Atomic layer deposition of copper for CMOS interconnects

This work concerns the atomic layer deposition (ALD) of copper. ALD is a technique that allows conformal coating of difficult topographies such as narrow trenches and holes or even shadowed regions. However, the deposition of pure metals has so far been less successful than the deposition of oxides except for a few exceptions. Challenges include difficulties associated with the reduction of the metal centre of the precursor at reasonable temperatures and the tendency of metals to agglomerate during the growth process. Cu is a metal of special technical interest as it is widely used for interconnects on CMOS devices. These interconnects are usually fabricated by electroplating, which requires the deposition of thin Cu seed layers onto the trenches and vias. Here, ALD is regarded as potential candidate for replacing the current PVD technique, which is expected to reach its limitations as the critical dimensions continue to shrink. This work is separated into two parts. In the first part, a laboratory-scale ALD reactor was constructed and used for the thermal ALD of Cu. In the second part, the potentials of the application of Cu ALD on industry scale fabrication were examined in a joint project with Applied Materials and Intel. Within this project precursors developed by industrial partners were evaluated on a 300 mm Applied Materials metal-ALD chamber modified with a direct RF-plasma source. A feature that makes ALD a popular technique among researchers is the possibility to produce high- level thin film coatings for micro-electronics and nano-technology with relatively simple laboratory- scale reactors. The advanced materials and surfaces group (AMSG) at Tyndall National Institute operates a range of home-built ALD reactors. In order to carry out Cu ALD experiments, modifications to the normal reactor design had to be made. For example a carrier gas mechanism was necessary to facilitate the transport of the low-volatile Cu precursors. Precursors evaluated included the readily available Cu(II)-diketonates Cu-bis(acetylacetonate), Cu-bis(2,2,6,6-tetramethyl-hepta-3,5-dionate) and Cu-bis(1,1,1,5,5,5-hexafluoacetylacetonate) as well as the Cu-ketoiminate Cu-bis(4N-ethylamino- pent-3-en-2-onate), which is also known under the trade name AbaCus (Air Liquide), and the Cu(I)- silylamide 1,3-diisopropyl-imidazolin-2-ylidene Cu(I) hexamethyldisilazide ([NHC]Cu(hmds)), which was developed at Carleton University Ottawa. Forming gas (10 % H2 in Ar) was used as reducing agent except in early experiments where formalin was used. With all precursors an extreme surface selectivity of the deposition process was observed and significant growth was only achieved on platinum-group metals. Improvements in the Cu deposition process were obtained with [NHC]Cu(hmds) compared with the Cu(II) complexes. A possible reason is the reduced oxidation state of the metal centre. Continuous Cu films were obtained on Pd and indications for saturated growth with a rate of about 0.4 Å/cycle were found for deposition at 220 °C. Deposits obtained on Ru consisted of separated islands. Although no continuous films could be obtained in this work the relatively high density of Cu islands obtained was a clear improvement as compared to the deposits grown with Cu(II) complexes. When ultra-thin Pd films were used as substrates, island growth was also observed. A likely reason for this extreme difference to the Cu films obtained on thicker Pd films is the lack of stress compensation within the thin films. The most likely source of stress compensation in the thicker Pd films is the formation of a graded interlayer between Pd and Cu by inter-diffusion. To obtain continuous Cu films on more materials, reduction of the growth temperature was required. This was achieved in the plasma assisted ALD experiments discussed in the second part of this work. The precursors evaluated included the AbaCus compound and CTA-1, an aliphatic Cu-bis(aminoalkoxide), which was supplied by Adeka Corp.. Depositions could be carried out at very low temperatures (60 °C Abacus, 30 °C CTA-1). Metallic Cu could be obtained on all substrate materials investigated, but the shape of the deposits varied significantly between the substrate materials. On most materials (Si, TaN, Al2O3, CDO) Cu grew in isolated nearly spherical islands even at temperatures as low as 30 °C. It was observed that the reason for the island formation is the coalescence of the initial islands to larger, spherical islands instead of forming a continuous film. On the other hand, the formation of nearly two-dimensional islands was observed on Ru. These islands grew together forming a conductive film after a reasonably small number of cycles. The resulting Cu films were of excellent crystal quality and had good electrical properties; e.g. a resistivity of 2.39 µΩ cm was measured for a 47 nm thick film. Moreover, conformal coating of narrow trenches (1 µm deep 100/1 aspect ratio) was demonstrated showing the feasibility of the ALD process.

Childhood obesity in Ireland: recent trends and modifiable determinants

Background: Childhood obesity is a global epidemic posing a significant threat to the health and wellbeing of children. To reverse this epidemic, it is essential that we gain a deeper understanding of the complex array of driving factors at an individual, family and wider ecological level. Using a social-ecological framework, this thesis investigates the direction, magnitude and contribution of risk factors for childhood overweight and obesity at multiple levels of influence, with a particular focus on diet and physical activity. Methods: A systematic review was conducted to describe recent trends (from 2002-2012) in childhood overweight and obesity prevalence in Irish school children from the Republic of Ireland. Two datasets (Cork Children’s Lifestyle [CCLaS] Study and the Growing Up in Ireland [GUI] Study) were used to explore determinants of childhood overweight and obesity. Individual lifestyle factors examined were diet, physical activity and sedentary behaviour. The determinants of physical activity were also explored. Family factors examined were parental weight status and household socio-economic status. The impact of food access in the local area on diet quality and body mass index (BMI) was investigated as an environmental level risk factor. Results: Between 2002 and 2012, the prevalence of childhood overweight and obesity in Ireland remained stable. There was some evidence to suggest that childhood obesity rates may have decreased slightly though one in four Irish children remained either overweight or obese. In the CCLaS study, overweight and obese children consumed more unhealthy foods than normal weight children. A diet quality score was constructed based on a previously validated adult diet score. Each one unit increase in diet quality was significantly associated with a decreased risk of childhood overweight and obesity. Individual level factors (including gender, being a member of a sports team, weight status) were more strongly associated with physical activity levels than family or environmental factors. Overweight and obese children were more sedentary and less active than normal weight children. There was a dose response relationship between time spent at moderate to vigorous physical activity (MVPA) and the risk of childhood obesity independent of sedentary time. In contrast, total sedentary time was not associated with the risk of childhood obesity independent of MVPA though screen time was associated with childhood overweight and obesity. In the GUI Study, only one in five children had 2 normal weight parents (or one normal weight parent in the case of single parent families). Having overweight and obese parents was a significant risk factor for overweight and obesity regardless of socio-economic characteristics of the household. Family income was not associated with the odds of childhood obesity but social class and parental education were important risk factors for childhood obesity. Access to food stores in the local environment did not impact dietary quality or the BMI of Irish children. However, there was some evidence to suggest that the economic resources of the family influenced diet and BMI. Discussion: Though childhood overweight and obesity rates appear to have stabilised over the previous decade, prevalence rates are unacceptably high. As expected, overweight and obesity were associated with a high energy intake and poor dietary quality. The findings also highlight strong associations between physical inactivity and the risk of overweight and obesity, with effect sizes greater than what have been typically found in adults. Important family level determinants of childhood overweight and obesity were also identified. The findings highlight the need for a multifaceted approach, targeting a range of modifiable determinants to tackle the problem. In particular, policies and interventions at the shared family environment or community level may be an effective mean of tackling this current epidemic.