Initiated and Oxidative Chemical Vapor Deposition of Polymeric Thin Films: iCVD and oCVD

The techniques of initiated chemical vapor deposition (iCVD) and oxidative chemical vapor deposition (oCVD) enable the fabrication of chemically well‐defined thin polymeric films on complex objects with micro‐ and nano‐scale features. By depositing polymers from the vapor phase, many wetting and solution effects are avoided, and conformal films can be created. In iCVD, a variant of hot filament CVD, the deposition rate is enhanced and chemical functionalities of the polymers' constituents are maintained by including a thermally labile initiator in the feed stream. Due to the low energy required when using an initiator, delicate substrates can be coated. In oCVD, infusible, electrically conductive films are formed directly on the substrate of interest as the oxidant and monomer are introduced into the reactor simultaneously. This Feature Article provides an overview of the work that has been done to develop iCVD and oCVD into platform technologies. Relevant background, fundamentals, and applications will be discussed.     

Ultralow Dielectric Constant Tetravinyltetramethylcyclotetrasiloxane Films Deposited by Initiated Chemical Vapor Deposition (iCVD)

Simultaneous improvement of mechanical properties and lowering of the dielectric constant occur when films grown from the cyclic monomer tetravinyltetramethylcyclotetrasiloxane (V4D4) via initiated chemical vapor deposition (iCVD) are thermally cured in air. Clear signatures from silsesquioxane cage structures in the annealed films appear in the Fourier transform IR (1140 cm^?1) and Raman (1117 cm^?1) spectra. The iCVD method consumes an order of magnitude lower power density than the traditional plasma‐enhanced CVD, thus preserving the precursor's delicate ring structure and organic substituents in the as‐deposited films. The high degree of structural retention in the as‐deposited film allows for the beneficial formation of intrinsically porous silsesquioxane cages upon annealing in air. Complete oxidation of the silicon creates ‘Q’ groups, which impart greater hardness and modulus to the films by increasing the average connectivity number of the film matrix beyond the percolation of rigidity. The removal of labile hydrocarbon moieties allows for the oxidation of the as‐deposited film while simultaneously inducing porosity. This combination of events avoids the typical trade‐off between improved mechanical properties and higher dielectric constants. Films annealed at 410 °C have a dielectric constant of 2.15, and a hardness and modulus of 0.78 and 5.4 GPa, respectively. The solvent‐less and low‐energy nature of iCVD make it attractive from an environmental safety and health perspective.     

MOCVD法制备MgZnO合金薄膜

采用金属有机化学气相沉积方法在C面蓝宝石衬底上生长MgxZn1-xO合金薄膜.c轴取向的MgxZn1-xO薄膜在600～630℃温度下沉积. 通过X射线衍射和透射光谱研究了薄膜的结构和光学特性. 研究表明当x的取值小于等于0.39时，合金薄膜保持ZnO的六角形纤锌矿结构，没有观察到MgO分相，此时薄膜的能带宽度可以在3.3～3.95eV之间调节.     

用Cat-CVD方法制备多晶硅薄膜及结构分析

以金属钨为催化热丝,采用热丝催化化学气相沉积,在300℃的玻璃衬底上沉积多晶硅薄膜。研究了H2稀释率、钨丝与衬底间的距离和反应室气体压力等沉积参数对制备多晶硅薄膜的影响,并通过XRD谱分析,确定了本实验系统的最佳多晶硅成膜条件:FR(SiH4)=5mL/min,FR(H2)=70mL/min,P=50Pa,L衬底与钨丝=7.5cm,T=30min,t衬底=300℃,特征峰在(111)面上。在接触式膜厚仪测量的基础上,计算出薄膜生长速率为0.6nm/s。对最佳成膜条件下制备的多晶硅薄膜进行刻蚀,形成不同的厚度,以便进行逐层分析。采用XRD和SEM方法对不同厚度的薄膜测试发现,随着薄膜厚度的减小,(111)面的XRD特征峰强度逐渐下降,(111)面上的晶粒尺寸基本没有变化,都是50nm左右。根据测试结果分析了薄膜的生长机制,提出了薄膜生长是分步成核,成核后沿(111)面纵向生长的观点。认为反应基元首先随机吸附在衬底上,在H原子的作用下在一些位置上成核,而在其他位置形成非晶相。已形成的晶核逐渐长大并沿(111)面纵向生长;已形成的非晶相也在生长,但上面不断有晶核形成。当薄膜达到一定厚度,非晶相表面完全被晶核占据,整个薄膜表面成为多晶相,此后整个薄膜处于沿(111)面的纵向生长阶段,直至反应结束,完整的晶粒结构呈柱状。     

Amphiphilic Poly(p‐phenylene)s for Self‐Organized Porous Blue‐Light‐Emitting Thin Films

Micro‐ and nanostructuring of conjugated polymers are of critical importance in the fabrication of molecular electronic devices as well as photonic and bandgap materials. The present report delineates the single‐step self‐organization of highly ordered structures of functionalized poly(p‐phenylene)s without the aid of either a controlled environment or expensive fabrication methodologies. Microporous films of these polymers, with a honeycomb pattern, were prepared by direct spreading of the dilute polymer solution on various substrates, such as glass, quartz, silicon wafer, indium tin oxide, gold‐coated mica, and water, under ambient conditions. The polymeric film obtained from C₁₂PPPOH comprises highly periodic, defect‐free structures with blue‐light‐emitting properties. It is expected that such microstructured, conjugated polymeric films will have interesting applications in photonic and optoelectronic devices. The ability of the polymer to template the facile micropatterning of nanomaterials gives rise to hybrid films with very good spatial dispersion of the carbon nanotubes.     

Site‐Selective Deposition of Nanostructured ZnO Thin Films from Solutions Containing Polyvinylpyrrolidone

When soluble zinc salts are hydrolyzed in water, usually elongated micrometer‐sized zincite crystals are formed. In this study, polyvinylpyrrolidone (PVP) in a methanolic solution is used as an agent to control the morphology of the deposition product. It prevents crystal growth and yields zinc oxide nanocrystals. Thin films consisting of zinc oxide nanocrystals are formed on self‐assembled monolayers (SAMs) of sulfonate‐terminated alkylsiloxanes. Patterned films are deposited after local decomposition of the SAM by UV irradiation. The films fabricated from methanolic solutions containing PVP are particularly smooth, uniform and stable. Their thickness is determined by the deposition time and the molar ratio [PVP]:[Zn²⁺], so that films of arbitrary thickness and nearly constant roughness can be obtained. The crystal grains are oriented preferentially with 〈001〉 direction perpendicular to the substrate surface. The films show ultraviolet, orange‐red and green‐yellow photoluminescence; the latter is quenched by heat treatment. Based on the obtained experimental results, a deposition mechanism is suggested.     

化学气相沉积TiO2薄膜的XPS研究

通过XPS分析了TiO2薄膜的结构。薄膜是通过化学气相沉积的方法生长，有机源遇热发生分解，沉积在硅衬底上形成TiO2薄膜。XPS分析表明：所得TiO2薄膜含有Ti,C,O,Al,Si元素。各元素的电子结合能与理论值并无太大的偏移，说明通过化学气相沉积法制备的TiO2薄膜，纯度高，质量好，晶型为锐钛矿。     

Chemical Solution Deposition of Silver Halide Films

Chemical solution deposition of semiconductor films has been confined almost entirely to chalcogenides. Here, we extend this technique to halide films. Silver halides (AgI, AgBr, and AgCl) were deposited using in‐situ homogeneous hydrolysis of organic haloalcohols to form halide ions that react with silver ions in aqueous solution. Also, a rapid precipitation method is described that gives AgCl films. Structural (XRD), morphological (TEM), and optical (transmission spectra) characterizations of the films are presented. Some preliminary results and ideas on other halide films are presented.     

气相沉积法制备聚酰亚胺薄膜的光、电特性研究

以均苯四甲酸二酐 (PMDA)和二氨基二苯醚 (ODA)为单体原料 ,研究了在 3× 10 - 3Pa真空度下 ,通过控制双源单体的加入摩尔计量、加热时间和其沉积速率 ,在玻璃衬底上合成了聚酰亚胺的预聚体聚酰胺酸 ,再经 15 0～ 2 0 0℃真空加热亚胺化 1h后得到了成膜性良好的均匀聚酰亚胺薄膜。通过红外吸收、X射线衍射和扫描电镜等方法对样品的组织结构和特性进行了研究和探讨。结果表明 ,气相沉积法制备的聚酰亚胺薄膜具有良好的电学特性和热稳定性     

Millimeter-Size All-inorganic Perovskite Crystalline Thin Film Grown by Chemical Vapor Deposition

The chemical vapor deposition (CVD) method is a dry approach that can produce high quality crystals and thin films at large scale which can be easily adapted by industry. In this work, CVD technology is employed to grow high quality, large size all-inorganic cesium lead bromide perovskite crystalline film for the first time. The obtained films have millimeter size crystalline domains with high phase purity. The growth kinetics are examined in detail by optical microscopy and X-ray diffraction. The deposition rate and growth temperature are found to be the key parameters allowing to achieve large scale crystal growth. The large crystalline grains exhibit exceptional optical properties including negligible Stokes shift and uniform photoluminescence over a large scale. This suggests a high degree of crystallinity free from internal strain or defects. A lateral diode within one large crystalline grain is further fabricated and significant photo-generated voltage and short circuit current are observed, suggesting highly efficient carrier transport and collections without scattering within the grain. This demonstration suggests that the CVD grown all-inorganic perovskite thin films enable a promising fabrication route suitable for photovoltaic or photo-detector applications.     

气相沉积法制备聚酰亚胺薄膜的光、电特性研究

以均苯四甲酸酐（ＰＭＤＡ）和二氨基二苯醚（ＯＤＡ）为单体原料,研究了在２×１０－５Ｔｏｒｒ真空度下,通过控制双源单体的加入摩尔计量、加热时间和其沉积速率,在玻璃衬底上合成了聚酰亚胺的预聚体聚酰胺酸,再经１５０～２００℃真空加热亚胺化,１小时后得到了成膜性良好的均匀聚酰亚胺薄膜。通过红外吸收、ｘ射线衍射、扫描电镜等方法对样品的组织结构和特性进行了研究和探讨。结果表明,气相沉积法制备的聚酰亚胺薄膜具有良好的电学特性和热稳定性,不失为聚合物合成的可能途径之一。     

Inside Front Cover: High‐Performance and Stable Organic Thin‐Film Transistors Based on Fused Thiophenes (Adv. Funct. Mater. 3/2006)

A series of new organic semiconductors for organic thin‐film transistors using dithieno[3,2‐b:2′,3′‐d]thiophene as the core have been synthesized. In work reported by Liu, Zhu, and co‐workers on p. 426, the phenyl‐substituted compound exhibited a high mobility of 0.42 cm² V^–1 s^–1 and an on/off ratio of 5 × 10⁶. Weekly shelf‐life tests of the transistors based on the bis(diphenyl)‐substituted thiophene under ambient conditions showed that the mobility was almost unchanged after more than two months, demonstrating potential for applications in future organic electronics. A series of new organic semiconductors for organic thin‐film transistors (OTFTs) using dithieno[3,2‐b:2′,3′‐d]thiophene as the core are synthesized. Their electronic and optical properties are investigated using scanning electron microscopy (SEM), X‐ray diffraction (XRD), UV‐vis and photoluminescence spectroscopies, thermal gravimetric analysis (TGA), and differential scanning calorimetry (DSC). The compounds exhibit an excellent field‐effect performance with a high mobility of 0.42 cm² V^–1 s^–1 and an on/off ratio of 5 × 10⁶. XRD patterns reveal these films, grown by vacuum deposition, to be highly crystalline, and SEM reveals well‐interconnected, microcrystalline domains in these films at room temperature. TGA and DSC demonstrate that the phenyl‐substituted compounds possess excellent thermal stability. Furthermore, weekly shelf‐life tests (under ambient conditions) of the OTFTs based on the phenyl‐substituted compounds show that the mobility for the bis(diphenyl)‐substituted thiophene was almost unchanged for more than two months, indicating a high environmental stability.     

气相沉积法制备含酞菁铜聚酰亚胺薄膜的光电性能

在2×10-3Pa真空度下,以酞菁铜、均苯四甲酸酐和二氨基二苯醚为原料,通过控制三源单体的加入摩尔计量、加热时间和沉积速率,在玻璃衬底上合成了含酞菁铜的聚酰胺酸,再经150℃～200℃真空加热亚胺化1 h后得到了成膜性良好的均匀含酞菁铜聚酰亚胺薄膜.红外谱图证实了所合成产物的结构,紫外-可见光吸收分析表明含酞菁铜聚酰亚胺薄膜在可见光区、近红外区具有较强的吸收,热失重分析表明所制备的含酞菁铜聚酰亚胺具有良好的热稳定性能;用简并四波混频方法测得薄膜的三阶非线性极化率为1.984×10-9esu,表现出良好的三阶非线性特性.     

化学气相沉积光学级金刚石薄膜的研究进展

化学气相沉积（CVD））金刚石薄膜优异的光学性能在近几年得到了广泛的重视,关于它的研究也在近几年取得了较大的突破。综述了CVD金刚石薄膜的光学性能,着重从成核、生长和后期处理三个方面对光学级CVD金刚石薄膜的制备进行了讨论,并对今后的研究作了展望。     

激光化学气相沉积法制备TiO2薄膜

利用激光化学气相沉积(LCVD)方法,以钛金属有机化合物为前驱体,以O2为反应气体,在激光功率PL为0～200 w、基板预热温度为400～700℃的条件下,制备出了金红石型TiO2薄膜和金红石型与锐钛矿型混合TiO2薄膜.研究表明,激光功率和基板预热温度对所沉积的TiO2薄膜的物相组成、截面组织,表面形貌和薄膜生长速度均有着显著的影响.     

Characteristics and Electrical Properties of SiNx：H Films Fabricated by Plasma-Enhanced Chemical Vapor Deposition

SiNx：H films with different N/Si ratios are synthesized by plasma-enhanced chemical vapor deposition （PECVD）. Composition and structure characteristics are detected by Fourier transform infrared spectroscopy （FTIR） and X-ray photoelectron spectroscopy （XPS）. It indicates that Si-N bonds increase with increased NH3/SiH4 ratio. Electrical property investigations by I-V measurements show that the prepared films offer higher resistivity and less leakage current with increased N/Si ratio and exhibit entirely insulating properties when N/Si ratio reaches 0.9, which is ascribed to increased Si-N bonds achieved.     

CVD异质外延金刚石膜最新研究进展

评论了国内外化学气相沉积的异质外延金刚石膜制备技术、性质表征以及应用和展望。     

Systematic Control of Nucleation Density in Poly(3‐Hexylthiophene) Thin Films

While molecular ordering via crystallization is responsible for many of the impressive optoelectronic properties of thin‐film semiconducting polymer devices, crystalline morphology and its crucial influence on performance remains poorly controlled and is usually studied as a passive result of the conditions imposed by film deposition parameters. A method for systematic control over crystalline morphology in conjugated polymer thin films by very precise control of nucleation density and crystal growth conditions is presented. A precast poly(3‐hexylthiophene) film is first swollen into a solution‐like state in well‐defined vapor pressures of a good solvent, while the physical state of the polymer chains is monitored using in situ UV–vis spectroscopy and ellipsometry. Nucleation density is selected by a controlled deswelling of the film or by a self‐seeding approach using undissolved crystalline aggregates that remain in the swollen film. Nucleation densities ranging successively over many orders of magnitude are achieved, extending into the regime of spherulitic domains 10 to 100 μm in diameter, a length scale highly relevant for typical probes of macroscopic charge transport such as field‐effect transistors. This method is presented as a tool for future systematic study of the structure‐function relation in semicrystalline semiconducting polymers in a broad range of applications.     

Synthesis of Poly(4‐vinylpyridine) Thin Films by Initiated Chemical Vapor Deposition (iCVD) for Selective Nanotrench‐Based Sensing of Nitroaromatics

A new nanoscale sensing concept for the detection of nitroaromatic explosives is described. The design consists of nitroaromatic‐selective polymeric layers deposited inside microfabricated trenches. As the layers are exposed to nitroaromatic vapors, they swell and contact each other to close an electrical circuit. The nitroaromatic selective polymer, poly(4‐vinylpyridine) (P4VP), is deposited in the trenches using initiated chemical vapor deposition (iCVD). P4VP is characterized for the first time as a selective layer for the absorption of nitroaromatic vapors. The Flory–Huggins equation is used to model the swelling response to nitroaromatic vapors. The Flory–Huggins interaction parameter for the P4VP–nitrobenzene system at 40 °C is 0.71 and 0.25 for P4VP–4‐nitrotoluene at 60 °C. Sensing of nitrobenzene vapors is demonstrated in a prototype device, while techniques to improve the performance of the design in terms of response time and sensitivities are described. Modeling shows that concentration and mass limits of detection of 0.95 ppb and 3 fg, respectively, can be achieved.     

High‐Performance and Stable Organic Thin‐Film Transistors Based on Fused Thiophenes

A series of new organic semiconductors for organic thin‐film transistors (OTFTs) using dithieno[3,2‐b:2′,3′‐d]thiophene as the core are synthesized. Their electronic and optical properties are investigated using scanning electron microscopy (SEM), X‐ray diffraction (XRD), UV‐vis and photoluminescence spectroscopies, thermal gravimetric analysis (TGA), and differential scanning calorimetry (DSC). The compounds exhibit an excellent field‐effect performance with a high mobility of 0.42 cm² V^–1 s^–1 and an on/off ratio of 5 × 10⁶. XRD patterns reveal these films, grown by vacuum deposition, to be highly crystalline, and SEM reveals well‐interconnected, microcrystalline domains in these films at room temperature. TGA and DSC demonstrate that the phenyl‐substituted compounds possess excellent thermal stability. Furthermore, weekly shelf‐life tests (under ambient conditions) of the OTFTs based on the phenyl‐substituted compounds show that the mobility for the bis(diphenyl)‐substituted thiophene was almost unchanged for more than two months, indicating a high environmental stability.