Vapor Pressures of Precursors for the CVD of Titanium Nitride and Tin Oxide

Mol, A.M.B. van; Driessen, J. P. A. M.; Linden, J.L.; Croon, M.H.J.M. de; Spee, C.I.M.A.; Schouten, J.C.

doi:10.1002/1521-3862(200105)7:3<101::aid-cvde101>3.0.co;2-z

Cited by 20 publications

(4 citation statements)

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“…Moreover, they have much higher reactivity than metal halides, since the metal-nitrogen bond is significantly weaker than the metal-halide bonds. In particular, tetrakis(dimethylamido)zirconium (TDMAZr) has thermal stability [28], sufficient volatility [29], and high reaction activity in the vapor deposition process. Therefore, TDMAZr and H 2 O as reaction precursors have been used for ALD processes of ZrO 2 films [30], Nevertheless, hydrogen and carbon impurities in ZrO 2 films have severe effects on the electrical properties of thin films.…”

Section: Introductionmentioning

confidence: 99%

Structure and Dielectric Property of High-k ZrO2 Films Grown by Atomic Layer Deposition Using Tetrakis(Dimethylamido)Zirconium and Ozone

Liu

et al. 2019

Nanoscale Res Lett

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s High- k metal oxide films are vital for the future development of microelectronics technology. In this work, ZrO 2 films were grown on silicon by atomic layer deposition (ALD) using tetrakis(dimethylamido)zirconium and ozone as precursors. The relatively constant deposition rate of 0.125 nm/cycle is obtained within the ALD temperature window of 200–250 °C. The film thickness can be precisely controlled by regulating the number of ALD cycle. The ZrO 2 films formed at 200–250 °C have an O/Zr atomic ratio of 1.85–1.9 and a low content of carbon impurity. ZrO 2 film begins to crystallize in ALD process above 210 °C, and the crystal structure is changed from cubic and orthorhombic phases to monoclinic and orthorhombic phases with increasing the deposition temperature to 350 °C. Moreover, the effect of annealing temperature on dielectric properties of ZrO 2 film was studied utilizing ZrO 2 -based MIS device. The growth of the interface layer between ZrO 2 and Si substrate leads to the decrease in the capacitance and the leakage current of dielectric layer in the MIS device after 1000 °C annealing. ZrO 2 film exhibits the relatively high dielectric constant of 32.57 at 100 kHz and the low leakage current density of 3.3 × 10 −6 A cm −2 at 1 MV/cm.

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Section: Introductionmentioning

confidence: 99%

Structure and Dielectric Property of High-k ZrO2 Films Grown by Atomic Layer Deposition Using Tetrakis(Dimethylamido)Zirconium and Ozone

Liu

et al. 2019

Nanoscale Res Lett

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“…Compared to metal halides, metal amides should be significantly more reactive toward a hydroxylated surface (such as the native oxide on silicon) because the metal−halide bond is significantly stronger than the metal−nitrogen bond (both are weaker than the metal−oxygen bond) are thermally stable, and have sufficient volatility to be used in vapor deposition processes. , …”

Section: Introductionmentioning

confidence: 99%

Atomic Layer Deposition of Hafnium and Zirconium Oxides Using Metal Amide Precursors

et al. 2002

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Atomic layer deposition (ALD) of smooth and highly conformal films of hafnium and zirconium oxides was studied using six metal alkylamide precursors for hafnium and zirconium. Water was used as an oxygen source during these experiments. As deposited, these films exhibited a smooth surface with a measured roughness equivalent to that of the substrate on which they were deposited. These films also exhibited a very high degree of conformality: 100% step coverage on holes with aspect ratios greater than 35. The films were completely uniform in thickness and composition over the length of the deposition reactor. The films were free of detectable impurities and had the expected (2:1) oxygen-to-metal ratio. Films were deposited at substrate temperatures from 50 to 500 °C from precursors that were vaporized at temperatures from 40 to 140 °C. The precursors were found to be highly reactive with hydroxylated surfaces. Their vapor pressures were measured over a wide temperature range. Deposition reactor design and ALD cycle design using these precursors are discussed.

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“…Each set of data was obtained at temperatures below the melting points of the precursors. The vapor pressures of 2 – 5b obey the general equation log P = A – B / T , where A and B are free parameters, with the corresponding enthalpy of vaporization or sublimation being deduced from parameter B (Table ) …”

Section: Resultsmentioning

confidence: 99%

“…The vapor pressures of 2-5b obey the general equation logP =A -B/T ; where A and B are free parameters, with the corresponding enthalpy of vaporization or sublimation being deduced from the parameter B (Table 5). 37 Figure 6: Vapor pressure measurements of 2-5b. As can be seen from the calculated vapor pressures of complexes 2-5b at 60 ºC, shown in Table 6, the order of volatility is 3b>4b>>2b>5b, which is attributed to the difference in cyclopentadienyl substituent such that the order of volatility can be viewed as Me-Cp > Et-Cp > H-Cp > i Pr-Cp; in fact comparison of the vapor pressures of 3b and 4b at 60 ºC with commercially available copper precursors, specifically Cyclopentadienyl(triethylphosphine)copper(I) and CupraSelect™ (200 mTorr and 150 mTorr respectively) shows 3b and 4b to be more volatile at these operating temperatures.…”

Section: B 4bmentioning

confidence: 99%

Tailoring Precursors for Deposition: Synthesis, Structure, and Thermal Studies of Cyclopentadienylcopper(I) Isocyanide Complexes

et al. 2015

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We report here the synthesis and characterization of a family of copper(I) metal precursors based around cyclopentadienyl and isocyanide ligands. The molecular structures of several cyclopentadienylcopper(I) isocyanide complexes have been unambiguously determined by single-crystal X-ray diffraction analysis. Thermogravimetric analysis of the complexes highlighted the isopropyl isocyanide complex [(η(5)-C5H5)Cu(CN(i)Pr)] (2a) and the tert-butyl isocyanide complex [(η(5)-C5H5)Cu(CN(t)Bu)] (2b) as possible copper metal chemical vapor deposition (CVD) precursors. Further modification of the precursors with variation of the substituents on the cyclopentadienyl ligand system (varying between H, Me, Et, and (i)Pr) has allowed the affect that these changes would have on features such as stability, volatility, and decomposition to be investigated. As part of this study, the vapor pressures of the complexes 2b, [(η(5)-MeC5H4)Cu(CN(t)Bu)] (3b), [(η(5)-EtC5H4)Cu(CN(t)Bu)] (4b), and [(η(5)-(i)PrC5H4)Cu(CN(t)Bu)] (5b) over a 40-65 °C temperature range have been determined. Low-pressure chemical vapor deposition (LP-CVD) was employed using precursors 2a and 2b to synthesize thin films of metallic copper on silicon, gold, and platinum substrates under a H2 atmosphere. Analysis of the thin films deposited onto both silicon and gold substrates at substrate temperatures of 180 and 300 °C by scanning electron microscopy and atomic force microscopy reveals temperature-dependent growth features: Films grown at 300 °C are continuous and pinhole-free, whereas films grown at 180 °C consist of highly crystalline nanoparticles. In contrast, deposition onto platinum substrates at 180 °C shows a high degree of surface coverage with the formation of high-density, continuous, and pinhole-free thin films. Powder X-ray diffraction and X-ray photoelectron spectroscopy (XPS) both show the films to be high-purity metallic copper.

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Vapor Pressures of Precursors for the CVD of Titanium Nitride and Tin Oxide

Cited by 20 publications

References 1 publication

Structure and Dielectric Property of High-k ZrO2 Films Grown by Atomic Layer Deposition Using Tetrakis(Dimethylamido)Zirconium and Ozone

Structure and Dielectric Property of High-k ZrO2 Films Grown by Atomic Layer Deposition Using Tetrakis(Dimethylamido)Zirconium and Ozone

Atomic Layer Deposition of Hafnium and Zirconium Oxides Using Metal Amide Precursors

Tailoring Precursors for Deposition: Synthesis, Structure, and Thermal Studies of Cyclopentadienylcopper(I) Isocyanide Complexes

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