# US 5,348,627 A · Process and system for the photoelectrochemical etching of silicon in an anhydrous environment > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 5,348,627 A - Document ID: US5348627A - Status: Granted - Kind: A - Application number: 08/061,090 - Filed: 1993-05-12 - Granted: 1994-09-20 - Earliest claimed: 1993-05-12 - Assignees: Georgia Tech Reserach Corporation - Inventors: Eric K. Propst; Paul A. Kohl - Web page: https://patentgrep.com/patent/US5348627A ## CPC - H10P 50/613: {of Group IV materials} - C25F 3/12: of semiconducting materials - C25F 3/14: locally - H10P: GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10 - C25F: PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR ## Abstract The photoelectrochemical oxidation and dissolution of silicon (Si) is performed in the absence of water and oxygen. Etch rates and photocurrents in an anhydrous HF-acetonitrile (MeCN) solution are directly proportional to light intensity up to at least 600 mW/cm.sup.2, producing a spatially selective etch rate of greater than 4 .mu.m/min. Four electron transfer reactions per silicon molecule occur with a quantum yield greater than 3.3 due to electron injection from high energy reaction intermediates. Further, the electrochemical oxidation of p-doped silicon in HF-MeCN results in the formation of porous silicon which electroluminescence in an aqueous solution. In an aprotic electrolyte, where tetrabutylammonium tetrafluoroborate (TBAFB) is used as both the supporting electrolyte and source of fluoride in MeCN, photo-induced etching of n-doped silicon occurs at quantum efficiency of 1.9. This indicates that the oxidation and dissolution mechanism of Si in MeCN can occur without protons. ## Claims ### Claim 1 A photoelectric etching process for high speed etching of silicon which is proportional to light intensity, comprising the steps of: placing a silicon semiconductor in an electrolytic solution having fluoride, said electrolytic solution being substantially devoid of oxygen-containing species that react with said silicon semiconductor to form oxide compounds; applying a potential to said semiconductor which is between the maximum potential of the valence band of said semiconductor and the minimum potential of the conductor band of said semiconductor; illuminating a surface part of said semiconductor to be etched with radiation of sufficient energy to produce holes in said valence band. ### Claim 2 (depends on 1) The process of claim 1, wherein said silicon is p-doped. ### Claim 3 (depends on 1) The process of claim 1, wherein said silicon is n-doped. ### Claim 4 (depends on 1) The process of claim 1, wherein said silicon semiconductor is amorphous. ### Claim 5 (depends on 1) The process of claim 1, wherein said silicon semiconductor is crystalline. ### Claim 6 (depends on 1) The process of claim 1, wherein said silicon semiconductor is polycrystalline. ### Claim 7 (depends on 1) The process of claim 1, wherein said electrolytic solution has less than about 50 ppm of water. ### Claim 8 (depends on 1) The process of claim 1, further comprising the step of creating a porous surface in said silicon semiconductor. ### Claim 9 (depends on 1) The process of claim 1, wherein said silicon semiconductor comprises a silicon oxide (SiO.sub.x) layer exposed to said electrolytic solution prior to said illuminating of said surface part. ### Claim 10 (depends on 1) The process of claim 1, wherein said fluoride comprises free-flowing ions within said electrolytic solution. ### Claim 11 (depends on 1) The process of claim 1, wherein said fluoride is a complexed material which decomposes within said electrolytic solution. ### Claim 12 (depends on 1) The process of claim 1, wherein said electrolytic solution comprises any fluoride source in the group consisting of hydrofluoric acid (HF), fluoroborate (BF.sub.4.sup.-), tetrabutylammonium tetrafluoroborate (TBAFB), aluminum hexaflouride (AlF.sub.6.sup.3-), and hydrogen difluoride (HF.sub.2.sup.-). ### Claim 13 (depends on 1) The process of claim 1, wherein said electrolytic solution comprises any supporting electrolyte in the group consisting of tetrabutylammonium perchlorate (C.sub.16 H.sub.36 NClO.sub.4) and tetramethylammonium perchlorate (C.sub.4 H.sub.12 NClO.sub.4). ### Claim 14 (depends on 1) The process of claim 1, wherein said electrolytic solution comprises any anhydrous solvent in the group consisting of acetonitrile (CH.sub.3 CN), dimethyl formamide (DMF), dimethyl sulfoxide (DMSO), propylene carbonate (C.sub.3 O.sub.3 H.sub.6), and methylene chloride (CH.sub.2 Cl.sub.2). ### Claim 15 (depends on 1) The process of claim 1, wherein said radiation comprises photon energy greater than 1.12 electron volts. ### Claim 16 (depends on 1) The process of claim 1, further comprising the steps of selectively etching a particular position on said semiconductor by selectively applying said radiation to said particular position. ### Claim 17 (depends on 1) The process of claim 1, further comprising the step of varying the rate of etching by varying the intensity of said radiation. ### Claim 18 A photoelectrochemical etching process, comprising the steps of: placing a silicon semiconductor in an electrolytic solution, and having fluoride, said electrolytic solution being substantially devoid of oxygen-containing species that react with said silicon semiconductor to form oxide compounds; applying a potential to said semiconductor which is between the maximum potential of the valence band of said semiconductor and the minimum potential of the conduction band of said semiconductor. ### Claim 19 (depends on 18) The process of claim 18, wherein said silicon semiconductor is p-doped. ### Claim 20 (depends on 18) The process of claim 18, wherein said silicon semiconductor is n-doped and further comprising the step of illuminating a surface part of said semiconductor to be etched with radiation of sufficient energy to produce holes in said valence band. ### Claim 21 A photoelectrochemical etching process for high speed etching of silicon which is proportional to light intensity, comprising the steps of: placing a silicon semiconductor in an electrolytic solution having fluoride, said electrolytic solution being substantially devoid of oxygen-containing species that react with said silicon semiconductor to form oxide compounds; applying a potential to said semiconductor which is between the maximum potential of the valence band of said semiconductor and the minimum potential of the conduction band of said semiconductor; illuminating a surface part of said semiconductor to be etched with radiation of sufficient energy to produce holes in said valence band; and preventing oxidation of said silicon semiconductor within said electrolytic solution during production of said holes in said valence band.