A method of drying silcion substrates

Abstract: A method of drying a substrate surface (1), comprising: dipping the substrate into a liquid bath (2); separating the substrate from the liquid bath (2), whereby the liquid of the liquid bath (2) comprises an aqueous HF solution (3), the substrate surface being hydrophobic upon separation from the liquid bath, the substrate being separated from the bath at a rate that permits the bath liquid to drain from the hydrophobic surface of the substrate to produce a dry substrate; and that a gas comprising an O 2 /O 3 mixture that forms a hydrophilic surface on the substrate is directed over the surface of the substrate (1) after separating the substrate (1) from the liquid bath.

Description: The invention relates to a procedure for cleanly drying surfaces of materials, such as semiconductors, ceramics, metals, glasses, plastics and, in particular, silicon wafers and laser disks, wherein a substrate is dipped in a liquid bath and its surfaces are dried as it is separated from the liquid, such as by directing a gas over the liquid surface, the gas being soluble in the liquid and lowering the surface tension of the liquid. When producing microelectronic devices, silicon, which is usually in the form of monocrystalline wafers, is badly contaminated or damaged as a result of cutting, polishing, varnishing or similar procedures. For that reason, the silicon is usually cleaned in multiple steps, which are usually performed in liquid baths. The different chemical treatments are usually selectively effective for different types of contaminants (i.e., particles, organic coatings, functional organic Si-CR 3 groups or groups of metals, which show similar chemical behavior with each other). The chemical treatments are typically separated by rinsing steps to make the silicon surface free of chemicals and to avoid mixtures of chemicals. Superior water purity is important to minimize the risk of recontamination by metals at pH neutrality. The silicon is at risk of being recontaminated by contaminants, such as particles or metals, of a type that was removed during a prior phase of the cleaning sequence because of contamination present in subsequent rinsing steps or in chemicals, such as stabilizers for H 2 O 2 , used in the subsequent cleaning steps. The total cleaning sequence is finished by a drying step. Many different drying procedures for silicon surfaces are known. These drying procedures include dry spinning by centrifugal forces and drying by solvents like trichlorethanol or methylenechloride. Furthermore, there are drying techniques using hot air, hot water or isopropyl alcohol. One disadvantage of these popular drying procedures is that immense stress is put on the silicon wafer by high mechanical forces. Accordingly, the danger of damaging the edges is high and, moreover, particle generation caused by movements of the silicon wafers relative to the carrier, is possible. In an extreme case, especially with thinner wafers or after thermal treatments, this stress can result in breaking of the wafer, thus destroying the complete drying object and contaminating the surrounding wafers with particles. The drying procedures can also lead to high operating costs due to the use of expensive chemicals, the disposal of which is necessary. Finally, one disadvantage of all the procedures mentioned above is the danger of metallic recontamination of the cleaned surfaces during the drying process. Patent Abstracts of Japan, vol. 012, no. 049 (E -582), JP 62-198 127 A discloses a cleaning and drying method in which a wafer is dipped into a fluoric acid liquid in a first step and into a cleaning water tank in a second step. Patent Abstracts of Japan, vol. 017, no. 203 (E-1354), JP 04-346 431 A discloses a cleaning method in which ammonia water and ozone containing oxygen are jetted together over a substrate surface. The underlying object of the present invention is therefore to provide a method for drying substrate surfaces according to the preamble of claim 1 which guarantees the maintenance of the degree of purity of the cleaned surfaces and the effective drying of the substrate with a simultaneous cleaning of the surface in a very quick but very effective way. This object is achieved by a method for drying substrate surfaces according to claim 1. Advantageous developments of the present invention are specified in the subclaims. The invention provides procedures for drying surfaces. The procedures of the invention guarantee the purity of the cleaned surfaces and the effective drying of the surface. The invention is applicable to surfaces of many materials, including semiconductors, metals (particularly aluminum), plastics, glasses, and ceramics. The invention is particularly useful for drying and cleaning laser discs and semiconductor silicon wafers. It is to be understood that the invention is, however, useful in drying substrates of any adequate physical form, especially in the form of wafers, plates or discs. The invention relates to a method of drying a substrate surface wherein the substrate is dipped into and subsequently separated from a liquid bath and a gas mixture is directed over the surface of the substrate after separating the substrate from the liquid bath. For example, a semiconductor silicon wafer can be dipped into an aqueous HF solution with a concentration of between .001 % and 50% and a gas mixture comprising O 2 /O 3 is directed over the silicon wafer surface upon removal from the aqueous HF solution. The invention is now described by reference to the figures in which: Fig. 1 shows the removal of a silicon wafer from a bath with an aqueous HF solution by adding an O 2 /O 3 gas mixture. Fig. 2 shows the removal of a silicon wafer from a bath with an aqueous HF solution without adding O 2 /O 3 . Fig. 3a-3c shows the chemical processes of the cleaning or hydrophilizing of the silicon surface using the procedure according to the invention. The gas mixture added over the surface of the HF solution contains O 2 /O 3 , and nitrogen or a similar gas can be used as a carrier gas. The carrier gas should be chemically inactive with the O 2 /O 3 component of the gas mixture. Suitable gases include air (N 2 , O 2 , CO 2 ), CO 2 , He, Ne, Ar, Kr, Xe and Rn. The share of O 3 in the O 2 /O 3 gas mixture is preferably I mg up to 0.5 g per liter of O 2 /O 3 gas mixture. The gas mixture can consist of only O 2 /O 3 . If a carrier gas is used, however, the share of the O 2 /O 3 gas mixture is preferably greater than 10%. The silicon atoms active on the surface are changed into Si-H and Si-F bondings. The resulting hydrophobic surface character allows drying even at very low temperatures. The pH value < 7 of an aqueous HF solution during drying prevents metallic recontamination. Furthermore, the HF removes metal contamination in the liquid bath, which exists in an oxidized (= ionized) form like Fe, and keeps it in the liquid as metal fluoride complexes. If ozone is added over the surface of the aqueous HF solution in accordance with the first embodiment of the invention, it dissolves partly in the aqueous HF solution and transfers covalently bonded Si-Me combinations to ionic combinations, Me designing metals. Moreover, when dissolving ozone in the aqueous HF solution, the MARANGONI effect occurs according to the ozone concentration. The silicon surface comes out hydrophilicly from the aqueous HF solution, meaning that it is wettable with water or aqueous solutions. With the procedure according to the invention, the gas mixture containing O 2 /O 3 is directed over the silicon surface only after its drying. Thus, making the silicon surface hydrophilic takes place only after the drying process. The advantage of this procedure is the very quick drying of the silicon. According to the invention, separating the silicon from the aqueous HF solution can be done either by lifting the silicon out of the HF solution or by down flowing the HF solution, or by a combination of both. The relative speed of separation between the silicon and the surface of the solution is about 0.1 to about 20 cm/sec and preferably about 0.5 to about 3.0 cm/sec, since the drying can be done very quickly. Furthermore, the aqueous HF solution can contain additives like organic compounds (such as alcohol, isopropyl alcohol and EDTA), organic acids (such as formic acid, acetic acid and citric acid), acids (such as HCl, H 3 PO 4 , HClO, HClO 2 , HClO 3 and HClO 4 ), surfactants (cationic or anionic) or solid additives like NH 4 F, provided they do not destroy the effects explained above and effective cleaning and drying of the silicon remain. Acids are added in the amount of 0% to about 50% weight, organic compounds are added in the amount of 0% to about 80% weight, surfactants are added in the amount of 0% to about 5% weight and solids are added in the amount of 0% to about 50% weight. Specific applications are possible, with which a stronger than mentioned effect or better cleaning and drying can be achieved by adding one or more acids to the aqueous HF solution. Preferred acids are HCl, H 2 SO 4 and H 3 PO 4 or mixtures thereof. However, any one or more of the acids described above can be added using the ranges listed above. Preferred mixtures of acids are HF/HCl, HF/HCl/H 2 SO 4 , HF/H 3 PO 4 , HF/H 3 PO 4 /HCl, HF/H 3 PO 4 /H 2 SO 4 and HF/H 3 PO 4 /HCl/H 2 SO 4 . Otherwise the HF solution can be skimmed out to a concentration of c=0 (pure water). Furthermore, enriching or saturating the aqueous HF solution with ozone before dipping the silicon is an advantage, which results in cleaner silicon surfaces. Multiple mono layers of silicon are oxidized and then eroded. Thus, the cleaning is effective even for metals closely beneath the surface (subsurface contamination). The HF-concentration is preferably between about .01 % and about .1 %. The range can be 0% (pure water) to 90% (concentrated HF). A stable ozone content comparable with a saturated status can be achieved by continuously supplying the HF solution tank with an O 2 /O 3 gas stream (for example, "bubbling"). Other parameters like temperature, concentration of HF and adding of additives (mainly surfactants) have an influence on the ozone content and the saturated status. A successful cleaning and drying procedure can be achieved with a continuous O 2 /O 3 gas stream. In a preferred embodiment, the gas stream is in the range of about 50 to about 300 1/h and the ozone generation is in the range of about 10 to about 50 g/h. An estimated value of the ozone concentration in the HF solution is in the range of 10 to 80 mg/l. Another advantage of the invention is that the procedure can be carried out in a temperature range between 0 and 100 degrees Celsius, the preferred temperature being 20 to 50 degrees Celsius. Example Fig. 1 shows a silicon wafer 1, which is slowly removed from a bath 2 with an aqueous HF solution 3 after being dipped completely into the bath. The direction of removal of the silicon wafer 1 is shown by the arrow pointing vertically upwards over the silicon wafer. The speed of removal is preferably about 3 to about 10 millimeters per second. The arrow diagonal to the silicon wafer surface shows the simultaneous adding of the O 2 /O 3 gas mixture over the aqueous solution near the wafer surface. When slowly removing the silicon wafer 1 from the aqueous HF solution 3, the surface of the aqueous HF solution sticks to the silicon surface, which is bent upwards. This is shown by an upwards curve of the liquid surface at the area between the surface of the solution and the surface of the silicon wafer 1. At point A more ozone is dissolved than at the other places of the surface of the solution, i.e., shown by point B. Since at point A there is a higher ozone concentration than at point B, there is a lower surface tension at point A than at point B. This gradient in the surface tension causes the aqueous HF solution to run from point A to point B, drying the silicon surface. Fig. 2 shows a silicon wafer 1, which is slowly removed from a bath 2 with an aqueous HF solution 3 after having been dipped completely into the bath. The direction of removal is shown by the arrow pointing vertically upwards over the silicon wafer. Because of the hydrophobicity of the silicon wafer, the surface of the liquid is bent downwards at the silicon surface. The hydrophilizing of the silicon surface by ozone takes place only after the drying process is finished. Fig. 3a shows that the HF solution in the aqueous solution guarantees the eroding of the silicon oxide layers into which metal ions like Fe may be embedded. Metal contamination like Cu, which are directly connected to an Si atom, are removed by a Redox process, as shown in Fig. 3b. Fig. 3c shows how the ozone causes the silicon surface to oxidize. Thus, the silicon leaves the drying bath perfectly clean, hydrophilic and dry. Other embodiments of the invention will be apparent to one of ordinary skill in the art. Although the preferred embodiments and examples describe the drying of silicon wafers, the invention is applicable to substrates of many materials in addition to silicon, such as metals, plastics, glasses, and ceramics. The term "substrate" is not limited to substrates that support electronic circuitry, but applies to any object supporting a surface, i. e. having any adequate physical form, such as the form of wafers, plates or discs. The invention is not limited to the specific examples and is defined by the following claims.

Claims: A method of drying a substrate surface (1), the substrate comprising silicon, comprising: dipping the substrate into a liquid bath (2) comprising an aqueous HF solution (3), separating the substrate from the liquid bath (2), the substrate surface being hydrophobic upon separation from the liquid bath, characterized in that the substrate is separated from the bath, whereby the relative speed of separation between the substrate (1) and the surface of the aqueous HF solution (3) is between 0.1 cm/sec and 20 cm/sec, permitting the bath liquid to drain from the hydrophobic surface of the substrate to produce a dry substrate; and that a gas comprising an O 2 /O 3 mixture that forms a hydrophilic surface on the substrate is directed over the surface of the dry substrate (1) after separating the substrate (1) from the liquid bath. The method according to claim 1, characterized in, that the relative speed of separation between the substrate (1) and the surface of the aqueous HF solution (3) is between 0.5 cm/sec and 3.0 cm/sec. The method according to claim lor 2, characterized in, that the liquid of the liquid bath (2) comprises an aqueous HF solution (3) with a concentration between .001% and 50%. The method according to claim 3, characterized in, that the HF concentration in the aqueous solution is between .01% and 0.1%. The method according to one of the claims 1 to 4, characterized in, that the substrate comprises a laser disk. The method according to anyone of claims 1 to 5, characterized in, that the substrate (1) and the liquid bath (3) are separated by lifting the substrate out of the liquid bath. The method according to anyone of claims 1 to 6, characterized in, that the substrate (1) and the liquid bath are separated by draining the liquid from the bath (2). The method according to anyone of the preceding claims, characterized in, that the liquid bath (3) contains at least one additive selected from the group consisting of acids, organic acids, surfactants and solid additives. The method of claim 8, characterized in, that said at least one additive is an acid selected from the group consisting of HCl, H 3 PO 4 , H 2 SO 4 , HClO, HClO 2 , HClO 3 and HClO 4 . The method of claim 8, characterized in, that said aqueous solution contains a mixture of acids selected from the group consisting of HCl/H 2 PO 4 , H 3 PO 4 /HCl, H 3 PO 4 /H 2 SO 4 and H 3 PO 4 /HCl/H 2 SO 4 . The method of anyone of claims 8 to 10, characterized in, that said acid is added to give a concentration of up to 50% by weight. The method of claim 8, characterized in, that said at least one additive is an organic acid selected from the group consisting of formic acid, acetic acid and citric acid. The method of claim 12, characterized in, that said organic acid is added to give a final concentration of up to 80% by weight. The method of claim 8, characterized in, that said surfactant is added to give a final concentration of up to 5% by weight. The method of claim 8, characterized in, that said solid additive is NH 4 F. The method of claim 8, characterized in, that said solid additive is added to give a final concentration of up to 50% by weight. The method according to anyone of claims 1 to 20, characterized in, that the method is carried out at a temperature between 0 and 100 degrees Celsius. The method according to claim 21, characterized in, that the method is carried out at a temperature between 20 and 50 degrees Celsius. The method according to anyone of the preceding claims, characterized in, that the proportion of O 3 in the O 2 /O 3 gas mixture is between 1 mg and 0.5 g per liter of O 2 /O 3 gas mixture.

Inventors: HERRMANNSDOERFER DIETER, SCHELLENBERGER WILHELM, HERRMANNSDOERFER, DIETER, SCHELLENBERGER, WILHELM, Herrmannsdörfer, Dieter 
Applicants: ICTOP ENTWICKLUNGS GMBH
Application year: 1996
Main classification: H01L21
IPC codes: H01L21