How to directly analyze the pore size distribution in mesoporous silica films with helium (@87K)? -Huaqiang Electronic Network

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Mesoporous silica film (usually referred to as thickness in

300?

To 900 nm film materials) in sensors, low dielectric films, etc.

A wide range of applications are available in many fields. The introduction of mesopores in the film facilitates further reduction of the dielectric constant of the material. It can be said that thin silicon dioxide

The dielectric constant of a film is closely related to the pore size distribution and pore volume of the material. Usually, a mesopores of less than 10 nm are used to reduce the film.

The dielectric constant can play an important role. Holes larger than 10 nm in the film are often caused by the development and manufacturing of such materials.

The cause of device manufacturing failure. However, measuring the pore size distribution and pore volume in such films is quite difficult. The gas adsorption method is 10 nanometers.

Conventional characterization of the right and left holes. In general, the adsorption of nitrogen, argon and helium at 77.35K or 87.27K can be used to calculate more

The specific surface area, pore size, pore distribution and pore volume of the pore material cannot be characterized by conventional nitrogen and argon. this is

Since the total pore volume and surface area of ​​the film material are very small, the pressure difference caused by the adsorption is also extremely small. ?

Recently, a new method for determining the pore size of thin film materials has been established, and helium gas is used for aperture measurement. This method has been built in

3H-2000

Series of fully automatic physical adsorption analyzers. This method is not only applicable to silica-based mesoporous film materials,

It is suitable for mesoporous materials with surface oxidizing properties. ?

? ? ? This method chooses to use liquid argon temperature (87K) instead of liquid nitrogen temperature (77K) because:
?

1)

The difference in saturated vapor pressure. Helium

77K

The saturated vapor pressure (sublimation) is about 1.6 torr, which is about 13 torr at 87K.

In the case of a device equipped with a molecular pump and a low pressure sensor, the saturated vapor pressure of 13torr can be pore size analysis, even

Microwell analysis (down to 0.7 nm) provides sufficient resolution. ?


2)

The mathematical relationship between the mathematical expression of the physical phenomenon and the pore size change is a prerequisite for the pore size analysis. Research shows that at 77K

At the temperature, helium gas will simultaneously undergo capillary condensation and desublimation in the pores. However, only capillary condensation occurs at 87K. ?

• When applying this method, the adsorption of helium at liquid argon temperature is first corrected. The calibration process is as follows:

1, using a well-recognized highly ordered mesoporous material as a reference sample (such as MCM-41, SBA-15 or MCM-48) in nitrogen

Adsorption measurements were carried out under gas (77K) and argon (87K) conditions, and geometrically shaped pores were calculated by the NLDFT method.

Diameter and pore volume (extrapolated to the microwell interval). ?

2. Measure the helium (87K) isotherm of the above materials and correlate the pore size according to the harvest of the first step. Thus, the film hole

The diameter distribution can be obtained by the NLDFT method. ?

3. The density of the liquid phase condensed in the pores can be (a) the pore volume of the known mesoporous material used in the first step and (b) the helium gas.

The amount of adsorption is calculated. The average liquid phase enthalpy density obtained in the test was 2.6 g/cm.

3

, consistent with theoretical calculations. Then,

The total pore volume of the film can be calculated from the density of the liquid phase. ?

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