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Chapter 22: Optical Properties

ISSUES TO ADDRESS... • What phenomena occur when is shined on a material? • What determines the characteristic of materials? • Why are some materials transparent and others are translucent or opaque? • How does a operate?

Chapter 22 - 1 Figun_22_p785c

Solar cells: Convert Light to electricity

Figun_22_p785a Figun_22_p785b Chapter 22 - 2 • 01 Introduction • 02 Electromagnetic Radiation • 03 Light Interactions with Solids • 04 Atomic and Electronic Interactions • 05 • 06 • 07 Absorption • 08 Transmission • 09 • 10 Opacity and Translucency in Insulators • 11 • 12 Photoconductivity • 13 • 14 Optical Fibers in Communications

Chapter 22 - 3 1. Optical Properties Optical property refers to a material's response to exposure to electromagnetic radiation and, in particular, to visible light. Light has both particulate and wavelike characteristics – - a quantum unit of light Light, heat (or radiant energy), radar, radio waves, and x-rays are all forms of electromagnetic radiation.

Chapter 22 - 4 2. Electromagnetic radiation

is related to the electric permittivity and the magnetic permeability of a vacuum

Fig_22_01 An electromagnetic wave showing electric field and magnetic field components and the wavelength and also direction of propagation.

Chapter 22 - Fig_22_02 Chapter 22 - 3. Light Interactions with Solids • Incident light is reflected, absorbed, scattered, and/or transmitted: I 0 = IT + IA + IR + IS

Reflected: IR Absorbed: IA

Transmitted: IT

Incident: I0 Scattered: IS • Optical classification of materials: Transparent Translucent Opaque

single polycrystalline polycrystalline dense porous Chapter 22 - 7 4. Atomic and electronic interactions • Electronic – to shift the cloud and light diffracted electron no transmitted cloud transmitted + + distorts light light

• Electron transition

Chapter 22 - 8 Fig_22_03 Optical Properties of Metals: Absorption

• Absorption of by electron transitions: Energy of electron

unfilled states

DE = hν required!

filled states Planck’s constant freq. of -34 (6.63 x 10 J/s) incident light • Unfilled electron states are adjacent to filled states • Near-surface absorb visible light.

Chapter 22 - 9 Reflection of Light for Metals

• Electron transition from an excited state produces a photon.

Energy of electron I unfilled states R “conducting” electron photon emitted Electron transition from metal surface filled states

Chapter 22 - 10 Reflection of Light for Metals (cont.)

• Reflectivity = IR /I0 is between 0.90 and 0.95. • Metal surfaces appear shiny • Most of absorbed light is reflected at the same wavelength • Small fraction of light may be absorbed • Color of reflected light depends on wavelength distribution – Example: The metals copper and gold absorb light in blue and => reflected light has gold color

Chapter 22 - 11 5. Refraction • Transmitted light distorts electron clouds. electron no transmitted cloud transmitted + + distorts light light

• The velocity of light in a material is lower than in a vacuum.

n = index of refraction

-- Adding large ions (e.g., lead) to glass Material n decreases the speed of light in the glass. Typical glasses ca. 1.5 -1.7 -- Light can be “bent” as it passes through a 1.3 -1.6 transparent prism PbO (Litharge) 2.67 Diamond 2.41

Chapter 22 - 12 In ionic materials, the larger the size of the component ions the greater the degree of electronic polarization and the higher the n values.

Chapter 22 - 13 6. Reflectivity of Nonmetals

• For normal incidence and light passing into a solid having an index of refraction n:

2  n 1 Rreflectivity  Ir/Io   n 1

• Example: For Diamond n = 2.41

\ 17% of light is reflected

Chapter 22 - 14 Example: Diamond in air

• What is the critical angle ϕc for light passing from diamond (n1 = 2.41) into air (n2 = 1)?

• Solution: At the critical angle, and

Rearranging the equation

Substitution gives

Chapter 22 - 15 Total Internal Reflectance: the Smell’s law

n2 < n1

n 2 ϕ1 = incident angle n 1 ϕ2 = refracted angle

ϕc = critical angle

ϕc exists when ϕ2 = 90°

For ϕ1 > ϕc light is internally reflected

Fiber optic cables are clad in low n material so that light will experience

total internal reflectance and not escape from the optical fiber.

Chapter 22 - 16 Scattering of Light in Polymers

• For highly amorphous and pore-free polymers – Little or no scattering – These materials are transparent • Semicrystalline polymers – Different indices of refraction for amorphous and crystalline regions – Scattering of light at boundaries – Highly crystalline polymers may be opaque • Examples: – Polystyrene (amorphous) – clear and transparent – Low-density polyethylene milk cartons – opaque

Chapter 22 - 17 7. Light Absorption The amount of light absorbed by a material is calculated using Beer’s Law

β = absorption coefficient, cm-1  = sample thickness, cm I 0 = incident (nonreflected) light intensity I T = transmitted light intensity Rearranging and taking the natural log of both sides of the equation leads to

Chapter 22 - 18 Selected Light Absorption in Semiconductors

Absorption of light of frequency ν by by electron transition occurs if hν > Egap Energy of electron Examples of photon energies: unfilled states blue light: hν = 3.1 eV red light: hν = 1.8 eV

Egap incident photon energy hν filled states

• If Egap < 1.8 eV, all light absorbed; material is opaque (e.g., Si, GaAs)

• If Egap > 3.1 eV, no light absorption; material is transparent and colorless (e.g., diamond)

• If 1.8 eV < Egap < 3.1 eV, partial light absorption; material is colored

Chapter 22 - 19 Computations of Minimum Wavelength Absorbed (a) What is the minimum wavelength absorbed by

Ge, for which Eg = 0.67 eV? Solution:

(b) Redoing this computation for Si which has a band gap of 1.1 eV

Note: the presence of donor and/or acceptor states allows for light absorption at other wavelengths.

Chapter 22 - 20 8. Light transmission

Fig_22_07

Chapter 22 - 21 9. Color of Nonmetals • Color determined by the distribution of wavelengths: -- transmitted light -- re-emitted light from electron transitions • Example 1: Cadmium Sulfide (CdS), Eg = 2.4 eV -- absorbs higher energy visible light (blue, violet) -- color results from red/orange/yellow light that is transmitted

• Example 2: Ruby = Sapphire (Al2O3) + (0.5 to 2) at% Cr2O3

-- Sapphire is transparent and 80 colorless (Eg > 3.1 eV) sapphire -- adding Cr O : 70 2 3 ruby • alters the band gap 60 50 • blue and orange/yellow/green wavelength, λ (= c/ν)(μm) light is absorbed (%) Transmittance 40 • red light is transmitted 0.3 0.5 0.7 0.9 • Result: Ruby is deep red in color

Chapter 22 - 22 10. Opacity and translucency in insulators

• depends to a great degree on their internal reflectance and transmittance characteristics. – interior reflection and refraction. • diffuse as a result of multiple scattering events. • Opacity results from extensive scattering that virtually none of the incident beam is transmitted

Transparent Translucent Opaque

single polycrystalline polycrystalline crystal dense porous Chapter 22 - 23 11. Luminescence • Luminescence – reemission of light by a material – Material absorbs light at one frequency and reemits it at another (lower) frequency. – Trapped (donor/acceptor) states introduced by impurities/defects

Conduction band • If residence time in trapped state is relatively long (> 10-8 s) -- phosphorescence

• For short residence times (< 10-8 s) trapped -- fluorescence states Eemission Eg Example: Toys that glow in the dark. level Charge toys by exposing them to light. Reemission of light over time— phosphorescence Valence band

Chapter 22 - 24 : Fluorescent lamps Hg

UV light

electrode electrode • Arc between electrodes excites electrons in mercury in the lamp to higher energy levels. • As electron falls back into their ground states, UV light is emitted (e.g., suntan lamp). • Inside surface of tube lined with material that absorbs UV and reemits visible light - - - For example, Ca10F2P6O24 with 20% of F replaced by Cl • Adjust color by doping with metal cations Sb3+ blue Mn2+ orange-red Chapter 22 - 25 Cathodoluminescence

• Used in cathode-ray tube devices (e.g., TVs, computer monitors) • Inside of tube is coated with a material – Phosphor material bombarded with electrons – Electrons in phosphor atoms excited to higher state – Photon (visible light) emitted as electrons drop back into ground states – Color of emitted light (i.e., photon wavelength) depends on composition of phosphor ZnS (Ag+ & Cl-) blue (Zn, Cd) S + (Cu++Al3+) green

Y2O2S + 3% Eu red

• Note: light emitted is random in phase & direction – i.e., is noncoherent

Chapter 22 - 26 Photoconductivity • Additional charge carriers may be generated as a consequence of photon-induced electron transitions in which light is absorbed – a photoconductive material is illuminated, the conductivity increases. – CdS is commonly used in light meters. • Sunlight may be directly converted into electrical energy in solar cells ( p-n semiconductors). • This conversion of electrical energy into light energy is termed electroluminescence, and the device that produces it is termed a light-emitting diode (LED).

Chapter 22 - 27 13. The LASER

• The laser generates light waves that are in phase (coherent) and that travel parallel to one another

– LASER • Light • Amplification by • Stimulated • Emission of • Radiation

• Operation of laser involves a of energy states process

Chapter 22 - 28 Population Inversion

• More electrons in excited energy states than in ground states

Chapter 22 - 29 Operation of the Ruby Laser

• “pump” electrons in the lasing material to excited states – e.g., by flash lamp (incoherent light).

– Direct electron decay transitions — produce incoherent light

Chapter 22 - 30 Operation of the Ruby Laser (cont.)

• Stimulated Emission – The generation of one photon by the decay transition of an electron, induces the emission of other photons that are all in phase with one another. – This cascading effect produces an intense burst of coherent light.

• This is an example of a pulsed laser

Chapter 22 - 31 Continuous Wave Lasers

• Continuous wave (CW) lasers generate a continuous (rather than pulsed) beam • Materials for CW lasers include semiconductors (e.g., GaAs), gases (e.g., CO2), and yttrium-aluminum-garnet (YAG) • Wavelengths for laser beams are within visible and infrared regions of the spectrum • Users of CW lasers 1. Welding 2. Drilling 3. Cutting – laser carved wood, eye surgery 4. Surface treatment 5. Scribing – ceramics, etc. 6. Photolithography – Excimer laser

Chapter 22 - 32 Semiconductor Laser Applications

• Apply strong forward bias across semiconductor layers, metal, and heat sink. • Electron-hole pairs generated by electrons that are excited across band gap. • Recombination of an electron-hole pair generates a photon of laser light

electron + hole  neutral + hν

recombination ground state photon of Fig. 22.17, Callister & Rethwisch 9e. light

Chapter 22 - 33 Semiconductor Laser Applications

• Compact disk (CD) player – Use red light • High resolution DVD players – Use blue light – Blue light is a shorter wavelength than red light so it produces higher storage density • Communications using optical fibers – Fibers often tuned to a specific frequency • Banks of semiconductor lasers are used as flash lamps to pump other lasers

Chapter 22 - 34 Other Applications of • New materials must be developed to make new & improved optical devices. – Organic Light Emitting Diodes () • More than one color available from a single diode • Also sources of white light (multicolor)

Chapter 22 - 35 Other Applications - Solar Cells • p-n junction: • Operation: -- incident photon of light produces elec.-hole pair. P-doped Si -- typical potential of 0.5 V produced across junction conductance Si -- current increases w/light intensity. electron creation of Si P Si hole-electron light pair Si n-type Si - - - p-n junction - n-type Si p-type Si + p-n junction + + + p-type Si • Solar powered weather station: hole Si Si B Si Si B-doped Si polycrystalline Si Los Alamos High School weather station (photo courtesy P.M. Anderson)

Chapter 22 - 36 14. Other Applications - Optical Fibers

Schematic diagram showing components of a fiber optic communications system

Fig. 22.18, Callister & Rethwisch 9e.

Chapter 22 - 37 Optical Fibers (cont.)

• fibers have diameters of 125 μm or less • cladding 60 μm thick is applied to fibers

Fig. 22.20, Callister & Rethwisch 9e.

Chapter 22 - 38 Optical Fiber Designs Step-index Optical Fiber

Graded-index Optical Fiber Fig. 22.21, Callister & Rethwisch 9e.

Fig. 22.22, Callister & Rethwisch 9e.

Chapter 22 - 39 SUMMARY • Light radiation impinging on a material may be reflected from, absorbed within, and/or transmitted through • Light transmission characteristics: -- transparent, translucent, opaque • Optical properties of metals: -- opaque and highly reflective due to electron energy band structure. • Optical properties of non-Metals: -- for Egap < 1.8 eV, absorption of all wavelengths of light radiation -- for Egap > 3.1 eV, no absorption of visible light radiation -- for 1.8 eV < Egap < 3.1 eV, absorption of some range of light radiation wavelengths -- color determined by wavelength distribution of transmitted light • Other important optical applications/devices: -- luminescence, photoconductivity, light-emitting diodes, solar cells, lasers, and optical fibers

Chapter 22 - 40