Silicon wafer etching process and composition
View Patent ↗A process for etching silicon wafers using a caustic etchant in the form of an aqueous solution comprising water, a hydroxide ion source, and a chelating agent. The process produces silicon wafers substantially free from diffused metal ions.
1. An etching process for etching silicon from the surface of a silicon wafer, the process comprising contacting the silicon wafer with a caustic etchant in an etching apparatus to remove a layer of silicon from the surface of the silicon wafer, the layer having a thickness of at least about 2.5 μm, the caustic etchant comprising, upon initiation of said contact, water, at least about 40% by weight of a hydroxide ion source, and a metal chelating agent to sequester metal ion impurities in the caustic etchant from the surface of the silicon wafer,
wherein the chelating agent is selected from the group consisting of ethylenediaminetetraacetic acid, diethylenetriaminepentacetic acid, glycolic acid, glycine (oxidase), dimethylgloxime, iminodisuccinic acid, nitrilotriacetic acid, and mixtures thereof,
wherein before initiating said contact, the concentration of free metal ions in the caustic etchant is less than about 1 ppb, and
wherein the concentration of free metal ion impurities in the caustic etchant is maintained at a value of less than about 100 ppb after initiating said contact.
2. The etching process of claim 1 wherein the chelating agent is ethylenediaminetetraacetic acid.
3. The process of claim 1 wherein the caustic etchant comprises, upon initiation of said contact, at least about 100 ppm by weight of free chelating agent or no more than 50 ppb by weight of free metal ions.
4. The etching process of claim 1 wherein the amount of chelating agent combined with the hydroxide ion source is sufficient to form chelates with substantially all of the metal ion impurities present in the hydroxide ion source.
5. The etching process of claim 1 wherein the molar ratio of the chelating agent added to the etching solution relative to the concentration of metal ion impurities introduced to the etchant from the hydroxide ion source is at least about 5:1.
6. The etching process of claim 1 wherein the etchant is periodically replenished by adding water, hydroxide ion source, or metal chelating agent to the caustic etchant.
7. The etching process of claim 1 wherein the hydroxide ion source comprises potassium hydroxide, wherein the concentration of the potassium hydroxide ions in the caustic etchant is about 45 wt %.
8. The etching process of claim 1 wherein prior to initiation of said contact, the concentration of free metal ions is less than about 0.5 ppb.
9. The etching process of claim 1 wherein the layer of silicon removed from the surface of the silicon wafer has a thickness of between about 5.0 μm to about 15 μm.
10. The etching process of claim 1 wherein the caustic etchant comprises at least about 100 ppm of free ethylenediaminetetraacetic acid and at least about 40 wt % of potassium hydroxide.
11. The etching process of claim 1 wherein the hydroxide ion source is selected from the group consisting of potassium hydroxide, ammonium hydroxide, tetramethylammonium hydroxide, sodium hydroxide, lithium hydroxide, cesium hydroxide, and mixtures thereof.
12. The etching process of claim 11 wherein the hydroxide ion source comprises potassium hydroxide.
13. An etching process for etching silicon from the surface of a silicon wafer, the process comprising:
forming an aqueous caustic etchant comprising water, at least about 40% by weight of a hydroxide ion source, and a chelating agent, wherein the etchant further comprises chelates formed between the chelating agent and metal ion impurities in the hydroxide ion source to thereby sequester the metal ion impurities from the surface of the silicon wafer such that the concentration of free metal ions in the caustic etchant is less than about 1 ppb;
introducing the caustic etchant into an etching tank; and
contacting the surface of the silicon wafer with the caustic etchant in the etching tank for a time so as to remove a layer of silicon from the surface of the silicon wafer, the layer having a thickness of at least about 2.5 μm, wherein the concentration of free metal ion impurities in the caustic etchant is maintained at a value of less than about 100 ppb after initiating said contact.
14. The etching process of claim 13 wherein the etchant is periodically replenished by adding water, hydroxide ion source, or metal chelating agent to the caustic etchant.
15. The etching process of claim 13 wherein the layer of silicon removed from the surface of the silicon wafer has a thickness of between about 5.0 μm to about 15 μm.
16. The etching process of claim 13 wherein the molar ratio of the chelating agent added to the etching solution relative to the concentration of metal ion impurities introduced to the etchant from the hydroxide ion source is at least about 5:1.
17. The etching process of claim 13 wherein the caustic etchant comprises at least about 100 ppm of free ethylenediaminetetraacetic acid as the chelating agent and at least about 40 wt % of the hydroxide ion source, the hydroxide ion source comprising potassium hydroxide.