Access Type

Open Access Dissertation

Date of Award

January 2012

Degree Type


Degree Name




First Advisor

Charles H. Winter


The advancing complexity of advanced microelectronic devices is placing rigorous demands on currently used PVD and CVD deposition techniques. The ALD deposition method is proposed to meet the film thickness and conformality constraints needed by the semiconductor industry in future manufacturing processes. Unfortunately, there is a limited number of chemical precursors available that have high thermal stability, reactivity, and vapor pressure suitable for ALD film growth to occur. These properties collectively contribute to the lack of suitable transition metal precursors available for use in ALD. In this thesis, we report the discovery of a series of novel transition metal diazadienate precursors that promising properties deemed suitable for ALD. The volatility and thermal stability of the new transition metal diazadienyl compounds were studied by preparative sublimation and capillary tube melting point/decomposition experiments. Thermogravimetric analyses (TGA) demonstrate precursor residues of less than 4% at 500 °C. In addition, sublimation data, melting points, and decomposition temperatures for all complexes are presented. The manganese diazadienyl complex has the highest decomposition temperature of the series of complexes produced (325 °C). During preparative sublimations, the product recoveries of all transition metal diazadienyl complexes were greater than 92.0% with nonvolatile residues of less than 7.0%. This is an excellent indication that these complexes may be suitable candidates as metal precursors for ALD.

Nickel nitride (NixN) films have been studied as an intermediate material for the formation of both nickel metal and nickel silicide using chemical vapor deposition. Herein, we describe the ALD growth of nickel nitride thin films from bis(1,4-di-tert-butyl-1,3-diazabutadiene) nickel(II) (Ni(tBu2DAD)2) and 1,1-dimethylhydrazine. An ALD window for the deposition of nickel nitride films on 500 nm thermal SiO2 substrates was observed between 225 and 240 °C with a constant growth rate of 0.70 Å/cycle. X-Ray photoelectron spectroscopy (XPS) showed all expected ionizations with carbon concentrations below the detection limit after argon ion sputtering. Due to preferential nitrogen sputtering in XPS, Rutherford backscattering spectrometry (RBS) and nuclear reaction analysis (NRA) were performed and subsequently revealed Ni:N ratios between 2-4 for films deposited within the ALD window. AFM measurements revealed a RMS roughness value of 10.8 nm on an as-deposited film at 225°C. All as-deposited films were amorphous as determined by X-ray diffraction.

Copper is the primary interconnect material in microelectronics devices, due to its high conductivity and low affinity towards electromigration. With transistor gate lengths scheduled to reach 14 nm by 2014, there are severe demands upon the current film growth techniques used in device fabrication. The ALD film growth method is ideally suited for future microelectronics manufacturing, since it inherently provides highly conformal thin films, even in high aspect ratio nanoscale features, and allows sub-nanometer control over film thicknesses. In Chapter 4, we describe the atomic layer deposition of high purity, low resistivity copper metal thin films using a three precursor sequence entailing Cu(dmap)2, formic acid, and hydrazine. In this process, Cu(dmap)2 is unreactive towards hydrazine but is transformed to copper(II) formate, which is then readily reduced to copper metal by subsequent hydrazine exposure. The present work therefore addresses a central problem with the ALD growth of metal thin films: low reactivity of metal precursors toward common reducing agents. A constant growth rate of 0.47-0.50 Å/cycle upon prime grade Si(100) was observed at substrate temperatures between 100 and 170 °C. Compositional analyses (XPS and TOF-ERDA) revealed copper films with low levels of carbon, oxygen, nitrogen, and hydrogen. Powder X-ray diffraction spectra of all films showed polycrystalline copper. The resistivities of films grown between 100 and 140 °C ranged between 9.6 and 16.4 μΩ*cm, demonstrating the growth of high purity, low resistivity copper films. An AFM measurement revealed a RMS roughness value of 3.5 nm on an as-deposited 50 nm Cu film at 120 °C.