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Top 20 Most Read Articles
December 2011
The 20 articles with the most full-text downloads during the month, in descending order.
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Photovoltaic manufacturing: Present status, future prospects, and research needs J. Vac. Sci. Technol. A 29, 030801 (2011); doi:10.1116/1.3569757 (16 pages) Online Publication Date: 29 March 2011
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In May 2010 the United States National Science Foundation sponsored a two-day workshop to review the state-of-the-art and research challenges in photovoltaic (PV) manufacturing. This article summarizes the major conclusions and outcomes from this workshop, which was focused on identifying the science that needs to be done to help accelerate PV manufacturing. A significant portion of the article focuses on assessing the current status of and future opportunities in the major PV manufacturing technologies. These are solar cells based on crystalline silicon (c-Si), thin films of cadmium telluride (CdTe), thin films of copper indium gallium diselenide, and thin films of hydrogenated amorphous and nanocrystalline silicon. Current trends indicate that the cost per watt of c-Si and CdTe solar cells are being reduced to levels beyond the constraints commonly associated with these technologies. With a focus on TW/yr production capacity, the issue of material availability is discussed along with the emerging technologies of dye-sensitized solar cells and organic photovoltaics that are potentially less constrained by elemental abundance. Lastly, recommendations are made for research investment, with an emphasis on those areas that are expected to have cross-cutting impact.
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Plasma-Assisted Atomic Layer Deposition: Basics, Opportunities, and Challenges J. Vac. Sci. Technol. A 29, 050801 (2011); doi:10.1116/1.3609974 (26 pages) Online Publication Date: 18 August 2011
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Plasma-assisted atomic layer deposition (ALD) is an energy-enhanced method for the synthesis of ultra-thin films with Å-level resolution in which a plasma is employed during one step of the cyclic deposition process. The use of plasma species as reactants allows for more freedom in processing conditions and for a wider range of material properties compared with the conventional thermally-driven ALD method. Due to the continuous miniaturization in the microelectronics industry and the increasing relevance of ultra-thin films in many other applications, the deposition method has rapidly gained popularity in recent years, as is apparent from the increased number of articles published on the topic and plasma-assisted ALD reactors installed. To address the main differences between plasma-assisted ALD and thermal ALD, some basic aspects related to processing plasmas are presented in this review article. The plasma species and their role in the surface chemistry are addressed and different equipment configurations, including radical-enhanced ALD, direct plasma ALD, and remote plasma ALD, are described. The benefits and challenges provided by the use of a plasma step are presented and it is shown that the use of a plasma leads to a wider choice in material properties, substrate temperature, choice of precursors, and processing conditions, but that the processing can also be compromised by reduced film conformality and plasma damage. Finally, several reported emerging applications of plasma-assisted ALD are reviewed. It is expected that the merits offered by plasma-assisted ALD will further increase the interest of equipment manufacturers for developing industrial-scale deposition configurations such that the method will find its use in several manufacturing applications.
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J. Vac. Sci. Technol. A 30, 010802 (2012); doi:10.1116/1.3670745 (11 pages) Online Publication Date: 14 December 2011
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Atomic layer deposition (ALD) is a technique capable of producing ultrathin conformal films with atomic level control over thickness. A major drawback of ALD is its low deposition rate, making ALD less attractive for applications that require high throughput processing. An approach to overcome this drawback is spatial ALD, i.e., an ALD mode where the half-reactions are separated spatially instead of through the use of purge steps. This allows for high deposition rate and high throughput ALD without compromising the typical ALD assets. This paper gives a perspective of past and current developments in spatial ALD. The technology is discussed and the main players are identified. Furthermore, this overview highlights current as well as new applications for spatial ALD, with a focus on photovoltaics and flexible electronics.
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Compositional study of vacuum annealed Al doped ZnO thin films obtained by RF magnetron sputtering J. Vac. Sci. Technol. A 29, 051514 (2011); doi:10.1116/1.3624787 (9 pages) Online Publication Date: 18 August 2011
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Aluminum doped zinc oxide (AZO) thin films were obtained by RF magnetron sputtering. The effects of deposition parameters such as power, gas flow conditions, and substrate heating have been studied. Deposited and annealed films were characterized for composition as well as microstructure using x ray photoelectron spectroscopy and x ray diffraction. Films produced were polycrystalline in nature. Surface imaging and roughness studies were carried out using SEM and AFM, respectively. Columnar grain growth was predominantly observed. Optical and electrical properties were evaluated for transparent conducting oxide applications. Processing conditions were optimized to obtain highly transparent AZO films with a low resistivity value of 6.67 × 10−4 Ω cm.
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Atomic layer deposition for nanostructured Li-ion batteries J. Vac. Sci. Technol. A 30, 010801 (2012); doi:10.1116/1.3660699 (10 pages) Online Publication Date: 21 November 2011
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Nanostructuring is targeted as a solution to achieve the improvements required for implementing Li-ion batteries in a wide range of applications. These applications range in size from electrical vehicles down to microsystems. Atomic layer deposition (ALD) could be an enabling technology for nanostructured Li-ion batteries as it is capable of depositing ultrathin films (1–100 nm) in complex structures with precise growth control. The potential of ALD is reviewed for three battery concepts that can be distinguished, i.e., particle-based electrodes, 3D-structured electrodes, and 3D all-solid-state microbatteries. It is discussed that a large range of materials can be deposited by ALD and recent demonstrations of battery improvements by ALD are used to exemplify its large potential.
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Imaging and phase identification of Cu2ZnSnS4 thin films using confocal Raman spectroscopy J. Vac. Sci. Technol. A 29, 051203 (2011); doi:10.1116/1.3625249 (11 pages) Online Publication Date: 26 August 2011
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Copper zinc tin sulfide (Cu2ZnSnS4 or CZTS) is a potential candidate for next generation thin film solar cells because it contains abundant and nontoxic elements and exhibits high light absorption. Thin films of CZTS are typically synthesized by sulfidizing a stack of zinc, copper, and tin films. In addition to CZTS, a variety of binary and ternary metal sulfides can form and distinguishing among phases with similar crystal structure can be difficult. Herein, the authors show that confocal Raman spectroscopy and imaging can distinguish between CZTS and the other binary and ternary sulfides. Specifically, Raman spectroscopy was used to detect and distinguish between CZTS (338 cm−1), Cu2SnS3 (298 cm−1), and Cu4SnS4 (318 cm−1) phases through their characteristic scattering peaks. Confocal Raman spectroscopy was then used to image the distribution of coexisting phases and is demonstrated to be a useful tool for examining the heterogeneity of CZTS films. The authors show that, during sulfidation of a zinc/copper/tin film stack, ternary sulfides of copper and tin, such as Cu2SnS3 form first and are then converted to CZTS. The reason for formation of Cu2SnS3 as an intermediary to CZTS is the strong tendency of copper and tin to form intermetallic alloys upon evaporation. These alloys sulfidize and form copper tin sulfides first, and then eventually convert to CZTS in the presence of zinc. As a consequence, films sulfidized for 8 h at 400 °C contain both CZTS and Cu2SnS3, whereas films sulfidized at 500 °C contain nearly phase-pure CZTS. In addition, using Cu Kα radiation, the authors identify three CZTS X-ray diffraction peaks at 37.1° [(202)], 38° [(211)], and 44.9° [(105) and (213)], which are absent in ZnS and very weak in Cu2SnS3.
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J. Vac. Sci. Technol. A 30, 010601 (2012); doi:10.1116/1.3665217 (3 pages) Online Publication Date: 2 December 2011
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This paper describes the elaboration of high aspect ratio (250), high linear density (500 cm−1) suspended silicon nanobridges into low concentrated alkaline solutions. Trenches were first etched into silicon using the deep reactive ion etching STiGer process. These structures were immersed into low concentrated potassium hydroxide (KOH) or tetramethylammonium hydroxide (TMAH) solutions. The behaviors of KOH and TMAH as silicon trenches etching agents (kinetic and quality of etching) were studied to optimize the silicon nanowires (SiNWs) formation and the elaboration of the suspended structures. The limits of the SiNWs thickness in these conditions were also discussed.
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Mechanisms for sealing of porous low-k SiOCH by combined He and NH3 plasma treatment J. Vac. Sci. Technol. A 29, 051305 (2011); doi:10.1116/1.3626534 (8 pages) Online Publication Date: 22 August 2011
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Porous dielectric materials, such as SiOCH, are used as the insulator in interconnect wiring in microelectronics devices to lower the dielectric constant and so decrease the RC time delay. Sealing of the pores (up to a few nm in diameter) is necessary to prevent degradation of the low-k properties during subsequent processing steps by diffusion of reactants through the pores into the material. Sequential treatment of porous SiOCH by He and NH3 plasmas is potentially a means of sealing pores while maintaining the low-k of the dielectric. The He plasma activates surface sites to accelerate the reactions responsible for pore sealing. NH3 plasma treatment completes the sealing through one of two mechanisms resulting from the adsorption of NHx radicals — catalyzing the formation of a densified surface layer or formation of Si-N, C-N and N-N bonds to bridge over the pore. In this paper, we discuss mechanisms for pore sealing bridging bonds based on results from an integrated computational investigation of the etching, cleaning, activation and sealing of porous SiOCH in sequential Ar/C4F8/O2, Ar/O2, He and Ar/NH3 plasmas. The authors found that pores in excess of 1 nm in radius are difficult to seal due to the inability of N-bonding to bridge the pore opening. Factors affecting the sealing efficiency, such as treatment time, average pore radius and aspect ratio are discussed.
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J. Vac. Sci. Technol. A 29, 051302 (2011); doi:10.1116/1.3620494 (6 pages) Online Publication Date: 9 August 2011
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Transparent dielectric layers with varying compositions of TiO2 and SiO2, and ITO are deposited on sapphire and Si substrates by using an RF sputter system. Inductively coupled plasma (ICP) reactive ion etching (RIE) of the ITO hard mask is examined under H2, CH4, and Cl2 chemical environments. The slope of the sidewall and the etch residue on the sidewall of the ITO hard mask are controlled by the flow rates of H2, CH4, and Cl2. ICP-RIE dry etch of TiO2 and SiO2 is investigated under fluorinated environments. Comparable etch rates of TiO2 and SiO2 (ratio ≈ 2:1) and high selectivity ≫ 1 over ITO are found. Graded-refractive-index (GRIN) layers, made up of multiple dielectric layers of TiO2 and SiO2, are patterned to form cylindrical pillars by ICP etching using the ITO hard mask. Fluorine containing residues are identified on the TiO2 and SiO2 surfaces. Various etch chemistries are investigated to obtain smooth, vertical, and residue-free sidewalls of the GRIN pillars.
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Plasma deposition of optical films and coatings: A review J. Vac. Sci. Technol. A 18, 2619 (2000); doi:10.1116/1.1314395 (27 pages)
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Plasma enhanced chemical vapor deposition (PECVD) is being increasingly used for the fabrication of transparent dielectric optical films and coatings. This involves single-layer, multilayer, graded index, and nanocomposite optical thin film systems for applications such as optical filters, antireflective coatings, optical waveguides, and others. Beside their basic optical properties (refractive index, extinction coefficient, optical loss), these systems very frequently offer other desirable “functional” characteristics. These include hardness, scratch, abrasion, and erosion resistance, improved adhesion to various technologically important substrate materials such as polymers, hydrophobicity or hydrophilicity, long-term chemical, thermal, and environmental stability, gas and vapor impermeability, and others. In the present article, we critically review the advances in the development of plasma processes and plasma systems for the synthesis of thin film high and low index optical materials, and in the control of plasma–surface interactions leading to desired film microstructures. We particularly underline those specificities of PECVD, which distinguish it from other conventional techniques for producing optical films (mainly physical vapor deposition), such as fabrication of graded index (inhomogeneous) layers, control of interfaces, high deposition rate at low temperature, enhanced mechanical and other functional characteristics, and industrial scaleup. Advances in this field are illustrated by selected examples of PECVD of antireflective coatings, rugate filters, integrated optical devices, and others. © 2000 American Vacuum Society. |
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J. Vac. Sci. Technol. A 25, 1317 (2007); doi:10.1116/1.2764082 (19 pages) Online Publication Date: 30 July 2007
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Physical vapor deposition under conditions of obliquely incident flux and limited adatom diffusion results in a film with a columnar microstructure. These columns will be oriented toward the vapor source and substrate rotation can be used to sculpt the columns into various morphologies. This is the basis for glancing angle deposition (GLAD), a technique for fabricating porous thin films with engineered structures. The origin of the columnar structure characteristic of GLAD films is discussed in terms of nucleation processes and structure zone models. As deposition continues, the columnar structures are influenced by atomic-scale ballistic shadowing and surface diffusion. Competitive growth is observed where the tallest columns grow at the expense of smaller features. The column shape evolves during growth, and power-law scaling behavior is observed as shown in both experimental results and theoretical simulations. Due to the porous nature of the films and the increased surface area, a variety of chemical applications and sensor device architectures are possible. Because the GLAD process provides precise nanoscale control over the film structure, characteristics such as the mechanical, magnetic, and optical properties of the deposited film may be engineered for various applications. Depositing onto prepatterned substrates forces the columns to adopt a planar ordering, an important requirement for photonic crystal applications.
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Atomic layer deposition of GaN at low temperatures J. Vac. Sci. Technol. A 30, 01A124 (2012); doi:10.1116/1.3664102 (4 pages) Online Publication Date: 1 December 2011
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The authors report on the self-limiting growth of GaN thin films at low temperatures. Films were deposited on Si substrates by plasma-enhanced atomic layer deposition using trimethylgallium (TMG) and ammonia (NH3) as the group-III and -V precursors, respectively. GaN deposition rate saturated at 185 °C for NH3 doses starting from 90 s. Atomic layer deposition temperature window was observed from 185 to ∼385 °C. Deposition rate, which is constant at ∼0.51 Å/cycle within the temperature range of 250 – 350 °C, increased slightly as the temperature decreased to 185 °C. In the bulk film, concentrations of Ga, N, and O were constant at ∼36.6, ∼43.9, and ∼19.5 at. %, respectively. C was detected only at the surface and no C impurities were found in the bulk film. High oxygen concentration in films was attributed to the oxygen impurities present in group-V precursor. High-resolution transmission electron microscopy studies revealed a microstructure consisting of small crystallites dispersed in an amorphous matrix.
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Summary Abstract: Collision induced dissociation and desorption: CH4 and CO on Ni (111) J. Vac. Sci. Technol. A 6, 903 (1988); doi:10.1116/1.575027 (2 pages)
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Substrate grain size and orientation of Cu and Cu–Ni foils used for the growth of graphene films J. Vac. Sci. Technol. A 30, 011401 (2012); doi:10.1116/1.3663877 (7 pages) Online Publication Date: 2 December 2011
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Graphene growth on Cu foils by catalytic decomposition of methane forms predominantly single-layer graphene films due to the low solubility of carbon in Cu. On the other hand, graphene growth on Cu–Ni foils can result in the controlled growth of few-layer graphene films because of the higher solubility of carbon in Ni. One of the key issues for the use of graphene grown by chemical vapor deposition for device applications is the influence of defects on the transport properties of the graphene. For instance, growth on metal foil substrates is expected to result in multidomain graphene growth because of the presence of grains within the foil that exhibit a variety of surface terminations. Therefore, the size and orientation of the grains within the metal foil should influence the defect density of the graphene. For this reason, we have studied the effect of total anneal time and temperature on the orientation and size of grains within Cu foils and Cu–Ni alloy foils with a nominal concentration of 90/10 by weight. The graphene growth procedure involves preannealing the foil in a H2 background followed by the graphene growth in a CH4/H2 atmosphere. Measurements of the substrate grain size have been performed with optical microscopy and scanning electron microscopy. These results show typical lateral dimensions ranging from a few millimeters up to approximately a centimeter for Cu foils annealed at 1030 °C for 35 min and from tens of microns up to a few hundred microns for the 90/10 Cu–Ni foils annealed at 1050 °C for times ranging from 45 to 90 min. The smaller grains within the Cu–Ni foils are attributed to the higher melting point of the Cu–Ni alloy. The crystallographic orientation within each substrate grain was studied with electron backscatter diffraction, and shows that the preferred orientation for the Cu foil is primarily toward the (100) surface plane. For the 90/10 Cu–Ni foils, the orientation of the surface of the grains is initially toward the (110) plane and shifts into an orientation midway between the (100) and (111) planes as the anneal time is increased.
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Status and potential of atmospheric plasma processing of materials J. Vac. Sci. Technol. A 29, 020801 (2011); doi:10.1116/1.3559547 (17 pages) Online Publication Date: 4 March 2011
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This paper is a review of the current status and potential of atmospheric plasma technology for materials processing. The main focus is the recent developments in the area of dielectric barrier discharges with emphasis in the functionalization of polymers, deposition of organic and inorganic coatings, and plasma processing of biomaterials. A brief overview of both the equipment being used and the physicochemical reactions occurring in the gas phase is also presented. Atmospheric plasma technology offers major industrial, economic, and environmental advantages over other conventional processing methods. At the same time there is also tremendous potential for future research and applications involving both the industrial and academic world.
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Metal–organic interface and charge injection in organic electronic devices J. Vac. Sci. Technol. A 21, 521 (2003); doi:10.1116/1.1559919 (11 pages) Online Publication Date: 18 March 2003
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Charge injection at the interface between metallic electrodes and organic semiconductors plays a crucial role in the performance of organic (opto-)electronic devices. This article discusses the current understanding of the formation of the metal–organic contact and the parameters which control the injection current. Organic semiconductors differ significantly from their inorganic counterparts, primarily because they are amorphous van der Waals solids. As a result the electronic states are highly localized, and charge transport is by site-to-site hopping. Organics can also form clean interfaces with many metals, free of interface states in the gap. Nevertheless, there is generally found to be a significant vacuum level offset, the origins of which are not yet fully understood. Organic semiconductors are frequently free of donor and acceptor dopants, and as a result the depletion depth is larger than the organic layer thickness. Thus the Fermi level in the organic and the charge injection barriers depend most directly on the interface offset. The charge injection process is described as thermally assisted tunneling from the delocalized states of the metal into the localized states of the semiconductor, whose energy includes contributions from the mean barrier height, the image potential, the energetic disorder, and the applied electric field. There is no completely satisfactory analytic theory for the field and temperature dependence of the injection current, which, for well characterized interfaces, exhibits behavior relating to both thermionic emission and field-induced tunneling. © 2003 American Vacuum Society. |
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Work function of fluorine doped tin oxide J. Vac. Sci. Technol. A 29, 011019 (2011); doi:10.1116/1.3525641 (4 pages) Online Publication Date: 5 January 2011
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Fluorine doped tin oxide (FTO) is a commonly used transparent conducting oxide in optoelectronic device applications. The work function of FTO is commonly cited as 4.4 eV, which is incommensurate with recent device performance results. Using x-ray photoelectron spectroscopy, the authors measured the work function of commercial FTO to be 5.0±0.1 eV. UV ozone treatment was found to increase the work function by ∼ 0.1 eV due to surface band bending. The origins of the much lower work function previously reported are also discussed and are found to be a result of carbon contamination and UV induced work function lowering.
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Structural and electrical characterization of HBr/O2 plasma damage to Si substrate J. Vac. Sci. Technol. A 29, 041301 (2011); doi:10.1116/1.3596606 (7 pages) Online Publication Date: 23 June 2011
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Silicon substrate damage caused by HBr/O2 plasma exposure was investigated by spectroscopic ellipsometry (SE), high-resolution Rutherford backscattering spectroscopy, and transmission electron microscopy. The damage caused by H2, Ar, and O2 plasma exposure was also compared to clarify the ion-species dependence. Although the damage basically consists of a surface oxidized layer and underlying dislocated Si, the damage structure strongly depends on the incident ion species, ion energy, and oxidation during air and plasma exposure. In the case of HBr/O2 plasma exposure, hydrogen generated the deep damaged layer (∼10 nm), whereas ion-enhanced diffusion of oxygen, supplied simultaneously by the plasma, caused the thick surface oxidation.
In-line monitoring of damage thicknesses by SE, developed with an optimized optical model, showed that the SE can be used to precisely monitor damage thicknesses in mass production. Capacitance–voltage (C–V) characteristics of a damaged layer were studied before and after diluted-HF (DHF) treatment. Results showed that a positive charge is generated at the surface oxide–dislocated Si interface and/or in the bulk oxide after plasma exposure. After DHF treatment, most of the positive charges were removed, while the thickness of the “Si recess” was increased by removing the thick surface oxidized layer. As both the Si recess and remaining dislocated Si, including positive charges, cause the degradation of electrical performance, precise monitoring of the surface structure and understanding its effect on device performance is indispensable for creating advanced devices.
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Nanosphere lithography: A materials general fabrication process for periodic particle array surfaces J. Vac. Sci. Technol. A 13, 1553 (1995); doi:10.1116/1.579726 (6 pages)
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In this article nanosphere lithography (NSL) is demonstrated to be a materials general fabrication process for the production of periodic particle array (PPA) surfaces having nanometer scale features. A variety of PPA surfaces have been prepared using identical single‐layer (SL) and double‐layer (DL) NSL masks made by self‐assembly of polymer nanospheres with diameter, D=264 nm, and varying both the substrate material S and the particle material M. In the examples shown here, S was an insulator, semiconductor, or metal and M was a metal, inorganic ionic insulator, or an organic π‐electron semiconductor. PPA structural characterization and determination of nanoparticle metrics was accomplished with atomic force microscopy. This is the first demonstration of nanometer scale PPA surfaces formed from molecular materials. © 1995 American Vacuum Society |
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Reaction mechanisms for atomic layer deposition of aluminum oxide on semiconductor substrates J. Vac. Sci. Technol. A 30, 01A127 (2012); doi:10.1116/1.3664090 (10 pages) Online Publication Date: 2 December 2011
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In this work, we have studied the TMA/H2O (TMA = Al(CH3)3) atomic layer deposition (ALD) of Al2O3 on hydroxyl (OH) and thiol (SH) terminated semiconductor substrates. Total reflection x-ray fluorescence reveals a complex growth-per-cycle evolution during the early ALD reaction cycles. OH and SH terminated surfaces demonstrate growth inhibition from the second reaction cycle on. Theoretical calculations, based on density functional theory, are performed on cluster models to investigate the first TMA/H2O reaction cycle. Based on the theoretical results, we discuss possible mechanisms for the growth inhibition from the second reaction cycle on. In addition, our calculations show that AlCH3 groups are hydrolyzed by a H2O molecule adsorbed on a neighboring Al atom, independent of the type of backbonds (Si-O, Ge-O, or Ge-S) of AlCH3. The coordination of Al remains four-fold after the first TMA/H2O reaction cycle.
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