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    Metal Semi-Conductor E

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    Mohammad Rameez
    When a semiconductor and metal come into contact, they must reach equilibrium. For an n-type semiconductor, this results in a depletion region near the interface as electrons flow from the semiconductor into the metal. The Fermi level of the metal and semiconductor must align at equilibrium. Similarly, when a semiconductor contacts an electrolyte solution containing a redox couple, charge transfer occurs until the Fermi level of the semiconductor and redox potential of the solution are equal. Changing the pH of the solution affects the surface charge and band bending in the semiconductor.

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    Metal Semi-Conductor E

    Uploaded by

    Mohammad Rameez
    26 views29 pages
    When a semiconductor and metal come into contact, they must reach equilibrium. For an n-type semiconductor, this results in a depletion region near the interface as electrons flow from the semiconductor into the metal. The Fermi level of the metal and semiconductor must align at equilibrium. Similarly, when a semiconductor contacts an electrolyte solution containing a redox couple, charge transfer occurs until the Fermi level of the semiconductor and redox potential of the solution are equal. Changing the pH of the solution affects the surface charge and band bending in the semiconductor.

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    When a semiconductor and metal come into contact, they must reach equilibrium. For an n-type semiconductor, this results in a depletion region near the interface as electrons flow from the semiconductor into the metal. The Fermi level of the metal and semiconductor must align at equilibrium. Similarly, when a semiconductor contacts an electrolyte solution containing a redox couple, charge transfer occurs until the Fermi level of the semiconductor and redox potential of the solution are equal. Changing the pH of the solution affects the surface charge and band bending in the semiconductor.

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    Attribution Non-Commercial (BY-NC)
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    26 views29 pages

    Metal Semi-Conductor E

    Uploaded by

    Mohammad Rameez
    When a semiconductor and metal come into contact, they must reach equilibrium. For an n-type semiconductor, this results in a depletion region near the interface as electrons flow from the semiconductor into the metal. The Fermi level of the metal and semiconductor must align at equilibrium. Similarly, when a semiconductor contacts an electrolyte solution containing a redox couple, charge transfer occurs until the Fermi level of the semiconductor and redox potential of the solution are equal. Changing the pH of the solution affects the surface charge and band bending in the semiconductor.

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    of 29

    If we bring a metal and a semiconductor into contact what will happen?

    Semiconductor

    Metal E

    EF Fermi Level, EF

    The semiconductor and the metal must equilibrate. What does this signify?

    Will energy of Fermi level in the metal change?

    Chemical Potential
    Relation to voltage (potential)
    If T and P constant,

    At equilibrium: The same number of electrons leave the semiconductor as enter the metal (dN), so dN1 = dN2, so 1 = 2 at equilibrium Electrochemical potential Voltage

    In this case, the SC is driven to depletion if it is n-type


    EF is higher in SC than in metal, so e- flow from SC to metal

    Schottky Barrier

    e- e-

    In this case, the SC is driven to accumulation if it is p-type

    e-

    +++

    Equilibrium
    A similar concept applies to the semiconductor-solution interface. What is the Fermi level of a solution? If you have a solution with both the reduced and oxidized forms of a redox couple, a Nernst potential of the solution can be defined

    Fermi level in solution


    OX + ne- = RED
    Vrdx # RT & # [ RED] & = V 0 % ( ln% ( $ nF ' $ [OX ] '

    Vrdx : Erdx = q Vrdx If we put a metal electrode into a solution with both OX and RED forms of the the redox couple, charge will flow across the interface until equilibrium is reached, resulting in net oxidation or reduction of some molecules in solution.

    Put another way


    Fe3+ + e- = Fe2+

    Fe 2+ K eq = Fe 3+e
    1 Fe 2+ e = K eq Fe 3+

    Electrochemical vs. Absolute scales: (Fermi level of SHE relative to vacuum) vs. SHE EC EF EV -1V 0 1V vs. vacuum -3.5V -4.5V -5.5V Reference: Electron at rest in vacuum

    How wide is the bandgap?

    If you know that EF is at 0V vs. SHE, then If you know the bandgap, you can place EC at -1V and EV at +1V

    Potential changes at interfaces


    >OH >OH >OH H+ H+ >OH2+ >OH >OH2+ H+

    >Me-O-Me< In bulk metal oxide solid +H2O >MeOH HOMe< At surface in water Call >MeOH a surface site, us S symbol: >SOH

    Surface reactions, surface charge


    Closest Approach = Helmholtz Layer >OH >OH2+ >O>L >OMe+ >O >Me >O >SOH + H+ = >SOH2+ >SOH + >SO- + H+ >SOH + L- = >SL + OH>SOH + Me2+ = >SOMe+ + H+ 2>SOH + Me2+ = (>SO2Me) + 2H+

    Diffuse Layer
    >OH2+ >OH2+ >OH2
    +

    + + -

    + + -

    >OH2+ >OH2+ >OH2


    +

    >OH2+

    Surface charge on one side, DL on other: = Electric Double Layer + + + + + + + Ccation Canion Surface electric field: Must do charge-potential work to bring ions to surface, or remove them from surface

    % 8N A I ( =' * &1000kT )

    1 I = zi2 M i 2 i

    ( x ) = (0) exp(x )

    (A bit more complex if (0) is > ~25mV)

    EDL thickness
    1.0 Surface potential I/I0 0.8 0.6 0.4 0.2 0 0 2 4 6 8 10 12 Nanometers from solid surface 0.1M 0.001M (1:1) 0.01M

    EDL thickness
    1.0 Surface potential I/I0 0.8 0.6 0.4 0.2 0 0 + + + + + + + + + + + + 0.1M + + 2 4 6 8 10 12 Nanometers from solid surface

    EDL thickness
    1.0 Surface potential I/I0 0.8 0.6 0.4 0.2 0 + 0.1M + + + + + + + + + + -

    0 2 4 6 8 10 12 Nanometers from solid surface

    If we bring a redox couple in solution and a semiconductor into contact what will happen? Semiconductor E The semiconductor and the solution must equilibrate.

    Solution

    EF E0

    In this case, the SC is driven to depletion if it is n-type Schottky Barrier

    e- e-

    E0

    SC and Solution at Flatband potential, solution at pHpzc: Semiconductor

    Solution

    EF

    How do we get here? H EC


    D

    EV
    +

    Now we raise pH to create negative surface charge:


    EC
    EV
    +
    +
    Negative surface charge drives n carriers out of the space charge layer (which has residual positive charge). At the same time, positive ions are attracted to the surface from solution in the diffuse layer. Ions generally more concentrated in solution, so potential drop off (diffuse layer) is thinner than space charge layer

    + + - + + + + + +

    If we want to put the semiconductor back at Flatband Potential, what must we do?

    Now we raise pH to create negative surface charge:


    EC
    EV
    +
    +

    + + - + + + + + +

    We must apply a more negative potential to the semiconductor to flatten the bands! This demonstrates that EFB is a function of pH, more negative a high pH and more positive at low pH.

    SC at Flatband potential, in contact with redox couple Semiconductor

    Solution

    EF

    E0 Assume that we now raise the pH of the solution in the presence of a pHindependent redox couple. What will happen?

    Remember Eh pH:

    SC at Flatband potential, in contact with redox couple Semiconductor

    Solution

    EC
    EV
    +
    -

    E0 If redox couple is pH independent, barrier increases. If redox couple becomes more reducing, it will drive SC toward EFB

    Reactions to change in pH SemiSolution conductor EC


    E +
    EV
    -EC
    +
    EV
    -

    If redox couple becomes more reducing, it will drive SC toward EFB E0

    E0

    Charge accumulation/depletion in space charge layer can be quantied through capacitance measurements

    Flatband Potential Blocking layer


    EC
    EF
    - bias
    EC
    + bias
    EV
    +

    Accumulation Layer

    +
    +

    EC
    EV

    EV
    +

    pH moves band positions at surface through change in surface charge


    SCL = Space Charge Layer


    Helmholtz Layer = H Diffuse Layer = D H EC
    D 0.1M salt solution has about 1020 ions per cubic cm. Typical semiconductor has smaller concentration of mobile charges than solution Hence, layer is thicker in solid than in solution

    EV
    +

    Photocurrent, VPO, Charge Separation, Recombination: Probes of Semiconductor Properties

    EC
    h
    EV

    + +

    VPO

    Examples of hematite photocurrents:! Photocurrent!

    Current in the dark!

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