Project Guide: Dr.R.K.

Nahar
(Emeritus Scientist)

SNG Group, CEERI, PILANI

Presented By: Ashok Kumar (Student Trainee) DAVIET , jalandhar

Contents:1.introduction 2. Hafnium oxide thin film gas sensor. 3. Thin Deposition Techniques. 4. CO-sensing characteristics of hafnium oxide thin film 5. Hafnium oxide Film Applications. 6. Hafnium Oxide Gas Sensor : Experimental. 7. Experimental Results 8. Conclusion

Introduction
Gas sensor measures the concentration of gas in its vicinity. Gas sensor interacts with a gas to measure its concentration.
The adsorption of a gas onto the surface of a metal oxide can produce a large change in its electrical resistivity. These devices offer low cost and relative simplicity, advantages that should work in their favour as new applications .

metal oxide for gas sensing

Metal oxides are suitable for detecting combustible,

reducing, or oxidizing gases by conductive measurements. metal oxides generally used in gas sensing application are: Cr2O3, Mn2O3, Co3O4, NiO, CuO, SrO, In2O3, WO3, TiO2, V2O3, Fe2O3, GeO2, Nb2O5, MoO3, Ta2O5, La2O3, CeO2, Nd2O3 , HfO2.

 Application of gas detection instruments:

1. Process control industries 2.Environmental monitoring 3.Fire detection 4.Detection of harmful gases in mines 5.Home safety 6.Grading of agro-products like coffee and spices

Issues
Sensitivity Selectivity Stability

Hafnium oxide thin film gas sensor

Good chemical stability
Thermal stability Mechanical stability Easily changing the metal oxidation states Experimental results show that for the same insulator

thickness, the HfO2 sensor is more sensitive than other metal oxide sensors. Most of the work on HfO2 has been focused on amorphous films to replace SiO2.

General Properties of HfO2

Relative static dielectric constant Refractive Index Enthalpy of formation (eV/O atom) Energy Band Gap Conduction band offset with Si (eV) Valence band offset Structural Property
Hf atoms are in a FCC structure

: 15 , 26 : 2.24, 2.45 : -5.77 : 5.6, 6.2 : 2.0b, 1.3d : 2.5, 3.4d : Cubic & Tetragonal Cubic structures

O atoms are at the tetrahedral interstitial sites

Ref. : M. Houssa, High-k Gate Dielectrics, 2004, Page-331

Thin Deposition Techniques

Hafnium oxide (HfO2) films are deposited by a variety of techniques :
Sputtering

Atomic Layer Deposition

Plasma Enhanced Atomic Layer Deposition Chemical Vapor Deposition Plasma Enhanced Chemical Vapor Deposition Sol-gel Deposition Technique

Sputtering
Takes place under vacuum and is a type of physical vapor

deposition process. Process involves bombarding a target with high energy ions. In conventional sputtering systems, these ions are formed from argon gas. The target in the system is a solid disc which serves as the source of the deposition material. Film characteristics controlled by deposition parameters such as process pressure, power, and temperature of substrate.

 Target is electrically grounded.

Argon gas is ionized to a positive charge. Positively charged atoms are accelerated towards grounded

target. Argon atom hit target and sputter target molecules .

Sputtering additional methods

Reactive sputtering
RF sputtering Magnetron sputtering

Collimated sputtering
Hot sputtering

RF sputtering

DC sputter deposition is not suitable for insulator deposition, because the positive charge on the target surface rejects the ion flux and stop the sputtering process. RF voltages can be coupled capacitively through the insulating target to the plasma, so conducting electrodes are not necessary. The RF frequency is high enough to maintain the plasma discharge.

 During the first few complete cycles more electrons

than ions are collected at each electrode (high mobility), and cause to negative charge to be buildup on the electrodes. Thus, both electrodes maintain a steady-state DC potential that is negative with respect to plasma voltage, Vp. A positive Vp aids the transport of the slower positive ions and slow down the negative electrodes.

 The wafer will be sputtered at the same rate as the

target since the voltage drops would be the same at both electrodes for symmetric system. It would thus be very difficult to deposit any material in that way. Smaller electrode requires a higher RF current density to maintain the same total current as the larger electrode.

 By making the area of the target electrode smaller than

the other electrode, the voltage drop at the target electrode will be much greater than at the other electrode. Therefore almost all the sputtering will occur at the target electrode.

CO-sensing characteristics of hafnium oxide thin film

Surface interaction of metal oxide with gases species

includes following three steps : adsorption and desorption , Reactions , Catalyst and catalysis . Interaction of carbon monoxide with a thin hafnium oxide film includes two steps. First, molecular oxygen in the atmosphere reacts with the oxygen vacancies in the film. Oxygen is chemisorbed in the form of O2, O, O2 depending on the operating temperature of the sensor . The following reactions take place

The following reactions take place :O2(gas) O2(ads) O2(ads) + e O2(ads) (Top< 100 C) O2(ads) + e 2O (ads) (100 <Top< 300 C) O(ads) + e O2 (ads) (Top> 300 C) The initial temperature of the sensor in air was about 70 C which was also the initial sensing temperature of CO. These reactions create oxygen adsorbates and deplete electrons from the conduction band of the semiconducting film.

 At temperatures higher than 200 C, the effect of these

reactions is more significant than thermal excitation, and the conductivity decreases. The second step involves the reaction of the tested gas (CO in our case) with the adsorbed oxygen species. The relevant reactions are the following: 2CO + O2 2CO2 +e

CO + O
CO + O2

CO2 +e
CO2 +2e

(Top< 100 C) (100 <Top< 300 C) (Top> 300 C)

Hafnium oxide Film Applications

High-k gate dielectrics DRAM capacitors & memory applications HfO2 system in high-quality Anti Reflective

coatings Humidity Sensor Gas sensing applications

An incipient application to gas sensors has been proposed Pollution prevention and Evaluation of air quality Process Control The precise control of the air / fuel ratio

Hafnium Oxide Gas Sensor

Experimental:
Cleaning
Silicon wafers cleaned by Piranha cleaning Chemicals used :
Sulfuric Acid (H2SO4 96%)
Hydrogen Peroxide (H2O2 30%) HF (1:20)

Piranha Cleaning: 10-20 min Dried in dry N2 immediately before loading in the vacuum

chamber.

Hafnium oxide deposition done by sputtering method.

Target Materials Vacuum Ambient gas Pre-sputtered time Thin films of HfO2 Film thickness measured HfO2 10-6 Torr high purity argon gas 15 mins sputtering voltage 0.8 kV for 60mins ~700 (by Ambios step profiler )

Gas characterization done by Kelvin Probe method for CO and H2 gases.

Experimental Results

Fig1 . Change in CPD with time at different concentration of CO at room temperature.

 Fig2. Change in CPD with time at 200ppm concentration of

hydrogen at temperature.

 Fig3. Change in CPD with time at different concentration of

CO at 150,C temperature.

 Fig 4..Hafnium oxide thin film characteristics with dry air

after experiment.

Conclusion
The CO gas showed a reducing effect in fig 1 leading to a decrease in the Contact Potential Difference (CPD).
In fig 2 concentration of CO is 2ooppm at room temperature showed reducing effect leading decrease in CPD. fig 3 showed CO gas exposed at 150C on hafnium oxide film continuously increase in CPD with increase in concentration of CO.