D. Nest

Relationship between nanoscale roughness and ion-damaged layer in argon plasma exposed polystyrene films

The uncontrolled development of nanoscale roughness during plasma exposure of polymer surfaces is a major issue in the field of semiconductor processing. In this paper, we investigated the question of a possible relationship between the formation of nanoscale roughening and the simultaneous introduction of a nanometer-thick, densified surface layer that is formed on polymers due to plasma damage. Polystyrene films were exposed to an Ar discharge in an inductively coupled plasma reactor with controllable substrate bias and the properties of the modified surface layer were changed by varying the maximum Ar+ ion energy. The modified layer thickness, chemical, and mechanical properties were obtained using real-time in situ ellipsometry, x-ray photoelectron spectroscopy, and modeled using molecular dynamics simulation. The surface roughness after plasma exposure was measured using atomic force microscopy, yielding the equilibrium dominant wavelength λ and amplitude A of surface roughness. The comparison of mea...

Plasma-surface interactions of model polymers for advanced photoresists using C4F8∕Ar discharges and energetic ion beams

Plasma based transfer of photoresist (PR) patterns into underlying films and substrates is basic to micro- and nanofabrication but can suffer from excessive surface and line edge roughness in the photoresist and resulting features. The authors have studied the interaction of a set of adamantyl methacrylate-based model polymers with fluorocarbon∕Ar discharges and energetic Ar+ ion beams. Through systematic variation of the polymer structure, the authors were able to clarify the contributions of several critical polymer components on the chemical and morphological modifications in the plasma environment. Etching rates and surface chemical and morphological changes for the model polymers and fully formulated 193 and 248nm photoresists were determined by ellipsometry, atomic force microscopy, time of flight static secondary ion mass spectrometry, and x-ray photoelectron spectroscopy. The polymer structure in the near surface region (∼10nm) of all materials is destroyed within the first seconds of exposure to a fluorocarbon∕Ar plasma. The plasma-induced changes include destruction of polymeric structure in the near surface region and oxygen and hydrogen loss along with fluorination. For the 193nm PR material, the initial densification of the near surface region was followed by the introduction of pronounced surface roughness. This change was not seen for 248nm PR processed under identical conditions. When comparing the responses of different polymer materials, the authors observed a strong dependence of plasma-induced surface chemical and morphological changes on polymer structure. In particular, the adamantane group of 193nm PR showed poor stability under plasma exposure. On the other hand, the plasma-induced changes for polymer resins with or without the low molecular weight chemicals required to make the photoresist system photoactive did not differ significantly. The behavior of the same materials during energetic argon ion beam bombardment was also investigated. No significant differences in etch yield and surface roughness evolution for the different materials were seen in that case.Plasma based transfer of photoresist (PR) patterns into underlying films and substrates is basic to micro- and nanofabrication but can suffer from excessive surface and line edge roughness in the photoresist and resulting features. The authors have studied the interaction of a set of adamantyl methacrylate-based model polymers with fluorocarbon∕Ar discharges and energetic Ar+ ion beams. Through systematic variation of the polymer structure, the authors were able to clarify the contributions of several critical polymer components on the chemical and morphological modifications in the plasma environment. Etching rates and surface chemical and morphological changes for the model polymers and fully formulated 193 and 248nm photoresists were determined by ellipsometry, atomic force microscopy, time of flight static secondary ion mass spectrometry, and x-ray photoelectron spectroscopy. The polymer structure in the near surface region (∼10nm) of all materials is destroyed within the first seconds of exposure to ...

Synergistic effects of vacuum ultraviolet radiation, ion bombardment, and heating in 193nm photoresist roughening and degradation

The roles of ultraviolet/vacuum ultraviolet (UV/VUV) photons, Ar+ ion bombardment and heating in the roughening of 193nm photoresist have been investigated. Atomic force microscopy measurements show minimal surface roughness after UV/VUV-only or ion-only exposures at any temperature. Simultaneous UV/VUV, ion bombardment, and heating to surface temperatures of 60–100°C result in increased surface roughness, and is comparable to argon plasma-exposed samples. Ion bombardment creates a modified near-surface layer while UV/VUV radiation results in loss of carbon-oxygen bonds up to a depth of ∼100nm. Enhanced roughness is only observed in the presence of all three effects.

Study of ion and vacuum ultraviolet-induced effects on styrene- and ester-based polymers exposed to argon plasma

Plasma-polymer interactions are important for the purpose of etching, deposition, and surface modification in a wide range of different fields. An Ar discharge from an inductively coupled plasma reactor was used to determine the factors in a simple plasma that control etch and surface roughness behavior for three styrene-based and three ester-based model polymers. The authors compared the etch behavior of polymers in Ar plasma discharges with low and high energy ions by changing the substrate bias, compared cooled and elevated substrate temperature conditions, and compared fully plasma-exposed conditions and vacuum ultraviolet (vuv)-only conditions by employing a magnesium fluoride window to prevent ion bombardment in the vuv-only case. It was found that ions, vuv radiation, and temperature all had significant impact on the etch behavior of polymers. The dependence of polymer structure on etch and surface roughness was also compared. Polymers with styrene and ester side groups were compared and polymers w...

Near-surface modification of polystyrene by Ar+: Molecular dynamics simulations and experimental validation

Results are presented from molecular dynamics (MD) simulations of 100eV Ar+ bombardment of a model polystyrene (PS) surface. The simulations show that the system transitions from an initially high sputter yield (SY) for the virgin polymer to a drastically lower SY as steady state is approached. This is consistent with corresponding ion beam experiments. The MD indicates that this drop in SY is due to the formation of a heavily cross-linked, dehydrogenated damaged layer. The thickness and structure of this layer are also consistent with ellipsometry and x-ray photoelectron spectroscopy measurements of Ar plasma-exposed PS samples.

Photoresist modifications by plasma vacuum ultraviolet radiation: The role of polymer structure and plasma chemistry

While vacuum ultraviolet (VUV) photon irradiation has been shown to significantly contribute to material modifications of polymers during plasma exposures, the impact of radiation-induced material alterations on roughness development during plasma processing has remained unclear. The authors have studied the interaction of the radiation of Ar and C4F8/Ar plasma discharges with 193 and 248 nm advanced photoresists (PRs). Optical filters were used to vary the radiation exposure wavelength range in the ultraviolet (UV) and VUV emission spectra. This enables clarification of the respective roles of plasma photon radiation wavelength and PR polymer structure on the chemical and structural changes produced in the materials. Chemical changes in polymer composition at the film surface and in the material bulk were determined by vacuum transfer x-ray photoelectron spectroscopy and Fourier-transform infrared spectroscopy. Morphological changes, film thickness reduction, and changes in surface and pattern morphology...

Molecular dynamics simulations of near-surface modification of polystyrene: Bombardment with Ar+ and Ar+/radical chemistries

Molecular dynamics (MD) simulations have been carried out to examine the effects of Ar+, Ar+/H, and Ar+/F bombardment of a model polystyrene (PS) surface. For bombardment with 100 eV Ar+ only, the simulations show the formation of a heavily cross-linked dehydrogenated damaged layer in the near-surface region after some initial fluence, consistent with plasma and beam system experimental results. The 1–2 nm thick amorphous carbon-rich modified layer has a much lower sputter yield compared to that of the virgin PS, which has a H:C ratio of 1. Simultaneous bombardment of the damaged dehydrogenated PS layer with 300 K H or F radicals and 100 eV Ar+ can facilitate the removal of the layer as well as inhibit its initial formation. The development of the steady-state dehydrogenated layer under Ar+-only bombardment results from a competition between the breaking of carbon-hydrogen bonds (which leads to dehydrogenation and subsequent cross-linking) and the breaking of carbon-carbon bonds (which leads to sputtering...

Absolute vacuum ultraviolet flux in inductively coupled plasmas and chemical modifications of 193 nm photoresist

Vacuum ultraviolet (VUV) photons in plasma processing systems are known to alter surface chemistry and may damage gate dielectrics and photoresist. We characterize absolute VUV fluxes to surfaces exposed in an inductively coupled argon plasma, 1–50 mTorr, 25–400 W, using a calibrated VUV spectrometer. We also demonstrate an alternative method to estimate VUV fluence in an inductively coupled plasma (ICP) reactor using a chemical dosimeter-type monitor. We illustrate the technique with argon ICP and xenon lamp exposure experiments, comparing direct VUV measurements with measured chemical changes in 193 nm photoresist-covered Si wafers following VUV exposure.

Comparing 193 nm photoresist roughening in an inductively coupled plasma system and vacuum beam system

We present a comparison of blanket 193nm photoresist (PR) roughening and chemical modifications of samples processed in a well-characterized argon (Ar) inductively coupled plasma (ICP) system and an ultra-high vacuum beam system. In the ICP system, PR samples are irradiated with Ar vacuum ultraviolet (VUV) and Ar ions, while in the vacuum beam system, samples are irradiated with either a Xe-line VUV source or Ar-lamp VUV source with Ar ions. Sample temperature, photon flux, ion flux and ion energy are controlled and measured. The resulting chemical modifications to bulk 193nm PR and surface roughness are analysed with Fourier transform infrared (FTIR) spectroscopy and atomic force microscopy. We demonstrate that under VUV-only conditions in the vacuum beam and ICP (with no substrate bias applied) systems 193nm PR does not roughen. However, roughness increases with simultaneous high energy (>70eV) ion bombardment and VUV irradiation and is a function of VUV fluence, substrate temperature and photon-to-ion flux ratio. PR processed in the ICP system experiences increased etching, probably due to release of H- and O-containing gaseous products and subsequent chemical etching, in contrast to samples in the vacuum beam system where etch-products are rapidly pumped away. The surface roughness structure and behaviour, however, remain similar and this is attributed to the synergy between VUV-photon and positive ions. (Some figures in this article are in colour only in the electronic version)

Plasma-surface interactions of advanced photoresists with C4F8∕Ar discharges: Plasma parameter dependencies

One recurring problem in nanoscale processing is roughening of photoresist (PR) materials during plasma etch. We studied the plasma etch behavior of 248nm PR, 193nm PR, and poly methyladamantyl methacrylate while changing the source power level (400–1200W), adjusting the bias power to change the self-bias voltage Vdc (−50to−150V), and varying the pressure (10–80mTorr) and the amount of fluorocarbon gas additive to the Ar discharge (0%–10% c-C4F8 in Ar). The authors found that the PR removal is dominated by the ion energy and fluence. Surface fluorination enhanced the removal rates. Two linked mechanisms for the roughening behavior of the films during processing were identified. Changes of PR top surface roughening behavior in response to variations of bias power and pressure could be interpreted by a model of roughness formation which is dominated by a physical pattern transfer mechanism, i.e., roughness amplification through selective ion-induced transfer. When the plasma source power was varied, they ob...