Bohr quantized the atom… An atom has a set of energy levels Some (but not all) occupied by electrons Not really dealing with isolated atoms, but 3D solids As atoms approach each other, each affects the other Energy levels are altered, splitting into bands Each atom in the system produces another energy level in the band structure Electronic structure of Solids Outer levels begin to interact Overlapping levels Electron energy gas Broadening of energy levels as atoms approach Degenerate: All electrons in an orbital have the same (lowest) energy Solid Gas E=0 Electron energy N=5 N=4 N=3 N=2 3.67Å Internuclear distance continuum E=0 Electron energy Overlapping bands N=4 N=3 N=2 Energy bands for solid sodium at internuclear distance of 3.67Å Solid Gas E=0 Electron energy N=5 N=4 N=3 N=2 3.67Å Internuclear distance Immediate implication for X-Ray microanalysis… Electron transitions from split levels (bands) will result in photon emission energies that do not reflect the discrete degenerate level… Conduction band: First empty band above the highest filled band Electron energy Valence band: Outermost band containing electrons Conduction band Empty band Bandgap Partially full Bandgap Full Bandgap Full nucleus Outermost band containing elelectrons Valence band Transitions from the valence band involved in characteristic X-ray emission will be energy shifted depending on bond lengths, etc. Conduction band Empty band Electron energy Bandgap Partially full N=2 (L) Resulting X-Rays will not be monochromatic These will be Kα X-rays for ultra-light elements N=1 (K) nucleus Valence band Classification of solids: Conductors Insulators Semiconductors Conductors: Outermost band not completely filled Essentially no band gap overlap lots of available energy states if field is applied Metals and Alkali metals Insulators: Conduction band Empty Valence band full or nearly full Eg Wide band gap with empty conduction band Essentially no available energy states to which electron energies can be increased Wide bandgap Valence band Full Dielectric breakdown at high potential Semiconductors: Zinc blende (FCC ZnS) Similar to insulators but narrow band gap At electrical temperatures some electrons can be promoted to the conduction band Most are cubic Diamond FCC (single element) Conduction band Almost Empty Eg Valence band Almost Full Conduction band Empty bandgap Valence band Full T > 0K T = 0K Some common band gaps: Element gap (ev) Ge 0.6 Si 1.1 GaAs 1.4 SiO2 9.0 Mark McClure, UNCPembroke S Zn Semiconductors are either intrinsic or extrinsic Intrinsic Semiconductors: Pure state Example: Covalently bonded, tetravalent Si lattice Promotion of an electron to the conduction band leaves “hole” in the valence band = electron-hole pair Apply an electric field and the electron will migrate to + The hole will migrate to – (that is, the electron next to the hole will be attracted to the +, leaving a hole toward -) + - Ec Eg Ev Net propagation of hole Extrinsic Semiconductors: Doped with impurity atoms p-type n-type n-type Dope Si with something like pentavalent antimony (5 valence electrons) Narrows the band gap relative to Si easy to promote Sb electron Majority carriers are electrons in conduction band Minority carriers are holes in valence band Lattice doped with donor atoms localized energy levels just below conduction band Ed Ec Ev Si Si lattice with n-type dopant Sb p-type Dope Si with something like trivalent indium (3 valence electrons) Incomplete bonding with Si Nearby electron from Si can fill hole Majority carriers are holes in the valence band Minority carriers are electrons in the conduction band Lattice doped with acceptor atoms localized energy levels just above valence band Ec Ea Ev Si Si lattice with p-type dopant In Fermi Level: That energy level for which there is a 50% probability of being occupied by an electron Conduction band Intrinsic Ec Eg Ef Ev Valence band Conduction band n-type Eg Ev Valence band Recombination Electron-hole pairs not long lasting Electron encountering hole can “fall” into it Free time = microsecond or less Ec Ef The p-n junction Single crystal of semiconductor Make one end p-type (dope with acceptors) Make the other end n-type (dope with doners) The junction of the two leads to rectification Current only passed in one direction (diode) In the region of the junction Recombination = depletion of region with few charge carriers Results in “built-in” electric field p - Depletion width W Direction of built-in field Space-charge layers + + + + + + n Energy band diagram for p-n junction at equilibrium Ecp eV0 Ecn Efp Efn Evp Evn Apply eV0 to get diffusion p - Depletion width W Direction of built-in field Space-charge layers + + + + + + n Energy band diagram for p-n junction – applied forward bias Ecp eV Ecn Efp Efn Evp Evn Depletion width reduced Built-in field reduced Apply small V to get diffusion Barrier height reduced Diffusion current increased + p - - Depletion width W Direction of built-in field Space-charge layers + + + + + + If Vforward = V0 No barrier n Pass large current in one direction Energy band diagram for p-n junction – applied reverse bias Ecp eV Evp Ecn Depletion width increased Built-in field increased Barrier height increased - Diffusion current decreased p - Evn + Depletion width W Direction of built-in field Space-charge layers + + + + + + Becomes Capacitor n No current passed So: Can use reversed bias p-n junction as voltage regulator Zener diode Voltage too high? Overcome gap energy and pass current Can use forward bias p-n junction for rectification AC → DC transformer Analog-to-digital conversion LED Recombination – “tune” bandgap to achieve photon emission at the required wavelength GaAs (IR) GaInN (blue) GaAsP (red) YAG:Ce (white) Ternary and quaternary compounds allow precise bandgap engineering PIN diode (p and n sections separated by high resistance material) light detection X-ray detection electron detection -Each of these serve to excite electron-hole pairs -Bias properly and get amplification rather than simple propagation Bipolar transistor = pair of merged diodes - NPN or PNP base N P collector base N P emitter collector N P emitter Three voltages (NPN) Collector = + relative to base (collects electrons) Emitter = - relative to base (emits electrons) Small adjustments of the current on the base results in large changes in collector current. = current amplifier Amplify weak signals Use small currents to switch large ones Simple optical encoding: Generate sine wave by LED passing ruled slide Phototransistor sees varying light intensity current output varies with base current Diode rectifies AC→DC Square waves Digital output to counter