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

The scaling of complementary metal oxide semiconductor transistors has led to the silicon dioxide layer, used as a gate dielectric, being so thin (14?nm) that its leakage current is too large It is necessary to replace the SiO2 with a physically thicker layer of oxides of higher dielectric constant (?) or 'high K' gate oxides such as hafnium oxide and hafnium silicate These oxides had not been extensively studied like SiO2, and they were found to have inferior properties compared with SiO2, such as a tendency to crystallize and a high density of electronic defects Intensive research was needed to develop these oxides as high quality electronic materials This review covers both scientific and technological issues?the choice of oxides, their deposition, their structural and metallurgical behaviour, atomic diffusion, interface structure and reactions, their electronic structure, bonding, band offsets, electronic defects, charge trapping and conduction mechanisms, mobility degradation and flat band voltage shifts The oxygen vacancy is the dominant electron trap It is turning out that the oxides must be implemented in conjunction with metal gate electrodes, the development of which is further behind Issues about work function control in metal gate electrodes are discussed

https://iopscience.iop.org/article/10.1088/0034-4885/69/2/R02/pdf

High dielectric constant gate oxides for metal oxide Si transistors

An object is to provide a semiconductor device of which a manufacturing process is not complicated and by which cost can be suppressed, by forming a thin film transistor using an oxide semiconductor film typified by zinc oxide, and a manufacturing method thereof. For the semiconductor device, a gate electrode is formed over a substrate; a gate insulating film is formed covering the gate electrode; an oxide semiconductor film is formed over the gate insulating film; and a first conductive film and a second conductive film are formed over the oxide semiconductor film. The oxide semiconductor film has at least a crystallized region in a channel region.

Semiconductor device, and manufacturing method thereof

The scaling of complementary metal oxide semiconductor (CMOS) transistors has led to the silicon dioxide layer used as a gate dielectric becoming so thin (1.4 nm) that its leakage current is too large. It is necessary to replace the SiO2 with a physically thicker layer of oxides of higher dielectric constant (κ) or 'high K' gate oxides such as hafnium oxide and hafnium silicate. Little was known about such oxides, and it was soon found that in many respects they have inferior electronic properties to SiO2 ,s uch as a tendency to crystallise and a high concentration of electronic defects. Intensive research is underway to develop these oxides into new high quality electronic materials. This review covers the choice of oxides, their structural and metallurgical behaviour, atomic diffusion, their deposition, interface structure and reactions, their electronic structure, bonding, band offsets, mobility degradation, flat band voltage shifts and electronic defects. The use of high K oxides in capacitors of dynamic random access memories is also covered.

/pdf/high-dielectric-constant-oxides-cotu2e70vd.pdf

High dielectric constant oxides

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

We present theoretical and experimental results regarding the thermodynamic stability of the high-k dielectrics ZrO2 and HfO2 in contact with Si and SiO2 The HfO2/Si interface is found to be stable with respect to formation of silicides whereas the ZrO2/Si interface is not The metal–oxide/SiO2 interface is marginally unstable with respect to formation of silicates Cross-sectional transmission electron micrographs expose formation of nodules, identified as silicides, across the polycrystalline silicon/ZrO2/Si interfaces but not for the interfaces with HfO2 For both ZrO2 and HfO2, the x-ray photoemission spectra illustrate formation of silicate-like compounds in the MO2/SiO2 interface

Thermodynamic stability of high-K dielectric metal oxides ZrO2 and HfO2 in contact with Si and SiO2

We report here that Fermi pinning at the polysilicon/metal-oxide interface causes high threshold voltages in MOSFET devices. In Part I, we investigated the different gatestack regions and determined that the polysilicon/metal oxide interface plays a key role on the threshold voltages. Now in Part II, the effects of the interfacial bonding are examined by experiments with submonolayer atomic-layer deposition (ALD) metal oxides and atomistic simulation. Results indicate that pinning occurs due to the interfacial Si-Hf and Si-O-Al bonds for HfO/sub 2/ and Al/sub 2/O/sub 3/, respectively. Oxygen vacancies at polysilicon/HfO/sub 2/ interfaces also lead to Fermi pinning. This fundamental characteristic affects the observed polysilicon depletion.

Fermi-level pinning at the polysilicon/metal-oxide interface-Part II

Polycrystalline-silicon (poly-Si) gate compatibility issues with HfO2 and Al2O3 capped HfO2 gate dielectrics are reported. It can be generally stated that chemical vapor deposition (CVD) silicon gates using silane deposited directly onto HfO2 results in electrical properties much worse compared to similar HfO2 films using platinum metal gates. However, depositing CVD silicon gates directly onto Al2O3 capped HfO2 showed greater than a 104 times reduction in gate leakage compared to the poly-Si/HfO2 and poly-Si/SiO2 controls of similar electrical thickness.

Compatibility of polycrystalline silicon gate deposition with HfO2 and Al2O3/HfO2 gate dielectrics

We present experimental results regarding the thermodynamic stability of the high-k dielectrics ZrO2 and HfO2 in contact with Si and SiO2. The HfO2/Si interface is found to be stable with respect to formation of silicides whereas the ZrO2/Si interface is not. The metal oxide/SiO2 interface is marginally unstable with respect to formation of silicates. Cross-sectional transmission electron micrographs expose formation of nodules, identified as silicides, across the polysilicon/ZrO2/Si interfaces but not for the interfaces with HfO2. For both ZrO2 and HfO2, the X-ray photoemission spectra illustrate formation of silicate-like compounds in the MO2/SiO2 interface.

Thermodynamic Stability of High-K Dielectric Metal Oxides ZrO 2 and HfO 2 in Contact with Si and SiO2

Smooth, 4–6-nm thick hafnium oxide films were grown by atomic layer deposition from HfI4 or HfCl4 and H2O on SiO2/Si(1 0 0) substrates at 300 °C. Non-uniform films were obtained on hydrogen-terminated Si(1 0 0). The stoichiometry of the films corresponded to that of HfO2. The films contained small amounts of residual chlorine and iodine. The films deposited on SiO2/Si(1 0 0) were amorphous, but crystallized upon annealing at 1000 °C. In order to decrease the conductivity, the HfO2 films were mixed with Al2O3, and to increase the capacitance, the films were mixed with Nb2O5. The capacitance–voltage curves of the Hf–Al–O mixture films showed hysteresis. The capacitance–voltage curves of HfO2 films and mixtures of Hf–Al–Nb–O were hysteresis free.

Raghaw S. Rai

Papers

Thermodynamic stability of high-K dielectric metal oxides ZrO2 and HfO2 in contact with Si and SiO2

Fermi-level pinning at the polysilicon/metal-oxide interface-Part II

Compatibility of polycrystalline silicon gate deposition with HfO2 and Al2O3/HfO2 gate dielectrics

Thermodynamic Stability of High-K Dielectric Metal Oxides ZrO 2 and HfO 2 in Contact with Si and SiO2

Atomic layer deposition of HfO2 thin films and nanolayered HfO2-Al2O3-Nb2O5 dielectrics