Hydrogen-terminated silicon surface

Last updated

Hydrogen-terminated silicon surface is a chemically passivated silicon substrate where the surface Si atoms are bonded to hydrogen. [1] The hydrogen-terminated surfaces are hydrophobic, luminescent, and amenable to chemical modification. [2] Hydrogen-terminated silicon is an intermediate in the growth of bulk silicon from silane: [3]

Contents

SiH4 → Si + 2 H2

Preparation

Idealized view of Si surface before (top) and after (bottom) treatment with HF. Partially oxidized Si is shown in red, bulk Si in blue. H-terminatedSi ideal.svg
Idealized view of Si surface before (top) and after (bottom) treatment with HF. Partially oxidized Si is shown in red, bulk Si in blue.

Silicon wafers are treated with solutions of electronic-grade hydrofluoric acid in water, buffered water, or alcohol. One of the relevant reactions is simply removal of silicon oxides:

SiO2 + 4 HF → SiF4 + 2 H2O

The key reaction however is the formation of the hydrosilane functional group.

atomic force microscope (AFM) has been used to manipulate hydrogen-terminated silicon surfaces. [4] [5]

Properties

Idealized structure of alkene addition to hydrogen-terminated silicon. Self-assembled monolayer.svg
Idealized structure of alkene addition to hydrogen-terminated silicon.

Hydrogen termination removes dangling bonds. All surface Si atoms are tetrahedral. Hydrogen termination confers stability in ambient environments. So again, the surface is both clean (of oxides) and relatively inert. These materials can be handled in air without special care for several minutes. [6]

The Si-H bond in fact is stronger than the Si-Si bonds. Two kinds of Si-H centers are proposed, both featuring terminal Si-H bonds. One kind of site has one Si-H bond. The other kind of site features SiH2 centers. [3]

Like organic hydrosilanes, the H-Si groups on the surface react with terminal alkenes and diazo groups. The reaction is called hydrosilylation. Many kinds of organic compounds with various functions can be introduced onto the silicon surface by the hydrosilylation of a hydrogen-terminated surface. The infrared spectrum of hydrogen-terminated silicon shows a band near 2090 cm−1, not very different from νSi-H for organic hydrosilanes. [6]

Potential applications

One group proposed to use the material to create digital circuits made of quantum dots by removing hydrogen atoms from the silicon surface. [4]

See also

Related Research Articles

<span class="mw-page-title-main">Silicon</span> Chemical element, symbol Si and atomic number 14

Silicon is a chemical element with the symbol Si and atomic number 14. It is a hard, brittle crystalline solid with a blue-grey metallic luster, and is a tetravalent metalloid and semiconductor. It is a member of group 14 in the periodic table: carbon is above it; and germanium, tin, lead, and flerovium are below it. It is relatively unreactive.

Silane (Silicane) is an inorganic compound with chemical formula SiH4. It is a colourless, pyrophoric, toxic gas with a sharp, repulsive, pungent smell, somewhat similar to that of acetic acid. Silane is of practical interest as a precursor to elemental silicon. Silane with alkyl groups are effective water repellents for mineral surfaces such as concrete and masonry. Silanes with both organic and inorganic attachments are used as coupling agents. Silanes are commonly used to apply coatings to surfaces or as an adhesion promoter.

<span class="mw-page-title-main">Double bond</span> Chemical bond involving four bonding electrons; has one sigma plus one pi bond

In chemistry, a double bond is a covalent bond between two atoms involving four bonding electrons as opposed to two in a single bond. Double bonds occur most commonly between two carbon atoms, for example in alkenes. Many double bonds exist between two different elements: for example, in a carbonyl group between a carbon atom and an oxygen atom. Other common double bonds are found in azo compounds (N=N), imines (C=N), and sulfoxides (S=O). In a skeletal formula, a double bond is drawn as two parallel lines (=) between the two connected atoms; typographically, the equals sign is used for this. Double bonds were first introduced in chemical notation by Russian chemist Alexander Butlerov.

<span class="mw-page-title-main">Catenation</span> Bonding of atoms of the same element into chains or rings

In chemistry, catenation is the bonding of atoms of the same element into a series, called a chain. A chain or a ring shape may be open if its ends are not bonded to each other, or closed if they are bonded in a ring. The words to catenate and catenation reflect the Latin root catena, "chain".

In organic chemistry, a substituent is one or a group of atoms that replaces atoms, thereby becoming a moiety in the resultant (new) molecule.

<span class="mw-page-title-main">Dangling bond</span>

In chemistry, a dangling bond is an unsatisfied valence on an immobilized atom. An atom with a dangling bond is also referred to as an immobilized free radical or an immobilized radical, a reference to its structural and chemical similarity to a free radical.

<span class="mw-page-title-main">Organosilicon chemistry</span> Organometallic compound containing carbon–silicon bonds

Organosilicon chemistry is the study of organometallic compounds containing carbon–silicon bonds, to which they are called organosilicon compounds. Most organosilicon compounds are similar to the ordinary organic compounds, being colourless, flammable, hydrophobic, and stable to air. Silicon carbide is an inorganic compound.

<span class="mw-page-title-main">Binary silicon-hydrogen compounds</span>

Silanes are saturated chemical compounds with the empirical formula SixHy. They are hydrosilanes, a class of compounds that includes compounds with Si−H and other Si−X bonds. All contain tetrahedral silicon and terminal hydrides. They only have Si−H and Si−Si single bonds. The bond lengths are 146.0 pm for a Si−H bond and 233 pm for a Si−Si bond. The structures of the silanes are analogues of the alkanes, starting with silane, SiH4, the analogue of methane, continuing with disilane Si2H6, the analogue of ethane, etc. They are mainly of theoretical or academic interest.

Hydrosilylation, also called catalytic hydrosilation, describes the addition of Si-H bonds across unsaturated bonds. Ordinarily the reaction is conducted catalytically and usually the substrates are unsaturated organic compounds. Alkenes and alkynes give alkyl and vinyl silanes; aldehydes and ketones give silyl ethers. Hydrosilylation has been called the "most important application of platinum in homogeneous catalysis."

Hydrosilanes are tetravalent silicon compounds containing one or more Si-H bond. The parent hydrosilane is silane (SiH4). Commonly, hydrosilane refers to organosilicon derivatives. Examples include phenylsilane (PhSiH3) and triethoxysilane ((C2H5O)3SiH). Polymers and oligomers terminated with hydrosilanes are resins that are used to make useful materials like caulks.

<span class="mw-page-title-main">Local oxidation nanolithography</span>

Local oxidation nanolithography (LON) is a tip-based nanofabrication method. It is based on the spatial confinement on an oxidation reaction under the sharp tip of an atomic force microscope.

<span class="mw-page-title-main">Disiloxane</span> Chemical compound

Disiloxane has the chemical formula Si
2
H
6
O
. It is the simplest known siloxane with hydrogen only R groups. The molecule contains six equivalent Si-H bonds and two equivalent Si-O bonds. Disiloxane exists as a colorless, pungent gas under standard conditions. However, it is generally safe for human use as evidence in its widespread use in cosmetics. It is also commonly known as disilyl ether, disilyl oxide, and perhydrodisiloxane

Reductions with hydrosilanes are methods used for hydrogenation and hydrogenolysis of organic compounds. The approach is a subset of ionic hydrogenation. In this particular method, the substrate is treated with a hydrosilane and auxiliary reagent, often a strong acid, resulting in formal transfer of hydride from silicon to carbon. This style of reduction with hydrosilanes enjoys diverse if specialized applications.

Direct bonding, or fusion bonding, describes a wafer bonding process without any additional intermediate layers. The bonding process is based on chemical bonds between two surfaces of any material possible meeting numerous requirements. These requirements are specified for the wafer surface as sufficiently clean, flat and smooth. Otherwise unbonded areas so called voids, i.e. interface bubbles, can occur.

Silanization of silicon and mica is the coating of these materials with a thin layer of self assembling units.

<span class="mw-page-title-main">Non-contact atomic force microscopy</span>

Non-contact atomic force microscopy (nc-AFM), also known as dynamic force microscopy (DFM), is a mode of atomic force microscopy, which itself is a type of scanning probe microscopy. In nc-AFM a sharp probe is moved close to the surface under study, the probe is then raster scanned across the surface, the image is then constructed from the force interactions during the scan. The probe is connected to a resonator, usually a silicon cantilever or a quartz crystal resonator. During measurements the sensor is driven so that it oscillates. The force interactions are measured either by measuring the change in amplitude of the oscillation at a constant frequency just off resonance or by measuring the change in resonant frequency directly using a feedback circuit to always drive the sensor on resonance.

<span class="mw-page-title-main">Functionality (chemistry)</span> Presence of functional groups within a molecule

In chemistry, functionality is the presence of functional groups in a molecule. A monofunctional molecule possesses one functional group, a difunctional two, a trifunctional three, and so forth. In organic chemistry, a molecule's functionality has a decisive influence on its reactivity.

Silanes refers to diverse organosilicon charge-neutral compounds with the formula SiR
4
. The R substituents can any combination of organic or inorganic groups. Most silanes contain Si-C bonds, and are discussed under organosilicon compounds. Some contain Si-H bonds and are discussed under hydrosilanes.

In chemistry, transition metal silyl complexes describe coordination complexes in which a transition metal is bonded to an anionic silyl ligand, forming a metal-silicon sigma bond. This class of complexes are numerous and some are technologically significant as intermediates in hydrosilylation. These complexes are a subset of organosilicon compounds.

A silicon–oxygen bond is a chemical bond between silicon and oxygen atoms that can be found in many inorganic and organic compounds. In a silicon–oxygen bond, electrons are shared unequally between the two atoms, with oxygen taking the larger share due to its greater electronegativity. This polarisation means Si–O bonds show characteristics of both covalent and ionic bonds. Compounds containing silicon–oxygen bonds include materials of major geological and industrial significance such as silica, silicate minerals and silicone polymers like polydimethylsiloxane.

References

  1. Fenner, D. B.; Biegelsen, D. K.; Bringans, R. D. (1989). "Silicon surface passivation by hydrogen termination: A comparative study of preparation methods". Journal of Applied Physics. 66 (1): 419–424. Bibcode:1989JAP....66..419F. doi: 10.1063/1.343839 .
  2. Lauerhaas, Jeffrey M.; Sailor, Michael J. (1993). "Chemical Modification of the Photoluminescence Quenching of Porous Silicon". Science. 261 (5128): 1567–1568. Bibcode:1993Sci...261.1567L. doi:10.1126/science.261.5128.1567. PMID   17798116. S2CID   12722221.
  3. 1 2 Waltenburg, Hanne Neergaard; Yates, John (1995). "Surface Chemistry of Silicon". Chem. Rev. 95: 1589–1673. doi:10.1021/cr00037a600.
  4. 1 2 "Manipulating silicon atoms to create future ultra-fast, ultra-low-power chip technology". www.kurzweilai.net. 2017-02-17. Retrieved 2017-02-22.
  5. Labidi, Hatem; Koleini, Mohammad; Huff, Taleana; Salomons, Mark; Cloutier, Martin; Pitters, Jason; Wolkow, Robert A. (2017-02-13). "Indications of chemical bond contrast in AFM images of a hydrogen-terminated silicon surface". Nature Communications. 8: 14222. Bibcode:2017NatCo...814222L. doi:10.1038/ncomms14222. ISSN   2041-1723. PMC   5316802 . PMID   28194036.
  6. 1 2 "Organic modification of hydrogen terminated silicon surfaces1". Journal of the Chemical Society, Perkin Transactions 2: 23–34. 2002. doi:10.1039/B100704L.