Epitaxial atomic layer deposition

There are numerous materials, both metallic and ceramic, that are produced via CVD processes, including some exciting new applications such as CVD diamond, but they all involve deposition on some substrate, making them fundamentally composite materials. There are equally numerous modifications to the basic CVD processes, leading to such exotic-sounding processes as vapor-phase epitaxy (VPE), atomic-layer epitaxy (ALE), chemical-beam epitaxy (CBE), plasma-enhanced CVD (PECVD), laser-assisted CVD (LACVD), and metal-organic compound CVD (MOCVD). We will discuss the specifics of CVD processing equipment and more CVD materials in Chapter 7. 

Fundamental concepts of the molecular layering method have been developed and applied by the team headed by Professor Valentine Aleskovsky in Russia. This method, similar to atomic layer epitaxy and atomic layer deposition, has been used to create monolayers on oxides and polymers as humidity sensors, flame retardants, and agents to enhance sintering in ceramic materials. 

ALE or ALD atomic layer epitaxy or atomic layer deposition... 

Electron diffraction investigations showed that epitaxy did indeed exist when one metal was electrodeposited on another, but that it persisted for only tens or hundreds of atomic layers beyond the interface. Thereafter the atomic structure (or lattice) of the deposit altered to one characteristic of the plating conditions. Epitaxy ceased before an electrodeposit is thick enough to see with an optic microscope, and at thicknesses well below those at which pseudomorphism is observed. 

Numerous works have been implemented on tellurium electrochemistry and its adsorption at metal surfaces. The morphological structures of electrodeposited Te layers at various stages of deposition (first UPD, second UPD, and bulk deposition) are now well known [88-93]. As discussed in the previous paragraphs, Stickney and co-workers have carried out detailed characterizations of the first Te monolayer on Au single-crystal surfaces in order to establish the method of electrochemical atomic layer epitaxy of CdTe. 

Gregory BW, Suggs DW, Stickney JL (1991) Conditions for the deposition of CdTe by electrochemical atomic layer epitaxy. J Electrochem Soc 138 1279-1284 Suggs DW, Stickney JL (1991) Characterization of atomic layers of tellurium electrodeposited on the low-index planes of gold. J Phys Chem 95 10056-64 Suggs DW, Stickney JL (1993) Studies of the structures formed by the alternated electrodeposition of atomic layers of Cd and Te on the low-index planes of Au. 1. LEED and Auger studies. Surf Sci 290 362-374... 

Colletti LP, Teklay D, Stickney JL (1994) Thin-layer electrochemical studies of the oxidative underpotential deposition of sulfur and its application to the electrochemical atomic layer epitaxy deposition of CdS. J Electroanal Chem 369 145-152... 

Foresti ML, Pezzatini G, CavaUini M, Alois G, Innocent M, GuideUi R (1998) Electrochemical atomic layer epitaxy deposition of CdS on Ag(lll) An electrochemical and STM investigation. J Phys Chem B 102 7413-7420... 

Innocent M, Pezzatini G, Fomi F, Foresti ML (2001) CdS and ZnS deposition on Ag(l 11) by electrochemical atomic layer epitaxy. J Electrochem Soc 148 C357-C362... 

Venkatasamy V, Mathe MK, Cox SM, Happek U, Stickney JL (2006) Optimization studies of HgSe thin film deposition by electrochemical atomic layer epitaxy (EC-ALE). Electrochim Acta 51 4347-4351... 

In molecular beam epitaxy (MBE), the constituent elements of the desired film in the form of molecular beams are deposited epitaxially onto a heated crystalline substrate. These molecular beams are typically from thermally evaporated elemental sources (e.g., evaporation of elemental As produces molecules of As2, As3, and As4). A refinement of this is atomic layer epitaxy (ALE) (also known as atomic layer deposition, ALD) in which the substrate is exposed alternately to two... 

The deposition of a wide range of materials using beams of elemental sources in high-vacuum apparatus (10-4—10-8 torr), essentially by physical methods, is known as molecular beam epitaxy (MBE)8 12 and atomic layer epitaxy (ALE). These methods will be mentioned where there is an overlap with CVD techniques, but will not be fully reviewed. (They are mentioned also in Chapter 9.15). 

Mg2+ ion. 49 has been used to deposit MgO by atomic layer epitaxy,222 and is commonly employed as a />-type dopant for semiconductors, particularly GaAs,223 GaN,224,225 and AlGaN.226 In GaN, Mg doping induces a blue 2.8 eV photoluminescence band arising from donor-acceptor (D-A) pair recombination.227 It is likely that isolated Mg... 

Historically, EC-ALE has been developed by analogy with atomic layer epitaxy (ALE) [76-82], ALE is a methodology used initially to improve epitaxy in the growth of thin-films by MBE and VPE. The principle of ALE is to use surface limited reactions to form each atomic layer of a deposit. If no more than an atomic layer is ever deposited, the growth will be 2-D, layer by layer, epitaxial. Surface limited reactions are developed for the deposition of each component element, and a cycle is formed with them. With each cycle, a compound monolayer is formed, and the deposit thickness is controlled by the number of cycles. 

EC-ALE is the combination of UPD and ALE. Atomic layers of a compound s component elements are deposited at underpotentials in a cycle, to directly form a compound. It is generally a more complex procedure than most of the compound electrodeposition methods described in section 2.4.2, requiring a cycle to form each monolayer of the compound. However, it is layer-by-layer growth, avoiding 3-D nucleation, and offering increased degrees of freedom, atomic level control, and promoting of epitaxy. 

A second application of current interest in which widely separated length scales come into play is fabrication of modulated foils or wires with layer thickness of a few nanometers or less [156]. In this application, the aspect ratio of layer thickness, which may be of nearly atomic dimensions, to workpiece size, is enormous, and the current distribution must be uniform on the entire range of scales between the two. Optimal conditions for these structures require control by local mechanisms to suppress instability and produce layer by layer growth. Epitaxially deposited single crystals with modulated composition on these scales can be described as superlattices. Moffat, in a report on Cu-Ni superlattices, briefly reviews the constraints operating on their fabrication by electrodeposition [157]. 

The use of UPD layers can in principle generate deposits with composition modulated on the atomic scale, and Pauling et al. have produced what they call hetero-structured ultra-thin films containing Ag, Pd and T1 by this method [158], Stickney and coworkers have assembled multilayered deposits of CdTe and GaAs by addition of one atomic layer of the individual components at a time, a process they call electrochemical atomic-layer epitaxy [159 162], The essential controlling feature in the UPD mechanism is that the deposited layers are allowed to reach equilibrium. Hence, the process represents an extreme of local, reversible control. 

The electrochemical atomic layer epitaxy (ECALE) technique, also known as electrochemical atomic layer deposition (EC-ALD), is based on layer-by-layer electrodeposition. Each constituent of the thin him are deposited separately using underpotential deposition (UPD) of that element. UPD is a process wherein an atomic layer of one element is deposited on the surface of a different element at a potential under that needed to deposit the element on itself. ECALE has been used to grow mainly II-VI and III-V compounds. A thorough review of ECALE research has been published by Stickney.144 A summary of the materials deposited using ECALE are given in Table 8.4, with a more detailed discussion for a few select examples given below. 

Cecconi, T. Atrei, A. Bardi, U. Forni, F. Innocenti, M. Loglio F. Foresti M. Rovida G. 2001. X-ray photoelectron diffraction (XPD) study of the atomic structure of the ultrathin CdS phase deposited on Ag(lll) by electrochemical atomic layer epitaxy (ECALE). J. Electron Spectrosc. Relat. Phenom. 114-116 563-568. 

Villegas, I. Stickney, J. L. 1992. Preliminary studies of gallium arsenide deposition on gold (100), (110), and (111) surfaces by electrochemical atomic layer epitaxy. J. Electrochem. Soc. 139 686-94. 

Chemical Vapor Deposition Electrochemical Deposition Molecular Beam Epitaxy Atomic Layer Deposition Thermal Oxidation Spin Coating... 

Alaboson, J.M.P., et ah, Seeding atomic layer deposition of high-kdielectrics on epitaxial graphene with organic self-assembled monolayers. ACS Nano, 2011. 5(6) p. 5223-5232. 

Substrates DME = dropping mercury electrode FTO = fluorine-doped tin oxide G = graphite GC = glassy carbon GrC = graphic carbon ITO = indium tin oxide-coated glass SC = single crystals SS = stainless steel TCO = transparent conducting oxide VC = vitrious carbon. Miscellaneous ECALE = electrochemical atomic layer epitaxy ED = electrodeposition ML = monolayer RT = room temperature SMD = sequential monolayer deposition V = vacuum. 

The principle of ALE is that deposits are formed one atomic layer at a time using surface-limited reactions. That appears to be the case with ECALE. The name electrochemical atomic layer epitaxy, however, suggests that the deposits should be epitaxial, and the first 100 cycle deposits appeared anything but epitaxial (Eig. 21a). These initial deposits looked like they were composed of a large number of particles, which fell out of solution. 

Au is an excellent electrode material. It is inert in most electrochemical environments, and its surface chemistry is moderately well understood. It is not, however, the substrate of choice for the epitaxial formation of most compounds. One major problem with Au is that it is not well lattice matched with the compounds being deposited. There are cases where fortuitous lattice matches are found, such as with CdSe on Au(lll), where the Vs times the lattice constant of CdSe match up with three times the Au (Fig. 63B) [115,125]. However, there is still a 0.6% mismatch. A second problem has to do with formation of a compound on an elemental substrate (Fig. 65) [384-387]. Two types of problems are depicted in Fig. 65. In Fig. 65A the first element incompletely covers the surface, so that when an atomic layer of the second element is deposited, antiphase boundaries result on the surface between the domains. These boundaries may then propagate as the deposit grows. In Fig. 65b the presence of an atomically high step in the substrate is seen to also promote the formation of antiphase boundaries. The first atomic layer is seen to be complete in this case, but when an atomic layer of the second element is deposited on top, a boundary forms at the step edge. Both of the scenarios in Fig. 65 are avoided by use of a compound substrate. 

An electrochemical scarming probe microscopy and Raman spectroscopy investigation of thin CdS films grown by electrochemical atomic layer epitaxy (ECALE) aimed at understanding the role played by the order of deposition on film quality were reported [161]. 

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