Many materials systems are currently under consideration as potential replacements for SiO2 as the gate dielectric material for sub-0.1 μm complementary metal–oxide–semiconductor (CMOS) technology. A systematic consideration of the required properties of gate dielectrics indicates that the key guidelines for selecting an alternative gate dielectric are (a) permittivity, band gap, and band alignment to silicon, (b) thermodynamic stability, (c) film morphology, (d) interface quality, (e) compatibility with the current or expected materials to be used in processing for CMOS devices, (f) process compatibility, and (g) reliability. Many dielectrics appear favorable in some of these areas, but very few materials are promising with respect to all of these guidelines. A review of current work and literature in the area of alternate gate dielectrics is given. Based on reported results and fundamental considerations, the pseudobinary materials systems offer large flexibility and show the most promise toward success...

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High-κ gate dielectrics: Current status and materials properties considerations

Atomic layer deposition: an overview.

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

Method and structures are provided for conformal capacitor dielectrics over textured silicon electrodes for integrated memory cells. Capacitor structures and first electrodes or plates are formed above or within semiconductor substrates. The first electrodes include hemispherical grain (HSG) silicon for increasing the capacitor plate surface area. The HSG topography is then exposed to alternating chemistries to form monolayers of a desired dielectric material. Exemplary process flows include alternately pulsed metal organic and oxygen source gases injected into a constant carrier flow. Self-terminated metal layers are thus reacted with oxygen. Near perfect step coverage allows minimal thickness for a capacitor dielectric, given leakage concerns for particular materials, thereby maximizing the capacitance for the memory cell and increasing cell reliability for a given memory cell design. Alternately pulsed chemistries are also provided for depositing top electrode materials with continuous coverage of capacitor dielectric, realizing the full capacitance benefits of the underlying textured morphology.

Conformal thin films over textured capacitor electrodes

Methods are disclosed for selective deposition on desired materials In particular, barrier materials are selectively formed on insulating surfaces, as compared to conductive surfaces In the context of contact formation and trench fill, particularly damascene and dual damascene metallization, the method advantageously lines insulating surfaces with a barrier material The selective formation allows the deposition to be “bottomless,” thus leaving the conductive material at a via bottom exposed for direct metal-to-metal contact when further conductive material is deposited into the opening after barrier formation on the insulating surfaces Desirably, the selective deposition is accomplished by atomic layer deposition (ALD), resulting in highly conformal coverage of the insulating sidewalls in the opening

Method for bottomless deposition of barrier layers in integrated circuit metallization schemes

The electrical characteristics of SiOx/ZrO2 and SiOx/Ta2O5 gate dielectric stacks are investigated. The current–density JG in these dielectric stacks is shown to be strongly temperature dependent at low voltage (below about 2 V), the more so in the ZrO2 stack. On the other hand, JG is much less temperature dependent at higher voltage. These results are consistent with a model which takes into account the direct tunneling of electrons across the SiOx layer and the trap-assisted tunneling of electrons through traps with energy levels below the conduction band of the high permittivity dielectric layer. The energy levels and densities of these electron trapping centers are estimated by fitting this trap-assisted tunneling model to the experimental results.

Trap-assisted tunneling in high permittivity gate dielectric stacks

A method of manufacturing a high performance MOS device and transistor gate stacks comprises forming a gate dielectric layer over a semiconductor substrate; forming a barrier layer over the gate dielectric layer by an ALD type process; and forming a gate electrode layer over the barrier layer. The method enables the use of hydrogen plasma, high energy hydrogen radicals and ions, other reactive radicals, reactive oxygen and oxygen containing precursors in the processing steps subsequent to the deposition of the gate dielectric layer of the device. The ALD process for forming the barrier layer is performed essentially in the absence of plasma and reactive hydrogen radials and ions. This invention makes it possible to use oxygen as a precursor in the deposition of the metal gates. The barrier film also allows the use of hydrogen plasma in the form of either direct or remote plasma in the deposition of the gate electrode. Furthermore, the barrier film prevents the electrode material from reacting with the gate dielectric material. The barrier layer is ultra thin and, at the same time, it forms a uniform cover over the entire surface of the gate dielectric.

Method of depositing barrier layer from metal gates

A method for forming a conductive thin film includes depositing a metal oxide thin film on a substrate by an atomic layer deposition (ALD) process. The method further includes at least partially reducing the metal oxide thin film by exposing the metal oxide thin film to a reducing agent, thereby forming a seed layer. In one arrangement, the reducing agent comprises one or more organic compounds that contain at least one functional group selected from the group consisting of —OH, —CHO, and —COOH. In another arrangement, the reducing agent comprises an electric current.

Suvi Haukka

Papers

Conformal thin films over textured capacitor electrodes

Method for bottomless deposition of barrier layers in integrated circuit metallization schemes

Trap-assisted tunneling in high permittivity gate dielectric stacks

Method of depositing barrier layer from metal gates

Method of growing electrical conductors