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Terminology
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Wet Etching - Substrates are immersed in a reactive solution (etchant). The layer to be etched is removed by chemical reaction or by dissolution. The reaction products must be soluble and are carried away by the etchant solution. Generally, wet etching is isotropic. Dry Etching - Substrates are immersed in a reactive gas (plasma). The layer to be etched is removed by chemical reactions and/or physical means (ion bombardment). The reaction products must be volatile and are carried away in the gas stream.
Anisotropic Etch - Etch rate is not equal in all directions. Isotropic Etch - Etch rate is equal in all directions. Etching - The process by which material is removed from a surface. Mask - Used to protect regions of the wafer surface. Examples include photoresist, Ni, Cr, or oxide layer. Selectivity - The ratio of etch rate of film to etch rate of substrate or mask. Aspect Ratio - Ratio of depth to width of an etched feature. Plasma - Partially ionized gas containing an equal number of positive and negative charges, as well as some other number of none ionized gas particles. Glow Discharge - Globally neutral, but contains regions of net positive and negative charge. (Many thin film processes utilize glow discharges, but “plasma” and “glow discharge” are often used interchangeably) |
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Oxford Plama Etching Media Center
General Materials
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Aluminum Oxide
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From a quick search, seems to be typically etched in high density plasmas with a chlorine based chemistry - JCW The ETCH Mechanism for Al2O3 in Fluorine and Chlorine Based RF Dry Etch Plasmas Temperature dependence on dry etching of Al2O3 thin films in BCl3/Cl2/Ar plasma Dry Etching of Al2O3 Thin Films in O2/BCl3/Ar Inductively Coupled Plasma |
General - Will it etch
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Materials can generally be etched in the RIEs as long as they form volatile byproducts, or products for which the vapor pressure (at the temperature of the etch) is higher than the pressure of the chamber.
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- Will it etch?
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Materials can generally be etched in the RIEs as long as they form volatile byproducts, or products for which the vapor pressure (at the temperature of the etch) is higher than the pressure of the chamber. Etching is very complicated and this will be massive oversimplification...but generally volatile byproducts can be determined from literature, or as a fallback, the CRC Handbook of Chemistry and Physics Online, (4) Properties of the Elements & Inorganics, Physical Constants of Inorganic Compounds: https://hbcp.chemnetbase.com/faces/documents/04_02/04_02_0001.xhtml. From there, click "Go to Interactive Table", and find products that may be formed (i.e. chloride, fluorides, oxides, depending on the gasses). A compound is deemed volatile if it has a boiling point at a reasonable temperature range for the temperature and pressure of the system. Note that at lower pressures, boiling points decrease, so these are just a good staring point reference. As a VERY general rule of thumb, anything with a boiling point (tbp) < 185 C will be volatile in the ICP RIEs. As an example, aluminum chloride is volatile, and aluminum fluoride and aluminum are not. Neither Copper chloride or copper fluoride is volatile, which is why it is not allowed in any chamber: Byproducts of silicon are very volatile: Many times different fluorides/chlorides of the same material will have drastically different boiling points. It's important to research which will be formed in the plasma. Titanium is a good example of this, with TiCl2 and TiCl3 being non-volatile, and TiCl4 being volatile: are very volatile: Many times different fluorides/chlorides of the same material will have drastically different boiling points. It's important to research which will be formed in the plasma. Titanium is a good example of this, with TiCl2 and TiCl3 being non-volatile, and TiCl4 being volatile: |
A selection of potentially dry-etchable materials
Information from "Physical Constants of Organic Compounds," in CRC Handbook of Chemistry and Physics, 104th Edition (Internet Version 2023), John R. Rumble, ed., CRC Press/Taylor & Francis, Boca Raton, FL. Link.
Note: The presence of a material here does not mean your etch will work or that you should etch this material in a particular system. It is only for reference.
Material | Gas Type | Volatile Etch Byproduct - Name | Volatile Etch Byproduct - Formula | CAS | Boiling Point (ºC) | Selected reaction and solubility notes |
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Ruthenium | Oxygen | Ruthenium tetroxide | RuO4 | 20427-56-9 | 40 | slightly soluble in H2O; reacts with ethanol |
Boron | Fluorine | Trifluoroborane | BF3 | 7637-07-2 | -99.9 | soluble in H2O |
Silicon | Fluorine | Silicon tetrafluoride | SiF4 | 7783-61-1 | -86 | reacts with H2O |
Germanium | Fluorine | Germanium tetrafluoride | GeF4 | 7783-58-6 | -36.5 (sublimation point) | reacts with H2O |
Tungsten | Fluorine | Tungsten hexafluoride | WF6 | 7783-82-6 | 17.1 | reacts with H2O; very soluble in cyclohexane |
Rhenium | Fluorine | Rhenium hexafluoride | ReF6 | 10049-17-9 | 33.8 | soluble in HNO3 |
Molybdenum | Fluorine | Molybdenum hexafluoride | MoF6 | 7783-77-9 | 34.0 | reacts with H2O; very soluble in hexane |
Osmium | Fluorine | Osmium hexafluoride | OsF6 | 13768-38-2 | 47.5 | reacts with H2O |
Vanadium | Fluorine | Vanadium pentafluoride | VF5 | 7783-72-4 | 48.3 | reacts with H2O |
Iridium | Fluorine | Iridium hexafluoride | IrF6 | 7783-75-7 | 53.6 | reacts with H2O |
Arsenic | Fluorine | Arsenic trifluoride | AsF3 | 7784-35-2 | 57.13 | reacts with H2O; soluble in ethanol |
Platinum | Fluorine | Platinum hexafluoride | PtF6 | 13693-05-5 | 69.1 | |
Rhenium | Fluorine | Rhenium heptafluoride | ReF7 | 17029-21-9 | 73.7 | |
Selenium | Fluorine | Selenium tetrafluoride | SeF4 | 13465-66-2 | 101.6 | reacts with H2O; very soluble in ethanol |
Tin | Fluorine | Stannic chloride | SnCl4 | 7646-78-8 | 114.15 | reacts with H2O; soluble in ethanol and acetone |
Chromium | Fluorine | Chromium(V) fluoride | CrF5 | 14884-42-5 | 117 | reacts with H2O |
Antimony | Fluorine | Antimony pentafluoride | SbF5 | 7783-70-2 | 141 | reacts with H2O |
Tantalum | Fluorine | Tantalum pentafluoride | TaF5 | 7783-71-3 | 229.5 | soluble in H2O and ethanol |
Niobium | Fluorine | Niobium pentafluoride | NbF5 | 7783-68-8 | 239 | reacts with H2O |
Boron | Chlorine | Trichloroborane | BCl3 | 10294-34-5 | 12.5 | reacts with H2O and ethanol |
Silicon | Chlorine | Silicon tetrachloride | SiCl4 | 10026-04-7 | 57.65 | reacts with H2O |
Germanium | Chlorine | Germanium tetrachloride | GeCl4 | 10038-98-9 | 86.55 | reacts with H2O; soluble in ethanol |
Arsenic | Chlorine | Arsenic trichloride | AsCl3 | 7784-34-1 | 130 | |
Titanium | Chlorine | Titanium tetrachloride | TiCl4 | 7550-45-0 | 136.45 | reacts with H2O; soluble in ethanol |
Vanadium | Chlorine | Vanadium tetrachloride | VCl4 | 7632-51-1 | 151 | reacts with H2O; soluble in ethanol |
Aluminum | Chlorine | Aluminum trichloride | AlCl3 | 7446-70-0 | 180 (sublimation point) | |
Gallium | Chlorine | Gallium trichloride | GaCl3 | 13450-90-3 | 201 | |
Tantalum | Chlorine | Tantalum pentachloride | TaCl5 | 7721-01-9 | 239 | reacts with H2O; soluble in ethanol |
Niobium | Chlorine | Niobium pentachloride | NbCl5 | 10026-12-7 | 247.4 | reacts with H2O |
Iron (maybe) | Chlorine | Iron(III) chloride | FeCl3 | 7705-08-0 | 316 | soluble in ethanol and acetone |
A selection of likely non-dry-etchable materials
Notable materials that can be deposited at Birck but not chemically dry etched at Birck:
Ag, Au, Co, Cu, Er, ITO (Indium), Mg, Mn, Ni, Pd, Sc
All of these except Au may be etched (with ion milling, a physical process rather than chemical) in the AJA ICP Argon Ion Mill Etcher.
Specific Materials
Aluminum Oxide
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From a quick search, seems to be typically etched in high density plasmas with a chlorine based chemistry - JCW The ETCH Mechanism for Al2O3 in Fluorine and Chlorine Based RF Dry Etch Plasmas Temperature dependence on dry etching of Al2O3 thin films in BCl3/Cl2/Ar plasma Dry Etching of Al2O3 Thin Films in O2/BCl3/Ar Inductively Coupled Plasma |
Mounting
Small samples may be mounted to carrier wafers with Crystalbond 555 HMP. More info here: A09_18.pdf and 821-1-2-3-4-6-TN.pdf
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