Observation of Intrusion Rates of Hexamethyldisilazane During Supercritical Carbon Dioxide Functionalization of Triethoxyfluorosilane Low-k Films

2005 ◽  
Vol 863 ◽  
Author(s):  
P.M. Capani ◽  
P.D. Matz ◽  
D.W. Mueller ◽  
M.J. Kim ◽  
E.R. Walter ◽  
...  

AbstractWater adsorption by porous low-k silica films results in increased dielectric constants and is often due to silanol groups on the pore surfaces. Reacting the silanols with silylating agents (e.g., hexamethyldisilazane (HMDS) and trimethylchlorosilane (TMCS)) in supercritical CO2 (SC-CO2) can increase film hydrophobicity and can remove adsorbed water. In porous methylsilsesquioxane (MSQ) films (average pore size ∼ 3-4nm), it has been determined that supercritical silylation reactions do not substantially penetrate beyond the film surface.1,2 In this work we have examined the supercritical penetration behavior of silylating agents in low-k films with larger pore sizes (5-10nm). The depth and extent of reactants was determined by in situ infrared spectroscopy (FTIR), and surface hydrophobicity was examined by contact angle experiments.

2002 ◽  
Vol 17 (5) ◽  
pp. 1162-1171 ◽  
Author(s):  
Oomman K. arghese ◽  
Dawei Gong ◽  
Maggie Paulose ◽  
Keat G. Ong ◽  
Craig A. Grimes ◽  
...  

The effect of pore size and uniformity on the humidity response of nanoporous alumina, formed on aluminum thick films through an anodization process, is reported. Pore sizes examined range from approximately 13 to 45 nm, with a pore size standard deviations ranging from 2.6 to 7.8 nm. The response of the material to humidity is a strong function of pore size and operating frequency. At 5 kHz an alumina sensor with an average pore size of 13.6 nm (standard deviation 2.6 nm) exhibits a well-behaved change in impedance magnitude of 103 over 20% to 90% relative humidity. Increasing pore size decreases the humidity range over which the sensors have high sensitivity and shifts the operating range to higher humidity values. Cole–Cole plots of 5 to 13 MHz measured impedance spectra, modeled using equivalent circuits, are used to resolve the effects of water adsorption and ion migration within the adsorbed water layer. The presence of impurity ions within the highly ordered nano-dimensional pores, accumulated during the anodization process, appear highly beneficial for obtaining a substantial variation in measured impedance over a wide range of humidity values.


1999 ◽  
Vol 565 ◽  
Author(s):  
Ryo Muraguchi ◽  
Miki Egami ◽  
Hiroki Arao ◽  
Atsushi Tounai ◽  
Akira Nakashima ◽  
...  

AbstractWe studied the effect of pore diameter on the film properties of low-density porous material with special interest in the pore diameter range below 5nm. A novel low-density material, Interpenetrated SOG (IPS), was designed to realize such porous character. It is composed of a pyrolic template, which is an organic olygomer, and framework, made from SOG polymer and silica sol, forming an interpenetrated structure. Thermal decomposition of the organic component successfully resulted in films with pore diameter range below 5nm. It is found that the dielectric constant and the pore diameter depended on the density and the film strength was affected by the average pore diameter. Practically, films with the average pore size below 5nm possessed dielectric constants as low as 2.2–2.0 and sufficient strength.


2001 ◽  
Vol 714 ◽  
Author(s):  
Hae-Jeong Lee ◽  
Eric K. Lin ◽  
Howard Wang ◽  
Wen-Li Wu ◽  
Wei Chen ◽  
...  

ABSTRACTA novel methodology using a combination of ion scattering, x-ray reflectivity (SXR), and small angle neutron scattering was used to characterize the structure and properties of a hydrogen silsesquioxane (HSQ) based porous low-k dielectric films after varying process conditions. The dielectric constant and the remaining Si-H fraction (degree of cure) of the samples were varied from 1.5 to 2.2 and from 30 % to 52 %, respectively, by controlling the mass ratio of the solvent and the HSQ resin in the initial solutions and the wet ammonia treatment time. We determined the density depth profile, average mass density, wall density, porosity, average pore size, average wall thickness, pore connectivity and atomic composition. The chemical bond structures were also measured using Fourier transform infrared (FTIR) spectroscopy. The density profile of each porous low-k film was uniform and only two layers were required to fit the experimental SXR data. Higher dielectric constant films show significantly higher wall densities and lower porosities and pore sizes. The measured increases in the wall density with lower Si-H fractions are consistent with the FTIR results.


2002 ◽  
Vol 716 ◽  
Author(s):  
Ben Zhong ◽  
Herman Meynen ◽  
Francesca Iocopi ◽  
Ken Weidner ◽  
Stephane Mailhouitre ◽  
...  

AbstractA ULK material based on a siloxane resin has been developed that can be processed using spin-coating and thermal cure to yield porous low-k films. The chemical bonds between the resin and porogen groups prevent the phase separation of the porogen from the resin during curing and lead to extremely small pores. The highly hydrophobic thin films made from this material displayed dielectric constant of 1.8, breakdown voltage of 4 MV/cm, a cohesive strength > 60 MPa, excellent crack resistance, and an average pore size of 2.2 nm by Positron Annihilation Lifetime Spectroscopy (PALS) and 2.5-3.0 nm by Ellipsometric Porosimetry (EP). In this paper, our strategy for designing low-k materials, the material properties and initial integration results for this new material will be discussed.


2001 ◽  
Vol 703 ◽  
Author(s):  
Deok-Yang Kim ◽  
Henry Du ◽  
Suhas Bhandarkar ◽  
David W. Johnson

ABSTRACTTetramethyl ammonium silicate (TMAS) is known as a structuring agent in zeolite synthesis. We report its first use to prepare porous silica films for low k dielectric applications in microelectronics. A solution of TMAS 18.7 wt. % was spin coated on silicon substrates with a 3000 Å thick thermal oxide. The spin coated films were subsequently heat-treated at 450°C to obtain porous silica. The use of TMAS solution without gelation led to films of only moderate porosity value of 10%. The addition of methyl lactate, a gelling agent, significantly increased film porosity and improved the pore size distribution. For example, 50% porosity and uniform pore size distribution (average pore size ∼ 40 Å) has been achieved. Dielectric constants (k) of our porous films are as low as 2.5.


2003 ◽  
Vol 766 ◽  
Author(s):  
Brian Landes ◽  
Brandon Kern ◽  
Ted Stokich ◽  
Jason Niu ◽  
Dorie Yontz ◽  
...  

AbstractThe continual drive for faster interconnects requires the development of new interlayer dielectricmaterials with k values less than 2.1. Porous SiLKTM semiconductor dielectric resin wasdeveloped to achieve these low dielectric constants by introducing nanometer-sized pores intothe dense SiLK resin matrix. A quantitative description of the nano-porous morphology in low-kinterlayer dielectrics can be difficult to achieve for many reasons, including: complexities in theporous structure (size range, geometry, pore/pore interaction), inadequate mathematicaldescriptors, limitations of existing metrology technology, and availability of “tailor-made” experimental samples with a wide range of pore morphologies. On-wafer quantification of poremorphology is even more difficult as data must be obtained from extremely limited samplevolumes (thin films of ∼100-500 nm) residing on thick silicon (Si) wafer substrates.This paper will focus on the design, development and successful application of on-wafer smallangle x-ray scattering (SAXS) technology to characterize the morphology of porous SiLK resin.It will be demonstrated, by example, that this technology is able to deliver rapid quantificationover the entire pore size range for these systems. Recently developed data acquisition, reductionand analysis tools will be described. Direct evaluation of the strengths and challenges of severalmodels used to generate average pore size and pore size distribution will be reviewed. Finally,additional capabilities offered by this technology (wafer mapping and detection of “killer” pores)will also be discussed.


2018 ◽  
Author(s):  
K. A. Rubin ◽  
W. Jolley ◽  
Y. Yang

Abstract Scanning Microwave Impedance Microscopy (sMIM) can be used to characterize dielectric thin films and to quantitatively discern film thickness differences. FEM modeling of the sMIM response provides understanding of how to connect the measured sMIM signals to the underlying properties of the dielectric film and its substrate. Modeling shows that sMIM can be used to characterize a range of dielectric film thicknesses spanning both low-k and medium-k dielectric constants. A model system consisting of SiO2 thin films of various thickness on silicon substrates is used to illustrate the technique experimentally.


2017 ◽  
Vol 54 (3) ◽  
pp. 181-201
Author(s):  
Rebecca Johnson ◽  
Mark Longman ◽  
Brian Ruskin

The Three Forks Formation, which is about 230 ft thick along the southern Nesson Anticline (McKenzie County, ND), has four “benches” with distinct petrographic and petrophysical characteristics that impact reservoir quality. These relatively clean benches are separated by slightly more illitic (higher gamma-ray) intervals that range in thickness from 10 to 20 ft. Here we compare pore sizes observed in scanning electron microscope (SEM) images of the benches to the total porosity calculated from binned precession decay times from a suite of 13 nuclear magnetic resonance (NMR) logs in the study area as well as the logarithmic mean of the relaxation decay time (T2 Log Mean) from these NMR logs. The results show that the NMR log is a valid tool for quantifying pore sizes and pore size distributions in the Three Forks Formation and that the T2 Log Mean can be correlated to a range of pore sizes within each bench of the Three Forks Formation. The first (shallowest) bench of the Three Forks is about 35 ft thick and consists of tan to green silty and shaly laminated dolomite mudstones. It has good reservoir characteristics in part because it was affected by organic acids and received the highest oil charge from the overlying lower Bakken black shale source rocks. The 13 NMR logs from the study area show that it has an average of 7.5% total porosity (compared to 8% measured core porosity), and ranges from 5% to 10%. SEM study shows that both intercrystalline pores and secondary moldic pores formed by selective partial dissolution of some grains are present. The intercrystalline pores are typically triangular and occur between euhedral dolomite rhombs that range in size from 10 to 20 microns. The dolomite crystals have distinct iron-rich (ferroan) rims. Many of the intercrystalline pores are partly filled with fibrous authigenic illite, but overall pore size typically ranges from 1 to 5 microns. As expected, the first bench has the highest oil saturations in the Three Forks Formation, averaging 50% with a range from 30% to 70%. The second bench is also about 35 ft thick and consists of silty and shaly dolomite mudstones and rip-up clast breccias with euhedral dolomite crystals that range in size from 10 to 25 microns. Its color is quite variable, ranging from green to tan to red. The reservoir quality of the second bench data set appears to change based on proximity to the Nesson anticline. In the wells off the southeast flank of the Nesson anticline, the water saturation averages 75%, ranging from 64% to 91%. On the crest of the Nesson anticline, the water saturation averages 55%, ranging from 40% to 70%. NMR porosity is consistent across the entire area of interest - averaging 7.3% and ranging from 5% to 9%. Porosity observed from samples collected on the southeast flank of the Nesson Anticline is mainly as intercrystalline pores that have been extensively filled with chlorite clay platelets. In the water saturated southeastern Nesson Anticline, this bench contains few or no secondary pores and the iron-rich rims on the dolomite crystals are less developed than those in the first bench. The chlorite platelets in the intercrystalline pores reduce average pore size to 500 to 800 nanometers. The third bench is about 55 ft thick and is the most calcareous of the Three Forks benches with 20 to 40% calcite and a proportionate reduction in dolomite content near its top. It is also quite silty and shaly with a distinct reddish color. Its dolomite crystals are 20 to 50 microns in size and partly abraded and dissolved. Ferroan dolomite rims are absent. This interval averages 7.1% porosity and ranges from 5% to 9%, but the pores average just 200 nanometers in size and occur mainly as microinterparticle pores between illite flakes in intracrystalline pores in the dolomite crystals. This interval has little or no oil saturation on the southern Nesson Anticline. Unlike other porosity tools, the NMR tool is a lithology independent measurement. The alignment of hydrogen nuclei to the applied magnetic field and the subsequent return to incoherence are described by two decay time constants, longitudinal relaxation time (T1) and transverse relaxation time (T2). T2 is essentially the rate at which hydrogen nuclei lose alignment to the external magnetic field. The logarithmic mean of T2 (T2 Log Mean) has been correlated to pore-size distribution. In this study, we show that the assumption that T2 Log Mean can be used as a proxy for pore-size distribution changes is valid in the Three Forks Formation. While the NMR total porosity from T2 remains relatively consistent in the three benches of the Three Forks, there are significant changes in the T2 Log Mean from bench to bench. There is a positive correlation between changes in T2 Log Mean and average pore size measured on SEM samples. Study of a “type” well, QEP’s Ernie 7-2-11 BHD (Sec. 11, T149N, R95W, McKenzie County), shows that the 1- to 5-micron pores in the first bench have a T2 Log Mean relaxation time of 10.2 msec, whereas the 500- to 800-nanometer pores in the chlorite-filled intercrystalline pores in the second bench have a T2 Log Mean of 4.96 msec. This compares with a T2 Log Mean of 2.86 msec in 3rd bench where pores average just 200 nanometers in size. These data suggest that the NMR log is a useful tool for quantifying average pore size in the various benches of the Three Forks Formation.


2006 ◽  
Vol 514-516 ◽  
pp. 1005-1009 ◽  
Author(s):  
José V. Araújo ◽  
J.A. Lopes da Silva ◽  
Margarida M. Almeida ◽  
Maria Elisabete V. Costa

Porous chitosan/brushite composite scaffolds were prepared by a freeze-drying technique, starting from brushite suspensions in chitosan solutions. The obtained scaffolds showed a regular macroporous and interconnected structure with brushite particles uniformly distributed in the chitosan matrix. The variation of the brushite concentration affected the microstructure of the final freeze-dried scaffold, in particular, its porosity and its average pore size. The yield strengths of the composite scaffolds could also be improved by the increase of the brushite content.


2021 ◽  
Vol 13 (14) ◽  
pp. 7593
Author(s):  
Farooq Khan Niazi ◽  
Malik Adeel Umer ◽  
Ashfaq Ahmed ◽  
Muhammad Arslan Hafeez ◽  
Zafar Khan ◽  
...  

Ultrafiltration membranes offer a progressive and efficient means to filter out various process fluids. The prime factor influencing ultrafiltration to a great extent is the porosity of the membranes employed. Regarding membrane development, alumina membranes are extensively studied due to their uniform porosity and mechanical strength. The present research work is specifically aimed towards the investigation of nanoporous alumina membranes, as a function of sintering parameters, on ultrafiltration performance. Alumina membranes are fabricated by sintering at various temperatures ranging from 1200–1300 °C for different holding times between 5–15 h. The morphological analysis, conducted using Scanning electron microscopy (SEM), revealed a homogeneous distribution of pores throughout the surface and cross-section of the membranes developed. It was observed that an increase in the sintering temperature and time resulted in a gradual decrease in the average pore size. A sample with an optimal pore size of 73.65 nm achieved after sintering at 1250 °C for 15 h, was used for the evaluation of ultrafiltration performance. However, the best mechanical strength and highest stress-bearing ability were exhibited by the sample sintered at 1300 °C for 5 h, whereas the sample sintered at 1250 °C for 5 h displayed the highest strain in terms of compression. The selected alumina membrane sample demonstrated excellent performance in the ultrafiltration of sugarcane juice, compared to the other process liquids.


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