Surface adhesion and demolding force dependence on resist composition in ultraviolet nanoimprint lithography

Demolding, the process to separate stamp from molded resist, is most critical to the success of ultraviolet nanoimprint lithography (UV-NIL). In the present study we investigated adhesion and demolding force in UV-NIL for different compositions of a model UV-curable resist system containing a base (either tripropyleneglycol diacrylate with shorter oligomer length or polypropyleneglycol diacrylate with longer oligomer length), a cross-linking agent (trimethylolpropane triacrylate) and a photoinitiator (Irgacure 651). The demolding force was measured using a tensile test machine with homemade fixtures after imprinting the UV resist on a silicon stamp. While decreasing the cross-linking agent content from 49 to 0 wt% has little effect on the resist surface energy, it reduces the resist's elastic modulus drastically. The decrease in elastic modulus results in a decreased adhesion force at the resist/stamp interface thereby facilitating the demolding. The decrease in elastic modulus and, therefore, demolding force by lowering the cross-linking agent content was markedly less pronounced in tripropyleneglycol diacrylate-based resists due to its shorter oligomer length. These general findings will be useful in designing new resists for UV-NIL process.     

Bonding at Compatible and Incompatible Amorphous Interfaces of Polystyrene and Poly(Methyl Methacrylate) Below the Glass Transition Temperature

Abstract

Films of high‐molecular‐weight amorphous polystyrene (PS, M _w = 225 kg/mol, M _w/M _n = 3, T _g‐bulk = 97°C, where T _g‐bulk is the glass transition temperature of the bulk sample) and poly(methyl methacrylate) (PMMA, M _w = 87 kg/mol, M _w/M _n = 2, T _g‐bulk = 109°C) were brought into contact in a lap‐shear joint geometry at a constant healing temperature T _h, between 44°C and 114°C, for 1 or 24 hr and submitted to tensile loading on an Instron tester at ambient temperature. The development of the lap‐shear strength σ at an incompatible PS–PMMA interface has been followed in regard to those at compatible PS–PS and PMMA–PMMA interfaces. The values of strength for the incompatible PS–PMMA and compatible PMMA–PMMA interfaces were found to be close, both being smaller by a factor of 2 to 3 than the values of σ for the PS–PS interface developed after healing at the same conditions. This observation suggests that the development of the interfacial structure at the PS–PMMA interface is controlled by the slow component, i.e., PMMA. Bonding at the three interfaces investigated was mechanically detected after healing for 24 hr at T _h = 44°C, i.e., well below T _g‐bulks of PS and PMMA, with the observation of very close values of the lap‐shear strength for the three interfaces considered, 0.11–0.13 MPa. This result indicates that the incompatibility between the chain segments of PS and PMMA plays a negligible negative role in the interfacial bonding well below T _g‐bulk.     

Morphology of Fractured Polymer‐Polymer Interfaces Bonded at Ambient Temperature as Studied by Atomic Force Microscopy

The amorphous polymer surfaces of polystyrene (PS, M _n=200 kg/mol, M _w/M _n=1.05) and poly(methyl methacrylate) (PMMA, M _n=51.9 kg/mol, M _w/M _n≤1.07) were brought into contact at 21°C to form PS‐PS (for 54 days) and PMMA‐PMMA auto‐adhesive joints (for 11 days). After contact at that temperature corresponding to T _g‐bulk ?81°C for PS and to T _g‐bulk–88°C for PMMA, where T _g‐bulk is the calorimetric glass transition temperature of the bulk sample, the bonded interfaces were fractured and their surfaces were analyzed by atomic force microscopy (AFM). The surface roughness, R _q, of the fractured interfaces was larger by a factor of 3–4 than was that of the free PS and PMMA surfaces aged for the same period of time. A similar increase in R _q was found by comparison of the free PS surface aged at T _g‐bulk+15°C for 1 h and of the surface of the PS‐PS interface fractured after healing at T _g‐bulk+15°C for 1 h. These observations, indicative of the deformation of the fractured interfaces, suggest the occurrence of some mass transfer across the interface even below T _g‐bulk ?80°C.     

Structure Formation of Blend and Sheath/Core Conjugated Fibers in High-Speed Spinning of PET,Including a Small Amount of PMMA

The blend of poly(ethylene terephthalate) (PET) and a small amount of polymer that has higher T _g than PET, such as polymethylmethacrylate (PMMA)—and is dispersed finely as immiscible particles in PET—exhibits lower molecular orientation than pure PET under high-speed fiber spinning. To obtain insight into the mechanism of the lower molecular orientation of the blend fiber, the sheath/core structure of PET (sheath)/PMMA (core) conjugated fiber (the same PET/PMMA weight ratio as in the blend fiber), was produced as a model. The thinning profile of the fiber diameter along the spinning line and the birefringence distribution of the cross-section were examined and compared among pure PET fiber, the conjugated fiber, and the blend fiber. The conjugated fiber had the lowest molecular orientation of PET in the sheath part, and its thinning process was accelerated similar to the blend fiber. As a result of the distribution of molecular orientation across the diameter of the conjugated fiber, it is considered that PMMA, having the high T _g , tends to solidify at a higher temperature (upstream) than PET in the thinning process, making the flow of PET accelerate as if it was pushed by PMMA. This causes the maximum dv/dx just before the solidification point to be smaller; therefore, the lower spinning stress, resulting in smaller birefringence of PET, can be considerable. This acceleration was generated at the interface of PET and PMMA, and spread toward the fiber surface as both polymers were thinning in elongational flow (in melt). On the other hand, close to the interface, molecules of PET were stretched by PMMA, resulting in an increase of birefringence. Such discussion is also considered to apply to the blend fiber. However, because the blend fiber had a significantly larger interface area compared with the conjugated fiber, it is considered that the increase of birefringence of PET by the interface drag force cannot be neglected. The larger particles of PMMA dispersed in PET results in the lower birefringence of PET that is supported by the elongation effect (i.e., the interface drag force).     

Photoemission study of the growth of the NdF3/Si(111) interface

Photoemission spectroscopy with synchrotron radiation was used to study the NdF₃/Si(111) interface as a function of annealing temperature for NdF₃ films. These films range in thickness from 1–20 monolayers and were deposited at room temperature. Without annealing, both F-Si and Nd-Si bonding is observed, indicating that the planar triangular NdF₃ molecules lie flat on the Si(111) substrate. At annealing temperatures between 400 and 500° C, the NdF₃/Si(111) interface is dominated by Nd-Si bonding as evidenced from a line-shape analysis of the Si 2 p and Nd 4 f core levels. By resonant excitation of the giant 4 d-4 f absorption resonance, the photoemission signal from the partially occupied 4 f orbitals is enhanced and can be distinguished from the photoemission signal of the overlapping F 2 p valence band. At higher temperatures F is completely lost due to the decomposition of NdF₃.     

Coalescence process of monodispersed Co cluster assemblies

Cluster-cluster coalescence process of monodispersed Co clusters with mean diameter d = 8.5 and 13 nm deposited a plasma-gas-condensation-type cluster beam deposition system was investigated by in situ electrical conductivity measurements and ex situ scanning electron microscopy (SEM) and transmission electron microscopy (TEM), and analyzed by percolation concept. The electrical conductivity measurement and TEM observation indicated that, below temperature T≈ 100^°C, the Co clusters in the assemblies maintain their original structure as deposited at room temperature, while that the inter-cluster coalescence takes place at T > 100^°C, although the size distribution and the interface morphology of the clusters showed no marked change at substrate temperatures T _s≤200^°C. Received 29 November 2000     

Strained and strain-relaxed epitaxial Ge1-xSnx alloys on Si（100） substrates

Epitaxial Ge1-xSnx alloys are grown separately on a Ge-buffer/Si(100) substrate and directly on a Si(100) substrate by molecular beam epitaxy (MBE) at low temperature. In the case of the Ge buffer/Si(100) substrate, a high crystalline quality strained Ge0.97Sn0.03 alloy is grown, with a χmin value of 6.7% measured by channeling and random Rutherford backscattering spectrometry (RBS), and a surface root-mean-square (RMS) roughness of 1.568 nm obtained by atomic force microscopy (AFM). In the case of the Si(100) substrate, strain-relaxed Ge0.97Sn0.03 alloys are epitaxially grown at 150°C-300°C, with the degree of strain relaxation being more than 96%. The X-ray diffraction (XRD) and AFM measurements demonstrate that the alloys each have a good crystalline quality and a relatively flat surface. The predominant defects accommodating the large misfit are Lomer edge dislocations at the interface, which are parallel to the interface plane and should not degrade electrical properties and device performance.     

Kinetic Monte Carlo simulation of thin film growth

A three-dimensional kinetic Monte Carlo technique has been developed for simulating growth of thin Cu films. The model involves incident atom attachment, diffusion of the atoms on the growing surface, and detachment of the atoms from the growing surface. The related effect by surface atom diffusion was taken into account. A great improvement was made on calculation of the activation energy for atom diffusion based on a reasonable assumtion of interaction potential between atoms. The surface roughness and the relative density of the films were simulated as the functions of growth substrate temperature and film thickness. The results showed that there exists an optimum growth temperatureT _opt at a given deposition rate. When the substrate temperature approaches toT _opt, the growing surface becomes smoothing and the relative density of the films increases. The surface roughness minimizes and the relative density saturates atT _opt. The surface roughness increases with an increment of substrate, temperature when the temperature is higher thanT _opt.T _opt is a function of the deposition rate and the influence of the deposition rate on the surface roughness depends on the substrate temperatures. The simulation results also showed that the relative density decreases with the increasing of the deposition rate and the average thickness of the film.     

Nanoimprint lithography using IR laser irradiation

A new technique called “infrared laser-assisted nanoimprint lithography” was utilised to soften the thermoplastic polymer material mR-I 8020 during nanoimprint lithography. A laser setup and a sample holder with pressure and temperature control were designed for the imprint experiments. The polymer was spin coated onto crystalline Si <1 1 1> substrates. A prepatterned Si <1 1 1> substrate, which is transparent for the CO₂ laser irradiation, was used as an imprint stamp as well. It was shown, that the thermoplastic resist mR-I 8020 could be successfully imprinted using the infrared CW CO₂ laser irradiation (λ = 10.6 μm). The etching rate of the CO₂ laser beam irradiated mR-I 8020 resist film under O₂ RF (13.56 MHz) plasma treatment and during O₂ reactive ion beam etching was investigated as well.     

On the interface stiffness of the random field ising model

Recent results of Grinstein, Ma, Villain and Binder on interface roughening incontinuum andlattice random field Ising models are related by introducing an effective interface stiffness function {ei247-1}. Ford3 dimensions the continuum theory is shown to be valid for non-zero random field strengthh for all temperatures and on a length scaleL>l _d (h,T) _d (h,T). Ford=2 and smallT a smeared spin-glass transition occurs at ₂(h,T)h. It is argued, that for 3<d<5 interface roughening occurs only forh larger than a critical field strengthh _R (T).     

Dimuon production in ultrarelativistic nuclear collisions and QCD phase transitions

Dilepton production rates in nuclear collisions are calculated in order to study their sensitivity to the quark-gluon plasma and to the hadronic phases. This treatment differs from previous work on the subject in two respects: The width of the rho-meson, being exchanged in annihilation, is made temperature dependent, thus taking into account resonance melting as the critical deconfinement temperatureT _d is approached. Secondly, we study in addition to the standard scenario where chiral symmetry restoration and deconfinement occur at the same temperature (T _c =T _d ), an alternative possibility where deconfinement preceeds chiral symmetry restoration (T _d T _c ). Results differ substantially from those obtained assuming a temperature independent rho-meson width, andT _c =T _d .     

Energy relaxation of warm electrons in (100)-Si-MOSFETs under substrate bias

We have studied the energy loss of warm electrons in a two- dimensional electron gas at the SiSiO₂ interface of (100)-Si- MOSFETs. The application of a negative substrate bias decreases the inelastic electron-phonon interaction considerably at T₁ = 1.8 K. The temperature dependence of the energy loss suggests that at zero substrate bias and low temperatures deformation potential scattering by Si-bulk phonons cannot entirely account for the experimental findings.     

Adhesion,morphology, and heat resistance properties of polyurethane coated poly(methyl methacrylate)/fullerene-C60 composite films

Novel polyurethane (PU) adhesive was prepared and coated on poly(methyl methacrylate) (PMMA) and poly(methyl methacrylate)/fullerene (PMMA/Full-C₆₀) composite. Dip-coating technique was employed as facile and cost-effective procedure to coat polyurethane on film substrate. The properties of PU/PMMA and PU/PMMA/Full-C₆₀ composite were studied using Fourier transform infrared spectroscopy, Field Emission Scanning Electron Microscopy, tensile, adhesion, thermal and flammability measurement. Testing polyurethane-coated PMMA exhibited crumpled surface while fullerene addition formed unique pattern of dispersed spherical structures. Fullerene nanofiller loading improved the adhesion and mechanical properties of composite films due to polymer–carbon interaction. In PU/PMMA/Full-C₆₀ 0.5 composite with 0.5 wt.% nanofiller, tensile strength (71.4 MPa) was increased by 18.6% while tensile modulus was increased by 143.85% compared with PU/PMMA. In PU/PMMA/Full-C₆₀ 0.5, T₀ of 473 °C and T_max of 655 °C were observed. Increasing the fullerene content up to 0.5 wt.% decreased the peak heat release rate to 131 kW/m². Novel polyurethane-coated PMMA/Full-C₆₀ composite have potential applications as adhesive coatings in electronic and automotive appliances.     

Asymptotic degeneracy of the transfer matrix spectrum for systems with interfaces: Relation to surface stiffness and step free energy

Two- and three-dimensional Ising-type systems are considered in the finite-cross-section cylindrical geometry. An interface is forced along the cylinder (strip in 2d) by the antiperiodic or +– boundary conditions. Detailed predictions are presented for the largest asymptotically degenerate set of the transfer matrix eigenvalues. For rough interfaces, i.e., for 0<T<T _c in 2d,T _R<T<T _c in 3d, the eigenvalues are split algebraically, and the spectral gaps are governed by thesurface stiffness coefficient. For rigid interfaces, i.e., 0<T<T _R in 3d, the eigenvalues are split exponentially, with the gaps determined by thestep free energy.     

Deposition of NiFe(200) and NiFe(111) textured films onto Si/SiO<Subscript>2</Subscript> substrates by DC magnetron sputtering

The effect of substrate temperature T_sub and bias voltage U_bias on the texture of NiFe films with thickness d ～ 30–340 nm deposited by DC magnetron sputtering onto Si(111)/SiO₂ substrates under working gas pressure ～ 0.2 Pa has been investigated. It has been demonstrated that films grown at room substrate temperature have the (111) texture that is refined under a negative bias voltage. The deposition of films onto a grounded (U_bias ～ 0) substrate heated to T_sub ～ 440–640 K results in the formation of textured NiFe(200) films.     

Origin of the metallic to insulating transition of an epitaxial Bi(111) film grown on Si(111)

Transport characteristics of single crystal bismuth films on Si(111)-7×7 are found to be metallic or insulating at temperatures below or above T_C, respectively. The transition temperature T_C decreases as the film thickness increases. By combining thickness dependence of the films resistivity, we find the insulating behaviour results from the states inside film, while the metallic behaviour originates from the interface states. We show that quantum size effect in a Bi film, such as the semimetal-to-semiconductor transition, is only observable at a temperature higher than T_C.     

Electrical performance of Ti/Pt thin films on glass-ceramic substrates after high temperature loading

In this study, the influence of post-deposition annealings (PDA) up to temperatures of T _PDA=700°C on the room-temperature resistivity of e-beam evaporated titanium/platinum (Ti/Pt) bi-layers on low temperature co-fired (LTCC) substrates covered with a glass encapsulate is investigated. The thickness of the platinum top layer is varied between 24 and 95 nm (titanium film thickness: 5 nm) and between 23 and 90 nm (titanium film thickness: 15 nm), respectively. In the “as-deposited” state and up to post-deposition annealing temperatures of T _PDA=450°C, the film resistivity is linearly correlated with the reciprocal value of the platinum film thickness according to the size effect. When applying, however, solely the Fuchs-Sondheimer model for evaluation, the effective mean free path for electrons is substantially above the value reported for crystalline platinum at room temperature. Compared to similar investigations on smooth Si/SiO₂ substrates yielding interpretable results within this theoretical approach, this is due to the increase of the thickness-dependent fraction in film resistivity which is strongly affected by the enhanced LTCC/glass surface roughness. At T _PDA>600°C, diffusion of titanium into the platinum top layer and the roughening of the LTCC/glass substrate dominate the electrical behavior, both causing an increase in film resistivity above average. In contrast to Si/SiO₂ substrates, thermal induced grooving effects in the Pt top layer play a minor role as the temperature coefficients of expansion of metallization and glass-ceramic substrate match better and the effective temperature difference for stress generation is lower due a glass softening temperature of about 450°C.     

Molecular-weight dependence of the glass transition temperature of freely-standing poly(methyl methacrylate) films

We have used transmission ellipsometry to measure the glass transition temperature, T_g, of freely-standing films of atactic and syndiotactic poly(methyl methacrylate) (PMMA). We have prepared films with different molecular weights, MW, (159×10³ < M _w < 1.3×10⁶) and film thicknesses, h, ( 30nm < h < 200 nm). For the high-MW ( M _w > 509×10³) atactic PMMA films, we find that T_g decreases linearly with decreasing h, which is qualitatively similar to previous results obtained for high-MW freely-standing polystyrene (PS) films. However, the overall magnitude of the T_g reduction is much less (by roughly a factor of three) for the high-MW freely-standing PMMA films than for freely-standing PS films of comparable MW and h. The observed differences between the freely-standing PMMA and PS film data suggest that differences in chemical structure determine the magnitude of the T_g reduction and we discuss the possible origins of these differences. Our analysis of the MW-dependence of the T_g reductions suggests that the mechanism responsible for the MW-dependent T_g reductions observed in the high-MW freely-standing films is different than that responsible for the MW-independent T_g reductions observed in the low-MW freely-standing and supported films.     

A new metallic state in two dimensions

We report the discovery of a new and unexpected kind of metal in two dimensions (2D), which exists in the presence of scattering by local magnetic moments. The experiment was carried out on a 2D electron system in silicon, where the local magnetic moments have been induced by disorder and their number was varied using substrate bias (V_sub). In the new metal, the conductivity decreases as σ(n_s,T)=σ(n_s,T=0)+A(n_s)T² (n_s – carrier density) to a non-zero value as temperature T→0. In three dimensions, this T² dependence is well known, and results from Kondo scattering by local magnetic moments. In 2D, however, the existence of a metal with dσ/dT>0 is very surprising. As the number of local moments is reduced, the range of temperatures [T<T_m(V_sub)] where they dominate transport becomes smaller. For T>T_m, we observe the usual 2D metallic behavior with dσ/dT<0.     

Temperature dependence of muonium spin exchange with O2 in the range 88 K to 478 K

Our group at TRIUMF reported earlier a study of the spin exchange reactions of Mu with O₂ and NO in the range 295 K to 478 K. We have extended the measurement with O₂ to a low temperature region down to 88 K. From 135 K to 296 K, the spin depolarization rate constantk _d(T) was found to vary according to the relative velocity of the colliding species,T ^1/2, which indicates that the spin exchange cross section of Mu-O₂ is temperature independent in this temperature range. The value ofk _d(T) at 296 K is in good agreement with our earlier study. However, it was found that below 105 K and above 400 K,k _d(T) tends to have stronger temperature dependences (T ⁿ , withn>1/2). This deviation fromT ^1/2-behavior can be attributed to the velocity (energy) dependence of the spin exchange cross section.