Atomic layer deposition(ALD), a chemical vapor deposition technique based on sequential self-terminating gas–solid reactions, has for about four decades been applied for manufacturing conformal inorganic material layers with thickness down to the nanometer range. Despite the numerous successful applications of material growth by ALD, many physicochemical processes that control ALD growth are not yet sufficiently understood. To increase understanding of ALD processes, overviews are needed not only of the existing ALD processes and their applications, but also of the knowledge of the surface chemistry of specific ALD processes. This work aims to start the overviews on specific ALD processes by reviewing the experimental information available on the surface chemistry of the trimethylaluminum/water process. This process is generally known as a rather ideal ALD process, and plenty of information is available on its surface chemistry. This in-depth summary of the surface chemistry of one representative ALD process aims also to provide a view on the current status of understanding the surface chemistry of ALD, in general. The review starts by describing the basic characteristics of ALD, discussing the history of ALD—including the question who made the first ALD experiments—and giving an overview of the two-reactant ALD processes investigated to date. Second, the basic concepts related to the surface chemistry of ALD are described from a generic viewpoint applicable to all ALD processes based on compound reactants. This description includes physicochemical requirements for self-terminating reactions,reaction kinetics, typical chemisorption mechanisms, factors causing saturation, reasons for growth of less than a monolayer per cycle, effect of the temperature and number of cycles on the growth per cycle (GPC), and the growth mode. A comparison is made of three models available for estimating the sterically allowed value of GPC in ALD. Third, the experimental information on the surface chemistry in the trimethylaluminum/water ALD process are reviewed using the concepts developed in the second part of this review. The results are reviewed critically, with an aim to combine the information obtained in different types of investigations, such as growth experiments on flat substrates and reaction chemistry investigation on high-surface-area materials. Although the surface chemistry of the trimethylaluminum/water ALD process is rather well understood, systematic investigations of the reaction kinetics and the growth mode on different substrates are still missing. The last part of the review is devoted to discussing issues which may hamper surface chemistry investigations of ALD, such as problematic historical assumptions, nonstandard terminology, and the effect of experimental conditions on the surface chemistry of ALD. I hope that this review can help the newcomer get acquainted with the exciting and challenging field of surface chemistry of ALD and can serve as a useful guide for the specialist towards the fifth decade of ALD research.

Surface chemistry of atomic layer deposition: A case study for the trimethylaluminum/water process

This article reviews the progress of atomic force microscopy in ultrahigh vacuum, starting with its invention and covering most of the recent developments. Today, dynamic force microscopy allows us to image surfaces of conductors and insulators in vacuum with atomic resolution. The most widely used technique for atomic-resolution force microscopy in vacuum is frequency-modulation atomic force microscopy (FM-AFM). This technique, as well as other dynamic methods, is explained in detail in this article. In the last few years many groups have expanded the empirical knowledge and deepened our theoretical understanding of frequency-modulation atomic force microscopy. Consequently spatial resolution and ease of use have been increased dramatically. Vacuum atomic force microscopy opens up new classes of experiments, ranging from imaging of insulators with true atomic resolution to the measurement of forces between individual atoms.

https://hep.physics.utoronto.ca/WilliamTrischuk/courses/phy189/AFM_revmodphys.pdf

Advances in atomic force microscopy

Atomic layer deposition (ALD) is gaining attention as a thin film deposition method, uniquely suitable for depositing uniform and conformal films on complex three-dimensional topographies. The deposition of a film of a given material by ALD relies on the successive, separated, and self-terminating gas–solid reactions of typically two gaseous reactants. Hundreds of ALD chemistries have been found for depositing a variety of materials during the past decades, mostly for inorganic materials but lately also for organic and inorganic–organic hybrid compounds. One factor that often dictates the properties of ALD films in actual applications is the crystallinity of the grown film: Is the material amorphous or, if it is crystalline, which phase(s) is (are) present. In this thematic review, we first describe the basics of ALD, summarize the two-reactant ALD processes to grow inorganic materials developed to-date, updating the information of an earlier review on ALD [R. L. Puurunen, J. Appl. Phys. 97, 121301 (2005)], and give an overview of the status of processing ternary compounds by ALD. We then proceed to analyze the published experimental data for information on the crystallinity and phase of inorganic materials deposited by ALD from different reactants at different temperatures. The data are collected for films in their as-deposited state and tabulated for easy reference. Case studies are presented to illustrate the effect of different process parameters on crystallinity for representative materials: aluminium oxide, zirconium oxide, zinc oxide, titanium nitride, zinc zulfide, and ruthenium. Finally, we discuss the general trends in the development of film crystallinity as function of ALD process parameters. The authors hope that this review will help newcomers to ALD to familiarize themselves with the complex world of crystalline ALD films and, at the same time, serve for the expert as a handbook-type reference source on ALD processes and film crystallinity.

Crystallinity of inorganic films grown by atomic layer deposition: Overview and general trends

Along with extensive research on the three-dimensional (3D) printing of polymers and metals, 3D printing of ceramics is now the latest trend to come under the spotlight. The ability to fabricate ceramic components of arbitrarily complex shapes has been extremely challenging without 3D printing. This review focuses on the latest advances in the 3D printing of ceramics and presents the historical origins and evolution of each related technique. The main technical aspects, including feedstock properties, process control, post-treatments and energy source–material interactions, are also discussed. The technical challenges and advice about how to address these are presented. Comparisons are made between the techniques to facilitate the selection of the best ones in practical use. In addition, representative applications of the 3D printing of various types of ceramics are surveyed. Future directions are pointed out on the advancement on materials and forming mechanism for the fabrication of high-performance ceramic components.

3D printing of ceramics: A review

Microfluidics is an emerging field that has given rise to a large number of scientific and technological developments over the last few years. This review reports on the use of various materials, such as silicon, glass and polymers, and their related technologies for the manufacturing of simple microchannels and complex systems. It also presents the main application fields concerned with the different technologies and the most significant results reported by academic and industrial teams. Finally, it demonstrates the advantage of developing approaches for associating polymer technologies for manufacturing of fluidic elements with integration of active or sensitive elements, particularly silicon devices.

https://iopscience.iop.org/article/10.1088/0960-1317/17/5/R01/pdf

Lab-on-chip technologies: making a microfluidic network and coupling it into a complete microsystem : a review

For the past six years, Digital Light Processing technology from Texas Instruments has made significant inroads in the projection display market. With products enabling the world’s smallest data and video projectors, HDTVs, and digital cinema, DLP technology is extremely powerful and flexible. At the heart of these display solutions is Texas Instruments Digital Micromirror Device (DMD), a semiconductor-based “light switch” array of thousands of individually addressable, tiltable, mirror-pixels. With success of the DMD as a spatial light modulator for projector applications, dozens of new applications are now being enabled by general-use DMD products that are recently available to developers. The same light switching speed and “on-off” (contrast) ratio that have resulted in superior projector performance, along with the capability of operation outside the visible spectrum, make the DMD very attractive for many applications, including volumetric display, holographic data storage, lithography, scientific instrumentation, and medical imaging. This paper presents an overview of past and future DMD performance in the context of new DMD applications, cites several examples of emerging products, and describes the DMD components and tools now available to developers.

https://eti.pg.edu.pl/documents/176568/264302/emerging_dmd_applications.pdf

Emerging digital micromirror device (DMD) applications

We report a new method of achieving tip–sample distance regulation in an atomic force microscope (AFM). A piezoelectric quartz tuning fork serves as both actuator and sensor of tip–sample interactions, allowing tip–sample distance regulation without the use of a diode laser or dither piezo. Such a tuning fork has a high spring constant so a dither amplitude of only 0.1 nm may be used to perform AFM measurements. Tuning-fork feedback is shown to operate at a noise level as low as that of a cantilever-based AFM. Using phase-locked-loop control to track excursions in the resonant frequency of a 32 kHz tuning fork, images are acquired at scan rates which are fast enough for routine AFM measurements. Magnetic force microscopy using tuning-fork feedback is demonstrated.

Fast, high-resolution atomic force microscopy using a quartz tuning fork as actuator and sensor

Insitu spectral ellipsometry for real-time measurement and control

An embodiment of the instant invention is a scanning-probe microscope for measuring the topography of a surface of a sample, the scanning-probe microscope comprising: an XYZ piezo drive (piezo drive 1); a quartz tuning-fork oscillator (fork 2) having a first electrode (electrode 3 or 4) and a second electrode (electrode 3 or 4), wherein the quartz tuning-fork oscillator is attached to the XYZ piezo drive, and wherein the quartz tuning-fork oscillator is oriented such that the tines of the quartz tuning-fork oscillator each lie in the XY plane and their fundamental mode of oscillation vibrates the ends of the tines in the Z direction; a probe tip (probe tip 6) affixed to one of the tines, the probe tip comes to a point in the Z direction and directed away from the XYZ piezo drive; a signal source (source 7) to provide a drive signal to drive the first electrode at a mechanical resonant frequency of the quartz tuning-fork oscillator; a current-to-voltage amplifier (preamp 8) to monitor the electrical current flowing through the second electrode and having an output, wherein the electrical impedance of the quartz tuning-fork oscillator may be measured, and the resonant vibration amplitude of the quartz tuning-fork oscillator is monitored; and wherein the XYZ piezo drive is operable to move the probe tip close to the surface of the sample until the probe tip lightly taps the sample surface thereby decreasing and oscillation amplitude the electrical impedance of the quartz tuning-fork oscillator and wherein the interaction between the probe tip and the sample surface can be used to regulate the distance between the probe tip and the sample surface.

Scanning-probe microscope including non-optical means for detecting normal tip-sample interactions

We report on the successful growth of ordered GaInP by atomic layer epitaxy on a GaAs substrate. The growth was achieved by alternate exposures to TEI, PH3, TMGa, and PH3 fluxes, and epilayers were found to closely match the GaAs substrate irrespective of the growth conditions. Room‐temperature photoreflectance results indicate a band gap of 1.78 eV, the lowest value yet reported for such ordered alloys. Photoluminescence shows an anomalous temperature dependence behavior and transmission electron microscopy studies indicate that ordering takes place preferentially on (111) alternating planes.

Walter M. Duncan

Papers

Emerging digital micromirror device (DMD) applications

Fast, high-resolution atomic force microscopy using a quartz tuning fork as actuator and sensor

Insitu spectral ellipsometry for real-time measurement and control

Scanning-probe microscope including non-optical means for detecting normal tip-sample interactions

Atomic layer epitaxy of GaInP ordered alloy