(Digital Presentation) Porous Silicon Formed by Electrochemical, Chemical and Combined Etching
Authors: Zhumabay Zhumabay 
Published: February 2024

This work is devoted the thermophysical characteristics (TPC) of PS formed by Electrochemical, Metal-assisted chemical and combined etching methods. The TPC of PS/MACE+EC formed by the MACE+EC– method is higher than those of the PS/EC and PS/MACE samples formed by the EC and MACE methods. The energy activity of water splitting on the surface of PS/MACE+EC is higher than the energy activity of the PS/EC and PS/MACE samples. The combined (MACE+EC) method is the best method for obtaining PS, which has the highest energy activity in water splitting processes. The activation energy of water splitting processes Ea(PS/MACE+EC) is higher than the energy activity of the Ea(PS/EC) and Ea(PS/MACE) samples. The presence of Ni particles in the pores of PS<Ni> stabilizes the them TPC. The TPC of PS were studied in comparison with the TPC of crystalline (c-Si) and powdered silicon (powder-Si). It is known that PS has a high catalytic activity of hydrogen evolution during photoelectrochemical splitting of water. For example, the use of a surface enriched Ni layer on the surface of a PS photocathode PS<Ni> made it possible to increase its catalytic activity two times higher than the catalytic activity of the Pt- electrode in the reaction of hydrogen evolution [1].
The TPC of PS samples formed by EC, MACE and combined (MACE+EC)- etching methods are studied in comparison with the TPC of c-Si and powder-Si samples, Table.

Method

Electrolyte

Composition

Marked

I

Et1

HF:H2O2=1:1

EC

II

Et2

HF:H2O2: Ni(NO3)2
=1:1:1

МАСЕ

III

Et3

HF:H2O2: Ni(NO3)2 =1:1:1

EC+МАСЕ

According of electron microscopy research the highest porosity is observed on the PS/MACE+EC samples, the smallest - on the PS/MACE sample formed by the MACE- method. The Raman spectra testify this, PS/MACE+EC(Et3) samples have a higher intensity of the Raman peak at a high-frequency shift due to electron-phonon scattering, the intensity and frequency of which depend on the concentration of scattering centers and, consequently, on the conditions for the formation of pores [2]. The TPC of differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) spectra record changes in the mass Δm of the sample and heat flux ΔQ with an isobaric temperature change ΔT at the points of T-characteristic. An analysis of the calorimetric TPC and the TGA and DSC spectra shows that c-Si and powder have almost the same patterns of change in thermal conductivity, in contrast to the PS-spectra. The PS/EC, PS/MACE samples have the maximum change in heat flux Q(PS/EC)=187.6 mW, Q(PS/MACE)=231.6 mW, in contrast to powder-Si Q(powder-Si)=107.1 mW and c-Si ΔQ(c-Si)=65.02 mW. This dependence, which is responsible for the heat flux ΔQ change in the high T-range is associated with the maximum developed surface PS. Due to the fact that the presence of the Ni in the pores of PS<Ni>/MACE and PS<Ni>/MACE+EC stabilizes the TPC of PS, and thereby prevents significant changes in the TPC of Ni-containing PS<Ni>, in contrast to PS that does not Ni-contain in pores. Also have carried out experiments on the evaporation of water droplets at room temperature from the surface of c-Si and PS/EC, PS/MACE PS/MACE+EC samples. Experiments on the evaporation of water droplets at Troom from the surface of crystalline and PS samples obtained by various etching methods showed that the highest energy activity is observed in PS/MACE+EC samples, Ea(PS/MACE+EC) = 0.2087 eV, which is much higher than Ea(PS/EC) = 0.070 eV, Ea(PS/MACE) = 0.050 eV and Еа(c-Si) = 0.025 eV,
The porous surface of the PS/MACE+EC sample has the highest energy activity compared to the PS/EC and PS/MACE samples, which is due to the high porosity of PS/MACE+EC. The PS/MACE and PS/MACE+EC samples showed high energy stability over 1 year in water evaporation experiments.

The values of the heat capacities of various EC-, MACE-, EC+MACE - etching methods are established: - Cp(c -Si) = 20.7 KJ/gK, Cp(powder-Si) = 13.11 KJ/gK, Cp(PS/MACE) = 12.79 KJ/gK, Cp(PS/AE) = 5.62 KJ/gK.

Combination of electrochemical etching with Ni-stimulated and chemical etching (EC+MACE) makes the possibility Ni-containing nanoporous silicon with high energy activity in water splitting processes: - Еа(PS/MACE+EC) = 0.2087 eV, Еа(PS/MACE) = 0.070 eV , Еа(PS/АЕ) =0.050 eV.

The Ni- presence in the pores stabilizes the TPC of PS/MACE and PS/MACE+EC. The stability of Ni-containing samples PS/MACE+EC) and Ea(PS/MACE) is maintained for one year.

[1] K.B. Tynyshtykbayev et al. Russian Microelectronics, 2016, Vol. 45, Nos. 8–9, pp. 603–612. https://doi.org/10.1134/S106373971608014X
[2] K. Tynyshtykbayev et al. ECS Journal of Solid State Science and Technology, 2021 10 013009 DOI: 10.1149/2162-8777/abdd86