A new microcalorimeter for measuring heat capacity of thin films in the range 1.5–800 K is described. Semiconductor processing techniques are used to create a device with an amorphous silicon nitride membrane as the sample substrate, a Pt thin film resistor for temperatures greater than 40 K, and either a thin film amorphous Nb–Si or a novel boron‐doped polycrystalline silicon thermometer for lower temperatures. The addenda of the device, including substrate, is 4×10−6 J/K at room temperature and 2×10−9 J/K at 4.3 K, approximately two orders of magnitude less than any existing calorimeter used for measuring thin films. The device is capable of measuring the heat capacity of thin film samples as small as a few micrograms.

http://research.physics.berkeley.edu/hellman/papers/microcalorimeter.pdf

Thin film microcalorimeter for heat capacity measurements from 1.5 to 800 K

Modulation calorimetry and related techniques

Classical temperature-modulated calorimetry: A review

Vapor-deposited glasses of toluene and ethylbenzene have been characterized by in situ ac chip-nanocalorimetry. The high sensitivity of this method allows the detection of small changes in the heat capacity of nanogram size samples. We observe that vapor-deposited glasses have up to 4% lower heat capacities than the ordinary glass. The largest heat capacity decrease and the most kinetically stable glasses of toluene and ethylbenzene are observed in a range of deposition temperatures between 0.75 Tg and 0.96 Tg. Compared to larger molecules, deposition rate has a minor influence on the kinetic stability of these glasses. For both toluene and ethylbenzene, the kinetic stability is strongly correlated with the heat capacity decrease for deposition temperatures above 0.8 Tg. In addition, ac-nanocalorimetry was used to follow the isothermal transformation of the stable glasses into the supercooled liquid at temperatures slightly above Tg. Toluene and ethylbenzene stable glasses exhibit a constant transformatio...

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In situ investigation of vapor-deposited glasses of toluene and ethylbenzene via alternating current chip-nanocalorimetry.

Physical vapor deposition can be used to produce thin films with interesting material properties including extraordinarily stable organic glasses. We describe an ac chip calorimeter for in situ heat capacity measurements of as-deposited nanometer thin films of organic glass formers. The calorimetric system is based on a differential ac chip calorimeter which is placed in the vacuum chamber for physical vapor deposition. The sample is directly deposited onto one calorimetric chip sensor while the other sensor is protected against deposition. The device and the temperature calibration procedure are described. The latter makes use of the phase transitions of cyclopentane and the frequency dependence of the dynamic glass transition of toluene and ethylbenzene. Sample thickness determination is based on a finite element modeling of the sensor sample arrangement. In the modeling, a layer of toluene was added to the sample sensor and its thickness was varied in an iterative way until the model fit the experimental data.

Differential alternating current chip calorimeter for in situ investigation of vapor-deposited thin films.

An analysis is presented of the performance of an ideal ac calorimeter limited only by thermodynamic noise. A calorimeter based on this analysis is described which is designed for studies of the heat capacity of monolayers and multilayers of atoms and molecules adsorbed on a variety of surfaces. The calorimeter consists of Ge:Ga thermometers and NiCr heaters mounted on one side of a sapphire substrate, with an evaporated film deposited on the other side. The calorimeter is mounted on a 4He cold finger in a UHV system allowing heat capacity measurements down to 1.6 K. In order to verify the performance of the calorimeter, measurements have been made of the heat capacity of 25‐μg samples of indium, and of submonolayer coverages of 4He on sapphire. The measured sensitivity corresponds to <10−2 monolayers of 4He adsorbed on the surface of the calorimeter in the gas phase.

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T. W. Kenny

Papers

ac calorimeter for measurements of adsorbed gases on metal films at 4He temperatures