Chemistry of Epitaxy

 Epitaxy is an interface between a thin film and a substrate The term epitaxy describes an ordered crystalline growth on a monocrystalline substrate

Epitaxial films may be grown from gaseous or liquid precursors

Because the substrate acts as a seed crystal, the deposited film takes on a lattice structure and orientation identical to those of the substrate

 Epitaxy is different from other thin film deposition methods which deposit polycrystalline or amorphous films, even on single - crystal substrates If a film is deposited on a substrate of the same composition, the process is called homoepitaxy Otherwise it is called heteroepitaxy Homoepitaxy is a kind of epitaxy performed with only one material in which a crystalline film is grown on a substrate or film of the same material This technology is applied to growing a more purified film than the substrate and fabricating layers with different doping levels

 Heteroepitaxy is a kind of epitaxy performed with materials that are different from each other in which a crystalline film grows on a crystalline substrate or film of another material This technology is often applied to growing crystalline films of materials of which single crystals cannot be obtained and to fabricating integrated crystalline layers of different materials

Examples include gallium nitride (GaN) on sapphire or aluminum gallium indium phosphide (AlGaInP) on gallium arsenide (GaAs)
Heterotopotaxy is a process similar to heteroepitaxy except for the fact that thin film growth is not limited to two dimensional growth In this process, the substrate is similar only in 4 structure to the thin film material

 Epitaxy is used in silicon - based manufacturing processes for BJTs and modern CMOS, but it is particularly important for compound semiconductors such as gallium arsenide Manufacturing issues include control of the amount and uniformity of the deposition's resistivity and thickness, the cleanliness and purity of the surface and the chamber atmosphere, the prevention of the typically much more highly doped substrate wafer's diffusion of dopant to the new layers, imperfections of the growth process, and protecting the surfaces during the manufacture and handling

Applications of Epitaxy Epitaxy has applications in nanotechnology and in semiconductor fabrication. Epitaxy is the only affordable method of high crystalline quality growth for many semiconductor materials, including technologically important materials as silicon -germanium, gallium nitride, gallium arsenide and indium phosphide Epitaxy is also used to grow layers of pre - doped silicon on the polished sides of silicon wafers, before they are processed into semiconductor devices.

 Epitaxy is one of the most vital processes in semiconductor device manufacturing

This is especially true in nanotechnology, as it provides the means of growing very thin films in a controlled way to achieve the necessary accuracy, purity, and orientation of the film Chemistry plays an important role in the process of epitaxial layer growth The constituents of the film are often presented to the substrate in the form of compounds with other elements They must be extracted from these compounds and react with the substrate and possibly other constituents to form the epitaxial layer

 There are many approaches to growing epitaxial films

Vapor Phase Epitaxy (VPE)

Liquid Phase Epitaxy (LPE) Metallorganic Chemical Vapor Deposition (MOCVD) Molecular Beam Epitaxy (MBE) Atomic Layer Epitaxy (ALE)

Several of these methods are based on Chemical Vapor Deposition (CVD)

Chemical Vapor Deposition (CVD) CVD is used to produce high - purity, high performance solid materials, usually in the form of a thin film on a substrate

In a typical CVD process, the wafer (substrate) is exposed to one or more volatile precursors, which react and/or decompose on the substrate surface to produce the desired deposit
Frequently, volatile byproducts are also produced, which are removed by gas flow through the reaction chamber

 Microfabrication processes widely use CVD to deposit materials in various forms, including: monocrystalline, polycrystalline, amorphous, and epitaxial These materials include: silicon, carbon fiber, carbon nanofibers, filaments, carbon nanotubes, SiO2, silicon-germanium, tungsten, silicon carbide, silicon nitride , titanium nitride, and various high - k dielectrics

The CVD process is also used to produce synthetic diamonds

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Types of chemical vapor deposition

A number of forms of CVD are in wide use and are frequently referenced in the literature
These processes differ in the means by which chemical reactions are initiated (e.g., activation process) and process conditions

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 These processes can be classified by operating pressure

Atmospheric pressure CVD (APCVD) - CVD processes at atmospheric pressure Low-pressure CVD (LPCVD) - CVD processes at subatmospheric pressures Reduced pressures tend to reduce unwanted gasphase reactions and improve film uniformity across the wafer Most modern CVD process are either LPCVD or UHVCVD Ultrahigh vacuum CVD (UHVCVD) - CVD processes at a very low pressure, typically below 10 -6 Pa (~ 10 -8 torr)

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 Classified by physical characteristics of vapor

Aerosol assisted CVD (AACVD) - A CVD process in which the precursors are transported to the substrate by means of a liquid/gas aerosol, which can be generated ultrasonically.
This technique is suitable for use with nonvolatile precursors Direct liquid injection CVD (DLICVD) - A CVD process in which the precursors are in liquid form (liquid or solid dissolved in a convenient solvent) Liquid solutions are injected in a vaporization chamber towards injectors (typically car injectors). The precursor vapors are then transported to the substrate as in classical CVD process This technique is suitable for use on liquid or solid precursors High growth rates can be reached using this technique13

 Microwave plasma-assisted CVD (MPCVD)

Plasma-Enhanced CVD (PECVD) - CVD processes that utilize a plasma to enhance chemical reaction rates of the precursors
PECVD processing allows deposition at lower temperatures, which is often critical in the manufacture of semiconductors Remote plasma-enhanced CVD (RPECVD) - Similar to PECVD except that the wafer substrate is not directly in the plasma discharge region

Removing the wafer from the plasma region allows processing temperatures down to room temperature
Atomic layer CVD (ALCVD) Deposits successive layers of different substances to produce layered, crystalline films

Hot wire CVD (HWCVD) - Also known as Catalytic CVD (CatCVD) or hot filament CVD (HFCVD)
Uses a hot filament to chemically decompose the source gases 14

 Metallorganic chemical vapor deposition (MOCVD) - CVD processes based on metallorganic precursors
Hybrid Physical-Chemical Vapor Deposition (HPCVD) - Vapor deposition processes that involve both chemical decomposition of precursor gas and vaporization of solid a source Rapid thermal CVD (RTCVD) - CVD processes that use heating lamps or other methods to rapidly heat the wafer substrate Heating only the substrate rather than the gas or chamber walls helps reduce unwanted gas phase reactions that can lead to particle formation Vapor phase epitaxy (VPE)

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Polysilicon
Polycrystalline silicon is widely used as the gate oxide in MOSFETs
Polycrystalline silicon is deposited from silane (SiH4), using the following reaction:

Si H 4 Si 2 H 2
This reaction is usually performed in LPCVD systems, with either pure silane feedstock, or a solution of silane with 70-80% nitrogen Temperatures between 600 and 650 C and pressures between 25 and150 Pa yield a growth rate between 10 and 20 nm per minute. An alternative process uses a hydrogen - based solution

The hydrogen reduces the growth rate, but the temperature is raised to 850 or even 1050 C to compensate
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 Polysilicon may be grown directly with doping, if gases such as phosphine, arsine or diborane are added to the CVD chamber Diborane increases the growth rate, but arsine and phosphine decrease it

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TEOS TEOS is a material commonly used to grow silicon dioxide layers on semiconductors It stands for Tetra - Ethyl - Ortho - Silicate, or equivalently tetra - ethoxy - silane: TEOS slowly hydrolyzes into silicon dioxide and ethanol when in contact with ambient moisture

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 The key to understanding the difference between TEOS and silane is to note that in TEOS the silicon atom is already oxidized The conversion of TEOS to silicon dioxide is essentially a rearrangement rather than an oxidation reaction, with much reduced changes in free enthalpy and free energy

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 The basic overall reaction for the deposition of silicon dioxide requires the removal of two oxygen atoms

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 While gas phase reactions can occur, particularly at the high end of the temperature range, deposition is probably the result of TEOS surface reactions TEOS chemisorbs onto silanol groups (Si-OH) at the surface, as well as strained surface bonds

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 TEOS will not adsorb onto the resulting alkylcovered surface, so deposition is probably limited by removal of the surface alkyl groups These groups can undergo elimination reactions with neighboring molecules to form Si-O-Si bridges

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 This process proceeds in an inert atmosphere: TEOS can be its own oxygen source, and SiO2 can be deposited from TEOS in nitrogen However, addition of oxygen increases the deposition rate, presumably through providing an alternative path for removal of the ethyl groups from the surface TEOS/O2 is generally performed in tube reactors at pressures of a few Torr

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Silicon dioxide
Silicon dioxide (SiO2) is commonly used in integrated circuits and nanodevices as an insulator and as a capacitor dielectric Silicon dioxide may be deposited by several different processes Common source gases include silane and oxygen, dichlorosilane (SiCl2H2) and nitrous oxide (N2O), or tetraethylorthosilicate (TEOS; Si(OC2H5)4) The reactions are as follows:

SiH4 + O2 SiO2 + 2H2

SiCl2H2 + 2N2O SiO2 + 2N2 + 2HCl Si(OC2H5)4 SiO2 + byproducts

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 The choice of source gas depends on the thermal stability of the substrate; for instance, aluminum is sensitive to high temperature Silane deposits at temperatures between 300 and 500 C, dichlorosilane at around 900 C, and TEOS between 650 and 750 C, resulting in a layer of Low Temperature Oxide (LTO) However, silane produces a lower-quality oxide than the other methods (lower dielectric strength, for instance), and it deposits nonconformally Any of these reactions may be used in LPCVD, but the silane reaction is also done in APCVD CVD oxide invariably has lower quality than thermal oxide, but thermal oxidation can only be used in the earliest stages of IC manufacturing

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 Silicon dioxide may also be grown with impurities (alloying or "doping") for one of two purposes (1) During further process steps that occur at high temperature, the impurities may diffuse from the oxide into adjacent layers (most notably silicon) and dope them

Oxides containing 5% to 15% impurities by mass are often used for this purpose
(2) silicon dioxide alloyed with phosphorus pentoxide ("Pglass") can be used to smooth out uneven surfaces

P-glass softens and reflows at temperatures above 1000 C

This process requires a phosphorus concentration of at least 6%, but concentrations above 8% can corrode aluminum Phosphorus is deposited from phosphine gas and oxygen: 4PH3 + 5O2 2P2O5 + 6H2
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 Glasses containing both boron and phosphorus (borophosphosilicate glass, BPSG) undergo viscous flow at lower temperatures; around 850 C is achievable with glasses containing around 5 weight % of both constituents, but stability in air can be difficult to achieve Phosphorus oxide in high concentrations interacts with ambient moisture to produce phosphoric acid Crystals of BPO4 can also precipitate from the flowing glass on cooling; These crystals are not readily etched in the standard reactive plasmas used to pattern oxides, and will result in circuit defects in integrated circuit manufacturing

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 Besides these intentional impurities, CVD oxide may contain byproducts of the deposition process. TEOS produces a relatively pure oxide, whereas silane introduces hydrogen impurities, and dichlorosilane introduces chlorine

Lower temperature deposition of silicon dioxide and doped glasses from TEOS using ozone rather than oxygen has also been explored (350 to 500 C)
Ozone glasses have excellent conformality but tend to be hygroscopic -- that is, they absorb water from the air due to the incorporation of silanol (Si-OH) in the glass Infrared spectroscopy and mechanical strain as a function of temperature are valuable diagnostic tools for diagnosing such problems

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Silicon Nitride
Silicon nitride is often used as an insulator and chemical barrier in manufacturing ICs
Silicon nitride The following two reactions deposit nitride from the gas phase: 3SiH4 + 4NH3 Si3N4 + 12H2 3SiCl2H2 + 4NH3 Si3N4 + 6HCl + 6H2 Silicon nitride deposited by LPCVD contains up to 8% hydrogen. It also experiences strong tensile stress , which may crack films thicker than 200 nm However, it has higher resistivity and dielectric strength than most insulators commonly available in microfabrication (1016 cm and 10 MV/cm, respectively)

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 Another two reactions may be used in plasma to deposit SiNH:

2SiH4 + N2 2SiNH + 3H2 SiH4 + NH3 SiNH + 3H2 These films have much less tensile stress, but worse electrical properties (resistivity 106 to 1015 cm, and dielectric strength 1 to 5 MV/cm)

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Vapor-phase Epitaxy (VPE) In VPE, one or more materials to be deposited are transported to the substrate as compounds in vapor form In this manner, single materials, doped materials, or compounds may be deposited in single crystal form Once the materials reach the substrate, they are extracted from the compound and attach themselves to the surface atoms on the substrate One of the most common examples of VPE is the growth of a doped silicon film on a silicon substrate This process can be used to fabricate individual transistors and to fabricate transistors and isolation regions on integrated circuits

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 There are four major chemical sources of silicon for commercial epitaxial deposition: 1) silicon tetrachloride (SiCl4)

2) trichlorosilane (SiHCl3)
3) dichlorosilane (SiH2Cl2) 4) silane (SiH4)

Each of the chemical sources mentioned above may be described by an over-all reaction equation that shows how the vapor phase reactants form the silicon epitaxial film
For example, the over-all reaction for silicon epitaxy by silane reaction may be written as follows: SiH4 Si + 2H2
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 Silicon is most commonly deposited from silicon tetrachloride in hydrogen at approximately 1200 C:

SiCl4(g) + 2H2(g) Si(s) + 4HCl(g)

This reaction is reversible, and the growth rate depends strongly upon the proportion of the two source gases Growth rates above 2 m/minute produce polycrystalline silicon, and negative growth rates (etching) may occur if too much hydrogen chloride byproduct is present An additional etching reaction competes with the deposition reaction:

SiCl4(g) + Si(s) 2SiCl2(g)

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 The reaction is actually a complex series of reactions that ultimately result in the deposition of pure silicon SiCl4 + H2 SiHCl3 + HCl; SiHCl3 + H2 SiH2Cl2 + HCl; SiH2Cl2 SiCl2 + H2; SiHCl3 SiCl2 + HCl; SiCl2 + H2 Si + 2HCl;

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 Silicon VPE may also use silane, dichlorosilane, and trichlorosilane source gases For instance, the silane reaction occurs at 650 C in this way:

SiH4 Si + 2H2
This reaction does not inadvertently etch the wafer, and takes place at lower temperatures than deposition from silicon tetrachloride However, it will form a polycrystalline film unless tightly controlled, and it allows oxidizing species that leak into the reactor to contaminate the epitaxial layer with unwanted compounds such as silicon dioxide

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VPE (vapor phase epitaxy)

All reactants in vapor phase, deposited on heated substrate
halide: AsCl3, H2, dopants hydride: AsH3, H2, dopants Reducing atmosphere

As4

II, III
substrate

HCl

I
Ga metal GaAs

halide: AsCl3, H2 hydride: HCl, H2

Halide or hydride process: I: GaAs (s) + HCl (g) GaCl (g) + As4 (g) + H2 (g) II: 3 GaCl (g) + As4 (g) 2 GaAs (s) + GaCl3 (g) III: GaCl (g) + As4 (g) + H2 (g) GaAs (s) + HCl (g) Advantage: fast rate (.1 - .5 m.min), easy, safe (w/o arsine process) Disadvantage: Al compounds difficult, thickness resolution

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Epitaxial growth
LPE (liquid phase epitaxy)

direction of sliding

H2 reducing atmosphere

Thermodynamic equilibrium growth saturated melt (As in Ga) cool which reduces solubility of As, so GaAs deposits can do in bath melt, or slider technique advantage; inexpensive, easy disadvantages: no in situ diagnostics > binaries hard; x = x(t) surface morphology thickness control not very precise
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Metallorganic Chemical Vapor Deposition (MOCVD)

Metallorganic Chemical Vapor Deposition (MOCVD) is a method of epitaxial growth of materials, especially compound semiconductors, from the surface reaction of organic compounds or metallorganics and metal hydrides containing the required chemical elements For example, indium phosphide could be grown in a reactor on a substrate by introducing Trimethylindium ((CH3)3In) and phosphine (PH3)

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 Formation of the epitaxial layer occurs by final pyrolisis of the constituent chemicals at the substrate surface.
In contrast to molecular beam epitaxy (MBE) the growth of crystals is by chemical reaction and not physical deposition. This takes place not in a vacuum, but from the gas phase at moderate pressures (2 to 100 kPa) As such this technique is preferred for the formation of devices incorporating thermodynamically metastable alloys

It has become the dominant process for the manufacture of laser diodes, solar cells, and LEDs
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Growth Process of MOCVD

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MOCVD Reactor Block Diagram

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Reactor Components

A reactor is a chamber made of a high - temperature material that does not react with the chemicals being used The chamber is composed of reactor walls, a liner, a susceptor, gas injection units, and temperature control units

The reactor walls are typically made from stainless steel or quartz To prevent overheating, cooling water must flow through the channels within the reactor walls

Special glasses, such as quartz or ceramic, are often used as the liner in the reactor chamber between the reactor wall and the susceptor
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 A substrate sits on a susceptor which is held at a controlled temperature. The susceptor is made from a material resistant to the metalorganic compounds used, such as graphite For growing nitrides and related materials, a special coating on the graphite susceptor is necessary to prevent corrosion by ammonia (NH3) gas

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 Gas inlet and switching system

Gas is introduced via devices known as 'bubblers'. In a bubbler a carrier gas (usually nitrogen or hydrogen) is bubbled through the metallorganic liquid, which picks up some metallorganic vapor and transports it to the reactor

The amount of metallorganic vapor transported depends on the rate of carrier gas flow and the bubbler temperature
Allowance must be made for saturated vapors

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 Gas Exhaust and cleaning System

Toxic waste products must be converted to liquid or solid wastes for recycling (preferably) or disposal

Ideally processes will be designed to minimize the production of waste products

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MOCVD Process

Basic reaction for GaAs: Ga(CH3)3+AsH3 GaAs+3CH4 Al(CH3)3+AsH3 AlAs+3CH4 For GaN Ga(CH3)3+NH3 GaN+3CH4

Process:
1. MO sources and hydrides mixed inside reactor and transferred to the substrate 2. high temperature of substrate results in the decomposition of sources, forming the film precursors. 3. film precursors transport & absorb on the growth surface 4. precursors diffuse to the growth site, incorporate 5. by-products of the surface reactions absorb from surface
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MOCVD System

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Molecular Beam Epitaxy

The Molecular Beam Epitaxy System is used to grow and characterize thin crystalline films of oxides and ceramics Molecular beam epitaxy (MBE), is one of several methods of depositing single crystals
MBE takes place in high vacuum or ultra high vacuum (108 Pa) The most important aspect of MBE is the slow deposition rate (typically less than 1000 nm per minute), which allows the films to grow epitaxially

However, the slow deposition rates require proportionally better vacuum in order to achieve the same impurity levels as other deposition techniques

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 In solid - source MBE, ultra - pure elements such as gallium and arsenic are heated in separate quasiKnudsen effusion cells until they begin to slowly sublimate The gaseous elements then condense on the wafer, where they may react with each other In the example of gallium and arsenic, singlecrystal gallium arsenide is formed.

The term "beam" simply means that evaporated atoms do not interact with each other or any other vacuum chamber gases until they reach the wafer, due to the long mean free paths of the atoms

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 During operation, RHEED (Reflection High Energy Electron Diffraction) is often used for monitoring the growth of the crystal layers A computer controls shutters in front of each furnace, allowing precise control of the thickness of each layer, down to a single layer of atoms. Intricate structures of layers of different materials may be fabricated in this manner

Such control has allowed the development of structures where the electrons can be confined in space, giving quantum wells or even quantum dots Such layers are now a critical part of many modern semiconductor devices, including semiconductor lasers and light-emitting diodes
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 In systems where the substrate needs to be cooled, the ultra-high vacuum environment within the growth chamber is maintained by a system of cryopumps and cryopanels, chilled using liquid nitrogen or cold nitrogen gas to a temperature close to 77 oK (196 oC) However, cryogenic temperatures act as a sink for impurities in the vacuum, and so vacuum levels need to be several orders of magnitude better to deposit films under these conditions In other systems, the wafers on which the crystals are grown may be mounted on a rotating platter which can be heated to several hundred oC during operation
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 Molecular beam epitaxy is also used for the deposition of some types of organic semiconductors In this case, molecules, rather than atoms, are evaporated and deposited onto the wafer

Other variations include gas-source MBE, which resembles chemical vapor deposition

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MBE

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AlAs GaAs AlAs

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Growth process
UHV (< 10-8) Knudsen sources As flux, sticking coeff. < 0.5 growth ~ JIII; excess JV high As/Ga flux, low T - As stabilized low As/Gas flux, high T - Ga stabilized

Congruent sublimation Tcs (C) GaAs 650 AlAs ~850 AlP >700 GaP 670 InP 363 InAs 380 if T < Tcs, group V stable if T > Tcs, group III stable
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Comparison of Epitaxial Methods

Growth method LPE (Liquid phase epitaxy) VPE (Vapor phase epitaxy MBE (Molecular Beam Epitaxy) MOCVD (Metal-Organic Chemical Vapor Deposition) time 1963 features Growth form supersaturated solution onto substrate Use metal halide as transport agents to grow Deposit epilayer at ultrahigh vacuum limit Limited substrate areas and poor control over the growth of very thin layers No Al contained compound, thick layer

1958

1958 1967 1968

Hard to grow materials with high vapor pressure Some of the sources like AsH3 are very toxic.

Use metallorganic compounds as the sources

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Atomic Layer Epitaxy (ALE) Atomic layer epitaxy (ALE), or Atomic Layer Deposition (ALD), is a specialized form of epitaxy that typically deposit alternating monolayers of two elements onto a substrate, making it ideal to generate nanostructures The crystal lattice structure achieved is thin, uniform, and aligned with the structure of the substrate The reactants are brought to the substrate as alternating pulses with "dead" times in between. ALE makes use of the fact that the incoming material is bound strongly until all sites available for chemisorption are occupied The dead times are used to flush the excess material
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 Atomic layer epitaxy (ALE) or atomic layer deposition (ALD) is a technique mostly used in semiconductor fabrication to grow thin films of thickness of the atomic order The main approach used for this technique is the use of a self limiting chemical reaction to control in a very accurate way the thickness of the film deposited Compared to basic CVD for example, chemical reactants are pulsed alternatively in a reacting chamber and then chemisorb on to the surface of the substrate in order to form the monolayer The reaction is very easy to set up and doesnt require that many restrictions over the reactants, allowing the use of a wide range of materials
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 ALE introduces two complementary precursors (e.g. Al(CH3)3 and H2O) alternatively into the reaction chamber. Typically, one of the precursors will adsorb onto the substrate surface, but cannot completely decompose without the second precursor. The precursor adsorbs until it saturates the surface and further growth cannot occur until the second precursor is introduced Thus the film thickness is controlled by the number of precursor cycles rather than the deposition time as is the case for conventional CVD processes In theory ALCVD allows for extremely precise control of film thickness and uniformity
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