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Semiconductor Doping

In semiconductor production, doping is the intentional introduction of impurities into an intrinsic semiconductor for the purpose of modulating its electrical properties. The doped material is referred to as extrinsic semiconductors. A semiconductor doped to such high levels that it acts more like a conductor than a semiconductor is referred to as a degenerate semiconductor.

In the context of phosphors and scintillators, doping is better known as activation. Doping is also used to control the color in some pigments.

Silicon dopants

  • Acceptors, p-type
    • Boron is a p-type dopant. Its diffusion rate allows easy control of junction depths. Common in CMOS technology. Can be added by diffusion of diborane gas. The only acceptor with sufficient solubility for efficient emitters in transistors and other applications requiring extremely high dopant concentrations. Boron diffuses about as fast as phosphorus.
    • Aluminium, used for deep p-diffusions. Not popular in VLSI and ULSI. Also a common unintentional impurity.
    • Gallium is a dopant used for long-wavelength infrared photoconduction silicon detectors in the 8–14 µm atmospheric window. Gallium-doped silicon is also promising for solar cells, due to its long minority carrier lifetime with no lifetime degradation; as such it is gaining importance as a replacement of boron doped substrates for solar cell applications.
    • Indium is a dopant used for long-wavelength infrared photoconduction silicon detectors in the 3–5 µm atmospheric window.
  • Donors, n-type
    • Phosphorus is a n-type dopant. It diffuses fast, so is usually used for bulk doping, or for well formation. Used in solar cells. Can be added by diffusion of phosphine gas. Bulk doping can be achieved by nuclear transmutation, by irradiation of pure silicon with neutrons in a nuclear reactor. Phosphorus also traps gold atoms, which otherwise quickly diffuse through silicon and act as recombination centers.
    • Arsenic is a n-type dopant. Its slower diffusion allows using it for diffused junctions. Used for buried layers. Has similar atomic radius to silicon, high concentrations can be achieved. Its diffusivity is about a tenth of phosphorus or boron, so is used where the dopant should stay in place during subsequent thermal processing. Useful for shallow diffusions where well-controlled abrupt boundary is desired. Preferred dopant in VLSI circuits. Preferred dopant in low resistivity ranges.
    • Antimony is a n-type dopant. It has a small diffusion coefficient. Used for buried layers. Has diffusivity similar to arsenic, is used as its alternative. Its diffusion is virtually purely substitutional, with no interstitials, so it is free of anomalous effects. For this superior property, it is sometimes used in VLSI instead of arsenic. Heavy doping with antimony is important for power devices. Heavily antimony-doped silicon has lower concentration of oxygen impurities; minimal autodoping effects make it suitable for epitaxial substrates.
    • Bismuth is a promising dopant for long-wavelength infrared photoconduction silicon detectors, a viable n-type alternative to the p-type gallium-doped material.
    • Lithium is used for doping silicon for radiation hardened solar cells. The lithium presence anneals defects in the lattice produced by protons and neutrons. Lithium can be introduced to boron-doped p+ silicon, in amounts low enough to maintain the p character of the material, or in large enough amount to counterdope it to low-resistivity n type.
  • Other
    • Germanium can be used for band gap engineering. Germanium layer also inhibits diffusion of boron during the annealing steps, allowing ultrashallow p-MOSFET junctions. Germanium bulk doping suppresses large void defects, increases internal gettering, and improves wafer mechanical strength.
    • Silicongermanium and xenon can be used as ion beams for pre-amorphization of silicon wafer surfaces. Formation of an amorphous layer beneath the surface allows forming ultrashallow junctions for p-MOSFETs.
    • Nitrogen is important for growing defect-free silicon crystal. Improves mechanical strength of the lattice, increases bulk microdefect generation, suppresses vacancy agglomeration.
    • Gold and platinum are used for minority carrier lifetime control. They are used in some infrared detection applications. Gold introduces a donor level 0.35 eV above the valence band and an acceptor level 0.54 eV below the conduction band. Platinum introduces a donor level also at 0.35 eV above the valence band, but its acceptor level is only 0.26 eV below conduction band; as the acceptor level in n-type silicon is shallower, the space charge generation rate is lower and therefore the leakage current is also lower than for gold doping. At high injection levels platinum performs better for lifetime reduction. Reverse recovery of bipolar devices is more dependent on the low-level lifetime, and its reduction is better performed by gold. Gold provides a good tradeoff between forward voltage drop and reverse recovery time for fast switching bipolar devices, where charge stored in base and collector regions must be minimized. Conversely, in many power transistors a long minority carrier lifetime is required to achieve good gain, and the gold/platinum impurities must be kept low.

Semiconductor doping is the process that changes an intrinsic semiconductor to an extrinsic semiconductor. During doping, impurity atoms are introduced to an intrinsic semiconductor. Impurity atoms are atoms of a different element than the atoms of the intrinsic semiconductor. Impurity atoms act as either donors or acceptors to the intrinsic semiconductor, changing the electron and hole concentrations of the semiconductor. Impurity atoms are classified as either donor or acceptor atoms based on the effect they have on the intrinsic semiconductor.

Donor impurity atoms have more valence electrons than the atoms they replace in the intrinsic semiconductor lattice. Donor impurities “donate” their extra valence electrons to a semiconductor’s conduction band, providing excess electrons to the intrinsic semiconductor. Excess electrons increase the electron carrier concentration (n0) of the semiconductor, making it n-type.

Acceptor impurity atoms have fewer valence electrons than the atoms they replace in the intrinsic semiconductor lattice. They “accept” electrons from the semiconductor’s valence band. This provides excess holes to the intrinsic semiconductor. Excess holes increase the hole carrier concentration (p0) of the semiconductor, creating a p-type semiconductor.

Semiconductors and dopant atoms are defined by the column of the periodic table in which they fall. The column definition of the semiconductor determines how many valence electrons its atoms have and whether dopant atoms act as the semiconductor’s donors or acceptors.

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