Plasma-enhanced chemical vapor deposition
Encyclopedia
Plasma-enhanced chemical vapor deposition (PECVD) is a process used to deposit thin films from a gas
Gas
Gas is one of the three classical states of matter . Near absolute zero, a substance exists as a solid. As heat is added to this substance it melts into a liquid at its melting point , boils into a gas at its boiling point, and if heated high enough would enter a plasma state in which the electrons...

 state (vapor
Vapor
A vapor or vapour is a substance in the gas phase at a temperature lower than its critical point....

) to a solid
Solid
Solid is one of the three classical states of matter . It is characterized by structural rigidity and resistance to changes of shape or volume. Unlike a liquid, a solid object does not flow to take on the shape of its container, nor does it expand to fill the entire volume available to it like a...

 state on a substrate. Chemical reaction
Chemical reaction
A chemical reaction is a process that leads to the transformation of one set of chemical substances to another. Chemical reactions can be either spontaneous, requiring no input of energy, or non-spontaneous, typically following the input of some type of energy, such as heat, light or electricity...

s are involved in the process, which occur after creation of a plasma
Plasma (physics)
In physics and chemistry, plasma is a state of matter similar to gas in which a certain portion of the particles are ionized. Heating a gas may ionize its molecules or atoms , thus turning it into a plasma, which contains charged particles: positive ions and negative electrons or ions...

 of the reacting gases. The plasma
Plasma (physics)
In physics and chemistry, plasma is a state of matter similar to gas in which a certain portion of the particles are ionized. Heating a gas may ionize its molecules or atoms , thus turning it into a plasma, which contains charged particles: positive ions and negative electrons or ions...

 is generally created by RF
Radio frequency
Radio frequency is a rate of oscillation in the range of about 3 kHz to 300 GHz, which corresponds to the frequency of radio waves, and the alternating currents which carry radio signals...

 (AC
Alternating current
In alternating current the movement of electric charge periodically reverses direction. In direct current , the flow of electric charge is only in one direction....

) frequency or DC
Direct current
Direct current is the unidirectional flow of electric charge. Direct current is produced by such sources as batteries, thermocouples, solar cells, and commutator-type electric machines of the dynamo type. Direct current may flow in a conductor such as a wire, but can also flow through...

 discharge between two electrode
Electrode
An electrode is an electrical conductor used to make contact with a nonmetallic part of a circuit...

s, the space between which is filled with the reacting gases.

Discharges for processing

A plasma is any gas in which a significant percentage of the atoms or molecules are ionized. Fractional ionization in plasmas used for deposition and related materials processing varies from about 10−4 in typical capacitive discharges to as high as 5–10% in high density inductive plasmas. Processing plasmas are typically operated at pressures of a few millitorr to a few torr
Torr
The torr is a non-SI unit of pressure with the ratio of 760 to 1 standard atmosphere, chosen to be roughly equal to the fluid pressure exerted by a millimetre of mercury, i.e., a pressure of 1 torr is approximately equal to 1 mmHg...

, although arc discharges and inductive plasmas can be ignited at atmospheric pressure. Plasmas with low fractional ionization are of great interest for materials processing because electrons are so light, compared to atoms and molecules, that energy exchange between the electrons and neutral gas is very inefficient. Therefore, the electrons can be maintained at very high equivalent temperatures – tens of thousands of kelvins, equivalent to several electronvolts average energy—while the neutral atoms remain at the ambient temperature. These energetic electrons can induce many processes that would otherwise be very improbable at low temperatures, such as dissociation of precursor molecules and the creation of large quantities of free radicals.

A second benefit of deposition within a discharge arises from the fact that electrons are more mobile than ions. As a consequence, the plasma is normally more positive than any object it is in contact with, as otherwise a large flux of electrons would flow from the plasma to the object. The voltage between the plasma and the objects in its contacts is normally dropped across a thin sheath region. Ionized atoms or molecules that diffuse to the edge of the sheath region feel an electrostatic force and are accelerated towards the neighboring surface. Thus, all surfaces exposed to the plasma receive energetic ion bombardment. The potential across the sheath surrounding an electrically-isolated object (the floating potential) is typically only 10–20 V, but much higher sheath potentials are achievable by adjustments in reactor geometry and configuration. Thus, films can be exposed to energetic ion bombardment during deposition. This bombardment can lead to increases in density of the film, and help remove contaminants, improving the film's electrical and mechanical properties. When a high-density plasma is used, the ion density can be high enough that significant sputtering
Sputtering
Sputtering is a process whereby atoms are ejected from a solid target material due to bombardment of the target by energetic particles. It is commonly used for thin-film deposition, etching and analytical techniques .-Physics of sputtering:...

 of the deposited film occurs; this sputtering can be employed to help planarize the film and fill trenches or holes.

Reactor types

A simple direct-current (DC) discharge can be readily created at a few torr
Torr
The torr is a non-SI unit of pressure with the ratio of 760 to 1 standard atmosphere, chosen to be roughly equal to the fluid pressure exerted by a millimetre of mercury, i.e., a pressure of 1 torr is approximately equal to 1 mmHg...

 between two conductive electrodes, and may be suitable for deposition of conductive materials. However, insulating films will quickly extinguish this discharge as they are deposited. It is more common to excite a capacitive discharge by applying an alternating-current (AC) or radio-frequency (RF) signal between an electrode and the conductive walls of a reactor chamber, or between two cylindrical conductive electrodes facing one another. The latter configuration is known as a parallel plate reactor. Frequencies of a few tens of Hz
Hertz
The hertz is the SI unit of frequency defined as the number of cycles per second of a periodic phenomenon. One of its most common uses is the description of the sine wave, particularly those used in radio and audio applications....

 to a few thousand Hz will produce time-varying plasmas that are repeatedly initiated and extinguished; frequencies of tens of kilohertz to tens of megahertz result in reasonably time-independent discharges.

Excitation frequencies in the low-frequency (LF) range, usually around 100 kHz, require several hundred volts to sustain the discharge. These large voltages lead to high-energy ion bombardment of surfaces. High-frequency plasmas are often excited at the standard 13.56 MHz frequency widely available for industrial use; at high frequencies, the displacement current from sheath movement and scattering from the sheath assist in ionization, and thus lower voltages are sufficient to achieve higher plasma densities. Thus one can adjust the chemistry and ion bombardment in the deposition by changing the frequency of excitation, or by using a mixture of low- and high-frequency signals in a dual-frequency reactor. Excitation power of tens to hundreds of watts is typical for an electrode with a diameter of 200 to 300 mm.

Capacitive plasmas are usually very lightly ionized, resulting in limited dissociation of precursors and low deposition rates. Much denser plasmas can be created using inductive discharges, in which an inductive coil excited with a high-frequency signal induces an electric field within the discharge, accelerating electrons in the plasma itself rather than just at the sheath edge. Electron cyclotron resonance reactors and helicon wave antennas have also been used to create high-density discharges. Excitation powers of 10 kW or more are often used in modern reactors.

Film examples & Applications

Plasma deposition is often used in semiconductor manufacturing to deposit films conformally (covering sidewalls) and onto wafers containing metal layers or other temperature-sensitive structures. PECVD also yields some of the fastest deposition rates while maintaining film quality (such as roughness, defects/voids), as compared with sputter deposition
Sputter deposition
Sputter deposition is a physical vapor deposition method of depositing thin films by sputtering, that is ejecting, material from a "target," that is source, which then deposits onto a "substrate," such as a silicon wafer...

 and thermal/electron-beam evaporation, often at the expense of uniformity.

Silicon dioxide
Silicon dioxide
The chemical compound silicon dioxide, also known as silica , is an oxide of silicon with the chemical formula '. It has been known for its hardness since antiquity...

 can be deposited using a combination of silicon precursor gasses like dichlorosilane
Dichlorosilane
Dichlorosilane , or DCS as it is commonly known, is usually mixed with ammonia in LPCVD chambers to grow silicon nitride in semiconductor processing.A higher concentration of DCS:NH3 Dichlorosilane (H2SiCl2), or DCS as it is commonly known, is usually mixed with ammonia (NH3) in LPCVD chambers to...

 or silane
Silane
Silane is a toxic, extremely flammable chemical compound with chemical formula SiH4. In 1857, the German chemists and Friedrich Woehler discovered silane among the products formed by the action of hydrochloric acid on aluminum silicide, which they had previously prepared...

 and oxygen precursors, such as oxygen
Oxygen
Oxygen is the element with atomic number 8 and represented by the symbol O. Its name derives from the Greek roots ὀξύς and -γενής , because at the time of naming, it was mistakenly thought that all acids required oxygen in their composition...

 and nitrous oxide
Nitrous oxide
Nitrous oxide, commonly known as laughing gas or sweet air, is a chemical compound with the formula . It is an oxide of nitrogen. At room temperature, it is a colorless non-flammable gas, with a slightly sweet odor and taste. It is used in surgery and dentistry for its anesthetic and analgesic...

, typically at pressures from a few millitorr to a few torr. Plasma-deposited silicon nitride
Silicon nitride
Silicon nitride is a chemical compound of silicon and nitrogen. If powdered silicon is heated between 1300° and 1400°C in an atmosphere of nitrogen, trisilicon tetranitride, Si3N4, is formed. The silicon sample weight increases progressively due to the chemical combination of silicon and nitrogen...

, formed from silane
Silane
Silane is a toxic, extremely flammable chemical compound with chemical formula SiH4. In 1857, the German chemists and Friedrich Woehler discovered silane among the products formed by the action of hydrochloric acid on aluminum silicide, which they had previously prepared...

 and ammonia
Ammonia
Ammonia is a compound of nitrogen and hydrogen with the formula . It is a colourless gas with a characteristic pungent odour. Ammonia contributes significantly to the nutritional needs of terrestrial organisms by serving as a precursor to food and fertilizers. Ammonia, either directly or...

 or nitrogen
Nitrogen
Nitrogen is a chemical element that has the symbol N, atomic number of 7 and atomic mass 14.00674 u. Elemental nitrogen is a colorless, odorless, tasteless, and mostly inert diatomic gas at standard conditions, constituting 78.08% by volume of Earth's atmosphere...

, is also widely used, although it is important to note that it is not possible to deposit a pure nitride in this fashion. Plasma nitrides always contain a large amount of hydrogen
Hydrogen
Hydrogen is the chemical element with atomic number 1. It is represented by the symbol H. With an average atomic weight of , hydrogen is the lightest and most abundant chemical element, constituting roughly 75% of the Universe's chemical elemental mass. Stars in the main sequence are mainly...

, which can be bonded to silicon
Silicon
Silicon is a chemical element with the symbol Si and atomic number 14. A tetravalent metalloid, it is less reactive than its chemical analog carbon, the nonmetal directly above it in the periodic table, but more reactive than germanium, the metalloid directly below it in the table...

 (Si-H) or nitrogen
Nitrogen
Nitrogen is a chemical element that has the symbol N, atomic number of 7 and atomic mass 14.00674 u. Elemental nitrogen is a colorless, odorless, tasteless, and mostly inert diatomic gas at standard conditions, constituting 78.08% by volume of Earth's atmosphere...

 (Si-NH); this hydrogen has an important influence on IR and UV absorption, stability, mechanical stress, and electrical conductivity.

Silicon Dioxide can also be deposited from a tetraethoxysilane (TEOS) silicon precursor in an oxygen or oxygen-argon plasma. These films can be contaminated with significant carbon and hydrogen as silanol
Silanol
Silanol, also known as silyl alcohol, is a chemical with formula SiH3OH. It is the simplest silicon alcohol, and is a heavy, volatile, colorless, flammable liquid. At room temperature it is a polar liquid...

, and can be unstable in air. Pressures of a few torr and small electrode spacings, and/or dual frequency deposition, are helpful to achieve high deposition rates with good film stability.

High-density plasma deposition of silicon dioxide from silane and oxygen/argon has been widely used to create a nearly hydrogen-free film with good conformality over complex surfaces, the latter resulting from intense ion bombardment and consequent sputtering of the deposited molecules from vertical onto horizontal surfaces.
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