Kinetics of Silicon Oxidation in a Rapid Thermal Processor
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1 Kinetics of Silicon Oxidation in a Rapid Thermal Processor Asad M. Haider, Ph.D. Texas Instruments Dallas, Texas USA Presentation at the National Center of Physics International Spring Week 2010 Islamabad Pakistan March 01, 2010
2 PRESENTATION OUTLINE Introduction and motivation to study Si oxidation Mechanism of Si oxidation Mathematical model for Si oxidation Hardware design of a Rapid Thermal Processor (RTP) Experimental data and the model parameter estimation Oxide quality Conclusions
3 INTRODUCTION: Importance of SiO 2 in SC Industry During semiconductor device manufacturing SiO 2 is thermally grown to be used as a: a) Gate oxide b) Isolation oxide liner between devices (STI liner) c) Masking element (for eg., during ion implantation) d) Surface passivation (for eg., Pad oxide. A sacrificial layer for contamination control) Gate Gate Oxide Isolation Source L g Substrate Drain Isolation Please note the difference between grown SiO 2 and deposited SiO 2 This presentation is about thermally grown SiO 2
4 MOTIVATION TO STUDY OXIDATION IN RTP 1. To indirectly measure across wafer temperature uniformity of a Rapid Thermal Processor in > 900C range. 2. Understand the Si oxidation kinetics in a RTP chamber and measure Deal-Grove oxidation model parameters for < 30nm thick oxides. 3. Understand the impact of various process parameters on SiO 2 growth in a RTP chamber. 4. Compare the oxide quality grown in a RTP with that grown in a furnace.
5 OXIDATION OF SILICON Si has great affinity for oxygen and is easily oxidized in a number of ways: 1. Chemical oxidation Boil Si in HNO 3,,for example. 2. Anodic oxidation In an electrolytic bath use Si as an anode and a noble metal as a cathode. 3. Plasma oxidation Uses ions of an oxidant species to grow oxide film. 4. Thermal oxidation Used exclusively in semiconductor device fabrication. Gives by far the best quality oxide. Typically done in a furnace. Two types of thermal oxides: Si + O2 SiO 2 Dry oxidation Si + 2 H 2 O SiO H 2 Wet Oxidation Dry oxidation: Slow, high density, good quality Thin gate oxides Wet oxidation: Fast, low density, poorer quality Thick mask/passivation This study looks at kinetics of dry oxidation in a Rapid Thermal Processor.
6 MECHANISM OF Si OXIDATION Question: Is it the Si atoms that diffuse through the oxide to react with O 2 at the oxide surface or is it the O 2 that diffuses through the oxide to react with Si at the Si/SiO 2 interface? Answer: For thermal oxidation, it has been established through radioactive tracer studies that it is the O 2 that diffuses through the oxide and reacts with Si at the Si/SiO 2 interface. SiO 2 Si O 2 Consequently, thermal oxidation always takes place on fresh Si surface rather than the original surface that may have been exposed to ambient contaminants. Next, we look at a detailed mathematical model for the oxidation of Si.
7 MATHEMATICAL MODEL FOR SILICON OXIDATION Si + O 2 SiO 2 Dry Oxidation Gas Oxide Silicon C g δ C s C o Deal and Grove, J. Appl. Physics, vol 36, p 3770, (1965) C i N 1 N 2 N 3 x C g Concentration of oxidant molecules in the bulk gas C s Concentration of oxidant molecules immediately adjacent to the oxide surface C o Equilibrium concentration of oxidant molecules at the oxide surface C i Concentration of oxidant molecules at the Si/SiO 2 interface Note: i) Cg > Cs due to depletion of the oxidant at the oxide surface ii) Cs > Co due to solubility limits of the oxide δ Oxide thickness at a given time N i Flux of oxidant molecules
8 MATHEMATICAL MODEL FOR SILICON OXIDATION Contd. N 1 = Oxidant flux from bulk gas to the oxide surface N = k ( C C ) 1 m g s (Eq. 1) N 2 = Oxidant flux through the oxide N 2 = D dc dx r + Cv = D dc dx Integration across the oxide film gives: N 2 = ( ) D C o C i δ (Eq. 2) C g p g Gas Oxide Silicon p s Cs C o δ C* C i N 1 N 2 N 3 x C* = Equilibrium conc in bulk oxide N 3 = kc i Henry s law dictates that: (Eq. 3) * C = and C = Hpg o Hp s Therefore, Eq. 1 becomes: N = km HRT * ( C C ) 1 (Eq. 4) o
9 MATHEMATICAL MODEL FOR SILICON OXIDATION Contd. Express C o and C i in terms of measurable quantities. At steady state: N 1 = N 2 = N 3 This results in: C o = C * kδ 1 + D khrt kδ 1+ + km D (Eq. 5) C g p g Gas Oxide Silicon p s Cs C o δ C* C i N 1 N 2 N 3 C i = C * 1+ khrt k m 1 + kδ D (Eq. 6) x C* = Equilibrium conc in bulk oxide Case 1: Mass transfer controlled process: Oxide growth rate depends only on how fast oxidant is supplied to the Si/SiO 2 interface. Hence, D << k C i ~ 0 and C o ~ C* Case 2: Kinetics controlled process: Oxide growth rate depends only on how fast the oxidant reacts at the Si/SiO 2 interface. Hence, D >> k C i = C o C = 1 + * khrt k m
10 MATHEMATICAL MODEL FOR SILICON OXIDATION Contd. Oxide Growth Rate: Let Γ be the number of oxidant molecules per unit volume of the oxide film. Then, d dt ( Γδ ) = N = kc * kc = khrt 1+ km 3 i (Eq. 7) + kδ D Integrating Eq. 7 with initial condition: At t = 0 ; δ = δ i results in: Where, ( t E) δ 2 + A δ = B + (Eq. 8) 1 A = 2D + k * 2DC B = Γ E 2 δ i + Aδi = B HRT k m A and B are the only two model parameters to be found experimentally.
11 MATHEMATICAL MODEL FOR SILICON OXIDATION Contd. Special Cases: A. For very short times, δ is very small and the process is kinetics limited. In this regime Eq. 8 becomes: B δ = ( t + E) (Eq. 9) A B. For very long times, δ is pretty thick and the process is diffusion limited. In this regime Eq. 8 becomes: δ = Bt (Eq. 10) To find model parameters A and B requires collecting oxide thickness vs. time data. Since A and B are in turn functions of temperature, oxide thickness data needs to be collected at different temperatures in order to develop a general equation to predict oxide thickness as a function of time and temperature, δ = δ(time, temperature) But first, let us look at the hardware design of a RTP chamber.
12 DESIGN OF RTP (Rapid Thermal Processor) Transfer chamber and chambers A and B.
13 DESIGN OF RTP Contd. Close-up of the reflector plate. Pyrometers and lift pin holes visible. View of an open RTP chamber.
14 Wafer Edge Ring and Support Cylinder Assembly Schematic
15 DESIGN OF RTP Contd. Assembled parts: SiC wafer edge ring sitting on top of the support cylinder around the reflector plate.
16 DESIGN OF RTP Contd. Reflector plate showing raised wafer lift pins.
17 RTP Centura Lamp Zones and Temperature Probe Locations
18 DESIGN OF RTP Contd. Close up of the RTP multi-zone lamp heater assembly capable of precision controlled temperature ramp rates of >100C/s.
19 KEY PROCESS PARAMETERS AND THEIR EFFECT ON OXIDATION KINETICS 1.2 Oxide Growth Rate vs. Pressure at 1050C 1 Oxide Growth Rate, A/s Pressure, torr Recall, B = 2DC Γ * ; As P increases, C* increases
20 SiO2 Growth Rate Vs. O2 Flow Rate T = 1050C ; P = 780 torr SiO2 Growth Rate, A/s O2 Flow Rate, slm All Si oxidation tests were conducted in O 2 ambient at 5 slm at a chamber pressure of 780 torr at various temperatures.
21 Arrhenius Plot for SiO2 Growth P = 780 torr, O2 = 5 slm ln (Rate), A/s y = x R 2 = E = kj/mole /Temp, 1/K Next, estimate model constants A and B by doing a least squares fit of the model to the experimentally collected Si oxidation data.
22 EXPERIMENTAL DATA AND CALCULATION OF MODEL PARAMETERS 200 Oxide Growth at 1050C in RTP Reactor Theory Measured Oxide Thickness, A Oxidation Time, s A = 40 A B = 131 A 2 /s
23 EXPERIMENTAL DATA AND CALCULATION OF MODEL PARAMETERS 250 Oxide Growth at 1075C in RTP Reactor 200 Theory Measured Oxide Thickness, A A = 55 A B = A 2 /s Oxidation Time, s Repeat these tests at multiple temperatures to get dependency of A and B on temperature.
24 Rate Constant A vs. Temperature y = x R 2 = A, Ang Temp, C
25 B, Ang^2/s Parabolic Rate Constant B vs. Temperature y = x x R 2 = Temp, C
26 Semi Empirical Model to Predict SiO 2 Thickness Near Atmospheric Pressures in RTP δ 2 ( t E) + A δ = B + A = T B 2 = T T E = 2 δ i + Aδi B δ = Oxide thickness grown at any time δ i = Initial oxide thickness t = Time T = Temperature
27 OXIDE QUALITY Best way to tell the quality of oxide is by measuring the charges in it. K + Na + SiO 2 SiO x Si Mobile ionic charges Oxide trapped charges Fixed oxide charges Interface trapped charges Source: Mostly humans. Contaminated water or if it is not fully deionized. Effect: Wreaks havoc on transistor characteristics. Fix: Use chlorine oxidation bubble O 2 through TCE. Be careful, too much Cl will result in halogen pitting. Source: Exposure to radiation environment. Hot electron effect in short channel MOSFET devices. Effect: Interferes with electronic activity. Fix: Typically not caused by processing itself. Source: Incomplete oxidation Effect: Pushes V T in ve direction Fix: At the end of oxidation step purge the system with N 2 or Ar gas and then drop the temperature. Source: Mechanical damage in Si wafer. Dangling Si bonds left unreacted after oxidation. Effect: Trap and de-trap electrons affecting MOS device performance. Fix: Do a low temp (~450C) anneal in H 2 ambient post oxidation.
28 SUMMARY AND CONCLUSIONS Deal and Grove model was successfully applied to oxidation of Si in a RTP reactor for oxide thicknesses less than 30nm. Model parameters A and B were empirically found as a function of temperature at 780 torr to obtain a generalized model capable of accurately predicting dry Si oxidation rates between 975C and 1100C for oxide thicknesses less than 30nm. Activation energy of dry Si oxidation in RTP was found to be 115 kj/mole. Discussed various types of charges in SiO 2 that determine the quality of oxide and how to mitigate them.
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