International audienceResistance switching is studied in Au/HfO2 (10 nm)/(Pt, TiN) devices, where HfO2 is deposited by atomic layer deposition. The study is performed using different bias modes, i.e., a sweeping, a quasistatic and a static (constant voltage stress) mode. Instabilities are reported in several circumstances (change in bias polarity, modification of the bottom electrode, and increase in temperature). The constant voltage stress mode allows extracting parameters related to the switching kinetics. This mode also reveals random fluctuations between the ON and OFF states. The dynamics of resistance switching is discussed along a filamentary model which implies oxygen vacancies diffusion. The rf properties of the ON and OFF states are also presented (impedance spectroscopy). © 2010 American Institute of Physic

Porous ultralow-k films are required by the microelectronics industry as interlayer dielectrics for 65 nm technologies and below. These porous insulating films can be deposited by plasma-enhanced chemical vapor deposition using a porogen approach. It consists of the codeposition of a matrix precursor and a sacrificial organic porogen, and then on a post-treatment to remove the organic porogen phase and create porosity in the film. In this work, an e-beam assisted thermal curing was compared to an ultraviolet-assisted thermal curing. Basic film properties such as k, film shrinkage, porosity, pore size, and pore size distribution were evaluated. NMR and Fourier transform infrared analyses were used to study the chemical modifications induced by the post-treatment. These analyses show that the post-treatment impact depends on the radiation used. Both treatments lead to a removal of terminal nonbridging bonds such as Si-OH, Si-H, and Si-CH 3 and can contribute to a subsequent formation of Si-O-Si crosslinks. Both treatments remove methyls from Si-CH 3 , but the e-beam induces a Si-H bond increase while the UV bulb used decreases the Si-H contribution. The cross-linking improvement induces an increase of Young's modulus, the elastic properties being mainly correlated to the Si-O-Si volumic bond concentration in the film.A new challenge for the semiconductor industry is to reach the low permittivity ͑k Ͻ 2.4͒ required for advanced interconnections by ITRS for sub-65 nm technology nodes. Porosity introduction in an a-SiOC:H matrix ͑written down SiOCH in the following͒ is the main research field investigated. The porogen approach is one way to produce porous materials using plasma-enhanced chemical vapor deposition ͑PECVD͒. It consists of the codeposition of a matrix precursor and a sacrificial organic porogen. 1-3 After deposition, porogens are eliminated in subsequent steps, leaving their initial sites empty and creating porosity. To decrease the porogen removal duration and temperature, thermally assisted processes can be used, with UV irradiation or electronic bombardment ͑e-beam͒. 4-6 Many works were performed on the impact of e-beam or UV curing on an insulating SiOCH matrix as a hardener treatment. In this case, the main results reported are an increase of mechanical properties, the exact mechanism being not fully understood. 7-9 Yoda et al. reported also the use of e-beam curing to enhance the mechanical properties of porous films. 10 In this study, an e-beam thermally assisted curing treatment used to remove porogens is compared to a UV thermally assisted one. Basic film properties after deposition and curing are described: investigations with physicochemical analyses, porosity measurements by ellipsometry coupled with solvent adsorption, and grazingincidence small-angle x-ray scattering ͑GISAXS͒. Mechanical and electrical studies were carried out to better understand the impact of each porogen removal treatment on the chemical structure of the dielectric films. After a brief presentation of the experimental tec...

To improve integrated circuit performance, microelectronic chip interconnections need dielectric materials with ultralow k (ULK) values. Porous a-SiOCH, an ULK material, can be created using a two step strategy called a porogen approach. The first step consists of a hybrid film deposition, which is an a-SiOCH matrix containing an organic sacrificial phase. Afterwards, the organic phase is removed during a post-treatment to generate the porosity. In this work, hybrid deposition was performed by plasma enhanced chemical vapor deposition and the post-treatment was a thermal annealing. Firstly, hybrid films with different a-SiOCH matrix structures were created using two matrix precursors [decamethylcyclopentasiloxane (DMCPS) and diethoxymethylsilane (DEMS)] and an O2 addition in a plasma gas feed. For the same porogen loading, the shrinkage behavior during the porogen removal is correlated to the matrix structure. Fourier transform infrared spectroscopy and Si29 solid nuclear magnetic resonance are both used to determine the structure. The O3SiMe1 is favorable to prevent high film shrinkage and the O2SiMe2 leads to high film shrinkage and absence of porosity generation. To prevent the existence of this type of structure, DEMS+O2 appears more appropriate as a matrix precursor than DEMS only or DMCPS. Secondly, using the appropriate matrix structure, the influence of the porogen loading on the porosity creation is studied. Hybrids with different porogen loadings are achieved by changing the porogen precursor ratio in the plasma gas feed. The porogen conversion into porosity is studied for different porogen loadings and the results indicate the existence of a porogen loading threshold. Above it, there is no more porosity generation because of the too high film shrinkage during the porogen removal. This behavior is explained by a too low matrix ratio in the hybrid film. For the high porogen loadings, the matrix skeleton (mainly constituted by SiOSi bridging bonds) is not in sufficient quantity to prevent such film shrinkage. The porous a-SiOCH created with the most favorable matrix structure and porogen loading has the ultralow k value of 2.3.

Metallic contamination was key to the discovery of semiconductor nanowires, but today it stands in the way of their adoption by the semiconductor industry. This is because many of the metallic catalysts required for nanowire growth are not compatible with standard CMOS (complementary metal oxide semiconductor) fabrication processes. Nanowire synthesis with those metals which are CMOS compatible, such as aluminium and copper, necessitate temperatures higher than 450 C, which is the maximum temperature allowed in CMOS processing. Here, we demonstrate that the synthesis temperature of silicon nanowires using copper based catalysts is limited by catalyst preparation. We show that the appropriate catalyst can be produced by chemical means at temperatures as low as 400 C. This is achieved by oxidizing the catalyst precursor, contradicting the accepted wisdom that oxygen prevents metal-catalyzed nanowire growth. By simultaneously solving material compatibility and temperature issues, this catalyst synthesis could represent an important step towards real-world applications of semiconductor nanowires.Comment: Supplementary video can be downloaded on Nature Nanotechnology websit

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This paper presents an in-depth overview of the application and impact of UV/VUV light in advanced interconnect technology. UV light application in BEOL historically was mainly motivated by the need to remove organic porogen and generate porosity in organosilicate (OSG) low-k films. Porosity lowered the film's dielectric constant, k, which enables one to reduce the interconnect wiring capacitance contribution to the RC signal delay in integrated circuits. The UV-based low-k film curing (λ > 200 nm) proved superior to thermal annealing and electron beam curing. UV and VUV light also play a significant role in plasma-induced damage to pSiCOH. VUV light with λ < 190–200 nm is able to break Si-CH3 bonds and to make low-k materials hydrophilic. The following moisture adsorption degrades the low-k properties and reliability. This fact motivated research into the mechanisms of UV/VUV photon interactions in pSiCOH films and in other materials used in BEOL nanofabrication. Today, the mechanisms of UV/VUV photon interactions with pSiCOH and other films used in interconnect fabrication are fairly well understood after nearly two decades of research. This understanding has allowed engineers to both control the damaging effects of photons and utilize the UV light for material engineering and nanofabrication processes. Some UV-based technological solutions, such as low-k curing and UV-induced stress engineering, have already been widely adopted for high volume manufacturing. Nevertheless, the challenges in nanoscaling technology may promote more widespread adoption of photon-assisted processing. We hope that fundamental insights and prospected applications described in this article will help the reader to find the optimal way in this wide and rapidly developing technology area.

Structural, chemical and electronic properties of electroforming in the TiN/HfO(2) system are investigated at the nanometre scale. Reversible resistive switching is achieved by biasing the metal oxide using conductive atomic force microscopy. An original method is implemented to localize and investigate the conductive region by combining focused ion beam, scanning spreading resistance microscopy and scanning transmission electron microscopy. Results clearly show the presence of a conductive filament extending over 20 nm. Its size and shape is mainly tuned by the corresponding HfO(2) crystalline grain. Oxygen vacancies together with localized states in the HfO(2) band gap are highlighted by electron energy loss spectroscopy. Oxygen depletion is seen mainly in the central part of the conductive filament along grain boundaries. This is associated with partial amorphization, in particular at both electrode/oxide interfaces. Our results are a direct confirmation of the filamentary conduction mechanism, showing that oxygen content modulation at the nanometre scale plays a major role in resistive switching.