Thin Film Semiconductor Metal Oxide Oxygen Sensors: Limitations, Challenges, and Future Progress
Abstract
:1. Introduction
2. Oxygen Sensor Market
- Increased regulatory requirements for monitoring air quality and industrial emissions;
- Development of medical technologies and the need to monitor patients’ condition in real time;
- Growing demand for energy efficiency and optimization of industrial processes.
3. Classification of Oxygen Sensors in Terms of Their Sensing Mechanism
3.1. Optical Sensors
3.2. Schottky Diode
3.3. Electrochemical Devices
3.4. Magnetic Sensors
3.5. Chemiresistive Sensors
4. Thin Films Fabrication
5. Resistive Oxygen Sensors
6. Critical Discussion
7. Conclusions and Perspectives
Author Contributions
Funding
Data Availability Statement
Acknowledgments
Conflicts of Interest
References
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Sector | Special Requirements |
---|---|
Healthcare |
|
Food |
|
Automotive |
|
Environmental monitoring |
|
HI-TECH |
|
IoT |
|
Working Temperature | Analyte | ||||
---|---|---|---|---|---|
H2 | CO | NH3 | H2S | O2 | |
250 °C | 1.4 | 1.4 | 1.4 | 6.6 | 4.4 |
300 °C | 1.3 | 1.3 | 1.3 | 4.8 | 3.7 |
350 °C | ~1 | <1 | 1.9 | 3.5 | 4.3 |
400 °C | ~1 | <1 | 2.9 | 1.9 | 3.7 |
450 °C | ~1 | <1 | 1.8 | <1 | 2.6 |
Type of Oxygen Sensor | Mechanism of Operation | Key Materials | Applications | Ref. |
---|---|---|---|---|
Optical | This type of sensor uses dyes emitting light (luminescence) when exposed. The emitted light intensity is proportional to the amount of oxygen in the environment. | Luminescent dyes, polymers | Medical diagnostics, environmental monitoring, industrial process control | [18,54,55,56] |
Schottky diode | It acts as a gas sensor due to the change in the electron work function resulting from the adsorption of gas molecules on the metal surface, which influences the conductivity of the metal–semiconductor junction. | Gold, nickel, platinum, SiC, GaAs | Industrial monitoring processes, environmental sensing, healthcare diagnostics | [57,58] |
Electrochemical | Operation by the reaction of the electrolyte with the target gas, which generates an electrical signal proportional to the gas concentration. | Zirconia, Yttria-stabilized zirconia | Industrial, automotive, medical diagnostics | [6,59,60] |
Magnetic | They are based on the paramagnetic properties of oxygen that cause the attraction of its molecules to a strong magnetic field, enabling accurate measurements of oxygen concentration. | Paramagnetic materials | Industrial process control, medical diagnostics | [36,37] |
Chemiresistive (resistive) | They work based on the adsorption of oxygen molecules on the surface of the semiconductor material, which changes its resistance—the changes in this parameter are proportional to the concentration of oxygen. | SMO, carbon materials | Combustion engines sensors, harsh environment sensors | [61,62,63,64] |
Magnetron Sputtering | Chemical Vapor Deposition | Atomic Layer Deposition |
---|---|---|
+ Fast + Low cost + No harmful byproducts + Selection of the sputtered material independent of its melting point or chemical reactivity | + Very efficient + Very fast + Deposition possible on a complex surfaces + Simple process + Easy doping process | + Very precise + Deposition possible on very complex surfaces + Very high control of final product + Allows for repetitively obtaining extremely thin layers + Allows for simultaneous deposition on large quantities of samples + Very easy and precise doping or mixing of materials + Produces very homogeneous films |
- Unable to conformally coat complex surfaces - Size of batches limited by the 2D size of chamber | - Many harmful byproducts - Aggressive precursors may damage substrates - Often needs high temperature, plasma, or lasers to activate precursors | - Slow process - Expensive - Harmful byproducts |
Ref. | Material | Optimal Working Temperature [°C] | Thickness [nm] | Deposition Method | Min Range [%] | Max Range [%] | T90 [s] | Trec [s] |
---|---|---|---|---|---|---|---|---|
Low Temperature Sensors | ||||||||
[89] | CNT | 20 | - | Dip casting | 0.3 | 100 | 60 | 180 |
[90] | Bi2O2Se | 20 | 8.4 | CVD | 2.5 × 10−5 | 0.004 | - | - |
[91] | SWCN:SrTiO3 | 20 | - | CVD, PLD | 10−5 | 10−3 | 21 | 170 |
[92] | ZnO | 20 | - | Thermal evaporating | - | - | - | - |
[93] | ZnO | 20 | - | Microwave–hydrothermal | 0 | 15 | 120 | 60 |
[94] | CdO:ZnO (1:3) | 32 | 200 | Spin coating | - | - | 18 | 10 |
[94] | ZnO | 32 | 200 | Spin coating | - | - | 38 | 30 |
[94] | CdO | 100 | 200 | Spin coating | - | - | 14 | 38 |
[52] | Ti2CTx | 125 | 50,000 | Micro-plotter printing | 1 | 20 | - | - |
[94] | CdO:ZnO (3:1) | 150 | 200 | Spin coating | - | - | 20 | 35 |
[95] | MWCNT | 160 | - | Drop casting | 0.3 | 50 | - | 0.9 |
[96] | CdO:ZnO | 200 | - | RF magnetron sputtering | - | - | 25 | 45 |
[50] | Nb2O5 | 200 | - | Screen printing | 0.4 | 20 | 71 | 57 |
[97] | SnO2 | 225 | 120 | Electron bean evaporation | 0.05 | 0.4 | - | - |
[97] | SnO2:2.72%Pt | 225 | 120 | Electron bean evaporation | 0.05 | 0.4 | - | - |
[97] | SnO2:2.88%Pt | 225 | 120 | Electron bean evaporation | 0.05 | 0.4 | - | - |
[97] | SnO2:3.74%Pt | 225 | 120 | Electron bean evaporation | 0.05 | 0.4 | - | - |
[98] | CNT | 250 | PVD | - | - | - | - | |
[99] | SnO2 | 270 | - | RGTO | 1 | 4 | - | - |
[99] | SnO2 | 277 | 100 | Magnetron sputtering | 1 | 4 | - | - |
[100] | ZnO NW: C MF | 280 | - | Chemical electrodeposition | 2 × 10−4 | 0.06 | 11 | 9 |
[101] | CaCu3Ti4O12 | 300 | 450 | Spin coating | 0.05 | 12 | - | - |
[102] | MoS2 | 300 | - | Dip casting | 2 | 100 | - | - |
[103] | SnO2 | 300 | - | Screen printing | 0.1 | 100 | - | - |
[104] | TiO2 | 300 | 30 | Molecular layering | 0.2 | 10 | 42 | 70 |
[105] | Zn1−xAlxO (x = 0.2–10) | 300 | - | Spray pyrolysis | - | - | 170 | 270 |
Medium Temperature Sensors | ||||||||
[106] | TiO2 | 320 | 200 | Dip coating | - | - | - | - |
[107] | ZrO2 | 320 | - | Screen printing | 0.003 | 100 | 15 | - |
[108] | ZrO2:FeO2 (4:1) | 320 | - | Screen printing | 20 | - | 15 | - |
[109] | Nb2O5 | 350 | - | Screen printing | 1 | 20 | - | - |
[109] | Nb2O5—10% TiO2 | 350 | - | Screen printing | 1 | 20 | - | - |
[109] | Nb2O5—5%TiO2 | 350 | - | Screen printing | 1 | 20 | - | - |
[110] | Ce0.771Hf0.229O2 | 400 | 220 | RF magnetron sputtering | 20 | 100 | 37 | 48 |
[110] | Ce0.801Hf0.199O2 | 400 | 220 | RF magnetron sputtering | 20 | 100 | 30 | 33 |
[110] | Ce0.875Hf0.125O2 | 400 | 220 | RF magnetron sputtering | 20 | 100 | 15 | 20 |
[110] | Ce0.888Hf0.112O2 | 400 | 220 | RF magnetron sputtering | 20 | 100 | 8 | 10 |
[110] | Ce0.894Hf0.106O2 | 400 | 220 | RF magnetron sputtering | 20 | 100 | 8 | 10 |
[110] | Ce0.91Hf0.09O2 | 400 | 220 | RF magnetron sputtering | 20 | 100 | 12 | 15 |
[110] | Ce0.939Hf0.061O2 | 400 | 220 | RF magnetron sputtering | 20 | 100 | 15 | 17 |
[111] | CeO2 | 400 | 55 | Sol–gel | 0.4 | 20 | 15 | 28 |
[111] | CeO2—10% ZrO2 | 400 | 55 | Sol–gel | 0.4 | 20 | 15 | 28 |
[111] | CeO2—20% ZrO2 | 400 | 55 | Sol–gel | 0.4 | 20 | 15 | 28 |
[111] | CeO2—30% ZrO2 | 400 | 55 | Sol–gel | 0.4 | 20 | 15 | 28 |
[111] | CeO2—5% ZrO2 | 400 | 55 | Sol–gel | 0.4 | 20 | 15 | 28 |
[112] | Ga2O3+Si | 400 | 170 | RF magnetron sputtering | 9 | 100 | 11 | 70 |
[113] | ZnO | 400 | 80 | Spin coating | 15 | 33 | - | - |
[114] | CeO2 + 10%Y2O3 | 450 | 70 | Dip coating | 1 | 20 | 8 | - |
[114] | CeO2 + 15% Y2O3 | 450 | 70 | Dip coating | 1 | 20 | 8 | - |
[115] | ZnO (nano particles) | 450 | - | EDOC | 1 | 80 | 60 | 150 |
[115] | ZnO (thin layer) | 450 | 250 | PE-MOCVD | 1 | 10 | - | - |
[116] | BaFe0.3Ta0.7O3 | 500 | 3300 | Cold press | 1 | 100 | - | - |
[116] | BaFe0.4Ta0.6O3 | 500 | 3300 | Cold press | 1 | 100 | - | - |
[116] | BaFe0.5Ta0.5O3 | 500 | 3300 | Cold press | 1 | 100 | - | - |
[116] | BaFe0.6Ta0.4O3 | 500 | 3300 | Cold press | 1 | 100 | - | - |
[116] | BaFe0.7Ta0.3O3 | 500 | 3300 | Cold press | 1 | 100 | - | - |
[116] | BaFe0.8Ta0.2O3 | 500 | 3300 | Cold press | 1 | 100 | - | - |
[117] | TiO2 | 500 | 50 | RF magnetron sputtering | 0.4 | 0.6 | - | - |
[118] | TiO2:CNT | 500 | - | Drop casting | 10−3 | - | 5 | - |
[118] | TiO2:Nb | 500 | - | Drop casting | 10−3 | - | 1.5 | - |
[118] | TiO2:Nb, CNT | 500 | - | Drop casting | 10−3 | - | 5 | - |
[113] | ZnO:Cu (10:1) | 500 | 120 | Spin coating | 15 | 33 | - | - |
[118] | TiO2 | 550 | - | Drop casting | 10−3 | - | 1.5 | - |
[119] | Ce0.9Hf0.1O2 | 600 | 20,000 | Screen printing | 9 | 100 | - | - |
[119] | Ce0.9Zr0.1O2 | 600 | 20,000 | Screen printing | 9 | 100 | - | - |
[119] | CeO2 | 600 | 20,000 | Screen printing | 9 | 100 | - | - |
[120] | CeO2 | 600 | 500 | (MO)CVD | - | - | 9 | - |
[120] | CeO2 | 600 | 500 | Magnetron sputtering | - | - | 9 | - |
[121] | CeO2:Hf | 600 | 27,000 | Screen printing | 10−15 | 100 | - | - |
[122] | LaCu0.3Fe0.7O3 | 600 | 20,000 | Screen printing | 0.1 | 100 | 0.001 | 0.01 |
[123] | YBa2Cu3O3 | 600 | 150,000 | Screen printing | 0.009 | 100 | 60 | 180 |
[113] | ZnO:Al (10:1) | 600 | 40 | Spin coating | 15 | 33 | - | - |
[124] | BaFe0.74Al0.01Ta0.25O3 | 650 | - | Screen printing | 0.1 | 100 | - | - |
[61] | LaFeO3 (fibers) | 650 | - | Screen printing | 0.7 | 50 | 20 | 18 |
[61] | LaFeO3 (powder + fibers) | 650 | - | Screen printing | 0.7 | 50 | 10 | 19 |
[61] | LaFeO3 (powder) | 650 | - | Screen printing | 0.7 | 50 | 16 | 23 |
[125] | SrFe0.6Ti0.4O3 | 650 | 30,000 | screen printing | 2.5 | 20 | - | - |
[125] | SrFe0.6Ti0.4O3 | 650 | 10,000 | Screen printing | 2.5 | 20 | - | - |
[126] | SrTi0.4Fe0.6O2.8 | 650 | - | Dipping | 1 | 16 | 25 | - |
[126] | SrTi0.6Fe0.4O2.8 | 650 | - | Dipping | 1 | 16 | 25 | - |
[127] | SrTi0.6Fe0.4O2.8 | 650 | 30,000 | Screen printing | 2.5 | 15 | 5 | 350 |
[128] | CeO2 | 663 | 30,000 | Screen printing | 1 | 100 | 6 | - |
High Temperature Sensors | ||||||||
[129] | Ga2O3 | 700 | 200 | RF magnetron sputtering | 9 | 100 | 20 | 50 |
[122] | La0.05Sr0.95Ti0.65Fe0.35O3 | 700 | 20,000 | Screen printing | 0.1 | 100 | 0.01 | 0.02 |
[130] | Sr(Ti0.4Fe0.6)O3 | 700 | - | Screen printing | 1 | 20 | - | - |
[130] | Sr(Ti0.6Fe0.4)O3 | 700 | - | Screen printing | 1 | 20 | - | - |
[3] | Sr0.95La0.05(Ti0.7Fe0.3)0.95Ga0.05O3 | 700 | 677,000 | Screen printing | - | - | - | - |
[130] | SrFeO3 | 700 | - | Screen printing | 1 | 20 | - | - |
[3] | SrTi0.5Fe0.5O2.8 | 700 | 677,000 | Screen printing | - | - | - | - |
[3] | SrTi0.7Fe0.3O2.8 | 700 | 677,000 | Screen printing | - | - | - | - |
[3] | SrTi0.8Fe0.2O2.8 | 700 | 677,000 | Screen printing | - | - | - | - |
[130] | SrTiO3 | 700 | - | Screen printing | 1 | 20 | - | - |
[3] | SrTiO3 | 700 | 677,000 | Screen printing | - | - | - | - |
[131] | BaFe0.74Al0.01Ta0.25O3 | 750 | 5000 | Powder aerosol deposition | 1 | 100 | - | - |
[132] | LaFe0.7Cu0.3O3 | 750 | 20,000 | Screen printing | 0.1 | 100 | - | - |
[132] | LaFe0.8Cu0.2O3 | 750 | 20,000 | Screen printing | 0.1 | 100 | - | - |
[132] | LaFe0.9Cu0.1O3 | 750 | 20,000 | Screen printing | 0.1 | 100 | - | - |
[132] | LaFeO3 | 750 | 20,000 | Screen printing | 0.1 | 100 | - | - |
[133] | Ce0.8Zr0.2O2 | 800 | - | Screen printing | - | - | 9 | - |
[133] | Ce0.95Zr0.05O2 | 800 | - | Screen printing | - | - | - | - |
[133] | Ce0.9Zr0.1O2 | 800 | - | Screen printing | - | - | - | - |
[133] | CeO2 | 800 | - | Screen printing | - | - | 12 | - |
[134] | CeO2 | 800 | 8000 | Screen printing | 10−20 | 100 | - | - |
[87] | CeO2 | 800 | - | Screen printing | - | - | 0.05 | - |
[44] | CeO2 | 800 | 25,000 | Screen printing | 1 | 100 | 10 | - |
[135] | CeO2 | 800 | 1000 | Magnetron sputtering | 10−8 | 100 | 0.005 | - |
[135] | CeO2 | 800 | 2500 | Magnetron sputtering | 10−8 | 100 | 0.01 | - |
[134] | CeO2—10% ZrO2 | 800 | 8000 | Screen printing | 10−20 | 100 | 0.016 | - |
[134] | CeO2—20% ZrO2 | 800 | 8000 | Screen printing | 10−20 | 100 | 0.009 | - |
[134] | CeO2—5% ZrO2 | 800 | 8000 | Screen printing | 10−20 | 100 | - | - |
[136] | Sr(Ti,Fe)O3:Al2O3 (4:1) | 800 | 7500 | Aerosol deposition | 0.001 | 100 | - | - |
[137] | Sr(Ti0.65Fe0.35)O3 | 800 | 15,000 | Screen printing | - | - | 0.003 | - |
[138] | Ce0.85Zr0.15O2 | 900 | - | Screen printing | - | - | - | - |
[138] | Ce0.95Zr0.05O2 | 900 | - | Screen printing | - | - | - | - |
[138] | Ce0.9Zr0.1O2 | 900 | - | Screen printing | - | - | 16 | 49 |
[139] | CeO2 | 900 | 10,800 | Screen printing | 10−4 | 100 | 11 | 38 |
[138] | CeO2 | 900 | - | Screen printing | - | - | - | - |
[53] | CeO2 | 900 | 10,000 | Screen printing | - | - | 0.012 | 0.001 |
[140] | CeO2 | 900 | - | Screen printing | 2.5 | 6.5 | 0.012 | 0.001 |
[141] | CeO2 | 900 | 10,000 | Screen printing | 2.5 | 6.5 | 0.012 | 0.001 |
[88] | CeO2 | 900 | - | Screen printing | 1 | 100 | - | 11 |
[142] | Ce0.9Zr0.1O2 | 950 | - | Screen printing | 1 | 100 | 13 | 29 |
[142] | CeO2 | 950 | - | Screen printing | 1 | 100 | 21 | 59 |
[143] | Ga2O3 | 1000 | 1000 | RF magnetron sputtering | 0.001 | 100 | 10 | 24 |
[143] | Ga2O3 | 1000 | 106 | Single-crystal growth | 0.001 | 100 | 11 | 17 |
[143] | Ga2O3 | 1000 | 700 | Spin coating | 0.001 | 100 | 12 | 25 |
Thickness | Area | Density | Temperature | Heat Capacity |
---|---|---|---|---|
[cm] | [cm2] | [g/cm3] | [K] | |
0.002 | 1 | 7.6 | 1173 | 390 |
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Bulowski, W.; Knura, R.; Socha, R.P.; Basiura, M.; Skibińska, K.; Wojnicki, M. Thin Film Semiconductor Metal Oxide Oxygen Sensors: Limitations, Challenges, and Future Progress. Electronics 2024, 13, 3409. https://doi.org/10.3390/electronics13173409
Bulowski W, Knura R, Socha RP, Basiura M, Skibińska K, Wojnicki M. Thin Film Semiconductor Metal Oxide Oxygen Sensors: Limitations, Challenges, and Future Progress. Electronics. 2024; 13(17):3409. https://doi.org/10.3390/electronics13173409
Chicago/Turabian StyleBulowski, Wojciech, Rafał Knura, Robert P. Socha, Maciej Basiura, Katarzyna Skibińska, and Marek Wojnicki. 2024. "Thin Film Semiconductor Metal Oxide Oxygen Sensors: Limitations, Challenges, and Future Progress" Electronics 13, no. 17: 3409. https://doi.org/10.3390/electronics13173409