 nm的聚苯乙烯微球,在温度为55℃,质量分数为0.3%的情况下,当液体表面下降的速度约为每天3 mm时,可以得到高质量的胶体光子晶体。这种高质量的胶体光子晶体可以为利用模板技术制备具有完全带隙的有序孔结构提供较理想的模板。     

单分散性sio2胶体微球自组装光子晶体的实验研究

光子晶体是一种周期性电介质材料,具有光子带隙和光子局域等一系列优异的光学特性。制备了多种不同直径的单分散二氧化硅胶体微球,采用垂直沉积法将不同直径,以及同一直径不同浓度的二氧化硅胶体微球自组装成多种光子晶体薄膜,并用扫描电子显微镜和紫外—可见—近红外分光光度计对其微观结构和光学特性进行了表征,结果表明所得晶体薄膜具有三维有序结构,其表面存点、线缺陷。自组装得到的光子晶体薄膜存在明显的光子带隙特征,带隙位置与二氧化硅胶体微球直径有关,带隙中心波长与理论值一致。随着二氧化硅胶体微球浓度的增加,光子带隙深度增加,特性更好,但是,当浓度大于10%时,光子带隙的深度反而减小。     

LED用图形化蓝宝石衬底的干法刻蚀工艺

近年来,图形化蓝宝石衬底(PSS)作为GaN基LED外延衬底材料被广泛应用。采用感应耦合等离子体(ICP)技术对涂覆有光刻胶阵列图案的蓝宝石衬底进行刻蚀。通过研究及优化不同ICP刻蚀工艺参数对刻蚀速率和选择比的影响,分别成功制备出蒙古包形和圆锥形图形化蓝宝石衬底片,并在其表面完成InGaN/GaN多量子阱外延及芯片工艺。借助光致发光和电致发光等手段测试其LED器件的光电学性能。实验结果发现圆锥形的图形化蓝宝石衬底拥有更强的光功率和更窄的半峰宽,说明这种形貌的衬底在GaN外延时有效减少了晶格失配造成的缺陷,提高了晶体质量,从而更有效地增加LED出光效率。     

大面积规则排布的AlN纳米柱阵列制备

采用金属有机化合物化学气相沉积(MOCVD)方法在2英寸(1英寸=2.54 cm)c面蓝宝石衬底上异质外延厚度1μm、具有原子级平整表面的高质量氮化铝(AlN)外延层.并在此高质量AlN薄膜的基础上开发了基于纳米压印光刻技术、干法刻蚀和湿法腐蚀相结合的工艺,通过自上而下的方法制备得到了大面积范围内规则排列的AlN纳米柱阵列,纳米柱的高度和直径分别为1μm和535 nm.研究结果表明,高晶体质量的AlN材料以及基于AZ400K溶液的湿法腐蚀工艺是制备无腐蚀坑且侧壁光滑的垂直AlN纳米柱阵列的关键.AlN纳米柱阵列的制备为深紫外纳米柱发光器件的研究奠定了基础.     

全息光刻和二次显影法制备柱形二维光子晶体

采用全息光刻和二次显影的方法制备了柱形二维光子晶体.在此过程中,二维点状的周期结构首先在正性光刻胶上直接形成,然后经由Si3N4硬掩模转移到衬底材料上.利用二次显影的方法,曝光强度最强和曝光强度中等区域的光刻胶能够被同时充分显影,而曝光强度最弱区域的光刻胶则可以完全被保留下来.通过调节入射角,可以方便地调节二维结构的周期.利用此方法,在相对较大的面积上制备了不同周期的二维结构,二维结构具有很好的均匀性和重复性.文章对有关的工艺参数进行了详细讨论.     

倾斜底涂法制备聚苯乙烯胶体晶体及其光学特性研究

采用倾斜底涂法将单分散的聚苯乙烯胶体微球自组装生长成为胶体晶体,并用扫描电子显微镜和紫外-可见光分光光度计对其形貌和光学特性进行测量。结果表明,聚苯乙烯微球自组装为面心立方密堆积结构,胶体晶体的光子带隙位于可见光波段。分别对不同胶体颗粒的粒径、悬浮液的浓度、基片倾斜角度及环境温度等制备条件下生成的聚苯乙烯光子晶体样品逐一分类对比,分析了影响光子带隙宽度和深度的因素。     

全息光刻可以制造三维光子晶体

拟用于可见和红外区的三维光子晶体的制造，较其二维晶体困难得多。其制造技术包括常规光刻与全息光刻。已发展出各种方法以制造三维晶体，包括聚合物球的自装配和光刻图样层的堆叠。但是，用第一种方法制出的晶体头一个样品和下一个无法重复；第二种方法则要求逐层制作图样。现在，牛津大学Andrew Tuberfield和Bob Denning领导的一个组将全息光刻扩展至三维，在一次曝光中产生的三维晶体厚度可达80层。研究者使用发射355 nm光的Q开关三倍频Nd:YAG激光曝光厚10~60 mm的环氧树脂型光刻胶层。光刻胶旋涂到熔凝石英盘上，盘的折射率与厚玻…     

Patterning Colloidal Crystals and Nanostructure Arrays by Soft Lithography

As one of the most robust and versatile routes to fabricate ordered micro‐ and nanostructures, soft lithography has been extensively applied to pattern a variety of molecules, polymers, biomolecules, and nanomaterials. This paper provides an overview on recent developments employing soft lithography methods to pattern colloidal crystals and related nanostructure arrays. Lift‐up soft lithography and modified microcontact printing methods are applied to fabricate patterned and non‐close‐packed colloidal crystals with controllable lattice spacing and lattice structure. Combining selective etching, imprinting, and micromolding methods, these colloidal crystal arrays can be employed as templates for fabrication of nanostructure arrays. Realization of all these processes is favored by the solvent swelling, elasticity, thermodecomposition, and thermoplastic characteristics of polymer materials. Applications of these colloidal crystals and nanostructure arrays have also been explored, such as biomimetic antireflective surfaces, superhydrophobic coatings, surface‐enhanced Raman spectroscopy substrates, and so on.     

Multifaceted and Nanobored Particle Arrays Sculpted Using Colloidal Lithography

A novel method of fabricating multifaceted and nanobored particle arrays via colloidal lithography using colloidal‐crystal layers as masks for anisotropic reactive‐ion etching (RIE) is reported. The shape of the sculpted particles is dependent on the crystal orientation relative to the etchant flow, the number of colloidal layers, the RIE conditions, and the matrix (or mask) structure in colloidal lithography. Arrays of non‐spherical particles with sculpted shapes, which to date could not otherwise be produced, are fabricated using a tilted anisotropic RIE process and the layer‐by‐layer growth of a colloidal mask. These non‐spherical particles and their ordered arrays can be used for antireflection surfaces, biosensors, and nanopatterning masks, as well as non‐spherical building blocks for novel colloidal crystals. In addition, polymeric particles with patterned holes of controlled depths obtained by the present method can be applied to the fabrication of functional composite particles.     

Designing 3D Polymeric Structures through Capillary Wetting on Colloidal Monolayer

Colloidal lithography has provided a facile means to create regular micro- and nano-patterns by employing colloidal crystals as masks. However, the patterns are usually restricted to 2D as most techniques do not exploit the spherical shape of colloidal masks. Here, 3D structures are designed by utilizing capillary wetting of liquified photoresists on colloidal monolayers of silica particles. The silica particles are anchored at planar air-photoresist interfaces to have an equilibrium contact angle without interfacial deformation for thick polymer layers. By contrast, when the polymer layers are thin enough, they wet the colloidal monolayer by forming periodic wavy interfaces to provide a constant Laplace pressure. The photo-crosslinking of the photoresist and subsequent removal of silica particles leave behind periodic nanostructures with 3D-undulated surfaces. Importantly, the structure and waviness are further controllable by adjusting the polymer thickness relative to the particle radius. As the shape of the interface is determined by capillarity, the 3D structures are reproducible as long as the dimension is smaller than the capillary length. The use of photoresists enables the production of micropatterns of the periodic wavy structures by photolithography. As one of the potential applications, structurally-colored patterns are demonstrated with enhanced plasmonic and diffraction colors.     

腔室状态对图形化蓝宝石衬底刻蚀工艺的影响

图形化蓝宝石衬底是近年来针对高度发光二极管的应用要求发展起来的一种新技术。通过利用自主研制的工业化感性耦合等离子体刻蚀机对图形化蓝宝石衬底的刻蚀工艺进行了研究。采用光学发射光谱仪和扫描电镜研究了PSS生产过程中腔室状态的变化对蓝宝石的刻蚀速率、选择比和图形形貌的影响。研究结果表明:随着反应腔累积放电时间的增加,刻蚀速率呈现下降趋势,选择比呈先上升然后下降的趋势。该趋势由反应腔室内表面上的沉积物所引起。     

Fabrication of Ordered Nanostructured Arrays Using Poly(dimethylsiloxane) Replica Molds Based on Three‐Dimensional Colloidal Crystals

Hexagonally arrayed structures of colloidal crystals with uniform surface are a good candidate for master molds to be used in soft lithography. Here, the fabrication of periodically arrayed nanostructures using poly(dimethylsiloxane) (PDMS) molds based on three‐dimensionally (3D) ordered colloidal crystals is reported. A robust, high‐quality 3D colloidal‐crystal master molds is prepared using the colloidal suspension containing a water‐soluble polymer. The surface patterns of the 3D colloidal crystals can then be transferred onto a polymer film via soft lithography, by means of the replication of the surface pattern with PDMS. Various hexagonally arrayed nanostructure patterns can be fabricated, including close‐packed and non‐close‐packed 2D arrays and honeycomb structures by the structural modification of the 3D colloidal‐crystal templates. The replicated hexagonally arrayed structures can also be used as templates for producing colloidal crystals with 2D superlattices.     

Cover Picture: A Hierarchically Structured Ni(OH)2 Monolayer Hollow‐Sphere Array and Its Tunable Optical Properties over a Large Region (Adv. Funct. Mater. 4/2007)

The fabrication of hierarchically structured Ni(OH)₂ monolayer hollow‐sphere arrays with the shell composed of building blocks of nanoflakelets is reported on p. 644 by Weiping Cai and co‐workers. The morphology can be easily controlled by the synthesis parameters, and the arrays show a tunable optical transmission stop band. Tuning can be achieved by changing the size or morphology of the hollow spheres. Such arrays may have potential applications in optical devices, photonic crystals, and as sensors for gas detection. The fabrication of a hierarchically structured Ni(OH)₂ monolayer hollow‐sphere array with the shell composed of building blocks of nanoflakelets is demonstrated based on a colloidal monolayer and electrochemical deposition. The morphology can be easily controlled by the colloidal monolayer and deposition parameters. Importantly, such monolayer hollow‐sphere array shows a morphology‐ and size‐dependent tunable optical transmission stop band. This stop band can be easily tuned from 455–1855 nm by changing the size of the hollow spheres between 1000 and 4500 nm, and also fine‐adjusted by changing the deposition time. The array exhibits a nearly incident‐angle‐independent position of the stop band that 3D photonic crystals do not possess. This structure may have potential applications in optical devices, photonic crystals, and sensors for gas detection.     

图形蓝宝石衬底GaN基发光二极管的研制

采用抗刻蚀性光刻胶作为掩膜,并利用光刻技术制作周期性结构,进行ICP干法刻蚀C面(0001)蓝宝石制作图形蓝宝石衬底(PSS);然后,在PSS上进行MOCVD制作GaN基发光二极管(LED)外延片;最终,进行芯片制造和测试。PSS的基本结构为圆孔,直径为3μm,间隔为2μm,深度为864 nm,呈六角形分布。与同批生长的普通蓝宝石衬底(CSS)GaN基LED芯片相比,PSS芯片的光强和光通量比CSS分别提高57.32%和28.33%(20 mA),并可减小芯片的反向漏电流,且未影响芯片的波长分布和电压特性。     

Direct Transcription of Two‐Dimensional Colloidal Crystal Arrays into Three‐Dimensional Photonic Crystals

A simple protocol for the fabrication of three‐dimensional (3D) photonic crystals in silicon is presented. Surface structuring by nanosphere lithography is merged with a novel silicon etching method to fabricate ordered 3D architectures. The SPRIE method, sequential passivation reactive ion etching, is a one‐step processing protocol relying on sequential passivation and reactive ion etching reactions using C₄F₈ and SF₆ plasma chemistries. The diffusion of fresh reactants and etch product species inside the etched channels is found to play an important role affecting the structural uniformity of the designed structures and the etch rate drift is corrected by adjusting the reaction times. High quality photonic crystals are thus obtained by adding the third dimension to the two‐dimensional (2D) colloidal crystal assemblies through SPRIE. Careful adjustments of both mask design and lateral etch extent balance allow the implementation of even more complex functionalities including photonic crystal slabs and precise defect engineering. 3D photonic crystal lattices exhibiting optical stop‐bands in the infrared spectral region are demonstrated, proving the potential of SPRIE for fast, simple, and large‐scale fabrication of photonic structures.