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Encyclopedia > Porous silicon

Porous Silicon (pSi) is a form of the chemical element silicon which has an introduced nanoporous holes in its microstructure, rendering a large surface to volume ratio in the order of 500m2/cm3. Not to be confused with Silicone. ...

Contents

History

Porous silicon was first discovered by accident in 1956 by Arthur Uhlir Jr. and Ingeborg at the Bell laboratories in US. At the time, Ulhir and Ingeborg were in the process of developing a technique for polishing and shaping the surfaces of silicon and germanium. However, it was found that under several conditions a crude product in the form of thick black, red or brown film were formed on the surface of the material. At the time, the findings were not taken further and were only mentioned in Bell’s labs technical notes .[1] Ingeborg is a Scandinavian name carried by many prominent women in Scandinavian history and mythology, including: The daughter of the Norwegian king Beli, in Friðþjófs saga ins frÅ“kna. ... Not to be confused with Silicone. ... General Name, Symbol, Number germanium, Ge, 32 Chemical series metalloids Group, Period, Block 14, 4, p Appearance grayish white Standard atomic weight 72. ...


Despite the discovery of porous silicon in the 1950’s, the scientific community was not interested in porous silicon until the late 1980’s. At the time, Leigh Canham – whilst working at the Defence Research Energy in England – reasoned that the porous silicon may display quantum confinement effects [2]. The intuition was followed by successful lab results published in the 1990. In the published experiment, it was revealed that silicon wafers can emit light if subjected to electrochemical and chemical dissolution.


The published result stimulated the interest of the scientific community in its non-linear optical and electrical properties. The growing interest was evidenced in the number of published work concerning the properties and potential applications of porous silicon. In an article published in 2000, it was found that the number of published work grew exponentially in between 1991 and 1995 [3]


In 2001, a team of scientists at the Technical University of Munich inadvertently discovered that hydrogenated porous silicon reacts explosively with oxygen at cryogenic temperatures, releasing several times as much energy as an eqivalent amount of TNT, at a much greater speed (an abstract of the study can be found below). Explosion occurs because the oxygen, which is in a liquid state at the necessary temperatures, is able to oxidize through the porous molecular structure of the silicon extremely rapidly, causing a very quick and efficient detonation. Although hydrogenated porous silicon would probably not be effective as a weapon, due to its functioning only at low temperatures, other uses are being explored for its explosive properties, such as providing thrust for satellites. This article is about the year. ... Technische Universität München (TUM) (English: Technical University of Munich) is a German university, part of the Deutsche Forschungsgemeinschaft, a society of Germanys leading research universities in Munich. ... Hydrogenation is a class of chemical reactions which result an addition of hydrogen (H2) usually to unsaturated organic compounds. ... This article is about the chemical element and its most stable form, or dioxygen. ... Cryogenics is the study of very low temperatures or the production of the same, and is often confused with cryobiology, the study of the effect of low temperatures on organisms, or the study of cryopreservation. ... R-phrases S-phrases Related Compounds Related compounds picric acid hexanitrobenzene Except where noted otherwise, data are given for materials in their standard state (at 25 Â°C, 100 kPa) Infobox disclaimer and references Trinitrotoluene (TNT) is a chemical compound with the formula C6H2(NO2)3CH3. ... An abstract is a brief summary of a research article, thesis, review, conference proceeding or any in-depth analysis of a particular subject or discipline, and is often used to help the reader quickly ascertain the papers purpose. ... The most fundamental reactions in chemistry are the redox processes. ... A weapons cache is detonated at the East River Range on Bagram Airfield, Afghanistan Detonation is a process of supersonic combustion in which a shock wave is propagated forward due to energy release in a reaction zone behind it. ... This article is about artificial satellites. ...


Fabrication of Porous Silicon

Fabrication of porous silicon may range from its initial formation through stain-etching or anodization cell, drying and storage of porous silicon and surface modification needed.


Formation of Porous Silicon by Anodization

One method of introducing pores in silicon is through the use of an anodization cell. A possible anodization cell employs platinum cathode and silicon wafer anode immersed in Hydrogen Fluoride (HF) electrolyte. Corrosion of the anode is produced by running electrical current through the cell. It is noted that the running of constant DC current is usually implemented to ensure steady tip-concentration of HF resulting in a more homogenous porosity layer although pulsed current is more appropriate for the formation of thick silicon wafers bigger than 50µm [4] Hydrogen fluoride is a chemical compound with the formula HF. Together with hydrofluoric acid, it is the principal industrial source of fluorine and hence the precursor to many important compounds including pharmaceuticals and polymers (e. ... For the hazard, see corrosive. ... Diagram of a zinc anode in a galvanic cell. ...


It was noted by Halimaoui that hydrogen evolution occurs during the formation of porous silicon.

“When purely aqueous HF solutions are used for the PS formation, the hydrogen bubbles stick to the surface and induce lateral and in-depth homogeneity”

The hydrogen evolution is normally treated with absolute ethanol in concentration exceeding 15%. It was found that the introduction of ethanol eliminates hydrogen and ensures complete infiltration of HF solution within the pores. Subsequently, uniform distribution of porosity and thickness is improved.

Formation of Porous Silicon by Stain Etching

It is possible to obtain porous silicon through stain-etching with hydrofluoric acid, nitric acid and water. A publication in 1957 revealed that stain films can be grown in dilute solutions of nitric acid in concentrated hydrofluoric acid [5].Porous silicon formation by stain-etching is particularly attractive because of its simplicity and the presence of readily available corrosive reagents; namely Hydrogen Nitride (HNO3) and Hydrogen Fluoride (HF). Furthermore, stain-etching is useful if one needs to produce a very thin porous Si films [6]. A publication in 1960 by R.J. Archer revealed that it is possible to create stain films as thin as 25Šthrough stain-etching with HF-HNO3 solution. R-phrases , S-phrases , , , , Flash point nonflammable Related Compounds Other anions Hydrochloric acid Hydrobromic acid Hydroiodic acid Related compounds Hydrogen fluoride fluorosilicic acid Supplementary data page Structure and properties n, εr, etc. ... The chemical compound nitric acid (HNO3), also known as aqua fortis and spirit of nitre, is an aqueous solution of hydrogen nitrate (anhydrous nitric acid). ... Impact from a water drop causes an upward rebound jet surrounded by circular capillary waves. ...


Drying of Porous Silicon

Porous silicon is systematically prone to presence of cracks when the water is evaporated. The cracks are particularly evident in thick or highly porous silicon layers [7]. The origin of the cracks has been attributed to the large capillary stress due to the minute size of the pores. In particular, it has been known that cracks will appear for porous silicon samples with thickness larger than a certain critical value. Bellet concluded that it was impossible to avoid cracking in thick porous silicon layers under normal evaporating conditions. Hence, several appropriate techniques have been developed to minimize the risk of cracks formed during drying.


Supercritical Drying
Supercritical drying is reputed to be the most efficient drying technique but is rather expensive and difficult to implement. It was first implemented by Canham in 1994 and involves superheating the liquid pore above the critical point to avoid interfacial tension. In physics, superheating (sometimes referred to as boiling retardation, boiling delay, or defervescence) is the phenomenon in which a liquid is heated to a temperature higher than its standard boiling point, without actually boiling. ...


Freeze Drying
Freeze drying was first implemented by Gruning and Yelon in 1995. After the formation of porous silicon, the sample is frozen at a temperature of around -500C and sublimed under vacuum.


Pentane Drying
The technique uses pentane as the drying liquid instead of water. In doing so the capillary stress is reduced because pentane has a lower surface tension than water. Pentane (also known as amyl hydride or skellysolve) is an alkane hydrocarbon with the chemical formula CH3(CH2)3CH3. ...


Slow Evaporation Rate
Slow evaporating technique can be implemented following the water or ethanol rinsing. It was found that slow evaporation decreased the trap density


Surface Modification of Porous Silicon

The surface of porous silicon may be modified to exhibit different properties. Often, freshly etched porous silicon may be unstable due to the rate of its oxidation by the atmosphere or unsuitable for cell attachment purposes. Therefore, it can be surface modified to improve stability and cell attachment The most fundamental reactions in chemistry are the redox processes. ...


Surface Modification Improving Stability

Following the formation of porous silicon, its surface is covered with covalently bonded hydrogen. Although the hydrogen coated surface is sufficiently stable when exposed to inert atmosphere for a short period of time, prolonged exposure render the surface prone to oxidation by atmospheric oxygen. The oxidation promotes instability in the surface and is undesirable for many applications. Thus, several methods were developed to promote the surface stability of porous silicon.


An approach that can be taken is through thermal oxidation. The process involves heating the silicon to a temperature above 1000 C to promote full oxidation of silicon. The method reportedly produced samples with good stability to ageing and electronic surface passivation [8] In microfabrication, thermal oxidation is a way to produce a thin layer of oxide (usually silicon dioxide) on the surface of a wafer (semiconductor). ...


Porous silicon exhibits a high degree of biocompatibility. The large surface area enables bio-organic molecules to adhere well. It degrades to silicic acid, which causes no harm to the body. This has opened potential applications in medicine such as a framework of the growth of bone. Silicic acid is a general name for a family of chemical compounds of silicon, hydrogen, and oxygen, with the general formula [SiOx(OH)4-2x]n. ... This article is about the skeletal organs. ...


Surface Modification Improving Cell Adhesion

Surface modification can also affect properties that promote cell adhesion. One particular research in 2005 studied the mammalian cell adhesion on the modified surfaces of porous silicon. The research used rat PC12 cells and Human Lens Epithelial (HLE) cells cultured for four hours on the surface modified porous silicon. Cells were then stained with vital dye FDA and observed under fluorescence microscopy. The research concluded that ‘amino silanisation and coating the pSi surface with collagen enhanced cell attachment and spreading’ [9] Schematic of cell adhesion The study of cell adhesion is part of cell biology. ... PC12 is a cancer cell line derived from a pheochromocytoma of the rat adrenal medulla. ... Microscopy is any technique for producing visible images of structures or details too small to otherwise be seen by the human eye. ...


Classification of Porous Silicon

Porosity

‘The porosity is defined as the fraction of void within the PS layer and can be determined easily by weight measurement’.4 During formation of porous silicon layer through anodisation, the porosity of a wafer can be increased through increasing current density, decreasing HF concentration and thicker silicon layer. The porosity of porous silicon may range from 4% for macroporous layers to 95% for mesoporous layers. A study by Canham in 1995 found that ‘a lum thick layer of high porosity silicon completely dissolved within a day of in-vitro exposure to a simulated body fluid’ [10]It was also found that a silicon wafer with medium to low porosity displayed more stability. Hence, the porosity of porous silicon is varied depending on its potential application areas.


Pore Size

The porosity value of silicon is a macroscopic parameter and doesn’t yield any information regarding the microstructure of the layer. It is proposed that the properties of a sample are more accurately predicted if the pore size and its distribution within the sample can be obtained. Therefore, porous silicon has been divided into three categories based on the size of its pores; macroporous, mesoporous, and microporous. A mesoporous material is a material containing pores with diameters between 2 and 50 nm. ...

Type Microporous Mesoporous Macroporous
Pore width (Nanometer) less than 2 Between 2 and 50 Larger than 50

Key Characteristic of Porous Silicon

Highly Controllable Properties

Porous silicon studies conducted in 1995 showed that the behaviour of porous silicon can be altered in between ‘bio-inert’, ‘bioactive’ and ‘resorbable’ by varying the porosity of the silicon sample. 10The in-vitro study used simulated body fluid containing ion concentration similar to the human blood and tested the activities of porous silicon sample when exposed to the fluids for prolonged period of time. It was found that high porosity mesoporous layers were completely removed by the simulated body fluids within a day. In contrast, low to medium porosity microporous layers displayed more stable configurations and induced hydroxyapatite growth.


Bioactive

The first sign of porous silicon as a bioactive material was found in 1995. In the conducted study, it was found that hydroxyapatite growth was occurring on porous silicon areas. It was then suggested by author L.T. Canham that ‘hydrated microporous Si could be a bioactive form of the semiconductor and suggest that Si itself should be seriously considered for development as a material for widespread in vivo applications’10 Another paper published the finding that porous silicon may be used a substrate for hydroxyapatite growth either by simple soaking process or laser-liquid-solid interaction process [11] ... Hydroxylapatite is a naturally occurring form of calcium apatite with the formula Ca5(PO4)3(OH), but is usually written Ca10(PO4)6(OH)2 to denote that the crystal unit cell comprises two molecules. ... In vivo (Latin for (with)in the living). ...


Since then, in-vitro studies have been conducted to evaluate the interaction of cells with porous silicon. One particular study in 1995 studied the interaction of B50 rat hippocampal cells with porous silicon and found that B50 cells have clear preference for adhesion to porous silicon over untreated surface. The study indicated that porous silicon can be suitable for cell culturing purposes and can be used to control cell growth pattern [12] In vitro (Latin: within the glass) refers to the technique of performing a given experiment in a test tube, or, generally, in a controlled environment outside a living organism. ...


Non Toxic Waste Product

Another positive attribute of porous silicon is the degradation of porous silicon into monomeric silicic acid (SiOH4). Silicic acid is reputed to be the most natural form of element in the environment and is readily removed by kidneys. Silicic acid is a general name for a family of chemical compounds of silicon, hydrogen, and oxygen, with the general formula [SiOx(OH)4-2x]n. ...


The human blood plasma contains monomeric silicic acid at levels of less than 1mg Si/l, corresponding to the average dietary intake of 20-50mg/day. It was proposed that the small thickness of silicon coatings presents minimal risk to a toxic concentration being reached. The proposal was supported by an experiment involving volunteers and silicic-acid drinks. It was found that concentration of the acid rose only briefly above the normal 1mg Si/l level and was efficiently expelled by urine excretion [13] Blood plasma is the liquid component of blood, in which the blood cells are suspended. ...


See also

Not to be confused with Silicone. ... Porosity is a measure of the void spaces in a material, and is measured as a fraction, between 0–1, or as a percentage between 0–100%. The term porosity is used in multiple fields including manufacturing, earth sciences and construction. ... In condensed matter physics, a quantum wire is an electrically conducting wire, in which quantum effects are affecting transport properties. ... Etching is used in microfabrication to chemically remove layers from the surface of a wafer during manufacturing. ...

External links

  • Abstract of the study of porous silicon as an explosive

References

  • Porous Silicon, edited by Z C Feng & R Tsu, World Scientific (Singapore), 1994 ISBN 981-02-1634-3
  • Properties of Porous Silicon, edited by L.T Canham,Inspec, IEE, London, 1997
  1. ^ Canham 1993 A glowing future for silicon, New Scientist. Available from: <http://www.newscientist.com/article/mg13818683.800.html >
  2. ^ Sailor Research Group 17 February 2003, Introduction to Porous Si, Sailor research group at UCSD, Department of Chemistry, University of California. Available from: < http://chem-faculty.ucsd.edu/sailor/research/porous_Si_intro.html >
  3. ^ Parkhutik V. 2000, 'Analysis of Publications on Porous Silicon: From Photoluminescence to Biology', Journal of Porous Materials, Vol 7, Issue 1-3, pp363-6.
  4. ^ Halimaoui A. 1997, ‘Porous silicon formation by anodization, in Properties of Porous Silicon. Canham, LT, Institution of Engineering and Technology, London, pp. 12-22.
  5. ^ Archer RJ. 1960 ‘Stain Films on Silicon’. The Journal of physics and chemistry of solids. Vol 14. pp. 104-10.
  6. ^ Coffer JL.1997, ‘Porous silicon formation by stain etching, in Properties of Porous Silicon, Canham, LT, Institution of Engineering and Technology, London, pp. 23-28.
  7. ^ Bellet D. 1997, ‘Drying of porous silicon’, in Properties of Porous Silicon, Canham, LT, Institution of Engineering and Technology, London, pp. 38-43.
  8. ^ Chazalviel JN. Ozanam F. 1997, ‘Surface modification of porous silicon’, in Properties of Porous Silicon, Canham, LT, Institution of Engineering and Technology, London, pp. 59-65.
  9. ^ Low SP. Williams KA. Canham LT. Voelcker NH. 2006. ‘Evaluation of mammalian cell adhesion on surface-modified porous silicon’, Biomaterials, Vol 27. pp. 4538-46.
  10. ^ Canham LT.1995, 'Bioactive Silicon Structure Through Nanoetching Techniques', Advanced Materials, Vol 7, No. 12, pp. 1033-7.
  11. ^ Pramatarova L. Pecheva E. Dimova-Malinovska. Pramatarova R. Bismayer U. Petrov T. Minkovskis N. 2004, ‘Porous silicon as a substrate for hydroxyapatite growth’, Vacuum, Vol. 76. pp 135-8
  12. ^ Sapelkin AV. Bayliss SC. Unal B. Charalambou A. 2005. ‘Interaction of B50 rat hippocampal cells with stain-etched porous silicon’. Biomaterial, Vol. 27, pp. 842-6.
  13. ^ Canham, L T. 2001, 'Will a chip every day keep the doctor away?' Physics World

 
 

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