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Chemistry of Epitaxy

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Chemistry of Epitaxy Polysilicon layers may be formed by CVD Sources :Solid State Electronic Devices B. Streetman and S. Banerjee Prentice Hall 2005 (6th Edition ... – PowerPoint PPT presentation

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Title: Chemistry of Epitaxy


1
Chemistry of Epitaxy
2
  • 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

3
  • 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

4
  • 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
    structure to the thin film material

5
  • 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

6
  • 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.

7
  • 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

8
  • 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)

9
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

10
  • 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

11
  • 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

12
  • 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
    gas-phase 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)

13
  • 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
    technique

14
  • 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 (Cat-CVD) or hot filament CVD (HFCVD)
  • Uses a hot filament to chemically decompose the
    source gases

15
  • 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)

16
  • Polysilicon
  • Polycrystalline silicon is widely used as the
    gate oxide in MOSFETs
  • Polycrystalline silicon is deposited from silane
    (SiH4), using the following reaction
  • 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

17
  • 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

18
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

19
  • 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

20
  • The basic overall reaction for the deposition of
    silicon dioxide requires the removal of two
    oxygen atoms

21
  • 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

22
  • TEOS will not adsorb onto the resulting
    alkyl-covered 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

23
  • 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

24
  • 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

25
  • 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

26
  • 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 ("P-glass") 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

27
  • 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

28
  • 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

29
  • 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 Ocm and 10 MV/cm,
    respectively)

30
  • 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 Ocm, and dielectric strength 1 to 5 MV/cm)

31
  • 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

32
  • 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

33
  • 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)

34
  • 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
35
  • 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

36
VPE (vapor phase epitaxy)
  • All reactants in vapor phase, deposited on heated
    substrate
  • Halide or hydride process
  • I GaAs (s) HCl (g) ? GaCl (g) ¼ As4 (g) ½
    H2 (g)
  • II 3 GaCl (g) ½ As4 (g) ? 2 GaAs (s) GaCl3
    (g)
  • III GaCl (g) ¼ As4 (g) ½ H2 (g) ? GaAs (s)
    HCl (g)
  • Advantage fast rate (.1 - .5 mm.min), easy, safe
    (w/o arsine process)
  • Disadvantage Al compounds difficult, thickness
    resolution

halide AsCl3, H2, dopantshydride AsH3, H2,
dopants
Reducing atmosphere
As4
II, III
I
HCl
substrate
halide AsCl3, H2hydride HCl, H2
Ga metal
GaAs
36
37
Epitaxial growth
direction of sliding
  • LPE (liquid phase epitaxy)
  • 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
  • gt binaries hard x x(t)
  • surface morphology
  • thickness control not very precise

H2 reducing atmosphere
37
38
  • 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)

39
  • 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

40
Growth Process of MOCVD
41
MOCVD Reactor Block Diagram
42
  • 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

43
  • 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

44
  • 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

45
  • 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

46
MOCVD Process
  • Basic reaction for GaAs
  • Ga(CH3)3AsH3 ? GaAs3CH4
  • Al(CH3)3AsH3 ? AlAs3CH4
  • For GaN
  • Ga(CH3)3NH3 ? GaN3CH4
  • Process
  • MO sources and hydrides mixed inside reactor and
    transferred to the substrate
  • high temperature of substrate results in the
    decomposition of sources, forming the film
    precursors.
  • film precursors transport absorb on the growth
    surface
  • precursors diffuse to the growth site,
    incorporate
  • by-products of the surface reactions absorb from
    surface

46
47
MOCVD System
47
48
  • 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 (10-8 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

49
  • In solid - source MBE, ultra - pure elements such
    as gallium and arsenic are heated in separate
    quasi-Knudsen 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,
    single-crystal 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

50
  • 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

51
  • 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

52
  • 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

53
MBE
53
54
54
55
Growth process
  • UHV (lt 10-8)
  • Knudsen sources
  • As flux, sticking coeff. lt 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 650AlAs 850A
lP gt700GaP 670InP 363InAs 380 if T lt Tcs,
group V stable if T gt Tcs, group III stable
55
56
Comparison of Epitaxial Methods
limit
features
time
Growth method
Limited substrate areas and poor control over the
growth of very thin layers
Growth form supersaturated solution onto
substrate
1963
LPE (Liquid phase epitaxy)
No Al contained compound, thick layer
Use metal halide as transport agents to grow
1958
VPE (Vapor phase epitaxy
Hard to grow materials with high vapor pressure
Deposit epilayer at ultrahigh vacuum
1958 1967
MBE (Molecular Beam Epitaxy)
Some of the sources like AsH3 are very toxic.
Use metallorganic compounds as the sources
1968
MOCVD (Metal-Organic Chemical Vapor Deposition)
56
57
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

58
  • 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

59
  • 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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