Thanks to Prof. Brand and Bakir for some of the included slides.
Common Methodologies for Thin Film Silicon Dioxide
Thermal Silicon Dioxide Chemical Vapor Deposited SiO 2
Physical Vapor Deposited SiO 2 Sol Gel Deposited SiO 2
Electro-chemical (anodization) SiO 2 Ion Implantation of O 2 in Silicon (SIMOX Process)
Oxidation of Si? Thermal Oxidation Silicon wafer is oxidized in an O 2
or water vapor atmosphere at temperatures ranging from 900- 1200C Ability to grow a high quality thermal oxide has propelled Si into the forefront of all semiconductor technologies Thermal oxidation consumes silicon: for 1 m grown oxide, approximately 440 nm of silicon are consumed Thermal oxidation generally results in the best quality oxide
Sze, Fig. 11.3
t Si = 0.44 t SiO2 Application of Thermal Oxidation Thermal oxidation is used for Growth of field oxide separating neighboring transistors Growth of high quality gate oxide of MOS structure Growth of diffusion mask (even though ion implantation is mostly used for pre-deposition today) When to use it and when not to use it Use when highest quality silicon dioxide layers are required Do not use when process temperature is restricted (e.g. after aluminum metallization)
Structure of Thermal SiO 2 The form of thermally grown SiO 2 is fused silica, which is an amorphous solid SiO 2 is a glass (similar to window glass) and can be reflown if heated above its glass transition temperature Fused silica consists of silicon atoms sitting at the center of oxygen polyhedra; the polyhedra are randomly connected at bridging oxygen sites, i.e. O atoms that bond to two silicon atoms Dry oxides have a larger ratio of bridging to non-bridging sites compared to wet oxides, and are thus more stable Doping SiO 2 with boron or phosphorus (so called network modifiers) reduces the bridging-to-nonbridging ratio, which allows the glass to reflow at lower temperatures, smoothing surface topographies (known as phosphosilicate glass, PSG, and borophosphosilicate glass, BPSG) Campbell, Fig. 4.7 Structure of Thermal SiO 2 (a) Polyhedra (Tetrahedron) Basic Structure of SiO 2
(b) Quartz crystal (c) Amorphous SiO 2
Horizontal (Oxidation) Furnace Horizontal furnace is most common furnace type; it comprises four components: (1) the gas cabinet, (2) the furnace cabinet, (3) the load station and (4) the computer controller Resistive furnace heating elements are wound around fused silica tube; wafers are placed vertically in fused quartz boat and inserted into heated furnace tube using cantilevered load system Sze, Fig. 11.2 http://www.thermcosystems.eu Vertical (Oxidation) Furnace Vertical furnace are similar to a horizontal furnace turned on end; the wafers are pushed from below the furnace up into the tube Advantages of vertical furnaces: Simplified wafer handling by pushing carrier up instead of using long (transversally loaded) cantilevers; support system can remain in tube during thermal process (long cantilevers tend to warp) Uniform spacing between wafers improves process uniformity Smaller cleanroom footprint compared to horizontal furnace As a result, vertical furnaces have become the standard, especially for large diameter wafer processing (200 and 300mm wafers)
Figure 3.11 Furnaces used for oxidation and diffusion (a) A three-tube horizontal furnace with multizone temperature control (b) Vertical furnace (Courtesy of Crystec, Inc.) (a) (b) R. C. Jaeger 2002 3.1 Dry/Wet Thermal Oxidation Reaction Chemistry
Dry Oxidation
Wet Oxidation
Si (solid) + O 2 (gas) SiO 2
Si (solid) + 2H 2 O(gas) SiO 2 + 2H 2 Wet/Dry Oxidation Charts Easiest way to determine oxidation parameters (wet/dry, temperature) for a desired oxide thickness If pre-oxidized wafer is further oxidized at temperature T, the final oxide thickness is found by Finding first the time required to grow the initial oxide at the planned T Add to the intended oxidation time and find resulting overall thickness
Sze, Fig. 11.8 Dry Thermal Oxidation See also http://www.lelandstanfordjunior.com for an on-line calculator Sze, Fig. 11.8 Wet Thermal Oxidation Sze, Fig. 11.8 A <100> silicon wafer has a 2000- oxide on its surface
(a) How long did it take to grow this oxide at 1100 o C in dry oxygen?
(b)The wafer is put back in the furnace in wet oxygen at 1000 o C. How long will it take to grow an additional 3000 of oxide? (a) According to Figure, it would take 2.8 hr to grow 0.2 m oxide in dry oxygen at 1100 o C.
(b) The total oxide thickness at the end of the oxidation would be 0.5 m which would require 1.5 hr to grow if there was no oxide on the surface to begin with. However, the wafer thinks it has already been in the furnace 0.4 hr. Thus the additional time needed to grow the 0.3 m oxide is 1.5-0.4 = 1.1 hr. 4.2 Deal-Grove Model for Oxidation Diffusivity of Si in SiO 2 is several orders of magnitude smaller than that of O 2 ; thus, O 2 diffuses through the already existing oxide and reacts with Si at the Si-SiO 2 interface, further growing the oxide layer As a result, the interface at which the SiO 2 grows is not exposed to the environment and thus free of impurities At room temperature, a native oxide layer with a thickness of 25 grows on top of silicon Deal-Grove model is suitable for predicting thermal oxide thicknesses > 30 nm Assuming a dry oxidation, the Deal-Grove model considers transport of O 2 through the stagnant gas layer to the SiO 2
surface, diffusion of O 2 through the SiO 2 layer and reaction of the O 2 with Si at the SiO 2 -Si interface Deal-Grove Oxidation Model Oxygen flux by diffusion of O 2
through the stagnant gas layer
or more general
with thickness of stagnant gas layer t sl and mass transport coefficient h g C g is related to the partial pressure of O 2 in the furnace via the ideal gas law
C g oxygen conc. in gas far from wafer C s oxygen conc. in gas at wafer surface C o oxygen conc. in oxide at wafer surface C i oxygen conc. at Si-SiO 2 interface Campbell, Fig. 4.1
J 1 ~ D O2,gas C g C s t sl
J 1 = h g (C g C s )
C g = n V = p g kT Deal-Grove Oxidation Model (cont.) Oxygen flux by diffusion of O 2 through the oxide layer
Oxygen flux associated with oxygen reacting with Si at Si-SiO 2
interface
with chemical rate constant k s In equilibrium, the three fluxes must be equal, J 1 = J 2 = J 3 , resulting in two equations with three unknowns C s , C o , and C i In addition, Henrys law states that the concentration of an adsorbed species at a surface of a solid is proportional to the partial pressure of that species in the gas above the solid
with Henrys gas constant H (not really a constant, but depending on species, surface, T, etc.) as the proportionality constant
J 2 ~ D O2,SiO2 C o C i t ox
J 3 = k s C i
C o = Hp g = HkTC s Deal-Grove Oxidation Model (cont.) The resulting three equations with three unknowns can be solved, yielding
The oxide growth rate is given by the ratio of the oxygen flux J [s -1 cm -2 ] and the number N 1 of oxygen molecules per unit volume of SiO 2 [cm -3 ]:
with D = D O2,SiO2 ; dry oxidation: N 1 = 2.2 10 22 cm -3 (because O 2
diffuses); wet oxidation: N 1 = 4.4 10 22 cm -3 (because O diffuses)
The above rate equation is a differential equation for t ox ; it can be solved assuming the boundary condition
C i = Hp g 1+ k s h g / HkT + k s t ox D C i 0 for D 0 C i
Hp g 1+ k s h g / HkT for D
t ox (t = 0) = t 0
R = dt ox dt = J N 1 = Hk s p g N 1 1+ k s h g / HkT + k s t ox D
(
( Diffusion limited Reaction limited Deal-Grove Oxidation Model (cont.) The solution of the DE is
Typically, the coefficients A and B are known for a variety of process conditions; for oxidation at atmospheric pressure, we have k s << h = h g /HkT and the growth rate becomes independent of gas phase mass transport and thus reactor geometry; A and B are proportional to D and thus will follow an Arrhenius function The time is the time needed to grow the initial oxide thickness t 0 ; thus, the oxidation actually starts at time and at t=0, the oxide thickness is t 0
t ox 2 + A t ox = B(t + t) A = 2D 1 k s + 1 h | \
| . | B = 2DHp g N 1 t = t 0 2 + A t 0 B
t ox = A + A 2 + 4B(t + t) 2 Deal-Grove Oxidation Model (cont.) Thin Oxides: For sufficiently thin oxides, we can neglect the quadratic term and the oxide thickness becomes
with the linear rate coefficient B/A [m/hr] Thick Oxides: For sufficiently thick oxides, we can neglect the linear term and the oxide thickness becomes
with the parabolic rate coefficient B [m 2 /hr]
t ox ~ B A (t + t)
t ox 2 ~ B(t + t) Campbell, Tab. 4.1 Linear/Parabolic Rate Coefficient B B/A Campbell, Figs. 4.2/4.3 Deal Grove Model Rate Constants Impurity Segregation Coefficient
k = EquilibriumImpurityConcentrationinSilicon EquilibriumImpurityConcentrationinSiliconDioxide Masking Diffusions using SiO 2
Determining the Thickness of SiO 2
1. Color Charts 2. Ellipsometry 3. Controlled Etching 4. Optical Interference 1. based on reflected light intensity spectra
n ox = real part of the oxide refractive index = difference in the wavelength between the min and max intensity in the fringe pattern spectra Determining the Thickness of SiO 2
Practical Considerations Metallic Impurity Gettering: Halogen species (Cl, F, etc.) are often introduced to getter metallic impurities from the tube during an oxidation; this also tends to increase the oxidation rate for thin oxides (linear term). HCl is the safest to use (bubbled into the furnace as described in the diffusion discussion) but is highly corrosive to the gas tubing; trichloroethylene (TCE) and trichloroethane (TCA) are less corrosive but can be toxic. TCA can form phosgene (COCl 2 ) at high temperatures. Thick Oxides: The growth of thick oxides is proportional to B and thus to the oxygen partial pressure in the gas p g ; thus, the growth rate can be increased by growing the oxide at high pressure. Thin Oxides: Most thin (t ox few hundred angstroms) dry oxides grow at a rate faster than Deal-Grove predicts. Corrections can be made to work down to ~ 300 , but modern MOS gate oxides are < 100 . Orientation Dependence: Oxidation rate depends on orientation. MOS uses <100> oriented wafers because it has the fewest atoms per cm 2 , results in lower interface state density. Isolation technology in MOS processes
Provides isolation between nearby devices
Fully recessed process attempts to minimize birds beak Local Oxidation of Silicon (LOCOS) R. C. Jaeger 2002 Local Oxidation of Silicon (LOCOS)