Ni-Al alloys as alternative EUV mask absorber

Extreme ultraviolet (EUV) lithography is being industrialized as the next candidate printing technique for high-volume manufacturing of scaled down integrated circuits. At mask level, the combination of EUV light at oblique incidence, absorber thickness, and non-uniform mirror reflectance through incidence angle, creates photomask-induced imaging aberrations, known as mask 3D (M3D) effects. A possible mitigation for the M3D effects in the EUV binary intensity mask (BIM), is to use mask absorber materials with high extinction coefficient k and refractive coefficient n close to unity. We propose nickel aluminide alloys as a candidate BIM absorber material, and characterize them versus a set of specifications that a novel EUV mask absorber must meet. The nickel aluminide samples have reduced crystallinity as compared to metallic nickel, and form a passivating surface oxide layer in neutral solutions. Composition and density profile are investigated to estimate the optical constants, which are then validated with EUV reflectometry. An oxidation-induced Al L2 absorption edge shift is observed, which significantly impacts the value of n at 13.5 nm wavelength and moves it closer to unity. The measured optical constants are incorporated in an accurate mask model for rigorous simulations. The M3D imaging impact of the nickel aluminide alloy mask absorbers, which predict significant M3D reduction in comparison to reference absorber materials. In this paper, we present an extensive experimental methodology flow to evaluate candidate mask absorber materials

Electronic properties of manganese impurities in germanium

The electronic properties of manganese in crystalline germanium have been investigated by means of deep level transient spectroscopy (DLTS). Mn was diffused in the material by a thermal treatment at 700 degrees C. Next to the deep levels of nickel and copper, which are known contaminants in Ge treated at high temperature, three not previously reported levels were observed. These two hole and one electron traps, with apparent energy level positions at EV +0.136 eV, EV +0.342 eV and EC - 0.363 eV, were assigned to substitutional Mn. The analysis of the carrier capture cross-sections, the absence of field-assisted emission and the observation of the Mn2- electron paramagnetic resonance spectrum in n-type Ge: Mn at low temperature are all compatible with Mn introducing two acceptor and one donor levels in the band gap of Ge

Impact of changes in bond structure on ovonic threshold switching behaviour in GeSe2

Raman spectroscopy measurements are performed on sputtered GexSe1x thin films to identify bond presence. A large amount of homopolar bonds are found, including Ge–Ge bonds that can be attributed to Ge clustering. A time-resolved approach to Raman spectroscopy is explored to observe the effect of the high power-density laser on the sample material. Several methods are then used to tailor the structural bond homogeneity (homopolar–heteropolar bonds): annealing, varying sputter deposition pressure and the addition of dopants. In particular doping can reduce homopolar bond presence and increase heteropolar bonds presence. The impact of each dopant is supported by calculations of bond enthalpies according to Pauling equation using the approach of Lankhorst/Bicerano–Ovshinsky. Finally, in order to correlate the structural bond presence to the Ovonic Threshold Switching behaviour of (doped) GexSe1x thin films, both DC and pulsed (AC) measurement are performed on metal–insulator– metal (MIM) type test structures. It is found that minimizing homopolar bond presence is beneficial for the leakage current and electrical stability of the materia

Impact of changes in bond structure on ovonic threshold switching behaviour in GeSe2 (vol 35, pg 151, 2020)

Correction for 'Impact of changes in bond structure on ovonic threshold switching behaviour in GeSe2' by Jonas Keukelier et al., J. Mater. Chem. C, 2021, DOI: ; 10.1039/d0tc04086j

Effect of Annealing Ferroelectric HfO₂ Thin Films: In Situ, High Temperature X-Ray Diffraction

The ferroelectricity in fluorite oxides has gained increasing interest due to its promising properties for multiple applications in semiconductor as well as energy devices. The structural origin of the unexpected ferroelectricity is now believed to be the formation of a non-centrosymmetric orthorhombic phase with the space group of Pca2₁. However, the factors driving the formation of the ferroelectric phase are still under debate. In this study, to understand the effect of annealing temperature, the crystallization process of doped HfO₂ thin films is analyzed using in situ, high-temperature X-ray diffraction. The change in phase fractions in a multiphase system accompanied with the unit cell volume increase during annealing could be directly observed from X-ray diffraction analyses, and the observations give an information toward understanding the effect of annealing temperature on the structure and electrical properties. A strong coupling between the structure and the electrical properties is reconfirmed from this result

Al3_3Sc thin films for advanced interconnect applications

Al$_x$Sc$_{1-x}$ thin films have been studied with compositions around Al$_3$Sc ($x = 0.75$) for potential interconnect metallization applications. As-deposited 25 nm films were x-ray amorphous but crystallized at 190{\deg}C with a recrystallization observed at 440{\deg}C. After annealing at 500{\deg}C, 24 nm thick stoichiometric Al$_3$Sc showed a resistivity of 12.6 ${\mu}{\Omega}$cm, limited by a combination of grain boundary and point defect (disorder) scattering. Together with ab initio calculations that found a mean free path of the charge carriers of 7 nm for stoichiometric Al$_3$Sc, these results indicate that Al$_3$Sc bears promise for future interconnect metallization schemes. Challenges remain in minimizing the formation of secondary phases as well as in the control of the non-stoichiometric surface oxidation and interfacial reaction with the underlying dielectrics.Comment: 15 pages, 4 figure

Ovonic threshold-switching GexSey chalcogenide materials : stoichiometry, trap nature, and material relaxation from first principles

Density functional theory simulations are used to identify the structural factors that define the material properties of ovonic threshold switches (OTS). They show that the nature of mobility-gap trap states in amorphous Ge-rich Ge50Se50 is related to Ge-Ge bonds, whereas in Se-rich Ge30Se70 the Ge valence-alternating-pairs and Se lone-pairs dominate. To obtain a faithful description of the electronic structure and delocalization of states, it is required to combine hybrid exchange-correlation functionals with large unit-cell models. The extent of localization of electronic states depends on the applied external electric field. Hence, OTS materials undergo structural changes during electrical cycling of the device, with a decrease in the population of less exothermic Ge-Ge bonds in favor of more exothermic Ge-Se. This reduces the amount of charge traps, which translates into coordination changes, an increase in mobility-gap, and subsequently changes in the selector-device electrical parameters. The threshold voltage drift process can be explained by natural evolution of the nonpreferred Ge-Ge bonds (or "chains"/clusters thereof) in Ge-rich GexSe1-x. The effect of extrinsic doping is shown for Si and N, which introduce strong covalent bonds into the system, increase both mobility-gap and crystallization temperature, and decrease the leakage current

Pulsed chemical vapor deposition of conformal GeSe for application as an OTS selector

The ovonic threshold switch (OTS) selector based on the voltage snapback of amorphous chalcogenides has received tremendous attention as it provides several desirable characteristics such as bidirectional switching, a controllable threshold voltage, high drive currents, and low leakage currents. GeSe is a well-known OTS selector that fulfills all the requirements imposed by future high-density storage class memories. Here, we report on pulsed chemical vapor deposition (CVD) of amorphous GeSe by using GeCl2 center dot C4H8O2 as a Ge source and two different Se sources namely bis-trimethylsilylselenide ((CH3)(3)Si)(2)Se (TMS)(2)Se and bis-triethylsilylselenide ((C2H5)(3)Si)(2)Se (TES)(2)Se. We utilized total reflection X-ray fluorescence (TXRF) to study the kinetics of precursor adsorption on the Si substrate. GeCl2 center dot C4H8O2 precursor adsorption on a 300 mm Si substrate showed under-dosing due to limited precursor supply. On the other hand, the Se precursor adsorption is limited by low reaction efficiency as we learned from a better within-wafer uniformity. Se precursors need Cl sites (from Ge precursor) for precursor ligand exchange reactions. Adsorption of (TMS)(2)Se is found to be much faster than (TES)(2)Se on a precoated GeClx layer. Atomic layer deposition (ALD) tests with GeCl2 center dot C4H8O2 and (TMS)(2)Se revealed that the growth per cycle (GPC) decreases with the introduction of purge steps in the ALD cycle, whereas a higher GPC is obtained in pulsed-CVD mode without purges. Based on this basic understanding of the process, we developed a pulsed CVD growth recipe (GPC = 0.3 angstrom per cycle) of GeSe using GeCl2 center dot C4H8O2 and (TMS)(2)Se at a reactor temperature of 70 degrees C. The 20 nm GeSe layer is amorphous and stoichiometric with traces of chlorine and carbon impurities. The film has a roughness of similar to 0.3 nm and it starts to crystallize at a temperature of similar to 370 degrees C. GeSe grown on 3D test structures showed excellent film conformality