TW492102B - Wet processing methods for the manufacture of electronic components using liquids of varying density - Google Patents

Abstract

The present invention is directed to wet processing methods for the manufacture of electronic component precursors, such as semiconductor wafers used in integrated circuits. More specifically, this invention relates to methods of manufacturing electronic component precursors using liquids of varying temperature.

Description

492102 A7 _____B7 _ V. Field of the Invention The invention relates to a wet processing method for manufacturing semiconductor wafer electronic components and electronic component precursors used in integrated circuits. More specifically, the present invention relates to a method for treating electronic element precursors using, for example, liquids of different densities. BACKGROUND OF THE INVENTION Wet processing is widely used in the manufacture of integrated circuits, and typically contains electronic component precursors such as semiconductor wafers or flat boards. Generally, the electronic component precursor is placed in a washing tank or container and then contacted with a series of reactive chemical treatment liquids and washing liquids. The processing liquid can be used without limitation in the etching, photoresist etching stripping, pre-diffusion cleaning and other electronic component precursor cleaning steps. See, for example, U.S. Patent Nos. 4,577,650; 4,740,249; 4,738,272; 4,856,544; 4,633,893; 4,778,532; 4,917,123; and EP ◦ 0 233 184, assigned to a trustee, And Burkman et al., "Wet Chemical Process-Aqueous Cleaning Processes" in Handbook of Semiconductor Wafer Cleaning Technology (Editor of Werner Kern, Noyes Publication Parkridge, New Jersey 1993), pages 111-151, the disclosure of which is fully incorporated For reference purposes. In the typical wet processing technology, the electronic component precursor is processed in a full-flow container (a container closed to the environment), a single tank, a small wet workbench, a traditional wet workbench, or a washing tank. In a typical wet processing technique, the precursor of the electronic component is exposed to a reactive chemically treated liquid with 3 ----------------- (Please read the precautions on the back before (Fill in this page) ja · 丨 line · This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) 492102 A7 ___ B7___ 5. Description of the invention (Y) Remove (ie clean) the electronic component precursor Contaminants, or etched parts of the surface. After this cleaning or etching is performed, chemicals will adhere to the surface or surfaces of the electronic component precursor. Usually the attached chemical may be removed before the electronic component precursor is treated with a reactive chemical treatment liquid so that the chemical residue does not contaminate the next reactive chemical treatment liquid. Traditionally, attached chemicals are removed by rinsing with deionized (DI) water. After the chemical processing step is completed, the wafer is usually dry. Drying of electronic component precursors can be accomplished using a variety of methods. The goal is to ensure that no contaminants are generated during the drying process. Drying methods include evaporation, centrifugal force of a rotary dryer, steam or chemical drying of wafers, including, for example, the methods and devices disclosed in U.S. Patent Nos. 4,778,532 and 4,911,761. As a reference. The most important consideration for an effective wet processing method is that the wafers produced by this method are ultra-clean (i.e., have the least amount of particulate contamination and the least amount of chemical residues). Some techniques use deionized water after each chemical treatment step to remove particulate matter and chemical residues. Traditionally, electronic component precursors are delivered from a reaction chamber containing chemicals to a decontamination tank containing deionized water. In addition, the electronic component precursor may be left in the reaction chamber containing chemicals, and the chemicals may be removed from the reaction chamber by introducing deionized water into the reaction chamber. Deionized water can be introduced into the reaction chamber from the top or bottom of the reaction chamber. See, for example, U.S. Patent Nos. 4,778,532 and 4,984,597 and 5,826,601, the disclosure of which 4 ν This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (Please read the notes on the back first (Fill in this page again)

492102 A7 ____ Β7 ____ V. Description of the Invention ()) All of them are incorporated here for reference. In this reaction chamber, the electronic component precursors are stationary and chemicals are removed by deionized water. Usually water is introduced from the bottom of the tank, and chemicals are discharged from the top of the tank. However, it may also introduce water from the top of the tank and discharge chemicals from the bottom of the tank. Traditionally, the chemicals in the reaction chamber have the same temperature as the deionized water used for removal, which tends to cause intimate mixing of chemicals and deionized water. This will cause the chemicals to be continuously diluted by water, which is undesirable because recycling chemical solutions is better for the environment and more cost effective. In addition, rinsing takes longer when mixing occurs than when no mixing occurs. If only minimal mixing occurs, the chemical solution will be quickly removed from the container, just like plug-flow techniques. If mixing takes place continuously, decanting will take longer and is theoretically closer to the CSTR (Continuous Stirred Tank Reactor) model. Verhaverbeke, S., McConnell, C., Parker, JW and Bay, S. Scientific Rinsing and Drying on Macro and Microscale (SPWCC, 1996) at the Semiconductor Pure Water and Chemicals Conference (Balazs Analytical Laboratory in Santa Clara, California) (March 4-7, 1996), its disclosure is fully incorporated here for reference. In other examples, one cleaning solution can directly replace another cleaning solution without the need for an intermediate deionized water step. It is important to minimize the mixing of the two solutions. Therefore, there is a need in the art for a simple and efficient method that allows a processing solution to be efficiently removed by another during the processing of a wet electronic component precursor, while providing an environmentally safe and economical method. Its 5 paper sizes are in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page)

492102 A7 ____B7 _ V. Description of Invention ($) • It is found that the selective control of the density of the processing liquid during the wet processing technology can greatly affect the removal efficiency. Summary of the Invention The present invention relates particularly to a wet processing method for manufacturing electronic components and electronic component precursors such as semiconductor wafers used in integrated circuits. More specifically, the present invention relates to a method for processing electronic component precursors such as wet processing techniques using liquids having different densities. It has been found that by selectively controlling the density of the processing liquid used in the wet processing technology, the dilution of the first chemical by the second chemical can be minimized during, for example, the direct-removal technology. Because mixing is minimized, processing efficiency can be optimized. Therefore, controlling density can save time, money, and increase throughput. Generally, according to the method of the present invention, an electronic component precursor is placed in a reaction chamber; a reactive chemical treatment liquid is introduced into the reaction chamber; the electronic component precursor is exposed to the chemical treatment liquid for a period of time; and then the second chemical The treatment liquid or the rinse liquid is introduced into the reaction chamber to remove the first chemical treatment liquid, wherein the second chemical treatment liquid and / or the rinse liquid has a density different from that of the first reactive chemical treatment liquid. Specifically, the density of the two solutions can be controlled by temperature and / or the concentration of the solution. It has been found that when a closed and / or hydraulic full reaction chamber is used (such as disclosed in U.S. Patent No. 4,778,532), in which a washing liquid, such as deionized water, is introduced from the bottom to remove the reactive chemical solution, compared to The removed chemical is at least 0.001 g / cm3 (that is, about 5 ° C cooler) in a washing solution. It is more efficient to remove the chemical; in general, as long as there is no clear _ 6 (please read the back first) (Notes for filling in this page)

This paper size applies to China National Standard (CNS) A4 specifications (210 X 297 mm) 492102 A7 _____B7_ V. Description of the invention (^) • To reduce the flow rate, water should be as heavy as possible. When water comes in contact with lighter treated liquid At the same time, the introduction of a denser liquid from the bottom of the container can minimize the mixing of the chemicals in the tank and the cleaning liquid used for removal, thereby making the removal more efficient. More generally, a denser liquid system It is introduced from the bottom, and the less dense solution is removed from the top. Therefore, one aspect of the present invention relates to a method for manufacturing a precursor of an electronic component; it comprises a) placing an electronic component precursor on a substrate having a top and a bottom; In the reaction chamber; b) introducing the first reactive chemical processing liquid into the reaction chamber; c) exposing the electronic component precursor to the first reactive chemical processing liquid for a period of time; d) introducing the second processing liquid into the reaction chamber To directly remove the reactive chemical treatment liquid, wherein the second treatment liquid system is introduced into the reaction chamber from the bottom of the reaction chamber and has a higher level than the first reactive chemical treatment liquid Degrees (i.e., denser 0.001 g / cc); and e) removing the second treatment liquid from the reaction chamber; wherein steps b) to d) may be repeatedly performed. On the other hand, if the cleaning solution water (the most commonly used cleaning solution in deionized water) is introduced from the top of the reaction chamber, use a chemical that is at least less dense than 0.001 g / cm3 (that is, hotter 5 ° C) washing solution is more efficient; usually, the water should be as light as possible without significantly reducing the flow, otherwise it will affect the method in a harmful way. Therefore, another aspect of the present invention relates to a method for manufacturing an electronic component precursor, comprising: a) placing the electronic component precursor in a reaction chamber having a top and a bottom; b) subjecting a first reactive chemical treatment The liquid is introduced into the reaction chamber; c) the precursor of the electronic component is exposed to the first reactivity 7 The paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) ---------- ------- (Please read the precautions on the back before filling this page) Order;;. 492102 A7 ______B7__ V. Description of the invention (L) Chemical treatment liquid for a period of time; d) Introducing the second treatment liquid into the reaction The reaction chemical treatment liquid is directly removed from the chamber, wherein the second treatment liquid system is introduced into the reaction chamber through the top of the reaction chamber, and has a lower density than the first chemical treatment liquid (that is, at least less dense than about 0). .OOi g / cm3): and e) removing the second treatment liquid from the reaction chamber; wherein steps b) to d) can be repeated. _ When implementing the method of the patented invention, electronic component precursors should generally be washed with a processing liquid of about 1-5 container volume, preferably about 2-3 container volume, which may be less dense (i.e. at least About 0.001 g / cm3) or denser (ie at least about 0.001 g / cm3), depending on whether the liquid is introduced from the top or the bottom of the container, as explained above. For example, if the method container has a volume of 5 gallons, it is better to rinse with a HM 5 gallon of removal liquid having a different density as described herein. Since then, it has been found that density is less important and that continued washing or processing at any density may be effective. During wet processing, electronic component precursors can be exposed to a variety of reactive and non-reactive chemically treated liquids. The number and type of treatment fluids used will depend on the particular end result desired (ie, whether it is cleaned, etched, and / or peeled). After the last step, the liquid system is removed from the reaction chamber and the electronic component precursor is dried. Brief Description of the Drawings Figure 1 is a graphical depiction of a typical concentration distribution in a CFM Full-Flow ™ container during a complete etch cycle. During the injection phase, chemicals are injected into the water that is flowing into the container. In the soaking period, the chemicals are still in the capacity. 8 The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) ---- 1 ------------ ( (Please read the precautions on the back before filling this page) Order · ά # · 492102 A7 ___E7___ 5. In the description of the invention (^). The exposure time is the total time that the wafer is exposed to chemicals (that is, the injection time and soaking temperature) Phase). In the removal phase, the plutonium washing system is used to remove the uranium etchants from the container. Because of the nature of the method's first-in (nrst-〇ut) 'This phase is injection Mirror image of the stage. For example, when the bottom of the wafer is first exposed to the uranium etchant during the injection process, it is then cleaned first, so the wafer surface is uniformly exposed to the uranium etchant. Figure 2 Series No picture, it shows that the number of particles increased during wafer processing using the standard cleaning technology or the cleaning technology of the present invention is based on the method listed in Example 1 below. Figure 3 is A graphical depiction of the density distribution of water versus temperature. Detailed description of the invention Terms used herein '' Reactive treatment liquid π, π reactive chemical treatment liquid ", " treatment liquid ", " chemical liquid π, " active chemical " or " reactive chemical treatment liquid " The liquid exposed during the wet processing technology performs certain functions on the surface of the electronic component. For example, the liquid can be active to move contaminants such as particles, metals, or organic materials from the surface of the electronic component In addition, or the liquid may have some activity to etch the surface of the electronic component, and have the activity to grow the oxide layer on the surface of the electronic component. An example of this reactive chemical treatment liquid is an aqueous solution of hydrofluoric acid (HF), It can have a concentration greater than 1000: l (H2O: HF). These terms can be used interchangeably. The term `` washing liquid '' as used herein refers to deionized water or some used to wash electronic components. Other liquids, just like treating electronic components with active chemicals or reactive chemical treatment liquids. The cleaning liquid can be such as deionization 9 ----------------- (please first Read the notes on the reverse side and fill out this page) -11-° J · • The size of the paper is applicable to the Chinese National Standard (CNS) A4 (210 X 297 mm) 492102 A7 __B7 _ V. Description of the invention ((^)- ---------------- (Please read the precautions on the back before filling out this page) Very diluted of water or active or reactive chemicals (such as hydrochloric acid or acetic acid) Aqueous solution to avoid metal deposition such as on the surface of electronic components. Surfactants, anti-erosion agents, and / or ozone are examples of other additives that can be used in the cleaning liquid. The concentration of this additive in the cleaning liquid is very low. For example, based on the total weight of the washing liquid, the concentration is preferably not more than about 1,000 ppm by weight, and more preferably not more than 10 ppm by weight. In the case of ozone, the concentration in the washing liquid is preferably 5 ppm or less. In general, the goal of the washing liquid is to remove chemicals, particles, or reaction products from the surface of the electronic component and the reaction chamber to suppress the re-deposition of the particles. The terms "non-reactive chemically treated liquid π" or "inert" liquid as used herein may also be used. As used herein, the term "pi chemical treatment step" refers to exposing an electronic component precursor to a series of processing liquids to clean or etch the surface of the electronic component precursor. • Line · The term π reaction chamber as used herein refers to Containers, full-flow containers or single tank systems, wash tanks, wet benches, and other reservoirs suitable for wet processing methods. The term π container volume as used herein, when using a reaction chamber, refers to this The volume of liquid that the reaction chamber can hold. The term "full-flow container" as used herein refers to a container that is closed to the environment and is used in one embodiment of the sink system of the π-full-flow method. The term " single container " as used herein refers to any wet processing system in which electronic component precursors are maintained in one container during wet chemical processing technology. 10 This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 492102 A7 _____B7___ V. Description of the invention (1) The term 'electronic component precursors' used herein includes semiconductor crystals without limitation. Circles, flat plates, and other components used in the manufacture of electronic components (ie, integrated circuits). The method of the present invention can generally be applied to any wet processing equipment, in which the same reaction chamber will be included without limitation by Full-flow method, single sink system with small wet bench and direct removal of the overflow sink to perform (2 or more) chemical conditioning steps and any decontamination steps. Multiple steps are available The multiple steps may include a reactive chemically treated liquid followed by a rinse or a reactive chemically treated liquid followed by a reactive chemically treated liquid, or a rinsed followed by a reactive chemically treated liquid. See, for example, Werner Kern's "Overview and Evolution of Semiconductor" Water Contamination and Cleaning Technology "Chapter 1, with Don C. Burkman, Donald Deal, Donald C. Grant and Chapter 3 of "Aqueous Cleaning Processes" by Charlie A. Peterson, "Handbook of Semiconductor Wafer Cleaning Technology" (edited by Werner Kern, Noyes Publication Parkridge, New Jersey 1993), and Hiroyuki Horiki and Takao Nakazawa in "Ultraclean Technology Handbook" The disclosure of Wet Etch Cleaning (edited by Tadahiro Ohmi, published by Marcel Dekker) in Volume 1 is fully incorporated herein by reference. Semiconductor manufacturing is often described, for example, by P. Gise et al. Semiconductor and Integrated Circuit Fabrication Techniques "(Reston Publishing Company, Reston, Virginia, 1979), the disclosure of which is hereby incorporated by reference in its entirety. 11 This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) -------------- Loading --- (Please read the precautions on the back before filling in this Page). I ·· 492102 A7 --------- B7____ 5. Description of the invention () Reactive chemical treatment liquids suitable for carrying out the invention include, without limitation, deionized water, aqueous hydrogen chloride solution and containing the same ingredients Buffer, ammonium hydroxide and buffer containing the same ingredients, hydrogen peroxide, sulfuric acid and buffer containing the same ingredients, mixture of sulfuric acid and ozone, hydrofluoric acid and buffer containing the same ingredients, acetic acid and containing the same ingredients Buffer solution, phosphoric acid and a buffer solution containing the same composition, ammonium fluoride buffered with hydrofluoric acid, and combinations thereof. The specific treatment liquid used, the equipment used, the exposure time, and experimental conditions (ie, the temperature, concentration, and flow rate of the treatment liquid) will vary according to the specific purpose of the specific wet treatment method. Non-reactive treatment liquids suitable for carrying out the present invention include without limitation deionized water, or very dilute solutions of deionized water and active chemicals or organic solvents. Examples of this chemical in the washing liquid include, without limitation, hydrochloric acid, hydrofluoric acid, hydrogen peroxide, ozone, and surfactants. Examples of the organic solvent include, without limitation, acetic acid, isopropyl alcohol (IPA), and fluorocarbons. When implementing the claimed invention, the first reactive chemical treatment liquid system included without limitation deionized water, an aqueous solution of hydrochloric acid and a buffer solution containing the same ingredients, ammonium hydroxide and a buffer solution containing the same ingredients, and hydrogen peroxide. Sulfuric acid and buffers containing the same ingredients, mixture of sulfuric acid and ozone, hydrofluoric acid and buffers containing the same ingredients, acetic acid and buffers containing the same ingredients, phosphoric acid and buffers containing the same ingredients, buffered with hydrofluoric acid Ammonium fluoride, and combinations thereof. When implementing the claimed invention, the second treatment liquid system includes without limitation water, an aqueous solution of hydrochloric acid and a buffer solution containing the same component, ammonium hydroxide and a buffer solution containing the same component, hydrogen peroxide, sulfuric acid and the same composition 12 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page)

492102 A7 —___ B7__ 5. Description of the invention (u). Parts of buffer solution, a mixture of sulfuric acid and ozone 'hydrofluoric acid and a buffer solution containing the same ingredients, acetic acid and a buffer solution containing the same ingredients, phosphoric acid and a solution containing the same ingredients Buffer solution, very dilute solution of ammonium fluoride buffered with hydrofluoric acid, deionized water or deionized water and active chemicals or organic solvents, and combinations thereof. After chemical treatment, electronic component precursors can be dried using any method known to those skilled in the art. A typical processing area for processing electronic component precursors will have storage tanks for chemicals, including, for example, ammonium hydroxide (NH4OH) or hydrofluoric acid (HF). These agents are typically stored in their concentrated form, which are: hydrogen peroxide (H2O2) (31%), NH4OH (28%), hydrochloric acid (HC1) (37%), and HF (49%) (Percentage means weight percentage in aqueous solution). The reaction chamber for processing the precursors of electronic components is connected in liquid state to the storage tank. Control valves and pumps can be used as processing equipment between the storage tank and the reaction chamber. It is preferably that the electronic component precursors processed according to the method of the present invention are stored in a closed container (ie, a "full-flow" container or single tank system), preferably disclosed in, for example, US Patent No. 4,778,532; No. 4,984,597; No. 4,911,761; No. 4,633,893; No. 4,917,123; No. 4,738,272; and No. 4,577,650, the disclosures of which are hereby incorporated by reference for all purposes. This "full stream" or " The "single-tank" method is preferred because it can produce a more uniform and efficient treatment of electronic component precursors. In addition, chemicals commonly used in the chemical treatment of electronic component precursors are quite dangerous because It may be a strong acid, alkali, or volatile solvent. The full-flow container can avoid atmospheric pollution and people's exposure to chemicals. 13 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)- ------------ Installation—— (Please read the notes on the back before filling this page) Order · 丨 Line-492102 A7 __B7_____ V. Description of the Invention (Iy) ------- ---------- (Please read the note on the back first (Please fill out this page again) and minimize the crisis related to the processing liquid by relatively safe handling of chemicals. Although the container disclosed in the above-mentioned U.S. patent is better, anyone familiar with this The reaction chamber, which is well known to those skilled in the art, can also be used without departing from the spirit of the present invention.-Line · Generally, when implementing the preferred embodiment of the present invention, the electronic component precursor is placed in a single tank, and The processing (reactive and / or non-reactive) liquid will be introduced into the container through a valve or injection port (liquid inlet and / or outlet). For example, in one aspect of the invention, the electronic component precursor is During the chemical treatment process (ie, cleaning, washing, and drying), it is maintained in a single reaction chamber, and the processing liquid (reactive and / or non-reactive) is introduced into the reaction chamber. In this aspect of the invention, The electronic component precursor is placed in the reaction chamber, and the surface of the electronic component precursor is in contact with one or more processing liquids for a selected period of time without removing the electronic component precursor from the reaction chamber. Remove. In general, a reactive chemical treatment liquid system is introduced into the reaction chamber and after the electronic component precursor is exposed to the treatment liquid for a specific period of time, a rinse liquid is introduced into the reaction chamber, but the reactive chemical treatment is not first performed. The liquid is removed from the reaction chamber. The rinsing liquid directly removes the reactive chemically treated liquid from the surface of the electronic component precursor and the non-reactive chemically treated liquid and / or the rinsing liquid is different from the reactive chemically treated liquid. Density. For example, in the case where the cleaning liquid is introduced from the bottom, it is more efficient to remove the chemical with a cleaning liquid that is at least about 0.001 g / cm3 heavier than the chemical being removed. If the cleaning solution system is introduced from the top of the reaction chamber, it is more efficient to use a cleaning solution that is at least about 0.001 g / cm3 lighter than the chemical being removed. 14 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 492102 A7 ------ B7 _—— 5. Description of the invention (1) Handling liquids, including, for example, ammonium hydroxide (NHUOH) Hydrogen peroxide (H2O2), hydrochloric acid (HC1), and hydrofluoric acid (HF) are stored in a storage tank outside the reaction chamber. The reaction chamber in which the electronic component precursor is processed is in liquid communication with the chemical storage tank via a liquid line. Usually it uses control valves and pumps to transfer the processing liquid from the storage area to the reaction chamber via a liquid line. Typically, a process control system, such as a personal computer, is used as a device for detecting reaction conditions (ie, flow rate, mixing rate, exposure time, and temperature). For example, the process control system will be used to plan the flow rate and injection rate so that the appropriate concentration of chemicals will be present in the reactive chemical treatment liquid (or non-reactive chemical treatment liquid). Generally, more than one "active chemical" treatment liquid is introduced into the reaction chamber in a single chemical treatment step. For example, the first step in the cleaning process may be standard cleaning 1 (SC1). The typical concentration range in SCI is from about 5: 1: 1 (water: H2O2: NBUOH) to about 1000: 1: 1 concentrated solution volume (which is actually 31% by weight of H2O2 in aqueous solution and 28% by weight of NH4OH). Each component of SCI is maintained in a separate storage container, and the amount of each processing liquid will be injected (via a program control system) into a catheter (liquid line), which is related to The reaction chamber is in liquid communication so that the appropriate ratio of each component can be achieved. Using the method of the present invention, electronic component precursors can be processed with any number of processing liquids. For example, electronic component precursors can be processed with three processing liquids. One treatment liquid is a solution of water, concentrated hydrogen peroxide and concentrated ammonium hydroxide (about 80: 3: 1) (SC1); the second treatment liquid is water, concentrated 15 (please read the precautions on the back first) (Fill in this page again)

This paper size is applicable _ Home Standard (CNS) A4 size (210 x 297 mm) 492102 A7 _____B7__ 5. Description of the invention (iH〇 ----------------- (please first Read the notes on the back and fill in this page) • Solution of hydrogen peroxide and concentrated hydrochloric acid (about 80: 1: 1) (SC2); and the third treatment liquid is hydrofluoric acid (about 4: 1 to about 1000) : 10) (Water: HF). The approximate concentration series of concentrated chemicals are shown in Table 1. This order can also be arranged in different orders (for example, HF, SCI, SC2). This method is particularly useful for cleaning and etching (That is, the oxide is removed from the wafer surface.) After each treatment liquid is processed, the reaction chamber is rinsed. The density of the rinse liquid can be changed by changing the temperature of the rinse liquid. Use the temperature of the rinse or淸 The washing liquid system is based on the temperature and concentration of the processing liquid and the configuration of the reaction chamber. Those skilled in the art can easily determine the desired operating parameters. The following information is provided for illustration purposes: Table I: Description Concentration Chemical Concentration and Density Chemical Name & Chemical Formula HC1 HF NH40H H202 Percent Intensity (W / W) 37.2 49 56.6 * 31% Approximately specific gravity L19 1.18 0.9 1.11 * equal to NH3 i 28.0 i. For example, an HF solution at 60 ° C 100: 1 will have a density of about 0.9850. Pure H20 is a lower 0.98320, so in order to remove it from the bottom, the water should be cooled to at least 54. (: or a density of 0.9862 g / cm3 for better removal. (See Figure 3 for the density of deionized water) Distribution of temperature). In the system of the aforementioned embodiment, the removal is performed from the bottom (it is for illustration purposes only); the preferred temperature of the washing water is such that the density is sufficiently higher than that of the improved treatment Density: 16 scales applicable to China National Standard (CNS) A4 specifications (210 X 297 mm)

A7 B7 SC1 @ 45 ° C Deionized water is preferably equal to or lower than 40 ° C SC2 @ 45 ° C Deionized water is preferably equal to or lower than 40 ° C HF @ 35 ° C Deionized water is preferably equal to Or below 30 ° C 492102 V. Description of the invention (lf) It has been acknowledged that changes in temperature can change the flow rate of various liquids, but even so it is preferable that the density of the washing liquid is at least about 0.001 g / cm2 greater or less than The chemical treatment liquid 'depends on the rinsing solution system being introduced from the top or bottom (as explained above). Smaller or larger rinsing liquid systems are introduced into the container to expose the electronic component precursor system to the rinsing liquid in about 1-5 times the container volume in some specific embodiments. After this exposure, the density of the washing liquid can be adjusted to the point where the maximum flow rate is produced. For example, in a preferred embodiment of the present invention, the rinsing liquid (i.e., deionized water) is introduced from the bottom of the reaction chamber and is at least about 5 ° C (i.e., at least about 0.001 g / cm3 or more dense). A temperature lower than the temperature of the reactive chemical treatment liquid (usually, the washing liquid should be cooled or dense as much as possible without reducing the flow rate) and the electronic component precursor system is exposed to a cooler washing liquid of about M container volume Medium, and more preferably, a relatively cold rinsing liquid with a volume of about 2-3 containers. After this exposure of the electronic component precursor to the colder washing liquid, the temperature of the washing liquid is adjusted to achieve the maximum flow rate. For example, in a CFM Full-Flow ™ system, the maximum flow rate is achieved around 35 ° C. The best method is that the washing liquid is about 5 ° C colder than the reactive chemical treatment liquid (that is, at least more densely about o.ooi g / cm3), and this cooler temperature can also produce the maximum flow rate. Those skilled in the art can easily determine the maximum flow rate temperature in any wet processing technology. If the maximum flow rate determined by this paper is 17 Chinese paper size (CNS) A4 (210 X 297 mm). (Please read the precautions on the back before filling out this page) Installation-丨 '' 492102 A7 ______B7 _____ V. Description of the invention ([L) • If the temperature is outside the range of removal density used for selection (that is, density), the electronic element or the displacer can be washed with a washing liquid of about 1-5 container volume. More preferably, the volume is about 2-3 containers, and then the washing liquid should be adjusted to a temperature that produces the maximum flow rate. In some other specific embodiments, the second treatment liquid system is introduced from the top of the reaction chamber and is at least less dense than the removed reactive chemical treatment liquid by about 0.001 g / cm3 (usually when from the top When introducing, the liquid should be as light as possible without reducing the flow rate). This preferred embodiment of the top introduction system is similar to the one discussed above regarding the second liquid being denser (i.e., about 5 ° C cold) than the reactive chemically treated liquid, with the difference that the starting temperature is warmer. In general, processing performance is optimized (i.e., the most throughput and the least amount of chemicals are used) by introducing a significantly denser solution from the bottom and a significantly less dense solution from the top. To optimize performance, the density and direction of flow should be considered in any wet processing technique, such as a direct-removal tool. If the temperature and concentration of the removed liquid are determined by method, the direction of flow should be changed to optimize removal. Where temperature or concentration can be changed (i.e., with a wash), the density of the removed liquid should be set initially to optimize removal. If removal occurs from the bottom of the container, a significantly denser solution should be introduced. If removal occurs from the top (see US Patent No. 5,826,601, the disclosure of which is incorporated herein by reference in its entirety), then a significantly less dense solution should be used for the initial removal. In other specific embodiments of the present invention, the electronic component precursor may be further processed by a series of processing liquids, such as sulfuric acid saturated with ozone. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm). ---------------- (Please read the precautions on the back before filling this page) One SJ. Line · 492102 ___B7___ V. Description of the invention (^) ---- I-- -------. II (Please read the notes on the back before filling this page) Solution, followed by a solution of hydrogen peroxide and ammonium hydroxide and then a solution of hydrogen peroxide, hydrochloric acid and water. This method is particularly useful for removing organics and general cleansing (ie, particle removal with minimal metal precipitation) to obtain a hydrophilic surface. The concentrations and temperatures listed above are applicable in this embodiment. The method of the present invention can also be used to etch the surface of a semiconductor wafer to remove any unwanted oxide layers from the silicon surface. The invention can also be used to control the etching of oxides. Typical etchants for silicon dioxide include, without limitation, hydrofluoric acid, or hydrofluoric acid buffered ammonium fluoride. The concentrations and temperatures listed above can also be applied in these specific embodiments. After the electronic component precursor is treated with the last reactive chemical treatment liquid and washed as described above, any drying method known to those skilled in the art can be used without departing from the spirit of the present invention. After the electronic component precursor is dried, it can be removed from the reaction chamber. -_Line- Example Cold Removal Example 1 The effect of high-density scrubbing on particle performance in semiconductor wafer processing will be discussed. The bare-bones test wafer is processed in CFM Technology's Full-Flow 8100 ™. The wafer is processed using the SC1-HF method. Twenty batches of 100 test wafers were processed by standard cleaning. In this washing method, the chemical (reactive treatment liquid) is removed from the processing vessel as a washing liquid (i.e., water) at the same temperature and flow rate as the reactive treatment liquid. This washing method is used to make the distribution of chemical injection concentration versus time and Figure 1 19 This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 492102 A7 ___B7______ 1 tablet) The chemical removal shown in the figure is compatible. In a standard rinse, after one minute of removal (or approximately 2-4 container volumes (in this example, the container volume is approximately 6.2 gallons), the temperature of the rinse liquid is reduced to a value that can be reached at Full-Flow The point of the maximum flow rate obtained in the ™ tool. Then during the rinsing period, the rinsing period is cycled between high and low and flow rate in a one minute cycle. For example, after the SCI processing step at 45 ° C, the rinse will be performed at 45 ° C and 18 gpm for 1 minute. Rinse and then at 35. Cycle back and forth between 25 gpm and 12 gpm in one minute. During rinsing (about 5 minutes), rinsing will cycle between these two set points. After the HF step, the starting chemical (reactive treatment liquid) was removed at 35 ° C. with a washing liquid for 1 minute (2-3 container volumes). This is because the maximum flow rate that can be obtained with the most installed Full-Flow ™ tools is around 35. (: Achieved, so the washing temperature cannot be lowered, but will remain fixed. The washing is then cycled back and forth between 25 gpm and 12 gpm in one minute at 35 °. During the washing (that is, about 5 minutes), Cleaning will cycle back and forth between these two set points. Each wafer is tested in 26 batches of standard cleaning. Measure the wafer particle count before and after cleaning, and add particles to the wafer during processing. The numbers are recorded in Table 3. The method used to manage the first 26 batches of wafers is summarized in Table 1. 20 This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) ---- --------- Install --- (Please read the precautions on the back before filling this page) 5J ·-I line-492102 A7 B7 V. Description of the invention (Table 1. For standard SC1-HF Jijie's processing parameters: Process step temperature Total processing time Flow rate concentration SCI 45 ° C 5 minutes 18 gpm 80: 2: 1 (water: Η2〇2 ·· ΝΗ4〇Η) during chemical injection ! 1 / Chemical Removal 45 ° C 1 minute 18 gpm ΝΑ Wash 35 ° C 5 minutes 25 gpm and 12 gpm Cycle Ν HF 35 ° C 2 minutes Chemical injection 18 gpm 100: 1 Initial detergent / chemical removal 35 ° C 1 minute 18 gpm ΝΑ Wash 35 ° C 5 minutes 25 gpm and 12 gpm pm ΝΝΑ IPA drying 8 minutes Second group 26 The wafers were processed under the same conditions, with the difference being the beginning of the cleaning process (removal step). The wafers were processed with the removal cleaning agent initially colder than the previous chemical processing step In other words, the chemical (reactive treatment liquid) is removed from the container with deionized water (washing liquid) that is substantially denser than the chemical step. The flow rate is the same as that of the chemical injected into the container. After the step, the cleaning process is performed again at a temperature at which the maximum flow rate can be reached, which is about 35 ° C. The flow rate is circulated during the remainder of the 1 minute cleaning cycle, not the temperature. Again, during the cleaning process The particle count on a wafer was measured before and after and the number of particles increased during processing is recorded in Table 3. The method of using the second batch of 26 wafers to clean is shown in Table 2. Note that the removal step is at 1 18 gpm in minutes, or 18 gallons of water. The volume of the container is about 6.2 gallons. Therefore, the removal is between 2 and 3 container volumes. 21 This paper size applies to China National Standard (CNS) A4 (210 X 297 cm) ）) · Ι2 * ν words. (Please read the notes on the back before filling this page)

492102 A7 B7 V. Description of the invention (>) Table 1 Processing parameters for SC1-HF washing in Qiaoli: Step temperature Total processing time Flow rate concentration SCI 45 ° C 5 minutes during chemical injection 18 gpm 80: 2: 1 (water: h2〇2: nh4〇h) Initial rinse / chemical removal 35 ° C 1 minute 18 gpm ΝΑ Wash 35 ° C 5 minutes 25 gpm and 12 gpm cycle ΝΑ HF 35 ° C 2 minutes during chemical injection 18 gpm 100: 1 Initial detergent / chemical removal 25 ° C 1 minute 18 gpm ΝΑ Wash 35 ° C 5 minutes 25 gpm and 12 gpm cycle ΝΑ IPA drying The increase in the number of particles on the wafers tested during the 8-minute process for each of the two methods is shown in Table 3. Mean changes and standard deviations are also listed. The increased number of particles is also plotted in FIG. 2. These results suggest that washing with a denser liquid and simultaneous removal from the bottom can reduce the number of particles that increase during processing, as the average number of particles added is less for wafers that are cleaned using cold cleaning . In addition, wafers that were cleaned using cold heading were consistently cleaner as shown by standard deviation. Wafers cleaned in a standard wash show a large change in the number of particles added. Execution number Increase particle (standard rinse) Increase particle (cold rinse) 1 41 3 2 29 18 3 4 11 4 -23 15 5 21 11 6 6 21 7 53 0 8 8 0 9 53 11 10 8 29 11 577 6 12 426 27 22 This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) ------- I --------- (Please read the notes on the back before filling (This page) Order: -1 line · 492102 A7 B7 V. Description of the invention (v \) 13 113 0 14 76 22 15 34 28 16 45 6 17 25 14 18 25 26 19 -1 31 20 307 14 21 6 .12 22 7 20 23 15 13 24 11 16 25 9 25 26 -3 22 Standard deviation 142.3598 9.36877 ----------------- (Please read the precautions on the back before filling this page) Order · Although the invention has been described with reference to preferred embodiments, those skilled in the art will recognize that changes can be made in form and detail without departing from the spirit and scope of the invention. Furthermore, the embodiments cited herein are for illustration purposes and should not be used to limit the scope of the claimed invention, and those skilled in the art will recognize that the embodiments disclosed herein may be Change without departing from the spirit of the invention. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)

Claims (1)

492102 Employees' Cooperatives Seal of the Intellectual Property Bureau of the Ministry of Economic Affairs?衣 __ 6. Scope of Patent Application 1. A method for manufacturing electronic component precursors; comprising: a) placing an electronic component precursor in a reaction chamber having a top and bottom fluid inlet and / or outlet; b) introducing the first reactive chemical processing liquid into the reaction chamber; c) exposing the electronic component precursor to the first reactive chemical processing liquid for a selected period of time; · d) introducing the second processing liquid into the reaction chamber, To directly remove the reactive chemical treatment liquid, wherein the second treatment liquid system is introduced into the reaction chamber from the bottom of the reaction chamber and has a density greater than that of the first reactive chemical treatment liquid; and e) removed from the reaction chamber The second treatment liquid; wherein steps b) to d) can be repeatedly performed. 2. The method according to item 1 of the scope of patent application, wherein the first reactive treatment liquid system is selected from the group consisting of deionized water, an aqueous solution of hydrochloric acid and a buffer solution containing the same component, ammonium hydroxide and a buffer solution containing the same component, and Hydrogen oxide, sulfuric acid and buffer containing the same ingredients, mixture of sulfuric acid and ozone, hydrofluoric acid and buffer containing the same ingredients, chromic acid and buffer containing the same ingredients, phosphoric acid and buffer containing the same ingredients, acetic acid and One or more liquids consisting of a buffer solution containing the same composition, nitric acid and a buffer solution containing the same composition, ammonium fluoride buffered with hydrofluoric acid, and a combination thereof. 3. The method according to item 1 of the scope of patent application, wherein the second treatment liquid is selected from the group consisting of deionized water, a dilute solution of deionized water and an organic solvent, an organic solvent, an aqueous solution of hydrochloric acid, a buffer solution containing the same component, and hydrogen. 1 'This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the notes on the back before filling this page) ϋ · Binding · · • Λ »492102 A8 B8 C8 D8 VI. Application Scope of patentsAmmonium oxide and buffers containing the same ingredients, hydrogen peroxide, sulfuric acid and buffers containing the same ingredients, a mixture of sulfuric acid and ozone, hydrofluoric acid and buffers containing the same ingredients, chromic acid and those containing the same ingredients Cluster consisting of buffer solution, phosphoric acid and buffer containing the same component, acetic acid and buffer containing the same component, nitric acid and buffer containing the same component, ammonium fluoride buffered with hydrofluoric acid, and combinations thereof. · 4. The method according to item 1 of the patent application scope, wherein the reaction chamber is a single sink system. 5. —A method for manufacturing an electronic component precursor, comprising: a) placing the electronic component precursor in a reaction chamber having a top and bottom fluid inlet and / or outlet; b) subjecting a first reactive chemical treatment Introducing the liquid into the reaction chamber; c) exposing the electronic component precursor to the first reactive chemical treatment liquid for a selected period of time; d) introducing the second processing liquid into the reaction chamber to directly remove the reactive chemical treatment liquid, The second treatment liquid system is introduced into the reaction chamber through the top of the reaction chamber and has a density lower than that of the first chemical treatment liquid; and e) removing the second treatment liquid from the reaction chamber; wherein steps b) to d ) Can be performed repeatedly. 6. The method according to item 5 of the scope of patent application, wherein the first reactive chemical treatment liquid system is selected from the group consisting of deionized water, an aqueous solution of hydrochloric acid and a buffer solution containing the same component, ammonium hydroxide and a buffer solution containing the same component, Hydrogen peroxide, sulfuric acid and buffers containing the same ingredients, sulfuric acid and ozone 2 (Please read the precautions on the back before filling out this page) Binding · Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Consumption Cooperatives This paper applies Chinese national standards (CNS) A4 specifications (210 X 297 mm) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 492102 A8 B8 C8 D8 ____ VI. Patent application mixture, hydrofluoric acid and buffer solution containing the same ingredients, chromic acid and containing Cluster consisting of buffers of the same composition, phosphoric acid and buffers containing the same components, acetic acid and buffers containing the same components, nitric acid and buffers containing the same components, ammonium fluoride buffered with hydrofluoric acid, and combinations thereof One or more liquids. 7. The method according to item 5 of the scope of patent application, wherein the second treatment liquid is selected from the group consisting of deionized water, a dilute solution of deionized water and an organic solvent, an organic solvent, an aqueous solution of hydrochloric acid, a buffer solution containing the same component, and hydrogen. Ammonium oxide and buffer containing the same ingredients, hydrogen peroxide, sulfuric acid and buffer containing the same ingredients, mixture of sulfuric acid and ozone, hydrofluoric acid and buffer containing the same ingredients, chromic acid and buffer containing the same ingredients, One or more liquids consisting of phosphoric acid and a buffer solution containing the same ingredient, acetic acid and a buffer solution containing the same ingredient, nitric acid and a buffer solution containing the same ingredient, ammonium fluoride buffered with hydrofluoric acid, and a combination thereof . 8. The method according to item 5 of the patent application, wherein the reaction chamber is a single sink system. 9. A method for manufacturing an electronic component precursor; comprising: a) placing an electronic component precursor in a reaction chamber having a top and bottom fluid inlet and / or outlet; b) subjecting a first reactive chemical treatment The liquid is introduced into the reaction chamber; c) the electronic component precursor is exposed to the first reactive chemical treatment liquid for a selected period of time; d) the second processing liquid is introduced into the reaction chamber to directly remove the first reactive chemical treatment liquid 'Where the second treatment liquid system is from the bottom of the reaction chamber 3 This paper size applies to China National Standard (CNS) A4 (210 x 297 mm) (Please read the precautions on the back before filling this page) 492102 A8 B8 C8 D8 VI. Application for patent scope. The part is introduced into the reaction chamber and has a higher or greater density than the first reactive chemical treatment liquid; e) The precursor of the electronic component is exposed to the second treatment liquid to Exposing the electronic component precursor to the second processing liquid at approximately 1-5 container volumes; f) continuing to expose the electronic component precursor to an additional volume of the second processing liquid for a selected period of time; and g) reacting from the reaction The chamber removes this second processing liquid; wherein steps b) to d) can be performed repeatedly. 10. The method according to item 9 of the scope of patent application, wherein the first reactive chemical treatment liquid system is selected from the group consisting of deionized water, an aqueous solution of hydrochloric acid and a buffer solution containing the same component, ammonium hydroxide and a buffer solution containing the same component, Hydrogen peroxide, sulfuric acid and buffer containing the same ingredients, mixture of sulfuric acid and ozone, hydrofluoric acid and buffer containing the same ingredients, chromic acid and buffer containing the same ingredients, phosphoric acid and buffer containing the same ingredients, acetic acid One or more liquids consisting of a buffer solution containing the same composition, nitric acid and a buffer solution containing the same composition, ammonium fluoride buffered with hydrofluoric acid, and a combination thereof. 11. The method according to item 9 of the scope of patent application, wherein the second treatment liquid is selected from the group consisting of deionized water, a dilute solution of deionized water and an organic solvent, an organic solvent, an aqueous solution of hydrochloric acid, a buffer solution containing the same component, and hydrogen. Ammonium oxide and buffer containing the same ingredients, hydrogen peroxide, sulfuric acid and buffer containing the same ingredients, mixture of sulfuric acid and ozone, hydrofluoric acid and buffer containing the same ingredients, chromic acid and buffer containing the same ingredients, Phosphorus 4 (Please read the precautions on the back before filling out this page) Packing. Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Employees' Cooperatives. This paper is sized for the Chinese National Standard (CNS) A4 (210 X 297 mm) 492102 A8 B8 C8 D8 VI. Patent application Clusters consisting of acid and buffer containing the same ingredients, acetic acid and buffer containing the same ingredients, nitric acid and buffer containing the same ingredients, ammonium fluoride buffered with hydrofluoric acid, and combinations thereof One or more liquids. 12. The method according to claim 9 in which the reaction chamber is a single sink system. 13. The method according to item 9 of the scope of patent application, further comprising the step of changing the density used in step e) to the density of the second treatment liquid in step f). 14. A method for manufacturing an electronic component precursor, comprising: a) placing the electronic component precursor in a reaction chamber having a top and a bottom; b) introducing a first reactive chemical treatment liquid into the reaction chamber; c ) Exposing the electronic component precursor to the first reactive treatment liquid for a selected period of time; d) introducing the second treatment liquid into the reaction chamber to directly remove the reactive chemical treatment liquid, wherein the second treatment liquid system passes through The top of the reaction chamber is introduced into the reaction chamber and has a smaller density than the first chemical treatment liquid; e) exposing the electronic component precursor to the second processing liquid to expose the electronic component precursor to about 1-5 A container volume of the second processing liquid; and f) continuing to expose the electronic component precursor to an additional volume of the second processing liquid for a selected period of time; and g) removing the non-reactive processing liquid from the reaction chamber; b) to d) can be performed repeatedly. 5 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) ----------------- (Please read the precautions on the back before filling this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 492102 A8 B8 C8 D8 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 6. Scope of Patent Application 15. According to the method of item 14 of the scope of patent application, where the first reaction The chemical treatment liquid system is selected from the group consisting of deionized water, an aqueous solution of hydrochloric acid and a buffer solution containing the same component, ammonium hydroxide and a buffer solution containing the same component, hydrogen peroxide, sulfuric acid and a buffer solution containing the same component, and sulfuric acid and ozone. Mixture, hydrofluoric acid and buffer containing the same ingredients, chromic acid and buffer containing the same ingredients, phosphoric acid and buffer containing the same ingredients, acetic acid and buffer containing the same ingredients, nitric acid and buffer containing the same ingredients One or more liquids of a cluster consisting of ammonium fluoride buffered with hydrofluoric acid and a combination thereof. 16. The method according to item 14 of the scope of patent application, wherein the second treatment liquid is selected from the group consisting of deionized water, a dilute solution of deionized water and an organic solvent, an organic solvent, an aqueous solution of hydrochloric acid, a buffer solution containing the same component, and hydrogen. Ammonium oxide and buffer containing the same ingredients, hydrogen peroxide, sulfuric acid and buffer containing the same ingredients, mixture of sulfuric acid and ozone, hydrofluoric acid and buffer containing the same ingredients, chromic acid and buffer containing the same ingredients, One or more liquids consisting of phosphoric acid and a buffer solution containing the same ingredient, acetic acid and a buffer solution containing the same ingredient, nitric acid and a buffer solution containing the same ingredient, ammonium fluoride buffered with hydrofluoric acid, and a combination thereof . Π. A method according to item 14 of the patent application, wherein the reaction chamber is a single sink system. 6 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) • ---------------- (Please read the precautions on the back before filling this page) Order: